GROWTH OF ZINC OXIDE NANOSTRUCTURES AND FILMS

AND P-DOPING OF FILMS

IN AQUEOUS SOLUTION

TAY CHUAN BENG

B. Eng (Hons.), M. Eng

A THESIS SUBMITTED

FOR THE DEGREE OF DOCTOR OF PHILOSOPHY

DEPARTMENT OF ELECTRICAL AND COMPUTER ENGINEERING

NATIONAL UNIVERSITY OF SINGAPORE

2009
 ACKNOWLEDGEMENTS

First and foremost, I would like to express my sincere appreciation to both of my

supervisors, Prof Chua Soo Jin and Prof Loh Kian Ping, whose patience, guidance and
insights are crucial to this body of work.

I would also like to express my thanks to:

• Dr S. Tripathy, Dr C.B. Soh, Dr H.Q. Le and Dr H.F. Liu from IMRE, whose instructions
and guidance were important lifelines during the early stages of my research,
• H. Musni and B. H. Tan from Centre for Optoelectronics, NUS whose experience,
skill and time helped to keep the lab equipments and experiments running
smoothly and properly,
• Wang Miao and Haryono from Singapore MIT-Alliance, as well as Lin Fen, Huang
Leihua, Tian Feng, Mantavya Sinha, Vivek Dixit for all the good memories,
• Liu Minghui, Deng Suzi, Zhong Yulin from Chemistry Dept, NUS, for opening up the
world of chemistry to me,
• and all the others at NUS and IMRE that have helped me one way or another.

Finally, and most importantly, my profound gratitute goes to my Dad, Mom, Chuan
Hock, MIchelle, Benjamin and Matthew. Without your constant support, motivation
and love, I would not have been able to finish this work. Thank you for everything.

i
 TABLE OF CONTENTS

1 Introduction ............................................................................................................... 1

1.1 Introduction......................................................................................................... 1

1.2 Background.......................................................................................................... 1

1.3 Crystal Structure .................................................................................................. 2

1.4 ZnO Growth Techniques...................................................................................... 3

1.4.1 Vapor phase transport ................................................................................. 3

1.4.2 Chemical vapor deposition (CVD) and metal-organic chemical vapor

deposition (MOCVD) .................................................................................................. 4

1.4.3 Molecular beam epitaxy (MBE) ................................................................... 4

1.4.4 Aqueous solution-based synthesis .............................................................. 5

1.4.5 Comparison of gas and solution phase growth methods ............................ 5

1.5 Doping in ZnO ...................................................................................................... 8

1.6 Motivation and objectives ................................................................................ 13

1.7 Organization of the thesis ................................................................................. 14

2 Aqueous solution growth of ZnO ............................................................................. 16

2.1 Introduction....................................................................................................... 16

2.2 Basic terminologies and concepts ..................................................................... 16

2.3 Temperature-dependent ionic equilibrium of ZnAc2 and NH3 ......................... 19

2.4 Nucleation and growth...................................................................................... 26

2.4.1 Homogeneous nucleation .......................................................................... 26

2.4.2 Heterogeneous nucleation ........................................................................ 28

2.4.3 Crystal growth ............................................................................................ 29

2.5 Effect of pH on ZnO surface .............................................................................. 33

2.6 Conclusion ......................................................................................................... 35

ii
3 Experimental methods for growth and characterization of ZnO............................ 36

3.1 Introduction....................................................................................................... 36

3.2 Growth procedure and apparatus .................................................................... 36

3.2.1 Pre-coating of substrate with ZnO seeds................................................... 36

3.2.2 ZnO growth in solution .............................................................................. 38

3.3 Characterization tools ....................................................................................... 40

3.4 Field-emission scanning electron microscopy (FESEM) .................................... 40

3.5 Photoluminescence spectroscopy .................................................................... 41

3.6 Raman spectroscopy ......................................................................................... 45

3.7 Secondary ion mass spectrometry (SIMS) ........................................................ 49

3.8 Hall effect measurement................................................................................... 50

3.9 Conclusion ......................................................................................................... 54

4 Prediction of Length and Density of ZnO Nanorods on GaN Substrate .................. 55

4.1 Introduction....................................................................................................... 55

4.2 Experimental Procedure.................................................................................... 57

4.3 Results ............................................................................................................... 58

4.4 Discussion .......................................................................................................... 61

4.5 Effect of Solubility of Zinc on Density and Length of ZnO Nanorod Arrays ...... 62

4.6 Effect of Temperature on Density and Length .................................................. 66

4.7 ZnO Nanorod Length and Density Maps ........................................................... 68

4.8 Limitations of Model ......................................................................................... 69

4.9 Conclusion ......................................................................................................... 71

5 Growth and Defects of ZnO Nanorods Grown from a ZnO Seed Layer ................... 72

5.1 Introduction....................................................................................................... 72

5.2 Experimental Procedure.................................................................................... 73

5.3 Results ............................................................................................................... 74

iii
 5.4 Discussion .......................................................................................................... 80

5.4.1 Role of solubility in growth morphology ................................................... 80

5.5 Role of interfacial properties in aqueous solution............................................ 85

5.6 Defects and the growth mechanism ................................................................. 87

5.7 Conclusion ......................................................................................................... 88

6 Growth of p-ZnO film using multiple growth cycles ............................................... 90

6.1 Introduction....................................................................................................... 90

6.2 Experiment ........................................................................................................ 92

6.3 Results and discussion....................................................................................... 94

6.3.1 Evolution of film morphology using a multi-step growth approach ......... 94

6.4 Role of K as a dopant for ZnO films ................................................................... 96

6.5 Effect of electric field on the growth and doping of ZnO films in solution....... 98

6.6 Effect of annealing in nitrogen ambient on p-type doping by K ..................... 103

6.7 Fabrication of p-ZnO / n-GaN LED ................................................................... 105

6.8 Conclusion ....................................................................................................... 106

7 Conclusions and Recommendations ...................................................................... 108

7.1 Conclusions...................................................................................................... 108

7.2 Recommendations .......................................................................................... 111

8 Bibliography ........................................................................................................... 113

iv
 SUMMARY

ZnO is a wide bandgap material with a large exciton binding energy (60 meV) and highly
polar surfaces which promote anisotropic growth of many interesting nanostructures.
Due to its multifunctional properties, ZnO has been proposed for a wide variety of
applications such as transparent conducting electrodes, gas sensors, piezoelectric
sensors and generator, acoustic wave devices, light emitting diodes and solar cells.

This work studies the growth of ZnO nanorods and films in aqueous solution using zinc
acetate and ammonium hydroxide in detail. Regardless of the type of substrate used,
the solubility of zinc (SZn), interface properties of the substrate and growth
temperature emerged as the main factors determining the growth rate and
morphology of the nanorods. For GaN substrates, the activation energies for density
and length of nanorods are -2.11 and 0.77 eV respectively. An empirical growth map
for growth prediction of the density and length of nanorods is generated. For
substrates with a pre-coated layer of ZnO nanoparticles, a uniform coverage of
nanorods is obtained when SZn < 0.88 mM, and large clustered rods are obtained when
SZn > 1.56 mM. For values of SZn that lies in between, both nanorods and large clustered
rods can be obtained.

Using photoluminescence and Raman spectroscopy, the native defects were identified
and associated with the growth conditions. When growth pH < PZC, the growth rate is
very slow and hydrogen defects are the major defects with very strong UV emissions.
When growth pH > PZC, the growth rate is fast and the major defects are interstitial
oxygen, interstitial zinc and zinc vacancies with strong visible emissions. Interstitial zinc
and zinc vacancies contributes to the green emission while interstitial oxygen, the red
component.

Next, ZnO films were grown and doped with potassium using a new growth strategy
which can be applied to any substrate, regardless of its lattice matching. The p-type
conductivity in ZnO:K films is confirmed using Hall effect, SIMS and XPS measurements.
An optimum hole concentration of 3.8 x 1017 cm-3 is obtained at 0.07 M KAc without
any applied bias and 3.98 x 1017 cm-3 when -0.4 V is applied. To the best of our
v
knowledge, this is the first report of p-type doping of ZnO films in aqueous solution at
low temperatures using potassium from group I as a p-dopant.

Annealing above 400°C activates the hydrogen defects and converts the film to n-type
with electron concentrations to 1 x 1019 cm-3. By extending the annealing time beyond
30 min at 800°C, the hydrogen defects can be reduced and the p-type conductivity can
be recovered.

Finally, a p-ZnO / n-GaN junction is fabricated with a rectifying I-V characteristic and a
weak orange electroluminescence at a forward bias current of 75.9 to 98.3 mA. The
reverse bias leakage current ranges from 1.3 to 1.5 mA at 3 V.

vi
 LIST OF TABLES

Table 1.1. Summary of intrinsic doping levels of undoped ZnO polycrystalline films and
single crystals which have been grown using various methods. ....................................... 8

Table 1.2. Summary of various group III elements as well as their corresponding growth
methods and levels of n-doping. ....................................................................................... 9

Table 1.3. Calculated bond lengths and the defect energy levels in ZnO for group I and
V dopants. Ideal ZnO bond length (ro) is 1.93 Å. Taken from [32]................................... 10

Table 1.4. Summary of p-type mono-doping of ZnO using group V elements. .............. 11

Table 2.1. List of Enthalpy Values [58-60]. Enthalpy alues with an asterisk * denotes
calculated values of enthalpy of formation from tabulated enthalpy of reaction.......... 21

Table 3.1. Lattice parameters of various substrate materials for ZnO growth [69]. ...... 37

Table 3.2. Frequency and symmetry of the fundamental optical modes in ZnO............ 48

Table 4.1. Summary of different results and methods for aqueous solution growth. ... 56

Table 4.2. Summary of effects of temperature and reactant concentrations on density

and length of ZnO nanorods. ........................................................................................... 62

Table 5.1. Summary of observed growth behavior with solution pH ............................. 81

Table 6.1. Summary of reported investigators, precursors, growth temperature and

substrates for epitaxial ZnO growth in aqueous solution. .............................................. 91

Table 6.2. Summary of carrier parameters obtained from Hall effect measurements for
samples grown without KAc and with 0.07 and 0.24 M KAc. The film thickness is
obtained from the SEM image of the cross-section of the film. ..................................... 97

Table 6.3. Summary of carrier parameters obtained from Hall effect measurements for
samples grown with 0.24 M KAc at different bias voltages. The film thickness is
obtained from the SEM image of the cross-section of the film. ..................................... 99

Table 6.4. Summary of percentage atomic concentrations from quantifation of the

fitted components of Zn 2p, O 1s and K 2s in the XPS survey spectra. The relative

vii
sensitivity factors (RSF) that were used for quantification are indicated beside the
element in parenthesis. ................................................................................................. 101

viii
 LIST OF FIGURES

Figure 1.1. Schematic diagram of wurtzite crystal structure of ZnO and its common
surface planes. ................................................................................................................... 2

Figure 1.2. Schematic showing the free energy of the precursors in gaseous and
hydrated states and the final ZnO product........................................................................ 6

Figure 1.3. Carrier concentrations as a function of the preservation period after

deposition. A very stable p-type conductivity is obtained when Li-N codoping method is
used. Graph was taken from [45]. ................................................................................... 12

Figure 2.1. Equilibrium complex concentrations and solubility of zinc as a function of pH

at 300K. The pH is increased by adding more NH3 while keeping the mass of ZnAc2
constant at 0.016 M. Curves show the equilibrium concentrations of (a) zinc acetate
complexes, (b) Zn2+ ions, (c) zinc ammine complexes, (d) zinc hydroxide complexes and
(e) total zinc ion concentration respectively. .................................................................. 22

Figure 2.2. Variation of solubility of zinc with pH. The solubility of zinc was calculated
using Eq. (2.15). The data for each curve is obtained by keeping the concentration of
ZnAc2 fixed while varying the concentration of NH3. The concentrations of ZnAc2 are
indicated on each curve. .................................................................................................. 25

Figure 2.3. Variation of solubility of zinc and pH when the concentration of NH3 is
varied while ZnAc2 is kept constant at 0.02 M. The solubility of zinc was calculated using
Eq. (2.15). ......................................................................................................................... 25

Figure 2.4. The Gibbs free energy of nucleation with respect to embryo radius. The
critical radius r* and energy ∆G* depends on the balance between the surface and
volume energy of the growing embryo. .......................................................................... 28

Figure 2.5. Processes involved in heterogeneous nucleation on a substrate surface. ... 28

Figure 2.6. Hydrolysis of hydrated metal ions in aqueous solution. The positively
charged metal ion attracts the electrons away from the O-H bond, leading to the
breakage of the O-H bond and release of the H+ ion into the solution........................... 30

Figure 2.7. (A) Aggregation and (B) coalescence of individual particles. ........................ 32

ix
Figure 2.8. A model for adsorption of Zn2+ on ZnO surface. ........................................... 34

Figure 2.9. Adsorption of Zn2+ ions depends on the pH of the solution. Highest rate of
adsorption when the pH is higher than the PZC of ZnO. ................................................. 34

Figure 3.1 TEM image of the ZnO nanoparticles that are grown by refluxing 0.02 M KOH
and 0.01 M ZnAc2 in methanol for 2 h. The diameter of the nanoparticles range from 10
to 20 nm. Agglomeration of the nanoparticles can be clearly seen................................ 38

Figure 3.2. Apparatus for growth of ZnO on a substrate. ............................................... 39

Figure 3.3 (a) Band structure and symmetries of wurtzite ZnO. The splitting into three
valence bands (A, B and C) is caused by field and spin-orbit splitting [75]. (b) Schematic
drawing of the exciton states. (c) Summary of various optical transitions near the band
gap and their corresponding energy and wavelength ranges. ........................................ 43

Figure 3.4. Comparison of the low-temperature PL (4 K) spectra from (a) a bulk single
crystal ZnO grown by VPT [77] and (b) ZnO nanorods grown using a solution containing
zinc nitrate, HMT and PEI [78] on a pre-coated Si substrate which had been pre-coated
using ZnAc2 solution. Both samples have been annealed in forming gas at 600°C. ....... 44

Figure 3.5. Rayleigh and Raman scattering ..................................................................... 46

Figure 3.6. Depth profiling using a dual beam technique. .............................................. 49

Figure 3.7. Schematic of the Hall effect in a long, thin bar of semiconductor with four
ohmic contacts. The direction of the magnetic field B is along the z-axis and the sample
has a finite thickness d. .................................................................................................... 50

Figure 3.8. Schematic of a van der Pauw configuration used in the determination of the
two characteristic resistances RA and RB. ........................................................................ 52

Figure 3.9. Schematic of a van der Pauw configuration used in the determination of the
Hall voltage VH.................................................................................................................. 53

Figure 4.1. SEM images of ZnO nanorods grown at temperatures (a) 60°C, (b) 80°C, (c)
100°C and (d) 150°C in solutions containing 0.016 M Zn(Ac)2 and 0.173 M NH4OH. ..... 59

Figure 4.2. The effect of growth temperature on (a) length and (b) density of ZnO
nanorods. ......................................................................................................................... 59

x
Figure 4.3. SEM images of ZnO nanorods with different molar ratios: (a) 0.016 M
Zn(Ac)2, 0.1 M NH4OH, (b) 0.016 M Zn(Ac)2, 0.143 M NH4OH, (c) 0.016 M Zn(Ac)2, 0.204
M NH4OH and (d) 0.016 M Zn(Ac)2, 0.306 M NH4OH. ..................................................... 60

Figure 4.4. Effect of molar ratio on (a) length and (b) density of ZnO nanorods. The
concentration of Zn(Ac)2 is kept constant at 0.016 M and the concentration of NH4OH is
varied from 0.1 M to 0.4 M to increase the molar ratio. ................................................ 60

Figure 4.5. Effect of increasing concentration of precursors while maintaining a

constant molar ratio on (a) length and (b) density of ZnO nanorods. Zn(Ac)2 is increased
from 0.01 to 0.03 M , and concentration of ammonia by a proportional amount to
maintain a constant molar ratio of 6.27. ......................................................................... 61

Figure 4.6. Logarithm of ZnO nanorods lengths plotted against the total concentration
of zinc ions in the precursor solution.
represents the data points when the Zn(Ac)2
concentration is kept constant at 0.016 M and the NH4OH concentration is varied from
0.1 to 0.4 M while  represents the data points when concentration of Zn(Ac)2 is
increased from 0.01 to 0.033 M with a constant molar ratio [NH4+]/[Zn2+]. The growth
temperature is kept constant at 373 K. ........................................................................... 63

Figure 4.7. Logarithm of rod density (cm-2) plotted against the total concentration of
zinc ions in the precursor solution. The inset shows the corresponding initial degree of
supersaturation of zinc in the precursor solution at the growth temperature 373K. The
data points for varying the ratio of reactant concentrations are represented by
,
while the increasing reactant concentrations with a constant ratio by . .................... 64
n
Figure 4.8. Plot of (a) Y = ln B AB1S Zn [ ( )]m
and (b) Y= ln L AL1S Zn [ (
against 1/T.  and
)]
represent the density and length data points respectively when temperature is varied
from 60 to 150°C. The inset shows the degree of supersaturation of zinc, S, against
temperature for a precursor solution containing 0.016 M Zn(Ac)2 and 0.173 M NH4OH.
.......................................................................................................................................... 67

Figure 4.9. Black lines show the contour plot of (a) log[B(cm-2)] and (b) length (nm) for
various concentrations of ZnAc2 and NH4OH. The validity limits for pH between 9.7 and
10.6, and degree of supersaturation of zinc between 20 and 60 are shown in red and
blue lines respectively...................................................................................................... 70
xi
Figure 5.1. SEM morphology of ZnO nanorods grown on Si substrates with a pre-coat of
ZnO nanoparticles using growth solutions with 0.02 M ZnAc2 and (a) 0.02 M, (b) 0.04 M,
(c) 0.1 M, (d) 0.3 M, (e) 0.4 M and (f) 1.1 M NH4OH. The concentration of NH4OH and
the corresponding initial solution pH values in square parentheses are indicated on the
top left corner. Scale bar shows 1 µm. ............................................................................ 75

Figure 5.2. SEM image showing the morphologies of ZnO nanorods grown in various
concentrations of ZnAc2 and NH4OH. (a), (b) and (c) were grown with 0.4 M, 0.8 M and
1.1 M NH4OH respectively while keeping ZnAc2 fixed at 0.01 M. (d), (e) and (f) were
grown with 0.4 M, 0.8 M and 1.1 M NH4OH respectively while keeping ZnAc2 fixed at
0.02 M. (g), (h) and (i) were grown with 0.4 M, 0.8 M and 1.1 M NH4OH respectively
while keeping ZnAc2 fixed at 0.03 M. The scale bar is 1 µm and all images were taken
with the same magnification. .......................................................................................... 75

Figure 5.3. The Raman spectra measured from samples grown with 0.4, 0.8 and 1.1 M
NH4OH on a glass substrate. Inset shows the shift of the E2H peak to higher frequencies
as concentration of NH4OH is increased.......................................................................... 77

Figure 5.4. Photoluminescence spectra recorded from samples grown in 0.02 M (black
line), 0.04 M (blue line), 0.3 M (green line) and 1.1 M NH4OH (red line) while the
concentration of ZnAc2 is kept constant at 0.02 M. ........................................................ 77

Figure 5.5. PL spectra of sample grown in high pH (10.7) after annealing at various
temperatures in (a) air and (b) nitrogen ambient, as well as low pH sample (7) annealed
in (c) air and (d) nitrogen ambient. The sharp peak at 650 nm is due to the doubling of
the 325 nm laser line and should be ignored. ................................................................. 78

Figure 5.6. Plot showing the solubility of zinc, SZn, against the concentration of NH4OH
for 0.006 M (black dotted line), 0.01 M (blue line), 0.02 M (green line) and 0.03 M (red
line) of ZnAc2. The SZn data points which are labeled (a) to (i) corresponds to the SEM
images in Figs 5.2 (a) to (i) respectively which have been reproduced here for ease of
comparison. The value of SZn when 0.006 M ZnAc2 and 0.4 M NH4OH is marked with a
square (
) and the corresponding SEM image is shown in Fig 5.7. Growth in region 1
produces uniform nanorods, region II a mixed morphology of nanorods and large rods
and region III only large rods. .......................................................................................... 82

xii
Figure 5.7. SEM image showing the top and cross-sectional view of a sample grown in
0.006 M ZnAc2 and 0.4 M NH4OH. The mixed morphology confirms the dependence of
SZn which shown in Fig 5.6. .............................................................................................. 83

Figure 5.8. Plot of solubility of zinc against pH for 0.006 M (black dotted line), 0.01 M
(blue line), 0.02 M (green line) and 0.03 M (red line) of ZnAc2. The corresponding SEM
images from Fig 5.2 are shown here for ease of comparison. ........................................ 85

Figure 5.9. SEM image showing the top view of a sample grown in (a) 0.02 M and (b)
1.1 M NH4OH. The concentration of ZnAc2 is kept constant at 0.02 M. The scale bar
shows 1 µm. ..................................................................................................................... 86

Figure 6.1. Modified growth setup to study the effect of internal electric field on the
growth and doping of ZnO films. ..................................................................................... 93

Figure 6.2. Morphology evolution from the seed layer to the film layer growth on n-
Si(100). ............................................................................................................................. 94

Figure 6.3. Morphology evolution from the seed layer to the film layer growth on n-
GaN epilayer..................................................................................................................... 95

Figure 6.4. PL spectra of as-grown seed layer (black) and the subsequent film growth
layers (blue for 30 min, green for 90 min and red for 180 min). The film layer growth
step significantly enhances UV emission while slightly reducing the visible emissions.. 95

Figure 6.5. SEM image shows the top view of the ZnO film after one cycle of seed layer
growth followed by two cycles of film layer growth for the samples that are grown (a)
without KAc and with (b) 0.07 and (c) 0.24 M KAc. ......................................................... 96

Figure 6.6. SIMS depth profile for Zn, O and K. ............................................................... 97

Figure 6.7. SIMS depth profile for Zn, O and K for samples grown in the presence of
0.24 M KAc and varying bias voltages from 0, -0.1, -0.4 to -0.9 V................................... 99

Figure 6.8. Typical XPS survey spectrum of a ZnO sample doped with K. The peak
positions of Zn, O, K and C have been marked. Au peaks are from the calibration
reference. ....................................................................................................................... 100

Figure 6.9. Typical component fitting of Zn, O and K using Zn 2p3/2, O 1s and K 2s peaks
for atomic concentration quantification. Synthetic peaks were fitted to the measured
xiii
peaks using a Shirley background and Gaussian-Lorentian distributions. Quantification
was performed using the fitted synthetic peaks to improve estimation accuracy. ...... 100

Figure 6.10. XPS valence band spectra of Zn 3d for samples grown with (a) -0.9V, (b) -
0.1V and (c) -0.4V. The corresponding hole concentrations in cm-3 has been indication
in the legend. A larger core level shift is observed for a higher hole concentration. ... 101

Figure 6.11. Plot of core energy level Zn 2p3/2 against the hole concentration as
measured using Hall effect. The as-measured as well as the C 1s and O 1s calibrated
peak values are shown. A line is fitted to show the increasing binding energy with hole
concentration. ................................................................................................................ 102

Figure 6.12. Effect of anneal temperatures on the carrier concentration and mobility
for ZnO films grown (a) without any KAc, and with (b) 0.07 and (c) 0.24 M KAc. (d) The
effect of anneal duration at 800°C for sample grown in 0.24 M KAc. Annealing for all
samples were done in a nitrogen ambient. Data points for as-grown samples were
represented at 100 °C. The electron concentrations and mobilities are marked by ● and
● respecQvely, while the hole concentraQon and mobility by ○ and ○ respecQvely. ... 103

Figure 6.13. I-V characteristic plotted in (a) logarithmic and (b) linear scale. Each line
shows the I-V from measured from a different device. Inset of (a) shows a schematic
diagram of the device while the inset of (b) confirm the ohmic behavior of the top and
bottom contacts after annealing at 700°C 1 h............................................................... 107

Figure 6.14. The electroluminescence spectra at various current injection levels from
20 mA to 70 mA. ............................................................................................................ 107

xiv
1 Introduction

1.1 Introduction
This chapter begins with a brief historical background and some basic properties of ZnO.
Various growth techniques and their achievements in p- and n-type doping are then
presented. This is followed the motivation and objectives of this thesis. Finally, the
organization of this thesis is presented.

1.2 Background
Zinc oxide (ZnO) is classified as a IIb-VI compound semiconductor, which comprises of
the binary compounds of Zn, Cd, and Hg with O, S, Se and Te and their ternary or
quaternary alloys. ZnO is a wide band gap semiconductor with a direct gap of around
3.4 eV and crystallizes preferentially in the hexagonal wurtzite-type structure. It occurs
naturally as zincite and usually contains some manganese, iron and other elements.
The color of zincite ranges from yellow to red, depending on the type of impurities.
Synthetically-grown pure ZnO, however, is colourless and clear due its large band gap.

ZnO is not a new material despite the recent surge in research work. Work on ZnO had
begun gradually in the 1930s and peaked around the end of the 1970s and the early
1980s. The focus of research was on bulk ZnO covering topics such as growth, doping,
transport, deep centres, band structure, excitons, bulk and surface polaritons,
luminescence, high excitation effects and lasing. Several reviews [1-3] cover the work
done during this early period. The research interest faded for several reasons: difficulty
in obtaining a p-type ZnO and a shift in interest to lower dimension structures such as
quantum wells which were exclusively based on GaAs/Al1-xGaxAs. A revival in ZnO
research began in mid-1990s based on the possibility to grow epitaxial layers, quantum
wells, nanorods or quantum dots and its possible applications in blue/UV

1
optoelectronics, radiation
adiation hard electronic devices, visible-blind
visible blind electronic circuits,
semiconductor spintronics and transparent conducting oxides. Several excellent
reviews covering the current progress have been published [4-6].

1.3 Crystal Structure

ZnO has a hexagonal wurtzite structure. Part of its wurtzite structure is shown in Fig 1.1.
The Zn2+ and O2- sublattices exhibit hexagonal close packing and interpenetrate
interpen each
other along the c-axis.
axis. The lattice parameters are a = 3.2495 Å and c = 5.2069 Å with a
density of 5.605 g cm-3 [7].
[7]

Figure 1.1. Schematic diagram of wurtzite crystal structure of ZnO and its
common surface planes.

In the wurtzite structure, each Zn2+ is surrounded tetrahedrally by four O2- and vice
versa. This tetrahedral coordination characterizes covalent bonds with sp3 hybridisation.
It is known that when moving from the group IV over the III-V
III and II-VI
VI to the I-VII
I
semiconductors, the bonds will show an increasing amount of ionic bonding.
bon As such,
ZnO shows a substantial amount of ionic bonding and lies at the borderline between
being classed as a covalent and ionic compound. The bottom of the conduction band is
formed essentially from the 4s levels of Zn2+ and the top of the valence band from the
2p levels of O2-. The band gap between the conduction and valence bands is about
3.437 eV at low temperatures of about 4 K [8].

2
Furthermore, the tetrahedral coordination gives a polar symmetry along the c-axis. This
polarity is responsible for its piezoelectricity, spontaneous polarization, anisotropic
crystal growth habit, etching behaviour and defect generation.

Fig 1.1 also shows the common polar and non-polar planes in the wurtzite structure.
Common polar face terminations of wurtzite ZnO are the Zn-terminated (0001) and O-
terminated (000-1) faces which are both c-axis oriented. The common non-polar faces
are (11-20) which is a-axis oriented, (10-10) and (1-102) faces, which both have equal
number of Zn and O atoms.

1.4 ZnO Growth Techniques

ZnO is a versatile material with a rich chemistry. It can be grown using a wide variety of
methods, ranging from simple thermal evaporation to more sophisticated state-of-the-
art epitaxial growth techniques. Vapor phase transport growth methods are most
commonly used. They consist of thermal evaporation, ion sputtering, pulsed laser
deposition, CVD, MOCVD and MBE. An alternative method which has not gained wide
spread adoption is the aqueous chemical growth method. These techniques will be
described briefly in the sections below.

1.4.1 Vapor phase transport

In vapor phase transport, material is vaporized from a ZnO solid source, typically in
powder form, and transported onto a substrate where it condenses and deposits. ZnO
source can be vaporized by thermal evaporation, laser ablation, sputtering, or electron
beam.

High temperatures are required for vaporization of ZnO powder as its melting point is
about 1975°C. In thermal evaporation, for example, ZnO powders are heated to a
temperature range of 1100 to 1400°C in order produce Zn vapors. The Zn vapors are
transported by a carrier gas and deposited as ZnO on a substrate placed downstream of
the carrier gas [9, 10].

3
Lower growth temperatures can be achieved by using sub-oxides of zinc (ZnOx, 0 ≤ x <
1) which have a melting point of about 419°C. ZnOx can be obtained by reduction of
ZnO using graphite [10, 11] as shown in the reactions (1.1) and (1.2) below:

1 1
ZnO + C
→ Zn + CO2 (1.1)
2 2

→ ZnOx + (1 − x)CO2 , where 0 ≤ x < 1

ZnO + (1 − x)CO  (1.2)

Reduction can also be achieved using hydrogen [12], or reduction of zinc salts such as
ZnS [13].

1.4.2 Chemical vapor deposition (CVD) and metal-organic chemical vapor

deposition (MOCVD)

The use of volatile Zn sources in CVD and MOCVD methods allows even lower
vaporization temperatures to be applied. In CVD, zinc acetylacetonate hydrate (hereon
denoted as Zn(acac)2), with vaporization temperatures between 130 and 140°C, is
typically used as a source. Upon vaporization, Zn2+ vapor is transported by nitrogen for
reaction with oxgen at temperatures ranging from 500 to 600°C.

°C 2 ,500−600°C
Zn(acac) 2 ⋅ H 2 O 160
 → Zn 2+ O  → ZnO

In MOCVD, a metal-organic source, typically dimethyl zinc or diethyl zinc with

vaporization temperatures ranging from 117 to 130°C, is used. The metal-organic
source is decomposed to form Zn vapor and then transported into the reaction
chamber using inert gas argon where it reacts with oxygen to form ZnO. This reaction
typically takes place at temperatures ranging from 300 to 500°C [14, 15].

117 −130 ° C O , 300 − 500 ° C

→ Zn 2 +  
DeZn     2

→ ZnO

1.4.3 Molecular beam epitaxy (MBE)

In MBE, high purity Zn metal (melting point 420°C) is thermally evaporated in a

Knudsen effusion cell. Under ultrahigh vacuum conditions (< 10-8 Pa), Zn vapor is
directed onto the substrate which typically has a thin layer of Ag as a catalyst. In the

4
presence of O2 and a growth temperature of 300 to 500°C, growth of ZnO on the
substrate can be achieved [16].

1.4.4 Aqueous solution-based synthesis

In general, oxides are particularly suited for growth in solution. Literature is rich with
reports of nanostructures fabricated in chemical solutions. The ease of ZnO growth in
solution is reflected in the low growth temperatures of 60 to 90°C. Growth precursors
in aqueous solution generally consists of a zinc salt, such as zinc acetate, zinc nitrate or
zinc chloride, and a base such as sodium hydroxide and aqueous ammonia.
Occasionally a surfactant is added to influence the growth habit. In water, hydration of
the zinc salt leads to free Zn2+ ions which undergoes hydrolysis and condensation to
give ZnO. The growth method and mechanisms will be explored in detail in Chapter 2.

Growth of ZnO in aqueous solution is an attractive alternative to MOCVD because it is a

simple, cheap, non-toxic and low temperature method. Large-scale processing has also
been demonstrated [17].

1.4.5 Comparison of gas and solution phase growth methods

Growth of ZnO is more readily achieved with precursors in gaseous state than in
aqueous state. Obviously, the higher free energy of growth units in gaseous state
results in a large driving force and a lower activation energy barrier as shown in Fig 1.2.
Since the growth units have sufficient energy for diffusion, adsorption, surface
reactions, nucleation and growth, growth can be achieved over a wide range of
conditions and precursor concentrations.

The opposite is true for aqueous chemical growth methods which have a small driving
force and high activation energy barrier as shown in Fig 1.2. While formation of ZnO
can be encouraged by shifting the chemical equilibrium to favor hydrolysis and
condensation of ZnO, the growth species have much lower free energy due to low
growth temperatures. Careful control of precursor concentrations and zinc solubility is
needed to achieve growth of ZnO. As such, understanding of chemical equilibriums is
essential in controlling the growth process.

5
Natural growth processes in nature has shown that it is possible to grow perfectly
crystalline structures at ambient temperatures and pressure. One example is the
growth of single crystal calcium carbonate by sea urchins. A recent paper described the
conversion of amorphous calcium carbonate to single crystal calcium carbonate
through a secondary nucleation mechanism at an ambient temperature of 15°C [18]. It
is possible that an organic catalyst exists to lower the activation energy and aid the
dissolution and secondary nucleation process. Unraveling this process and applying it
to the case of ZnO will help to establish aqueous chemical growth as a viable
alternative to gas phase methods.

Diffusion ZnO in solid

Zn, O precursor atoms, Adsorption phase
ions cluster molecules Surface reaction
or complexes in fluid (air Nucleation and
or solution) Growth
Free Energy, G

∆Gg* Activation energy (∆G*)

Precursors in
gaseous state
∆Gaq*

Precursors in
hydrated state ∆ Gg

Driving force ∆Gaq ZnO (s)

Figure 1.2. Schematic showing the free energy of the precursors in gaseous
and hydrated states and the final ZnO product.

When compared in terms of energy, material and processing, aqueous chemical growth
methods have clear advantages over gas phase methods. Gas phase methods generally
waste a large amount of energy and material. A huge amount of energy is needed to
convert the solid state Zn source to free Zn2+ ions in vapor state as growth precursors.
6
Upon condensation of the solid ZnO, this excess energy is simply discarded into the
environment. Furthermore, recycling waste of material is uneconomical because the
exhaust gases are emitted in large diluted volumes, especially when high vacuum
systems are used.

In contrast, very little extra energy is needed in aqueous chemical growth methods to
break the lattice bonds of the solid Zn source to form free Zn2+ ions. This is because the
energy needed to dissolve the zinc salt and break the lattice bonds are provided by the
hydration energy in water at room temperature. Upon dissolution, growth proceeds by
hydrolysis and condensation which can be induced by manipulating the chemical
equilibrium of precursors. The growth system is typically a closed system which allows
easy separation and recycling of materials. As such, wastage of energy and material are
minimized.

In solution phase, growth precursors has higher concentration and better homogeneity
than the gas phase, especially when high vacuum growth conditions are used. It follows
that aqueous chemical growth methods should give high homogeneity and faster
growth rates than that of the gas phase. However, it is noted that due to much lower
growth temperatures typically less than 100 °C in solution methods, growth units may
not have enough kinetic energy to diffuse across the surface to obtain a smooth film
layer growth.

Finally, growing in solution is a low cost, safe and simple process. Basic equipment
consists of a growth vessel, water bath or convection oven is sufficient. In comparison,
gas phase methods will need a special setup in order to operate at high temperatures
and vacuum conditions. In the case of CVD or MOCVD, the growth precursors are
hazardous and additional safety systems are needed.

In summary, the additional complexity in understanding the growth process and

mechanism of aqueous chemical growth methods are more than compensated by its
energy, materials and processing advantages over gas phase methods.

7
1.5 Doping in ZnO
For a growth method to gain wide acceptance and application in device fabrication, it
must be able to produce ZnO with a low density of intrinsic defects as well as
demonstrate reliable p- and n-doping beyond 1019 cm-3. Reliable p- and n- doping partly
depends on the ability to produce ZnO with a low density of intrinsic defects such as
oxygen vacancies, zinc interstitials and hydrogen donor impurities. These intrinsic
defects typically render the undoped ZnO as n-type.

Table 1.1. Summary of intrinsic doping levels of undoped ZnO

polycrystalline films and single crystals which have been grown using
various methods.

Type of film Growth Intrinsic electron Substrate Ref.

method conc. (cm-3)

Polycrystalline PLD 1018 - 1020 fused silica and Si [19]

Polycrystalline Magnetron 1019 glass and sapphire [20]

sputtering

Polycrystalline MOCVD 1017 - 1018 sapphire [21]

Polycrystalline Aqueous 1019 MgAl2O4 (111) [22]

solution

Single crystal hydrothermal 1013 to 1014 ZnO seed [23]

at 300-400°C

Single crystal vapor phase 1014-1015 Not reported [24]

transport

A summary of reported intrinsic doping in undoped ZnO polycrystalline films and single
crystals which have been grown using various methods are summarized in Table 1.1.
Two important points can be drawn from the table:

• Firstly, the intrinsic doping concentrations in undoped ZnO single crystals is

about five orders of magnitude less than those in polycrystalline ZnO. This large
difference of intrinsic doping concentrations shows that there is plenty of room
to reduce the concentration of intrinsic defects.

8
 • Secondly, a comparable intrinsic defect density in polycrystalline ZnO film is
obtained using both gas phase and solution phase growth methods. This
suggests that solution phase growth methods are capable of growing the same
quality of ZnO as gas phase methods. Together with the advantage of being able
to minimize energy and material wastages, solution phase methods are indeed
a promising growth method for ZnO.

By substituting Zn with group III elements such as Ga [25, 26], Al [27, 28] and In [29],
high levels of n-doping beyond 1020 cm-3 have been achieved. Success in n-doping was
not limited to gas phase methods. Aqueous chemical growth methods have also
achieved electron concentrations of approximately 1019 cm-3 using Al [28] and In [30].
Table 1.2 summarizes the various dopants and methods that have been reported.

Table 1.2. Summary of various group III elements as well as their

corresponding growth methods and levels of n-doping.

Dopant Electron conc. (cm-3) Growth method Substrate Ref.

Ga 1018 - 1020 MBE ScAlMgO4 [26]

Ga > 1020 PLD glass [25]

Al > 1021 Filtered cathodic p-doped 4H-SiC [27]

vacuum arc

Al > 1021 Aqueous solution glass [28]

In > 1020 Magnetron glass [29, 31]

sputtering

In 1019 Hydrothermal ZnO seed [30]

In contrast, p-type doping is more difficult to achieve. This difficulty is due to the high
densities of intrinsic defects as shown in table 1.1 as well as low solubility of dopant
species in ZnO and tendencies of dopants to form deep level instead of shallow level
acceptor states [8]. There are two groups of candidates for p-type dopants: group I
elements which substitute Zn atoms and group V elements which substitute O atoms.

9
The calculated bond lengths and defect energy levels for various dopants from group I
and V are shown in Table 1.3. In terms of strain energy, Li and N are the best
candidates as they have almost the same bond length as the ideal ZnO. Also, all group I
elements have a shallower energy level compared to group V elements. Therefore, in
theory, it appears that group I elements, particularly Li, will be promising candidates as
p-dopants.

Table 1.3. Calculated bond lengths and the defect energy levels in ZnO for
group I and V dopants. Ideal ZnO bond length (ro) is 1.93 Å. Taken from [32].

Element Bond lengths Strain (%) Defect energy level

r (Å) r − ro E (eV)
ε= × 100
ro

Li 2.03 5 0.09
Na 2.10 9 0.17
K 2.42 25 0.32
N 1.88 -3 0.40
P 2.18 13 0.93
As 2.23 16 1.15

However, experimental results show otherwise. Hydrothermally-grown bulk ZnO

crystals are typically grown in a high concentrations of KOH or LiOH bases as
mineralizers. As such, they typically have a high concentration of K or Li incorporated.
The high doping concentration of Li did not give a good p-type conductivity and the
ZnO crystals were highly resistive. This contradiction is explained by Li occupation of
interstitial sites where it acts as a donor [33] and compensates the acceptor
contributions. This may also be the reason why hydrothermally-grown LEO films were
n-type instead of p-type, despite the presence of Na in the growth solution [34].

Contrary to theoretical predictions, reports have shown that group V elements are
more promising in achieving p-type doping. Among group V elements, N is considered
as the most ideal p-type dopant since its bond length is closest to the ideal Zn-O bond
length and it has the shallowest acceptor energy level as seen from Table 1.3.

10
Therefore, it is not surprising that most reports on doping with a group V element
focused on N as a shallow acceptor dopant.

Table 1.4 summarizes the p-type doping that has been achieved using various dopants
from group V. It can be seen from the table that the level of p-doping appears to be
comparable to the intrinsic n-doping concentrations shown in Table 1.1. Therefore, it is
not surprising that the p-type conductivity from doping with an element from group V
is unstable and may disappear with time [35, 36].

Table 1.4. Summary of p-type mono-doping of ZnO using group V elements.

Dopant Hole concentration (cm-3) Method Substrate Reference

N 2 x 1016 MBE ScAlMgO4 [37]

P 1.9 x 1016 – 3.8 x 1019 RF sputtering Glass, n-Si [38]

As 2.5 x 1017 – 1.2 x 1018 PLD c-sapphire [39]

Sb 1 x 1016 MBE p-Si (111) [40]

One way to improve the stability of p-type conductivity is to increase the solubility of
nitrogen and lower its ionization energy though a donor-acceptor codoping method
[41]. Typically the acceptor concentration is higher than the donor concentration in
order to obtain a p-type layer. This method has been successfully demonstrated using
Al-N [42], In-N [43] and Ga-N [44] combinations using magnetron sputtering. Reported
hole concentrations range from 1017 to 1018 cm-3.

Another successful method was the dual-acceptor codoping method using Li and N [45].
This combination has achieved very reproducible and stable hole concentrations of
about 1019 cm-3. As shown in Fig 1.3, the hole concentrations arising from Li or N
monodoping schemes deteriorate and disappear completely after 3 months. In contrast,
the Li-N scheme gives a very stable hole concentration. The mechanism leading to the
enhanced p-type stability is still unclear.

11
 Figure 1.3. Carrier concentrations as a function of the preservation period
after deposition. A very stable p-type conductivity is obtained when Li-N
codoping method is used. Graph was taken from [45].

It is interesting to note in Fig 1.3 that in a mono-doping scheme, Li does give a

comparable, or better, doping results than N, although it is unstable and disappears
after 3 months. Very recently, Lin et al successfully fabricated Na-doped ZnO film using
pulsed laser deposition on glass and quartz substrates and obtained stable p-type
conductivity in the range of 1016 to 1018 cm-3. Although the doping levels are low, they
appear to be stable. Fig 1.3, Lin’s result and theoretical calculations point to the
possibility of using group I elements as p-dopants despite earlier difficulties.

Looking back at Tables 1.2 and 1.4, gas phase methods, such as magnetron sputtering
and pulsed laser deposition, appear to be the method of choice for growth and in-situ
p- and n-type doping. There are only a few reports employing solution methods for n-
type ZnO and none for p-type ZnO. This is surprising because:

• aqueous chemical growth methods offer a comparable intrinsic defect density

to other gas phase methods.

12
 • the dopant concentrations in aqueous solution are very much higher than that
in gaseous state, and this leads to a more homogeneous dopant distribution
and a higher level of dopant incorporation in ZnO.

In fact, Chapter 6 of this thesis will describe how the aqueous solution growth method
is employed to grow and dope a p-type ZnO film with potassium from group I as the p-
dopant. To the best of our knowledge, this is the first report of extrinsic p-type doping
using aqueous solution growth methods. This successful demonstration shows that
aqueous chemical growth methods have an important role to play in the growth and
doping of ZnO.

1.6 Motivation and objectives

Gas phase growth methods have emerged as the preferred growth method due to
ability to grow and dope ZnO films and nanostructures although these methods are
expensive and not environmentally-friendly. Solution methods offer an alternative
processing route that is environmentally-friendly, are low cost, non-toxic and suitable
for large scale processing. Due to lack of understanding of underlying growth
mechanisms as well as difficulty in growing and doping ZnO epitaxial layers, solution
methods have not been accepted as one of the mainstream growth methods.

The understanding of growth mechanisms of ZnO in solution has been lacking because
of the wide variety of precursors and growth methodology that are available in the
literature. The current focus on achieving functional devices based on ZnO has not
helped to encourage further research on growth mechanism in aqueous solution.
Therefore, it is an important objective of this thesis to understand the growth
mechanisms for one particular growth solution, namely the aqueous system based on
zinc acetate and ammonia. This system is chosen because the materials are readily
available in the laboratory. It is also believed that other growth systems, as long as they
consist of a zinc salt and base, will behave in a similar manner.

A further objective of this thesis is to study how ZnO thin films, with a thickness range
of 1 to 5 µm, can be formed from ZnO nanostructures in aqueous solution. This

13
objective is motivated by the ease of growth of nanostructures in solution and the
ready application of ZnO films in device fabrication, such as transparent conductive
oxides for LEDs and optoelectronic devices.

As mentioned earlier, doping is important challenge to be overcome. There are only a

few reports of n-type doping and none of p-type using aqueous chemical growth
methods. Current achievements in p-type doping have mainly focused on group V
elements as well as codoping using group I and V elements using gas phase methods.
Considering that theory favors group I elements as acceptors, and the recent report of
successful p-type doping using Na using PLD [46] and the processing advantages of
doping in solution phase, it is another objective of this thesis to investigate p-doping of
ZnO using group I elements using aqueous chemical growth methods.

1.7 Organization of the thesis

In this section, the layout of this thesis is described.

The first chapter introduces the material properties of ZnO, its growth methods and
doping while the second chapter covers the aqueous solution growth method in more
detail. The third chapter describes the experimental setup and characterization
methods that will be regularly referenced by the experimental chapters that follows.

Chapters four and five presents the experimental results and discussions on the growth
of nanostructures on various substrates. In particular, chapter four looks into the
growth factors of ZnO nanorods on GaN substrates and chapter five extends this
understanding to other substrates that have a larger lattice mismatch compared to ZnO,
where growth is initiated from ZnO nanoparticles that have been spincoated onto the
substrate.

Chapter six focuses on the growth and p-type doping of the ZnO film. A new growth
film growth strategy is presented for substrates that are closely lattice-matched, such
as GaN, as well as substrates with large lattice mismatches, such as glass, sapphire and
Si. The p-doping of ZnO film using potassium from group I is explored using two setups:
the traditional closed vessel without any applied voltage bias, and a new growth setup

14
with an applied voltage bias. The electrical properties of the unintentionally-doped and
potassium-doped ZnO films are studied and compared. The effects of thermal
annealing on the electrical properties are also presented. This is followed by the
description of the fabrication and characterization of a p-ZnO / n-GaN light emitting
diode.

Finally, chapter eight summarizes and concludes the work done and presents the
future directions for further work.

15
2 Aqueous solution growth of ZnO

2.1 Introduction
Aqueous solution growth has been widely used to grow highly oriented ZnO nanowires
and other nanostructures. The first report was by Andres-Verges et al [47] in 1990
where he reported on the formation of ZnO rods in aqueous solutions containing zinc
nitrate, zinc chloride and hexamethylenetetramine. About ten years later, Vayssieres et
al. [48] used this method to grow nanorods on conducting glass and Si substrates using
a seed layer. Mende et al[49] and Govender et al [50] has reviewed the various growth
precursors in solution and the resulting nanostructures. In addition, Le et. al has
studied the growth of ZnO nanorods on GaN substrates using zinc acetate (ZnAc2) and
ammonium hydroxide (NH3) [51]. This thesis will focus mainly on the growth solution
consisting of ZnAc2 and NH3.

In this chapter, a brief introduction to the chemical principles related to aqueous

solution growth of ZnO is provided. First, the basic terminologies and concepts such as
concentration, supersaturation, pH, solubility product and complexation are introduced.
Then the calculation ionic equilibrium of the ZnAc2 and NH3 system is discussed. Finally,
nucleation and growth processes are described in terms of homogeneous and
heterogeneous nucleation and crystal growth. Further details on the principles
described herein can be readily obtained from several excellent authors [52-54].

2.2 Basic terminologies and concepts

Growth solutions usually consist of at least two components such as zinc acetate
dihydrate (Zn(CH3COO)2.2H2O), hereon denoted as ZnAc2 for brevity, and aqueous
ammonia (NH3). The concentration of any component in the solution is typically
expressed in molar (M), i.e. the number of moles of solute per litre of the solution, and

16
is denoted by square brackets. For example, [Zn2+] represents the concentration of Zn2+
ions. When 0.3 g of ZnAc2 powder is dissolved in 42 ml of water, and assuming all the
powder dissolves in the water, then the number of moles of ZnAc2 in water is

mass of ZnAc2 added 0.3

n( ZnAc2 ) = = = 0.001367 mol or 1.367 mmol (2.1)
molar mass of ZnAc2 219.5

Assuming complete dissociation of ZnAc2, then 1.367 mmol of ZnAc2 will dissociate to
give 1.367 mmol of Zn2+ ions and 2.734 mmol of CH3COO- ions. Then the concentration
of Zn2+ ions in the solution is then given by
number of moles of ZnAc 2 0.001367
[ Zn 2+ ] = = = 0.0325 M (2.2)
volume of water in litres (42 1000)

The pH of a solution is another important variable in aqueous solution growth. The pH

value of a solution given by the negative logarithm of the hydrogen ion concentration
in the solution:

pH = − log H +[ ] (2.3)

The pH of pure water is 7. Addition of a base such as ammonia will increase the pH
value while an acid will decrease the pH value.

When ZnAc2 powder is added to an aqueous solution, it dissolves quickly to form a

homogeneous solution. At any given temperature, there is a maximum amount of
ZnAc2 that can dissolve in a given amount of water giving rise to a saturated solution.
The concentration of ZnAc2 required to make a saturated solution is called solubility
concentration.

The growth solution is supersaturated when ZnAc2 concentration exceeds its solubility
concentration. The degree of supersaturation is defined as

C
S= (2.4)
S Zn

where C is the actual concentration of ZnAc2 added, and SZn is the solubility
concentration. When S < 1, no growth or nucleation will occur. For low to moderate
17
values of S greater than 1, heterogeneous nucleation on a substrate will occur. When S
is very large, precipitation via homogenous nucleation in the solution will occur in the
solution.

For example, consider the sparingly soluble Zn(OH)2 in equilibrium with its saturated
aqueous solution:

Zn(OH ) 2 (s) ⇔ Zn 2+ (aq) + 2OH − (aq) (2.5)

Zn(OH)2 dissolves in water to give a small concentration of Zn2+ and OH-. This
concentration is defined by the solubility product Ksp, which is the product of the
concentrations of the dissolved ions:

[ ][
K sp = Zn 2+ ⋅ OH − ]
2
= 1 × 10 −16 (2.6)

To prevent precipitation of Zn(OH)2, a complexing agent can be added. The complexing

agent reduces the concentration of free Zn2+ ions and helps to prevent rapid bulk
precipitation of the desired product. For example, in equation (2.5), OH- can play the
role of a complexing agent in the precipitation of Zn(OH)2 as it forms complexes with
Zn2+ such as Zn(OH)42-. Formation of Zn complexes removes Zn2+ ions from the solution,
shifts the balance in equation (2.5) to the right, and thus reduces the degree of
precipitation. With sufficiently high concentrations of OH-, Zn(OH)2 precipitate can be
completely dissolved. As such, it is misleading to rely solely on the solubility product of
Zn(OH)2 in equation (2.5) and (2.6) to estimate of the amount of zinc acetate that can
be dissolved in the growth solution before Zn(OH)2 is precipitated. The presence of
zinc complexes in the solution should also be taken into consideration.

As such, a better way to capture the true solubility of zinc in aqueous solution is to
calculate the temperature-dependent ionic equilibrium of the solution. Such a model
will account for all the possible zinc complex species and is very useful in understanding
aqueous solution growth. One such model for the growth system using ZnAc2 and NH3
will be described in next section.

18
2.3 Temperature-dependent ionic equilibrium of ZnAc2
and NH3
As mentioned earlier, a temperature-dependent model of the ionic equilibrium of the
growth solution can provide the concentrations of all the possible zinc complex species.
The equilibrium concentrations of every species can be calculated by taking into
account the various hydroxide, ammine and acetate complex species are formed when
ZnAc2 and NH3 is mixed in an aqueous solution. The reaction equations and the
corresponding rate constants at 298 K are given below.

Hydroxide complex formation [55]

2+ − + [ Zn (OH ) + ]
Zn + OH ↔ Zn (OH ) K1 = 2+ −
= 10 4.4 (2.7a)
[ Zn ][OH ]

1
Zn(OH ) + + OH − ↔ Zn(OH ) 2 ↓ K2 = + −
= 1011.71 (2.7b)
[Zn(OH ) ][OH ]

Zn(OH )2 ↓↔ Zn(OH ) 2 K3 = [Zn(OH )2 ] = 10−4.5 (2.7c)

[ Zn (OH ) 3− ]
Zn (OH ) 2 ↓ +OH − ↔ Zn (OH ) 3− K4 = −
= 10 −1.71 (2.7d)
[OH ]

− 2− [ Zn (OH ) 24 − ]
Zn (OH ) 2 ↓ +2OH ↔ Zn (OH ) 4 K5 = − 2
= 10 −0.61 (2.7e)
[OH ]

Acetate complex formation [55]

2+ − + [ Zn( Ac)+ ]
Zn + Ac ↔ Zn( Ac) K6 = 2+ −
= 10−1.3 (2.8a)
[ Zn ][ Ac ]

[Zn( Ac) 2 ]
Zn( Ac) + + Ac− ↔ Zn( Ac) 2 K7 = + −
= 10−0.8 (2.8b)
[Zn( Ac) ][ Ac ]

Ammine complex formation [56]

19
 2+ 2+ [ Zn( NH 3 ) 2+ ]
Zn + NH 3 ↔ Zn( NH 3 ) K8 = 2+
= 10 2.59 (2.9a)
[ Zn ][ NH 3 ]

2+ 2+ [ Zn( NH 3 ) 22+ ]
Zn + 2 NH 3 ↔ Zn( NH ) 3 2 K9 = 2+ 2
= 10 4.91 (2.9b)
[ Zn ][ NH 3 ]

2+ 2+ [ Zn( NH 3 ) 32+ ]
Zn + 3NH 3 ↔ Zn( NH ) 3 3 K10 = 2+ 3
= 106.92 (2.9c)
[ Zn ][ NH 3 ]

2+ 2+ [ Zn( NH 3 ) 24+ ]
Zn + 4 NH 3 ↔ Zn( NH ) 3 4 K11 = 2+ 4
= 108.62 (2.9d)
[ Zn ][ NH 3 ]

[ NH 3 ]
NH 4+ + OH − ↔ NH 3 + H 2 O K 12 = + −
= 10 4.39 (2.9e)
[ NH 4 ][OH ]

The ionic equilibrium for the aqueous solution can be obtained by solving
simultaneously the reaction equations, the mass and charge balance. The mass balance
equation can be written as

c Ac = [ Ac − ] + [ Zn( Ac) + ] + 2[ Zn( Ac) 2 ] (2.10)

4
c N = [ NH 4+ ] + [ NH 3 ] + ∑ m ⋅ [ Zn( NH 3 ) 2m+ ] (2.11)
m =1

where cAc and cN are the total concentrations of acetate and ammine ions.

The charge balance equation equates the positive and negative charges in the aqueous
solution and can be written as

4
2[ Zn 2+ ] + [ Zn(OH ) + ] + [ Zn( Ac) + ] + [ NH 4+ ] + 2∑ [ Zn( NH 3 ) m2+ ]
m =1 (2.12)
− 2− − −
= [ Zn(OH ) ] + 2[ Zn(OH ) ] + [ Ac ] + [OH ]
3 4

The temperature dependence [57] of the rate constants in the reaction equations
[2.7a-e], [2.8a-b] and [2.9a-e] is estimated using

20
  K  ∆r H
o
1 1
log T 2  =  −  (2.13)
 K T 1  2.3R  T1 T2 

where the ideal gas constant R = 8.314 × 10-3 kJ.mol-1K-1, KT1 and KT2 are rate constants
at temperature T1 and T2 respectively, and ∆rH0 is the standard enthalpy of reaction
and is given by

∆ r H 0= ∑ n j ∆ f H 0j − ∑ n i ∆ f H i0 (2.14)
j i

where ∆fH0 is the standard enthalpy of formation, i and j specify reactants and products
respectively, and ni and nj are the amounts in moles of each substance in the chemical
reaction. The standard enthalpy values for the product and reactants for reaction
equations (2.7), (2.8) and (2.9) are summarized in Table 2.1.

Table 2.1. List of Enthalpy Values [58-60]. Enthalpy alues with an asterisk *
denotes calculated values of enthalpy of formation from tabulated enthalpy
of reaction.

Species ∆fH0 (kJ/mol)

Zn2+ -153.64
Zn(OH)+ -388.35
Zn(OH)2 -611.95
Zn(OH)2 ↓ -641.90
Zn(OH)3- -817.97
Zn(OH)42- -1125.64
Zn(NH3)2+ -244.81 *
Zn(NH3)22+ -338.07 *
Zn(NH3)32+ -434.68 *
Zn(NH3)42+ -536.72 *
H20 -285.83
OH- -230
NH3 -80.29
NH4+ -132.5

21
 Figure 2.1. Equilibrium complex concentrations and solubility of zinc as a
function of pH at 300K. The pH is increased by adding more NH3 while
keeping the mass of ZnAc2 constant at 0.016 M. Curves show the
equilibrium concentrations of (a) zinc acetate complexes, (b) Zn2+ ions, (c)
zinc ammine complexes, (d) zinc hydroxide complexes and (e) total zinc ion
concentration respectively.

In the calculation of the ionic equilibrium, it is assumed that the equilibrium

concentrations of zinc acetate complex species are very small compared to the other
species. Thus, in the range of 0 to 150°C, the temperature dependence of K6 and K7 in
equations (2.8a) and (2.8b) is neglected.

Using the model described above, the ionic equilibrium of the ZnAc2 and NH3 in an
aqueous solution can be calculated for various ZnAc2 and NH3 precursor concentrations
and temperature. A detailed description of the procedure to calculate the ionic
equilibrium is provided in the Appendix. Fig 2.1 shows the solubility of zinc and
concentration of the major zinc complexes as a function of pH at 300 K respectively.
The pH is increased by adding more NH3 while keeping the mass of ZnAc2 constant at
0.016 M.

Several important points can be seen from Fig 2.1:

22
• As shown by curve (a) in Fig 2.1, the concentrations of zinc acetate complexes are
small compared to the other zinc complexes. This justifies the omission of
temperature effect on equilibrium constants K6 and K7 in equations (2.8a) and
(2.8b).

• The “true” solubility of zinc is given by the sum of all its zinc complexes, namely the
hydroxides, ammines and acetates. The solubility shows a minimum point in the pH
range of 8.5 to 9.5. Interestingly, this pH range coincides with the point of zero
charge of ZnO surface which will be described later in this chapter.

• At pH values greater than 9.7, the increase in zinc solubility is contributed mainly by
the increasing concentration of zinc ammine complexes. On the other hand, at pH
values lower than 8, the increase is due to Zn2+ ions. In chapter 4, we will see how
these different dominant species play an important role in determining the growth
rate and the structural defects of ZnO.

Proceeding from the equilibrium concentrations, the “true” solubility of zinc and the
degree of supersaturation of zinc, which are related to the nucleation density, can be
calculated:

The solubility of zinc, or the total concentration of zinc ions in the precursor solution is
given by the sum of all the zinc species in the solution:

4 4 2
*
CZn = [ Zn2 + ] + ∑[Zn(OH )(m2−m)+ ] + ∑[Zn( NH3 )n2+ ] + ∑[ Zn( Ac)(p2 − p) + ] (2.15)
m =1 n =1 p =1

The degree of supersaturation of zinc in the solution in equation (2.4) can be rewritten
as

*
S = C / CZn (2.16)

where C is the original concentration of ZnAc2 that was added to the growth solution.

Although solubility is the main driving force for nucleation and growth in solution, it is
rarely used as a growth control variable due to measurement difficulties. Instead, pH is

23
the dominant growth control variable. This is reflected in the reported growth
procedures where a final adjustment to the pH range of 10 to 11 is usually practiced.

Using pH as the primary growth control variable presents several drawbacks.

• Firstly, for the same pH value, the solubility of zinc can vary with concentration
of ZnAc2 that is added. This is illustrated in Fig 2.2 which shows the variation of
the zinc solubility with pH. Each curve in Fig 2.2 is obtained by keeping the
ZnAc2 concentration fixed while varying the concentration of NH3 to change the
solution pH. This sequence is similar to typical experimental procedures for
adjustment of growth pH. The variation of the solubility of zinc, due to different
concentrations of ZnAc2, is smallest at pH 7 and increases with pH. At pH 10, the
difference in the solubility of zinc for initial ZnAc2 concentrations of 0.03 M and
0.06 M is large enough to cause differences in growth morphology as will be
shown later in chapter 4.

• Secondly, for a fixed concentration of ZnAc2, large increases in NH3

concentration shifts the pH only slightly while affecting the solubility of zinc
significantly. This is shown in Fig 2.3 where the solubility of zinc and pH is
plotted against the concentration of NH3. In the absence of an accurate pH
titration and measurement, this variation in the solubility of zinc in different
growth batches may produce an inconsistent growth morphologies between
batches.

By employing the calculated solubility of zinc as the primary growth control variable,
these drawbacks can be minimized. In fact, it will be shown in chapters 3 and 4 that
the solubility of zinc can be used a predictor of ZnO nanorod density and length on
GaN substrates, as well as its growth morphology on substrates.

24
 1.E-01

0.11 M
Solubility of zinc (M)

1.E-02
0.06 M

0.03 M

1.E-03
0.01 M

1.E-04
7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0
pH

Figure 2.2. Variation of solubility of zinc with pH. The solubility of zinc was
calculated using Eq. (2.15). The data for each curve is obtained by keeping
the concentration of ZnAc2 fixed while varying the concentration of NH3.
The concentrations of ZnAc2 are indicated on each curve.

1.E-02 12.0

11.5
pH 11.0

10.5
Solubility of Zn [M]

10.0
Solubility of Zn
pH

1.E-03 9.5
9.0

8.5
8.0

0.02 M ZnAc2 7.5

1.E-04 7.0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Concentration of NH3 [M]

Figure 2.3. Variation of solubility of zinc and pH when the concentration of

NH3 is varied while ZnAc2 is kept constant at 0.02 M. The solubility of zinc
was calculated using Eq. (2.15).

25
2.4 Nucleation and growth
As mentioned in Section 2.3, solubility of zinc and the degree of supersaturation is the
main driver for ZnO growth. Homogeneous nucleation of ZnO will occur when the
degree of supersaturation, S, is much larger than unity. At lower degrees of
supersaturation that is slightly greater than unity, heterogeneous nucleation is the
preferred growth mechanism.

2.4.1 Homogeneous nucleation

The first stage in homogeneous nucleation is the formation of embryos through

collision between individual ions or molecules. Embryos grow by collecting individual
species, most likely ions, that collide with them. Growth by collision between embryos
is also possible when the concentration of embryos is high.

Embryos are unstable thermodynamically because their large surface area to volume
ratio leads to a high surface energy. Many of these embryos will dissolve before they
can grow into stable nuclei. One way to increase the number of nuclei is to grow at a
lower temperature so that the longer lifetime of the embryos increases their chances
of growing to a thermodynamically stable size.

The thermodynamically stable size is determined by the energy balance between the
surface energy required to form the embryo and the energy released due to a phase
transformation from liquid phase to solid phase when a spherical particle is formed. Fig
2.4 shows this energy balance which is known as the Gibbs free energy of nucleation
(∆G) as a function of the embryo radius, r. It is clear that the newly formed embryo is
stable if its radius, r, is greater than r* and it will continue to grow bigger to reduce its
Gibbs free energy. On the other hand, when r < r*, the embryo will preferentially
dissolve into the solution to reduce its Gibbs free energy.

Mathematically, the Gibbs free energy can be expressed [61] as

4
∆G = 4πr 2 γ + πr 3 ∆G V
3 (2.17)

26
where r is the radius of the nucleus, γ is the interfacial energy and ∆Gv is the change of
Gibbs free energy per unit volume of the solid phase, given by the equation

kT  C  kT
∆GV = − ln  = − ln (S ) (2.18)
V  S Zn  V

where V is the atomic volume, k is the Boltzmann constant, T (K)is the growth
temperature, C [mol/l] is the concentration of dissolved zinc acetate, SZn [mol/l] is the
solubility of zinc and S is the degree of supersaturation of zinc.

By setting d∆G/dr = 0, the critical energy for nucleation to occur, ∆G* is given by,

16πV 2 γ3
∆G * = ⋅ (2.19)
3k 2 T 2 (ln S ) 2

while the critical radius, r* is given by

2γ 2γV
r* = − = (2.20)
∆GV kT ln(S )

Equations (2.19) and (2.20) show that both the free energy for nucleation and critical
size of the embryo can be reduced by growing at a higher temperature, a high degree
of supersaturation or by lowering the interfacial energy. The smaller free energy or
critical embryo size will lead to a higher nucleation density.

27
 Figure 2.4. The Gibbs free energy of nucleation with respect to embryo
radius. The critical radius r* and energy ∆G* depends on the balance
between the surface and volume energy of the growing embryo.

2.4.2 Heterogeneous nucleation

Besides homogeneous nucleation, another process that takes place in the solution is
heterogeneous nucleation. In heterogeneous nucleation, two processes occur as shown
in Fig 2.5. In the first process, individual ions adsorb onto the substrate surface and
create a nucleus for reaction and further growth.

The second process involves adsorption of sub-critical

sub critical embryos onto the surface. Upon
adsorption, the contact area between
between the embryo and the solution is reduced. Since
the interface energy between the embryo and the substrate surface is usually less than
that between the embryo and the solution, surface adsorption reduces the critical
energy for nucleation and may transform
transf a sub-critical
critical embryo into a super-critical
super
embryo. Due to a lower energy barrier, heterogeneous nucleation can occur near
equilibrium saturation conditions, i.e. when S has a low to moderate value of greater
than 1.

Figure 2.5. Processes involved in heterogeneous nucleation on a substrate

surface.

To encourage heterogeneous nucleation on the substrate surface, the interface energy

between the embryo and the substrate surface can be minimized by reducing the
lattice mismatch between
een the substrate and the embryo. For example, the lattice

28
constants a of gallium nitride (GaN) and ZnO are 3.189 Å and 3.2495 Å respectively. The
corresponding lattice mismatch works out to be

a substrate − a film 3.189 − 3.2495

∆a = = = −0.018618 ≈ −1.9% (2.21)
a film 3.2495

where the negative value indicates that the ZnO film is compressed. Due to the small
mismatch, it is not surprising that ZnO can nucleate readily on GaN substrates in
solution. Using equation (2.21) to compare ZnO to Si <100> which has a lattice constant
of 5.43 Å, the lattice mismatch is about 0.67103 ≈ 67%. The large tensile strain in ZnO
leads to a high interface energy at the ZnO – Si interface and limits nucleation on Si
<100> substrates surface. It is believed that if growth occurs on the Si surface, it is likely
to originate from surface defect sites on the Si substrate.

The high interface energy from large lattice mismatches can be reduced by applying a
pre-coat of ZnO nanoparticles on the substrate surface. These particles will form an
aggregate film which begins to coalesce when annealed at temperatures above 350°C
[62]. This aggregate ZnO film provides a lattice matched surface for nucleation and
growth on various substrates such as Si, glass, plastic and sapphire. As we will see in
chapter 4, the growth morphologies of ZnO nanorods on the aggregate film can be
predicted from the solubility of zinc in the growth solution, regardless of the underlying
substrate.

2.4.3 Crystal growth

As described earlier, heterogeneous nucleation involves the adsorption of ions or

nuclei onto the substrate. Once a stable nuclei is formed, the nuclei can grow by
several ways. One way is by self-assembly where ionic species from the solution adsorb
onto the nucleus. This process begins with the solvated Zn2+ ions in aqueous solution,

Zn2+ + 6H2O ↔ Zn(H2O)62+ (2.22)

The hydrated Zn2+ ion attracts the electrons from the oxygen of the attached water
molecules. The electron deficient oxygen, in turn attracts electrons from the O-H bonds.

29
This weakens and makes it easier to break the O-H
O H bonds. This process is known as
ydrated Zn2+ ion and is schematically shown in Fig 2.6.
hydrolysis of the hydrated

Figure 2.6. Hydrolysis of hydrated metal ions in aqueous solution. The

positively charged metal ion attracts the electrons away from the O-H
O bond,
+
leading to the breakage of the O-H
O bond and release of the H ion into the
solution.

Hydrolysis of the hydrated zinc ion is a sequential process and gives a range of zinc
hydroxide complexes,

Zn(H2O)62+ + nH2O ↔ Zn(H2O)6-n(OH)n(2-n)+ + nH3O+ (2.23)

It is customary to omit the water, thus equation (2.23) can be rewritten as

Zn2+ + nOH- ↔ Zn(OH)n(2-n)+ (2.24)

Each hydrolysis step has an equilibrium constant which has been presented earlier in
equations (2.7 a–e).

After hydrolysis, the condensation of the hydrolyzed zinc ions leads to the formation
and growth of ZnO. There are two types of condensation reactions, namely
na olation and
oxolation. In olation, an “ol” bridge is formed by a condensation reaction between a
hydroxo- and aquo-species,
species,

Zn-OH + Zn-OH2 → Zn-OH-Zn + H2O (2.25)

In oxolation, an “oxo” bridge is formed by the condensation reaction between two

hydroxo-species,

Zn-OH + Zn-OH → Zn-O-Zn + H2O (2.26)

30
A more detailed discussion on the growth mechanism, as well as crystal habit, based on
the zinc hydroxide complexes as the growth units is provided by Li et al. [63] where
ZnAc2 and NH3 are the growth precursors. Despite the wide range of precursors that
are used in the growth of ZnO, the equations (2.22) to (2.26) represent the typical
hydrolysis and condensation reactions that lead to the growth of ZnO. For example, the
reactions in the popular method of using a solution of zinc nitrate, Zn(NO3)2 and
hexamethyltetramine (HMT) can be written as:

(CH2)6N4 + 6H2O ↔ 6HCHO + 4NH3 (2.27)

NH3 + H2O ↔ NH4+ OH- (2.28)

2OH- + Zn2+ ↔ ZnO + H2O (2.29)

where equation (2.29) incorporates equations (2.24), (2.25) and (2.26).

Besides zinc hydroxide complexes, an alternative mechanism using zinc ammine

complexes as basic growth units, have been proposed by Xu et al [64] and Wei et al
[65], who grew ZnO nanorods and nanotubes, respectively, in solutions containing zinc
chloride and ammonia at a pH of 10. In their proposed mechanism, zinc ammine
complexes undergoes an ligand exchange with H2O before undergoing the typical
condensation reaction in the presence of OH- to form ZnO:

Zn(NH3)42+ + 2OH- ↔ ZnO + 4NH3 ↑ + H2O (2.30)

Two observations led to this alternative mechanism. Firstly, aging the growth solution
converted the nanorods to nanotubes. When the solution is aged, the concentration of
Zn(NH3)42+ is reduced and the equilibrium in equation (2.30) will shift to the left leading
to preferential dissolution of the top (0001) face of ZnO nanords to form nanotubes.
Secondly, a faster growth rate is observed when the sample is placed closer to the top
of the growth solution. During growth, NH3 evaporates out of the solution and fill the
air above the solution inside the sealed bottle. This leads to a lower concentration of
NH3 at the top of the solution and shifts the equilibrium in equation (2.30) to the right,

31
leading to faster growth rate compared to samples placed at the middle and bottom of
the growth solution.

Aggregation is another route for crystal growth. In the presence

presence of high concentration
of ZnO particles in the solution, the high probability of collisions between particles and
van der Waals forces cause the particles to stick together to form a large particle, or
stick on the surface of a substrate to form a film as
a shown in Fig 2.7 (a). This growth
mode will result in grain boundaries between individual particles. Deposition of
aggregated particles on substrates can be minimized by stirring during growth or
placing the substrate facing downwards to prevent particles
particles from falling onto the
surface. In our experiments, the substrate is always mounted facing downwards to
minimize aggregation on the surface. Detailed description of the experimental details
will be presented in chapter 3.

If the growth temperature is high enough, appreciable surface diffusion of crystal

atoms and coalescence between the aggregated particles can occur to form a large
particle as shown in Fig 2.7 (b). In aqueous solution growth, coalescence rarely occurs
in-situ
situ due to the low growth temperatures.
tempera Instead, post-anneal
anneal treatments are
usually used to achieve coalescence. In chapter 4 and 5, the effect of post-anneal
post
treatments in various ambient conditions on the native defects of ZnO, carrier
concentrations and mobility will be discussed.

Figure 2.7. (A) Aggregation and (B) coalescence of individual particles.

32
2.5 Effect of pH on ZnO surface
Another important aspect in the growth of ZnO in aqueous solution is the surface
chemistry of the ZnO. Two important points characterize the surface of ZnO: the
surface is electrically charged and highly hydrated [52].

The charge on the oxide surface results from ionization of hydroxyl groups on their
surface upon contact with water. There is a difference in chemical potential of the
constituents of ZnO (namely Zn and O atoms) in liquid and solid phases. Due to the low
mobility of Zn2+ in the solid and low solubility product of ZnO or Zn(OH)2, the migration
of Zn2+ ions towards the liquid phase and the dissolution of ZnO do not occur. Instead,
the difference in chemical potential of oxygen is reduced by adsorption of water and
the dissociation of the adsorbed molecules. This explains the presence of hydroxyl
groups on the ZnO surface. During ZnO growth in solution, hydroxyls groups continue
to be present at the surface since they come from the coordination sphere of the last
Zn2+.

These surface groups (Zn-OH) can ionize in the presence of water:

Zn-O- + H3O+ ↔ Zn-OH + H2O ↔ Zn-OH2+ + OH- (2.31)

The overall charge on the surface groups can be negative, neutral or zero, depending
on the external solution pH. It is important to note that for a particular pH value, the
surface charge is not homogeneously distributed over the entire surface: some sites
have opposite charges or higher density of charges. However, overall surface charge
density is a consistent function of pH. In acidic medium, the overall surface charge is
positive while in basic medium, it is negative. There exist a pH point where the ZnO
surface is neutral. This point corresponds to the point of zero charge (PZC) or the
isoelectric point (IEP). The PZC for ZnO is known to fall in the pH range of 8.7 to 9.7 [66,
67].

33
 Figure 2.8. A model for adsorption of Zn2+ on ZnO surface.

Figure 2.9. Adsorption of Zn2+ ions depends on the pH of the solution.

Highest rate of adsorption when the pH is higher than the PZC of ZnO.

Fig 2.8
8 illustrates a typical model for adsorption on a hydrated ZnO surface [53]. In
water, Zn2+ ions are hydrated through the adsorption of H2O molecules.
molecules As mentioned
in Section 2.4.3, the positive Zn2+ will lead to a weakening and breakage of the O-H
O
bond, leading to the first dissociation of H2O molecule, leaving behind an OH- ion. The
subsequent dissociation of the OH- ion depends on the pH of the solution. In a low pH
acidic solution, H+ ions will prefer to reside on the surface rather than enter into a
solution that is rich in H+. As the pH increases, the concentration of H+ in the solution
easi to dissociate H+ from the O-H
reduces and it becomes easier H bonds into the solution.
Once the OH- ion loses the H+ ion, another hydrated Zn2+ ion from the solution can
adsorb onto site OH- has dissociated. It is clear from Fig 2.9 that adsorption of Zn2+, and
thus the growth of ZnO, is fastest at high pH as there are many ready sites for
adsorption due to ready dissociation of the OH- ion.

34
In chapter 4, the role of the surface charges in determining the growth morphology and
growth rate of ZnO nanorods will be discussed.

2.6 Conclusion
A brief introduction to the basic terminologies and concepts related to aqueous
solution growth of ZnO in a growth system consisting ZnAc2 and NH3 has been
presented. The methodology to calculate the ionic equilibrium of the ZnAc2 and NH3
system has been discussed. Finally, nucleation and growth are described in terms of
homogeneous and heterogeneous nucleation and crystal growth.

35
3 Experimental methods for
growth and characterization of ZnO

3.1 Introduction
This chapter describes the experimental procedures and apparatus that are used for
growing ZnO nanorods in aqueous solution throughout this thesis. The primary
characterization methods are scanning electron microscopy, Raman and
photoluminescence spectroscopy and Hall effect measurements. Each of these
characterization methods will also be discussed in this chapter.

3.2 Growth procedure and apparatus

The growth process of ZnO can be divided into three steps. These steps are the pre-
coating of the substrate with ZnO seeds, growth in aqueous solution, and finally the
post-growth treatment such as thermal annealing under various ambient conditions.

3.2.1 Pre-coating of substrate with ZnO seeds

The first step is usually required for substrates with a large lattice mismatches with ZnO
such as Si, glass or sapphire. Table 3.1 shows the lattice parameters, the corresponding
lattice mismatches and the thermal expansion coefficients along the a- and c-axis for
several common substrates.

The pre-coating solution that is used throughout this thesis consists of ZnO
nanoparticles suspended in ethanol. They were prepared by stirring a solution
containing 0.02 M KOH and 0.01 M ZnAc2, in methanol at 60°C for 2 h, similar to
Pacholski’s method [68]. Fig 3.1 shows a typical TEM image of the ZnO nanoparticles,
which diameter ranges from 10 to 20 nm. Agglomeration of the nanoparticles, which is

36
clearly seen in Fig 3.1, can be minimized by adding surfactants such as
dodecylammonium (DDA) into the refluxing solution.

Table 3.1. Lattice parameters of various substrate materials for ZnO growth
[69].

Material Crystal Lattice Lattice Thermal-

structure parameters mismatch expansion
a (Å) (%) coefficient
c (Å) αa (10-6 K-1)
αc (10-6 K-1)
ZnO Hexagonal 3.252 0 2.9
5.213 4.75
ScAlMgO4 Hexagonal 3.246 0.09 Not
25.195 available
GaN Hexagonal 3.189 1.8 5.17
5.185 4.55
6H-SiC Hexagonal 3.080 3.5 4.2
15.117 4.68
AlN Hexagonal 3.112 4.5 5.3
4.980 4.2
α-Al2O3 Hexagonal 4.757 18.4 (after 7.3
12.983 30°in-plane 8.1
rotation)
Si Cubic 5.43 40.1 3.59
GaAs Cubic 5.652 42.4 6.0
Glass Amorphous Not Not Not
applicable applicable applicable

By pre-coating the substrate surface with ZnO nanoparticles, heterogeneous growth of

ZnO on the substrate can be enhanced. As mentioned earlier in chapter 2, when lattice
mismatch of the original bare substrate is minimized through the use of an
intermediate ZnO seed layer, the interfacial energy γ and thus the free energy for
nucleation in Equation (2.19) can be minimized to encourage growth. On the other
hand, when a substrate has a small lattice mismatch with ZnO, such as GaN as shown in
Table 2.1, no pre-coating of ZnO nanoparticles is required for heterogeneous growth of
ZnO to occur.

37
The ZnO nanoparticles are evenly coated on a clean substrate by spin-coating at 3000
rpm for 30 s. The spin-coating step is carried out three times before annealing the
seeded substrate at 400°C in air for 10 min.

Figure 3.1 TEM image of the ZnO nanoparticles that are grown by refluxing
0.02 M KOH and 0.01 M ZnAc2 in methanol for 2 h. The diameter of the
nanoparticles range from 10 to 20 nm. Agglomeration of the nanoparticles
can be clearly seen.

3.2.2 ZnO growth in solution

The growth of ZnO nanorods on the seeded substrate was carried out in a Schott Duran
laboratory borosilicate glass bottle with an autoclavable polypropylene screw cap. The
Schott Duran bottles were suitable for aqueous solution growth because of the
following properties [70]:

• Borosilicate glass is highly chemical resistant to water, acids, saline solutions,

organic substances and halogens. However, care must be taken to avoid
exposure to strongly alkaline solutions which erodes the glass. When exposed
to 1 M NaOH (pH ~ 14) at 50°C, some glass erosion can occur. Nonetheless, the
erosion is minimal as can be seen from the manufacturer’s datasheet which
estimates that about 1 mm of glass will be eroded after 25 years.

38
 • Polypropylene cap has high chemical resistance to alkaline solution, acids and
alcohols.

• High thermal shock resistance with maximum temperature difference of 100°C,

allowing safe immersion of the vessels, which contains growth solutions at
room temperature, directly into hot water baths or convection ovens up to
120°C. For gradual heating applications where the temperature differences is
less than 100°C, the maximum heating temperature of the glass bottles is
limited by the polypropylene caps which have a maximum operating
temperature of 140°C.

The growth solution was prepared by adding a certain amount of ZnAc2 (Merck, GR for
analysis) followed by NH3 (J.T. Baker, 30% w/w) into deionized water at room
temperature. All chemicals were used without any further purification process.

The substrate was suspended, facing downwards, away from the bottom of the bottle
as shown in Fig 3.2. The bottle was sealed tightly and placed into a water bath (or
convection oven), with a fixed growth temperature ranging from 80 to 95°C.

After the growth, the substrate was removed from the bottle, rinsed thoroughly with
deionized water and allowed to dry in air at room temperature.

temperature
sealable controlled
growth water bath
vessel

growth
solution

sample
substrate

Figure 3.2. Apparatus for growth of ZnO on a substrate.

39
3.3 Characterization tools
The growth method described earlier can be used to grow ZnO nanostructures and well
as thin films. In this work, the structural, optical and electron transport properties of
the resulting structures are examined using field-emission scanning electron
microscopy, micro-photoluminescence spectroscopy, micro-Raman spectroscopy and
Hall measurement. In the following sections, some background theory on the
characterization method as well as relevant ZnO-related characterization results will be
presented. This information will serve as the foundation for understanding the
experimental results that will be discussed in Chapters 4 through 7.

3.4 Field-emission scanning electron microscopy (FESEM)

The feature size of the ZnO nanorods and films, ranging from 100 to 1000 nm, can be
examined using an energetic electron beam in an electron microscope. The resolution
limit is approximately 0.5λ as dictated by Abbe’s Law. Compared to visible light in the
traditional optical microscope, the energetic electron beam has a much shorter de
Broglie wavelength and thus a smaller resolution limit. The resolution limit of SEM
typically ranges from 5 to 20 nm and depends on the specific emission volume arising
from the interaction between the electron beam and the irradiated surface. From this
interaction volume, various secondary signals such as secondary electrons,
backscattered electrons, Auger electrons, characteristic X-rays and photons are
produced [71]. SEM uses the secondary electrons and backscattered electrons to
reconstruct the topography of the surface.

The general morphology of the ZnO nanorods and films, such as the uniformity,
orientation, length, diameter distribution, spatial density and film thickness are
routinely examined using SEM. Two models of SEM are routinely used in this work:
Hitachi model S4100 FESEM located at Centre for IC Failure Analysis and Reliability and
JOEL model JSM6700F FESEM located at Institute for Materials Research and
Engineering. Both machines are operating in secondary electron imaging mode with
the acceleration voltage ranging from 5 to 30 kV.

40
For samples that are grown on insulating substrates such as GaN epilayer on sapphire
and glass substrates, a silver tape is used to create a conductive path from the ZnO
layer to the sample holder, thus preventing sample charging and image distortion.

3.5 Photoluminescence spectroscopy

Another characterization method that is routinely employed is Photoluminescence (PL)
spectroscopy. This is a simple, nondestructive yet sensitive method to characterize the
optical properties of ZnO nanostructure and film. In this method, electrons are excited
to a higher energy states by absorption of laser light with energy larger than the band
gap energy. These excited electrons then relax to their equilibrium state through
various radiative and non-radiative processes. The measured intensity and energy
distribution of this radiative relaxation process yields information on the properties and
dynamic processes in ZnO.

The probe depth of this method depends on the excitation wavelength. When a He-Cd
laser of 325 nm is used, the large absorption coefficient of ZnO leads to a penetration
depth of approximately 50 – 100 nm [72, 73]. Therefore, for a bulk ZnO sample, this
method only probes the upper surface of a thick ZnO film. On the other hand, for
nanorods with a diameter of 100-200 nm, the penetration depth is sufficient to provide
information on the bulk structure.

The characteristics of the PL emission from ZnO are determined by several factors:

• the fundamental band-to-band transition as shown in Fig 3.3 (a). The optically
allowed band-to-band transition is a function of the density of states with
respect to energy, i.e. the absorption coefficient is proportional to the square
root of photon energy for photon energies greater than the band gap energy.
The valence band splits into three bands, namely A, B and C, due to crystal-field
and spin-orbit interactions. A wide range of values ranging from 3.195 to 3.44
eV at room temperature have been reported [74]. As indicated in Fig 3.3 (a), EgA,
EgB and EgC have been reported to be 3.437, 3.4425 and 3.4813 eV respectively
at 4.2 K. The band gap temperature dependence up to 300 K is given by [75]:

41
 5.05 × 10 −4 T 2
E g (T ) = E g (T = 0) ⋅ (3.1)
900 − T

• free excitons which are formed from the Coulombic attraction between
electron and hole, leading to a series of hydrogen-like states below the band
gap as shown in Fig 3.3 (b). All exciton series from the A, B and C valence bands
into the conduction bands have an approximate exciton binding energy of 60
meV and an excitonic Bohr radius of 1.8 nm. Typically, the A and B exciton
peaks can be tracked up to 160 K, above which line broadening prevents a
satisfactory distinction between the two peaks. The intensity of A and B free
excitons increases with temperature up to 40 and 80 K respectively, and then
decreases as temperature is increased further. Free excitons are able move
freely through the crystal and scatter upon collision with defects or phonons.

• bound excitons which have no translational degrees of freedom due to

formation of complexes upon binding to a defect centre such as ionized or
neutral donors, or neutral acceptors. As such, bound exciton emission usually
dominate at low cryogenic temperatures, whereas free exciton emission takes
over at higher temperatures. Bound excitons emission usually disappear at 50
to 150 K, depending on the type of donors or acceptors. Donor-bound excitons
(DBE) and acceptor-bound excitons (ABE) have been reported in the range of
3.348 – 3.374 eV and 3.3481 – 3.3564 eV respectively.

• deep centres which are located deep within the band gap. Emission from these
deep centres is usually in the visible light range as compared to the intrinsic
emission in the near UV region. These deep centres can be intrinsic due to
native defects, such as oxygen vacancies or zinc interstitials, or extrinsic defects
such as Cu, Fe, Co or Mn.

Several excellent reviews on ZnO PL have been published [69, 75, 76] and a summary of
the important optical transitions and their corresponding energy as well as wavelength
ranges is provided in Fig 3.3 (c).

42
 Figure 3.3 (a) Band structure and symmetries of wurtzite ZnO. The splitting
into three valence bands (A, B and C) is caused by field and spin-orbit
splitting [75]. (b) Schematic drawing of the exciton states. (c) Summary of
various optical transitions near the band gap and their corresponding
energy and wavelength ranges.

The number of observed bound exciton peaks in ZnO nanostructures is typically lower
than in ZnO single crystals [76]. This is shown in Fig 3.4 which compares the low-
temperature PL spectra of (a) a bulk single crystal ZnO [77] and (b) ZnO nanorods
grown using a solution containing zinc nitrate, hexamethylenetetramine (HMT) and

43
polyethyleneimine (PEI)1 [78] on a pre-coated Si substrate which had been pre-coated
using ZnAc2 solution. Both samples have been annealed in forming gas at 600°C.

Figure 3.4. Comparison of the low-temperature PL (4 K) spectra from (a) a

bulk single crystal ZnO grown by VPT [77] and (b) ZnO nanorods grown
using a solution containing zinc nitrate, HMT and PEI [78] on a pre-coated Si
substrate which had been pre-coated using ZnAc2 solution. Both samples
have been annealed in forming gas at 600°C.

When ZnO nanorods are grown in aqueous solutions, UV emission is usually

accompanied by visible emissions [79, 80]. The visible emissions are usually attributed
to intrinsic defects and consists of orange and green components. Orange emission is
typically related to interstitial oxygen while the assignment of green emission remains
controversial as it has been attributed to various defects such as donor-acceptor pair,
oxygen vacancy, anti-site oxygen, zinc interstitials and zinc vacancies [76]. Both orange
and green emission can be present in the same sample [81]. This suggests a large
variety of defects are present in ZnO nanorods that are grown using solution methods.

1
PEI functions as a surfactant to increase the aspect ratio of the nanorods.

44
Furthermore, by examining the changes in PL spectra after annealing the samples in
various ambient gas and temperatures, the type of intrinsic defects can be deduced.

The quality of a ZnO sample can also be evaluated using its PL spectrum near the band
edge region. One prerequisite is the presence and clear distinction of A and B free
exciton peaks below 160 K. Another measure is the ratio between UV emission and the
visible emission from deep level centres [82, 83]. However, the ratio, being dependent
on the excitation density as well as excitation area [84], is not a good determining
factor of the crystalline quality of ZnO. Nonetheless, it is still useful for comparing the
quality of different samples when excitation conditions, such as the excitation laser
power, objective lens magnification, the detector integration time and neutral density
filter settings, are kept constant. One such application is the comparison of the PL
spectra after various thermal annealing conditions, allowing the deduction of type and
evolution of defects.

PL measurements in this work were carried out using a Renishaw 2000 micro-PL setup
with the 325 nm line from a Kimmon He-Cd laser as excitation source. Since the setup
combines a laser souce with a microscope, a spatial resolution of 1 µm or better can be
achieved. This setup is equipped with neutral density filters to decrease the intensity of
incident laser light and prevent the saturation of the photodetector.

3.6 Raman spectroscopy

Raman spectroscopy is based on the inelastic scattering process that occurs due to the
collision between incident photons and a molecule. As shown in Fig 3.5, most of the
incident photons undergo Rayleigh scattering and do not change their energy after
collision with the molecule while a very small percentage of incident photons undergo
inelastic scattering and exchange energy with the molecules upon collision.

45
 Figure 3.5. Rayleigh and Raman scattering

If the incident photon delivers (or receives) an hv quantum of energy to the molecule,
the energy of the scattered photon reduces to hvo - hv (or increases to hvo + hv) where
hvo is the energy of the incident photon. The scattered light having the frequency vo-v
and vo+v are known as Stokes Raman scattering and anti-Stokes Raman scattering
respectively.

Raman spectroscopy is theoretically capable of examining the energy changes that

accompany transition between different electronic, vibrational and rotational energy
levels. However, it has been associated almost exclusively with transitions between the
vibrational energy levels. In this work, Raman spectroscopy is used as a vibrational
spectroscopy method to examine the structural properties of ZnO such as crystallinity,
orientation, composition, strain and defects.

ZnO has a wurtzite symmetry and belongs to the C46v space group. There are 4 atoms
per unit cell leading to 12 phonon branches, 9 optical and 3 acoustic. Group theory
predicts that near the center of the Brillouin zone, there are eight sets of phonon
modes: 2E2, 2A1, 2E1 and 2B1. Both E2 sets, one of the A1 set and one of the E1 set are
Raman active while the B1 modes are silent. Furthermore, the A1 and E1 are polar and
split into transverse optical (TO) and longitudinal optical (LO) phonons.

The selection rules on the (0001) surface specifies that the E2 and A1(LO) mode can be
detected when the incident and scattered polarization are parallel, and only the E2
46
mode can be observed when the incident and scattered polarization are perpendicular.
In the case of the {10-10} surfaces, the optical modes E2, A1(TO) and E1(TO) can be
detected, depending on whether the incident and scattered polarization is parallel or
perpendicular [85]. At oblique angles, it is possible to observe the optical mode A1(LO)
[86]. For the case of ZnO nanorods that are randomly oriented, all of the above modes
will be observable. This is the case that will be seen later in Chapter 5 when randomly
oriented ZnO nanorods are grown on Si and glass substrates that have been precoated
with ZnO nanoparticles.

The reported values for the various fundamental and multi-phonon modes are
summarized in Table 3.2. In ZnO nanostructures, the Raman spectra always show a
shift from the bulk phonon frequencies. There are three main mechanisms that can
induce phonon shifts in ZnO nanostructures [87]:

• spatial confinement within nanostructure boundaries that are less than 4 nm

• phonon localization by defects (oxygen deficiency, excess zinc, surface

impurities, etc) leading to a frequency shift of a few cm-1

• laser induced heating in nanostructures leading to a frequency shift of tens of

cm-1

Since spatial confinement will not be applicable for nanorods with diameters of 80 –
200 nm, and if laser induced heating is avoided, the interpretation of frequency shifts
can be focused on structural defects and stresses.

Information on stress and crystalline quality can be extracted from the E2 phonon
frequency and linewidth. An increase in the E2 phonon frequency with respect to the
unstrained ZnO indicates compressive stress, whereas a decrease points to tensile
stress. A narrower linewidth indicates better crystallinity and vice versa. The same
applies to A1(LO) phonon, but with a much smaller magnitude of the frequency and
linewidth variations.

47
In addition to the fundamental modes, several multi-phonon modes and defect-
induced bands have been clearly identified in literature. For example, the 332 cm-1
peak has been ascribed to two E2L phonons from the K-M-Σ around 160 cm-1 and is
denoted as 2E2L(M) [88, 89]. Also, a broad asymmetric band from 540-670 cm-1 has been
assigned as a defect-induced band with strong dependence on oxygen stoichiometry
[90].

In this work, Raman spectra was recorded in a backscattering configuration using a

Jobin Yvon T64000 triple spectrograph micro-Raman setup with the 514.5 nm line of an
Ar ion laser as the excitation source.

By varying the excitation wavelength, selective probing of phonon, either on the

surface or averaged over the bulk, can be achieved. For example, a 514.5 nm (Ar ion
laser) excitation source will return an averaged bulk material properties 325 nm (He-Cd
laser) excitation source only provides information from the top surface layer of
approximately 50-100 nm.

Table 3.2. Frequency and symmetry of the fundamental optical modes in

ZnO

Symmetry Frequency
Remarks
character (cm-1)
E2L 101 The lower mode E2L is associated with vibration
E2H 437 of heavy Zn sublattice while the higher mode E2H
is associated with vibration of O atoms [87].
When compared to the bulk parameters,
compressive stress will result in a higher mode
frequency while poorer crystal quality gives a
larger peak width [85].

E1(TO) 407 Shows strength of polar lattice bonds. A lower

A1(TO) 380 mode frequency indicates existence of vacancy
point defects which diminishes long range
electrostatic forces [91].

E1(LO) 583 Higher crystallinity will result in stronger E1(LO)

A1(LO) 574 and A1(LO).

48
3.7 Secondary ion mass spectrometry (SIMS)
SIMS is one of the most sensitive and versatile technique for surface analysis. It is
capable of detecting all elements, including isotopes and molecular species. It can be
used to perform depth profiling, thin film analysis, surface contamination and dopant
diffusion in samples.

In this technique, the ZnO sample is sputtered with a primary ion beam resulting in
destructive removal of material from the sample. The sputtered species are then
analyzed by a mass spectrometer. Only about 1% of the sputtered species, which are
ejected as charged ions, can be detected by the system. The subsequent analysis of the
emitted charged ions provides detailed information on the elemental and molecular
composition of the surface.

Figure 3.6. Depth profiling using a dual beam technique.

Depth profiles of ZnO samples in this work were measured using TOF-SIMS IV from
ION-TOF GmbH. The lateral resolution is typically 100 nm and the depth resolution is 1
nm. A high resolution depth profile is obtained by employing a dual beam technique.
The first beam is a high current Ga ion beam which is used to sputter a crater on the
sample. The second beam is a low current Ar ion beam that progressively analyzes the
bottom of the crater.

49
3.8 Hall effect measurement

Figure 3.7. Schematic of the Hall effect in a long, thin bar of semiconductor
with four ohmic contacts. The direction of the magnetic field B is along the
z-axis and the sample has a finite thickness d.

The basic physical principle underlying the Hall effect is the Lorentz force. When an
electron moves along a direction perpendicular to an applied magnetic field, it
experiences a force acting normal to both directions and moves in response to this
force and the force effected by the internal electric field.

For an n-type, bar-shaped semiconductor shown in Fig 3.7, the majority of the carriers
is electrons of a bulk density n. When a constant current I flows along the x-axis from
left to right in the presence of a z-directed magnetic field, electrons are subjected to
the Lorentz force and drift towards the negative y-axis, resulting in an excess surface
electrical charge on the side of the sample. This charge results in the Hall voltage (VH), a
potential drop across the two sides of the sample with a magnitude equal to

IB
VH = (3.1)
qnd

50
where I is the current, B is the magnetic field, d is the sample thickness, and q is the
elementary charge (1.602 x 10-19 C).

In some cases, it is convenient to use sheet density (ns) instead of bulk density (n). Then,
rearranging Eq. (3.1) gives the equation

IB
n s = nd = (3.2)
q VH

Thus, by measuring the magnitude of VH and substituting the known values of I, B, and
q, ns can be determined. Furthermore, the type of majority carrier can be determined
by the sign of the VH: negative for n-type semiconductors and positive for p-type
semiconductors.

If the bulk resistivity (ρ) or the sheet resistance (RS) of the semiconductor is known,
then the Hall mobility (µ) can be determined from the following equation:

VH 1 1
µ= = = (3.3)
RS IB qn s RS ρ
qn s  
d 

A popular configuration for Hall measurements is the van der Pauw configuration. Its
popularity stems from its ability to measure both resistivity and the Hall voltage of any
arbitrary shape. A schematic of a rectangular van der Pauw configuration is shown in
Fig. 3.8.

51
 Figure 3.8. Schematic of a van der Pauw configuration used in the
determination of the two characteristic resistances RA and RB.

In resistivity measurements, a direct current I12 is injected into contact 1 and out of
contact 2 and the voltage V43 from contact 4 to contact 3 is measured as shown in Fig.
3.8. Next, a current I23 is injected into contact 2 and out of contact 3 while voltage V14
from contact 1 to contact 4 is measured. The characteristic resistances RA and RB are
calculated by means of the following expressions:

V 43
RA = (3.4a)
I 12

V14
RB = (3.4b)
I 23

Van der Pauw has demonstrated that these two characteristic resistances RA and RB,
are related to the sheet resistance RS through the van der Pauw equation

 πR A   πR 
exp −  + exp − B  = 1 (3.5)
 RS   RS 

52
which can be solved numerically for RS.

Figure 3.9. Schematic of a van der Pauw configuration used in the

determination of the Hall voltage VH.

For the Hall voltage measurement, the magnetic field B is kept constant and a constant
current I13 is forced through the opposing pair of contacts 1 and 3 while the VH (= V24) is
measured across contacts 2 and 4. This is shown schematically in Fig. 3.9. Once the Hall
voltage VH is acquired, the sheet carrier density ns can be calculated via Eq. (3.2) from
the known values of I13, B, and q.

To improve accuracy of Hall and resistivity measurements, several precautions are

taken. The lateral dimensions of the sample are large compared to the size of the
contacts (>20X) and the sample thickness (>15X). The contacts should be ohmic within
the measurement range. Ohmic contacts to n-ZnO were made by evaporating Al/Pt or
Ti/Al/Ni/Au while p-ZnO using Ni/Au. The thickness of the sample is kept below 1 mm
with thickness variations of less than 1%. Thermomagnetic effects due to non-uniform
temperature are minimized by injecting a small constant current. Finally,
photoconductive and photovoltaic effects is minimized by measuring in a dark
environment.

53
Hall measurements were done using Accent HL5500. The system applies a permanent
magnetic field of 0.32 T. Measurements are performed in DC mode at room
temperature or over a temperature range from 90 to 300 K. During Hall measurement,
the optimum current is automatically chosen by the system to provide an acceptable
signal to noise ratio, minimize specimen heating and limit potential gradients to 1 V/cm.

3.9 Conclusion
The experimental procedures and apparatus that are used for growing ZnO nanorods in
aqueous solution throughout this thesis have been described. Characterization
techniques such as scanning electron microscopy, Raman and photoluminescence
spectroscopy and Hall effect measurements were discussed. The background theory on
each characterization method as well as relevant ZnO-related characterization results
has been presented.

54
4 Prediction of Length and Density of ZnO
Nanorods on GaN Substrate

4.1 Introduction
The growth of ZnO nanorods in solution on various substrates such as glass and Si, has
been well-documented in various publications. Boyle et al. discussed the influence of
reactants, substrate pretreatment, growth time and temperature on the growth of
flower-like ZnO nanowires [92]. Govender et al compared the different growth
precursors and discussed the influence of reaction conditions, ligands, counter-ions, pH,
ionic strength, deposition time, influence of substrate and seed layers [50]. Tian et al
described the reduction of aspect ratio through the addition of citrate anions [93] while
Zhang et al discussed the influence of pH on growth solution for a zinc acetate, sodium
hydroxide and citric acid growth system [94, 95]. As can be seen in Table 4.1 which
summarizes the growth of ZnO nanostructures in aqueous solution, there is a
bewildering array of possible growth factors. One reason for this is that ZnO
nanostructures can be easily synthesized from a wide variety of precursors and the
growth habit can be modified by a large number of surfactants. Another reason is that
most of the identified factors are the ‘second-order’ growth drivers, which can lead to
many possible combinations.

It is well-known that the density and length of ZnO nanorods depends on the initial
nucleation and subsequent growth, both of which can be thermodynamically modeled
based on the Gibbs free energy. As described in Chapter 2, for a fixed growth system
and substrate surface, the Gibbs free energy depends on the growth temperature, the
interfacial energy and the solubility of zinc. The solubility of zinc indirectly includes the
effect of pH, effects of reactant concentrations and the effect growth temperature on
the speciation of the growth solution. Unlike the solution pH which can be easily
measured experimentally, the solubility can only be obtained by solving the ionic

55
equilibrium of the growth solution. For each different growth precursor, all the possible
chemical species need to be identified and a new ionic equilibrium computed. This
process is tedious and sometimes the required thermodynamic data, and hence the
equilibrium rate constants are not available for computation. Due to these difficulties,
the solubility of zinc is not a popular growth factor even though it may provide a better
prediction of the length and density of the nanorods.

Table 4.1. Summary of different results and methods for aqueous solution
growth.

Growth solution Resulting morphology Focus of investigation

Zinc nitrate, HMT
Zinc nitrate, HMT,
Zinc nitrate, HMT
Zinc-nitrate, HMT, citrate
Zinc nitrate, zinc acetate,
HMT
Zinc nitrate,
triethanolamine, HCl (pH 5)
Zinc nitrate, thiourea,
ammonium chloride,
ammonia
Zinc acetate, sodium
hydroxide, citric acid
Comparison of different
growth solutions
Zn foil, zinc sulfate,
ammonium ions, sodium
hydroxide
Zinc acetate, ammonia
Nanorods, microtubes
Nanorods, nanotubes
Aligned nanowire arrays
Oriented nanocolumns,
nanoplates
Highly aligned nanorods
Ordered nanorods
Nanowires, tower-like,
flower-like, tube-like
Disk-like, flower-like,
nanorods
Star-like,nanorods
Nanobelt arrays, ordered
nanowires
Nanorods
On Si and conducting glass
substrates [48]
Influence of substrate and
seed layer [96]
Influence of seed layer [62]
Control of aspect ratio:
addition of citrate anions
decreases aspect ratio [93]
Influence of substrate and
seed layer [97]
Influence of substrate and
counter ions in growth
solution [92]
Influence of reactants,
substrate pretreatment,
and growth time and
temperature [98]
Influence of pH on growth
solution [94, 95]
Influence of reaction
conditions: ligand, counter-
ions, pH, ionic strength,
and deposition time
Influence of substrate/seed
layer [50]
Influence of temperature
and concentration of
solutions [99]
Influence of temperature,
precursor molar ratios [80]

56
In this chapter, we will focus on the ZnAc2-NH4OH growth system because the
experimental data is readily available from Le et al’s work [80] and the ionic
equilibrium model has already been solved in Chapter 2. We will also attempt to
replace the ‘second-order’ growth drivers such as pH and degree of supersaturation
with the more fundamental factors, namely the solubility of zinc and growth
temperature. To do this, the solubility is calculated and compared with the
experimental data by Le et al. who has reported on the trends in the density and length
of hydrothermally-grown ZnO nanorods when precursor concentrations, molar ratios
and growth temperature were varied [80]. Then, a quantitative relationship between
the solubility and temperature is empirically derived for the ZnO nanorods density and
length. Finally a growth process map for length and density prediction is presented.
Although the work in this chapter focuses on GaN, it can readily be applied to any other
lattice-matched substrates.

4.2 Experimental Procedure

The ZnO nanorods were grown on a GaN epilayer. The GaN epilayer, which is 3 µm
thick, was grown on c-plane sapphire at 1020°C using an EMCORE D125 MOCVD.
Trimethylgallium and NH3 were used as the Ga and N source, respectively.

The growth methodology of ZnO nanorods in aqueous solution follows the

experimental procedure as described in Chapter 3 Section 3.2.2. Since the GaN epilayer
has a very low lattice mismatch with ZnO, no pre-coating was performed.

Three groups of experiments were carried out. The first group studies the effect of
growth temperature on the morphology of ZnO nanorods. The next two groups of
experiment aim to study the morphology dependence on reactant concentrations by
systematically varying the concentrations of ZnAc2 and NH4OH.

The three groups of experiments are as follows:

• Varying growth temperature: the growth temperature is varied from 60 to

150°C while maintaining the growth duration at 4 hours and the concentrations
of Zn(Ac)2 and NH4OH at 0.016 and 0.173 M respectively.
57
 • Varying the ratio of reactant concentration: [Zn(Ac)2] is maintained at the same
concentration as above at 0.016 M while the [NH4OH] is varied from 0.1 to 0.4
M.

• Increasing reactant concentrations with a constant concentration ratio: the

concentrations of Zn(Ac)2 and NH4OH are increased from 0.01 to 0.033 M in
order to maintain a constant molar ratio [NH4OH]/[Zn(Ac)2] of 6.27.

The growth duration for all three groups of experiments was maintained at 4 h.

After growth, the ZnO nanorods were examined using a field emission scanning
electron microscope. The top and cross-sectional views of the SEM images were used
to obtain the density and length of the ZnO nanorods respectively. The density of the
ZnO is defined as the number of nanorods in an area of 1 cm2. This was calculated by
counting the number of rods in a randomly chosen area of 5 µm2 in the top view
scanning electron micrograph.

4.3 Results
Fig 4.1 shows the SEM images of the ZnO nanorod for the first group of experiments
where the growth temperatures are (a) 60°C, (b) 80°C, (c) 100°C and (d) 150°C. When
the length and density of the nanorods are plotted on a temperature axis, both
parameters show an initial increase up to 95°C followed by a decrease at higher
temperatures, as shown by the curves (a) and (b) in Fig 4.2 respectively.

58
Figure 4.1. SEM images of ZnO nanorods grown at temperatures (a) 60°C,
(b) 80°C, (c) 100°C and (d) 150°C in solutions containing 0.016 M Zn(Ac)2
and 0.173 M NH4OH.
OH

Figure 4.2. The effect of growth temperature on (a) length and (b) density
of ZnO nanorods.

59
 Figure 4.3. SEM images of ZnO nanorods with different molar ratios:
ratios (a)
0.016 M Zn(Ac)2, 0.1 M NH4OH, (b) 0.016 M Zn(Ac)2, 0.143 M NH4OH, (c)
0.016 M Zn(Ac)2, 0.204 M NH4OH and (d) 0.016 M Zn(Ac)2, 0.306 M NH4OH.

Figure 4.4. Effect of molar ratio on (a) length and (b) density of ZnO
nanorods.
ds. The concentration of Zn(Ac)2 is kept constant at 0.016 M and the
concentration of NH4OH is varied from 0.1 M to 0.4 M to increase the molar
ratio.

Figss 4.3 and 4.4 show the results from the second group of experiments where the
ratio of reactant concentration is varied. From the trend plots of the density and length
in Fig 4.4 (a) and (b) respectively, an increasing ratio of [NH4OH]/[Zn(Ac)2] leads to a
lower density and longer length of the ZnO nanorods.
60
Finally, Fig 4.5 shows the trend plots of the length and density for the third group of
experiments when the reactant concentrations are increased while maintaining a
constant concentration ratio of 6.27. Fig 4.5 shows that a higher concentration of
precursors increases the length and reduces the density.

Figure 4.5. Effect of increasing concentration of precursors while

maintaining a constant molar ratio on (a) length and (b) density of ZnO
nanorods. Zn(Ac)2 is increased from 0.01 to 0.03 M , and concentration of
ammonia by a proportional amount to maintain a constant molar ratio of
6.27.

4.4 Discussion
The effects of the various growth variables on density and length of ZnO nanorods are
qualitatively summarized in Table 4.2. Table 4.2 shows that that the density and length
appears to be inversely correlated to each other.

To go beyond these qualitative observations, we will need to tease out more

information from the set of experiments. One way is to compute the ionic equilibrium
of the Zn(Ac)2-NH4OH system because the computation results provide the
concentrations of all the possible zinc complex species and the solubility of zinc which
can provide further insight to the roles the major growth species, solubility and
temperature play in the growth and nucleation processes. A detailed description of the
61
chemical equilibriums and the calculations that are required to obtain the equilibrium
concentrations of the various chemical species in the growth solution have been
presented earlier in Section 2.3.

Table 4.2. Summary of effects of temperature and reactant concentrations

on density and length of ZnO nanorods.

Growth variable Density Length

Temperature Increase up from 60 to Increase up from 60
95 °C. Decrease at higher to 95 °C. Decrease
temperatures at higher
temperatures

Increase reactant Decrease Increase

molar ratio
[NH4OH]/[ZnAc2]

Increase reactant Decrease Increase

concentrations with a
constant ratio of
[NH4OH]/[ZnAc2]

In the discussion that follows, we will show how the trends of length and density in
Table 4.2 can be explained by just two variables; namely solubility of zinc and
temperature. The discussion will begin by examining the experiments that are
conducted at the same growth temperature in order to isolate the temperature effects
and focus on the solubility effects. Once the relationships between solubility and length
as well as density are established, the temperature effects will be introduced and the
relationships will be modified accordingly.

4.5 Effect of Solubility of Zinc on Density and Length of

ZnO Nanorod Arrays
The length data in Figs 4.4 and 4.5 are combined in Fig 4.6 such that the length is now
plotted against the solubility of zinc for the fixed and varying reactant concentration
ratio experiments. The data points for varying the ratio of reactant concentrations are
represented by
, while the increasing reactant concentrations with a constant ratio
62
by . For both group of experiments, the length of the nanorods shows a positive
relationship with the solubility of zinc ions.
ions. A higher solubility provides a larger
reservoir of growth units in the solution which in turn leads to longer lengths. When
[ZnAc2] is kept constant, a higher [NH4OH] provides more complexing
omplexing agents which in
turn leads to a higher solubility and longer lengths as shown in Fig 4.4. On the other
hand, when both [NH4OH] and [ZnAc2] are increased in such a manner so as to
maintain constant ratio of [NH4OH]:[ZnAc2], there is an increasing concentration of Zn2+
and complexing agents which leads to a higher solubility and longer lengths as seen in
Fig 4.5. However, the relationship between the reactant concentrations and solubility
are non-linear.
linear. This can be seen in Figs 4.4 and 4.5 where thee length remains relatively
unchanged when the molar ratio is increased beyond 8 and when [ZnAc2] is increased
beyond 0.025 M at constant molar ratio.

Figure 4.6. Logarithm of ZnO nanorods lengths plotted against the total
concentration of zinc ions in the precursor solution.
represents the data
points when the Zn(Ac)2 concentration is kept constant at 0.016 M and the
NH4OH concentration is varied from 0.1 to 0.4 M while  represents the
data points when concentration of Zn(Ac)2 is increased from 0.01 to 0.033
M with a constant molar ratio [NH4+]/[Zn2+]. The growth temperature is
kept constant at 373 K.

63
Similarly, the density data in Figs 4.4 and 4.5 are combined in Fig 4.7 where the
logarithm of density (B),, log(B) is plotted against the solubility.
solubility The
he density shows a
negative correlation with the solubility.
solubility. This is expected from the thermodynamics of
nucleation because a lower solubility of zinc provides a more favorable Gibbs free
energy change which encourages nucleation and thus increases the density
den of the
nanorods.

Figure 4.7. Logarithm of rod density (cm-2) plotted against the total
concentration of zinc ions in the precursor solution. The inset shows the
corresponding initial degree of supersaturation of zinc in the precursor
solution at the
he growth temperature 373K. The data points for varying the
ratio of reactant concentrations are represented by
,, while the increasing
reactant concentrations with a constant ratio by .

The consistency of data fitting showed by solubility in Figs 4.6 and 4.7 cannot be
reproduced using other commonly quoted growth parameters such as the degree of
supersaturation of zinc and pH.

For example, the inset of Fig 4.7 shows the relationship between the degree
de of
supersaturation and solubility. While the density and solubility shows a clear negative
correlation, there is no clear correlation between the corresponding degree of

64
supersaturation and the solubility. The difficulty in applying the degree of
supersaturation as a density predictor arises from the two possible modes of
nucleation: heterogeneous and homogeneous. Heterogeneous nucleation occurs for a
slight degree of supersaturation, i.e. when the initial concentration of ZnAc2 is close to
the solubility limit. Higher levels of supersaturation tend to produce instantaneous
homogeneous nucleation in the solution which quickly brings the degree of
supersaturation down close to the solubility limit. This explains why solubility is much
more successful than the degree of supersaturation in predicting the density, as well as
the length of the nanorods.

Solution pH, by itself, is not a consistent predictor of length and density. In Fig 4.4, the
increasing length with NH4OH suggests that length increases with pH. On the other
hand, in Fig 4.5 where a constant molar ratio is maintained which in turn results in a
relatively constant pH, the length did not remain constant as expected. A similar
contradiction is obtained when Figs 4.4 and 4.5 are examined. Fig 4.4 suggests a
decreasing density with increasing pH while a constant pH in Fig 5 fails to maintain a
constant density.

The ability of solubility to provide a consistent correlation for both length and density
of the nanorods suggests that solubility is a more fundamental parameter for
prediction of length and density. In fact, quantitative expressions can be obtained from
Figs 4.6 and 4.7 to relate the length and density to the solubility of zinc in the growth
solution:

L = AL1S Zn
m
[10]

B = AB1 S Zn
n
[11]

where AB1, AL1, m and n are constants. The units for L, B, and SZn are nm, cm-2 and mol/l
respectively. The best fit is obtained when AL1 = 8.710 x 108, AB1 = 1.047 x 10-8, m = 1.81
and n = -5.22 as shown by the solid line in Figs 4.7 and 4.8.

65
4.6 Effect of Temperature on Density and Length
In this section, we will examine how the temperature affects the length and density of
the nanorods. When the growth temperature increases from 333K to 423 K, the
solubility of zinc is expected to increase. Since the concentration of ZnAc2 is kept
constant, the degree of supersaturation of zinc in the solution is expected to decrease
as shown in the inset of Fig 4.9. Based on equations [10] and [11], the length is
expected to increase while the density, decrease. However, experimental data in Fig
4.2 shows otherwise. This suggests that an additional temperature factor needs to be
included.

As mentioned earlier, the critical free energy for nucleation in Equation (2.19) is
dependent on solubility and growth temperature. While the temperature-dependence
of solubility has been explicitly included into the equilibrium rate constants the using
equation (2.13), the growth temperature factor has not yet been included in Equations
(10) and (11). In order to take into account this additional temperature dependence,
equations [10] and [11] are rewritten as

E 
L = AL1 S Zn
m
exp aL + AL 2  (12)
 kT 

E 
B = AB1S Zn
n
exp aB + AB 2  (13)
 kT 

where k = 8.62×10-5 eV.K-1 is the Boltzmann constant, T is the growth temperature in

Kelvins, and EaL, EaB, m, n, AB1, AB2, AL1 and AL2 are constants to be determined by curve
fitting to experimental data.

Taking the natural logarithm on both sides and rearranging, we arrive at

 L  E aL
ln m
=
 kT + AL 2 [14]
 AL1 S Zn 

 B  E aB
ln n
=
 kT + AB 2 [15]
 AB1 S Zn 

66
 [ ( n
4. show ln B AB1S Zn
Curves (a) and (b) in Fig 4.8 )] [ ( m
and ln L AL1S Zn )]
, respectively,

plotted against 1 T , using the values of m, n, AB1 and AL1 obtained earlier. The line of
best fit is obtained when EaL = 0.77 eV, EaB = -2.11eV, AL2=-24.3 and AB2 = 67.2.

[ ( n
)]
Figure 4.8. Plot of (a) Y = ln B AB1S Zn [ ( m
and (b) Y= ln L AL1S Zn )]
against 1/T.
 and
represent the density and length data points respectively when
temperature is varied from 60 to 150°C. The inset shows the degree of
supersaturation of zinc, S, against temperature for a precursor solution
containing 0.016 M Zn(Ac)2 and 0.173 M NH4OH.

The activation energy for length in Equation (12) is positive while density in Equation
(13) is negative. This implies that higher temperatures lead to a shorter length and
higher density. On the other hand, from ionic equilibrium calculation, we know that
higher temperatures increase the solubility which in turn leads to longer lengths and
lower density. The opposing effects of temperature and solubility gives rise to an
optimal point where maximum density and length is obtained. This optimal point is at
100 °C as shown in Fig 4.2.

A physical understanding of the activation energies of length and density can be

obtained by recalling that a higher temperature reduces the critical radius and
an
increases the nucleation rate. A higher nucleation rate directly leads
leads to a higher
67
nanorod density. As more zinc ions are nucleated on the substrate surface, less zinc
ions are available in the solution for subsequent growth. Furthermore, the remaining
zinc ions in the solution will be distributed over a larger number nucleation sites. Both
these factors lead to shorter nanorods.

4.7 ZnO Nanorod Length and Density Maps

The length, L, and density, B, defined using equations (12)-(13), the parameters of m, n,
Ea, A1 and A2 as determined by the best fit to the experimental data are summarized
below.

E 
L = AL1 S Zn
m
exp aL + AL 2  (4.16)
 kT 

E 
B = AB1S Zn
n
exp aB + AB 2  (4.17)
 kT 

where m = 1.81, n = -5.22, AL1 = 8.710 x 108, AL2 = -24.3, AB1=1.047 x 10-8, AB2=67.2, k =
8.62×10-5 eV.K-1, EaL = 0.77eV, EaB = -2.11eV. The units for B, L and SZn are cm-2, nm and
mol/l respectively.

These equations provide a convenient relative measure of length and density for a
given precursor concentration and temperature and is useful for prediction of the
length and density of ZnO nanorods for various growth conditions within the validity
range. In fact, the same approach can be applied for other lattice-matched substrates.
It's worth noting that the constants AB1 and AL1 are interface related constants as we
shall see in the next chapter. If the surface of the substrate is rougher, then the AB1 is
expected to be larger while AL1 smaller, leading to a higher density and shorter length
of nanorods.

Contour plots of log(B) and L at 373 K are shown in Fig 4.9 (a) and (b) respectively. The
validity ranges of pH and S are also indicated on the plots. Several important points can
be obtained from Fig 4.9:

68
1. The maximum achievable density for the ZnAc2-NH3 system is about 109.5 cm-2 with
a corresponding length of less than 1 µm. Higher densities of nanorods can be
obtained by growing in a pH less than 9.7 at the expense of poor substrate
coverage. It is also possible that higher densities of nanorods is likely to result in
coalescence of rods and formation of a film. One way to enhance the density is to
use surfactants such as PEI or AlCl3 to increase the aspect ratio of the rods.
2. The maximum length is about 8 µm with a corresponding density less than 107 cm-2.
Longer lengths can be obtained simply by extending the growth duration beyond 4h
or refreshing the growth solution after 4h. Due to the low density of rods, it is
expected that several growth cycles can be employed to extend the rod lengths.
3. It is clear that the densities and length cannot be maximized simultaneously in a
single growth step. In order to maximize density and length, a two-step process
may be required where the substrate is grown in a “high-density” solution and then
transferred to a second solution to maximize the length of the rods.

4.8 Limitations of Model

The parameters m, n, EaB, EaL, AB1, AB2, AL1 and AL2 are obtained through curve-fitting of
experimental data to the calculated equilibrium concentration of zinc in the solution.
Therefore, the validity of the expressions developed are limited to experimental
conditions, consisting of a temperature range between 333K to 423K, a solution pH
range from 9.7 to 10.6 and a degree of supersaturation between 20 and 60.

Furthermore, this model was based on the growth of ZnO on Ga-face of GaN substrates
grown on sapphire by MOCVD. For other lattice matched substrates or GaN substrates
with different surface roughness, the exact value of the constants will be different
because of different interface properties. However, the trend of density and length of
nanorods based on solubility can still be applied.

69
Figure 4.9. Black lines show the contour plot of (a) log[B(cm-2)] and (b)
length (nm) for various concentrations of ZnAc2 and NH4OH. The validity
limits for pH between 9.7 and 10.6, and degree of supersaturation of zinc
between 20 and 60 are shown in red and blue lines respectively.

70
4.9 Conclusion
In summary, we have shown that solubility and temperature provides a better
prediction than other commonly used parameters such as pH and degree of
supersaturation.

We have also provided an empirical model to predict the density and length of
hydrothermally-grown ZnO nanorods using zinc acetate and ammonium hydroxide as
reagents, on the Ga-face of an unintentionally doped GaN substrate for a growth
temperature ranging from 333 to 423 K. We have identified solubility of zinc ions and
temperature as the main factors affecting the density and lengths of the ZnO nanorods.

The density can be maximized by minimizing the solubility of zinc and increasing the
growth temperature, while the length, by maximizing the solubility and lowering the
growth temperature. The activation energy for density and length is found to be -2.11
eV and 0.77 eV respectively. Due to opposing dependence on solubility and
temperature, it is not possible to maximize density and length of nanorods in a single
growth step. Finally, growth maps indicating the predicted density and length of ZnO
nanorods on GaN substrates have been provided for a range of precursor
concentration.

71
5 Growth and Defects of ZnO Nanorods
Grown from a ZnO Seed Layer

5.1 Introduction
In Chapter 4, we have shown that solubility is a better predictor than pH and
supersaturation for the growth of ZnO nanorods on lattice-matched substrates. Here,
we will extend the application of solubility to predict the morphology and density of
non-lattice-matched substrates that have been pre-coated with a layer of ZnO
nanoparticles. In addition to solubility, we will also show that the interfacial properties
such as the surface roughness and surface charge, and the type of growth species are
important mechanisms that affect the growth habit and growth rate of ZnO in aqueous
solution.

Knowledge of the growth mechanisms provides the key to identifying and reducing the
defects in ZnO. The as-grown ZnO using solution methods have been reported to have
a high concentration of defects [17]. As a result, post-annealing treatments are often
required to improve the crystal quality and remove the defects in the structure.
Studenkin et al showed that orange and green PL emissions are due to oxygen-rich and
oxygen-deficient growth conditions respectively. He further claimed that these defects
are complementary and cannot exist simultaneously [100]. Meanwhile, Djurisic et al.
review the growth and defects in ZnO nanostructures and attributed the yellow PL
emission, that are typically observed in solution-grown nanorods, to oxygen interstitials
and Li impurities [76]. In general, the assignment of orange or yellow emission to
interstitial oxygen defects is widely accepted, regardless of the growth method.
However, the assignment of green emission remains open and controversial. Among
the possible assignments are singly ionized oxygen vacancies, anti-site oxygen, oxygen

72
vacancies, zinc interstitials, Cu impurities, donor-acceptor transitions and zinc
vacancies [69, 76]. The large number of candidates suggests that the green emission is
very sensitive to the fabrication method, growth conditions and the post-growth
treatments.

Contrary to Studenkin’s report, we will show in this chapter that both orange and blue
emission can be present simultaneously when ZnO is grown using solution methods.
We will also show that the high defect density in nanorods is a consequence of growing
in the pH range of 10.5-11 and propose a method to suppress these visible emissions
without any post-annealing treatment. Furthermore, we will attempt to identify the
defects in our samples based on Raman, PL and post-annealing data. Finally we will
relate the origin of the defects to the growth mechanisms based on solubility,
interfacial properties and growth species in aqueous solution.

5.2 Experimental Procedure

The ZnO nanorods were grown on silicon substrates. Prior to growth in solution, the
substrates are pre-coated with a layer of ZnO nanoparticles. The presence of this layer
of ZnO nanoparticles on the substrate surface reduces the significance of the substrate
orientation. The pre-coat and growth procedure follows the experimental procedure as
described in Chapter 3 Sections 3.2.1 and 3.2.2.

The two groups of experiments were carried out. The first group of experiments
explores the growth of ZnO over a wide range of pH by varying the concentration of
NH4OH while keeping the concentration of ZnAc2 fixed. The second group of
experiments systematically investigates the effect of varying the reactant
concentrations over a narrow range of pH. Their descriptions are as follows:

• Growth over a wide pH range: the concentration of NH4OH is varied from 0.02
to 1.1 M while the concentration the ZnAc2 is kept constant at 0.02 M.

• Systematic growth over a narrow pH range from 10.4 to 10.8: the concentration
of ZnAc2 is varied from 0.01 to 0.03 M and NH4OH from 0.4 to 1.1 M.

73
The growth durations for all three groups of experiments were maintained at 3 h at
97°C.

After growth, the ZnO nanorods were examined using a field emission scanning
electron microscope. The density of the ZnO nanorods is estimated in a similar manner
as described in Chapter 4. The crystal quality and defects of the ZnO nanorods were
studied using Raman scattering and PL measurements. Raman spectra were recorded
in a backscattering configuration using a JY-T64000 micro-Raman setup with the 514.5
nm line of an Ar ion laser as the excitation source. PL measurements were carried out
using a Renishaw 2000 micro-PL setup with the 325 nm line from a He–Cd laser as
excitation source. To study the effect of annealing on the defect PL, the samples were
annealed inside a rapid thermal annealing chamber at various temperatures.

5.3 Results
Fig 5.1 shows the morphology of the rods when the concentration of NH4OH is varied
from 0.02 M to 1.1 M, while the concentration of ZnAc2 is kept constant at 0.02 M. The
corresponding initial pH values of the growth solutions are shown in square
parentheses.

Fig 5.2 shows the images from the second set of experiments where the concentrations
of both ZnAc2 and NH4OH were varied systematically over the range of 0.01 to 0.03 M
and 0.4 to 1.1 M respectively.

From Fig 5.2, three distinct types of morphology can be seen:

• uniform coverage of nanorods is observed in the first column with 0.4 M NH4OH,
with an increase in nanorods density when [ZnAc2] is increased from 0.01 to 0.03 M.

• a mixture of small nanorods and large rods in the second column with 0.8 M NH4OH.

• large rods with 1.1 M NH4OH. Coverage improves and density increases when
[ZnAc2] is increased from 0.01 to 0.03 M.

74
Figure 5.1. SEM morphology of ZnO nanorods grown on Si substrates with a
pre-coat
coat of ZnO nanoparticles using growth solutions with 0.02 M ZnAc2
and (a) 0.02 M, (b) 0.04 M, (c) 0.1 M, (d) 0.3 M, (e) 0.4 M and (f) 1.1 M
NH4OH.. The concentration of NH4OH and the corresponding initial solution
pH values in square parentheses are indicated on the top left corner. Scale
bar shows 1 µm.

Figure 5.2. SEM image showing the morphologies of ZnO nanorods grown
in various concentrations of ZnAc2 and NH4OH. (a), (b) and d (c) were grown
with 0.4 M, 0.8 M and 1.1 M NH4OH respectively while keeping ZnAc2 fixed
at 0.01 M. (d), (e) and (f) were grown with 0.4 M, 0.8 M and 1.1 M NH4OH
respectively while keeping ZnAc2 fixed at 0.02 M. (g), (h) and (i) were grown
with 0.4 M, 0.8 M and 1.1 M NH4OH respectively while keeping ZnAc2 fixed
at 0.03 M. The scale bar is 1 µm and all images were taken with the same
magnification.
75
Fig 5.3 shows the Raman spectra of the ZnO grown in 0.02 M ZnAc2 and 0.4, 0.8 and 1.1
M NH4OH, corresponding to the pH range of 10.6 to 10.8. The corresponding SEM
images of these samples are shown in Figs 5.2(d), (e) and (f). A clean glass substrate
was used so that only the Raman peaks attributable to ZnO will be observed. The
observed peaks at about 332, 380, 413 and 439 cm-1 are assigned to 2E2L(M), A1(TO), E1(TO)
and E2H [86, 101]. In addition, a broad asymmetrical peak at 580 cm-1 has been
attributed to a defect-induced mode and will be discussed later.

The E2H peak position for 0.4, 0.8 and 1.1 M NH4OH are 439.7, 440.5 and 441.1 cm-1
respectively as shown in the inset of Fig 5.3. When compared against the E2H peak of
unstrained bulk ZnO at 439 cm-1, the increasing frequency indicates progressively
higher compressive stresses in ZnO nanorods with higher concentration of NH4OH in
the growth solution.

The width of the E2 peak increases with the concentration of NH4OH, indicating a
poorer crystal quality at higher pH. As all the samples were grown on similar glass
substrates, the increase compressive stress in the structure cannot be fully explained
by lattice mismatch between glass substrate and ZnO. It is likely that the compressive
stress arises from increased concentration of defects, such as zinc or oxygen
interstitials, incorporated into the structure during growth.

The broad asymmetric peak, which is centered at 580 cm-1, is strongest when
crystallinity is poorest at 1.1M NH3. This peak is unlikely to be A1(LO) or E1(LO) as LO
phonons becomes stronger with higher crystallinity. We attribute this peak to a defect-
induced band which have been reported to have a strong dependence of on the oxygen
stoichiometry [90]. In this case, the concentration of defects increases with the
concentration of NH4OH in the growth solution, agreeing with the trend of E2H band.

Finally, the multi-phonon band at 332 cm-1 is ascribed to E2L [102]. The low frequency
E2L is associated with the vibration of the heavy zinc sublattice while the high frequency
E2H mode involves only the oxygen atoms. With the E2H peak normalized, the E2L peak is
seen to increase with the amount of NH4OH in the growth solution. This can be

76
attributed to a more ordered zinc sublattice and/or a more disordered oxygen
sublattice.

Figure 5.3. The Raman spectra measured from samples grown with 0.4, 0.8
and 1.1 M NH4OH on a glass substrate. Inset shows the shift of the E2H peak
to higher frequencies as concentration of NH4OH is increased.

Figure 5.4. Photoluminescence spectra recorded from samples grown in

0.02 M (black line), 0.04 M (blue line), 0.3 M (green line) and 1.1 M NH4OH
(red line) while the concentration of ZnAc2 is kept constant at 0.02 M.

77
 Figure 5.5. PL spectra of sample grown in high pH (10.7) after annealing at
various temperatures in (a) air and (b) nitrogen ambient, as well as low pH
sample (7) annealed in (c) air and (d) nitrogen ambient. The sharp peak at
650 nm is due to the doubling of the 325 nm laser line and should be
ignored.

Fig 5.4 shows the PL spectra for samples grown at various NH4OH concentrations while
the concentration of ZnAc2 is fixed at 0.02 M. The visible defect emission decreases
while the ultraviolet band edge emission increases when the concentration of NH4OH is
reduced. A marked improvement of the ratio between the UV and visible emission can
be seen when the growth solution pH is less than PZC. The ability to suppress the
visible emission without any post-annealing treatment suggests that it is possible to
control the type and concentration of defects by carefully controlling the growth
conditions in aqueous solution.

Fig 5.5 shows the changes in PL spectra when samples are annealed in air and nitrogen
ambient at various temperatures. The spectra consists of two major components, a UV
78
component centered at 380 nm and a broad visible component which can be separated
into green and orange emission bands centered at 500 - 510 nm and 640 - 650 nm
respectively. The intensities are shown in logarithmic scale. The sharp peak at 650 nm
is due to the doubling of the 325 nm laser line and should be ignored. Two samples are
studied: the first sample is grown at a high pH of approximately 10.7, using 0.02 M
ZnAc2 and 0.8 M NH4OH while the second sample is grown at a low pH of
approximately 7, using 0.02 M ZnAc2 and 0.02 M NH4OH.

The variation of the PL of the sample grown in high pH when annealed in air and
nitrogen ambient is shown in Fig 5.5 (a) and (b) respectively. In air, the orange emission
does not change significantly, but in nitrogen, significant reduction was observed above
400°C. This suggests the presence of interstitial oxygen in the sample. In nitrogen,
interstitial oxygen readily diffuses out of the sample above 400°C while in air, the out-
diffusion of oxygen is balanced with adsorption of oxygen from air. This assignment of
interstitial oxygen to the orange emission agrees well with the reported literature [69,
76].

Continual reduction of green emission is observed for both air and nitrogen ambient as
annealing temperature is increased. The green emission is unlikely to be related to an
oxygen defect because its intensity reduces both in air and nitrogen ambient.
Considering the formation energy of native defects arising from growth in an oxygen-
rich environment, the likely point defects are zinc vacancies and interstitial zinc [103].
We believe that a combination of zinc vacancies and interstitial zinc is likely to be
related to the green emission. Interstitial zinc has a low migration energy barrier [103].
This allows the interstitial zinc to diffuse into zinc vacancy sites and thus reduce the
green emission intensity under various annealing conditions. The slight increase in
green emission after annealing at 800°C in nitrogen is attributed to removal of
hydrogen defects as water molecules [81].

These results indicate that when ZnO is grown at high pH, the major defects are zinc
interstitials, oxygen interstitials and zinc vacancies. This is consistent with the Raman
results. Both zinc and oxygen interstitials lead to compressive stress in the crystal
structure. As the pH increases, the concentration of these defects increase, leading to
79
stronger defect emission and higher compressive stresses. These defects are present in
the bulk of the rods and not just on the surface of the rods because the Raman spectra
were recorded using visible excitation wavelength, which penetrates into the bulk of
the rods.

The variations of the PL of the sample grown in low pH when annealed in air and
nitrogen ambient are shown in Fig 5.5 (c) and (d) respectively. The orange emission is
very low in as-grown samples and increases when annealed in air because oxygen from
air adsorbs into the bulk. As expected, the orange emission remains unchanged when
annealed in nitrogen ambient.

The green emission in a low pH sample remains roughly unchanged when annealed in
both air and nitrogen, and is possibly caused by zinc vacancies. The stability of the
green emission in a low pH sample stands in contrast against that of a high pH sample.
It is unclear what led to the different stability of the green emission: possible reasons
are lack of interstitial zinc and stability of hydrogen defects at vacancy sites. When the
sample is annealed at 800°C in nitrogen, the hydrogen defects are removed from the
structure as water molecules resulting in more zinc vacancies and a higher green
emission peak, similar to that observed in the high pH sample.

The UV intensity for both low and high pH samples generally peaks when annealed at
400°C, regardless ambient. This maximum intensity also corresponds with the
maximum electron concentration measured by Hall effect which is shown later in
Chapter 6. We believe that this is due to activation of hydrogen defects at 400°C.
Beyond 400°C, the UV intensity will decrease due to desorption of H from the sample

5.4 Discussion

5.4.1 Role of solubility in growth morphology

Table 1 shows the relationship between the growth pH values and the observed ZnO
grown as seen in Fig 5.1. Uniform growth is observed in the pH range of 7 to 7.5 and
10.6 to 10.8. From Chapter 2, we know that this pH range for uniform growth of
nanorods is far from the PZC of ZnO which has been reported to range from 8.7 to 9.7.
80
We also know that the interfacial energy γ reduces rapidly to a small constant value as
the pH moves away from the PZC.

Table 5.1. Summary of observed growth behavior with solution pH

pH range <7 7 – 7.5 9 - 10.2 10.6 – 10.8 > 11

ZnO None Slow and Poor Fast and None
nanorod uniform coverage uniform
growth

To understand how pH affects the Gibb’s free energy of nucleation, we will need to
examine Eq. (2.19) in Chapter 2. For the convenience of the following discussion, we
reproduce Eq. (2.19) which describes the critical Gibb’s free energy of nucleation.

16πV 2 γ3
∆G = 2 2 ⋅
*
2
(5.1)
3k T  C 
 ln 
 S 
 Zn 

where V is the atomic volume, k is the Boltzmann constant defined as 1.38 x 10-23 m2 k
g s-2 K-1, T [K] is the growth temperature, C [mol/l] is the concentration of zinc acetate
used in the experiment, SZn [mol/l] is the solubility of zinc and γ is the interfacial energy.

For constant values of interfacial energy γ, ZnAc2 concentration C and temperature T,

we can rewrite Eq. (5.1) as

16πV 2 γ3 K1
∆G * = ⋅ = (5.2)
3k 2T 2  C 
2
 K2 
2

 ln   ln 
 S   S 
 Zn   Zn 

where K1 and K2 are constants.

81
Figure 5.6. Plot showing the solubility of zinc, SZn, against the concentration
of NH4OH for 0.006 M (black dotted line), 0.01 M (blue line), 0.02 M (green
line) and 0.03 M (red line) of ZnAc2. The SZn data points which are labeled
(a) to (i) corresponds to the SEM images in Figs 5.2 (a) to (i) respectively
which have been reproduced here for ease of comparison. The value of SZn
when 0.006 M ZnAc2 and 0.4 M NH4OH is marked with a square (
) and the
corresponding SEM image is shown in Fig 5.7. Growth in region 1 produces
uniform nanorods, region II a mixed morphology of nanorods and large rods
and region III only large rods.

82
Eq. (5.2) is significant because it states that the solubility of zinc is the dominant factor
affecting the Gibbs free energy in the pH range where uniform growth of ZnO nanorods
occur. Since the initial value of SZn can be calculated from the ionic equilibrium of the
growth solution using thermodynamic data, we should be able to see a correlation
between SZn and the morphology of the nanorods.

The dominant role of SZn can be clearly seen when the growth morphologies in Fig 5.2 is
compared against their corresponding value of SZn in Fig 5.6. Fig 5.2 is reproduced
above Fig 5.6 for ease of comparison.

Firstly, when ZnAc2 is kept at 0.02 M to maintain a constant value of C, while NH4OH is
increased from 0.4 to 1.1 M to vary the pH within the range of 10.6 to 10.8, the density
of rods is observed to reduce with higher concentrations of NH4OH as shown in Figs 5.2
(d), (e) and (f). A higher concentration of NH4OH increases the solubility of zinc SZn and
thus, from Eq. (5.2), leads to a higher Gibbs free energy, a lower rate of nucleation and
a lower density of rods. The same behavior can be observed in Figs 5.2 (a), (b) and (c)
as well as Figs 5.2 (g), (h) and (i) when 0.01 and 0.03 M of ZnAc2 are used respectively.
This clearly shows the dominant role of solubility over interfacial energy in pH ranges
that uniform growth of ZnO occurs.

Figure 5.7. SEM image showing the top and cross-sectional view of a
sample grown in 0.006 M ZnAc2 and 0.4 M NH4OH. The mixed morphology
confirms the dependence of SZn which shown in Fig 5.6.

83
It can also be seen that the morphology of the rods can be predicted from the value of
SZn. There are three distinct regions in Fig 5.6:

• Region I where SZn is less than 0.88 mmol/l, we obtained uniform and dense
array of ZnO nanorods with good surface coverage as shown in Figs 5.6 (a), (d)
and (g).

• Region II where SZn is in between 0.88 and 1.56 mmol/l, a transition region
where both nanorods and large clustered rods exist in Figs 5.6 (b), (e) and (h).

• Region III of Fig 6 where SZn is greater than 1.56 mmol/l, large clustered rods
with poor surface coverage are obtained as shown in Figs 5.6 (c), (f) and (i).

To confirm the morphology dependence on SZn, and not on the concentration of

NH4OH, a sample is grown in a solution of 0.006 M ZnAc2 and 0.4 M NH4OH. The value
of SZn at this point is indicated by a square ‘
’ in Fig 5.6. The corresponding SEM image
in Fig 5.7 shows a mixed morphology which confirms a SZn dependence instead of
[NH4OH] dependence.

As in the case of growth of ZnO on GaN epilayers in Chapter 4, pH by itself is not a good
predictor for morphology. To illustrate this point, Fig 5.8 plots SZn against the pH
instead of [NH4OH] as in Fig 5.6. It can be seen clearly that the three types of
morphologies cannot be grouped using the pH variable alone. A combination of pH and
concentration of ZnAc2 is required to get a good prediction of the morphology. The
solubility of zinc which already incorporates the pH and various reactant
concentrations does a much better job in predicting the nanorods morphology.

Finally, we have observed that the dependence of these morphology trends on the
value of SZn is independent of substrate such as glass, ITO, silicon (111), silicon (100)
and plastic. This is attributed to the presence of a seed layer of ZnO nanoparticles on
the substrate which provides similar interface properties.

84
 Figure 5.8. Plot of solubility of zinc against pH for 0.006 M (black dotted
line), 0.01 M (blue line), 0.02 M (green line) and 0.03 M (red line) of ZnAc2.
The corresponding SEM images from Fig 5.2 are shown here for ease of
comparison.

5.5 Role of interfacial properties in aqueous solution

In the previous section, we have shown for a narrow range of pH > PZC where good
growth of nanorods can be achieved, that solubility is a good predictor of the free
Gibbs energy and thus the density and morphology of the nanorods. When the pH
varies over a wider range, however, other factors such as the interfacial energy and the
type and charge of growth species in the solution need to be considered in order to
understand the differences in growth habits and mechanisms. One such example that
we will discuss in this section is differences in the growth rate and habit between the
two ZnO growth zones at the pH ranges of 7-7.5 and 10.6-10.8.

85
When growth pH in the region of 7 to 7.5, the solution pH is less than the PZC of ZnO,
thus H+ ions will tend to reside on the surface of ZnO rather than dissociate into the H+
rich solution. This leads to a positively charged ZnO surface with hydrogen stabilizing
the oxygen sites [104] on the polar surfaces [105]. In the pH range of 7 to 7.5, the
major species in the solution are positively charged Zn2+ and Zn(OH)+. The positively
charged zinc surface and a low concentration of negatively charged growth species
result in a slow growth rate, preferentially along the [0001] direction. As the zinc polar
surfaces are stable with the adsorption of hydrogen [105], the rods appear flat-topped
as shown in Fig 5.9 (a) when 0.02 M NH4OH is used to obtain a solution pH of about 7.

When the growth pH is in the range of 10.6 to 10.8, the solution pH is greater than the
PZC of ZnO and the H+ ions readily enter the solution. This results in a negatively
charged surface of ZnO, except for the polar (0001) surface which remains positively
charged. In the pH range of 10.6 to 10.8, the major species in the solution are
negatively charged Zn(OH)42-. A positively charged polar surface and presence of
negatively charged major growth species leads to a fast growth rate in the [0001]
direction. It is known that crystal faces whose growth rate is fastest will be minimized,
thus the rods appear more tapered and sharp-tipped. The much larger and tapered
rods can be seen in Figs 5.9 (b) when 1.1 M NH4OH is used to obtain a solution pH of
10.8.

Figure 5.9. SEM image showing the top view of a sample grown in (a) 0.02
M and (b) 1.1 M NH4OH. The concentration of ZnAc2 is kept constant at 0.02
M. The scale bar shows 1 µm.

86
In this section, we have seen how the solubility, surface charge and the type of major
growth species affect the ZnO growth rates and growth habits. In the next section, we
will show that these factors are also determines the type of defects in the resulting
nanorods.

5.6 Defects and the growth mechanism

From the PL and Raman results, we know that the concentration of defects and
compressive stresses increase with the concentration of NH4OH. We also know that the
zinc sublattice becomes increasingly ordered at the expense of the oxygen sublattice.

In order to understand how the concentration NH4OH is related to the incorporation of

defects during growth, we will need to look at the interface properties and growth
species which affect the growth habit and growth rate of the nanorods.

As more NH4OH is added, the solution becomes more basic and pH increases. More H+
ions from the surface of ZnO enter into the solution and frees up more sites for
adsorption of zinc ions. This leads to a lower concentration of hydrogen defects as well
as zinc vacancies in the bulk, which improves the zinc sublattice.

As explained earlier for a high pH regime, the growth rate is fast in the polar direction
due to the surface charge and presence of majority negatively-charged growth units.
Increasing the concentration of NH4OH leads to an increasing concentration of
negatively charged growth species and thus a faster growth rate. This faster growth
rate leads to the more native defects such as interstitial zinc and zinc vacancies.

A higher pH also provides a growth environment that is richer in hydroxyl groups. The
excess hydroxyl groups normally leave the structure through dehydration. Fast growth
rates also prevents complete dehydration which in turn, leaves behind some hydroxyl
groups embedded in the structure in the form of interstitial oxygen. This creates a
more disordered oxygen sublattice as seen in the Raman spectra.

A marked improvement of the ratio between the UV and visible emission was seen
when pH is much less than PZC. This can be attributed to the slower growth rate which

87
results in less structural defects, as well as the incorporation of hydrogen in zinc
vacancy sites. When aligned along the c-axis, hydrogen is known form a stable shallow
donor [106] up to 1200°C [107] in hydrothermal samples grown above 300°C and this
contributes to the strong ultraviolet emission. In comparison to hydrothermal methods,
when ZnO is grown at temperatures below 100°C, desorption of H is observed at
temperatures above 400°C similar to the behavior of implanted H defects. The ability to
drive out hydrogen defects and lower the background doping concentration at lower
temperatures is important for p-type doping as will be shown later in Chapter 6.

Furthermore, at low pH, the growth environment is zinc rich as the concentration of
Zn2+ is much higher than that of OH-, leading to low concentrations of interstitial
oxygen and thus weak orange emission.

With these, it appears that our current understanding of the growth drivers consisting
of solubility, the interface properties and the majority growth species in the solution
sufficiently supports the experimental evidence of the growth morphology, density
distribution and intrinsic defects.

5.7 Conclusion
ZnO nanorods have been hydrothermally-grown on substrates pre-coated with ZnO
nanoparticles. When the pH is sufficiently far away from PZC and the interfacial energy
is at the minimum, good growth coverage of ZnO nanorods on the substrate can be
obtained. In this growth regime, we have shown that the solubility of zinc and surface
charges are important factors that determine the growth morphology of the rods.
When SZn < 0.88 mmol/l, a uniform coverage of nanorods is obtained and when SZn >
1.56 mmol/l, large clustered rods are obtained. Finally, when 0.88 < SZn < 1.56 mmol/l,
a transition region where both nanorods and large clustered rods exist.

We have shown that the visible light emissions from defects can be minimized while
the UV emission from band edge transitions can be enhanced simply by growing ZnO in
the regime where 7 < pH <7.5.

88
Finally, we have identified the different type of native defects in the bulk and
associated these defects with the different growth conditions. By growing in the region
where pH is less than PZC, hydrogen defects are the major defects. In this growth
regime, the growth rate is low and the visible defect emissions are minimized while the
UV band edge emissions are enhanced. The high UV emission intensity is attributed to
the shallow H defect states. When the sample is grown in a solution where the pH is
greater than PZC, the growth rate is fast and the major defects are interstitial oxygen,
interstitial zinc and zinc vacancies. In this growth regime, the bulk is rich with defects
and the intensity of the visible defect emissions is stronger than the UV emission. The
green component of the visible emission is attributed to interstitial zinc and zinc
vacancies while the red component is attributed to interstitial oxygen. Presence of
these defects results in a poorer crystal quality and a structure that is in compressive
stress.

89
6 Growth of p-ZnO film using
multiple growth cycles

6.1 Introduction
In this chapter, we will look at the feasibility of growing and doping ZnO films in
aqueous solution at low temperatures.

There are only a few reports on the epitaxial growth of ZnO using solution methods and
these reports can be traced to two main groups: Mader's group at University of Bonn
[108], Germany and Lange's group at Uni. of California, Santa Barbara, USA [22, 109].

Mader's group first reported the epitaxial growth of ZnO films on ScMgAlO4 [108] using
a sol-gel method followed by high temperature annealing at 850°C. This was followed
up by Lange's group who reported on the direct growth [109] as well as lateral epitaxial
growth [22] of ZnO films on MgAl2O4 (111) substrates. Kim et al extended the lateral
epitaxial growth method to grow ZnO thin film on GaN buffered Al2O3 (0001) substrates
[110]. Although Lange's group and Kim et al reported discontinuous film at pH 7.5, Sim
et al managed to obtain a continuous epitaxial film a single step by growing at 150°C
[111]. Since the same growth parameters were used by Lange and Sim, it can be
speculated that the growth duration was extended from 2 h to a much longer duration
to allow coalescence of individual rods and subsequent formation of a continuous film.
Table 6.1 below summarizes the precursors, substrates and growth temperatures used
in these reports.

90
 Table 6.1. Summary of reported investigators, precursors, growth
temperature and substrates for epitaxial ZnO growth in aqueous solution.

Investigator Precursor Temperature Substrate

1 Wessler et al ZnAc2, monoethanolamine, and 850°C ScMgAlO4
2-methoxyethanol. Solgel
method.
2 Andeen et al Zn(NO3)2 and NH4OH. Continuous 150 to 200°C MgAl2O4
film at pH 10.5-11. (111)
3 Andeen et al Zn(NO3)2, NH4OH and NaC3. Two 90°C MgAl2O4
step procedure: (1) pH 7.5 for (111)
epitaxial film, (2) LEO at pH 10.9
4 Kim et al Two step procedure: 90°C GaN-buffered
(1) Zn(NO3)2 & NH4OH at pH ~ 7.5 Al2O3 (0001)
(2) Zn(NO3)2, NH4OH & NaC3 at pH
~ 10.9
5 Sim et al Zn(NO3)2 and NH4OH. Continuous 150°C MgAl2O4
film at pH 7.5 (111)

The current state-of-the-art for growing a smooth continuous film requires a seed layer
to be grown at pH 7.5 and a subsequent film growth at pH 10.9 with the help of NaC3 as
a surfactant [22, 110]. Without NaC3, a rough surface arising from island mode growth
is obtained from both pH 7.5 [34] and 10.9 [109]. The rationale for the two-step
approach is as follows:

1. The slow growth at pH 7.5 allows a high density of ZnO islands to populate
substrate surface without introducing a large height difference between the
islands. This simplifies the eventual coalescence into a smooth film.
2. The fast growth at pH 10.9 minimizes the growth time needed to grow and
coalese these islands, as well as to cover the film discontinuity in the earlier
step. By employing NaC3 as a surfactant, lateral growth is enhanced while
vertical growth is retarded. Eventually, this leads to a smooth and continuous
film.

Although this approach succeeds in producing a smooth and continuous film, it fails to
minimize the native defects in the film. As we have shown from the photoluminescence

91
and Raman Scattering spectra in the previous chapter, the crystal quality of ZnO is
better at pH 7.5 than 10.9, although the coverage is poorer and growth rate is much
slower. Since the seed layer is grown at pH 7.5 and the bulk of the film at pH 10.9, it is
expected that the film has a rich density of defects. This can be seen from the low ratio
of UV to visible light intensity in the PL spectra [22].

Based on our earlier results, we propose an opposite process to obtain a high quality
thin film on surface. The initial seed layer of ZnO should be grown at pH 10-11. At this
pH range, a high density of nanorods with a very good coverage of the substrate can be
obtained in a short time. The subsequent film growth should be performed at low pH.
Although the growth rate is slow, it produces a low defect density and a flat-top
morphology which is suitable for coalescence into a smooth film as shown by Sim et al
[34].

In addition, we will look at how the K, a group I element, can be incorporated into the
film during growth. When K substitutes Zn, it contributes a hole and functions as a p-
type dopant. Its role as a p-type dopant will be investigated from the electrical
properties of the film with and without K. Next, we will explore the application of an
electric field in the growth solution to improve the growth rate at pH 7.5.

Finally a p-ZnO / n-GaN heterostructure is fabricated to confirm the p-doping of ZnO

using K.

6.2 Experiment
A thin film of ZnO was grown using a multiple step strategy with the general procedure
as described earlier in Chapter 3.

Firstly, a substrate is precoated with ZnO nanoparticles. For the seed layer growth, the
growth solution consists of 0.03 M ZnAc2 and 0.37 M NH4OH, for 30 min at 90°C while
the film layer growth consists of 0.03 M Zn(Ac)2, for 3 h at 90°C. The film layer growth
step is performed three times, to allow the rods to coalesce and form a continuous film.

92
To study the incorporation of K, the same amount of potassium acetate (KAc) is added
into the growth solution for both steps.

To study the effect of electric field on the doping efficiency, the growth setup was
modified to accommodate two electrodes in the growth vessel shown in Fig 3.2. The
modified growth setup is shown in Fig 6.1. The first electrode is the calomel reference
electrode which provide a reference voltage against the standard hydrogen electrode
potential. The second electrode is the platinum (Pt) counter electrode which closes the
circuit path.

Figure 6.1. Modified growth setup to study the effect of internal electric
field on the growth and doping of ZnO films.

For Hall measurements, the ZnO film was grown on Al2O3 (0001) in order to withstand
the high annealing temperatures. Aluminium contacts of 1 µm thickness were
evaporated on the four corners of the sample for Hall measurements. The carrier
concentration and mobility was measured using Accent HL5500 Hall measurement
system after growth and after annealing steps in nitrogen ambient at 200, 400, 600,
800 and 950°C for 10 min. Annealing was performed using ULVAC RTA system. The

93
annealing chamber was pumped down to a vacuum pressure of less than 10-5 mTorr
before nitrogen gas is flowed into the chamber with a flowrate of 100 sccm.

The film morphology was observed using Hitachi S4100 FESEM. XPS measurements
were done using a dual chamber VG ESCA/SIMSLAB system using a Al Kα beam. All the
measured XPS spectra was calibrated using the C 1s peak from a calibration standard.
The PL spectra measured using Renishaw Ramascope 2000 micro-PL with a He-Cd laser
as excitation source. Finally, the SIMS depth profile was obtained using TOF-SIMS IV.

6.3 Results and discussion

6.3.1 Evolution of film morphology using a multi-step growth approach

The evolution of the surface morphology from the first step of seed layer growth, to
the second step of first film layer growth and to the final step of the third film layer
growth is shown in Figs 6.2 and 6.3 on n-Si(100) and n-GaN substrates respectively. The
coalescence into a smooth continuous film is much better for GaN because of the good
lattice match between GaN and ZnO. For non-lattice matched substrates, the rods are
randomly orientated. Due to in-plane rotation among the rods, the rods take a longer
time to coalesce into a continuous film.

Figure 6.2. Morphology evolution from the seed layer to the film layer
growth on n-Si(100).

94
 Figure 6.3. Morphology evolution from the seed layer to the film layer
growth on n-GaN epilayer.

Fig 6.4 shows the development of the PL spectra from a seed layer growth step to the
film layer growth steps. As expected, the seed layer growth step produces a high
density of defects which leads to a low UV emission intensity and a high visible
emission intensity. A continual increase in the UV emission intensity and a slight
decrease in the visible emission intensity is observed as film layer growth proceeds
from 30, 90 to 180 min. This is expected because the top film layer, which has a much
lower density of defects, contributes the strong UV emission and decreases the
intensity of the excitation laser that reaches the underlying seed layer. In order to
minimize the defects from the seed layer growth, the seed layer growth duration is
kept short at 30 min, while the film layer growth is lengthened by growing for three
cycles of 3 h each.

Figure 6.4. PL spectra of as-grown seed layer (black) and the subsequent
film growth layers (blue for 30 min, green for 90 min and red for 180 min).
The film layer growth step significantly enhances UV emission while slightly
reducing the visible emissions.

95
When KAc is added into the growth solutions of the seed and film layer growth steps,
the growth rate of ZnO is enhanced. This effect can be seen in Fig 6.5 which shows the
top view of the film after one cycle of seed layer growth and two cycles of film layer
growth. Increasing the concentration of KAc increases both the rod diameters and
length. After the third cycle of film growth, the film thickness is 1.7, 1.9 and 2.0 µm for
without KAc, 0.07 M and 0.24 M KAc respectively.

Figure 6.5. SEM image shows the top view of the ZnO film after one cycle of
seed layer growth followed by two cycles of film layer growth for the
samples that are grown (a) without KAc and with (b) 0.07 and (c) 0.24 M
KAc.

6.4 Role of K as a dopant for ZnO films

To investigate the incorporation of K in the structure, Hall effect measurements and
SIMS depth profile were obtained for the samples grown without KAc and with 0.07 M
and 0.24 M KAc. The results for Hall effect measurements are summarized in Table 6.1
while the SIMS depth profile is shown in Fig 6.6.

By comparing the carrier concentrations in Table 6.2 and the depth profiles of K in Fig
6.6, we can establish a positive correlation between the hole concentration and the
concentration of K in the ZnO film. Without KAc, the actual K concentration is negligible
and the film is n-type.

Furthermore, the experimental data shows that that the amount of K incorporated in
the structure cannot be simply increased by increasing the concentration of KAc in the

96
growth solution. The optimum point with the highest K and hole concentration is
obtained with 0.07 M KAc, followed by 0.24 M KAc.

Table 6.2. Summary of carrier parameters obtained from Hall effect

measurements for samples grown without KAc and with 0.07 and 0.24 M
KAc. The film thickness is obtained from the SEM image of the cross-section
of the film.

Conc. Of KAc Film Type of Carrier conc. Carrier

(M) thickness majority (cm-3) mobility
(µm) carrier (cm2/V-s)

0 1.7 n 1.4 × 1016 0.45

0.07 1.9 p 3.8 × 1017 0.038

0.24 2.0 p 3.7 × 1014 11.8

100
Zn (No KAc)
Zn (0.07M KAc)
Zn (0.24M KAc)
O (No KAc)
10 O (0.07M KAc)
O (0.24M KAc)
Intensity (a.u.)

K (No KAc)
K (0.07M KAc)
1 K (0.24M KAc)

0.1

0.01
0 20 40 60 80 100 120 140
Time (s)

Figure 6.6. SIMS depth profile for Zn, O and K.

97
6.5 Effect of electric field on the growth and doping of
ZnO films in solution
The thickness and carrier concentrations for various bias voltages are summarized in
Table 6.3 while the SIMS depth profile is shown in Fig 6.7. The film thickness is
measured from the cross-sectional view of the sample using SEM. The carrier
concentrations and mobility are obtained from Hall effect measurements. Finally the
depth profile is obtained using SIMS.

When ZnO is grown in the presence of an increasing electric field, the growth rate
increases dramatically. For example, at a - 0.9 V bias, the thickness of the film increases
370% to 7.4 µm compared to 2.0 µm without any bias. Without any bias at pH 7.5,
growth is slow because the surface of the substrate and the majority growth units are
positively charged. By applying a negative bias, the positive growth units in the solution
are attracted towards the substrate and the growth rate can be increased significantly.

Unfortunately, the incorporation of K in the film does not increase with the bias voltage.
SIMS depth profile showed that the maximum incorporation of K occurs at a voltage
bias of -0.1 V. In fact, at -0.9V, the concentration of K in the structure is even lower
than that without any bias applied. It appears that there is a trade-off between the
growth rate and amount of K that incorporated inside the structure and the optimum
point is about -0.1 V. Higher negative bias voltages beyond -0.1 V results in thicker film
and lower K incorporation.

Further examination of the hole concentration and the concentration of K in the film
shows that although the level of K incorporation is highest at -0.1 V, it does not lead to
the highest concentration of holes. The highest hole concentration of 3.98 x 1017 cm-3 is
obtained by applying a bias of -0.4 V. One possible explanation of this phenomenon is
the occupation of interstitial sites by K atoms. To confirm this, XPS is performed and
Figs 6.8 and 6.9 shows the typical survey scan spectra and quantification peaks. A
summary of the atomic percentages from quantifying the survey scan, as well as the

98
calculated atomic percentages of K at lattice and interstitial sites, Zn vacancies and the
measured hole concentrations are shown in Table 6.4.

Table 6.3. Summary of carrier parameters obtained from Hall effect

measurements for samples grown with 0.24 M KAc at different bias
voltages. The film thickness is obtained from the SEM image of the cross-
section of the film.

Applied Film Type of Carrier Carrier

potential Thickness Majority conc. mobility
(V) (µm) Carrier (cm-3) (cm2/V-s)

0 2.0 hole 3.70 x 1014 11.8

-0.1 2.6 hole 1.17 x 1016 0.17

-0.4 5.7 hole 3.98 x 1017 0.046

-0.9 7.4 hole 3.21 x 1014 5.5

1000
Zn (No bias)
Zn (-0.1V)
Zn (-0.4V)
100
Zn (-0.9V)
O (No bias)
O (-0.1V)
O (-0.4V)
O (-0.9V)
Intensity (a.u.)

10
K (No bias)
K (-0.1V)
K (-0.4V)
K (-0.9V)
1

0.1

0.01
0 20 40 60 80 100 120 140
Time (s)

Figure 6.7. SIMS depth profile for Zn, O and K for samples grown in the
presence of 0.24 M KAc and varying bias voltages from 0, -0.1, -0.4 to -0.9 V.

The data in Table 6.4 resolves the discrepancy between the hole concentration and the
concentration of K in the ZnO film. Although the concentration of K for a bias of -0.1 V

99
is the highest, not all the K atoms are located at substitutional sites: only 23.4 at% are
in substitutional lattice sites compared to 23.9 at% at -0.4V. In fact, the bias of -0.1 V
has 11.7 at% which is the highest concentration of K at interstitial sites among the
three samples.

Since the hole concentration is correlated to concentration of K donors at

substitutional sites, the bias of -0.4 which has the highest atomic percentage of K at
lattice sites will have the highest concentration of holes, as measured by Hall effect
measurements.

Figure 6.8. Typical XPS survey spectrum of a ZnO sample doped with K. The
peak positions of Zn, O, K and C have been marked. Au peaks are from the
calibration reference.

Figure 6.9. Typical component fitting of Zn, O and K using Zn 2p3/2, O 1s and
K 2s peaks for atomic concentration quantification. Synthetic peaks were
fitted to the measured peaks using a Shirley background and Gaussian-
Lorentian distributions. Quantification was performed using the fitted
synthetic peaks to improve estimation accuracy.
100
 Table 6.4. Summary of percentage atomic concentrations from quantifation
of the fitted components of Zn 2p, O 1s and K 2s in the XPS survey spectra.
The relative sensitivity factors (RSF) that were used for quantification are
indicated beside the element in parenthesis.

Applied potential difference

Element (RSF) units -0.1 V - 0.4 V - 0.9 V

Zn (2p1/2 = 9.29, 2p3/2 = 18) at% 20.7 25.5 31.5

O (2.85) at% 44.1 50.6 55.2

K (1.95) at% 35.1 23.9 13.3

K at lattice sites at% 23.4 23.9 13.3

K at interstitial sites at% 11.7 0 0

Zn vacancy sites at% 0 1.3 10.4

Hole concentration cm-3 1.17 × 1016 3.98 × 1017 3.21 × 1014

Zn 3d
1 (a) 3.2E14
Normalised intensity (a.u.)

(b) 1.2E16
(c) 4.0E17

12 17
Binding energy (eV)

0
3 8 13 18
Binding energy (eV)

Figure 6.10. XPS valence band spectra of Zn 3d for samples grown with (a) -
0.9V, (b) -0.1V and (c) -0.4V. The corresponding hole concentrations in cm-3
has been indication in the legend. A larger core level shift is observed for a
higher hole concentration.

101
It is well-known that the hole concentration is related to the position of the Fermi level
(EF) in ZnO, which in turn affects the binding energy of core levels. When ZnO is doped
with p-type dopants, EF will shift away from the conduction band towards the valence
band, giving rise to a higher binding energy of Zn core levels. Thus, by examining the
core level shifts in binding energy, the shift in EF and the relative hole concentration
values can be deduced. Fig 6.10 shows the shift in the Zn 3d core levels in the XPS
spectra. A close-up of the Zn 3d, normalized for ease of comparison, is shown in the
inset of the figure. The shift to higher binding energy is largest for 4 x 1017 cm-3 which is
grown at a bias of -0.4 V, followed by 1.2 x 1016 cm-3 grown at -0.1 V and finally 3.2 x
1014 cm-3 grown at a bias of -0.9 V.

To make an accurate measurement of the core level shift, the Zn 2p3/2 peak was chosen
for comparison because it is relatively intense with minimal overlap with other peaks.
To account for charging, the peak position internally calibrated against the O 1s and C
1s peaks. The binding energy of the Zn 2p3/2 is plotted against its corresponding hole
concentration in Fig 6.11. As expected, the Zn 2p3/2 peak position will shift to a higher
binding energy when its hole concentration increases, confirming the role of K in p-
doping of ZnO.

1022.5
As-measured
Binding Energy of Zn 2p3/2 (eV)

C 1s1
O 1s1
Linefit
Power (Linefit)

1021.5
-3
1.E+14 Hole concentration (cm ) 1.E+18

Figure 6.11. Plot of core energy level Zn 2p3/2 against the hole
concentration as measured using Hall effect. The as-measured as well as
the C 1s and O 1s calibrated peak values are shown. A line is fitted to show
the increasing binding energy with hole concentration.

102
6.6 Effect of annealing in nitrogen ambient on p-type
doping by K
The effect of post-annealing treatments were studied using samples grown without
KAc, and with 0.07 and 0.24 M KAc. Annealing temperatures were varied from 200°C to
800°C in a nitrogen ambient. The rise time from room temperature to the desired
annealing temperature is 30 s. The anneal temperatures were held for 10 mins before
allowing the sample to cool down to room temperature again. The flow of nitrogen gas
was maintained until the sample has cooled down.

Figure 6.12. Effect of anneal temperatures on the carrier concentration and

mobility for ZnO films grown (a) without any KAc, and with (b) 0.07 and (c)
0.24 M KAc. (d) The effect of anneal duration at 800°C for sample grown in
0.24 M KAc. Annealing for all samples were done in a nitrogen ambient.
Data points for as-grown samples were represented at 100 °C. The electron
concentrations and mobilities are marked by ● and ● respectively, while
the hole concentration and mobility by ○ and ○ respectively.

103
Fig 6.12 (a) shows the results for the sample that has been grown without the presence
of KAc. The as-grown ZnO film is n-type with an intrinsic carrier concentration of about
1.4 x 1016 cm-3. The following observations can be seen:

• The film is intrinsically n-type without any extrinsic dopants, possibly due to the
presence of native defects in the structure.
• At 400°C, electron concentration increases to above 1018 cm-3. This sharp rise is
attributed to activation of hydrogen donors. Hydrogen is usually present in
samples grown in aqueous solution due to incomplete dehydration during the
formation of ZnO.
• Above 400°C, electron concentration decreases gradually to about 3 x 1018 cm-3
at 700°C. The gradual decrease can be attributed to desorption of hydrogen
from ZnO.

Fig 6.12 (b) shows the temperature dependence of the doping levels in a sample that is
grown with 0.07 M KAc in the growth solution. The as-grown film is p-type with a
carrier concentration of 3.8 x 1016 cm-3. Below 300°C, the p-type doping is stable with a
concentration range of 1017 to 1018 cm-3. When annealed at 400 °C and above, p-type
switches to n-type. The electron concentration appears to decrease gradually with
higher annealing temperatures, similar to that of undoped ZnO.

Fig 6.12 (c) shows the temperature dependence of a film grown in the presence of 0.24
M KAc. The hole concentration increases from 3.7 × 1014 to 5 × 1018 cm-3 when the as-
grown sample is annealed at 300°C. However, at 400 °C and above, a switch from p-
type to n-type is observed with a gradual decrease of electron concentration with
temperature, similar to the earlier two samples.

The switch from p to n-type at 400°C with an electron concentration of about 1 x 1019
cm-3, followed by a gradual decrease in electron concentration with annealing
temperatures is observed for all samples, regardless of the presence of K. We believe
that this phenomena is caused by hydrogen defects. Hydrogen defects have been
shown to be present in hydrothermal and aqueous solution-based growth methods and
are known to be donors in ZnO when activated. Our results show that these hydrogen
104
defects are activated at 400°C at higher concentrations than the extrinsic p-type doping
by K. This leads to the switch from p to n-type. However, the hydrogen defects are
unstable at high temperatures and can be driven out at high annealing temperatures
above 400°C. This manifests itself as a decreasing electron concentration at higher
annealing temperatures.

Due to the unstable nature of hydrogen defects, it is possible to drive out these
hydrogen defects to a concentration that is below the initial p-type doping and revert
back to p-type conductivity. Fig 6.12 (d) shows the changes in the doping
concentrations for the sample grown in 0.24 M KAc when it is annealed for different
durations at 800 °C. As observed earlier, a 10 min anneal will activate the hydrogen
defects which will lead to the over-compensation of the p-type film and the conversion
to n-type film. This conversion is reversed and the p-type conductivity is recovered
when the sample is annealed at 800°C for another 20 mins or more.

6.7 Fabrication of p-ZnO / n-GaN LED

To confirm the p-type conductivity, a ZnO film is grown using 0.07 M KAc on a n-GaN
epilayer that was grown on sapphire substrate. The n-GaN epilayer was grown by
MOCVD on a sapphire substrate. A window was opened for the growth of ZnO. Then,
Ni (20 nm) / Au (100 nm) and Ti (15 nm) / Al (220 nm) / Ni (40 nm) / Au (50 nm) were
deposited as p and n-contacts respectively. A schematic of the device is shown in the
inset of Fig 6.13 (a). Finally, a thermal anneal at 700 °C in vacuum for 1 h was
performed to form ohmic contacts, reduce the concentration of hydrogen defects and
activate the K dopants in the ZnO layer. Both Ni/Au and Ti/Al/Ni/Au shows ohmic
characteristic on p-ZnO:K and n-GaN respectively, as shown in the inset of Fig 6.13 (b).

The logarithmic and linear I-V plots of four different diodes are shown in Fig 6.13 (a)
and (b) respectively. At 3 V reverse bias, the leakage current ranges from 1.3 to 1.5 mA.
At a forward bias of 6 V, the current ranges from 75.9 to 98.3 mA.

The electroluminescence spectra consisting of a UV and broad yellow-orange emission

is shown in Fig 6.14. The UV emission at 20mA consists of a peak centered at 372 nm
with a shoulder at 378 nm and can be attributed to bound exciton emissions. At 70 mA,
105
these peaks shift to 375 and 386 nm, respectively, possibly due to a higher junction
temperature. A broad yellow-orange luminescence is also observed and is believed to
originate from the deep level defects that were introduced during the seed layer
growth.

Both the I-V characteristic and electroluminescence provides further evidence of p-

doping of the ZnO film.

6.8 Conclusion
We have demonstrated an alternative growth strategy which begins with a seed layer
growth at pH 10-11, followed by successive film layer growth at pH 7.5. This growth
method produces films with a lower defect density as seen from the PL spectra.

We have also doped the ZnO film with K and showed that the incorporation of K in ZnO
leads to p-type conductivity. An optimum doping concentration of 3.8 x 1017 cm-3 is
obtained at 0.07 M KAc without the presence of an electric field. When an electric field
is applied, the optimum bias is found to be -0.4 V which gives a doping concentration of
3.98 x 1017 cm-3. To the best of our knowledge, this is the first report of a p-type doping
with potassium from group I using aqueous solution methods at low temperature.

We have shown that the activation of intrinsic hydrogen defects through thermal
annealing at temperatures higher than 400°C can over-compensate the p-type doping
and convert the film to n-type with an electron concentration of 1 x 1019 cm-3. By
extending the annealing time beyond 30 min to reduce the hydrogen defect and
electron concentrations, the p-type conductivity can be recovered.

Finally, we fabricated a p-ZnO / n-GaN junction. The measured I-V characteristic is

rectifying and a weak orange electroluminescence is obtained.

106
Figure 6.13. I-V characteristic plotted in (a) logarithmic and (b) linear scale.
Each line shows the I-V from measured from a different device. Inset of (a)
shows a schematic diagram of the device while the inset of (b) confirm the
ohmic behavior of the top and bottom contacts after annealing at 700°C 1 h.

Figure 6.14. The electroluminescence spectra at various current injection

levels from 20 mA to 70 mA.

107
7 Conclusions and Recommendations

7.1 Conclusions
In this dissertation, ZnO nanorods and films were grown in aqueous solution. Besides
water, there were two other basic growth precursors: ZnAc2 and NH4OH. For p-type
doping, KAc was used as a dopant source.

ZnO nanorods were grown spontaneously on a GaN epilayer, which has a lattice
mismatch of 1.8% with ZnO. We showed that a good prediction of the density and
length of the vertically aligned nanorods can be obtained by using the zinc solubility
and growth temperature as predictors.

Using experimental results and the data from the ionic equilibrium of the solution, it
was shown that the density of nanorods can be increased by reducing the solubility of
zinc and increasing the growth temperature, while the length can be increased by
increasing the solubility and reducing the growth temperature. The activation energy
for density and length is found to be -2.11 eV and 0.77 eV respectively. Due to
opposing dependence of density and length of nanorods on the zinc solubility and
temperature, it is not possible to simultaneously maximize density and length of
nanorods in a single growth step.

Based on these experimental results, we produced an empirical growth map based on

the initial concentrations of ZnAc2 and NH4OH to predict the density and length of ZnO
nanorods that were grown on the Ga-face of an unintentionally doped GaN substrate
for a growth temperature ranging from 333 to 423 K. Although this model was based
on GaN as a substrate, it can be easily extended to any other substrates that have a
good lattice match with ZnO.

108
Next, we studied the growth of ZnO nanorods on substrates pre-coated with ZnO
nanoparticles. Pre-coating is done for substrates with poor lattice matching or where
the structure is not wurtzite. We found that good growth coverage of ZnO nanorods on
the substrate occurs when two conditions are fulfilled: firstly, the pH of the growth
solution is sufficiently far away from point of zero charge (PZC) and secondly, the
interfacial energy is at the minimum. We also showed that in this growth regime when
the two conditions are met, the solubility of zinc (SZn) and surface charges are
important factors that determine the growth morphology of the rods. When SZn < 0.88
mmol/l, a uniform coverage of nanorods is obtained and when SZn > 1.56 mmol/l, large
clustered rods are obtained. Finally, when 0.88 < SZn < 1.56 mmol/l, a transition region
where both nanorods and large clustered rods exist.

For both types of substrate, with and without good lattice matching, the zinc solubility
and growth temperature emerged as better predictors of density and length of ZnO
nanorods compare to other commonly used parameters such as pH and degree of
supersaturation.

The defects in ZnO has been studied using PL and Raman. Our results show that the
visible light emissions from defects can be minimized while the UV emission from band
edge transitions can be enhanced simply by growing ZnO in the regime where 7 < pH
<7.5. This improvement is brought about by the slow growth rate which leads to a
much lower concentration of defects in the structure.

The different types of native defects in the bulk were identified and associated with the
different growth conditions. By growing in the region where pH is less than PZC,
hydrogen defects are the major defects. In this growth regime, the visible defect
emissions are minimized while the UV band edge emissions are enhanced. The high UV
emission intensity is attributed to the shallow H defect states. When the sample is
grown in a solution where the pH is greater than PZC, the major defects are interstitial
oxygen, interstitial zinc and zinc vacancies. In this growth regime, the bulk is rich with
defects and the intensity of the visible defect emissions is stronger than the UV
emission. The green component of the visible emission is attributed to interstitial zinc
and zinc vacancies while the red component is attributed to interstitial oxygen.
109
Presence of these defects result in a poorer crystal quality and a structure that is in
compressive stress.

Based on this understanding of the growth and defect distribution for nanorods, we
proposed an alternative strategy for growing ZnO film in aqueous solution. This
strategy can be applied to a wide range of substrates, regardless of its lattice matching
with ZnO. For substrates with poor lattice matching, only an additional step of pre-
coating the substrate with ZnO nanoparticles will be needed. Our film growth approach
begins with a short seed layer growth at pH 10-11, followed by successive film layer
growth at pH 7.5. This growth method shows lower defect density as demonstrated by
the PL spectra.

We have also succeeded in doping the ZnO film with potassium. Hall effect, SIMS and
XPS measurements showed that the incorporation of K in ZnO leads to p-type
conductivity. An optimum doping concentration of 3.8 x 1017 cm-3 is obtained at 0.07 M
KAc without the presence of an electric field. When an electric field is applied in a
similar setup to a standard three-electrode electrodeposition setup, the optimum bias
is found to be -0.4 V which gives a doping concentration of 3.98 x 1017 cm-3.

When the films are subjected to thermal annealing in a nitrogen ambient, we have
observed a sharp increase in electron concentration to 1 x 1019 cm-3 regardless of
whether the film is doped with K. We attributed this increase to the activation of
intrinsic hydrogen defects which can over-compensate the p-type doping and convert
the film to n-type. By extending the annealing time beyond 30 min at 800°C to drive
out the hydrogen defects, the electron concentration can be reduced and the p-type
conductivity can be recovered. The ability to drive out hydrogen defects by annealing
underlines the importance of the low growth temperatures employed in aqueous
solution growth. Low growth temperatures below 100°C not only prevents the
activation of hydrogen defects in as-grown samples, but it also reduces the stability of
incorporated hydrogen defects and thus makes it easier to remove these defects
through annealing at temperatures above 400°C.

110
Finally, we fabricated a p-ZnO / n-GaN junction. Ni/Au is used for the p-ZnO contact
and Ti/Al/Ni/Au is used for the n-GaN. The measured I-V characteristic is rectifying and
a weak orange electroluminescence is observed at a forward bias current of 75.9 to
98.3 mA. The reverse bias leakage current ranges from 1.3 to 1.5 mA at 3V.

Our results demonstrate the ability and promise of aqueous solution growth methods
to grow and dope ZnO nanorods and films. In order to establish aqueous solution
growth methods as a viable alternative to favorites MOCVD and PLD, much more needs
to be done. Some of the work that lies ahead will be outlined briefly in the next section
where we will provide some recommendations for future work.

7.2 Recommendations
The current growth method can be improved by addressing several drawbacks of the
current growth method which is based on a closed bath. Firstly, the growth rate in a
closed bath is non-linear with the fastest growth rates is achieved between 55 and
65 °C and much slower growth rates for both higher and lower temperatures. Growth
eventually stops when the growth solution reaches its equilibrium at 90°C. Secondly,
the amount of growth that can be achieved is limited by its initial conditions such as
the precursor concentrations and temperature. Continuation of the growth process can
be achieved by refreshing the growth solution as shown in our multi-step film growth
strategy. At each step of changing the growth solution, defects are usually introduced
at the sample surface: for example adsorption of large ZnO powder on the sample
surface. To overcome these drawbacks, a continuous flow bath can be used. It
linearizes the growth rate by constantly introducing "fresh" growth solution and allows
continuous growth to occur with the need of removing the sample to a fresh solution.
This concept is similar to that discussed by Richardson et al for growth of epitaxial ZnO
in aqueous solution [112, 113].

Another area that can be explored is the extrinsic n-doping of ZnO. Although the ZnO
film is intrinsically n-type due to intrinsic defects and hydrogen-related defects, we
have seen that the electron concentrations can change significantly with annealing
temperatures. Heat treatment of ZnO films are usually required to obtain ohmic

111
contacts and this can lead to uncertainties in the final electron concentration. By
obtaining extrinsic doping to a level higher than the intrinsic doping, the temperature
dependence of n-type ZnO can be reduced.

Finally, the performance of metal contacts on both p and n-type ZnO films should be
systematically studied. The ability to obtain high quality ohmic contacts to ZnO films is
an important component for successful device fabrication. Currently, Ni/Au and
Ti/Al/Ni/Au have been successfully used to obtain ohmic contacts on p and n-type ZnO
respectively. The thickness and anneal temperatures have been borrowed from similar
metallization schemes for GaN. It is believed that the performance of the contacts can
be improved by optimizing the thickness and annealing temperatures.

112
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