PROJECT REPORT

Raman study of Zinc oxide thin film on Silicon

substrate by Pulsed laser deposition.

Project superviser : Prof.Shikha Verma, IOP,Bhubaneswar

BY ABHISIKTA MISHRA
DEPARTMENT OF PHYSICS, COLLEGE OF ENGINEERING & TECHNOLOGY ,BHUBANESWAR

ABSTRACT
This work reports on the results of the spectroscopic study of 300nm Zinc Oxide (ZnO) thin film

deposited on Si substrate at initial temperature 500C using pulsed laser ablation deposition of ZnO

ceramic targets in pure Oxygen environment of 5 mTorr partial vapour pressure. The surface

morphology of the ZnO thin film on the Si substrate has then been studied using Raman

spectroscopy which employed an Argon ion laser source of wavelength 514.5 nm using T64000

Holo-probe Raman Spectrometer.

 CONTENTS

i) ACKNOWLEDGEMENT 3

ii) INTRODUCTION 4-7

iii) EXPERIMENTAL TECHNIQUES 8-19

iv) EXPERIMENTAL DATA 20-22

v) DISCUSSION 22-23

vi) CONCLUSION 23

vii) REFERENCES 24-25

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ACKNOWLEDGEMENT

I would like to thank my project supervisor Professor Shikha Verma for introducing me
to the topic ,inspiring me to pursue this experiment and guiding me throughout.

I extend my heartfelt gratitude to Dr. Shalik ram Joshi for helping me understand the
topic, carrying out the Raman measurements and being a source of constant support
and inspiration at every stage of the project.

Many thanks also to Sangram K.Das for assisting me during our experiment educating
us about specifications of the pulsed laser deposition technique and Santosh Kumar
Choudhury for introducing me to the technicalities of Vacuum and gauges.

IOP,Bhubaneswar for providing the instruments, labs, library & computer facilities, a
wonderful scientific environment and an opportunity to experience research.

Last but not the least I would like to thank my family for their cooperation and
encouragement to carry out this project.

Abhisikta Mishra

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INTRODUCTION:
What is a THIN FILM?

The term thin film has often been loosely used in literatures to imply not only a layer of a solid
material but also of a liquid or a gaseous phase. However, there is neither any well-defined limit
of its thickness to imply the end of the thin film stage nor can one indicate its transition to the
thicker film region. So a thin film may arbitrarily be defined as a solid layer having a thickness
varying from a few A0 to about 10m or so. Since the thickness limitation is rather arbitrary,
even somewhat thicker films may also come within the scope of this definition.

Why Zinc Oxide ?

Transparent conducting oxide (TCO) thin films have attracted significant research attention in
the recent years due to their wide use in optoelectronic devices such as touch screens, liquid
crystal displays, solar cells and light emitting diodes. TCOs should exhibit both high electrical
conductivity and high optical transparency in the visible region. Indium tin oxide (ITO) is the
most commonly used TCO due to its high transparency to visible light and high electrical
conductivity. However, there has been a major concern to find suitable alternatives for ITO due
to the high cost, scarcity and toxicity of indium, which is its principal constituent element.
Furthermore, the optical and electrical properties of ITO are degraded when exposed to a
hydrogen plasma environment.

In this regard, transparent conducting Zinc Oxide (ZnO) is an extremely attractive replacement
material for ITO due to its good optical and electrical properties coupled with the low cost, non-
toxicity and abundance in nature of Zn. ZnO is an n-type semiconductor material with a direct
wide band gap energy (3.37 eV) and large exciton binding energy (60 meV) at room
temperature. Its other favourable properties include high electrochemical stability, high thermal
stability and good stability in hydrogen plasma, compared to ITO. Previous studies have also
reported on the good electrical stability of ZnO thin films and their use as an air stable anode for
organic light emitting diodes (OLEDs).

Zinc Oxide (ZnO) is a wide-bandgap semiconductor with an optical band gap of 3.36 eV at
room temperature. Wide-bandgap semiconductors are semiconductor materials which have a
relatively large band gap compared to typical semiconductors. Typical semiconductors like
Silicon have a bandgap on the order of 1 to 1.5 electronvolt (eV), whereas wide-bandgap
materials have bandgaps of the order of 2 to 4 eV. Generally, wide-bandgap semiconductors
have electronic properties which fall in between those of typical semiconductors and insulators.

Compared to circuits built with usual semiconductors, wide-bandgap semiconductors permit

devices to operate at much higher voltages, frequencies and temperatures than conventional
semiconductor materials like silicon and gallium arsenide. They are the key component used to
make green and blue LEDs and lasers, and are also used in certain radio
frequency applications, notably military radars. Their inherent qualities make them suitable for a

4
wide range of roles, and they are one of the leading contenders for next-generation devices for
general semiconductor use.

Deposition & Characterization Technology:

Thin Film Deposition is the technology of applying a very thin film of material between a few
nanometers to about 100 micrometers, or the thickness of a few atoms onto a substrate
surface to be coated, or onto a previously deposited coating to form layers.

ZnO thin films can be prepared by techniques such as thermal oxidation, chemical vapor
deposition , molecular beam epitaxy and pulsed laser deposition ,we preferred the Pulsed
laser deposition technique as it had the advantage that we could obtain high quality thin films
which did not require post-deposition annealing and investigated the optical properties using
Raman Spectroscopy .Even though there are several spectroscopy techniques such as the
XRD (X-Ray diffraction) which gives very fundamental information about crystal orientation,
structural quality, grain size and lattice parameters with Raman spectroscopy we not only get
information on crystal structure, carrier concentration and structural quality of the thin film it is
also sensitive to distortions in the crystal lattice, crystal defects, and phase transformation.

CHARACTERISTICS OF MATERIAL:

STRUCTURE:
Zinc Oxide is found in two structures Hexagonal Wurzite and cubic Zinc blende
structures among which the Wurzite structure is more stable and most commonly
accepted while The Zinc blende structure can be stabilized by growing Zinc oxide on
substrates with cubic lattice structures. In both cases the Zinc and Oxygen centres are
tetrahedral, the most common characteristic property of Zn(II). This tetrahedral
coordination gives rise to polar symmetry along the hexagonal axis which is responsible
for a number of the properties of ZnO, including its piezoelectricity and spontaneous
polarization, and is also a key factor in crystal growth, etching and defect generation.

The hexagonal and zinc blende polymorphs have no inversion symmetry. This and other
lattice symmetry properties show piezoelectricity and pyrolectricity. The hexagonal
structure has a point group 6 mm (Hermann-Mauguin notation) or C6V (Schoenflies
notation) and the space group is C6v4.

5
 FIG:-The hexagonal wurtzite structure of ZnO. O atoms are shown as large white
spheres, Zn atoms as smaller black spheres. One unit cell is outlined for clarity

Apart from causing the inherent polarity in the ZnO crystal, the tetrahedral coordination of this
compound is also a common indicator of sp 3 covalent bonding. However, the ZnO bond also
possesses very strong ionic character, and thus ZnO lies on the borderline between being
classed as a covalent and ionic compound, with an ionicity of f i =0.616 on the Phillips ionicity
scale. The lattice parameters of the hexagonal unit cell are a=3.2495 and c=5.2069, and the
density is 5.605gcm 3.

In Addition to the wurtzite phase, ZnO is also known to crystallize in the cubic zinc blende and
rocksalt (NaCl) structures, which are illustrated in figure :

FIG.:-The rock salt (left) and zincblende (right) phases of ZnO. O atoms are shown as
white spheres, Zn atoms as black spheres. Only one unit cell is illustrated for clarity.

ELECTRICAL PROPERTIES:
ZnO has a relatively large direct band gap of ~3.3 eV at room temperature. Advantages
associated with a large band gap include higher breakdown voltages, ability to sustain

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 large electric fields, lower electronic noise, and high-temperature and high-power
operation.

As in most group II-VI materials, the bonding in ZnO is largely ionic (Zn2+O2) with the
corresponding radii of 0.074 nm for Zn2+ and 0.140 nm for O2. This property accounts
for the preferential formation of wurtzite rather than zinc blende structure, as well as the
strong piezoelectricity of ZnO

Most ZnO has n-type character, even in the absence of

intentional doping. Nonstoichiometry is typically the origin of n-type character, but the
subject remains controversial. An alternative explanation has been proposed, based on
theoretical calculations, that unintentional substitutional hydrogen impurities are
responsible. Controllable n-type doping is easily achieved by substituting Zn with group-
III elements such as Al, Ga, In or by substituting oxygen with group-VII
elements chlorine or iodine

Reliable p-type doping of ZnO remains difficult. This problem originates from low
solubility of p-type dopants and their compensation by abundant n-type impurities.

Current limitations to p-doping limit electronic and optoelectronic applications of ZnO,

which usually require junctions of n-type and p-type material. Known p-type dopants
include group-I elements Li, Na, K; group-V elements N, P and As; as well as copper
and silver. However, many of these form deep acceptors and do not produce significant
p-type conduction at room temperature

MECHANICAL PROPERTIES:

ZnO is a relatively soft material with approximate hardness of 4.5 on the Mohs scale. Its
elastic constants are smaller than those of relevant III-V semiconductors, such as GaN.
The high heat capacity and heat conductivity, low thermal expansion and high melting
temperature of ZnO are beneficial for ceramics. ZnO exhibits a very long lived optical
phonon E2(low) with a lifetime as high as 133 ps at 10 K.

Among the tetrahedrally bonded semiconductors, it has been stated that ZnO has the
highest piezoelectric tensor, or at least one comparable to that of GaN and AlN. This
property makes it a technologically important material for
many piezoelectrical applications, which require a large electromechanical coupling.

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EXPERIMENTAL TECHNIQUES :
The experiment involved two major experimental techniques, The Pulsed Laser Ablation for thin
film deposition and Raman Spectroscopy for characterization of the deposited thin film.

I) LASER ABLATION- a brief outline

A laser plasma is created when a short laser pulse incident on a surface causes material to
evaporate and so, form a plasma (a charged gas). The incident laser pulse causes local thermal
heating at the target surface. This causes the irradiated area to melt and subsequently atoms,
electrons and ions evaporate making the plasma.

The conditions for deposition of contents of the plasma plume on a substrate are:

i) the plasma density must not become too high as then it will screen the laser from
reaching the target surface.

ii) the laser power must be below a certain critical value which causes laser breakdown
of the plasma (i.e. laser breakdown occurs when electrons in the plasma start absorbing the
laser energy). The critical value is <107 Wcm2.[23] If a background gas is introduced into the
plasma, or growth, chamber, the plume expansion will be slowed down and a shock front
develops as can be seen in Figure below :

:
FIG:-The top row of pictures shows the plasma plume expanding into vacuum with
time. The bottom row shows the plasma plume expanding into a background gas[22]

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Under these circumstances, the target-substrate distance would have to be carefully
reconsidered as the shock front may prevent the right stoichiometry of material from reaching
the substrate, or, may mean a decrease in the growth rate of the film as less material would be
reaching the substrate per unit time.

I) PLD EXPERIMENTAL SETUP:

FIG.:- Diagram of the PLD system.

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 1) Krypton Fluoride Excimer laser :The term excimer laser has been coined from the
words excited dimers. An excimer laser typically uses a combination of a noble
gas (argon, krypton, or xenon) and a reactive halogen gas (fluorine or chlorine). Under
the appropriate conditions of electrical stimulation and high pressure, a pseudo-
molecule called an excimer (or in the case of noble gas halides, exciplex) is created,
which can only exist in an energized state and can give rise to laser light in
the ultraviolet range. The excited compound can give up its excess energy by
undergoing spontaneous or stimulated emission, resulting in a strongly repulsive
ground state molecule which very quickly (on the order of a picosecond) dissociates
back into two unbound atoms. This forms a population inversion.This laser was used in
pulsed laser ablation technique due to production of laser light in the wavelength range
of UV light which gives rise to a high energy laser pulse which is necessary for ablation
of the target material.

2) High Vacuum pumps and gauges: Vacuum or low pressure environment was required
to provide a long mean free path for collision between vaporization source and
substrate. It also allowed control of the amount of gaseous and vapor contamination
during the thin film deposition. The vacuum environment was generated by a vacuum
system that consisted of

A deposition chamber
Introduction chamber or load-lock chamber
Vacuum pumping system
Exhaust system
Gas inlet system PHOTOGRAPH:
Associated plumbing THE PULSED LASER DEPOSITION CHAMBER

The standard temperature and

pressure conditions are 00C and 760
Torr, a mole of gas contains 22.4
liters of volume and 2.69 x1019
molecules in a volume of 1cm3.A
rough pump (10-3 Torr) is about 10-6
times the atmospheric pressure and
contains about 1013 molecules/cm3.A
high vacuum has a pressure 10-6
which is about 10-9 of the atmospheric
pressure or about 1010
molecules/cm3.An ultra high vacuum
is obtained at about 10-12 Torr and
contains about 104 molecules/cm3..

The deposition chamber was first

rough pumped by a rotary vane pump

10
 that brought the chamber pressure from an initial pressure of 760 Torr down to 10-3 Torr
or 1 mTorr, this measurement was done using a Pirani gauge which is a thermocouple
gauge that measures pressure using change in thermal conductivity of gas.

The chamber was then brought to high vaccum using the turbo molecular pump which
evacuated the chamber to a pressure of 10-7 Torr this measurement could be done using
a cold cathode gauge in which electrons were emitted and accelerated by an applied
high voltage by the existing crossed electric and magnetic fields, the electrons were
forced onto spiral paths which increased the probability that the accelerated electron
strikes a neutral gas particles and ionizes it due to the energy gained in the electric field .

PHOTOGRAPH : OBSERVATION OF THE PLASMA PLUME OF ZnO DURING PLD.

Why Pulsed Laser Deposition ?

Advantages:
(i) The Laser used in PLD has advantages over other methods of growth in that it is easier to
manipulate than a molecular beam. Also, as the laser is the ablation tool, ablation is, to a large
extent, independent of pressure as the laser-material interaction isnt greatly affected by the
chamber pressure. Therefore ablation can occur at any deposition pressure giving PLD a
greater pressure range than nearly any other deposition technique. The pressure in the
chamber only affects the deposition on the substrate.

11
(ii) Almost all materials absorb the energy from laser light of less than 250nm so this makes any
material a possible target for PLD provided a short wavelength laser is used. Therefore PLD can
evaporate refractory materials. Other methods depend a lot more on the properties of the
material.

(iii) Under the right conditions in PLD the stoichiometric composition of the target can be
maintained but the right conditions are complicated to predict and so, are mainly found
experimentally. Sputter deposition techniques, can also maintain stoichiometric composition to
high accuracy but there the plasma created by sputtering can also erode other materials apart
from the target, adding impurities into the film being deposited.

(iv) Good Quality PLD films can be deposited at lower temperatures than in other popular thin
film and bulk growth methods. This is because the energy the surface atoms use to re-organize
themselves and find their sites comes from the plasma itself as opposed to thermal energy from
the substrate heater. The plasma enhances surface atom mobility by bombardment. However, if
the energy of the incident atoms from the plume exceeds a certain limit then damage could be
done to the layers that have already been deposited.

v) PLD is a relatively quick process i.e. it has a high deposition rate and a film of a few hundred
nanometers in thickness can be grown in 15-20 minutes.

vi) PLD is a much safer method than CVD or MOCVD as no volatile gases or materials are
needed to create a chemical reaction.

Disadvantages:
(i) Particulate deposition is still a major problem area in PLD. Particulates are little molten
lumps of the target that splash onto the substrate and solidify and cause disruption to the crystal
lattice being formed. They occur when the laser energy is being transferred into heat energy
quicker than it takes a layer of material of a thickness of half the skin depth to evaporate.
Careful control and tailoring of growth parameters are needed. In this case the laser
characteristics and target material are the most important to consider. Of course, for good
quality growth of all types of crystal, all parameter change implications must be explored.

(ii) Another major disadvantage of PLD is that it is difficult to use for large area growth as the
plasma plume only has a narrow angular distribution. This leads to non-uniform deposition over
large areas. However this method is appropriate for small areas.

I) RAMAN SPECTROSCOPY---a brief outline

When monochromatic light is scattered from a surface 99.99% of it will be elastically scattered -
i.e. it will have the same wavelength upon scattering. This is known as Rayleigh Scattering. It is
considered elastic scattering because there is no net energy transfer between the incident

12
photons and the lattice vibrations. However, the rest of the light has an increased or decreased
wavelength upon scattering due to interactions with crystal excitations such as phonons. This
small amount occurs from Raman and Brillouin scattering. Brillouin scattering occurs when the
phonon that the incident light interacts with is acoustic. The process is called Raman scattering
when the phonon emitted or absorbed is optical (For the purposes of this section Brillouin
scattering is ignored). Raman Scattering can be considered inelastic scattering as the reflected
light has either gained or lost energy to phonons in the crystal lattice under observation.

A Raman spectrum consists of a series of lines whose position corresponds to a frequency

difference between the incident and scattered light (i.e. to a phonon mode of the crystal) versus
the intensity of light scattered at that frequency.

An example of a complete Raman spectra: FIG.:-Basic diagram to show Stokes and anti-Stokes
scatter.

A feature in a Raman spectrum is considered Stokes shifted when the incident light loses
energy so that a longer wavelength is scattered. When energy is gained by the photons the
spectrum is called anti-Stokes shifted.

General Raman Theory:

An outline of the Classical Raman effect and Quantum Raman effect follows.

i) Classical Treatment:

The condition for vibrational Raman Spectroscopy is that the amplitude of the dipole moment
induced by the E-field o f the incident radiation must change during the vibration. i.e. the

13
polarisability of the molecule should change as it vibrates. The relationship between the induced
dipole moment and the polarisability is:

where is the electric field component of the incident radiation. So as the E-field interacts with the
molecule, a dipole moment is induced and light is scattered at the same frequency as the
incident light i.e. Rayleigh scattering

For the case of anisotropic molecules, polarisibility, , is a tensor since polarisation along
each axis of the lattice or molecule is different. A common way of expressing this is as the
polarisibility ellipsoid (in this case the polarisibility coefficients are inversely proportional to the
co-ordinate axes but there are other forms of this equation):

where x, y and z are the principal axes of the ellipsoid.

in order for the vibrational Raman condition to be satisfied the polarisibility must change with
vibration i.e. with the vibrational co-ordinate, r:

where the vibrational co-ordinate, r, is related to the lattice vibration frequency, vP by:

A more detailed derivation would lead to second and third order terms in equation which
correspond to the second and third order Raman Scattering, however the intensities of these
effects are usually small compared with the first order effects.

Raman effect can be shown to be:

where, on the right hand side of the equality sign, the first term is equivalent to Rayleigh
scattering and the second term takes into account the changing polarisibility to account for both
Stokes and anti-Stokes Raman scatter.

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(ii) Quantum Treatment of the Raman Effect:

The main assumption behind the Quantum treatment is that vibrations of a system of atoms in a
molecule are described as a harmonic oscillator. When radiation interacts with crystal vibrations,
a discrete amount of energy is lost or gained from the photon energy i.e. hv E. This discrete
packet of energy is called a phonon. It is considered that there are different vibrational energy
levels and the energy difference between a transition corresponds to the frequency shifts in the
Raman spectrum.

FIG.- Quantum treatment of Raman scattering.

Since most optical vibrational modes will be in their ground state at room temperature before
any interaction with photons, then Stokes scattering is more likely. From a quantum mechanical
treatment the Stokes spectra will be more intense than the anti-Stokes as the transition
probability is higher for ground to first state transitions than higher states to ground states
transitions. In the classical treatment there is no distinction between which, Stokes or anti-
Stokes, interaction is most probable to occur. The quantum treatment agrees with experimental
results, and the Stokes/ anti-Stokes ratio is actually used as a measure of crystal temperature.
This is because thermal energy causes more vibrations to be in higher states and so anti-
Stokes scattering becomes more intense, i.e., the smaller the Stokes/anti-Stokes ratio, the
higher the crystal temperature.

The Raman Spectrometer

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Raman spectrometers have changed dramatically due to the advent of lasers, semiconductor
detectors and precision optics over the decades. When designing a Raman spectrometer there
are two main considerations:

(i) Raman scatter intensity is less than 1% o f the Rayleigh scatter making it very weak and
hard to distinguish.

(ii) The Raman shift is quite small and Raman peaks remain close to the main Rayleigh scatter
line worsening the situation because the Raman signal lies on an intense background signal.

Taking these considerations into account means that all aspects of a Raman system must be of
high quality and precision. Powerful light sources, sensitive detectors and accurate optic
systems are necessary to enhance the clarity and resolution of a Raman spectrum.

FIG.- A SIMPLIFIED RAMAN SPECTROMETER

The Holo-probe Raman Spectrometer :

The Raman system that was used to obtain the spectra is now described. A diagram of the
system is shown below in figure:

16
 FIG.-Diagram of the basic set up of the Raman System.

PARTS OF THE SETUP IN SOME DETAIL :

() Laser and Optics: The Holoprobe Head and Microscope:

Figure below is a diagram of the probe head. The notch filters here are used to eliminate the
contribution from the silica ,Raman spectra generated when the light passes through the optical
fibres. They are also used to partly eliminate Rayleigh scatter on the return signal.

FIG.- The probe head.

The light travels from the laser to the probe head via optical fibre and the scattered light from
the sample is also transported to the spectrograph from the probe head using Optical fibre
connections. The laser beam is incident on the sample through the microscope lens objective.
The scattered light is also collected through the objective. There is a small video camera

17
installed in the microscope and this is used so that one can focus clearly using the picture from
the video on the computer to see what part of the samples to focus the excitation beam on.

ii) The Filters and Spectrograph:

Figure : This figure shows a schematic of the Spectrograph.

The most important feature in the spectrograph is the holographic transmission grating and
filter. These holographic optics are collectively know as Volume Phase Holograms (VPH). The
VPH transmission gratings are period refractive index gradients. These periodic arrays diffract
light in a volume or Bragg style as opposed to conventional ones, which diffract in the surface
regime. The diffraction efficiency is greater than 80% and the transmission efficiency of the
VPHs is greater than 90%.

The main advantage of the Holoprobe system is that the Holoplex gratings which allow a huge
spectral region to be examined at once unlike more conventional gratings and the spectral
resolution of the spectra obtained with a Raman microprobe is of the order of a couple of wave
numbers.

18
 Probe Head

Grating & Filters

CCD Peltier Detector

Microscope

Sample Holder

PHOTOGRAPH : THE T64000 Holoprobe Spectrometer used in the experiment with Argon ion
laser source.

19
EXPERIMENTAL DATA

PRECISE GROWTH CONDITIONS:

Firstly the deposition chamber was evacuated to a background pressure of using 6.47x10-7 Torr
using a turbo-molecular pump and rotary vane pump. Then Oxygen gas (99.99% purity) was
introduced into the chamber until oxygen partial pressure was 5x10-3 Torr.

The laser used for ablation was a KrF (krypton fluoride) excimer laser of wavelength (248 nm)
and pulse duration 26 ns.It was focused through a Silica lens (f=50 mm) to a spot size of 2mm2
surface area of the ZnO target.The laser energy per unit area on target was 0.4x10-16 J/cm2 and
repetition rate of laser is 5Hz for 20 minutes.

The substrate and target were at a distance of 5 cm apart. The target was a ZnO sintered
ceramic disc (99.9% purity) and the substrate was a Si wafer initially cleaned with 10 ml
isopropyl alcohol in a Sonicator and then dried with forced air. The substrate was then attached
to a substrate heater using vacuum compatible Ag epoxy glue and the target to the target holder
using the same. The target was rotated for uniform ablation. The substrate temperature was
maintained at 5000C and was then slowly cooled down to room temperature of about 200 C. The
high initial temperature of the substrate was necessary for facilitating uniform diffusion of film
and substrate resulting in deposition of 300 nm thin film.

RAMAN SPECTROSCOPY RESULTS:

EXPERIMENTAL CONDITIONS:

The Sample was placed on a slide under the microscope. The spectra were taken in air at room
temperature using Ar+ (Argon ion laser) of wavelength=514.5 nm (green light) in the
backscattering configuration. The choice of the laser source was such that it could provide
continuous light emission and also not damage the sample with high energy beam.

As the samples are 2 mm x 2mm in size, the video mode was used to choose which parts of the
sample to use for Raman spectroscopy by avoiding defects and damaged parts.

All Raman spectra were taken with the CCD camera at -690C (minimum temperature).1800 mm
grating was used .The minimum resolution was of wave number = 0.15 cm-1 and maximum was
for wave number =5 cm-1.The backscattering light was filtered of the initial wavelength using
notch filter.

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Zinc Oxide Raman Spectra :
Figure below shows the non-resonant Zinc Oxide Raman spectra of the sample :

As can be observed there are five major peaks visible in the graph, summarized in table below:

OBSERVED FREQUENCY PEAK (cm-1) OPTICAL MODE

434.9 E2HIGH optical phonon

303.5 A1(TO)

273.2 B1HIGH-B1LOW

197.6 2TA; 2E2LOW

100.8 E2LOW

21
The Raman Active zone centre phonon vibrations predicted are: one A1 mode, one E1 mode
and two E2 modes. (Group Theory also predicts two B1 modes but these are silent.) The infrared
active vibrations are the A1 and E1 modes. In wurzite ZnO long range electrostatic forces
dominate over the short range interatomic forces. This leads to a split into longitudinal and
transverse components of the phonon normal modes that are infrared active i.e. the Ai and Ei
modes will be split. There will be A1(TO), A1(LO), E1(TO) and E1(LO) vibrational modes in the
Raman spectrum of ZnO as well as the two E2 modes (TO = Transverse Optical and LO =
Longitudinal Optical).

DISCUSSION

Like most wurtzite crystal structure materials, ZnO belongs to the hexagonal system with space
group C 6v 4 (P6 3 mc) with two formula units per primitive cell, where all atoms occupy C 3v sites
(17). The zone-center optical phonons can be classified according to the following irreducible
representations: =A 1 +E 1 +2E 2 +2B 1 .

According to the group theory, the Raman active phonons are A 1 (z direction), E 1 (xy direction),
and two E 2 . The Raman non-active phonons are B 1 . Both A 1 and E 1 are polarized phonons
having each longitudinal optical (LO) and transverse optical (TO) components. E 2 is non
polarized phonon having two frequencies E 2(high) and E 2(low).

The splitting of the LO mode into A1 and E1 components is due to the fact that electrostatic
forces dominate over the anisotropy of the crystal i.e local polarization fields induced by point
defects. The Stokes shift to lower frequencies is attributed to the presence of impurity defects
(20). The thin film ZnO deposited in this study showed negligible external impurity contamination
in the films. Therefore, the only defects present are intrinsic defects inherent to ZnO thin films.
In our case, the most probable defect is oxygen vacancies.

The E 2 optical mode is used to characterize the built-in inherent stress in the ZnO thin films. We
did not detect any LO phonon. However the film tends to result in Raman peaks at 273 cm -1
we attribute these peaks to the activation of the B 1 modes. It has been observed that the silent
B 1 mode can be activated due to the electric field (22). E1 modes were also not observed.

Another prominent peak is observed at 197 cm 1, which exhibits A 1 symmetry and thus can be
attributed to a TA overtone. In Ref. (23) this mode was assigned to 2TAL , and in Ref. (24) to 2E
low
2 with possible contributions of 2TA .

Ref.(25)The line shape function of most peaks is observed to possess a Lorenztian character ;
c << a, the incoherence sets in rapidly, so dephasing is the dominant energy loss channel
where rotation and collisions happen quickly. The resulting line shape is Lorentzian (due to the
exponential vibrational population relaxation), which is sharp in the center, but has long wings

22
However, the peak at 197 cm-1 can be observed to assume a prominent Gaussian character
which can be attributed to c >> a, the excited molecule relaxes before incoherence becomes
severe. This is the case when the environment is not in motion. The various molecules
experience a statistical distribution of environments, and the line shape takes on the bell curve
or Gaussian profile. This profile has the well-known shape from statistics, with a curving (not
sharp) center and wings that fall away relatively quickly.

(Where c is the coherence lifetime and a is the amplitude correlation time .)

The phonon lifetime can be derived from the Raman spectra via the energy-time uncertainty

relation: where E is the uncertainty in the energy of the phonon mode,

is the Planck constant, and is the FWHM of the Raman peak in units of cm 1.ref.(26).

CONCLUSION

We deposited ZnO thin film using Pulsed laser ablation/deposition technique(PLD).The Raman
spectroscopy study revealed a blue shift in Raman peak which is indicative of built in
compressive stress.

Our measurements show appearance of E2HIGH optical phonon at 434.9 cm-1 for 300 nm thick
ZnO thin film layer. The peak at 303.5 is indicative of A1(TO) mode. There was no indication of
LO phonons. The peak observed at 273 cm-1 could be attributed to activation of B2 silent modes
due to electric field. The 100.8cm-1 probably indicate towards the E2LOW optical phonon while
peak at 197.6 cm -1 could be due to overtones TA mode. We also did not detect E1 modes
optical phonon for the sample.

Since the Si substrate peak is observed only at 521cm-1 we obtained the experimental graph
within 450cm-1 which helped us conclude the observed spectra belonged only to the ZnO Thin
film.

23
REFERENCES
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