Tuning electrical properties of transparent p-NiO/n-MgZnO heterojunctions

with band gap engineering of MgZnO

Xinman Chen, Kaibin Ruan, Guangheng Wu, and Dinghua Bao

Citation: Appl. Phys. Lett. 93, 112112 (2008); doi: 10.1063/1.2987514

View online: http://dx.doi.org/10.1063/1.2987514
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 APPLIED PHYSICS LETTERS 93, 112112 2008

Tuning electrical properties of transparent p-NiO/ n-MgZnO heterojunctions

with band gap engineering of MgZnO
Xinman Chen, Kaibin Ruan, Guangheng Wu, and Dinghua Baoa
State Key Laboratory of Optoelectronic Materials and Technologies, School of Physics and Engineering,
Sun Yat-Sen University, Guangzhou 510275, Peoples Republic of China
Received 26 June 2008; accepted 26 August 2008; published online 18 September 2008
Transparent p-n heterojunctions composed of p-type NiO and n-type MgZnO thin films were
fabricated on indium-tin-oxide-coated glass substrates by sol-gel spin coating technique. The p-n
junctions exhibit typical current-voltage behaviors with good rectifying characteristics, and their
electrical properties can be effectively tuned by band gap engineering of n-MgZnO. With increment
of Mg content in n-MgZnO layer, enlarging band gap can lead to the higher forward threshold
voltage, higher breakdown voltage, and lower reverse saturation current. The electrical behaviors of
the p-n junctions can be further improved by using compositionally graded n-MgZnO layer instead
of single n-MgZnO layer. These results suggest that the transparent all-oxide p-NiO/ n-MgZnO
heterojunctions can find applications in transparent electronic devices. 2008 American Institute of
Physics. DOI: 10.1063/1.2987514

Wide band gap semiconductor zinc oxide ZnO thin
films have attracted extensive attention recently for their
various optoelectronic device applications.1 The band gap of
ZnO can be extended by formation of the solid solution of
MgxZn1xO, i.e., so-called band gap engineering of ZnO.1,2
Through the band gap engineering technique, some MgZnO-
based semiconductor materials and devices with tunable
properties can be designed.3 Meanwhile, high optical trans-
parency can be maintained in MgZnO system, which is es-
sential for transparent electronic device applications.
It is well known that p-n junction is the key structure for
most semiconductor devices. So far, many efforts have been
made to prepare the p-type ZnO or MgZnO, but there is
difficulty in reproducing p-type MgZnO.4,5 Recently, p-n
heterojunction devices combining intrinsic n-type ZnO with
various p-type materials including ZnRh2O4, NiO, and
SrCu2O2 have been studied,1,6 among which NiO is prefer-
able for its simple structure and composition. Several re-
search groups reported on fabrication and photoresponse
of p-NiO/ n-ZnO heterojunctions for UV detector applica-
tions.79 However, few efforts have been made to investigate
transparent p-NiO/ n-MgZnO heterostructures. Since band
gaps of ZnO thin films can be adjusted by Mg incorporation,
it should be of much interest to check whether electrical
properties of p-NiO/ n-MgZnO junctions can be tuned by the
band gap engineering of MgZnO.
In addition, it is known that in graded band gap semi-
conductor, the carrier transport properties can be influenced
by quasielectric fields due to the spatial dependence of band
gap,10,11 which have led to some physical phenomena or im-
proved properties in graded band gap semiconductors.12
Since band gap of hexagonal MgZnO almost linearly in-
creases with increasing Mg content, an attempt of using
compositionally graded layer CGL of MgZnO also having
graded band gap to replace n-MgZnO layer was worth mak-
ing to improve electrical properties of the p-n junctions.
a
Author to whom correspondence should be addressed. Electronic mail:
stsbdh@mail.sysu.edu.cn.
In this study, transparent p-NiO/ n-MgZnO heterojunc-
tions with different Mg contents were fabricated on indium-
tin-oxide ITO-coated glass substrates. The p-n junctions
exhibit typical current-voltage I-V behaviors with good
rectifying characteristics. It has been confirmed that the elec-
trical properties of the p-n junctions can be effectively tuned
by band gap engineering of n-MgZnO and can be further
improved by using compositionally graded n-MgZnO layer
instead of single n-MgZnO layer in the p-n junctions.
In our p-n junction diodes with the configuration
of Pt/ p-NiO/ n-MgZnO/ ITO/ glass, both the p-NiO
and n-MgZnO layers were prepared by sol-gel tech-
nique. MgZnO solutions were synthesized by using
ZnCH3COO2 2H2O and MgCH3COO2 4H2O as
source materials and 2-methoxyethanol and diethanola-
mine as solvent and stabilizer, respectively. NiO solution
0.3 mol/L was synthesized using similar method with
NiCH3COO2 4H2O as nickel source. The film layers were
prepared by spin coating solution on ITO-coated glass sub-
strates at 2500 rpm for 20 s. Each layer was preheated at
350 C for 5 min to evaporate solvent and remove organic
residuals. The procedure above was repeated until the de-
sired film thickness was achieved. Then, the NiO/MgZnO
heterojunctions were annealed at 600 C for 1 h at ambient
air. The thicknesses of the resultant NiO and MgZnO layers
are about 100 and 300 nm, respectively. The preparation pro-
cess of the CGL of n-MgZnO is similar to that of composi-
tionally graded ferroelectric films reported before.13,14 In
brief, three MgZnO layers with different Mg contents were
prepared on ITO-coated glass substrates in sequence and
then a suitable annealing process was used to realize compo-
sition gradient along thickness direction.
The crystalline phases of the p-n junctions were charac-
terized in -2 mode by a Rigaku D-MAX 2200 VPC x-ray
diffractometer XRD with Cu K radiation = 0.154 nm.
The transmission spectra were measured in the range of
300800 nm at room temperature by Shimadzu UV-3150
UV-visible-near-infrared spectrophotometer. The surface
morphologies were observed by JSM-6330F scanning elec-
tron microscopy SEM. The current-voltage I-V curves

0003-6951/2008/9311/112112/3/$23.00 93, 112112-1 2008 American Institute of Physics

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 112112-2 Chen et al. Appl. Phys. Lett. 93, 112112 2008

FIG. 1. Color online XRD patterns of NiO/MgZnO p-n heterojunctions

with different Mg contents.

were measured by Keithley 236 sourcemeter with Pt dots as

top electrodes.
Figure 1 shows -2 XRD patterns of the p-n junctions
with different Mg contents in n-type MgZnO layers. The
diffraction peaks of 100, 002, and 101 are assigned to
the hexagonal structure of the MgZnO layers with no pref-
erential orientation. The peaks around 37.3 and 43.3 are
attributed to 111 and 200, respectively, of the crystalline
p-type NiO film layers. SEM morphology observation not
shown confirmed that the surface of the p-n junctions is
smooth and dense with uniformly distributed grains.
Figure 2 illustrates the optical transmission spectra of
p-NiO/ n-MgZnO junctions with different Mg contents on
ITO-coated glass substrates. All resulting p-n heterojunctions
show optical transmission of 50%80% in visible region.
The sharp absorption edges of the junctions are visible in
UV region, showing a distinct dependence on Mg content.
With increasing Mg content, the absorption edges of
p-NiO/ n-MgZnO junctions shift toward the short wave-
length, implying that band gaps can be tuned by changing
the Mg content of n-type MgZnO layer. Additionally, the
blueshift of the absorption edges also suggests the formation FIG. 3. Color online I-V curves of NiO/MgZnO junctions with a x = 0,
of MgZnO solid solution despite the different crystal struc- b 0.05, and c 0.1, respectively. The inset of c shows I-V curves of
Pt/NiO/ITO and Pt/MgZnO x = 0.1 / ITO structures.
tures of both oxides. This is consistent with the above XRD
results since no MgO phases can be observed. The inset of
Fig. 2 shows the plot of h2 versus h, wherein is the absorption coefficient, calculated by d = ln1 / T, d and T
are thickness and transmittance of films, respectively. The
optical band gaps of the p-n junctions with Mg contents of 0,
0.05, and 0.1 are obtained to be 3.26, 3.34, and 3.41 eV,
respectively.
The current-voltage I-V behaviors of p-NiO/ n-MgZnO
junctions with different Mg contents of 0, 0.05, and 0.1 are
shown in Fig. 3. The good electrical rectifying characteristics
are evident for the asymmetric I-V curves between reverse
and forward bias. For comparison, rather symmetrical I-V
dependence of Pt/NiO/ITO and Pt/MgZnO x = 0.1 / ITO
structures is shown in the inset of Fig. 3c, suggesting that
the asymmetric I-V curves of p-NiO/ n-MgZnO junctions are
due to formation of a p-n junction. The NiO/ZnO p-n junc-
tion has the forward threshold voltage Von and reverse
breakdown voltage VBR of 1.5 and 1.8 V, respectively.
With increasing Mg content, the threshold voltage and the
FIG. 2. Color online Transmission spectra of NiO/MgZnO p-n junction. breakdown voltage of the junctions increase. Table I lists the
The inset shows the curve of h2 vs h. threshold voltage and the breakdown voltage values for the

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 112112-3 Chen et al.
TABLE I. Threshold voltage and breakdown voltage values for the p-n
junctions with different Mg contents.
Eg Von
Mg content eV V V
0 3.26 1.5
0.05 3.34 3.1
0.1 3.41 3.5
CGL 3.32 3.1
junctions with different Mg contents. In addition, Mg doping
also leads to lower leakage current in the junctions. The in-
creasing threshold voltage corresponds to the higher built-in
potential generated by difference of Femi-level of p-type
NiO and n-type MgZnO, which can be attributed to the en-
larged band gap. As for the increased reverse breakdown
voltage, the resistivity should be taken into consideration. It
is recognized that the reverse current consists of hole current
tunneling from n base region to p base region and electron
current moving in opposite direction. Partial substitution of
Mg2+ for Zn2+ can depress formation of oxygen defects due
to the more ionic character of MgO bond, enhancing the
resistivity.15,16 Thus, the lower leakage current and higher
reverse breakdown voltage can be obtained by increasing Mg
content. In addition, it can be seen that the reverse saturation
current decreases with increasing Mg content. These results
suggest that the properties of the p-NiO/ n-MgZnO junctions
can be effectively tuned by engineering MgZnO band gaps.
The function of the p-n junction can be further improved
using CGL of n-MgZnO as n-type layer to constitute a
p-NiO/ n-CGL junction as shown in the inset of Fig. 4.
Figure 4 shows the I-V behavior of the p-n junction. The
rectification property of I-V curve is seen with a forward
threshold voltage of about 3.1 V, comparable to the value of
p-NiO/ n-MgZnO x = 0.05. However, it is worth noting that
FIG. 4. Color online I-V curve of p-NiO/ n-CGL junction. The inset shows
schematic structure of the junction.
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Appl. Phys. Lett. 93, 112112 2008
the reverse breakdown voltage of p-NiO/ n-CGL increases
up to about 6.0 V, and the reverse saturation current de-
creases. The increasing reverse breakdown voltage and de-
VBR
creasing reverse saturation current of p-n junction devices
are desirable for some device applications. Previous theoret-
1.8 ical prediction also indicated that similar graded band gap
3.5 p-n structure can effectively reduce the reverse saturation
5.0 current.17
6.0
In conclusion, transparent p-n heterojunctions composed
of p-type NiO and n-type MgZnO film layers have been
fabricated on ITO-coated glass substrates by sol-gel spin
coating technique. The resultant p-n heterojunctions exhibit
typical I-V behaviors with good rectifying characteristics.
The electrical properties of the p-n junctions can be effec-
tively tuned by band gap engineering of n-MgZnO, and can
be further improved by using compositionally graded
n-MgZnO layer instead of single n-MgZnO layer. The trans-
parent p-NiO/ n-MgZnO heterojunctions can find applica-
tions in transparent electronic devices.
The authors gratefully acknowledge support from the
Natural Science Foundation of Guangdong Province, China
Grant No. 05003289, the Specialized Research Fund
for the Doctoral Program of Higher Education of China
Grant No. 20060558068, and NSFC Grant Nos. 10574164
and U0634006.
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