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Materials Science in Semiconductor Processing 13 (2010) 137–140

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Materials Science in Semiconductor Processing
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ZnO/p-Si heterojunction photodiode by sol–gel deposition of
nanostructure n-ZnO film on p-Si substrate
Fahrettin Yakuphanoglu a, Yasemin Caglar b, Mujdat Caglarb,, Saliha Ilican b
Firat University, Faculty of Arts and Sciences, Department of Physics, 23169 Elazig, Turkey
Anadolu University, Faculty of Science, Department of Physics, 26470 Eskisehir, Turkey

a r t i c l e in fo abstract

The electrical and photovoltaic properties of the nanostructure ZnO/p-Si diode have
Keywords: been investigated. The nanostructure ZnO/p-Si diode was fabricated using sol–gel spin
ZnO coating method. The ideality factor and barrier height of the diode were found to be
Sol–gel spin coating 3.18 and 0.78 eV, respectively. The obtained n ideality factor is higher than 2, indicating
Nanostructure that the diode exhibits a non-ideal behavior due to the oxide layer and the presence of
Photodiode surface states. The nanostructure of the ZnO improves the quality of ZnO/p-Si interface.
The diode shows a photovoltaic behavior with a maximum open circuit voltage Voc of
0.26 V and short-circuits current Isc of 1.87  10  8 A under 100 mW/cm2. It is evaluated
that the nanostructure ZnO/p-Si diode is a photodiode with the obtained electronic
& 2010 Elsevier Ltd. All rights reserved.

1. Introduction pyrolysis [7,8] and sol–gel spin coating [9,10]. Among
these, the sol–gel process presents an easy way to
In recent years, much research has been focused on integrate ZnO devices into the Si technology, since it
semiconductor-based ultraviolet (UV) photodiodes. offers the possibility of excellent compositional control,
Photodiodes operating in the short wavelength UV multicomponent oxide layers of many compositions on
region are important devices that can be used in substrate, simplicity, homogeneity, lower crystallization
various commercial and military applications. For temperature and low production costs.
example, visible–blind UV photodiodes can be used in ZnO-based UV photodetectors offer promising advan-
space communications, ozone layer monitoring and flame tages in research and development due to ZnO’s direct and
detection. Currently, light detection in the UV spectral wide band gap, strong UV-response, feasibility of simple
range still uses Si-based optical photodiodes. and low cost processing and capability of working in
Zinc-oxide (ZnO) films have been extensively studied harsh environments [4–6]. It is interesting that such a
for practical applications including bulk acoustic resona- simple photodiode structure as the n-ZnO/p-Si has not
tors [1], transparent conducting electrode materials for been widely reported except by a small number of studies
various electronic devices such as solar cells [2], electro- to date [11–16].
luminescence devices [3], etc. Various techniques have In the present study, the nanostructure ZnO/p-Si
been employed to obtain ZnO films. These include photodiode was fabricated using the sol–gel spin coating
metalorganic chemical vapour deposition [4], molecular method. The n-ZnO nanostructures directly were grown
beam epitaxy [5], pulsed laser deposition [6], spray on p-type substrate. We have evaluated that this gives a
high quality and well-defined interface between n-ZnO
and p-Si. We report the first investigation of electrical
 Corresponding author. properties of n-ZnO/p-Si photodiode fabricated by sol–gel
E-mail address: (M. Caglar). spin coating method.

1369-8001/$ - see front matter & 2010 Elsevier Ltd. All rights reserved.
138 F. Yakuphanoglu et al. / Materials Science in Semiconductor Processing 13 (2010) 137–140

2. Experimental measurements were performed using a 500 W halogen
lamp under 100 mW/cm2 intensity by a KEITHLEY 6517A
ZnO film was deposited on silicon substrate using Electrometer. The intensity of light was measured with a
sol–gel spin coating method. The Si used in study was solar power meter (DBTU1300).
p-type (boron-doped) single crystal /100S with a thick-
ness of 600 mm and a resistivity of 5–10 O-cm. Firstly, Si
3. Results and discussion
wafer was degreased through RCA cleaning procedure,
i.e., a 10 min boiling in NH4OH+ H2O2 + 6 deionized (DI) 3.1. Structural properties of the nanostructure ZnO film
(18 MO DI water), which was followed by a 10 min boiling
in HCl+H2O2 +6 DI. For ohmic contact, the high-purity Fig. 2 shows the XRD spectra of the nanostructure ZnO film. The
aluminium (99.999%) with a thickness of 150 nm was analyses of XRD data reveal the peaks corresponding to the (1 0 0),
thermally evaporated on the whole back surface of the Si (0 0 2), (1 0 1), (1 0 2), (1 1 0) and (1 0 3) planes of the hexagonal ZnO
crystal structure. From these results, it can be observed that the films
wafer and then Si wafer was sintered at 580 1C for 3 min in
reveal the existence of a ZnO phase with a hexagonal wurtzite structure.
N2 atmosphere. Before forming a ZnO layer on the p-type XRD of the ZnO film shows a strong ZnO (0 0 2) diffraction peak centered
Si substrate, the native oxide on the front surface of the at 34.3791 with a full-width at half-maximum (FWHM) of 0.1881. The
substrate was removed in HF:H2O (1:10) solution, and peak at around 701 belongs to Si substrate.
finally, the wafer was rinsed in DI water. To obtain the sol, The crystallite size of nanostructure ZnO film was calculated from
the following Scherrer’s equation [18] and found to be 46 nm for the
the precursor zinc acetate dehydrate was first dissolved
(0 0 2) direction:
into 2-methoxyethanol as a solvent and by adding
monoethanolamine, which acts as the stabilizer. Molar D¼ ð1Þ
b cos y
ratio of monoethanolamine to zinc acetate was main-
where b is the FWHM of the peak, D is the crystallite size, y is the
tained at 1:1 and the concentration of zinc acetate was
reflection angle, and l is the X-ray wavelength.
0.5 M. After stirring for 1 h, a clear and homogeneous Fig. 3 shows the SEM image of the nanostructure ZnO film used on
solution was obtained. The substrate was placed on the the ZnO/p-Si photodiode. It is seen that the surface morphology of the
sample holder and was rotated at a speed of 3000 rpm for nanostructure ZnO film is almost homogeneous and crystalline particle
30 s. After each spin coating the substrate was dried in a size is between 50 and 100 nm. The calculated crystallite size is very
close to that shown in the SEM image. So, the calculated and shown
furnace at 300 1C for 10 min to evaporate the solvents.
crystallite size values are in agreement with each other.
After this process was repeated 10 times, thermal
treatment was carried out at 450 1C for 1 h to decompose 3.2. Current–voltage characteristics of nanostructure ZnO/p-Si diode
completely the organic component from the film. Then,
the ZnO film was annealed at 750 1C for 1 h. In the The current–voltage (I–V) characteristics of nanostructure ZnO/p-Si
previous work, the effect of heat treatment on some diode are shown in Fig. 4. The diode shows a rectifying behavior with no
physical properties of the ZnO film growth on Si was incident light. The current–voltage characteristics of a heterojunction
reported in detail [17]. can be analyzed by the following relation [19]:
Aluminum rectifying contacts were deposited onto the I ¼ Io exp ð
1 ð2Þ
ZnO surface of the wafer using PVDHANDY/2S-TE (Vaksis nkT

Company, Turkey) vacuum thermal evaporation in the where Io is the reverse saturation current, q is the electronic charge, k is
pressure of 1  10  6 Torr and the contacts were formed in the Boltzmann constant, n is the ideality factor and T is the temperature.
The ideality factor and reverse saturation current values of the diode
the form of circular dots of 2 mm diameter and 100 nm
were determined from Fig. 4 and were found to be 3.18 and
thickness. The contact area of the diode was found to be 5.66  10  9 A, respectively. The obtained n ideality factor is higher than
7.85  10  3 cm2. The schematic diagram of the nanos- 2. This indicates that the diode exhibits a non-ideal behavior due to the
tructured ZnO/p-Si photodiode is shown in Fig. 1. The oxide layer and the presence of surface states. The ideality factor of the
crystal structure of the film was investigated using an
X-ray diffraction (XRD) system with a CuKa source.
Surface morphology was observed with a ZEISS EVO-50
model scanning electron microscope (SEM). The current–
voltage (I–V) characteristics of the diode were performed
using a KEITHLEY 2400 sourcemeter. The photocurrent



Fig. 1. The schematic diagram of the nanostructure ZnO/p-Si hetero-
junction photodiode. Fig. 2. XRD pattern of the nanostructure ZnO film.
F. Yakuphanoglu et al. / Materials Science in Semiconductor Processing 13 (2010) 137–140 139

Fig. 3. SEM image of the nanostructure ZnO film.

n-ZnO χ=4.05eV

ΔE C =0.3eV Eg =1.12eV

Eg=3.37eV ΔEV=2.55eV


Fig. 5. Energy band diagram of the nanostructure ZnO/p-Si photodiode.

diode is considerably high. This indicates that the nanostructure ZnO/
p-Si diode is a photodiode with a shift of the I–V curve by the amount of
photocurrent. The diode shows a photovoltaic behavior with a maximum
open circuit voltage Voc of 0.26 V and short-circuits current Isc of
1.87  10  8 A under 100 mW/cm2. Under illumination, the forward
current of the diode is higher than the dark current. This is not in
agreement with the theory of photovoltaic devices, as optical radiation
changes the nature of the dark current. Furthermore, since the exciton
binding energy is large in ZnO, dissociation occurs with the help of the
applied voltage and this affects the photocurrent in forward direction.
Fig. 4. Current–voltage characteristics of the nanostructure ZnO/p-Si
photodiode under dark and illumination.

4. Conclusions
nanostructure ZnO/p-Si diode is lower than that of ZnO nanorods and
nanodot/p-Si heterojunction diodes [20]. This shows that the quality of
nanostructure ZnO/p-Si interface is better than those diodes. The barrier The electrical and photovoltaic properties of the
height of the diode was determined using the Io value and was found to nanostructure ZnO/p-Si diode have been investigated.
be 0.78 eV. The barrier height of the diode is in agreement with A group The crystallite size of nanostructure ZnO film was
diodes, whereas it is higher than B group diodes in Ref. [20]. This
determined by both the XRD result and SEM image. The
suggests that the nanostructure of the ZnO has a significant effect on
barrier height of ZnO/p-Si diodes. The energy band diagram of the diode ideality factor (3.18) and barrier height (0.78 eV) of the
is shown in Fig. 5. As seen in Fig. 5, there is a large band discontinuity in diode were determined and these values showed that the
the valence band and a small conduction band discontinuity. We nanostructure of the ZnO has a significant effect on device
evaluated that ZnO/p-Si junction gives a high current under forward bias performance. The obtained results showed that the
and a very low current under reverse bias.
I–V characteristic of the diode under illumination is shown in Fig. 4.
nanostructure ZnO/p-Si diode was a photodiode with a
As seen in Fig. 4, both the reverse current and forward current increases maximum open circuit voltage Voc of 0.26 V and short-
with optical radiation. As expected, increase in reverse current of the circuit current Isc of 1.87  10  8 A under 100 mW/cm2.
140 F. Yakuphanoglu et al. / Materials Science in Semiconductor Processing 13 (2010) 137–140

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