Materials Science in Semiconductor Processing 66 (2017) 232–240

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Materials Science in Semiconductor Processing

journal homepage: www.elsevier.com/locate/mssp

Ultra-violet photo-response characteristics of p-Si/i-SiO2/n-ZnO MARK

heterojunctions based on hydrothermal ZnO nanorods
⁎
Waqar Khan, Sam-Dong Kim
Division of Electronics and Electrical Engineering, Dongguk University, 100-715 Seoul, Korea

A R T I C L E I N F O A B S T R A C T

Keywords: Hydrothermal zinc oxide (ZnO) nanorod (NR)-based p-Si/n-ZnO and p-Si/i-SiO2/n-ZnO heterojunctions were
ZnO nanorod fabricated, and the effects of interfacial native SiO2 (~4 nm) on the I-V characteristics of heterojunctions under
Seed layer dark and ultra-violet illumination conditions were investigated. First, the structural and optical properties of
Hydrothermal growth ZnO seed crystals grown by sol-gel method and hydrothermal ZnO NRs on two different substrates of p-Si and p-
I-V characteristics
Si/i-SiO2 were examined, and more improved optical and crystalline quality was obtained as revealed by
Structural properties
Optical properties
photoluminescence and X-ray diffraction. The p-i-n heterojunctions showed ~3 times greater forward-bias
Rectification ratio currents and enhanced rectifying property than those of p-n junctions, which is attributed to the role of native
Ideality factor SiO2 in carrier confinement by promoting the electron-hole recombination current through the deep level states
Photo response transient of ZnO crystal. The measured ratios of photocurrent to dark current of the p-i-n structure were also greater under
reverse bias (92–260) and forward bias (2.3–7.1) conditions than those (28–225 for reverse bias, 1.6–6.8 for
forward bias) of p-n structure, and the improved photosensitivity of the p-i-n structure under reverse bias is due
to lower density of recombination centers in the ZnO NR crystals. Fabricated ZnO NR heterojunction showed
repeatable and fast photo-response transients under forward bias condition of which response and recovery
times were 7.2 and 3.5 s for p-i-n and 4.3 and 1.7 s for p-n structures, respectively.

1. Introduction
The nanotechnology has been enriched with a wide variety of new
emerging semiconductor materials for the improved precision in
fabrication, higher efficiency, and faster response time of the nano-
electronic sensors and actuators. One of the most extensively investi-
gated materials is zinc oxide (ZnO) for its unique properties of a direct
band gap of 3.37 eV and a high exciton binding energy of 60 meV
enabling the excitonic emission processes to persist even at room
temperature (RT) [1,2]. It is also non-toxic and biocompatible, and
the material stability under elevated temperature and chemical envir-
onment enabled the ZnO material to be considered as a viable candidate
in various types of high-efficiency ultraviolet (UV) photodetectors for
the bio-medical and military applications. For example, extensive
research has been reported for the ZnO-based passive devices such as
p-n junction [3], p-i-n Schottky diodes [4], metal–semiconductor–metal
photodetectors [5], and heterojunction structures as well as active-type
sensors and actuators [6]. Moreover, pioneering research on the piezo-
electric, photonic, and piezo-phototronic applications based on ZnO
nanostructures has been successfully demonstrated for the environ-
mental, industrial, and military applications [7]. In recent decades, an
excessive amount of research work has been made on ZnO using the
various challenging but practical synthesis methods for the ZnO-based
nanomaterials. Among these synthesis procedures, the aqueous solution
method can be preferred because it can synthesize many different
geometrical morphologies of ZnO nanostructures with a high degree of
crystallinity and a controlled orientation at temperature lower than
100 °C.
As-grown ZnO nanostructures grown via hydrothermal route has
been regarded as a source of unintentional n-type conductive semi-
conductor due to native point defects such as zinc interstitials and
oxygen deficiencies [8]. Since high quality and stable p-type doping has
been a problem for a long time, to develop a reliable p-n ZnO-based
homojunction device has remained as a challenge [3]. An alternative
approach is to utilize p-type substrates of different materials such as p-
GaN [6], p-SiC [9], p-Si [3,4], and p-NiO [10] which are commercially
available at low cost and large area. The potential problem in the
formation of ZnO heterojunction using these p-type substrates is the
large lattice mismatch between the two different junction materials and
the high-density interface states [11]. Especially, the recombination
centers at the interface of two different materials significantly degrade
the performance of the electrical and optical properties of the hetero-

⁎
Corresponding author.
E-mail address: samdong@dongguk.edu (S.-D. Kim).

http://dx.doi.org/10.1016/j.mssp.2017.04.031
Received 21 December 2016; Received in revised form 7 March 2017; Accepted 30 April 2017
1369-8001/ © 2017 Elsevier Ltd. All rights reserved.
W. Khan, S.-D. Kim
Fig. 1. Schematic illustrations of (a) p-Si/n-ZnO NRs and (b) p-Si/i-SiO2/n-ZnO NRs heterojunctions. HR-TEM images of interfaces for the (c) p-Si/n-ZnO NRs and (d) p-Si/i-SiO2/n-ZnO
NRs heterostructures are shown.
junction devices of our concern.
Schematics of two different heterojunction structures examined in
this study were shown in Fig. 1(a) and (b). In the case of p-i-n structure,
a very thin native SiO2 was introduced intentionally at the interface
between the p-Si substrate and ZnO seed layer. It was reported that a
thin in-situ MgO layer (~8 nm) at the interface of n-Si/n-ZnO was
successfully grown in a metal organic chemical vapor deposition
(MOCVD) system without vacuum pause [12]. The presence of this
current blocking layer enabled the growth of high density MOCVD ZnO
NRs with an enhanced vertical alignment and showed significantly
improved UV photo-sensing performance. However, the role of this
interface oxide in the crystalline quality improvement for the vertically
grown NRs were not clearly understood, especially for the hydrother-
mal ZnO nanostructures.
In this study, we examined how the presence of native silicon oxide
grown on the surface of silicon in air ambient condition affects the
performance of our heterojunction devices as well as structural and
optical properties of the ZnO NRs to be grown thereupon. As shown in
Fig. 1(d), the high-resolution transmission electron microscopy (HR-
TEM) micrograph shows the presence of uniform native oxide on the Si
substrate of which thickness is ~4 nm in the case of p-i-n structure,
whereas no interfacial oxide is observed in the case of p-n structure as
shown Fig. 1(c). X-ray diffraction (XRD) and room temperature (RT)
photoluminescence (PL) have been carried out to compare the crystal-
line quality of ZnO nanostructures of two different heterojunction
structures. Comparative study was also performed through the analysis
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Materials Science in Semiconductor Processing 66 (2017) 232–240
of transient UV photo-response and I-V characteristics of the p-n and p-i-
n heterojunctions under dark and UV illumination conditions.
2. Experimetal procedure
To fabricate the n-ZnO NR-based heterojunction, we used p+-Si
(100) substrate (1×1 cm2) of a resistivity of 0.01 Ω-cm with typical
boron doping. The NRs were synthesized by using a low temperature
hydrothermal method of the following two respective process steps for
the seed layer and NRs. All the chemicals used in this work were of
reagent grade from Sigma-Aldrich and used without any further
purification.
First, a colloidal solution was prepared by dissolving 0.06g of zinc
acetate dihydrate [Zn(CH3COO)2·2H2O] in 30 mL n-propanol [C3H8O]
to form a 0.2 mol concentrated solution. The solution was then
sonicated for 30 min at RT and spun onto the substrate to deposit the
ZnO seed layer. Prior to the deposition of ZnO seed layer, the surface of
p-Si substrate was cleaned by acetone and isopropyl alcohol respec-
tively for 5 min, rinsed by de-ionized (DI) water, and dried with
nitrogen purge. For the heterojunction of p-Si/n-ZnO (no interfacial
native oxide), the substrate was put into the buffer oxide etchant (BOE)
for 5 min to remove the native oxide grown on the silicon surface. In the
case of p-Si/i-SiO2/n-ZnO heterojunction (with interfacial native oxide),
no BOE etching was performed, but the p-Si substrate was preheated at
300 °C for 10 min in an ambient condition to grow a uniform silicon
oxide of ~4 nm. The grown oxide film thickness was quite repetitive in
W. Khan, S.-D. Kim Materials Science in Semiconductor Processing 66 (2017) 232–240

many growth experiments under our process condition, as confirmed by

the cross-sectional transmission electron microscopy (TEM) and elec-
trical measurements of the devices fabricated thereafter. This thickness
was known to be the upper limit for direct tunneling of electrons across
the ultrathin SiO2 barrier to dominate in metal-oxide-Si structure [13].
The ZnO seed layer was then spin-coated on the substrate at 3000 rpm
for 30 s with no time delay (especially for the p-n structure) and
preheated on a hot plate at 100 °C for 60 s. This process was repeated
10 times to achieve a sufficient thickness (~20 nm) of the seed layer to
achieve high-density and vertically aligned NRs to be grown in the next
step. The seed layers on two different surface conditions were post-
annealed at 300 °C for 60 min to remove the remaining organic and
residual salts as well as to improve the crystalline quality of the seed
layer. This annealing condition for seed layers was employed in this
study to give improved crystallinity with well-aligned c-axis crystal
orientation for the subsequent NR growth and reduction of oxygen
vacancy defects in as-grown seeds based on the experimental results of
earlier studies [2,14].
To grow ZnO NRs on the seed layers, an aqueous solution containing
the growth precursors was prepared using equimolar (0.025 mol) zinc
nitrate hexahydrate (Zn(NO3)2.6H2O) and hexamethylenetetramine
(HMT, C6H12N4) in 200 mL DI water. This solution was stirred at RT
for 25 min to ensure complete mixing and transferred into a sealable
glass beaker. The samples were placed in the aqueous growth solution
fully covered and heated at 90 °C for 6 h. Finally, as-grown NRs were
washed with DI water to remove the residual sols on the surface and
dried with nitrogen blow. The starting and ending values of the pH
recorded from the solution were 7 and 6.5, respectively. After growth of
the heterojunction structures, the top electrode was formed by pasting
the thin indium contact (~ 100 µm2) on the top of ZnO NRs, as shown
in Fig. 1, to provide a good ohmic contact for the electrical measure-
ment circuitry with p-Si.
Surface morphology of ZnO NRs was investigated by field emission
scanning electron microscopy (FE-SEM, S-4800, Hitachi) operating at
25 keV. Optical properties of the seed layers and NRs were examined by
PL spectroscopy (MFP-3D Bio, Asylum Research) excited at 266 nm and Fig. 2. (a) θ–2θ scan XRD patterns of ZnO seed layer grown on (top) p-Si/i-SiO2 and
RT. The thicknesses of native oxide and seed layer were measured by (bottom) p-Si. (b) Comparison of (002) peaks from the ZnO seed layers of two different
using high-resolution TEM (HR-TEM, Hitachi 9500, operating at heterojunctions.
300 kV). Electrical transport measurements were performed using
Keithley 2400 source meter (Beaverton, OR, USA), and a light source peak intensity was measured from the seed layer grown on p-Si/i-SiO2
(220 nm, average intensity of 7 mW/cm2) was used for deep ultraviolet compared to that grown on p-Si, which reveals an improved crystalline
illumination on the heterojunctions. Preferred orientation of the ZnO quality along c-axis. We observed almost the same full-width at half-
NRs was measured by XRD spectrometer (D8 ADVANCE, Bruker AXS maximum (FWHM) of (002) diffraction (~0.14°) from two different
GmbH) using a CuKα radiation (1.540 Å wavelength). seed crystals. The (002) interplanar spacing d002 for the fully relaxed
ZnO crystal is 2.603 Ǻ, as shown in JCPDS files; however, the measured
d002 values of the seed crystals on p-Si/i-SiO2 and p-Si were 2.717 and
3. Results and discussion 2.719 Ǻ, respectively. The deviations in d002 values of the seed crystals
from the fully relaxed c-axis planar spacing show that the grown seed
A thin ZnO textured nanocrystals as a seed layer is formed prior to films are under large compressive stress along a-axis causing the unit
the growth of NRs to provide the preferential sites for homogenous cell elongation toward c-axis direction. Even though the difference of
nucleation of ZnO crystals and lower the lattice misalliance between the d002 values between the cases of two different substrates was negligibly
substrate and NRs [2]. Morphology and aspect ratio of the NRs are also small, the stress state for seed crystals grown on p-Si/i-SiO2 was slightly
known to be strong functions of crystalline state of the seed layer [15]. less compressive.
We first analyze the structural and optical characteristics of our seed RT photoluminescence spectra for ZnO seed layers grown on p-Si
layers grown on the p-Si substrates of two different surfaces depending and p-Si/i-SiO2 substrate were shown in Fig. 3, and two prominent
on the existence of surface native oxide. For this, RT PL and XRD θ−2θ emission regions were observed in both spectra. The first intense UV
scan were carried out for the seed layers as shown in Fig. 2(a) and (b). emission ranging from 350 to 400 nm in wavelength is mainly due to
From the XRD patterns, it was observed that all reflections were in good band-to-band excitonic recombination associated with the near-band-
agreement with the reported indexes of JCPDS files for the hexagonal edge emission of ZnO, and the highest peak position corresponds to the
phase ZnO (card number 36-1451, a =3.249 Ǻ, c =5.206 Ǻ). Diffrac- ZnO band gap [16]. The second region of lower-intensity yellow-green
tion peaks shown in XRD patterns were quite intensive and narrow; emission (420–650 nm) is known to be caused by the non-stoichio-
furthermore, no diffraction peak related to impurities was observed in metric intrinsic defects originating from a variety of forms such as zinc
the XRD pattern confirming the high purity of the ZnO nanostructures and oxygen vacancies or anti-sites defects, and this emission is due to
synthesized. Although the (002) peaks were the most intense exhibiting the recombination of photo-generated carriers with charge states of the
a growth pattern along the c-axis of the nanostructures, other peaks of crystalline defects [16,17]. 18.5% increase of intensity from the UV
(100) and (101) were also apparent. Moreover, 24.4% increase in (002)

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W. Khan, S.-D. Kim
Fig. 3. RT photoluminescence spectra from the ZnO seed layers of two different
heterojunction structures.
emission peak was observed in the seed layers grown on p-Si/i-SiO2
substrates (FWHM =21.4 nm) compared to those grown on p-Si
substrates (FWHM =22.7 nm). On the other hand, a higher intensity
of yellow-green emission was also shown from the seed layers on p-Si/i-
SiO2 than those on the p-Si substrates, especially at ~533 nm. Even
though there is still controversy in the literature about the origin of the
luminescence centers observed in ZnO materials, recent studies demon-
strated that the green emission at ~530 nm is related to oxygen
vacancies [18]. It can be understood such that even though our seed
crystals on p-Si substrates exhibit improved crystalline quality along c-
axis, as shown in XRD and PL UV luminescence, when a thin native
oxide added at the interface, they produce more intrinsic defects
associated with yellow-green emission most probably due to the
Fig. 4. FE-SEM (a-1) top-view and (a-2) cross-sectional micrographs of ZnO NRs grown on p-Si without interfacial oxide. (b-1) Top-view and (b-2) cross-sectional micrographs of ZnO NRs
grown on p-Si/i-SiO2 are also shown.
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Materials Science in Semiconductor Processing 66 (2017) 232–240
incoherent growth on the thin amorphous SiO2 layers. The intensity
increase of both UV and visible luminescence (especially green) is quite
contradictory to the previous reports that the intensity ratio of UV
emission to yellow or green emission is increased with the ZnO
crystalline quality and the recovery of Zn:O stoichiometry [4,17,18].
However, this trend is possible only when the luminescence in visible
light range is related to the deep acceptor levels because UV lumines-
cence should be decreased as deep-acceptor-associated luminescence is
increased. Therefore, our PL intensity increase in yellow-green lumi-
nescence is most likely caused by the transition from deep donor level,
such as oxygen vacancies in ZnO, to valence band as observed in the
vacuum-annealed ZnO films deposited by pulsed-laser deposition [19].
Higher yellow-green PL emission seed layers on p-Si/i-SiO2 can be also
associated with the recombination of delocalized electrons trapped by
thin i-SiO2 close to conduction band with deeply trapped holes in the
single ionized oxygen vacancies [20].
SEM top view and cross-sectional images of the ZnO NRs grown on
the seed layers were shown in Fig. 4. From the planar views of NRs
grown on p-Si, a clear wurtzite hexagonal morphology of NRs was
observed with diameters of 30–130 nm as shown in Fig. 4(a-1). Average
length of the NRs was ~1.4 µm with an aspect ratio of ~17 and a NR
density of ~60 rods/µm2. On the other hand, the NRs grown on p-Si/i-
SiO2 showed more uniform distribution of diameters ranging from 60 to
80 nm and an average length of ~1.37 µm (aspect ratio of ~20) as
shown in Fig. 4(b-1) and (b-2). Moreover, a higher NR density of ~100
rod/µm2 was observed in this case. In summary, more uniform in
diameter and higher density NRs were obtained from the growths on
the substrates of p-Si/i-SiO2 than those on the p-Si.
Fig. 5(a) shows the XRD patterns of as-grown ZnO NRs on two
different substrates. As reported by many experimental results, a
vertical growth of wurtzite ZnO NRs well-aligned along c-axis was
obtained from our samples by exhibiting single strong peak along (002)
orientation [6,15,16]. As shown in Fig. 5(b), ~30% increase of (002)
W. Khan, S.-D. Kim Materials Science in Semiconductor Processing 66 (2017) 232–240

Fig. 5. (a) XRD θ–2θ scan patterns of ZnO NRs grown on (top) p-Si and (bottom) p-Si/SiO2
substrates. (b) Comparison of (002) peaks from the NRs of two different heterojunction
structures.
Fig. 7. (a) I-V characteristics of p-Si/n-ZnO and p-Si/i-SiO2/n-ZnO under dark and UV
illumination conditions in a bias range of −5- ~ +5 V. (b) Schottky characteristics
measured from two different heterojunctions in a blown-up current scale under dark
condition. A good ohmic behavior is also measured between the NRs and indium contact
(top electrode) as shown in the inset.

Table 1
Summary of measured rectification ratios and built-in potential drops of p-Si/SiO2/n-ZnO
and p-Si/n-ZnO heterojunctions under dark and UV illumination conditions, where If and
Ir stands for current under forward bias (at V =+5 V) and reverse bias (at V =−5 V)
condition, respectively.

Structure Parameters Dark UV illumination

p-Si/n-ZnO If (µA) 11 68
Ir (µA) 0.00728 0.203
RR 1510 334
p-Si/i-SiO2/n-ZnO If (µA) 31.2 214
Ir (µA) 0.0197 0.578
RR 1583 370

compared to those of (100) (3.4 J/m2) and (101) (2.0 J/m2) planes
Fig. 6. RT PL spectra from the NRs of p-Si/n-ZnO and p-Si/i-SiO2/n-ZnO structures.
[21,22]. PL spectra for as-grown ZnO NRs were shown in Fig. 6. As
discussed earlier, sharp peaks at 373 and 533 nm in wavelength
respectively correspond to band-to-band excitonic recombination UV
peak intensity was obtained from the NRs grown on p-Si/i-SiO2
emission and recombination with O-vacancy while the broad peak of
substrate (FWHM =0.19°) compared to that on p-Si substrate (FWHM
green-yellow emission ranging from 450 to 700 nm is related to deep
=0.20°). This can be due to the improved crystalline quality of
level emission caused by a variety of intrinsic defects [18,23]. We also
polycrystalline seed layers preferentially aligned to c-axis when grown
observed a significant increase of UV emission (~56.8%) in PL spectra
on p-Si/i-SiO2 substrates. As revealed by earlier researches, each
from the NRs grown on substrates with interfacial native oxide (FWHM
crystalline surface of the seed layer grains acts as a nuclei for the
=14.4 and 19.8 nm for p-i-n and p-n structure, respectively), as shown
growth of NRs. Therefore, the NRs tend to dominantly grow along the
in Fig. 6, which can be due to the improved crystalline quality of
(002) crystal plane because of its lower surface free energy (1.6 J/m2)
underlying seed crystals. Intensity of broad green-yellow emission was

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W. Khan, S.-D. Kim
Fig. 8. Forward bias log (I)-V representations of p-Si/i-SiO2/n-ZnO and p-Si/n-ZnO
heterojunction under (a) dark and UV illumination condition. Forward bias ln (I)-V
representations of p-i-n and p-n heterojunction under (b) dark and (c) UV illumination
condition.
also reduced by ~14% from the NRs grown on the seed layers with p-
Si/i-SiO2 substrates; however, a more intense luminescence was shown
at ~530 nm on the contrary. This indicates that higher-density defects
of various forms except a luminescence center at ~530 nm (probably
due to deep donor O vacancies) are produced in the NRs atop the seed
layers when grown without native oxides. The role of native oxide in
suppressing the defect density of the NRs is not clearly understood.
However, thin native oxide at the interface can serve as a stress-buffer
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Materials Science in Semiconductor Processing 66 (2017) 232–240
accommodating the lattice mismatch for the initial ZnO seed growth,
thereby providing more highly c-axis oriented growth of seed crystals as
observed in our XRD. Therefore, the seed crystal quality of enhanced c-
axis preferential orientation, when grown on p-Si/i-SiO2 substrates, can
suppress the density of intrinsic defects because most of defect
formation in ZnO NRs is deeply related with the distortion of crystalline
structure and the interface with underlying seed-crystal grain bound-
aries [12].
I-V characteristics of two different heterojunctions were investi-
gated by probing the indium contact pasted on the NRs and the p-Si.
Indium is known as a donor impurity in n-ZnO enhancing the interface
doping, thereby promoting the tunneling current [24]. Shown in the
inset of Fig. 7(b) is a good ohmic characteristic measured from the n-
ZnO-NRs/indium electrode. Measured specific contact resistance was
~1×10−2 Ωcm2 (no alloy) which is close to those measured from as-
deposited Ti/Au, Ti/Al, or indium tin oxide [25]. As shown in Fig. 7(a)
and (b) (expanded view of I-V plot under dark condition), typical
characteristics of p-n junction were measured from two different
heterostructures under both dark and UV illumination conditions. The
peak wavelength of light source used for UV illumination was 220 nm.
Key parameters representing the rectifying properties of the hetero-
structures were summarized in Table 1. Under dark condition, the
amount of forward bias current If at 5 V measured from p-Si/i-SiO2/n-
ZnO junction was 31.2 µA which was ~3 times greater than If measured
from p-Si/n-ZnO structure. The reverse bias currents Ir at −5 V of the p-
i-n and p-n structure were 19.7 and 7.28 nA, respectively. The rectifica-
tion ratio, RR, defined by If/Ir for the p-i-n and p-n structure were 1583
and 1510 in the dark condition, respectively. When UV illuminated, the
RR were found to be 370 and 334 for the p-i-n and p-n structure,
respectively. 3 and 2.5 times greater diode currents were measured
under forward and reverse bias mode, respectively, from the p-i-n
structure than those of the p-n structure under UV illumination
condition.
The enhanced photocurrents of our heterojunctions in the presence
of UV light has its origin in the increase of carrier injection by photo-
generated electron-hole pairs and reduction of junction parasitic
resistance in n-type ZnO side due to oxygen desorption on the surface
of NR crystals [5,8]. When ZnO NRs are exposed to air ambient, oxygen
molecules will be adsorbed on its surface capturing electrons from its
conduction band as oxygen ions (O2−). This will create a low
conductivity depletion layer near the surface of the NR, and the NR
channel conductivity of individual NR is decreased. When the NRs are
exposed by UV, photo-generated holes will be attracted to the
negatively charged surface and neutralize the oxygen ions by the
reaction of h+ + O2− (ad) → O2 (gas). Therefore, UV excitation
reduces the NR channel resistance by narrowing the depletion layer
from the increased number of free electrons in the NR.
For further analysis of the non-ideal rectifying behavior of our
heterojunctions, ln(I)-V relationships under dark and UV illumination
conditions were plotted in Fig. 8. The current-voltage relation of p-n
diode with series resistance can be written as a function of applied
voltage as follows [23].
⎡ ⎛ q(V − Irs ) ⎞ ⎤
I = I0⎢exp⎜ ⎟ − 1⎥
⎣ ⎝ nkT ⎠ ⎦
where I0 is the reverse saturation current, q is the electronic charge, rs is
the series resistance, V is the applied voltage, n is the ideality factor, k is
Boltzmann's constant, and T is temperature in kelvin. For the V greater
than 3kT/q [26], the ideality factor can be calculated from the slope of
the linear region of forward bias ln(I)-V plot, as shown in Fig. 8(b) and
(c), under dark and UV illumination condition, respectively.
⎡ q ⎤ ⎡ dV ⎤
n = ⎢ ⎥⎢ ⎥
⎣ kT ⎦ ⎣ d (lnI ) ⎦
Significant increase in forward-bias photocurrent was observed as
W. Khan, S.-D. Kim Materials Science in Semiconductor Processing 66 (2017) 232–240

Fig. 9. Carrier transport of forward biased (a) p-n and (b) p-i-n structures in the dark condition. When UV illuminated, additional photocurrents are generated in (c) p-n and (d) p-i-n
structures under forward bias condition.

compared to dark current due to high photo-response characteristics of

Fig. 10. (a) log(I)-V plots and (b) Ratio of photo-to-dark currents (RPD) of p-Si/n-ZnO and
p-Si/i-SiO2/n-ZnO heterostructures under forward and reverse bias range of V = ± 5 ~
0 V.
ZnO nanorod under UV illumination condition, as shown in Fig. 8(a).
When UV irradiated, ~3 times higher forward-bias photocurrent was
measured from p-i-n heterojunction structure than that of p-n junction.
We presented in Fig. 8(b) and (c) the semi-logarithmic I-V plots of
which slopes correspond to the ideality factors of two different
heterojunction structures. The ideality factors n of each heterojunction
measured in a low bias range (< 0.6 V) under dark condition were 0.8
and 0.4 for the p-n and p-i-n heterojunction, respectively, which are
quite close to ideal values proposed by Sah-Noyce-Shockley theory
[27]. However, the n values were increased up to 13.2 and 5.4 for p-n
and p-i-n structures, respectively, above 3 V under dark condition as
shown in Fig. 8(c). Under UV irradiation, the n values for p-n and p-i-n
structures were 1.1 and 1, respectively, at low voltages, but they turned
out to be 12.4 and 9.5 above at 3 V. The large n values are known to be
ascribed to intrinsic defects, interface states, and large series resistances
of the rectifying junctions [26,28,29]. The reduction of n values when
UV illuminated, especially at high voltages, is most likely due to the
improved channel conductance of ZnO NRs caused by O2 ion deso-
rption, and this gives rise to the reduction in series resistance of the
heterojunctions. Regardless of illumination condition, we obtained
much higher n values from p-n junction than p-i-n structure over the
entire forward-bias range. When we have a higher density deep donor-
acceptor-pair recombination centers, such as in the case of our p-n
structure, it will give rise to more inter-defect recombination paths
instead of usual Shockley-Read-Hall recombination paths via two
neighboring defect levels, thereby leading to higher n values.
As shown in Fig. 9, different carrier transport mechanisms for the
dark and UV-illumination currents under forward bias condition are
described in ideal energy band diagrams of our p-n and p-i-n hetero-
junctions based on Anderson model [4,12]. The magnitudes of ideal
conduction band offset ΔEc =χZnO - χSi =0.3 eV, where χ is the
electron affinity (χZnO =4.35 eV, χSi=4.05 eV), and valence band
offset ΔEv =ΔEg,ZnO - ΔEg,Si +ΔEc =2.55 eV, where ΔEg is the energy
bandgap (ΔEg,ZnO =3.37 eV, ΔEg,Si =1.12 eV, ΔEg,SiO2 =9 eV) in p-n
junction. Because our p-Si (~0.01 Ω-cm) has much higher carrier

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W. Khan, S.-D. Kim
Fig. 11. (a) Transient UV photo-response of p-Si/n-ZnO and p-Si/i-SiO2/n-ZnO structures
at a forward bias voltage of +1 V and (b) the expanded view of response curves in a
single cycle.
density (~1×1020 cm−3) than that of undoped ZnO (1017–1018 cm−3),
negligible band bending in the space-charge region of p-side can be
assumed [30,31]. Fig. 9(a) illustrates that most of forward-bias current
in p-n junction is produced by injected electrons from n-ZnO to p-Si in
the dark condition, however the holes in p-Si side cannot move to n-side
because of large band offset in valence band (2.55 eV) at low applied
bias. Due to low electron population in n-side, the resulting dark
current will be limited. At higher voltages, as the EV of Si approaching
the deep level states (DLS), the holes in Si will tunnel into DLS to
recombine with electrons. Even in this case, the current contribution by
the holes through the tunneling-recombination process is quite limited
because majority of electrons will cross over the reduced potential
barrier to the p-side. However, thin interfacial SiO2 in p-i-n structure
can act as a good carrier confinement layer, as shown in Fig. 9(b),
promoting the electron-hole recombination through various DLS in the
space-charge region of ZnO. In p-i-n structure, accumulated holes at the
SiO2 interface due to a large ΔEv (2.38 eV) can now tunnel into either
valence band or DLS and recombine with electrons that are also highly
confined at the interface region (ΔEc =3.25 eV). This carrier transport
carried out simultaneously by electrons and holes can give rise to more
enhanced forward-bias dark current in p-i-n heterojunction.
The increase of forward-bias photocurrent under UV irradiation is
due to both electron hole pair generation and the reduction of junction
series resistance in n-type ZnO NRs (associated with O2 ion desorption)
239
Materials Science in Semiconductor Processing 66 (2017) 232–240
as discussed earlier. In p-i-n structure, the carrier confinement by the
presence of thin SiO2 can also significantly contribute to the enhance-
ment in photocurrent generation. Generated electrons in p-n junctions
will diffuse into n-side under forward bias condition, as shown in
Fig. 9(c), and this will limit the process of tunneling-recombination by
the holes as discussed earlier. However, excess electrons piled up at the
SiO2 interface in p-i-n structure can recombine with photo-generated
holes again by either radiative or non-radiative process, but some of
them can recombine with the holes transported from the p-side by
tunneling and produce more current as illustrated in Fig. 9(d).
Under reverse-bias mode, photocurrent can be mostly due to the
photo-carrier generation in the region of n-ZnO and strongly dependent
of the density of recombination centers, especially in the space-charge
region. Reverse-bias I-V characteristics were shown in Fig. 10(a) (from
0 to −5 V) under dark and UV illumination conditions. The photo-
sensitivity of the junction can be defined as a ratio of the photocurrent
to the dark current (RPD), and the RPD values measured from two
different heterojunctions under forward and reverse bias conditions
were summarized in Fig. 10(b). The forward-bias (from 0 to +5 V) RPD
values of p-i-n and p-n heterojunctions were in the ranges of 2.3–7.1 and
1.6–6.8, respectively. The reverse-bias (from 0 to −5 V) RPD is also a
function of bias voltage, ranging from 92 to 260 for p-i-n and from 28 to
225 for p-n, but the p-i-n structure also showed much greater photo-
sensitivity than that of p-n structure, which can be due to lower
densities of crystal defects and recombination centers in ZnO NR
crystals.
Photo-response transients were measured from two different hetero-
junctions by turning on and off the UV light source (λ=220 nm, 7 mW/
cm2) with a lapse of 30 s as shown in Fig. 11(a). The photo-responses of
our heterojunctions were highly stable and repeatable, but the photo-
currents of p-i-n structure were ~33% greater in average than those of
p-n junction. Response time (the time for the photocurrent to rise up to
90% of peak value) and recovery time (the time for the photocurrent to
decay to 10% of peak value) for the p-n heterojunction were 4.3 and
1.7 s, respectively, while those for the p-i-n heterojunction were 7.2 and
4.3 s. As shown in Fig. 11(a), the photocurrent ramp-up and fall-down
rates of two different devices were almost same. Therefore, the slower
response speed of the p-i-n devices can be due to the increased time for
reaching higher peak current through O2 ion desorption on the NR
surface and carrier recombination processes. The measured response
speed of our heterojunction photodetectors was fairly fast and compar-
able to those (few seconds ~ few tens of seconds) of single ZnO
nanowire photodetector grown by aqueous chemical deposition
[23,32].
4. Conclusions
UV photo-response characteristics of p-Si/n-ZnO and p-Si/i-SiO2/n-
ZnO heterojunction devices of hydrothermal ZnO NRs were investi-
gated under forward and reverse bias modes. Intentionally grown thin
native SiO2 greatly promoted I-V rectification properties and forward-
bias currents of the heterojunctions in the dark condition. Even when
UV illuminated, the p-i-n devices showed higher photosensitivity than
the p-n structure under both forward and reverse conditions. We
proposed in this study that higher photosensitivity of p-i-n devices
under forward-bias condition is attributed to the carrier confinement at
the interface of p-Si/i-SiO2 and increased hole current through tunnel-
ing and recombination, whereas higher crystalline quality of ZnO NR
crystals when grown in the presence of native oxide is associated with
the increased photosensitivity under reverse bias condition.
Acknowledgement
This work (project no. 2016006533) was supported by Mid-career
Researcher Program through National Research Foundation grant
funded by the Ministry of Education, Science and Technology. The
W. Khan, S.-D. Kim
authors would like to thank Muhammad Farooq Khan for his effort on I-
V measurements.
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