Chemically synthesized nanowire TiO2/ZnO core-shell p-n junction array for high

sensitivity ultraviolet photodetector

T. D. Dao, C. T. T. Dang, G. Han, C. V. Hoang, W. Yi, V. Narayanamurti, and T. Nagao

Citation: Applied Physics Letters 103, 193119 (2013); doi: 10.1063/1.4826921

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 APPLIED PHYSICS LETTERS 103, 193119 (2013)

Chemically synthesized nanowire TiO2/ZnO core-shell p-n junction array

for high sensitivity ultraviolet photodetector
T. D. Dao,1,2 C. T. T. Dang,1 G. Han,1 C. V. Hoang,1 W. Yi,3,a) V. Narayanamurti,3
and T. Nagao1,2,b)
1
International Center for Materials Nanoarchitectonics, National Institute for Materials Science, 1-1 Namiki,
Tsukuba, Ibaraki 305-0044, Japan
2
CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitana, 332-0012, Japan
3
School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, USA

(Received 27 August 2013; accepted 9 October 2013; published online 8 November 2013)
A sol-gel-based ultrathin TiO2 lamination coating was adapted to a hydrothermally grown
ZnO nanowire array to realize an all-oxide ultra-sensitive p-n photodiode. The core-shell
heterojunction—the key component of the device—is composed of a 5–10 nm thick p-type
Cr-doped TiO2 nanoshell and n-type single-crystalline ZnO nanowires (50 nm radius). Owing to
the enhanced light scattering and carrier separation in the core-shell architecture, this device
exhibits the highest performance among the ZnO nanowire-based photodetectors. At a moderate
reverse bias of 5 V and under ultraviolet light illumination at 104 lW, it shows a switch current
ratio of 140 and a responsivity as large as 250 A/W, while it shows nearly no response to the
C 2013 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4826921]
infrared and visible light. V

Nanocomposite transparent conductive oxides (TCOs)
constitute a promising class of optoelectronics materials,
especially for devices operating in the wavelength region
shorter than visible region. Among them, core-shell nano-
wire TCOs are considered to be one of the most effective
ones when they are aligned vertically and densely packed on
a planar electrode. The total surface area of the active hetero-
junction becomes two to three orders of magnitude larger
than planar devices, and the optical path length is largely
increased because of the strong light scattering by the nano-
wires. This leads to the dramatic enhancement of the light
absorption at the heterojunction. Recent developments in
nanowire synthesis techniques such as hydrothermal growth
of TCO nanowires1 have opened wide opportunities for
developing this type of optoelectronic materials with dramat-
ically reduced manufacturing cost and energy consumption.
Among many TCO materials, Zinc oxide (ZnO) is one of
the most extensively studied ones for the application in UV
photodetectors since 1980s.2 In the past decade, fabrication
techniques for precisely controlling the nanostructure as well
as engineering the native defects as n-type dopants have been
extensively studied,3–7 and several works for the ZnO
nanowire-based photodiodes have been reported.8–13 So far,
most of the works are based on the metal-semiconductor het-
erojunctions fabricated by dry process and limited number of
works are yet reported on the fabrication of nanowire p-n
junction photodetectors, especially by wet chemical methods.
While a variety of n-type TCO materials are available to
date, still relatively few number of p-type TCOs are avail-
able. Titania (TiO2) is a well-known UV active TCO which
normally shows n-type characteristics similar to ZnO.
However, by doping with refractory metals such as Fe,14
Mn,15 Cr,16 anatase TiO2 can be converted into a p-type
a)
Present address: HRL Laboratories, LLC, Malibu, California 90265, USA.
b)
E-mail: NAGAO.Tadaaki@nims.go.jp
TCO, and therefore, is considered as a promising candidate
to be combined with ZnO to form a UV active p-n junction.
In this Letter, we report on the fabrication of a core-
shell p-n heterojunction architecture that is composed of a
n-type ZnO nanowire array chemically laminated by an
ultrathin layer of p-type Cr-doped TiO2 shell. This core-shell
nanowire architecture realizes a remarkably enhanced heter-
ojunction area and can swiftly transport photoexcited carriers
across a nanometer-thick TiO2 lamination layer and
single-crystalline ZnO NWs. The p-type TiO2 was prepared
by a low-cost sol-gel process with small amount of Cr as
p-type dopant, which yielded complete coating of the ZnO
surface by single-step spin-coating with very small thickness
in the range of 5–10 nm. This TCO heterojunction operates
as an array of parallel diodes with large junction area and
shows excellent rectifying characteristics. This device exhib-
ited extremely high sensitivity in the UV region larger than
250 A/W and perfectly insensitive in the visible to infrared
regions (i.e., IR-VIS blind). Under UV illumination at
373 nm, it shows a switch current ratio of 140 at 5 V bias
and 104 lW incident power (shed onto the 0.1 cm2 device),
exhibiting a high potential for UV photodiode applications.
Figure 1(a) shows an SEM image of the ZnO NWs array
after the hydrothermal growth on indium tin oxide (ITO)
coated glass substrate. The ZnO NWs in the array are growing
nearly vertically on the ITO glass substrate with an average di-
ameter of 50 nm, average length of 1 lm, and wire density of
2  1010 cm 2. Following the synthesis of the ZnO NWs array,
Cr-doped TiO2 laminate was conformally coated onto the
NWs array to form a core-shell architecture. Figure 1(b) shows
the SEM image of the cross-section of the Cr-doped TiO2/ZnO
NWs p-n heterojunction array. It can be clearly seen that NWs
array is uniformly coated by a thin layer of TiO2. The structure
was further examined by TEM that evidences a uniform TiO2
shell layer with a thickness in the range of 5–10 nm (Fig. 1(c)).
Figure 1(d) presents a high-angle annular dark-field scanning
TEM image and energy dispersive x-ray spectroscopy (EDS)

0003-6951/2013/103(19)/193119/4/$30.00 103, 193119-1 C 2013 AIP Publishing LLC

V

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 193119-2 Dao et al.
elemental mapping of Zn, O, Ti, and Cr of a single nanowire
heterojunction. It is clearly seen that the shell layer of TiO2 is
well-formed on core ZnO NW with a uniform Cr doping and
smooth morphology.17
To examine the structural characteristics of the
Cr-doped TiO2 layer that used in our device, we analyzed
the Cr-doped TiO2 film on a Si substrate by X-ray diffraction
(XRD) and Fourier transform infrared spectroscopy (FTIR)
measurements. Figure 2(a) shows h-2h XRD patterns of a
FIG. 2. (a) XRD patterns of Cr-doped TiO2 film on Si substrate (red curve)
and Cr-doped TiO2/ZnO NWs on ITO-glass substrate (black curve). (b) The
FTIR spectra of pure TiO2 film (gray curve) and with Cr doping (red curve).
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Appl. Phys. Lett. 103, 193119 (2013)
FIG. 1. (a) Tilted-view SEM image of
ZnO NWs array and (b) Cross-
sectional SEM image of the Cr-doped
TiO2/ZnO NWs p-n heterojunction
nanowire array. (c) TEM image of
core-shell nanowire structure of
Cr-doped TiO2/ZnO NW. (d) High-
angle annular dark-field scanning TEM
image and EDX elemental mapping of
Zn, O, Ti, and Cr of a single Cr-doped
TiO2/ZnO NW.
planar Cr-doped TiO2 film (100 nm thick) formed on a Si
substrate (red curve) and the device made of Cr-doped
TiO2/ZnO NWs fabricated on an ITO substrate (black
curve). The XRD pattern of Cr-doped TiO2 film shows a
strong diffraction peak at 25.8 and a weak peak at 36.9 ,
indicating Cr-doped TiO2 crystallized into anatase phase
(JCPDS card No 84-1286). The black curve exhibits a dif-
fraction peak at 31 and 34 , indicating ZnO with hexagonal
Wurtzite structure (JCPDS card No 36-1451).
To inspect further the effect of Cr dopant on the TiO2
formation, the films were analyzed by FTIR spectroscopy
(Fig. 2(b)). The FTIR spectra of pure TiO2 film (gray curve)
and Cr-doped TiO2 (red curve) film were confirmed to be
identical showing two vibrational bands at around 262 cm 1
and 435 cm 1 originating from the transverse optical pho-
nons of anatase TiO2.18 This evidences that the Cr concentra-
tion (0.5%) chosen in the present work is below the critical
doping concentration for TiO2 for ensuring the formation of
anatase phase.19
The optical property of the core-shell structure was exam-
ined by measuring the device prior to the fabrication of Ag
back contact/reflector (Fig. 3). Figure 3(a) presents the photo-
luminescence (PL) spectra of the pure ZnO NWs (blue curve)
and core-shell NWs (red curve). In the case of pure ZnO
NWs, in addition to the band-edge emission at 384 nm, we
observed a broad visible emission around 550 nm mainly ori-
ginated from the surface oxygen vacancies5,6,20 known as
deep donors. However, the visible emission was significantly
reduced after the lamination by the TiO2 thin layer. This
reduction can be attributed to the transformation of the ZnO
deep levels into shallow donor levels by the thermal annealing
process21 during the TiO2 shell formation. This indicates that
the absorption in the visible (VIS) to near infrared (NIR)
region of ZnO in our device is efficiently suppressed12,22
which also prevents the unwanted photocurrent due to the
ZnO defects by the IR and VIS illumination.
Figure 3(b) shows the absorbance of the core-shell NWs
(red curve) together with that of pure ZnO NWs (blue curve).
A dramatic enhancement in the absorbance, a 30% enhance-
ment of absorption in the UV spectral region, is clearly
 193119-3 Dao et al.
FIG. 3. (a) Photoluminescence spectra of pristine ZnO NWs (blue curve)
and the ZnO NWs covered by the Cr-doped TiO2 laminate (red curve). (b)
Absorbance of the pristine ZnO wires and the wires after the TiO2 lamina-
tion measured in transmission geometry.
observed for core-shell NWs although the thickness of the
TiO2 shell layer is only around 10 nm, far smaller than the
wavelength of the incident light. This would indicate that ef-
ficient charge separation is realized owing to the formation
of p-n junctions. Although the band-gap of the pristine TiO2
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Appl. Phys. Lett. 103, 193119 (2013)
is 3.2 eV (387.5 nm), deep-level acceptors related to the Cr
doping and other defects in the disordered TiO2 shell layer
can induce the absorption in the lower energy region as well
as the slow response of the device (rising time in the
sub-second order). Slightly higher relative absorbance in the
high-energy portion of the VIS region than that of the pris-
tine ZnO NWs can then be attributed to the TiO2 shell layer.
The schematic illustration of the working device (at
reverse bias) is shown in Fig. 4(a). The p-n core-shell archi-
tecture is placed between an ITO glass and a Ag electrode,
while the ITO glass acts as transparent front contact and Ag
electrode as back contact and diffusive reflector in the UV
region. First, we measured the I-V characteristics of the de-
vice without the light illumination. In spite of the very small
thickness of the TiO2 shell layer and the rather complex
nanowire morphology of the current device, the stability of
this p-n heterojunction is remarkably high. It exhibits a very
small leakage current as well as surprisingly high breakdown
voltage (»15 V). For example, at the 5 V bias and without
light illumination, the rectification ratio (the ratio between
forward current and reverse current at the same bias voltage)
is 361, evidencing an ideal rectifying behavior of the device.
Next, the wavelength-dependent spectral response of the
device in UV, VIS, and IR region was studied separately by
illuminating the filtered light from the solar simulator. The
incident light was illuminated from the front side (glass side)
of the device.
Figure 4(b) shows I-V curves of the device under UV,
VIS, and IR illumination at the same integrated incident light
power of 104 lW. The inset presents the transmission char-
acteristics of the filters. It is clearly seen that the present de-
vice is nonresponsive in the IR region with wavelengths
above 650 nm. In the VIS region also, it is almost nonrespon-
sive, only giving little increase in the forward bias. This is
likely due to the reduction of deep levels of the ZnO
NWs12,21 and a weak response of deep acceptor/defect levels
FIG. 4. (a) Schematic illustration of
the fabricated p-n heterojunction de-
vice. (b) Spectral response of the de-
vice taken under the UV, VIS, and IR
illumination with the same power
(104 lW). The inset shows the trans-
mission characteristics of the filters
used in this measurement. (c) I-V
curves of p-n heterojunction under the
UV illumination at different values to
the incident power. (d) Rectification
ratio and reverse current of the device
taken as a function of illuminated UV
light power. The responsivity of the
device reads 250 A/W as determined
from the linear fit to the data from
10 to 70 lW.
 193119-4 Dao et al.
in the Cr-doped TiO2 layer23 as discussed and shown in
Fig. 3. In clear contrast to the VIS and the IR irradiations,
the I-V curves under the UV irradiation show pronounced
response, especially in the reverse bias. For example, at
5 V reverse bias, the current increases from 150 lA (in the
dark) to 21 mA; thus, the switch current ratio reads as high
as 140, exhibiting a high signal to noise ratio. This value can
be readily increased by increasing the TiO2 shell thickness
and reducing the dark current.
I-V characteristics of this p-n heterojunction were inves-
tigated more systematically under UV irradiation with vari-
ous incident powers ranging from 0 to 104 lW (Fig. 4(c)).
Majority of the induced photocurrent originates from the
electron-hole pairs generated in or near the depletion region,
and then they are separated into free electrons and holes by
the electrical field subsequently drifting to the electrodes. In
this sense, the small thickness of the TiO2 shell works rather
efficiently to transport the separated charges to the electro-
des. Because of this ultrathin nature of both the ZnO and
TiO2 materials, the generated diffusion current can be mini-
mized and the drift photocurrent reaches the electrodes
swiftly, which results in the operating reverse bias as small
as 0.5 V. At typical reverse bias of 5 V and 58 lW of
incident power, this device shows reverse current of 14 mA
and switch current ratio as high as 93. This value is more
than 3 times higher than the best data reported so far for the
ZnO NW-based p-n junction device.12
Figure 4(d) shows the dependence of rectification ratio
and reverse current of the p-n heterojunction on the UV light
power under an applied bias of 5 V. The rectification ratio
(black filled squares) decreases rapidly up to around 20 lW,
and then decreases slowly. This result evidences the efficient
generation of the photocurrent in the depletion region under
the UV illumination and shows good enough response of the
photodiode by using this reverse bias. The I-P characteristic
(blue filled cycle) of this device at the same reverse bias
shows that the reverse current I increases almost linearly
with the increase of the incident power P from 0 to 70 lW,
which features a useful linear response as an ideal photo-
diode. By evaluating the slope of this I-P characteristic in
this region, the responsivity of this device was found to be as
high as 250 A/W. This value should be improved to 325 A/W
if the UV light attenuation by the front glass window (30%)
is avoided by replacing to a UV-transparent window such as
sapphire, and even larger value is possible if the device
works at higher reverse bias.
By adopting a vacuum-free low-cost chemical fabrication
route, we fabricated an infrared/visible-blind high-sensitivity
UV photodetector composed of a p-n heterojunction core-
shell nanowire architecture using n-type ZnO and p-type TiO2
as two constituent TCO materials. The sol-gel fabrication
process of Cr-doped TiO2 shell layer yielded a high-quality
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Appl. Phys. Lett. 103, 193119 (2013)
conformal p-n heterojunction on a vertically grown ZnO
nanowire array, which renders efficient charge separaton and
carrier transfer. Surprisingly, in spite of its intricate 3D archi-
tecture with very small thickness of the TiO2 shell, the device
operates as a model p-n heterojunction with a linear response
and sensitivity larger than 250 A/W ( 5 V reverse bias, UV
illumination at 373 nm). The proposed combination of the
current fabrication methods with the core-shell device archi-
tecture would greatly widen the application of the two
commnly used TCOs—ZnO and TiO2—for optoelectronics as
well as for light harvesting nanomaterials for solar-hydrogen
generation.
This work was supported by a Grant-in-Aid for
Scientific Research (KAKENHI) from the Japan Society for
the Promotion of Science (JSPS) and World Premier
International Research Center Initiative on “Materials
Nanoarchitectonics” from MEXT (Japan). The early part of
the ZnO study was conducted in Harvard by TN.
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