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ZnO nanowire-embedded Schottky diode for effective UV detection by the barrier reduction

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2010 Nanotechnology 21 115205

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IOP PUBLISHING NANOTECHNOLOGY
Nanotechnology 21 (2010) 115205 (5pp) doi:10.1088/0957-4484/21/11/115205

ZnO nanowire-embedded Schottky diode


for effective UV detection by the barrier
reduction effect
Joondong Kim1,6 , Ju-Hyung Yun1 , Chang Hyun Kim1,2 ,
Yun Chang Park3 , Ju Yeon Woo1 , Jeunghee Park2 , Jung-Ho Lee4 ,
Junsin Yi5 and Chang-Soo Han1,6
1
Nano-Mechanical Systems Research Division, Korea Institute of Machinery and Materials
(KIMM), Daejeon 305343, Korea
2
Department of Chemistry, Korea University, Jochiwon 339700, Korea
3
Measurement and Analysis Division, National Nanofab Center (NNFC), Daejeon 305806,
Korea
4
Department of Materials and Chemical Engineering, Hanyang University, Ansan 426791,
Korea
5
School of Information and Communication Engineering, Sungkyunkwan University,
Suwon 440746, Korea

E-mail: joonkim@kimm.re.kr (Joondong Kim) and cshan@kimm.re.kr (Chang-Soo Han)

Received 14 January 2010, in final form 2 February 2010


Published 22 February 2010
Online at stacks.iop.org/Nano/21/115205

Abstract
A zinc oxide nanowire (ZnO NW)-embedded Schottky diode was fabricated for UV detection.
Two types of devices were prepared. The ZnO NW was positioned onto asymmetric metal
electrodes (Al and Pt) for a Schottky device or symmetric metal electrodes (Al and Al) for an
ohmic device, respectively. The Schottky device provided a rectifying current flow and was
more sensitive to UV illumination than the ohmic device. The Schottky barrier plays an
important role for UV detection by a UV-induced barrier reduction effect.
The fabrication of the ZnO NW-embedded Schottky diode and the UV reaction mechanism
are discussed in light of the UV light-induced Schottky barrier reduction effect.
(Some figures in this article are in colour only in the electronic version)

Nanomaterials, such as carbon nanotubes (CNTs) and oxide (ZnO) NW is currently considered to be a promising
nanowires (NWs), have emerged as potential one-dimensional metal oxide material for UV detectors and light-emitting
building blocks due to their unique features. Electric diodes [6–9]. Although the use of ZnO NWs has advantages, it
conductive NWs have been utilized as functional microscopy is difficult to achieve p-type conductivity, which is an obstacle
tips [1] and nanoscale interconnects [2, 3]. Recently, to applications in diodes.
researchers have attempted to address the substantial demand The Schottky barrier plays an important role in electronic
of nanomaterials for cost-effective solar cells [4]. applications, such as gas sensors [10], solar cells [11]
Photodetectors are among the most promising applications and nanogenerators [12]. Although many researchers
of semiconducting NWs. Dangling bonds on a NW easily have investigated the Schottky contact between CNTs and
trap holes, which induce a delay in recombination, thereby metal [13–15], few studies have been conducted on ZnO
causing an increase in the electron current. Furthermore, NW Schottky devices, and most used the same metal
wavelength-selective detection may be possible by combining electrodes [5, 16, 17]. With respect to device fabrication, it
different types of NWs [5]. Due to its direct and wide energy is necessary to verify the Schottky formation between the ZnO
bandgap (3.37 eV) and large surface-to-volume ratio, a zinc NW and the metal electrode for UV detection.
This study presents the systematic fabrication of a
6 Authors to whom any correspondence should be addressed.
ZnO NW-embedded Schottky diode using asymmetric metal

0957-4484/10/115205+05$30.00 1 © 2010 IOP Publishing Ltd Printed in the UK


Nanotechnology 21 (2010) 115205 J Kim et al

Figure 1. (a) A low-magnification TEM image. (b) A high-resolution TEM image. ZnO NW has a single-crystalline structure with a lattice
space of 0.258 nm. The inset is an FFT image. (c) Energy dispersive x-ray spectrum of ZnO NW.

Figure 2. (a) An SEM image of the ZnO NW connection between Pt and Al electrodes. (b) A schematic diagram of the ZnO NW-embedded
device. (c) The energy band diagram of ZnO and Pt. The high work function Pt metal forms a potential barrier for electrons. (d) The energy
band diagram of ZnO and Al. The low work function Al metal forms an ohmic contact.

electrodes. It was found that the Schottky device provides (RTP-3000, SNTEK, Korea) was subsequently performed for
higher UV responsivity than an ohmic device due to the 2 min under a nitrogen atmosphere at 500 ◦ C to improve the
existence of a potential barrier between the metal and the adhesion between the NW and the metal electrode contacts.
semiconductor. The fabrication of the ZnO NW-embedded Field emission transmission electron microscopy (FEI
Schottky diode and the UV reaction mechanism are discussed Tecnai F30 Super-Twin) was used to investigate the ZnO
in light of the UV light-induced barrier reduction effect. NW. Selected-area electron diffraction and fast Fourier
For ZnO NW growth, Au catalytic nanoparticles transformations (FFTs, GATAN) revealed a crystalline
(HAuCl4 · 3H2 O, Sigma) were deposited on an Si substrate. A structure and the growth direction of the ZnO NW. Energy
powder-type Zn source (99.998%, Aldrich) was placed inside dispersive x-ray spectroscopy (EDAX Genesis) was used to
a quartz tube reactor. The growth temperature was controlled investigate the NW composition. The ZnO NW was placed
to be 500 ◦ C under an Ar gas atmosphere. on a carbon-coated copper mesh grid for TEM and EDS
An ultrasonication process was performed for 30 min to analyses. The NW position on the metal electrodes was
detach the NWs from the substrate. They were then centrifuged observed via field emission scanning electron microscopy
at 5000 rpm for 100 min to remove residuals. The purified (FEI Sirion). The electrical characteristics of the ZnO NW-
ZnO NW solution was dropped onto metal electrodes under embedded devices were obtained using a probe station with an
ac bias. Two types of devices were prepared. The ZnO NW instrument (Keithley 2400).
was positioned onto asymmetric metal electrodes (Al and Pt) Figure 1(a) shows a low-magnification TEM image. A
for a Schottky device or symmetric metal electrodes (Al and high-resolution TEM (HRTEM) image of a ZnO NW projected
Al) for an ohmic device, respectively. Rapid thermal process in the [11̄0] zone axis is presented in figure 1(b). The space

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Nanotechnology 21 (2010) 115205 J Kim et al

Figure 2(c) is the energy band diagram of ZnO and Pt metal.


The Pt work function (pt = 5.3 eV) is higher than that of ZnO
(ZnO = 4.1 eV). When a contact is formed, electrons flow
from ZnO to Pt metal until the Fermi levels align, resulting in
band bending. In contrast, Al has a lower work function than
ZnO (Al = 4.06 eV < ZnO ), which has no barrier to the
electron flow and provides an ohmic contact, as depicted in
figure 2(d).
The Schottky device (Al–ZnO NW–Pt) clearly provided a
rectifying current flow, as shown in figure 3(a). Under forward
bias, the current flow is enhanced due to the reduction of
the potential barrier. In order to evaluate the performance of
the Schottky device comparatively, an ohmic device (Al–ZnO
NW–Al) was also investigated. The latter device showed a
linear current flow under both forward and reverse biases. This
implies that the design of metal contacts for ZnO NW is an
effective approach to form a Schottky diode, although some
reports presented Schottky formation by using homogeneous
metal contacts [5, 12, 18]. The semi-log plots are presented
in figure 3(b). While the ohmic device showed the symmetric
I –V characteristics, the Schottky device provided the diode
performance with a rectifying ratio of 371. Under thermionic
emission theory, the I –V characteristics are given by the
following relations:
J = Js (eqv/nkT − 1) or J = Js (eqv/nkT )
for V  kT /q (1)
 
∗∗ 2 qφB
Js = A T exp − (2)
kT
q ∂V q ∂V
n≡ = (3)
kT ∂(ln J ) kT 2.3 × ∂ log I
where Js , n , kT , A∗∗ and φB are the saturation current density,
ideality factor, thermal energy (eV), Richardson constant and
barrier height, respectively. The ideality factor of the ZnO NW
Figure 3. (a) I –V characteristics of a Schottky device (Pt–ZnO Schottky diode is given as 1.2, indicating a little problematic
NW–Al) and an ohmic device (Al–ZnO NW–Al). (b) Semi-log plots. recombination in the device [5, 19].
The ohmic device showed symmetric I –V characteristics. The
Schottky device provided a diode performance with a rectifying ratio
The barrier heights of metal–semiconductor systems are
of 371 and an ideality factor of 1.2. determined by both the metal work function and the surface
states. A general expression of the barrier height is given in
equation (2), where surface states are neglected:
between the adjacent planes was measured to be 0.258 nm,  
−kT J 1
corresponding to the (002) lattice plane of a hexagonal ZnO φB = ln qv/kT ∗∗ 2 . (4)
q e A T
structure [18]. The inset of the figure is an FFT image, which
confirms the single-crystalline structure. The growth direction In ZnO, the trapping mechanism governs the photocon-
is [001] perpendicular to the (001) basal plane of the hexagonal duction. The oxygen molecules are absorbed along the ZnO
system. The energy dispersive x-ray spectrum clearly shows NW surface and they capture electrons from the semiconduc-
Zn and O signals from the NW, as shown in figure 1(c). The tor [5]. Under UV illumination, the photon energy releases the
C Kα (0.28 keV) and Cu Kα (8.04 keV) peaks originate from trapped electrons and also generates photo-induced electrons,
the carbon-film-coated copper mesh TEM grid. causing an enhancement of the current.
A solution containing the prepared ZnO NWs (0.5 μl) The fabricated ZnO NW-embedded Schottky and ohmic
was dropped onto the patterned electrodes under an ac electric devices were investigated for UV responses. A relatively low
bias of 5 Vp−p at 1 MHz. Figure 2(a) shows the ZnO NW UV light (24 μW cm−2 , 254 nm) was illuminated onto the
connection between Pt and Al electrodes through a 700 nm devices. The responsivity ( R = IUV /Ii ) is defined as the ratio
space gap. A schematic view of the ZnO NW-embedded device of the UV illuminating current ( IUV ) versus the initial current
is presented in figure 2(b). ZnO has a work function () of ( Ii ).
4.3 eV and is known to be a natural n-type semiconductor due Figure 4(a) presents the Schottky device responses to UV
to the oxygen vacancy, which leads to a shallow donor level [6]. light with bias voltage modulation. Two different bias voltages

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Nanotechnology 21 (2010) 115205 J Kim et al

Responsivity

Figure 4. (a) UV responses of the Schottky device. The responsivity ( R = IUV /Ii ) was significantly affected by modulation of the bias
voltage. (b) I –V measurements of the Schottky device in the dark and under UV illumination. The turn-on voltage was lowered by UV
illumination. (c) UV responses of an ohmic device. The decay time, defined as 37% of the maximum photocurrent, was measured from (d) the
ohmic device at 1 V bias, (e) the Schottky device at 0.4 V, and (f) the Schottky device at 1.0 V.

of 0.4 and 1 V were applied to the Schottky device. While the is attributed to the reduction of the UV light-induced potential
Schottky device showed a low responsivity of approximately barrier, resulting in current enhancement at a fixed voltage
7 with a 1 V bias, a significantly improved responsivity of value.
nearly 200 was obtained with a 0.4 V bias, which is close The barrier height values were found to be 1.33 eV in the
to the diode turn-on voltage. Beyond a critical voltage, the dark condition, which is close to the difference between the
higher voltage bias reduces the potential barrier. This enhances Pt work function [21] of 5.3 eV and the electron affinity of
the electron flow, resulting in lower sensitivity to UV. This ZnO of ( X = 4.1 eV) [22]. The Richardson constant value
indicates that the potential barrier is an important factor in the was chosen as 32 A cm−1 K−2 . Under UV illumination, the
UV reaction mechanism. It should be noted that the applied Schottky barrier height was reduced to 1.037 eV. The barrier
voltage may greatly affect the UV detection performance in a reduction by UV illumination is thus obtained as 0.293 eV.
given device. To confirm the proposed mechanism of a UV light-
Figure 4(b) shows the I –V characteristics of the Schottky induced barrier reduction effect, the UV response of an ohmic
device measured both in the dark and under UV illumination. device was investigated as presented in figure 4(c).
There is no significant transition from Schottky to ohmic- As there is no barrier between the metal and semiconduc-
like characteristics [12, 19, 20]. In the dark, the reference tor, the electrons freely move to the metal, even without UV
turn-on current (20 nA) was reached at 0.467 V. Under UV illumination. This leads to a reduced UV response from the
illumination, the turn-on voltage was reduced to 0.176 V. This ohmic device.

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Nanotechnology 21 (2010) 115205 J Kim et al

The UV response times of the ZnO NW devices were also [2] Kim J and Anderson W A 2006 Nano Lett. 6 1356
obtained. The decay time, which is defined as the time to reach [3] Kim J, Park Y C, Shin D H, Lee E-S and Han C-S 2007 Appl.
37% of the maximum photocurrent [17, 23], was measured Phys. Lett. 90 253103
from the ohmic device at 1 V bias, the Schottky device at 0.4 V [4] Tian B, Zheng X, Kempa T J, Fang Y, Yu N, Yu G,
and the Schottky device at 1.0 V. These results are presented in Huang J and Lieber C M 2007 Nature 449 885
[5] Soci C, Zhang A, Xiang B, Dayeh S A, Aplin D P R, Park J,
figures 4(d), (e), and (f), respectively.
Bao X Y, Lo Y H and Wang D 2007 Nano Lett. 7 1003
The ohmic device required a relatively long decay time of
[6] Lu J G, Chang P and Fan Z 2006 Mater. Sci. Eng. R 52 49
19.886 s. The Schottky device (operating at 0.4 V) meanwhile [7] Law J B K and Thong J T L 2006 Appl. Phys. Lett. 88 133114
provided a significant decrease of the decay time of 0.58 s, [8] Lin D, Wu H, Zhang W, Li H and Pan W 2009 Appl. Phys. Lett.
indicating that the existence of the Schottky barrier is important 94 172103
for effective UV detection. With a bias of 1 V, the decay time of [9] Chosh R, Dutta M and Basak D 2007 Appl. Phys. Lett.
the Schottky device increased to be 16.435 s. This is attributed 91 073108
to the decrease of the potential barrier due to the high bias [10] Salehi A and Kalantari D J 2007 Sensors Actuators B 122 69
voltage, resulting in an insensitive reaction. [11] Kim J, Han C-S, Park Y C and Anderson W A 2008 Appl.
In conclusion, we have fabricated a ZnO NW-embedded Phys. Lett. 92 043501
Schottky device for UV detection. The potential barrier [12] Liu J, Fei P, Song J, Wang X, Lao C, Tummala R and
Wang Z L 2008 Nano Lett. 8 328
between the metal and semiconductor plays an important role
[13] Manohar H M, Wong E W, Schlecht E, Hunt B D and
in the UV responses. Due to the effect of reducing the UV Siegel P H 2005 Nano Lett. 5 1469
light-induced barrier, the bias voltage significantly affects the [14] Lu C, An L, Fu Q, Liu J, Zhang H and Murduck J 2006 Appl.
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[16] Kind H, Yan H, Messer B, Law M and Yang P 2002 Adv. Mater.
Acknowledgments 14 158
[17] Zhou J, Gu Y, Hu Y, Mai W, Yeh P, Bao G, Sood A K,
The authors acknowledge the financial support from the Center Polla D and Wang Z L 2009 Appl. Phys. Lett. 94 191103
for Nanoscale Mechatronics and Manufacturing (CNMM) of [18] JCPSD International Center for Diffraction Data 2001 JCPDS
the 21C Frontier Research Program and the National Research File No. 79-0205
Foundation (NRF, 2009-0082018 and 2009-0082527) of the [19] Heo Y W, Tien L C, Norton D P, Pearton S J, Kang B S,
Ministry of Education, Science and Technology (MEST) in Ren F and LaRoche J R 2004 Appl. Phys. Lett. 85 3107
Korea. J Park thanks the WCU (World Class University) [20] Keem K, Kim H, Kim G-T, Lee J S, Min B, Cho K,
program (R31-10035) for their support. Sung M-Y and Kim S 2004 Appl. Phys. Lett. 84 4376
[21] Graaf H, Maedler C, Kehr M and Oekermann T 2009 J. Phys.
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