APPLIED PHYSICS LETTERS 100, 223114 (2012)

Graphene/ZnO nanowire/graphene vertical structure based fast-response

ultraviolet photodetector
Xue-Wen Fu,1 Zhi-Min Liao,1,a) Yang-Bo Zhou,1 Han-Chun Wu,2 Ya-Qing Bie,1 Jun Xu,1
and Da-Peng Yu1,a)
1
State Key Laboratory for Mesoscopic Physics, Department of Physics, Peking University, Beijing 100871,
People’s Republic of China
2
CRANN and School of Physics, Trinity College Dublin, Dublin 2, Ireland

(Received 17 January 2012; accepted 17 May 2012; published online 1 June 2012)
We report the high performance vertical ultraviolet (UV) photodetectors based on single ZnO
nanowire (NW) sandwiched between two graphene sheets. The photocurrent on-off ratio, rising
time, and recovery speed of our UV detectors are 8  102, 0.7 s, and 0.5 s, respectively, which are
significantly improved compared to the conventional ZnO NWs photodetectors. The improved
performance is attributed to the existence of Schottky barriers between ZnO NW and graphene
electrodes. The graphene/ZnO NW/graphene vertical sandwiched structures may be promising
C 2012 American Institute of Physics.
candidates for integrated optoelectronic sensor devices. V
[http://dx.doi.org/10.1063/1.4724208]

ZnO, as a wide direct band gap (3.37 eV) compound
semiconductor with large exciton binding energy (60 meV),
has been widely investigated for its potential applications in
optoelectronic devices, gas and chemical sensors.1,2 Due to
large surface-to-volume ratio, ZnO nanowires (NWs) exhibit
highly susceptible photoelectric properties by means of
electron-hole generation or recombination during ultraviolet
(UV) illumination. Therefore, ZnO NWs have great potential
in high sensitivity and fast-response UV sensors,3 environ-
mental monitors, and optical communications.4 Recently, Hu
et al.5 reported ZnO NW based UV sensors using Schottky
contact formed between ZnO and Pt electrode and the device
performance such as the sensitive and UV response, is much
higher than that of the traditional ZnO NW photoconductiv-
ity based UV sensors. The UV detectors based on Schottky
barriers formed between ZnO NW and other metal electro-
des, such as gold electrodes, have also been studied.6,7
Nevertheless, metal electrodes are poor in transparency and
can dramatically influence the absorption efficiency of the
UV sensors. Graphene, a monolayer sp2 carbon atoms with
unique physical properties, such as high mobility and con-
ductivity,8 high optical transparency9 and mechanical flexi-
bility,10 etc., has attracted great research interest recently.
The high conductive and optical transparent properties make
graphene an ideal candidate for the application in transparent
electrode. The Schottky barrier is also expected to be existed
at the interface between ZnO nanowire and graphene, and it
has been utilized for light-emitting diodes11 and transparent
nanogenerators.12 In this letter, we have fabricated a vertical
sandwich structure of graphene/ZnO NW/graphene. We
demonstrate the high performance of our ZnO NW based
vertical UV photodetector due to the existence of Schottky
barriers between graphene electrodes and ZnO NW. The cur-
rent on-off ratio of the UV detector is up to 8  102 at a illu-
mination power density of 50 lw/lm2, the photocurrent
a)
Authors to whom correspondence should be addressed. Electronic
addresses: liaozm@pku.edu.cn and yudp@pku.edu.cn.
rising time is shorter than 0.7 s, and the recovery time is only
about 0.5 s, respectively. Taking advantages of both gra-
phene and ZnO NWs, the graphene/ZnO NW/graphene
based vertical sandwich structure may be a promising candi-
date for integrated optoelectronic devices.
The ZnO NWs were synthesized via a chemical vapor
deposition (CVD) technique,13 which grow along the [0001]
zone axis with a hexagonal cross-section. The high quality
uniform monolayer graphene with large area was grown on a
25 lm thick copper foil (Alfa Aesar) by a CVD method.14,15
The Raman spectra of the graphene were measured by a
Renishaw inVia micro Raman system with a excitation
wavelength of 514 nm. The UV response of our devices was
characterized by a 325 nm He-Cd laser with a maximum
power density of 100 lW/lm2 and a Keithley 4200 electric
measurement system in air conditions.
The sandwich structure of graphene/ZnO NW/graphene
is fabricated via the following processes as presented in
Fig. 1. Micromanipulation was used to transfer a poly
(methyl methacrylate) (PMMA)/graphene microstamp
(70  20 lm2) to contact with two prefabricated transverse
Au electrodes (A1 and A2 with a 60 nm thick Au) on a Si
substrate covered with a 300 nm SiO2 layer. Details of the
microstamp method are given elsewhere.15 After dissolving
the PMMA film by acetone, an individual ZnO NW (diame-
ter 300 nm and length 30 lm) was transferred onto the
graphene sheet without contacting with A1 or A2 electrodes,
as shown in Fig. 1 (steps 1-2). To further pattern the bottom
graphene electrode, the sample has been spin coated with a
PMMA film and exposed to open a window with specific
size on the middle of graphene/ZnO NW. After being etched
by O2 plasma, a graphene nanoribbon was formed under the
ZnO NW. Finally, after dissolving the spin coated PMMA
film, another PMMA/graphene microstamp (70  12 lm2)
was transferred on the top of the ZnO NW to contact with
the rest two longitudinal electrodes (B1 and B2). These pro-
cedures are shown in Fig. 1 (steps 3-5). The schematic of the
cross-section of the final graphene/ZnO NW/graphene

0003-6951/2012/100(22)/223114/4/$30.00 100, 223114-1 C 2012 American Institute of Physics

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223114-2 Fu et al.
FIG. 1. (Steps 1-5) Schematic diagrams of the processes to fabricate the gra-
phene/ZnO NW/graphene vertical sandwich device. (Step 6) Schematic dia-
gram of the cross-section of the graphene/ZnO NW/graphene based
sandwich structure UV detector.
structure is shown in Fig. 1 (panel 6). In our vertical sand-
wich structure, Schottky contacts were expected to form at
the interfaces between ZnO NW and the top and bottom gra-
phene layers.11,12
Figure 2(a) shows a typical scanning electron micro-
scope (SEM) image of the graphene/ZnO NW/graphene de-
vice. The Raman spectra collected at two different positions
(with (P1) and without (P2) graphene as denoted in Fig. 2(a))
are shown in Fig. 2(b). The Raman spectrum from P1 posi-
FIG. 2. (a) SEM image of graphene/ZnO NW/graphene sandwich structure.
(b) Raman spectra collected at two different positions of P1 and P2 denoted
in the Fig. 2(a) where there is a graphene sheet (P1) and the graphene is
etched by O2 plasma (P2), respectively. Source-drain current of (c) the bot-
tom layer graphene (A1 and A2 electrodes) and of (d) the top layer graphene
(B1 and B2 electrodes) as a function of the back-gate voltage applied on the
Si substrate.
Appl. Phys. Lett. 100, 223114 (2012)
tion where there is graphene sheet shows a strong 2D peak
(2687.5 cm1) and a strong G peak (1589.2 cm1), as
well as a weak D peak (1346.5 cm1). The Raman intensity
ratio of the 2D to G mode is 2 and the full widths at half
maximum of the 2D mode and G mode are 30 cm1 and
17 cm1, respectively, indicating the graphene is in single
layer nature and is of high quality.16 The Raman spectrum
from P2 position shows no peaks of 2D mode or G mode,
indicating that the graphene at this position has been etched
away completely. For this device, Au electrodes and gra-
phene form good Ohmic contacts, which were confirmed by
the linear current-voltage (I-V) curves. Figures 2(c) and 2(d)
are the source-drain current (Isd) of the bottom and top layer
graphene as a function of the back gate voltage (Vg) applied
on the Si substrate, respectively. The applied source-drain
voltages (Vsd) dropped on the electrodes A1-A2 and B1-B2
are 0.1 V and 0.05 V for the bottom and top layer graphene,
respectively. The Dirac point for the bottom graphene layer
is located in the negative gate voltage region, while it is
located in the positive gate voltage region for the top gra-
phene layer, which may indicate that the bottom graphene is
n-type doped by the ZnO NW while the top one is p-type
due to the PMMA.
Figure 3(a) shows the typical I-V characteristic of the
graphene/ZnO NW/graphene device in dark and in air. Dur-
ing the measurement, B1 electrode was forward biased and
A1 electrode was grounded. The nonlinear I-V curve may
indicate that Schottky barriers exist at the interfaces between
the ZnO NW and graphene. The asymmetric I-V curve may
also suggests that the Schottky barriers at the interfaces of
the bottom layer graphene/ZnO NW and the top layer gra-
phene/ZnO NW are asymmetric, which is attributed to the
different contact areas and doping levels of the bottom and
top graphene sheets. The electrical circuit of the device can
FIG. 3. (a) I-V characteristic of the graphene/ZnO NW/graphene device in
dark. Inset: the equivalent electric circuit of the device. (b) I-V characteris-
tics of the graphene/ZnO NW/graphene UV detector (electrodes B1 and A1)
under illumination of a 325 nm He-Cd laser with incident power densities
ranging from 0 to 100 lW lm2. Inset: the relationship between photocur-
rent sensitivity and the UV illumination power. (c) Time dependence of the
photocurrent with switching on/off the 325 nm UV laser illumination. The
bias applied on the electrodes between B1 and A1 is 2 V. (d) Magnification
of the detailed behavior of the photocurrent decay.
223114-3 Fu et al.
be considered as an individual ZnO NW contacted with two
asymmetric back-to-back Schottky diodes on the bottom and
top surface, as shown in the equivalent circuit in the insert of
Fig. 3(a). Under forward bias, the current (I) passing through
the Schottky barrier is determined by the thermionic emis-
sion of electrons, which can be described as 17
   
qV
I ¼ ISAT exp 1 ; (1)
gkT
 
q/
ISAT ¼ AA T 2 exp  SB ; (2)
gkT
where ISAT is the saturation current, q is the electron charge,
g is the ideality factor, T is the absolute temperature, k is the
Boltzmann constant, /SB is the Schottky barrier height, A is
the interface area of the Schottky barrier, and A* is the
Richardson constant, which is 32 A cm2 K2 for ZnO.18
One can see from Eqs. (1) and (2) that the current is very
sensitive to the height and width of the Schottky barriers.
The I-V curves of the graphene/ZnO NW/graphene de-
vice in air conditions and under UV laser illumination with
different power densities are presented in Fig. 3(b). It is clear
that the current increases remarkably under UV illumination
and the slop of the I-V curve increases with increasing the
laser power. We define the photocurrent on-off ratio as
Iph =Idark , where Iph ¼ Ilight  Idark and Ilight and Idark are the
current when the UV illumination is switched on and off,
respectively. We find that, at a forward bias of 3 V, the pho-
tocurrent on-off ratio first increases exponentially with
increasing the laser power and then riches a saturation value
of about 8  102 when the laser power density is upon
50 lW/lm2, as shown in the insert of Fig. 3(b). Another key
parameter to evaluate the sensitivity of the UV detector is
the photoconductive gain (G), which is defined as the
number of electrons collected by electrodes due to the exci-
tation by one incident photon. One can express G as
G¼ ðIph =Popt Þðhv=qÞ, where Popt is the effective light power
absorbed in the interface of the Schottky barrier region, hv is
the energy of the incident photon, and q is the electron
charge. Considering the diameter of the UV laser spot
(2 lm) and the diameter the ZnO NW (nm), the photo-
conductive gain of the UV detector was calculated to be
1.6 at the bias of 3 V and under a UV laser power of
50 lW/lm2. Figure 3(c) presents the time dependent photo-
current of the graphene/ZnO NW/graphene UV detector peri-
odically illuminated by a 325 nm UV laser with a power
density of 100 lW/lm2 and at a bias of 2 V. The current
increases from 0.05 lA to 6.06 lA within 0.7 s. Once the illu-
mination of the UV laser was switched off, the photocurrent
decreased following a fast recovery process first and then a
second slow recovery process. The magnification of the pho-
tocurrent recovery process is shown in Fig. 3(d). The decay
time of the current follows a second-order exponential decay
function. By fitting the experimental result, as shown in Fig.
3(d), the recovery time s1  0.5 s of the fast recovery process
is estimated as the current is reduced to 1/e (37%) times. The
current then slowly returns to the initial value within about
70 s. It is noting that the recovery speed of the previous
reported conventional ZnO NW UV detectors with Ohmic
contact is from several seconds to several minutes.19,20
Appl. Phys. Lett. 100, 223114 (2012)
The Schottky barriers should also be very sensitive to
O2 gas. Therefore, to further confirm the existence of
Schottky barriers in our devices, the I-V curves of another
similar graphene/ZnO nanowire/graphene device were meas-
ured at different vacuum status, as shown in Fig. 4. The de-
vice displayed a much enhanced conductance in vacuum,
which is ascribed to the fact that the Schottky barriers are
very sensitive to O2 gas. As the device was back to air again,
for the reverse bias the conductance completely returned to
its original state because of the fast recovery of the Schottky
barrier, however, for the forward bias the conductance was
still higher than its original state. For the forward bias, the
device conductance is influenced by both the Schottky bar-
rier and the series resistance of ZnO nanowire, and the
observed non-recovered conductance is due to the slow re-
covery of the ZnO nanowire itself.
For the existence of the Schottky barrier between gra-
phene and ZnO NW, the mechanisms of the photocurrent
generation and recovery process are different from that of
the conventional ZnO NW UV detectors with Ohmic contact.
In our case, the photocurrent is mainly contributed from two
factors: the ZnO NW itself and the Schottky barriers at the
interfaces between graphene and ZnO NW.21,22 The sche-
matic energy band structure of the graphene/ZnO NW/gra-
phene device in dark is shown in Fig. 5(a). When switching
on the UV illumination on the device, electron-hole pairs are
generated [hv ! e1 þ hþ ] and can be separated quickly by
the local electric field at the Schottky barrier region, which
would reduce the electron-hole recombination rates and
increase the carrier lifetime, resulting in an increase in the
free carrier density. The increased carrier density in ZnO lifts
the Fermi energy and thus reduces the work function of ZnO,
resulting in the reduction of the Schottky barrier height and
width between ZnO and graphene, as shown in Fig. 5(b).
Both of these account for the high photocurrent on-off ratio
and rapid rising speed of the graphene/ZnO NW/graphene
based UV detectors.5,18 Once the UV illumination is turned
off, as shown in Fig. 5(c), electron-hole pairs will quickly
recombine in the ZnO NW and the Schottky barrier is recov-
ered, which may explain the fast recovery speed in our UV
photodetector. Because the ZnO nanowire is not completely
packaged by the graphene, the re-adsorption process of oxy-
gen is also happened on the side face of the ZnO NW, which
FIG. 4. I-V curves of the graphene/ZnO NW/graphene device under differ-
ent vacuum status.
223114-4 Fu et al. Appl. Phys. Lett. 100, 223114 (2012)

ZnO NW/graphene based UV detectors could have larger

light absorption efficiency and effectual interface area than
other ZnO NWs based Schottky barrier UV detectors utiliz-
ing metal electrodes. Our proposed vertical sandwiched
structures may be promising candidates for integrated optoe-
lectronic sensor devices.
This work was supported by MOST (Nos. 2012CB933401
and 2009CB623703) and the Sino Swiss Science and Technol-
ogy Cooperation Program (2010DFA01810).

1
N. S. Ramgir, Y. Yang, and M. Zacharias, Small 6, 1705 (2010).
2
F. Fang, J. Futter, A. Markwitz, and J. Kennedy, Nanotechnology 20,
245502 (2009); S. J. Chang, T. J. Hsueh, C. L. Hsu, Y. R. Lin, I. Chen,
and B. R. Huang, Nanotechnology 19, 095505 (2008).
3
C. Soci, A. Zhang, B. Xiang, S. A. Dayeh, D. P. R. Aplin, J. Park, X. Y.
Bao, Y. H. Lo, and D. Wang, Nano Lett. 7, 1003 (2007).
4
E. Monroy, F. Omnes, and F. Calle, Semicond. Sci. Technol. 18, R33 (2003).
5
Y. Hu, J. Zhou, P. H. Yeh, Z. Li, T. Y. Wei, and Z. L. Wang, Adv. Mater.
22, 3327 (2010).
6
J. Zhou, Y. Gu, Y. Hu, W. Mai, P. H. Yeh, G. Bao, A. K. Sood, D. L.
Polla, and Z. L. Wang, Appl. Phys. Lett. 94, 191103 (2009).
7
G. Cheng, X. Wu, B. Liu, B. Li, X. Zhang, and Z. Du, Appl. Phys. Lett.
99, 203105 (2011).
8
K. I. Bolotin, K. J. Sikes, Z. Jiang, M. Klima, G. Fudenberg, J. Hone, P.
Kim, and H. L. Stormer, Solid State Commun. 146, 351 (2008).
9
FIG. 5. Schematic illustration of the energy band diagram of the graphene/ X. Li, Y. Zhu, W. Cai, M. Borysiak, B. Han, D. Chen, R. D. Piner, L.
ZnO NW/graphene sandwich structure under different illumination condi- Colombo, and R. S. Ruoff, Nano Lett. 9, 4359 (2009).
10
tions of (a) in dark, (b) under UV laser illumination, and (c) after UV laser is C. Lee, X. Wei, J. W. Kysar, and J. Hone, Science 321, 385 (2008).
11
turned off. Y. Ye, L. Gan, L. Dai, H. Meng, F. Wei, Y. Dai, Z. Shi, B. Yu, X. Guo,
and G. Qin, J. Mater. Chem. 21, 11760 (2011).
12
may account for the following slow photocurrent recovery D. Choi, M.-Y. Choi, W. M. Choi, H.-J. Shin, J.-S. Seo, J. Park, S.-M.
process in our UV device. It is worthy to note that, due to the Yoon, S. J. Chae, Y. H. Lee, S.-W. Kim, J.-Y. Choi, S. Y. Lee, and J. M.
Kim, Adv. Mater. 22, 2187 (2010).
excellent transparent property of graphene and PMMA, the 13
Y. Q. Bie, Z. M. Liao, H. J. Xu, X. Z. Zhang, X. D. Shan, and D. P. Yu,
graphene/ZnO NW/graphene based vertical sandwich struc- Appl. Phys. A 98, 491 (2010).
14
ture should have larger light absorption efficiency and effec- X. W. Fu, Z. M. Liao, J. X. Zhou, Y. B. Zhou, H. C. Wu, R. Zhang, G.
tual interface area than other ZnO NW based UV detectors Jing, J. Xu, X. Wu, W. Guo, and D. P. Yu, Appl. Phys. Lett. 99, 213107
(2011).
utilizing metal electrodes. These merits make the graphene/ 15
Y. Q. Bie, Y. B. Zhou, Z. M. Liao, K. Yan, S. Liu, Q. Zhao, S. Kumar, H.
ZnO NW/graphene based vertical sandwich structure has C. Wu, G. S. Duesberg, G. L. W. Cross, J. Xu, H. Peng, Z. Liu, and D. Yu,
potential applications in the large-scale integration UV nano- Adv. Mater. 23, 3938 (2011).
16
T. Yu, Z. Ni, C. Du, Y. You, Y. Wang, and Z. Shen, J. Phys. Chem. C
detectors.
112, 12602 (2008).
In summary, we have constructed vertical sandwich 17
B. L. Sharma, Metal-Semiconductor Schottky Barrier Junctions and Their
structure UV photodetector by graphene and an individual Applications (Plenum, New York, 1984).
18
ZnO NW. The photocurrent on-off ratio of the UV detector K. U. Hasan, N. H. Alvi, J. Lu, O. Nur, and M. Willander, Nanoscale Res.
Lett. 6, 348 (2011).
is up to 8  102 at the bias of 3 V. Under air conditions, the 19
D. Lin, H. Wu, W. Zhang, H. Li, and W. Pan, Appl. Phys. Lett. 94,
photocurrent rising time is shorter than 0.7 s and the recovery 172103 (2009).
20
speed is about 0.5 s. Due to the existence of Schottky barrier Z. M. Liao, Y. Lu, H. C. Wu, Y. Q. Bie, Y. B. Zhou, and D. P. Yu, Nano-
between graphene and ZnO NW, the photoresponse perform- technology 22, 375201 (2011).
21
K. Liu, M. Sakurai, M. Liao, and M. Aono, J. Phys. Chem. C 114, 19835
ance is much higher than that of the traditional ZnO NW (2010).
photoconductivity based UV detectors. Besides that, due to 22
Z. M. Liao, K. J. Liu, J. M. Zhang, J. Xu, and D. P. Yu, Phys. Lett. A 367,
the excellent transparent property of graphene, the graphene/ 207 (2007).