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


V
223114-2 Fu et al. 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
FIG. 1. (Steps 1-5) Schematic diagrams of the processes to fabricate the gra- n-type doped by the ZnO NW while the top one is p-type
phene/ZnO NW/graphene vertical sandwich device. (Step 6) Schematic dia- due to the PMMA.
gram of the cross-section of the graphene/ZnO NW/graphene based Figure 3(a) shows the typical I-V characteristic of the
sandwich structure UV detector.
graphene/ZnO NW/graphene device in dark and in air. Dur-
ing the measurement, B1 electrode was forward biased and
structure is shown in Fig. 1 (panel 6). In our vertical sand- A1 electrode was grounded. The nonlinear I-V curve may
wich structure, Schottky contacts were expected to form at indicate that Schottky barriers exist at the interfaces between
the interfaces between ZnO NW and the top and bottom gra- the ZnO NW and graphene. The asymmetric I-V curve may
phene layers.11,12 also suggests that the Schottky barriers at the interfaces of
Figure 2(a) shows a typical scanning electron micro- the bottom layer graphene/ZnO NW and the top layer gra-
scope (SEM) image of the graphene/ZnO NW/graphene de- phene/ZnO NW are asymmetric, which is attributed to the
vice. The Raman spectra collected at two different positions different contact areas and doping levels of the bottom and
(with (P1) and without (P2) graphene as denoted in Fig. 2(a)) top graphene sheets. The electrical circuit of the device can
are shown in Fig. 2(b). The Raman spectrum from P1 posi-

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-
FIG. 2. (a) SEM image of graphene/ZnO NW/graphene sandwich structure. tics of the graphene/ZnO NW/graphene UV detector (electrodes B1 and A1)
(b) Raman spectra collected at two different positions of P1 and P2 denoted under illumination of a 325 nm He-Cd laser with incident power densities
in the Fig. 2(a) where there is a graphene sheet (P1) and the graphene is ranging from 0 to 100 lW lm2. Inset: the relationship between photocur-
etched by O2 plasma (P2), respectively. Source-drain current of (c) the bot- rent sensitivity and the UV illumination power. (c) Time dependence of the
tom layer graphene (A1 and A2 electrodes) and of (d) the top layer graphene photocurrent with switching on/off the 325 nm UV laser illumination. The
(B1 and B2 electrodes) as a function of the back-gate voltage applied on the bias applied on the electrodes between B1 and A1 is 2 V. (d) Magnification
Si substrate. of the detailed behavior of the photocurrent decay.
223114-3 Fu et al. Appl. Phys. Lett. 100, 223114 (2012)

be considered as an individual ZnO NW contacted with two The Schottky barriers should also be very sensitive to
asymmetric back-to-back Schottky diodes on the bottom and O2 gas. Therefore, to further confirm the existence of
top surface, as shown in the equivalent circuit in the insert of Schottky barriers in our devices, the I-V curves of another
Fig. 3(a). Under forward bias, the current (I) passing through similar graphene/ZnO nanowire/graphene device were meas-
the Schottky barrier is determined by the thermionic emis- ured at different vacuum status, as shown in Fig. 4. The de-
sion of electrons, which can be described as 17 vice displayed a much enhanced conductance in vacuum,
    which is ascribed to the fact that the Schottky barriers are
qV
I ¼ ISAT exp 1 ; (1) very sensitive to O2 gas. As the device was back to air again,
gkT for the reverse bias the conductance completely returned to
  its original state because of the fast recovery of the Schottky
q/
ISAT ¼ AA T 2 exp  SB ; (2) barrier, however, for the forward bias the conductance was
gkT
still higher than its original state. For the forward bias, the
where ISAT is the saturation current, q is the electron charge, device conductance is influenced by both the Schottky bar-
g is the ideality factor, T is the absolute temperature, k is the rier and the series resistance of ZnO nanowire, and the
Boltzmann constant, /SB is the Schottky barrier height, A is observed non-recovered conductance is due to the slow re-
the interface area of the Schottky barrier, and A* is the covery of the ZnO nanowire itself.
Richardson constant, which is 32 A cm2 K2 for ZnO.18 For the existence of the Schottky barrier between gra-
One can see from Eqs. (1) and (2) that the current is very phene and ZnO NW, the mechanisms of the photocurrent
sensitive to the height and width of the Schottky barriers. generation and recovery process are different from that of
The I-V curves of the graphene/ZnO NW/graphene de- the conventional ZnO NW UV detectors with Ohmic contact.
vice in air conditions and under UV laser illumination with In our case, the photocurrent is mainly contributed from two
different power densities are presented in Fig. 3(b). It is clear factors: the ZnO NW itself and the Schottky barriers at the
that the current increases remarkably under UV illumination interfaces between graphene and ZnO NW.21,22 The sche-
and the slop of the I-V curve increases with increasing the matic energy band structure of the graphene/ZnO NW/gra-
laser power. We define the photocurrent on-off ratio as phene device in dark is shown in Fig. 5(a). When switching
Iph =Idark , where Iph ¼ Ilight  Idark and Ilight and Idark are the on the UV illumination on the device, electron-hole pairs are
current when the UV illumination is switched on and off, generated [hv ! e1 þ hþ ] and can be separated quickly by
respectively. We find that, at a forward bias of 3 V, the pho- the local electric field at the Schottky barrier region, which
tocurrent on-off ratio first increases exponentially with would reduce the electron-hole recombination rates and
increasing the laser power and then riches a saturation value increase the carrier lifetime, resulting in an increase in the
of about 8  102 when the laser power density is upon free carrier density. The increased carrier density in ZnO lifts
50 lW/lm2, as shown in the insert of Fig. 3(b). Another key the Fermi energy and thus reduces the work function of ZnO,
parameter to evaluate the sensitivity of the UV detector is resulting in the reduction of the Schottky barrier height and
the photoconductive gain (G), which is defined as the width between ZnO and graphene, as shown in Fig. 5(b).
number of electrons collected by electrodes due to the exci- Both of these account for the high photocurrent on-off ratio
tation by one incident photon. One can express G as and rapid rising speed of the graphene/ZnO NW/graphene
G¼ ðIph =Popt Þðhv=qÞ, where Popt is the effective light power based UV detectors.5,18 Once the UV illumination is turned
absorbed in the interface of the Schottky barrier region, hv is off, as shown in Fig. 5(c), electron-hole pairs will quickly
the energy of the incident photon, and q is the electron recombine in the ZnO NW and the Schottky barrier is recov-
charge. Considering the diameter of the UV laser spot ered, which may explain the fast recovery speed in our UV
(2 lm) and the diameter the ZnO NW (nm), the photo- photodetector. Because the ZnO nanowire is not completely
conductive gain of the UV detector was calculated to be packaged by the graphene, the re-adsorption process of oxy-
1.6 at the bias of 3 V and under a UV laser power of gen is also happened on the side face of the ZnO NW, which
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 FIG. 4. I-V curves of the graphene/ZnO NW/graphene device under differ-
contact is from several seconds to several minutes.19,20 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).

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