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10.1039/C7NR05143C.

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Decoration of reduced graphene oxide by gold nanoparticles: an

Published on 04 September 2017. Downloaded by Fudan University on 06/09/2017 14:37:42.

enhanced negative photoconductivity

Received 00th January 20xx,
Accepted 00th January 20xx Qi Wang,b Yudi Tu,a Takashi Ichii,a Toru Utsunomiya,a Hiroyuki Sugimura,*a Lifeng Hao,*b
Rongguo Wangb and Xiaodong Heb

Nanoscale Accepted Manuscript

DOI: 10.1039/x0xx00000x
Photodetection in a visible light region is important in various applications, including computation, environment
www.rsc.org/
monitoring, biological detection and industrial control. Due to that, researches to develop photoconductive devices have
great significance. We report a study on the photoconductivity of reduced graphene oxide (rGO)/gold nanoparticles
(AuNPs) nanocomposites, emphasizing the enhancement effect induced by AuNPs. rGO/AuNPs photoelectric devices were
prepared by spincoating rGO onto AuNPs-array-covered silicon substrate. Photoelectric responses under visible light
illumination were measured and the results showed that the negative photoelectric responsivity of rGO was improved by 3
orders of magnitude due to AuNPs. The effects of AuNPs on negative photoconductivity (NPC) property of rGO were
investigated, and it is found that AuNPs affected NPC in three aspects: (1) AuNPs form discrete electrodes separated by
nanoscale gaps which generated new conduction paths, and hence the conductivity of rGO was enhanced by 3 orders of
magnitude; (2) Localized surface plasmon resonance (LSPR) of AuNPs effectively enhance total light absorption of rGO; (3)
Photocurrent between AuNPs and rGO can weaken the NPC property of rGO. The low-cost and mass-producible
rGO/AuNPs nanocomposites demonstrate high photoelectric responsivity, which holds much promise for NPC devices.

potential material for NPC devices with high performance, wide

Introduction
Negative photoconductivity (NPC) is an abnormal phenomenon,
which a material becomes less electrically conductive under light
irradiation and can be potentially used in many fields such as
1-5
communication, space exploration, environment monitoring, etc.
Based on it, new photoelectric devices can be designed to meet the
needs of practical applications.6, 7 Besides, NPC devices can be
combined with positive photoconductivity (PPC) devices to
assemble photoelectric logic gates, e.g. Negated AND gates and
Negated OR gates,8, 9 to achieve fully functional logical operation
bandwidth and miniaturization characteristics. However, low yield
and low absorbance limit the application of graphene NPC
22-24
devices. Interestingly, light absorption of graphene can be
significantly enhanced in a visible light region by localized surface
25-28
plasmon resonance (LSPR) of metal nanoparticles. Based on this
principle, some researchers have developed graphene/gold
nanoparticles (AuNPs) optoelectronic devices with effectively
28, 29
improved photoelectric responsivity of graphene. To solve the
low yield problem of graphene, a promising alternative strategy is
the utilization of reduced graphene oxide (rGO), which can be mass-
produced by various cost-effective oxidation-reduction methods.
30,

and control. Although the materials with NPC property are 31

At the same time, rGO and rGO/nanoparticles have plenty of the
apparently rarer than PPC, recent studies have reported that some 32 33
excellent performances, including optical , absorbance and
materials,10-15 like Ag nanowires,10 InAs nanowires,11, 12 ZnO 34
electronic properties . Therefore, it has great application value for
13 14 5, 15 35, 36 34, 37
nanocrystals, carbon nanotubes and graphene, show NPC the photoconductive device , electronic device and
38, 39
characteristics, which are promising for practical applications of biomedical science , and has been widely studied. Briefly, rGO
NPC devices. have higher preparation efficiency compared with graphene, and
Among them, the discovery of NPC property in graphene is of the combination with nanoparticles can significantly improve the
great importance. Graphene, as the thinnest two-dimensional light absorbance and electrical properties. Therefore, rGO were
nano-material, possesses many excellent characteristics, including combined with nanoparticles to prepare the rGO/nanoparticles NPC
16-18 devices with high preparation efficiency and high photoelectric
high carrier mobility and broad light absorption ability ranging
19-21 responsivity.
from ultraviolet to mid-infrared. Therefore, graphene is a
In this work, we report a study on the photoconductivity of
rGO/AuNPs nanocomposites. The rGO/AuNPs photoelectric devices
a. were fabricated by coating rGO on AuNPs arrays on a Si substrate,
Department of Materials Science and Engineering, Graduate School of
Engineering, Kyoto University, Kyoto 606-8501, Japan. followed by electrodes patterning. The visible light photoelectric
b.
E-mail: sugimura.hiroyuki.7m@kyoto-u.ac.jp properties were investigated, which demonstrated that rGO/AuNPs
Center for Composite Materials and Structures, Harbin Institute of Technology,
Harbin 150080, China. possessed an enhanced NPC property with a negative photoelectric
E-mail: hlf@hit.edu.cn

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responsivity improved by 3 orders of magnitude, compared with
the bare rGO devices. The work is of great significance for the
development of rGO NPC devices.
Experimental
Materials and chemicals. GO sheets were prepared by a modified
31 +
Hummers method. SiO2 (300 nm)/p -Si substrates were
purchased from Furuya Metal Co. Ltd. 3-aminopropyltriethoxysilane
(APS, 97 %) and the suspension of citrate-stabilized AuNPs ( = 20
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3 nm, pH 6 ) were purchased from Sigma-Aldrich Co. Ethanol
(98%) and toluene (99.5 %) were purchased from Nacalai Tesque,
Inc. Ultrapure water (UPW) with a resistivity of 18.2 Mcm was
prepared using a water purification apparatus (RFD 250NB,
Advantec).
Preparation and characterization of rGO/AuNPs. The silicon
substrates were sonicated in ethanol and UPW for 20 min each in
sequence, followed by 172 nm vacuum-ultraviolet (VUV, 172 nm,
2
ca. 10 mWcm , Ushio) irradiation in air for 20 min to remove
organic contaminants and introduce silanol groups onto the
substrate surface. The APS self-assembled monolayer (SAM) was
formed on the silicon substrate surface by a chemical vapor
40, 41
deposition method. The silicon substrate and a glass vessel
holding APS/toluene solution (1:9 volume ratio) were set in a Teflon
container (120 mL, ARAM) filled with dry nitrogen gas. The Teflon
container was sealed and placed in an oven (DO-300A, As one) at
100 C for 2 h. After that, the samples were taken out and sonicated
in toluene, ethanol, and UPW for 5 min each and were dried by
blowing nitrogen gas. The APS-modified samples were immersed in
an Au colloidal suspension for 10 min. AuNPs were attached on the
surface of silicon substrate by the static attraction between
40,
negatively charged AuNPs and positively charged APS molecules.
41
After that, the GO aqueous solution was spin-coated onto the
3
substrates. The samples were then put into a high-vacuum (<10
Pa) chamber and irradiated by VUV light for 64 min to realize the
42, 43
reduction of GO. For comparison, bare rGO sample was
prepared by following the steps described above without the
deposition of APS and immersion in AuNPs.
The surface morphology was characterized by atomic force
microscope (AFM, MFP-3D, Oxford Instrument). Optical microscopic
(OM) images were taken by using an optical microscope (Nikon
eclipse ME600L with 100 objective lens). An elemental analysis of
the samples was conducted on an X-ray photoelectron
spectrometer (XPS, ESCA-3400, Shimadzu). UV-vis absorption
spectra were performed on a spectrophotometer (U-3500, Hitachi,
Ltd.). Raman spectroscopy measurements were conducted on a
home-made micro-Raman spectrometer (manufactured by Lucir
Inc.) that uses a 532 nm laser as the excitation source, which is
combined with an optical microscope (Eclipse LV100, Nikon Co.) and
a Raman spectrometer (Renospec-300, Lucir Inc.).
Fabrication and Characterization of devices. Field-effect transistors
(FETs) were fabricated using rGO and rGO/AuNPs channels. The
channel length and width of FETs were 40 m and 10 m,
respectively. Source and drain electrodes (10 nm Cr/100 nm Au)
were fabricated by lift-off process. A maskless Lithography Tool D-
light (DL-1000GS/KCH, NanoSystem Solutions, Inc.) was used to
define the electrodes. An electron beam physical vapor deposition
2 | Nanoscale, 2012, 00, 1-3
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(PVD) of Cr followed by resistance heating PVD of Au was used to
make the electrodes. The electrical measurements were carried out
by using a semiconductor parameter analyzer (4200-SCS, Keithley
Instruments, Inc.) and microprobe station (200PW, Apollowave
Co.). Photoelectric characteristics were measured by lasers with
wavelengths of 405, 532 and 660 nm as a light source (Photo
technica).
Results and discussion
The surface topography of rGO sheets was observed by AFM, as
shown in Fig. 1a. By measuring the height line profile, the thickness
of the rGO layer was ca. 0.7 nm, which is consistent with the
44
thickness of a monolayer. The morphology of rGO/AuNPs was
Nanoscale Accepted Manuscript
observed by an optical microscope (Fig. 1b), which showed clear
contrast between rGO nanosheets and the silicon substrate.
rGO/AuNPs was also observed by AFM, as shown in Fig. 1c. The rGO
nanosheets overlapped on AuNPs, forming rGO/AuNPs nano-
composites. Due to the distinctive difference in thickness, rGO was
ambiguous under the AFM observation. Highly magnified AFM
topographic image was taken to show the size and distribution of
AuNPs (Fig. 1d). AuNPs is ca. 20 nm high, which is consistent with its
diameter, while the lateral size of AuNPs is larger than its diameter
due to the abrasion of the AFM tip. They were homogeneously
distributed on the substrate, and a small amount of theminevitably
assembled due to the randam adsorption during preparation.
Fig. 1 (a) AFM topographic image of rGO. (b) OM image of rGO/AuNPs. (c) AFM
topographic image of rGO/AuNPs. (d) AFM topographic image of AuNPs.
The reduction degree of GO was studied by XPS. The C1s core-
level spectra of GO, rGO and rGO/AuNPs are shown in Fig. 2a~c. The
oxygen/carbon atomic ratio (RO/C) decreases from 0.37 for GO, to
0.22 for bare rGO and 0.28 for rGO/AuNPs, indicating that GO was
2
partially reduced by VUV irradiation. The fraction of sp carbon is
important for electrical conduction, which can be roughly estimated
45
from the percentages of C=C peak (284.4 eV). The value were
69.67 and 66.00 % for rGO, and rGO/AuNPs, respectively. In
addition, the atomic percentages of COC, C=O and COOH groups
for rGO/AuNPs (~1.44 %, ~7.06 % and ~3.03 %) and rGO (~0.00 %,
~4.95 % and ~1.13 %). The difference between RO/C and atomic
percentages of functional groups were ascribed to the citrate-
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capped stabilizer on AuNPs surface. The graphitization degree of
rGO and rGO/AuNPs were studied by Raman spectroscopy (Fig. 2d).
-1
The intensity ratio (ID/IG) of D band (located at 1339 cm ) and G
-1
band (located at 1599 cm ) were measured to be ~1.10 and ~1.16
for rGO and rGO/AuNPs respectively, indicating AuNPs did not
obviously affect the VUV reduction. Although the XPS elemental
analysis demonstrated the reduction of oxygen contents, Raman
results revealed that the graphene-like structure was not recovered.
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Fig. 2 (a~c) XPS C1s spectra of pristine GO, rGO and rGO/AuNPs, respectively. (d)
Raman spectra of rGO and rGO/AuNPs.
We investigated the visible light response of rGO-FET in air at
room temperature using a solid-state laser with a wavelength of
532 nm. The Ids ~ Vg curves of rGO-FET in the dark and under
illumination are shown in Fig. 3a. The results showed that the gate
voltage at Dirac point was ~37 V, indicating that rGO-FET was p-type.
The presence of absorbents (such as O2 and OH groups) can
induces p-type behavior in rGO.4, 15 It was calculated that the
conductivity of rGO was only 0.05 S m1 at Vg = 0 V, this can be
ascribed to the relatively low reduction degree of rGO. It was also
found that the current decreased under the light irradiation,
showing the NPC property. The localized states on rGO surface
induced by the absorbents (such as O2 and OH- groups)46 act as
scattering centers under light illumination, referred to as
photoinduced impurity scattering5, 15. This reduces the
conductance of rGO, and hence resulted in the rGO NPC property.
Fig. 3b shows the photoresponse curve of a rGO device. The 532 nm
laser light was switched on and off periodically to demonstrate the
reproducibility of photoresponse. The results show that the rGO
devices have a good reproducibility with the response and recovery
time of 94 s and 154 s, respectively. In order to accurately evaluate
the photoresponse of rGO devices, the photoelectric responsivity
was calculated from the following equation

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DOI: 10.1039/C7NR05143C
ARTICLE
responsivity, the visible light absorbance of rGO should be
improved. Since the visible light absorbance of rGO can be
25-29
significantly improved by AuNPs, rGO/AuNPs-FET was fabricated
to study the improvement of photoelectric responsivity of rGO by
AuNPs.
The visible light response of rGO/AuNPs-FET was measured at the
same condition as rGO-FET, and its Ids Vg curves are shown in Fig.
3c. The results showed that rGO/AuNPs-FET was also p-type and
showing the NPC property. The photoresponse curve (Fig. 3d) of a
rGO/AuNPs device also showed good reproducibility of response
against the periodic irradiation of 532 nm laser light. The response
time and recovery time were 58 s and 84 s, respectively. Compared
to rGO-FET, there are two significant differences: (1) the current
signal was enhanced from nanoampere level to microampere level
Nanoscale Accepted Manuscript
along with the conductivity increased from 0.05 S m1 to 88.54 S
m1 at Vg = 0 V; (2) the photoelectric responsivities of the devices
were improved by 3 orders of magnitude as well, which was as high
as 7.13 AW1 at Vg = 0 V. It is clear that the conductivity and
photoelectric responsivity of rGO was improved due to AuNPs.
Fig. 3 (a) Ids Vg curves for rGO devices in the dark and under illumination. (b)
Photocurrent as a function of time for rGO devices. (c) Ids Vg curves for
rGO/AuNPs devices in the dark and under illumination. (d) Photocurrent as a
function of time for rGO/AuNPs devices. (532 nm, 106.1 mWcm-2).
The mechanism for the improvement was studied. First of all, the
influence of AuNPs on the conduction mechanism of rGO device is
investigated. Fig. 3c shows that rGO/AuNPs device kept the p-type
behavior, and the gate voltage at Dirac point was still ~ 37 V,
indicating that the transfer characteristics of the overall device was
dominated by rGO and AuNPs have not connected to each other to
form a continuous conductive channel between the source and
drain electrodes. Hence, the conduction mechanism of the device is
the same as that of rGO. Furthermore, the Ids ~ Vds curves of the
rGO-FET were measured at different temperatures (Fig. 4a). The
conductivity increased along with the rising of temperature from
room temperature to 90 C, in consistence with the behavior of

  semiconductor materials. Besides, the percentages of peak CC
R

where ILight is the illumination current, IDark is the dark current, P is
the illumination intensities, S is the channel area of the devices.19
The photoelectric responsivity of rGO was calculated to be 4.55
mA W1 at Vg = 0 V. In order to improve the photoelectric
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(1)
bond (285.0 eV) was 9.28 % for rGO (Fig. 2b), and ID/IG ratio in
34
Raman spectrum was ~1.10 (Fig. 2d), indicating that the reduction is
3
incomplete. That is, rGO still contained sp C-C compositions and
2
the sp conjugated system was not fully repaired. Hence, the
conduction mechanism could be Mott variable range hopping (M-
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47, 48
VRH). The relationship between temperature and conductance
47
G can be described as

   exp   (2)
in which, the hopping parameter B is expressed as,
* reduction in currents of bare rGO-FET were almost identical when
  (3)
!" #$%& '()
where kB is the Boltzmann constant, N(EF) is the density of states
near Fermi level, and L is the localization length of electronic wave
1/3
function. Eqn (2) indicates that ln(G) is directly proportional to T
1/3
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for M-VRH model. As shown in Fig. 4c, the plot of ln(G) ~ T for
rGO with Vds = 30 V is linear, which is consistent with the M-VRH
model.
Fig. 4 Ids - Vds curves at different temperatures for (a) rGO and (b) rGO/AuNPs. (c)
The plot of ln(G) against T-1/3 for rGO and rGO/AuNPs at Vds = 30 V. (d)
rGO/AuNPs conductive network model.
The Ids~Vds curves of rGO/AuNPs measured at different
temperatures are shown in Fig. 4b. It was also found that the
conductivity increases along with the rising of temperature from
1/3
room temperature to 90 C. The plot of ln(G) ~ T for rGO/AuNPs
at Vds = 30 V is shown in Fig. 4c, which matched the M-VRH model in
the range from room temperature to 60 C with the slope of
124.15. The slope was very close to that of rGO, 124.31. According
1/3
to Eqn (3), the slope of ln(G) ~ T curve is B, and it is related to
intrinsic conduction mechanism of materials, further confirming
that there is no change in conduction mechanism of rGO due to
AuNPs from room temperature to 60 C.
Based on the results, it can be found that AuNPs played key
roles in the conduction and NPC property of rGO/AuNPs devices.
Because of rGO wrapped on the AuNPs (Fig. 1c), we considered the
AuNPs induced short circuits in the rGO nanosheet by forming
Schottky contact on it, and the contact resistance was formed
between rGO and AuNPs. As shown in Fig. 4d, AuNPs separated the
micron-scale rGO nanosheets into many nanoscale rGO devices.
AuNPs, rGO and the Schottky barrier between them formed a
complex conductive network. In the case, the resistance of system
still mainly depended on rGO. Therefore, the conduction
mechanism of rGO/AuNPs was the same as that of rGO. Since
AuNPs substantially replaced low-conductive rGO and generated
new conductive paths, the conductivity of the network enhanced
for 3 orders of magnitude. Consequently, it enhanced photoelectric
4 | Nanoscale, 2012, 00, 1-3
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responsivity of the rGO NPC property.
The LSPR effects of AuNPs on the photoelectric property of rGO
were investigated as well. The photoelectric response of
rGO/AuNPs were measured under visible light irradiation by 405,
532, and 660 nm lasers respectively (Fig. 5a). It was found that the
using different lasers. However, the current variation in rGO/AuNPs
FET was apparently larger when irradiated by 532 nm laser,
compared to 405 and 660 nm laser. The laser-wavelength-
depending current changes were ascribed to the visible light
absorbance of rGO/AuNPs. The UV-Vis absorption spectra of rGO
and rGO/AuNPs are shown in Fig. 5b. The distinctive peak at ca. 530
nm in rGO/AuNPs spectrum correlates to the LSPR of AuNPs, which
can significantly enhance the NPC property of rGO/AuNPs
Nanoscale Accepted Manuscript
compared to rGO.
Table1 A summary of photoresponse parameters of NPC Graphene devices
References Material system wavelength Responsivity
3 rGO/MoO3 650 nm ~50 mAW1
4 rGO/WS2 808 nm 6 AW1
8 rGO/SnO2 NPs 365 nm ~0.5 mAW1
1
49 N-doped GO White Light ~1.68 mAW
1
Our rGO/AuNPs 532 nm 10.05 AW
LSPR effect is able to enhance near-field oscillation and
scattering effect between AuNPs,28 as schematically shown in Fig.
5c. There is an oscillation of conduction electrons when AuNPs are
excited by a light with specific photon energy. With this oscillation,
light is trapped around the surface of AuNPs and the absorption of
rGO is effectively enhanced, as illustrated as the near-field
absorption (Fig. 5c). In addition, due to the coupling by a large
number of AuNPs, the scattered light is localized around AuNPs,
resulting in the effective enhancement on the light absorption of
rGO, as shown as the strong coupling absorption in Fig. 5c. In a
word, the LSPR of AuNPs can effectively enhance the light
absorption of rGO. The enhancement in conductivity and light
absorption of rGO induced by AuNPs will result in the improvement
of photoelectric responsivity. The maximum photoelectric
responsivity can reach 10.05 AW1 under 532 nm laser irradiation
at 42.44 mWcm-2, which is higher than those of the graphene NPC
devices in previous literature (Table 1).
Besides, we plotted photocurrent change ratio curves of rGO and
rGO/AuNPs against different intensities of lasers, as shown in Fig.
5d. It can be seen that the photocurrent change ratio of rGO/AuNPs
was less than that of rGO, indicating AuNPs might have a negative
impact on the NPC property of rGO. As emphasized above, the
interface between rGO and AuNPs was Schottky contact50. A large
number of e-h pairs can be produced in the barriers area and
51
distributed closely around AuNPs when exposed to light , and
positive current would generate immediately between AuNPs and
rGO in the external electric field to weaken the NPC property of
rGO. However, for overall effect of AuNPs, its positive impact on the
NPC property of rGO played a main role. In a word, AuNPs
enhanced photoelectric responsivity and reduced the photocurrent
change ratio of the rGO NPC property.
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Fig. 5 (a) Drain current of rGO and rGO/AuNPs devices under laser illumination of
different intensities. (b) UV-Vis absorption spectra of rGO and rGO/AuNPs. (c)
Schematic illustration of the light absorption of rGO/AuNPs. (d) Photocurrent
change ratio of rGO and rGO/AuNPs at different laser intensities.
Conclusions
In conclusion, we investigated visible light photoelectric responsive
behavior of rGO/AuNPs, the results showed that the
nanocomposite presents the NPC property, and having a negative
photoelectric responsivity 3 orders of magnitude larger than bare
rGO. Its maximum negative photoelectric responsivity could reach
10.05 AW1, which is higher than previous graphene NPC devices in
existing literature. Analysis showed that the effect of AuNPs is to
decentralize the micron scale rGO and to form a great number
nanoscale rGO devices. LSPR of the AuNPs can effectively enhance
the total light absorption of rGO. The nanocomposites are
promising to be potentially utilized for NPC devices with the high
preparation efficiency and high photoelectric responsivity.
Acknowledgements
This work was supported by JSPS KAKENHI Grant Number
JP15H02297, JP15K14161, JP16K14404 and JP16J10757, Kato
Foundation for Promotion of Science (KF2713), and by the China
Scholarship Council (NO. 201506120103). A part of this work was
supported by Kyoto University Nano Technology Hub in
"Nanotechnology Platform Project" sponsored by the Ministry of
Education, Culture, Sports, Science and Technology (MEXT), Japan.
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