AuCl3 chemical doping on defective graphene layer

Sooyeoun Oh, Gwangseok Yang, and Jihyun Kim

Citation: Journal of Vacuum Science & Technology A 33, 021502 (2015); doi: 10.1116/1.4902968
View online: http://dx.doi.org/10.1116/1.4902968
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 AuCl3 chemical doping on defective graphene layer
Sooyeoun Oh, Gwangseok Yang, and Jihyun Kima)
Department of Chemical and Biological Engineering, Korea University, Anam-dong, Sungbuk-gu,
Seoul 136-713, South Korea
(Received 11 September 2014; accepted 17 November 2014; published 1 December 2014)
This study investigated the effects of defects on chemical doping of graphene layer. Graphene
grown by the chemical vapor deposition method on copper foil was subjected to ultraviolet
treatments to introduce defects, including sp3 bonding and vacancies. The chemical doping process
was performed using a gold chloride (AuCl3)/nitromethane solution at a concentration of 20 mM.
Raman spectroscopy and four-point probe measurement were used to analyze the effects of AuCl3
doping on the electrical and optical properties of defective graphene. AuCl3 doping was effective
for lowering sheet resistance even for the highly damaged graphene. Additionally, the 2D-peak of
the defective graphene was partially recovered after AuCl3-based chemical doping. The authors
believe that the defect engineering in graphene can enhance the electrical properties and the long-
C 2014 American Vacuum Society.
term stability of chemical doping. V
[http://dx.doi.org/10.1116/1.4902968]

I. INTRODUCTION elevated temperatures. Chemical doping is achieved by

Indium tin oxide (ITO) has commonly been used as a
transparent and conductive electrode material in optoelec-
tronic devices such as light-emitting diodes, solar cells, and
liquid crystal displays because ITO films are highly conduc-
tive and transparent in the visible spectrum.1–3 However, the
limitations of ITO such as high processing and material
costs, low fracture strain, instability in acid and base solu-
tions, and poor transparency in the ultraviolet (UV) and
infrared spectral regions still need to be addressed.4,5 This
need has stimulated research to identify an alternative mate-
rial to replace ITO. Promising materials include graphene
(chemical vapor deposited graphene and reduced graphene
oxide), carbon nanotubes, metal nanowires, and metal
meshes.5–9 Among the possible replacements, graphene is a
strong candidate for a transparent electrode material because
it has superior flexibility, transparency, and carrier mobil-
ity.10,11 In particular, the optical transmittance of monolayer
graphene grown by chemical vapor deposition (CVD)
method was reported to be >90% in the spectral range of
300–1000 nm.10 However, compared with existing commer-
cial ITO that has a sheet resistance (RS) of 10–30 X/( with
a transmittance of 90% at a wavelength of 550 nm,12 gra-
phene has a higher RS (undoped graphene: monolayer
700–1000 X/(,13 bilayer 540 X/(.14 Therefore, the elec-
trical properties of graphene need to be improved to enable
commercial application of graphene.
Methods to enhance the electrical properties of graphene
include doping, formation of a hybrid structure with highly
conductive materials, and stacking of the graphene
layers.15,16 The doping methods including substitutional
doping performed during CVD growth and postgrowth
chemical doping have been investigated. The latter is more
simple and straightforward than the former because in the
former, the defects can be developed during the growth pro-
cess and it is difficult to adjust process conditions at the
a)
Electronic mail: hyunhyun7@korea.ac.kr
transferring electrons from graphene to the dopant for p-type
doping and vice versa for n-type doping. Various materials
have been used as a p-type dopant such as metal compound
solutions, acids, polymers, and various gases.15,17–21
However, both the optical transmittance and RS decreased
simultaneously when dopant concentrations were increased
due to the trade-offs between the optical transmittance and
the electrical conductivity. Bae et al. reported that a decrease
in the RS of graphene also depends on the chemicals selected
to facilitate the doping.3 Kim et al. reported the changes in
the RS and optical transmittance of graphene at various
AuCl3 concentrations, which is one of the most effective p-
type dopants.15
Defects in graphene have received a lot of attention
because they can change the fundamental properties of the
graphene including optical, electrical, magnetic, and me-
chanical properties of graphene.22–24 Defects in graphene are
generally classified as point defects (or vacancy defects),
line defects formed at the edge and grain boundary, and sp3
hybridizations such as the formation of oxygen-containing
functional groups and C-H bonds.25 These defects have dif-
ferent effects on the properties of graphene depending on the
defect type and their density. Hao et al. reported that the
Young’s modulus and thermal conductivity of graphene
decrease as defect density increases.22 Yuan et al. described
the changes in the electrical and optical properties of gra-
phene depending on ozone treatment time and temperature,
where optical transmittance and resistance increase with
increasing ozone treatment time.23 Zhang et al. demonstrated
that defective graphene was more sensitive to chemicals
than pristine graphene.24 In this study, the effects of AuCl3-
based chemical doping on defective graphene were investi-
gated. The defect density was controlled by adjusting the
UV irradiation time. Graphene with defects intentionally
induced by UV treatment was systematically characterized
by micro-Raman spectroscopy and sheet resistance measure-
ments. The results obtained with this approach suggest that
the electrical and optical properties of graphene can be

021502-1 J. Vac. Sci. Technol. A 33(2), Mar/Apr 2015 0734-2101/2015/33(2)/021502/5/$30.00 C 2014 American Vacuum Society
V 021502-1

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 021502-2 Oh, Yang, and Kim: AuCl3 chemical doping on defective graphene layer 021502-2

FIG. 1. (Color online) Schematic of the experimental procedures: (a) graphene grown by the CVD method on Cu-foil; (b) graphene transferred to SiO2/Si by a
wet transfer method using PMMA; (c) defects in the graphene generated by UV-ozone treatment; (d) defective graphene on SiO2/Si; (e) doping of graphene
with AuCl3/nitromethane solution; (f) chemically doped graphene with different defect densities.

improved via the combination of defect engineering and

chemical doping process.

II. EXPERIMENT
Figure 1 illustrates the schematic of the entire experimen-
tal procedure. The graphene used in our experiment was
grown on both sides of the copper (Cu) foil using the CVD
method. The front side of the graphene/Cu foil was spin-
coated with poly(methyl methacrylate) (PMMA). The gra-
phene on the other side was removed using reactive-ion etch
with oxygen plasma for 5 s (O2 20 sccm, plasma power
100 W). After Cu foil was chemically etched using 1 wt. %
ammonium persulfate [(NH4)2S2O8] solution for 6 h, the
PMMA/graphene structure was transferred onto a SiO2
(300 nm)/Si substrate, followed by drying the deionized
water (DI) using a hotplate at 70  C. Finally, the PMMA was
removed with acetone. To induce defects intentionally, a UV
cleaner (NOVASCAN, PSDP-UV4T) that emits both
185 nm and 254 nm wavelengths was used. The UV chamber
was purged with ultrahigh purity (UHP) air for 3 min before
the UV treatment to control humidity, wherein the UHP air
contained less than 3 ppm of H2O. Each sample was sub-
jected to UV treatment for 5–20 min at room temperature.
The defect-induced graphene was doped using AuCl3/nitro-
methane solution (Sigma-Aldrich) with a concentration of
20 mM. To prepare the AuCl3/nitromethane solution, AuCl3
powder was dissolved in nitromethane using an ultrasonic
cleaner (5510E-DTH, Branson) for an hour, followed by fil-
tration using a 200 nm polytetrafluorethylene filter
(Advantec). The prepared samples were then dipped in
AuCl3/nitromethane solution for 30 s and rinsed with DI
water. The effects of defects on AuCl3 doping were investi-
gated with micro-Raman spectroscopy using a diode-
pumped solid-state laser (Omicron) with a wavelength of
FIG. 2. (Color online) Raman spectra of all samples before and after the
532 nm under a back-scattering geometry, where a beam
UV-ozone treatment and AuCl3 doping; (a) ranging from 1100 to 3000 cm1;
spot size was approximately 3 lm at the sample. Raman (b) G peak; (c) 2D peak (undoped: [1], [3], [5], [7], [9]; AuCl3-doped: [2],
spectra were obtained at more than five random locations in [4], [6], [8], [10]).

J. Vac. Sci. Technol. A, Vol. 33, No. 2, Mar/Apr 2015

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 021502-3 Oh, Yang, and Kim: AuCl3 chemical doping on defective graphene layer
each sample after UV treatment and AuCl3 doping. The RS
of the samples was measured at more than ten positions
using a four-point probe equipment (Desk 205, MS Tech)
connected to a source meter (Keithley 2400). To investigate
the stability of the chemical doping, the samples were stored
in ambient air for a month. Then, the RS was remeasured at
more than ten locations with the same equipment.
III. RESULTS AND DISCUSSION
Figure 2 shows the evolution of the Raman spectra before
and after the UV treatments and AuCl3 doping. Raman spec-
troscopy is an effective tool to investigate the graphene qual-
ity, the number of layers, and the doping effect. Typical
Raman spectra obtained from pristine graphene grown by
the CVD method display two characteristic peaks: the G
peak at 1600 cm1 and the 2D peak at 2685 cm1, and
the peak pattern align well with the Raman spectrum gener-
ated from the pristine graphene used in this study. After UV-
ozone treatment, the D peak appeared at 1360 cm1. The
intensity ratio of D/G peaks (ID/IG) of the graphene used in
the experiments was 0.03 {[1] in Fig. 2(a)}, indicating that
it was of high quality. UV treatments were conducted to
induce intentional defects. Ozone and atomic oxygen adsorb
onto the surface of the graphene and react with it by forming
an oxygen-containing functional group such as a carbonyl
group; thereby, the surface is considered to have undergone
partial oxidation. Increasing the UV irradiation time also
induces higher densities of oxygen-containing functional
FIG. 3. (Color online) Evolution of (a) ID/IG and IG/I2D; (b) shift of G (bottom) and 2D peaks (top); (c) FWHM of G peak; (d) LD as a function of UV irradia-
tion time.
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021502-3
groups and creates vacancy defects. Previous studies have
demonstrated that the degradation stages of graphite and gra-
phene can be confirmed by monitoring ID/IG.26,27 An initial
increase in ID/IG indicates a transformation from crystalline
graphite to nanocrystalline graphite. The graphene in this
stage is considered to have a low density of defects. Then,
saturation in ID/IG after 15 min of UV treatment time was
observed. In this stage, nanocrystalline graphene becomes
more disordered with populated sp3 bonding and vacancy
defects because of prolonged surface oxidation. As other evi-
dence of vacancy defects, the D0 (1620 cm1) and (G þ D)
(2947 cm1) peaks appeared in Fig. 2 because the D0 peak
originated from vacancy defects in the graphene.28 The aver-
age distance between the neighboring defects, LD, can be
estimated using the following empirical formula:29
 
2 9 4 IG
LD ¼ ð1:860:5Þ  10  kD  ;
ID
where kD is the laser excitation wavelength. The calculated
values of LD were 65 6 10, 49 6 7, 48 6 7, 9 6 1, and
10 6 1.5 nm for the samples irradiated at times of 0, 5, 10,
15, and 20 min, respectively [Fig. 3(d)].
The G and 2D peaks up-shifted and broadened {[3], [5],
[7], and [9] in Figs. 2(b) and 2(c)} after UV treatment, which
suggests that UV treatment generated defects and simultane-
ously induced p-type doping because the oxygen-containing
functional groups could act as an p-type dopant. Raman
spectra in the low defect density region (UV exposure for
 021502-4 Oh, Yang, and Kim: AuCl3 chemical doping on defective graphene layer
0–10 min) after AuCl3 doping show that the G and 2D peaks
were upshifted and the full width at half maximum (FWHM)
were barely affected [Figs. 3(b) and 3(c)]. However, in the
high defect density region (UV exposure for 15–20 min), the
behaviors were different after AuCl3 doping. It is important
to note that the ID/IG decreased after AuCl3 doping in Fig.
3(a). For the sample UV-irradiated for 15 min, the FWHM of
G peak in the defective graphene decreased after AuCl3 dop-
ing, where it can provide information regarding structural
disorder. In addition, a sharp 2D peak was observed from [8]
and [10] in Fig. 2(c) after AuCl3 doping. The partial recov-
ery after the chemical doping can be attributed to the
increased ratio of C¼C bonding due to the charge transfer.30
Figure 4 displays the RS of graphene after UV treatment
and chemical doping. The change in the positions of the G
and 2D peaks, which were influenced by carrier concentra-
tions, was related to that of the RS in the doped samples. The
RS of graphene UV-treated for 5 min decreased from 581.3
to 492.4 X/(, which can be explained by p-type doping.
Then, the RS increased as UV irradiation time was increased
due to the lattice damage. In particular, the RS could not be
obtained from the graphene samples that had been UV irradi-
ated for 20 min because the increased UV treatment time
caused it to exceed the threshold of assessment. Yuan et al.
reported that short ozone exposure decreases the RS of gra-
phene by p-type doping, whereas prolonged exposure
increases resistance as a result of progressive oxidation to
FIG. 4. (Color online) (a) Sheet resistance (RS) of graphene before and after
AuCl3 doping as a function of UV irradiation time. (b) DRS in the AuCl3-
doped graphene stored in an air ambient for a month as a function of UV
irradiation time.
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021502-4
form graphene oxide. Note that AuCl3 doping was very
effective even for the highly damaged graphene, which were
UV-irradiated for 15 min. After storage in ambient air for a
month, the RS of the doped graphene increased by 32.4%
(non-UV-treated), 81.0% (5 min-UV-treated), 91.8% (10
min-UV-treated), and 13.7% (15 min-UV-treated). The
observed changes in the RS can be explained by the presence
of defective sites in graphene. Chemical doping methods are
usually unstable because of the adsorption of the environ-
mental molecules (CO2, O2, H2O, etc.) on the surface of the
graphene.15,21,31 Since defects can act as a stabilizer, chemi-
cal dopants might be more stable in the presence of a high
density of defects because they can be stabilized due to the
populated dangling bonds. Optimizing the amount of defects
in the graphene can also enhance the charge transfer,24
resulting in improving the electrical properties of graphene.
IV. SUMMARY AND CONCLUSIONS
Our study demonstrates a facile method to improve the
electrical properties of graphene through the use of defect en-
gineering and chemical doping. UV-ozone treatment was
employed to control the distance between the point defects.
AuCl3 acted as an effective p-type dopant by reducing the RS
of graphene even for the graphene with high density of defects.
Partial recovery of the Raman spectra was observed after a
chemical doping. Optimization of the density of defects can
help to improve the long-term stability of chemical dopants.
ACKNOWLEDGMENTS
This research was supported by the Basic Science Research
Program (2012R1A1A2042761), the Radiation Technology
Research and Development program (2013M2A2A6043608)
and the Center for Inorganic Photovoltaic Materials (2012-
0001171) grant through the National Research Foundation of
Korea funded by the Ministry of Science, Information
Communication Technology & Future Planning.
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