Carbon 148 (2019) 187e195

Contents lists available at ScienceDirect

Carbon
journal homepage: www.elsevier.com/locate/carbon

Thickness-dependent efficiency of directly grown graphene based

solar cells
Malik Abdul Rehman a, 1, Sanjib Baran Roy b, 1, Imtisal Akhtar a,
Muhammad Fahad Bhopal c, Woosuk Choi a, Ghazanfar Nazir b, d,
Muhammad Farooq Khan b, Sunil Kumar d, Jonghwa Eom b, Seung-Hyun Chun b, **,
Yongho Seo a, d, *
a
Faculty of Nanotechnology & Advanced Materials Engineering and HMC, Sejong University, Seoul, 05006, Republic of Korea
b
Department of Physics and Astronomy, Sejong University, Seoul, 05006, Republic of Korea
c
Department of Electronics Engineering, Sejong University, Seoul, 05006, Republic of Korea
d
Graphene Research Institute, Sejong University, Seoul, 05006, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: It is of immense interest to improve the power conversion efficiency of graphene/silicon Schottky
Received 11 December 2018 junction solar cells. The ultrathin graphene has essential properties, such as tunable work function to
Received in revised form increase Schottky barrier height and built-in potential for efficient charge transport in photovoltaic
19 March 2019
devices. Here, we use plasma-enhanced CVD to grow graphene directly on planar n-type silicon to
Accepted 24 March 2019
Available online 25 March 2019
fabricate solar cells compatible for industrial-level applications. A key component to our accomplishment
is the optimization of directly grown, continuous layers of graphene to achieve superior performance.
Thus, by controlling the graphene thickness, the work function is significantly improved, the open circuit
Keywords:
Solar cell
voltage is increased, and the energy conversion efficiency is enhanced. While the transfer of CVD grown
Schottky junction graphene has limitations due to cracks and impurities during the complex process, our direct growth
Graphene thickness dependence method demonstrates an efficiency of 5:51% on bare planar silicon with a large device area. Furthermore,
Directly grown graphene the efficiency is remarkably increased to 9:18% by adding and doping a polymer layer. Interestingly, with
Graphene doping the addition of a doped polymer layer, the cell exhibits excellent stability for at least one month. Our
Anti-reflecting coating result suggests a promising simple path to fabricate high efficiency solar cells at low temperature and
low cost.
© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

1. Introduction
The single-atom-thick two dimensional material, graphene ex-
hibits versatility in ultra-wideband applications including opto-
electronics and photonics [1,2]. The proliferation in use of graphene
is mainly due to unique attributes, such as tunable work function,
flexibility, extraordinary conductivity, optical transparency, and
high stability [3e5]. These emerging properties attract tremendous
interest for energy based devices such as super capacitors, solar
cells and lithium ion batteries [3,6e9]. Although, first generation
* Corresponding author. Faculty of Nanotechnology & Advanced Materials Engi-
neering and HMC, Sejong University, Seoul, 05006, Republic of Korea.
** Corresponding author.
E-mail addresses: schun@sejong.ac.kr (S.-H. Chun), yseo@sejong.ac.kr (Y. Seo).
1 Schottky junction has an efficiency of 1:5% reported by Li et al. [13]
Equally contributed.
silicon (p-n junction) solar cells have a much higher power con-
version efficiency of up to
26%, very close to the theoretical limit
of 29:1% [10], but it requires high cost and temperature during the
ion implantation process [11]. Additionally, graphene has a wide
absorption spectrum, including the UV and IR regions, which is
advantageous to photovoltaic device application. Another aspect is
that the rapid expansion in world energy consumption due to
global growth and modernization at an industrial scale demands
environment-friendly solar devices with low cost fabrication. To
overcome the barrier of high cost and to fulfill the energy demand,
high efficiency solar cells based on new materials are required.
Recently, there has been a boom in developing graphene based
solar cells in the research area [12]. Graphene has a zero band gap
behaving as a metal and makes a Schottky junction in combination
with semiconductors. The earliest successful graphene/silicon

https://doi.org/10.1016/j.carbon.2019.03.079
0008-6223/© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
188 M.A. Rehman et al. / Carbon 148 (2019) 187e195
There have been many attempts to improve the efficiency by
adopting an interfacial layer, doping and antireflective coating
[14e16]. The interfacial layer blocks the electrons and transmits
holes to suppress the recombination, and eventually it improves
conversion efficiency. Doping increases the carrier concentration
and conductivity of graphene. Similarly anti-reflecting coating in-
creases the absorption of photons by trapping the light. A power
conversion efficiency (PCE) of up to 15:6% was achieved by Song
et al. adopting all of them in 2015 [17]. Moreover, Li et al. reported
18:5% PCE on a few layer graphene/GaAs heterostructure by Fermi
level tuning with gate voltage, as well as doping and anti-reflecting
[12]. Surface texturing of silicon is another approach to enhance the
PCE [9,18].
High photocurrent generation on graphene/silicon junction is
limited by transparency, recombination, and short lifetime of ex-
citons in graphene. The junction between graphene and silicon is
much thinner than the ordinary p-n junction solar cell, and the
thickness of graphene needs to be controlled to adjust its work
function for the high efficiency of the solar cell. Also, the thick layer
of graphene may increase absorption in the photoactive layer. The
work function of graphene varies with the thickness, which also
influences the efficiency of the solar cell. In previous studies, Li et al.
have used layer by layer transfer of 1e6 layers to improve the ef-
ficiency on bare silicon, but their efficiency was limited to 1:48% for
4 layers [19]. Additional layers did not increase the efficiency due to
less transparency, though high efficiency on bare silicon is highly
required for industrial applications.
In this work, we propose a simple cost effective and low tem-
perature direct growth approach to directly grow different thick-
nesses of graphene on bare silicon. In this architecture, with a direct
growth approach, it is possible to grow graphene with high con-
ductivity, high work function, and controllability of optical trans-
parency. Our results manifested the importance of thickness
control of direct grown graphene to achieve an efficiency of 5:51%
on bare silicon, which is further improved to 9:18% with doping of
nitric acid on the polymer layer. Here, we also demonstrated that
carrier recombination is minimized with optimized thickness of
graphene and a relatively high Schottky barrier height. The
recombination which is a major concern is further reduced with
doping, which minimizes the transfer of electrons from n-type
silicon to p-type graphene, and over all the leakage current is
reduced. The scalability of our device is also guaranteed by means
of direct growth.
2. Experimental
2.1. Device fabrication procedure
A phosphorous doped n-type 〈100〉 monocrystalline polished
bare silicon wafer having a thickness of 650e700 mm and a re-
sistivity of 1e10 U cm was used to fabricate solar devices. To remove
organic residue, silicon substrates were cleaned by an RCA standard
method as described previously [9]. Prior to direct growth of gra-
phene, silicon substrates were immersed in buffered oxide etchant
for 30 s to remove native oxide. Following this etching, silicon
wafers were soaked in DI water and dried with inert gas. Then the
samples were placed in PECVD chamber to directly grow graphene.
The growth conditions were 50 W power with continuous flow of
hydrogen (H2, 20 sccm) and methane (CH4, 2 sccm) for RF plasma
generation. While the temperature was 550  C and pressure was
1  106 torr. Most importantly, before graphene growth,
annealing was performed for 1 h to remove any remaining metallic
impurities. By varying the time, graphene samples of different
thickness were grown. To provide good electrical connection, a
metal grid pattern was made by using a stainless steel shadow
mask having the dimension of (6:5mm  4:0mm). Ohmic contacts
on the graphene side were made with Cr (5 nm)/Au (95 nm), while
on the rear electrode Al (300 nm) was deposited by using an e-
beam evaporator having a chamber pressure of 6  107 Torr and a
deposition rate of
0.2 nm/s.
2.2. Characterization
The high resolution atomic force microscopy (AFM, Nano focus
Inc.) was utilized to distinguish thicknesses of graphenes. An ul-
trahigh resolution field emission scanning electron microscopy (FE-
SEM, Hitachi SU-8010) were used for energy dispersive X-ray (EDX)
analysis to obtain surface imaging and mapping analysis of the
elements as shown in the supporting information (Fig. S1-S3). Thus,
a smooth surface of directly grown graphene and change in thick-
ness of carbon with increasing growth time was confirmed. To
evaluate structural analysis and crystallinity of different thick-
nesses of direct grown graphene, Raman spectroscopy was per-
formed (Renishaw, in Via) having a wavelength of 514:5 nm. The
laser spot of less than (<0.8 mm) was used to focus, and incident
power of 1 mW was applied to avoid laser-induced heating damage.
The UVeViseNIR (Cary-5000) spectroscopy was used to measure
reflectance of the directly grown graphene on silicon substrates
with an integrating sphere. A Hall effect measurement system
(Ecopia, HMS-3000) was used to measure sheet resistance, doping
type and carrier concentration in directly grown graphene. To
measure (I-V) characteristics of graphene/silicon solar cells, a
multimeter (Keithley 2400) and solar simulator (Newport solar
simulator AM 1.5) were used under a light intensity of 100
mWcm2 . Prior to I-V measurement under illumination, it was
calibrated with a standard solar cell. The capacitance-voltage (C-V)
measurement was performed with a LCR meter (Agilent 4284) at a
fixed frequency of 10 kHz. The external quantum efficiency (EQE)
was also performed on a
4 nm thick solar cell (pristine), with
anti-reflecting coating (PMMA) and acid doped (HNO3) to measure
the ratio of created charge carriers to incident photons under
(QEX10) measurement system. The x-ray photoelectron spectros-
copy (XPS) measurement was performed with K-alpha having
monochromatic source energy of 1486.6 eV, under 12 kV. The ultra-
high vacuum with base pressure of 2.91  109 was maintained
during measurement. The detailed high resolution spectra was
carried out having a pass energy of 40 eV and step size of 0.1 eV. A
flood gun was also used to control charge compensation, and XPS
peak 4.1 software was used for fitting.
3. Results and discussion
Non-destructive resonant Raman scattering was carried out to
investigate the quality of the low-temperature directly grown
graphene like local bonding, structural disorders, doping charac-
teristics and number of layers. The Raman spectra were acquired for
graphenes with different thicknesses by varying the growth time.
The measurements were repeated from different positions/areas of
the sample to confirm its reproducibility, and the average data are
shown in Fig. 1a. The data highlight three remarkable features of
graphene: the D band which lies at 1350 cm1, G band 1580 cm1
and 2D band around 2700 cm1. The 2D band was blue-shifted from
2680 cm1 confirming intrinsic p-type behavior of the sample [20].
G band peak indicates sp2 bonded pairs of graphene, and 2D band
confirms the ultimate nature of graphene, while D peak is mainly
associated with sp3 defects sites and a structural disorder in gra-
phene [21,22]. The Raman spectrum of direct grown graphene
shows a sharp D peak, confirming the direct growth graphene
quality lower than that by catalyst based growth. Interestingly, with
the increase in growth time of directly grown graphene from 2.5 up
 M.A. Rehman et al. / Carbon 148 (2019) 187e195 189

Fig. 1. Raman and AFM images to show different thicknesses of directly grown graphene with variation in growth time. (a) Typical Raman spectra shows D, G, and 2D band of
graphenes grown in different growth times 2.5, 3.5 and 4.5 h. The ratio of I2D =IG less than 1 confirms multiple layers of graphene. (b) Combined plot of 2D bands with different
growth time. (c) FWHM of 2D band is plotted as a function of growth time. (d) The ratio of ID =IG as a function of growth time. The error bars indicate standard deviation of multiple-
time measurements. (e-g) AFM images and their respective line profiles at growth time of 2.5, 3.5 and 4.5 h, respectively. As growth time increases thickness of graphene also
increases. (A colour version of this figure can be viewed online.)

to 4.5 h, an increase in intensity was observed (Fig. 1b), which gives
evidence that the number of graphene layers was increased. In
addition, broadening or splitting of the 2D band with growth time
in direct growth of graphene (Fig. 1 (c)) was confirmed by calcu-
lating its FWHM by Gaussian fitting (Details supporting
information S4), implying enhanced interaction locally coupled
between the layers [22,23]. The intensity ratio ID =IG was used to
estimate the disorder in the graphene lattice [21,24]. As the thick-
ness of direct grown graphene was increased to 4.5 h growth time, a
value of ID =IG was increased. However, lower values of ID =IG were
obtained at 2.5 and 3.5 h, respectively, as shown in Fig. 1d and
attributed to similar levels of defects. The overall tendency of
I2D =IG < 1 reveals that the directly grown graphene have
multilayers.
The thickness control of the directly grown graphene by varying
the growth time was also revealed by line profiling of atomic force
microscopy (AFM). High resolution topographic images distinguish
clear contrast between graphene and silicon, and the height pro-
files along with cross sectional lines are shown in Fig. 1eeg. The
variation in height profile confirms that the thickness changes from

2 nm,
4 nm, and
8 nm, respectively, as the growth time was
increased from 2.5, 3.5e4.5 h. These finding are in accordance with
the EDX spectrum and mapping results shown in the supporting
information (S2, S3). It is worth mentioning here that growth
time is also a key factor in adjusting graphene nucleation and
growth. Besides, there is another method to grow graphene of
different thicknesses by varying the temperature. However, high
temperature may cause surface damage on bare silicon, which is
190 M.A. Rehman et al. / Carbon 148 (2019) 187e195
not favorable for directly grown graphene solar cells.
The device configuration is illustrated in Fig. 2aed with different
thicknesses, and the real device image is shown in Fig. 2(e) to
indicate the mechanism of device fabrication. Sheet resistance,
charge carrier concentration, and transmittance play essential
roles, to achieve high-performance of graphene-silicon Schottky
junction solar cells. The Hall effect was measured to estimate the
doping concentration and sheet resistance as listed in Table 1.
Additionally, the sheet resistance was also confirmed by the four
probe method, and the results indicated similar values. It was
observed that direct grown graphene has intrinsically highly doped
p-type behavior which was also confirmed by Dirac point mea-
surement as shown in the supporting information, Fig. S5. The re-
sults imply that
2 nm thin graphene has very high sheet
resistance 4.17 kU⁄sq. and low carrier concentration (Nb) 1:31 
1020 cm3 . In the case of
4 nm, there is almost a 3 times
decrease in sheet resistance, and an increase in Ns was observed.
The increment in number of graphene layers increased the bulk
concentration as the doping effect was intensified. Thus, a further
increase in thickness up to
8 nm follows the same trend. How-
ever, the efficiency of solar cells is also related with the trans-
parency of graphene sheets. In fact, when thickness of directly
grown graphene is increased from
4 nm to
8 nm, the overall
energy efficiency of the solar cell can be reduced due to reduced
transparency, and a balance between transparency and conduc-
tivity is required [23]. For photons with energies above 0.5 eV, a
single layer graphene yields a spectrally flat optical absorbance of
(2.3 ± 0.2)% [25]. The transmittance T of a multilayer graphene can
be calculated by Ref. [1].
 2
G0
T¼ 1þ N ;
2ε0 c
where G0 ¼ p2h
2
e is the optical conductivity [26], ε is free-space
0
permittivity, c is the speed of light and N is the number of layers
of graphene. The transmittance T value for each graphene layer is
shown in Table 1. (Supporting information Fig. S6) To achieve su-
perior performance the control of thickness, transparency and
Fig. 2. (a) Device schematics to illustrate the process of directly grown graphene-silicon Schottky junction solar cell. (bed) Schematic drawings of
2, 4, and 8 nm thin graphenes at
2.5, 3.5, and 4.5 h growth times, respectively. (e) Photographic image of the graphene based solar cell on bare silicon. (A colour version of this figure can be viewed online.)
sheet resistance is essential [19,27], and a previous study claimed
that 4 layers of graphene with 90% transmittance in the visible
region exhibited the best solar cell performance with a 2.5% effi-
ciency [23].
To elucidate the performance of our devices depending on the
number of layers of graphene, we fabricated these devices by
varying thicknesses of ~2, ~4, and ~8 nm, respectively. Due to the
direct growth of graphene on silicon, we were able to fabricate our
devices with a large active surface area of 0:3 cm2 , which was fully
covered with graphene in our devices. To ensure repeatability and
reproducibility more than 10 samples were prepared for each
thickness and tested. Most importantly, the direct growth graphene
film maintained a good contact as compared to the transferred
graphene. It is due to the strong adhesion between graphene and
silicon without interspace or air bubbles at their interface. We also
anticipated that these multiple layers of graphene are inter-
connected and overlapped, which give a conducting channel even if
there are vacancies, interstitial impurities and substitutional im-
purity atoms. In fact, due to the difference between Fermi level of
silicon and graphene, the built-in potential between silicon and
graphene is established, which causes asymmetric current-voltage
characteristics. A similar Schottky diode behavior was observed in
the heterostructure of GaAs/graphene [12].
Fig. 3a shows current-voltage (I-V) characteristics of graphene-
silicon Schottky junction of varied thicknesses under 1 sun illu-
mination. It is worth mentioning that these results were obtained
without any doping or interfacial layer. The curves exhibit well
defined diode rectification. One of the important performance pa-
rameters is the fill factor (FF);
(1)
Vmax  Imax
FF ¼ : (2)
Voc  Isc
here, Vmax and Imax are voltage and current at the maximum power,
respectively, and Voc is open circuit voltage and Jsc is short circuit
current density. The PCE is the fraction of incident solar light power
(Pin) converted to electricity, that is,
 M.A. Rehman et al. / Carbon 148 (2019) 187e195 191

Table 1
By using the van der Pauw method of four point probe. Thickness dependent comparison of the direct grown graphene on top of SiO2 (oxide, 300 nm) substrates.

Growth Time (hours) Thickness (nm) Carrier concentration Nb (cm3) Sheet Resistance Rsh (kU/sq.) Transmittance (%)

2.5 2 1.31  1020 4:17 86:3

3.5 4 1:41  1020 1:64 75:2
4.5 8 2:30  1020 1:16 58:6

Fig. 3. Comparison of photovoltaic characteristics and performance parameters with variation in growth time or thickness of direct grown graphene on bare silicon. (a) Under light
I-V curves of a Schottky junction solar cell with change in thickness of graphene. (b) J-V curves of the best solar cell with an optimized thickness of
4 nm in dark and under light.
(c) J-V plot in semi-log scale to confirm ideal behavior of a diode by calculating the ideality factor. (d) The extraction of series resistance by plotting dV/d(ln J) as a function of current
density. The arrow direction indicates reduction in series resistance depending on the thickness. (A colour version of this figure can be viewed online.)

that previous studies for transferred graphene with monolayer or

Voc  Jsc  FF multiple layers exhibited much lower energy conversion efficiency
PCE ¼ : (3) on bare silicon [16,19,28,29].
Pin
Furthermore, ideality factor was calculated by using the
The performance parameters Voc , Jsc , FF, and PCE decrease in following equation:
both thin (
2 nm) and thick (
8 nm) devices as illustrated in
Table 2. This calculation indicates that the sample with
4 nm J ¼ JRev ½expðqV=nkB TÞ  1; (4)
thickness has superior performance of Voc ¼ 0.391 V,
Jsc ¼ 25.17 mAcm2, and FF ¼ 56.03%. These parameters lead to a where JRev is the reverse bias saturation current density, n is the
PCE of 5:51%, which is the highest PCE of direct growth graphene on ideality factor, q is the elementary charge, and KB is the Boltzmann
bare silicon to date as presented in Fig. 3b. It is worth mentioning constant. By simplifying equation (4), n ¼ ðq=KB TÞðdV=dlnðJÞÞ, and

Table 2
Summary of photovoltaic parameters under 1 sun illumination depending on different thicknesses with respect to growth time for directly grown graphene.

Gr growth time (hour) Thickness (nm) Voc (V) Isc (mA) Jsc (mA/cm2) FF (%) PCE (%) Ideality factor (n) FSBH (eV)
2.5 ~2 0.331 7.74 25.8 41.82 3.57 1.73 0.649
3.5 ~4 0.391 7.5 25.17 56.03 5.51 1.55 0.685
4.5 ~8 0.381 7.09 23.66 34.02 3.06 2.28 0.679
192 M.A. Rehman et al. / Carbon 148 (2019) 187e195
n under light illumination was extracted by linear fitting in lnðJÞ
versus V plotting from J-V curve as shown in Fig. 3c. (See supporting
information S7(aec) for details). The ideality factor n for
4 nm
thickness is 1.55, while n ¼ 1.73 and 2.28 for samples
2 nm and

8 nm thick, respectively. The higher n factor and lower FF in-
dicates poor junction quality due to high recombination at the
interface between graphene and silicon [28]. The ideality factor
higher than 1 means that there was a leakage current, and shorter
life time of minority carriers. As it is clear from the results of Table 2
the thin (
2 nm) sample have low FF and high n. The decrease in n
factor for
4 nm thickness is related to the less carrier recombi-
nation and low leakage current. The thick (
8 nm) sample has low
transmittance (58.6%), resulting in low PCE. The series resistance is
also extracted from ðdV=dlnJÞ versus J plot as shown in Fig. 3d.
Notably, for
4 nm graphene silicon Schottky junction solar cell
series resistance is lowest as 11:4U, whereas high value is esti-
mated for
2 nm and
8 nm thicknesses 18:6U and 41:6U,
respectively. The second possible reason for improvement in effi-
ciency for
4 nm devices is mainly attributed to reduction in se-
ries resistance, better electrical conductivity and more efficient
charge transport.
The Schottky barrier height ðFSBH Þ is directly proportional to the
built-in potential Vbi as given by [19,30],
 
NC
FSBH ¼ Vbi þ e1 KB T$ln ; (5)
ND
where T is the temperature, ND represents doping level of the sil-
icon, and NC represents effective density of states in conduction
band. On the other hand, according to Schottky-Mott rule,
FSBH ¼ WGr  cSi ; (6)
where WGr is the work-function of graphene and cSi is the electron
affinity of silicon. While cSi is constant, WGr is increased with
thickness of graphene by ~0.1 eV per layer [31]. Thus, the built-in
potential increases as the thickness increases, and increase in Voc
is also expected [31,32]. From J-V characteristics under dark con-
ditions, FSBH can be calculated as shown in Fig. 4a. From the
thermionic emission model, FSBH is given by
Fig. 4. (a) A semi-log plot of J-V data under dark conditions to extract Schottky barrier height of different thicknesses at different growth times. (b) C-V measurement at room
temperature. Inverse square of capacitance was plotted as a function of voltage to observe change in built-in potentials of different thicknesses of graphene. (A colour version of this
figure can be viewed online.)
 
A T2
FSBH ¼ ln KB T; (7)
JRev
where JRev is the current density in reverse bias and A is the
Richardson constant (252 A cm2K2, for n-type Si) [9]. As ex-
pected, a higher value of FSBH ¼ 0:685 eV was obtained for
4 nm
thickness, while for
2 nm and
8 nm comparatively lower
values of 0:649 eV and 0:679 eV were achieved.
Additionally, the magnitude of Vbi is estimated from capacitance
voltage C-V analysis using the Schottky-Mott plot (Fig. 4b) [33]. The
Schottky diodes satisfy the relation,
1 V þ Vbi
¼ 2 ; (8)
C2 qA2 ND ε
where V is the reverse bias voltage and A is the area of the capacitor.
1/C2 scales linearly with V (Fig. 4b) and the intercept of the
extrapolated line in x-axis yields Vbi. Resultantly, Vbi for
4 nm
thickness is 0:449 eV while
2 nm and
8 nm have 0:285 eV
and 0:373 eV, respectively. The built-in potential also has the
highest value for the ~4 nm sample, similar to the Schottky height
barrier. The reason why the ~8 nm device has lower potential is not
clear, but it is attributed to the weak connectivity between the
layers of graphene as the Schottky barrier was formed at the lower
layer, but the electrode was connected to the upper layer. The C-V
measurement provides information about the depletion region,
while J-V data corresponds to current transport in Schottky junc-
tions [33]. From C-V experimental results, it is confirmed that
4
nm is an optimum thickness for graphene/silicon Schottky
junction.
To further improve the efficiency, chemical doping (HNO3) and
anti-reflecting coating of PMMA were carried out on the optimal
thickness graphene as described previously [34]. Fig. 5 shows an
energy band diagram of the Schottky junction and electron-hole
generation under illumination. Due to the difference between
Fermi level of graphene and n-type silicon, the Schottky barrier and
depletion region are formed at the interface. In presence of light,
electron-hole pairs are generated and separated by a built-in
 M.A. Rehman et al. / Carbon 148 (2019) 187e195 193

Fig. 5. Energy band schematics of graphene/n-silicon Schottky junction solar cell under light. The arrow indicates direction of holes and electrons (a) In the case of the thin layer
(
2 nm) less electrons and holes were transmitted but the majority of them recombine. (b) In the case of optimum thickness, (
4 nm) more electrons and holes were transmitted
and recombination become minimal. (c) With doping on optimal thickness of graphene, the probability of the electrons and holes recombination became less and more electrons
and holes were transmitted. (A colour version of this figure can be viewed online.)

potential. The electrons remain at n-type silicon, while holes move
to p-type graphene side. Thus, a photocurrent is generated. Here,
graphene not only behaves as a transparent electrode, but also acts
as an active material for hole transport. In the case of a thin gra-
phene device (Fig. 5a), a low Schottky barrier height is formed, and
electron-hole pairs can recombine immediately before they are
separated. Also, the low built-in potential causes has low open
circuit voltage. Increasing the number of graphene layers enhances
the conductivity, and ultimately higher work function and Schottky
barrier height are achieved as shown in Fig. 5b. To further increase
work function of graphene and carrier concentration, graphene can
be heavily doped, lowering Fermi level, which increases Schottky
barrier as shown in Fig. 5c. Thus, with doping, built-in potential is
also increased, therefore, restraining electrons from tunneling into
p-type graphene. So it reduces the probability of carrier recombi-
nation which improves overall performance of the device [29].
In order to improve the solar cell performances further, anti-
reflecting PMMA coating and acid doping were performed on the
as-grown graphene. It was reported that HNO3 doping intensifies
sp2 and sp3 hybridizations and forms weak chemical bonding be-
tween graphene layers through p-p interaction, resulting in the
Fermi level shift towards p-type doping [35]. The doping was
confirmed by XPS as shown in Supporting information S8. The
graphene C1s peaks in Fig. S8(a) are associated with sp2 and sp3
hybridized states [36]. The major C-C bond sp2 peak lies at
284.61 eV of un-doped graphene, which is shifted towards lower
energy of 284.23 eV of doped graphene, confirming the p-doping
by HNO3 [37]. To confirm the presence of nitrogen, the N1s spectra
are measured as shown in Fig. S8(b). While no N1s peak is found in
un-doped graphene, a peak at 406 eV observed from the doped
graphene confirms the presence of nitrate ions [37]. On the other
hand, it was noticed that the PMMA coating did not affect the
conductivity of graphene significantly as shown in Table 3.
Fig. 6a presents a comparison of I-V characteristics (under dark
and light) of samples with PMMA coating and HNO3 doping, as well
as pristine graphene. The details about the parameters are listed in
Table 3. Firstly, solar cell parameters with PMMA coating on pristine
graphene were improved as Voc, Jsc ; and PCE were 0.392 V,
30.3 mA/cm2, and 6.65%, respectively. It is noted that with polymer
coating (PMMA) efficiency of the pristine sample was increased.
The enhanced efficiency from 5:51% to 6:65% by PMMA coating is
mostly related with increment of light absorption as the polymer
layer reduces the reflection [33]. In order to increase PCE, doping
processes were performed. The nitric acid is known to be a p-type
dopant in graphene, where electrons are transferred from the
graphene to HNO3 molecules forming charge-transfer complex
[38]. With direct doping of HNO3 on top of pristine direct grown
graphene, efficiency improvements were observed up to 56%
(supporting information S9). Though acid based doping on pristine
graphene significantly improves the efficiency, it reverts back after
a short duration of time (a few days) [33,39,40]. This is allegedly
because of the rapid evaporation of acid molecules on top of gra-
phene [34]. On the other hand, the HNO3 doping molecules can
permeate through the polymer layer in the polymer-coated Gr/Si
solar cells [34]. By doping of HNO3 on top of PMMA, efficiency was
increased from 5:51% to 9:18% corresponding to 66% improvement.
Most importantly, after 30 days, polymer doped graphene reduces
its efficiency to 8:32%, while directly doped pristine graphene ef-
ficiency reduces almost to its original value (supporting
information S10). Though the mechanism of HNO3 doping on
polymer instead of graphene is controversial [41], we ascribe this
improvement to the polymer morphology. As the polymer has a
complicated network structure, it can trap HNO3 molecules into its
inside, resulting in exceptionally improved graphene conductivity
and junction quality for a long period of time. Moreover, the strong
adhesion of polymer may reduce the series resistance and

Table 3
Comparison of photovoltaic characteristics at optimized thickness of graphene with polymer coating of PMMA and doping of HNO3.

Graphene (~4 nm) Carrier Concentration Nb (cm3) Sheet Resistance (kU/sq.) Voc (V) Isc (mA) Jsc (mA/cm2) FF (%) Efficiency (%)
20
Without doping 1:41  10 1:64 0.391 7.5 25.17 56.03 5.51
With PMMA 1.43  1020 1:59 0.392 9.07 30.3 56.05 6.65
HNO3 doping on PMMA 3:61  1020 1:00 0.446 11.0 36.6 56.2 9.18
194
Fig. 6. Photovoltaic characteristics of optimized thickness graphene/silicon solar cell and EQE. (a) I-V characteristics under light pristine, with the polymer layer and with doping. (b)
EQE as a function of wavelength of the solar cell based on pristine graphene, with polymer layer and doping. (A colour version of this figure can be viewed online.)
guarantee the mechanical stability of the solar cell structure.
Additional characterization, external quantum efficiencies (EQE)
were measured for pristine (directly grown graphene), PMMA
coated, and doped solar cells as shown in Fig. 6b. Apparently, EQE is
identical to silicon based solar cells [42]. The pristine device shows
almost 60% collection of electron hole pairs at corresponding metal
electrodes, throughout the spectrum from the ultraviolet (UV) to
infrared region (IR). However, with the polymer layer and doping, it
is further increased almost up to 90% implying
10% change with
anti-reflecting coating and
20% with doping. Table 3 manifests
that not only charge carrier generation is increased with doping,
but charge collection and separation also become efficient. As a
result high EQE is achieved, and it is consistent with the photo-
voltaic data.
4. Conclusion
In this work, multilayer graphene directly grown on Si was
adopted for solar cell application, and an optimized performance
was accomplished via the control of graphene thickness and an
additional polymer layer. Because of the balance between the
transparency and the conductivity, the
4 nm thick graphene
device exhibited the best performance. We have obtained an effi-
ciency of 5:51% on bare silicon by using direct growth approach,
which was further improved to 9:18% after PMMA coating and
doping. The enhancement in efficiency is mainly due to an increase
in light absorption by anti-reflective coating and lowered Fermi
level by doping. In fact, the increased work function improves
collection of photo-generated carriers with intensified built-in
potential and reduction in sheet resistance due to less Ohmic
loss. Compared with the transfer process of CVD grown graphene,
direct growth approach of graphene is more promising for future
practical applications with low cost. The efficiency could be further
improved by introducing an interfacial layer in between silicon and
graphene, which were described previously in our group [9].
Contributions
Y.S. and S.H.C. conceived the project. M.A.R and S.B.R. designed
and carried out research, analyzed data. M.A.R and Y.S. wrote the
M.A. Rehman et al. / Carbon 148 (2019) 187e195
paper. I.A., M.F.B., W.C., G.N. and M.F.K. contributed in material
characterization and discussion. S.K., J.E. and S.H.C. provide scien-
tific advices. All authors contributed to the writing and editing.
Acknowledgments
This research was supported by the Priority Research Centers
Program (2010-0020207) and Basic Science Research Program
(2017R1A2B4002379 and 2018R1A5A6075964) through the Na-
tional Research Foundation of Korea (NRF) funded by the Ministry
of Education.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
https://doi.org/10.1016/j.carbon.2019.03.079.
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