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[] Dr. X. M. Li, Prof. H. W. Zhu, Prof. K. L. Wang, Prof. J. Q. Wei, Ms. C. Y. Li, Dr. Y. Jia, Dr. Z. Li, Dr. X. Li, Prof. D. H. Wu Key Laboratory for Advanced Manufacturing by Material Processing Technology and Department of Mechanical Engineering Tsinghua University Beijing 100084 (P. R. China) E-mail: hongweizhu@tsinghua.edu.cn; wangkl@tsinghua.edu.cn Prof. A. Y. Cao Department of Advanced Materials and Nanotechnology College of Engineering Peking University Beijing 100871 (P. R. China)
DOI: 10.1002/adma.200904383
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Figure 1. Characterizations of the GS/n-Si Schottky junction. A) Schematic illustration of the device conguration. Bottom-left inset: cross-sectional view, photogenerated holes (h+) and electrons (e) are driven into the GS and n-Si, respectively, by the built-in electric eld. Bottom-right inset: photograph of a GS/n-Si Schottky cell with a 0.1 cm2 junction area. B) A SEM top-view image of a GS/n-Si junction. Scale bar: 2 m. C) GS across the Au/SiO2 and D) SiO2/Si steps. Scale bars: 2 m and 1 m. The insets show the corresponding optical images. Scale bars: 10 m. E) TEM image of graphene. Scale bar: 500 nm.
is favorable for producing a relatively large built-in led (V0, 0.550.75 V) and charge separation (Figure 2A). A spacecharge region accompanied by V0 is formed in the n-Si near the GS/nSi interface. This indicates that the GS lm not only serves as a transparent electrode for light illumination, but also an active layer for electronhole separation and hole transport.
Dark-currentvoltage (IV) curves obtained from the GS/n-Si cells (Figure 2B) exhibit rectifying characteristics, and demonstrate that the GS/n-Si heterostructures behave as well-dened diodes with a rectication ratio of 104 106. A t to a ln(I)V curve recorded in forward bias from a typical GS/n-Si junction (left inset of Figure 2B) is nearly linear in the range of 0.1 0.4 V and yields
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A
Vacuum level G eVbias b e(V0-Vbias) n-si
10 10 10
-1
dV/d (lnI)
0.4 0.6
-2
-8 ln(I) -12
n=1.57
0.8
Rs=10.5
-3
0.4
Current (A)
10 10 10 10 10
-4
-16 0.2
0.00
0.05
-5
Voltage (V)
I (A)
EC EF Eg
-6
0.5 cm 0.1 cm
-4 -3
2
-7
hv
GS n-Si
EV
-8
-5
-2
-1
Voltage (V)
Jsc (mA/cm )
C
Current density (mA/cm )
2
D
8 0.48 0.45 0.42 0 0.7 2.2
(%)
3
2
-3
-6 0.0 0.2
0.4
0.6
100
Voltage (V)
Figure 2. Photovoltaic characterizations of GS/n-Si solar cells. A) Energy diagram of the forward-biased GS/n-Si Schottky junction upon illumination. G (4.8 5.0 eV), n-Si (4.25 eV) is the work function of GS and n-Si, respectively. V0 is the built-in potential. b is the barrier height. is the electron afnity of silicon (4.05 eV). Eg is the bandgap of silicon (1.12 eV) and EF is the energy of the Fermi level. Vbias is the applied voltage. The depth of the Fermi level below the Si conduction band edge (ECEF) is 0.25 eV for the n-Si used in this work. B) Semilogarhythmic-scale dark IV curves of two GS/n-Si cells of different junction areas. The ideality factor (n) and the series resistance (Rs) of the 0.1 cm2 cell extrapolated from the linear regimes in the insets are 1.57 and 10.5 , respectively. The shunt resistance is up to 45 M which is estimated from reverse bias IV sweep. C) Light JV curves of the cells illuminated with simulated AM 1.5 Global light. D) Light-intensity-dependent Jsc, Voc, FF, and plots of a 0.1 cm2 GS/n-Si cell.
a diode ideality factor (n) of 1.57. The reverse leakage current is nearly proportional to the area of the contact as the leakage current is restricted to the volume of n-Si directly under the GS/nSi Schottky contact. As shown in Figure 2C, the 0.1 cm2 Schottky diode has a slightly larger turn-on voltage thanks to the higher barrier height (b) of 0.78 eV estimated based on Equation 1 (see the Experimental Section), which is in agreement with the difference between G and (G = 4.8 4.05 = 0.75 eV). The photovoltaic properties of the GS/n-Si solar cells were characterized under air mass 1.5 (AM 1.5) illumination. The photogenerated carriers are separated by the built-in eld, and holes are diffused to the junction where they are swept to the GS side. The two-dimensional, highly conductive graphene will reduce or eliminate lateral potential drop along the GS, thereby enabling uniform carrier separation and collection. Light currentdensityvoltage (JV) data recorded from typical GS/n-Si cells yield down-shift curves with an open-circuit voltage (Voc) of 0.42 0.48 V, a short-circuit current density (Jsc) of 4 6.5 mA cm2 and a ll factor (FF) of 45 56%, which corresponds to an
overall solar energy conversion efciency () of 1.0 1.7%. As shown in Figure 2C, the 0.1 cm2 and 0.5 cm2 devices are characterized by a of 1.65% and 1.34%, respectively. These photovoltaic values have been easily reproducible and were repeatable for measurements made over an approximately twomonth period, thus exhibiting excellent stability of our GS/n-Si cells. The average of the unoptimized cells is 1.5%, which is still lower than that for reported a-C/Si, CNTs/Si devices, but might be improved through balancing the conductivity and transparency of GS and improving the GS/n-Si interface. It was also found that GS essentially acts as an antireection coating and reduces reection by 70% in the visible region and 80% in the near-IR region (see the Supporting Information). The overall efciency could also be further increased with improvements in Voc by means of, for example, surface passivation of silicon. In Figure 2D, the performance parameters of the GS/n-Si cell (Jsc, Voc, FF, and ) are plotted as functions of the incident light intensity. Jsc depends linearly on the light-intensity incident on the cell (Figure 2D), consistent with a systematic increase
Voc (V)
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1.0
dIPCE/dE
4
1.19 eV 1.12 eV
1.22 eV
0.3 0.0
Intensity (a.u.)
Current (mA)
1
In series
1 2
IPCE
E (eV)
2
In parallel
1 2
0.0
0.2
0.4
0.6
0.8
1.0
E (eV)
Voltage (V)
Figure 3. IPCE spectra versus photon energy (E) for three GS/n-Si cells. The inset shows a differential IPCE spectrum.
B 1.2
0.9
1
Iout Vout
0
in photogenerated carriers. A similar trend was observed for Voc. FF and fall off monotonically with an increase in the light intensity and approach 0.69 and 2.2%, respectively, under AM1.5 condition at 15 mW cm2. The normalized incident-photon-to-electron conversion efciencies (IPCE, dened as the number of charge carriers collected per incident photon) of the GS/n-Si devices were measured in the visible and near-infrared region (photon energy: 1 4 eV). Figure 3 displays typical IPCE spectra for three cells, which show similar photoresponse. At low energies, the IPCE spectra signicantly overlap but diverge as the incident photon energy increases past 1.5 eV and enters the visible region. This can be attributed to the difference in visible transmittance of GS used in these cells. The rst-order derivative of IPCE shown in the inset yields a sharp peak (1.22 eV) with two shoulder peaks (1.19 eV, 1.12 eV), which represent the fastest photon-to-electron conversion and can be assigned to the bandgap of silicon. The GS/n-Si photovoltaic cells were assembled into a solar array in series and in parallel to multiply the output voltage or (and) current, i.e., the output power. JV data recorded from two illuminated GS/n-Si cells (Figure 4A) show that interconnection of the two cells in series and parallel yields Voc and Jsc values, respectively, which equal to the sum of the values of the two base cells. The corresponding time-resolved onoff photoresponse of the interconnected GS/n-Si cells are plotted in Figure 4B. Notably, the interconnected cells can perform a selfpowered logical operation on two inputs and produce a logic output of voltage (Vout) or current (Iout) when the cell is opencircuited or short-circuited. The input state is dened as 1 (high) or 0 (low) when the corresponding cell is illuminated or not. The output voltages (open-circuited) Vout both show OR logic dependence on the input states for the interconnections in series and parallel, while the output current (short-circuited) Iout shows AND logic for series connection and OR logic for parallel connection. This result shows the potential for developing light-controlled sensors and switches especially that rely on remote activation and triggering. It is worth mentioning that there are a few drawbacks to the present GS/n-Si solar cells that deserve future work. JV data recorded using GS of different thicknesses exhibited essentially
Iout (mA)
Vout (V)
1.2
Vout (V)
Vout
Iout (mA)
0.8 0.4
0.2 0.0
0.0
00
01 10 Input state
11
Figure 4. A) Light JV curves of two GS/n-Si cells in series and parallel connections. The JV characteristics of individual cells are also plotted for comparison. The corresponding circuit connection schematics are plotted in the insets. B) GS/n-Si OR and AND logic gates powered by two cells in series (top) and parallel (bottom). The insets show the circuit schematics for the logic gates when the input state is 1 0.
the different photovoltaic response. The Jsc and Voc are smaller for cells with thicker GS because more carrier recombination occurs in the thicker lms, which also makes it difcult to achieve enough light absorption, thus indicating that the tradeoff between the conductivity and transparency of GS needs to be further optimized. The depletion width in the device was estimated to be 0.5 0.7 m, which is still small and needs to be appropriately increased to improve IPCE. Further enhanced uniformity of GS is also necessary to provide better holetransport, easy exciton separation, and suppression of chargecarrier recombination. The fabrication of Schottky junctions has the merits of low cost and simplicity. Although devices with partial replacements are still far lower in efciency than pure silicon cells, this simple concept of Schottky junctions made of GS and n-Si, with an improved understanding of electronic coupling, surface passivation, doping, and junction formation, will lead to much more efcient and stable graphene/graphite-based solar cells in the future. It is expected that after complete development, carbonbased photovoltaic cells may become more practicable than
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silicon-based cells by making full use of the above-mentioned advantageous characteristics and, unlike silicon, the material is highly environmentally friendly.
(1)
(2)
Experimental Section
GS Synthesis and Characterizations: GS were synthesized by a chemical vapor deposition method using nickel lms[2,3] or foils[23] as substrates. The growth parameters were carefully controlled to ensure uniform graphene precipitation. Ni was gradually heated to 1000 C in an Ar/H2 (200/100 mL min1) ow for 1 h. Then methane (ethanol) was introduced with a feeding speed of 20 mL min1 (20 L min1) in an Ar/H2 (800/200 mL min1) ow for 10 20 min. Carbon decomposed from methane (ethanol) was rst dissolved into Ni. After carburization, Ni was withdrawn from the heating zone and cooled down to room temperature at a fast cooling rate of 10 20 C s1. The growth is based on a non-equilibrium surface segregation process by controlled cooling as previously reported.[2,3,23] During the cool-down period, the carbon solubility in Ni decreases and carbon segregates at the surface of Ni substrate to form GS layers. Freestanding GS were obtained by detaching the GS from Ni in an acid solution (e.g., HNO3)[23] or FeCl3 solution,[3] followed by rinsing with deionized water. The raw GS lms were then immersed into a H2O2 solution (30%) for over 24 h to remove the amorphous carbon impurities and obtain a hydrophilic surface. The treated GS samples were then washed with deionized water. The resulting GS lms can be collected easily from the water surface with an arbitrary substrate. The microstructure of GS was investigated by TEM and SEM. As shown in Figure S1, Supporting Information, the GS consists of mono-layer, bi-layer, and most few-layer graphenes. The GS has a multi-layered structure to ensure conductive channels even cracks are present on the top layer. The GS have nominal thicknesses (dn) varied between 10 100 nm. dn was measured when considering the surface roughness of GS due to the presence of wrinkles, and the value is larger than the real thickness of GS. Figure S3A, Supporting Information, shows the transmission spectra of GS of different dn. Raman spectra were obtained with a Renishaw 2000 Raman system with a 633 nm (1.96 eV) laser. Figure S2, Supporting Information, shows the Raman spectra of as-grown graphenes of different layers. Monolayer graphene is identied unambiguously from the high I2D/IG ratio (4.5) and single peak 2D band with a full width at half maximum (FWHM) of 29 cm1. The G-band is located at a normal position (1581.6 cm1). The relatively small blueshift for the 2D band (10 cm1 comparing with 2650 cm1) further proves the weak grapheneNi interaction, revealing that the strain effect[24] caused by Ni grain deformation during hightemperature carburization is relaxed thanks to the wrinkle formation on Ni surface. Cell Assembly: n-Si (100) wafers (doping density: 1.5 3 1015 cm3) with a 300-nm SiO2 layer were patterned by photolithography and wet-etching of oxide (by hydrouoric acid solution) to prepare square windows (0.1 0.5 cm2) where n-Si was exposed. The front and back contacts were produced using sputtered Au on the SiO2 and Ti/Pd/Ag on the back side of the n-Si. GS was then transferred to the top of the patterned wafer and naturally dried to achieve a conformal coating with the Au layer and the underlying n-Si. In this conguration, GS serves as the semitransparent upper electrode and the antireection layer. Figure S3B, Supporting Information, shows the comparison of the reection spectra of n-Si and GS/n-Si. Schottky Junction Characterizations: Forward bias is dened as positive voltage applied to the GS. The currentvoltage data were recorded using a Keithley 2601 SourceMeter. It is well known that any semiconductor can form a Schottky junction with a certain metal if the difference between their work functions is large enough, and the carrier density of the semiconductor is moderate. The non-linear IV characteristic of the Schottky junction can be expressed by the thermoionic emission model:[25]
2V0 W = eND
1/2
(3)
where A is the contact area, A is the effective Richardson constant [252 A cm2 K2 for n-type silicon], T is the absolute temperature, e is electronic charge, b is the barrier height, k is the Boltzman constant, n is the diode ideality factor. Is is the reversed saturated current. Rs is the series resistance. W is the depletion width. ND is the doping density (1.5 3 1015 cm3). is the dielectric permittivity ( = 11.9 0 for silicon, 0 = 8.854 1014 F cm1). The reverse leakage current (Is) is 0.05 0.5 A for a 0.1 cm2 cell. Based on Equation 1, the barrier height (b) is estimated to be 0.75 0.8 eV, which is in agreement with the difference between G and (G = 4.8 4.05 = 0.75 eV), as illustrated in the thermal equilibrium energy band diagram of the GS/n-Si junction in the dark (Figure S4A, Supporting Information). The series resistance (Rs) can be determined from Equation 2 to be 9 12 in the range of 0.1 2.0 V. Reverse bias measurements show that the GS/n-Si diode breaks down at relatively low reverse-bias voltage (about 30 V). Estimated from Equation 3, the junctions have a depletion layer of 0.5 0.7 m, which was established in the n-Si. Light Characteristics of GS/n-Si Cells: The devices were tested with a solar simulator (Thermo Oriel 91192-1000) under AM 1.5 condition. The photocurrent action spectra of the GS/n-Si solar cells were measured with CEP-25/CH. Figure S4B, Supporting Information, shows the energy band diagrams of a short-circuited and an open-circuited Schottky junction upon illumination. When the GS/n-Si cell is short-circuited, the extracted photogenerated carriers can transit through the external circuit, generating a short-circuit current. When the GS/n-Si cell is open-circuited, the separation of photogenerated electrons and holes will produce an open-circuit voltage Voc. The quasi-Fermi levels of GS and n-Si are separated with an energy offset of eVoc, corresponding to applying a forward bias (Voc) to the Schottky junction. The photocurrent is opposite to the forward-biased current of the device. At V = Voc, these two currents will cancel each other and result in a zero net current.
Acknowledgements
This work is supported by the National Science Foundation of China (#50972067) and the Program for New Century Excellent Talents in University, State Education Ministry of China (#NCET-08-0322).
Supporting Information
Supporting Information is available online from Wiley InterScience or from the author. Received: December 22, 2009 Revised: February 2, 2010 Published online: April 9, 2010
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