Layered semiconductor molybdenum disulde nanomembrane based
Schottky-barrier solar cells
Mariyappan Shanmugam, Chris A. Durcan and Bin Yu * Received 21st August 2012, Accepted 27th September 2012 DOI: 10.1039/c2nr32394j We demonstrate Schottky-barrier solar cells employing a stack of layer-structured semiconductor molybdenumdisulde (MoS 2 ) nanomembranes, synthesized by the chemical-vapor-deposition method, as the critical photoactive layer. An MoS 2 nanomembrane forms a Schottky-barrier with a metal contact by the layer-transfer process onto an indium tin oxide (ITO) coated glass substrate. Two vibrational modes in MoS 2 nanomembranes, E 1 2g (in-plane) and A 1g (perpendicular-to-plane), were veried by Raman spectroscopy. With a simple stacked structure of ITOMoS 2 Au, the fabricated solar cell demonstrates a photo-conversion efciency of 0.7%for 110 nmMoS 2 and 1.8%for 220 nm MoS 2 . The improvement is attributed to a substantial increase in photonic absorption. The MoS 2 nanomembrane exhibits efcient photo-absorption in the spectral region of 350950 nm, as conrmed by the external quantumefciency. Asizable increase in MoS 2 thickness results in only minor change in MottSchottky behavior, indicating that defect density is insensitive to nanomembrane thickness attributed to the dangling-bond-free layered structure. Introduction Schottky-barrier solar cells have the appealing advantage of low- cost manufacture attributable to their simple and versatile fabrication process and thin-lm-like structure (reduced active material consumption as compared with pn or pin junction bulk semiconductor solar cells). Schottky-barrier solar cells rely mostly on a single semiconductor material (either p-or n-type doped) in association with a metal, leading to energy barrier formation and carrier dissociation at the metalsemiconductor (MS) interface. Various MS material systems have been used in Schottky-barrier solar cells, including Alamorphous carbon nitride, 1 Au, Al, Mg and CaPbSe quantum dots, 2 AlSnS, 3 and AuGaAs. 4 Recently, carbon derivatives have attracted attention due to their promising optical/electrical properties. Schottky junctions made by carbon nanotubeCdSe, 5 grapheneCdS nanowire, 6 graphene, carbon nanotubeSi, 7,8 and grapheneSi nanowire 911 have been reported. In general, MS interfacial behavior and carrier mobility/photon absorption in the semi- conductor material are key factors that impact the overall performance of Schottky-barrier solar cells. While a group of semiconductors such as boron doped diamond, 12 GaAs, 13,14 InP, 15 SiGe, 16 GaP, 17 GaN, 18 and SiC 19 can be used, the design of an MS system with appropriate material work function differ- ence is an essential factor to determine the Schottky-barrier height and efciency of carrier separation. The development of Schottky-barrier solar cells has been decelerated over the past decade due to several fundamental material challenges, including interfacial oxide layer formation and Fermi-level pinning caused by interfacial states (which are inevitable at MS interfaces). 2024 While poor interface properties play a substantial role in the impeded improvement of energy-conversion efciency, searching for a new class of semiconductor materials free of interfacial states (hence without Fermi level pinning) would be of strategic signicance to the ultimate realization of highly efcient Schottky-barrier solar cells. Transition-metal dichalcogenide semiconductors exhibit two dimensional (2D) layered lattice structures with strong in-plane covalent bonds and weak interlayer van der Waals interaction. Molybdenum disulphide (MoS 2 ), a layered semiconductor, has recently attracted attention in the elds of nanoelectronics, 2530 energy storage 3133 and photovoltaics. 34 Nanosheets of monolayer or multilayer MoS 2 can be obtained via mechanical or chemical exfoliation, 35,36 similar tothe way graphene is produced. Recently, direct assembly of MoS 2 nanosheets on SiO 2 by the chemical- vapor-deposition (CVD) method has been demonstrated. 37 MoS 2 exhibits direct energy bandgap (1.85 eV) in monolayer and indirect bandgap (1.3 eV) in multilayer/bulk form, respec- tively. 38 Onelectronic properties, it has beenrecently reportedthat MoS 2 shows carrier mobility values of 200 cm 2 V 1 s 1 in monolayer and 517 cm 2 V 1 s 1 in a few layers, suggesting promising conducting capacity. 39,40 Most importantly, the unique structure of layered semiconductors provides inherent advantages of forming a smooth surface free of any dangling chemical bonds, potentially enabling the design of highly efcient Schottky-barrier College of Nanoscale Science and Engineering, State University of New York, Albany, NY-12203, USA. E-mail: byu@albany.edu; Fax: +1 518 956-7492; Tel: +1 518 956-7492 This journal is The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 73997405 | 7399 Dynamic Article Links C < Nanoscale Cite this: Nanoscale, 2012, 4, 7399 www.rsc.org/nanoscale PAPER P u b l i s h e d
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View Article Online / Journal Homepage / Table of Contents for this issue solar cells. Various metal contacts, including Ag, Al, Au, Co and Fe, have been investigated for the formation of Schottky-barriers with MoS 2 bulk crystals. No Fermi level pinning was observed even for a high density of material defect (10 14 cm 3 ). 41 In this paper we demonstrate solar cells employing a layer- structured semiconductor MoS 2 nanomembranemetal (Au) Schottky barrier. The CVD-assembled MoS 2 nanomembrane also functions as the key photo-active layer. The solar cells are made by a simple stack structure of ITOMoS 2 Au. Basic material properties of MoS 2 , major solar cell device performance metrics, and the impact of MoS 2 nanomembrane thickness are discussed. The MoS 2 Au Schottky-barrier interface is charac- terized by capacitance vs. voltage (CV) measurements. Experimental section Large-area (up to several square centimeters) semiconductor MoS 2 nanomembranes were synthesized by the CVD approach. Fig. 1(a) is the schematic of the CVD growth furnace system showing Ar as a carrier gas and a sulphur (S) source owing towards a molybdenum (Mo)-coated SiSiO 2 substrate (where vaporsolid reaction occurs to assemble the MoS 2 nano- membrane). CVD growth of MoS 2 silicon coated with 100 nm of SiO 2 was used as the substrate for the pre-deposition of Mo. A thin Mo metal layer was deposited with an approximate thick- ness of 50 nm by the electron-beam evaporation method. The CVD growth process started with owing Ar of 200 sccm in the quartz-tube chamber with a pressure level of 1 Torr. The furnace was subsequently heated up to 750
Cand stabilized over
one hour. Pure S powder, placed upstream in the chamber, was heated to just above its melting temperature (115
C). The S vapor owed over the Mo thin lm pre-deposited on the SiO 2 Si substrate for approximately 30 minutes. Vaporsolid reaction took place at an elevated temperature (750
C), leading to the growth of an MoS 2 nanomembrane driven by increase in enthalpy. While the MoMo bond is relatively weak (metallic in Fig. 1 (a) Schematic of the CVDgrowth setup showing the reaction of sulphur vapor with Mo lmpre-deposited on SiSiO 2 substrate for the growth of an MoS 2 nanomembrane. (b) Major process steps involved in the synthesis of the MoS 2 nanomembrane, layer transfer, and subsequent fabrication of a Schottky-barrier solar cell. The KOH wet etching process was used to detach the MoS 2 nanomembrane from SiO 2 Si substrate. (c and d) Partially oating MoS 2 nanomembrane in KOH solution. (e) Free-oating MoS 2 nanomembrane in KOH to be transferred onto an ITO-coated glass substrate for solar cell fabrication. 7400 | Nanoscale, 2012, 4, 73997405 This journal is The Royal Society of Chemistry 2012 P u b l i s h e d
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View Article Online nature), the MoS bond is a strong ionic one and therefore more thermodynamically stable. As the temperature increases, Mo atoms gain sufcient thermal energy (exceeding the activation energy) and make covalent bonds with S atoms. After the completion of CVD growth, the sample was annealed at 1000
C for one hour to improve the crystalline quality and the unifor- mity of the resultant nanomembrane. The major steps in the MoS 2 layer transfer sequence are depicted in Fig. 1(b) starting from the SiSiO 2 substrate, Mo metal deposition, MoS 2 growth, and transfer to the target substrate in which the solar cells were fabricated. The CVD-assembled MoS 2 nanomembrane was transferred from the growth substrate (SiO 2 Si) to an indium tin oxide (ITO serving as transparent electrode) coated device substrate, involving a wet chemistry etching step of the SiO 2 layer in the growth substrate to yield a freestanding MoS 2 nanomembrane in potassium hydroxide (KOH) solution. Fig. 1(c)(e) show the optical images of the process to separate the MoS 2 nano- membrane from SiO 2 Si substrate. The MoS 2 nanomembrane was transferred onto the transparent conducting oxide (ITO) substrate to fabricate the Schottky-barrier solar cell. KOH solution with a concentration of 15 M was prepared in which the MoS 2 SiSiO 2 substrate was immersed to etch away the SiO 2 . A slow and smooth KOH etching of SiO 2 released the MoS 2 nanomembrane partially from the Si substrate. Within approx- imately 10 minutes a completely free-oating MoS 2 nano- membrane in KOH solution was obtained. The thickness of the MoS 2 nanomembrane is determined by that of the Mo lm deposited by electron beam evaporation (it is hence scalable). The surface morphology and thickness of the as-grown MoS 2 nanomembrane was characterized by Atomic Force Microscopy (AFM, dimension 3100). Raman spectroscopy (Horiba Scien- tic) with a laser of 532 nm was performed on the samples to conrm the growth of MoS 2 via identied vibrational modes. After transferring the MoS 2 nanomembrane onto the ITO- coated glass substrate, deposition of 50 nm of Au contact was made by electron-beam evaporation to form a Schottky-barrier (with MoS 2 ). The JV characteristics of the solar cell were measured under both dark and standard AM 1.5 illumination conditions using an Agilent B1500A semiconductor parameter analyzer. An Xe arc lamp was used to simulate the solar light. The EQE characteristics of the solar cells were measured in the wavelength range of 350950 nm using a Newport mono- chromator (equipped with the same Xe arc lamp that was used to measure the JV characteristics). The CV measurement was performed on the solar cell using a B1520A-FG Multi Frequency Capacitance Measurement Unit Module attached to an Agilent B1500A using a frequency of 1 kHz and AC perturbation of 10 mV at room temperature. Results and discussion Fig. 2(a) is the micrograph showing the surface morphology of an MoS 2 nanomembrane after being transferred onto the ITO substrate, as obtained from the 2D mapping measurement of an Atomic Force Microscope (AFM). The AFM line-scan was carried out, from point A to point B as shown in Fig. 2(a), to measure the physical thickness of the MoS 2 nanomembrane. The step height between MoS 2 and the ITO substrate, as seen in Fig. 2(b), conrmed the thickness of the MoS 2 nanomembrane to be about 55 nm, an average value from the measured data. We believe that the as-grown MoS 2 nanomembrane on the SiSiO 2 substrate in our CVD process is highly uniform in thickness, as reported by Y. Zhan et al. in a similar growth experiment. 37 The variation in AFM line-scan data (approximately 5 nm) could arise from deformation of the MoS 2 nanomembrane as a result of the layer transfer process. We expect that micro-level wrinkles might have been formed on the MoS 2 nanomembrane caused by various types of mechanical interactions during the wet chem- istry etching and transferring process. Material characterization using Raman spectroscopy was conducted on two transferred MoS 2 nanomembrane samples with different physical thicknesses. While the as-assembled MoS 2 exhibits an average thickness of 55 nm, as shown in Fig. 2(b), stacked MoS 2 nanomembranes were prepared via multiple (two and four, respectively, in our experiment) transfers. The samples were subsequently used for Raman spectroscopic investigation. The expected thicknesses of the two samples are 110 nm (two transfers) and 220 nm (four transfers), respec- tively. Prior research results show that there is a signicant difference in the signature modes in Raman spectra for Fig. 2 (a) 2D mapping micrograph of AFM surface scan obtained on an as-assembled MoS 2 nanomembrane after transferring onto an ITO substrate. The line-scan measurement was performed from point A to B to evaluate the physical thickness of MoS 2 . (b) Measured step prole of the MoS 2 nanomembrane on ITO substrate. This journal is The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 73997405 | 7401 P u b l i s h e d
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View Article Online monolayer, bilayer and few-layer MoS 2 . 37 In our experiment, a much thicker stack of MoS 2 was employed to enhance the photo- absorption in the Schottky-barrier solar cells. Fig. 3(a) shows the Raman spectra of the MoS 2 nanomembrane samples with thicknesses of 110 nm and 220 nm, respectively. Two signif- icant Raman active modes were identied at the wavenumbers of 383 cm 1 and 408 cm 1 which correspond to E 1 2g and A 1g modes respectively. Fig. 3(b) displays schematically both E 1 2g and A 1g modes. In the E 1 2g mode both Mo and S atoms vibrate along the in-plane direction (yet opposite to each other), whereas in the A 1g mode the S atoms vibrate in the perpendicular-to-plane direction. The Raman signature peaks observed in our experiment conrmboth in-plane and perpendicular-to-plane Raman active modes. As we used relatively thick MoS 2 (>100 nm), there are no blue- and red- shifts for the E 1 2g and A 1g modes, different from that observed in monolayer/bilayer MoS 2 nanomembranes. 37 The signicant variation in the peak intensity of Raman spectra, as observed in the two examined samples, was due to the substantial difference in physical thickness (100 nm). Fig. 4(a) shows the schematic cross-sectional view of the MoS 2 nanomembraneAu Schottky-barrier solar cell. The MoS 2 nano- membrane was transferred onto an ITO substrate (serving as the windowlayer through which the solar cell is illuminated). Fig. 4(b) shows the energy band diagramof the fabricated Schottky-barrier solar cell structure with a stack of ITOMoS 2 Au. In general, if the metal work function is higher than that of the n-type semiconductor, then an ideal Schottky-barrier could be formed. In our experiment, Au (work function: 5.1 eV) forms a barrier on the MoS 2 semiconductor (work function: 4.6 eV). The ITO used in this study is a heavily n-type doped transparent conductive oxide with a work function of 4.5 eV. It forms an almost perfect ohmic contact with the n-type doped MoS 2 nanomembrane. As shown in Fig. 4(b), the Fermi level of ITO is above the conduction band due to its heavily doped nature. Although layer-dependent optical properties (e.g., change of bandgap with number of layers) has been demonstrated in ultra- thin MoS 2 (from a monolayer to six layers) as reported by K. F. Mak et al., 39 the bulk properties dominate in thicker stacks of MoS 2 . In our experiment, MoS 2 nanomembrane stacks Fig. 3 (a) Raman spectra obtained on two samples of MoS 2 nano- membranes with thicknesses of 110 nm and 220 nm, respectively. The samples were prepared by multiple transfers/stacking of CVD-grown MoS 2 . (b) Schematic showing the two Raman active modes corre- sponding to the signature peaks observed in MoS 2 . Fig. 4 (a) Schematic cross-sectional view of the demonstrated Schottky barrier solar cell structure showing a stack of MoS 2 nanomembrane on an ITO substrate with Au contact. (b) Energy band diagram of the solar cell with formation of a Schottky-barrier between the MoS 2 nano- membrane and Au metal contact. 7402 | Nanoscale, 2012, 4, 73997405 This journal is The Royal Society of Chemistry 2012 P u b l i s h e d
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View Article Online (110 nm and 220 nm) were used for the fabrication of solar cells. Therefore layer dependency of the optical bandgap becomes negligible. We consider the MoS 2 stack with an optical bandgap of 1.3 eV which effectively absorbs photons in the wavelength region of 350950 nm. The Schottky-barrier solar cells are illuminated through the ITO window layer which does not absorb any photons in the visible light spectral region, as its bandgap is 3.8 eV and more than 95% optically transparent. Incident photons generate electronhole pairs in the MoS 2 nanomembrane and electrons are subsequently excited to the conduction band (E C ) of MoS 2 . As the work function difference between Au and MoS 2 results in a Schottky-barrier, the photo- excited electrons move from the E C of MoS 2 towards the Fermi level of ITO(where they can be collected to the load). Alarger work function difference between Au and n-type MoS 2 would generate a higher electric eld in the depletion region of MoS 2 . The built-in electric eld facilitates the dissociation of the photo-excited elec- tronhole pairs, transporting separated carriers towards ITO and Au contacts. The processes of photo-excitation in MoS 2 and elec- tron transport from MoS 2 to ITO are demonstrated in Fig. 4(b). Fig. 5(a) and (b) show the dark and illuminated JV charac- teristics of the fabricated Schottky-barrier solar cells with MoS 2 thicknesses of 110 nm and 220 nm, respectively. The output power as a function of voltage in each solar cell is shown in the insets of Fig. 5(a) and (b), respectively. For the Schottky-barrier solar cell with MoS 2 thickness of 110 nm key metrics J SC (short- circuit current density), V OC (open-circuit voltage), P MAX (maximum power), FF (ll factor) and h (photo-conversion efciency) are 2.52 mA cm 2 , 590 mV, 1.22 10 4 W, 0.48 and 0.7%, respectively. For the solar cell with MoS 2 thickness of 220 nm, J SC , V OC , P MAX , FF and h are 5.37 mAcm 2 , 597 mV, 2.99 10 4 W, 0.55 and 1.8% respectively. It is observed that an increase of MoS 2 thickness helps to signicantly enhance J SC of the solar cell (by 113%) due to more efcient photo-absorption in the thicker MoS 2 stack, and hence creates a noteworthy change in overall device performance. It should be noted that there is no sizable change in V OC between solar cells with different thick- nesses of MoS 2 stacks (merely 1% change). It is evident that an increase in thickness of the MoS 2 stack would not cause a notable change in the band structure (hence no change in the Fermi level) due to the absence of layer-dependent properties. Fig. 5(c) shows the schematic to compare carrier recombina- tion in conventional and layered semiconductors. Process 1 represents optical excitation leading to electronhole pair generation. In conventional semiconductors, the amount of interface states (recombination centers) in the bandgap is huge due to unsaturated chemical dangling bonds which capture electrons from the conduction band (Process 2) and holes from the valence band (Process 3), leading to recombination. In layered semiconductors, the amount of interface states is signif- icantly less due to the self-saturated surface bonds which do not actively participate in the recombination process. Thus, we attribute the enhancement in solar cell performance to the increase in MoS 2 thickness which improved photon absorption. We expect that as a layered material, defect density in MoS 2 does not increase drastically with increasing thickness compared to a conventional semiconductor. Fig. 6 shows External Quantum Efciency (EQE) spectra of the two Schottky-barrier solar cells with different MoS 2 thicknesses in the wavelength range of 350950 nm. The maximum EQE values of 41% and 52% were measured for solar cells with 110 nm and 220 nm of MoS 2 stack, respectively, at wavelength of 600 nm. The increase in MoS 2 thickness plays a vital role in photo-absorption. Our prior work on MoS 2 -based Fig. 5 Measured dark and illuminated JV characteristics of the Schottky-barrier solar cells with a stack of MoS 2 nanomembrane having thicknesses of (a) 110 nm and (b) 220 nm. Inset of each gure shows the power output as a function of voltage for the fabricated solar cell. (c) Recombination process via electronhole capture by interfacial trap states present in conventional and layered semiconductors, showing signicantly fewer traps in the latter. This leads to reduced probability of carrier recombination in a layered semiconductor. This journal is The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 73997405 | 7403 P u b l i s h e d
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View Article Online solar cells 34 employing a combination of monolayer/multi-layer stacks of MoS 2 on TiO 2 (serving as electron acceptor) has shown photon absorption of MoS 2 in the wavelength region of 350 750 nm. The measured EQE spectra in the extended wavelength region, as compared with the previously reported values (up to 950 nm), 34 suggests that an MoS 2 nanomembrane with an optical bandgap of 1.3 eV could effectively absorb photons in both visible and near infrared spectral regions due to the absence of the layer-dependent optical properties of MoS 2 as governed by its physical thickness. Fig. 7(a) shows the MottSchottky (C 2 V) characteristics of the Schottky-barrier solar cells. The C 2 V characteristics were used to estimate the Schottky-barrier heights associated with each of the two fabricated solar cells. Fig. 7(b) shows schemati- cally the energy-level alignment at the MoS 2 Au interface under zero, forward and reverse voltage bias conditions. Since the MoS 2 samples are n-type doped, Fermi levels in MoS 2 and Au shift upwards and downwards, respectively, with reference to the equilibrium Fermi level at zero voltage bias, yielding the maximum barrier height. In the case of reverse voltage bias, the situation becomes opposite. We found that both solar cells (with different MoS 2 thickness) resulted in nearly the same Schottky-barrier height (1.0 eV), as measured from the linear extrapolation in the reverse-biasing region (from 1 V to 4 V). It can be understood that a change of the MoS 2 should not make a difference in the Schottky-barrier height. While we expect that MoS 2 thickness (down to a few layers) may change the Schottky- barrier height, the layer dependence becomes insignicant in the nanomembranes used in our experiment. The observed linear behavior of the MottSchottky plots suggests that the MoS 2 nanomembranes possess a relatively low density of surface defects. J. M. Luther et al. reported a Schottky-barrier solar cell using PbSe quantum dots. 2 The result showed signicant variation in the voltage-dependent C 2 for two PbSe samples (thickness difference > 300 nm). 2 In our study, MoS 2 Au solar cells (with active layer thickness difference of 100 nm) exhibit no signicant change in the C 2 values with reverse bias. This could be attributed to the layered MoS 2 nanomembrane (defect-free or with negligibly low density of defects) as compared with conventional semiconductors in which unsaturated dangling bonds make the MS interface highly defective. In layered semiconductors the crystal lattice planes are weakly bound by van der Waals interactions and hence the surface exhibits self- saturated electronic bonds which are no longer active for surface reaction with the environment. The nature of a self-saturated surface in layered MoS 2 nanomembrane eliminates Fermi level pinning and interfacial oxide layer formation (both could impede the transport signicantly). The voltage-bias-dependent C 2 values are almost identical in both device samples (with different thicknesses) due to negligible change in the trap states at MoS 2
Au interface where carriers are stored and released, affecting the
junction capacitance. This is a key appealing property of layered semiconductors for solar cell applications as compared with bulk/thin lm semiconductors which possess a particular type of electronic bonding along and across the crystal planes (leading to defective bulk and surface upon cleaving). We project that the performance of the MoS 2 nanomembrane- based Schottky-barrier solar cell could be further improved. Layered semiconductors are typically very sensitive to growth conditions such as temperature and pressure. Temperature uc- tuation across the growth furnace plays a signicant role in inuencing the solidvapor reaction between pre-deposited Mo and S vapor, and eventually the electronic quality of the MoS 2 nanomembrane. In addition, defects and impurities introduced Fig. 6 Measured EQE spectra of the Schottky-barrier solar cells with a stack of MoS 2 nanomembranes having thicknesses of 110 nm and 220 nm, respectively, in the wavelength region of 350950 nm. This conrms an optical bandgap of approximately 1.3 eV for the prepared MoS 2 nanomembranes. Fig. 7 (a) The measured MottSchottky (C 2 V) plot of the Schottky- barrier solar cells with a stack of MoS 2 nanomembranes having thick- nesses of 110 nm and 220 nm, respectively, showing a linear C 2 dependency (shown in the circled region) on the applied reverse bias, V R . (b) Schematic showing MoS 2 Au interfacial energy level change at zero (equilibrium), forward, and reverse bias conditions and the effect on Schottky barrier height. 7404 | Nanoscale, 2012, 4, 73997405 This journal is The Royal Society of Chemistry 2012 P u b l i s h e d
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View Article Online during the CVD growth and deformation formed during layer transfer would all contribute to reduced carrier mobility and degraded carrier transport properties. We expect that further optimization of the growth process, use of a cleaner fabrication environment, and direct assembly of MoS 2 nanomembranes on an ITO substrate would produce less defective materials, leading to improved solar cell performance. Conclusions Schottky-barrier solar cells have been demonstrated using layer- assembled, CVD-grown MoS 2 semiconductor nanomembranes as the critical photo-active layer. While relatively thick MoS 2 nanomembranes are used in this experiment, the material is scalable via a controlled CVD growth process and large-area solar cell fabrication is potentially feasible. The dependency of solar cell performance on MoS 2 thickness was evaluated. Further improvement in solar cell performance is expected through optimizing the growth process, eliminating structural deforma- tion (induced during fabrication), and minimizing the amount of surface defects and impurities. The reported results would promote continued efforts towards developing highly efcient Schottky-barrier solar cells taking advantage of the unique interfacial properties of layered semiconductor nanostructures. References 1 Z. B. Zhou, R. Q. Cui, Q. J. Pang, G. M. Hadi, Z. M. Ding and W. Y. Li, Sol. Energy Mater. Sol. Cells, 2002, 70, 487493. 2 J. M. Luther, M. Law, M. C. Beard, Q. Song, M. O. Reese, R. J. Ellingson and A. J. Nozik, Nano Lett., 2008, 8, 34883492. 3 B. Ghosh, M. Das, P. Banerjee and S. Das, Solid State Sci., 2009, 11, 461466. 4 M. Soylu and F. Yakuphanoglu, Thin Solid Films, 2011, 519, 1950 1954. 5 L. Zhang, Y. Jia, S. Wang, Z. Li., C. Ji, J. Wei, H. Zhu, K. Wang, D. Wu, E. Shi, Y. Fang and A. Cao, Nano Lett., 2010, 10, 35833589. 6 Y. Ye, Y. 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