We demonstrate fabrication and characterization of photovoltaic (PV) devices made using pencil, paper, and commonly available economical chemicals with a power conversion efficiency of ∼1.8%. The current collecting electrode of the device composed of multilayered graphene (MuLG) was hand-drawn on the cellulosic paper using an H2B pencil. CdSe quantum dots (QD) were used for charge generation, and 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) as a bridging molecule to facilitate transfer of the photo-induced charges to the electrodes through MuLG. MuLG acted both as charge carrier and current collector electrode. The device fabrication and testing were accomplished in a wet lab under ambient conditions with minimum use of sophisticated instrumentation. The materials and devices were characterized using UV–visible, fluorescence, x-ray diffraction spectroscopy, and scanning and transmission electron microscopy. I–V characteristics of the PV devices fabricated on paper and polyester transparency substrates were performed using a solar simulator (AM 1.5) under ambient wet laboratory conditions. The use of pencil and paper makes the device fabrication simple, environmentally responsible, and accessible to layperson thus opening a new window for low cost PV and opto-electronic devices.
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N.S. Lewis and D.G. Nocera: Powering the planet: Chemical challenges in solar energy utilization. Proc. Natl. Acad. Sci. 103, 15729 (2006).
H. Rodhe: A comparison of the contribution of various gases to the greenhouse effect. Science 248, 1217 (1990).
D.A. Stainforth, T. Aina, C. Christensen, M. Collins, N. Faull, D.J. Frame, J.A. Kettleborough, S. Knight, A. Martin, J.M. Murphy, and C. Piani: Uncertainty in predictions of the climate response to rising levels of greenhouse gases. Nature 433, 403 (2005).
D.E. Carlson and C.R. Wronski: Amorphous silicon solar cell. Appl. Phys. Lett. 28, 671 (1976).
H. Keppner, J. Meier, P. Torres, D. Fischer, and A. Shah: Microcrystalline silicon and micromorph tandem solar cells. Appl. Phys. A: Mater. Sci. Process. 69, 169 (1999).
N.S. Lewis: Toward cost-effective solar energy use. Science 315, 798 (2007).
B. O’Regan and M. Grätzel: A low-cost, high-efficiency solar cell based on dye-sensitized. Nature 353, 737 (1991).
E. Singh and H.S. Nalwa: Stability of graphene-based heterojunction solar cells. RSC Adv. 5, 73575 (2015).
M. Bernardi, J. Lohrman, P.V. Kumar, A. Kirkeminde, N. Ferralis, J.C. Grossman, and S. Ren: Nanocarbon-based photovoltaics. ACS Nano 6, 8896 (2012).
K.S. Kim, Y. Zhao, H. Jang, S.Y. Lee, J.M. Kim, K.S. Kim, J.H. Ahn, P. Kim, J.Y. Choi, and B.H. Hong: Large-scale pattern growth of graphene films for stretchable transparent electrodes. Nature 457, 706 (2009).
S. Iijima: Helical microtubules of graphitic carbon. Nature 354, 56 (1991).
E. Singh and H.S. Nalwa: Graphene-based dye-sensitized solar cells: A review. Sci. Adv. Mater. 7, 1863 (2015).
Z. Fan, J. Yan, L. Zhi, Q. Zhang, T. Wei, J. Feng, M. Zhang, W. Qian, and F. Wei: A three-dimensional carbon nanotube/graphene sandwich and its application as electrode in supercapacitors. Adv. Mater. 22, 3723 (2010).
E. Singh and H.S. Nalwa: Graphene-based bulk-heterojunction solar cells: A review. J. Nanosci. Nanotechnol. 15, 6237 (2015).
A.L.M. Reddy, A. Srivastava, S.R. Gowda, H. Gullapalli, M. Dubey, and P.M. Ajayan: Synthesis of nitrogen-doped graphene films for lithium battery application. ACS Nano 4, 6337 (2010).
Y. Wang, Y. Shao, D.W. Matson, J. Li, and Y. Lin: Nitrogen-doped graphene and its application in electrochemical biosensing. ACS Nano 4, 1790 (2010).
L. Huang, Y. Huang, J. Liang, X. Wan, and Y. Chen: Graphene-based conducting inks for direct inkjet printing of flexible conductive patterns and their applications in electric circuits and chemical sensors. Nano Res. 4, 675 (2011).
N. Ruecha, R. Rangkupan, N. Rodthongkum, and O. Chailapakul: Novel paper-based cholesterol biosensor using graphene/polyvinylpyrrolidone/polyaniline nanocomposite. Biosens. Bioelectron. 52, 13–19 (2014).
F.Y. Kong, S.X. Gu, W.W. Li, T.T. Chen, Q. Xu, and W. Wang: A paper disk equipped with graphene/polyaniline/Au nanoparticles/glucose oxidase biocomposite modified screen-printed electrode: Toward whole blood glucose determination. Biosens. Bioelectron. 56, 77 (2014).
L. Hu, H. Wu, and Y. Cui: Printed energy storage devices by integration of electrodes and separators into single sheets of paper. Appl. Phys. Lett. 96, 183502 (2010).
G. Zheng, L. Hu, H. Wu, X. Xie, and Y. Cui: Paper supercapacitors by a solvent-free drawing method. Energy Environ. Sci. 4, 3368 (2011).
X. Liang, Z. Xiaogan, and S.Y. Chou: Graphene transistors fabricated via transfer-printing in device active-areas on large wafer. Nano Lett. 7, 3840 (2007).
V.V. Brus and P.D. Maryanchuk: Photosensitive Schottky-type heterojunctions prepared by the drawing of graphite films. Appl. Phys. Lett. 104, 173501 (2014).
Z. Fang, H. Zhu, Y. Yuan, D. Ha, S. Zhu, C. Preston, Q. Chen, Y. Li, X. Han, S. Lee, and G. Chen: Novel nanostructured paper with ultrahigh transparency and ultrahigh haze for solar cells. Nano Lett. 14, 765 (2014).
Y. Fujisaki, H. Koga, Y. Nakajima, M. Nakata, H. Tsuji, T. Yamamoto, T. Kurita, M. Nogi, and N. Shimidzu: Transparent nanopaper-based flexible organic thin-film transistor array. Adv. Funct. Mater. 24, 1657 (2014).
B. Wang and L.L. Kerr: Dye sensitized solar cells on paper substrates. Sol. Energy Mater. Sol. Cells 95, 2531 (2011).
M.C. Barr, J.A. Rowehl, R.R. Lunt, J. Xu, A. Wang, C.M. Boyce, S.G. Im, V. Bulović, and K.K. Gleason: Direct monolithic integration of organic photovoltaic circuits on unmodified paper. Adv. Mater. 23, 3500 (2011).
N. Kurra and G.U. Kulkarni: Pencil-on-paper: Electronic devices. Lab Chip 13, 2866 (2013).
J. Weaver, R. Zakeri, S. Aouadi, and P. Kohli: Synthesis and characterization of quantum dot–polymer composites. J. Mater. Chem. 19, 3198 (2009).
X. Peng, L. Manna, W. Yang, J. Wickham, E. Scher, A. Kadavanich, and A.P. Alivisatos: Shape control of CdSe nanocrystals. Nature 404, 59 (2000).
I.M. Dharmadasa: Latest developments in CdTe, CuInGaSe2 and GaAs/AlGaAs thin film PV solar cells. Curr. Appl. Phys. 9, e2 (2009).
U. Bach, D. Lupo, P. Comte, J.E. Moser, F. Weissörtel, J. Salbeck, H. Spreitzer, and M. Gratzel: Solid-state dye-sensitized mesoporous TiO2 solar cells with high photon-to-electron conversion efficiencies. Nature 395, 583 (1998).
S. Günes, H. Serap, and N.S. Sariciftci: Conjugated polymer-based organic solar cells. Chem. Rev. 107, 1324 (2007).
F.C. Krebs: Fabrication and processing of polymer solar cells: A review of printing and coating techniques. Sol. Energy Mater. Sol. Cells 93, 394 (2009).
T.P. Chou, Q. Zhang, G.E. Fryxell, and G.Z. Cao: Hierarchically structured ZnO film for dye-sensitized solar cells with enhanced energy conversion efficiency. Adv. Mater. 19, 2588 (2007).
K.J. Reynolds, J.A. Barker, N.C. Greenham, R.H. Friend, and G.L. Frey: Inorganic solution-processed hole-injecting and electron-blocking layers in polymer light-emitting diodes. J. Appl. Phys. 92, 7556 (2002).
A.P. Alivisatos: Semiconductor clusters, nanocrystals, and quantum dots. Science 271, 933 (1996).
L. Brus: Quantum crystallites and nonlinear optics. Appl. Phys. A: Solids Surf. 53, 465 (1991).
D.F. Swinehart: The beer-lambert law. J. Chem. Educ. 39, 333 (1962).
W.W. Yu, L. Qu, W. Guo, and X. Peng: Experimental determination of the extinction coefficient of CdTe, CdSe, and CdS nanocrystals. Chem. Mater. 15, 2854 (2003).
J. Sun and E.M. Goldys: Linear absorption and molar extinction coefficients in direct semiconductor quantum dots. J. Phys. Chem. C 112, 9261 (2008).
B. Partoens and F.M. Peeters: From graphene to graphite: Electronic structure around the K point. Phys. Rev. B: Condens. Matter Mater. Phys. 74, 075404 (2006).
B. Xu and K.M. Poduska: Linking crystal structure with temperature-sensitive vibrational modes in calcium carbonate minerals. Phys. Chem. Chem. Phys. 16, 17634 (2014).
R.J. Moon, A. Martini, J. Nairn, J. Simonsen, and J. Youngblood: Cellulose nanomaterials review: Structure, properties and nanocomposites. Chem. Soc. Rev. 40, 3941 (2011).
C.J. Garvey, I.H. Parker, and G.P. Simon: On the interpretation of x-ray diffraction powder patterns in terms of the nanostructure of cellulose I fibres. Macromol. Chem. Phys. 206, 1568 (2005).
M.A. Rahman, J. Halfar, and R. Shinjo: X-ray diffraction is a promising tool to characterize coral skeletons. Adv. Mater. Phys. Chem. 3, 120 (2013).
J. Keizer: Nonlinear fluorescence quenching and the origin of positive curvature in Stern–Volmer plots. J. Am. Chem. Soc. 105, 1494 (1983).
J.E. Weaver, M.R. Dasari, A. Datar, S. Talapatra, and P. Kohli: Investigating photoinduced charge transfer in carbon Nanotube−Perylene−quantum dot hybrid nanocomposites. ACS Nano 4, 6883 (2010).
B. Pan, D. Cui, C.S. Ozkan, M. Ozkan, P. Xu, T. Huang, F. Liu, H. Chen, Q. Li, R. He, and F. Gao: Effects of carbon nanotubes on photoluminescence properties of quantum dots. J. Phys. Chem. C 112, 939 (2008).
S. Geyer, V.J. Porter, J.E. Halpert, T.S. Mentzel, M.A. Kastner, and M.G. Bawendi: Charge transport in mixed CdSe and CdTe colloidal nanocrystal films. Phys. Rev. B: Condens. Matter Mater. Phys. 82, 155201 (2010).
Y.X. Xu, K.X. Sheng, C. Li, and G.Q. Shi: Self-assembled graphene hydrogel via a one-step hydrothermal process. ACS Nano 4, 4324 (2010).
T. Stocker, A. Kohler, and R. Moos: Why does the electrical conductivity in PEDOT:PSS decrease with PSS content? A study combining thermoelectric measurements with impedance spectroscopy. J. Polym. Sci., Part B: Polym. Phys. 50, 976 (2012).
Y.J. Kim, C.E. Park, and D.S. Chung: Interface engineering of a highly sensitive solution processed organic photodiode. Phys. Chem. Chem. Phys. 16, 18472 (2014).
S. Baskoutas and A.F. Terzis: Size-dependent band gap of colloidal quantum dots. J. Appl. Phys. 99, 013708 (2006).
K. Tvrdy, P.A. Frantsuzov, and P.V. Kamat: Photoinduced electron transfer from semiconductor quantum dots to metal oxide nanoparticles. Proc. Natl. Acad. Sci. 108, 29 (2011).
J. Liu, W. Yang, Y. Li, L. Fan, and Y. Li: Electrochemical studies of the effects of the size, ligand and composition on the band structures of CdSe, CdTe and their alloy nanocrystals. Phys. Chem. Chem. Phys. 16, 4778 (2014).
A.M. Smith, A.M. Mohs, and S. Nie: Tuning the optical and electronic properties of colloidal nanocrystals by lattice strain. Nat. Nanotechnol. 4, 56 (2009).
D.L. Klein, R. Roth, A.K. Lim, A. P Alivisatos, and P.L. McEuen: A single-electron transistor made from a cadmium selenide nanocrystal. Nature 389, 699 (1997).
E.D. Minot, F. Kelkensberg, M. Van Kouwen, J.A. Van Dam, L.P. Kouwenhoven, V. Zwiller, M.T. Borgström, O. Wunnicke, M.A. Verheijen, and E.P. Bakkers: Single quantum dot nanowire LEDs. Nano Lett. 7, 367 (2007).
I.L. Medintz, H.T. Uyeda, E.R. Goldman, and H. Mattoussi: Quantum dot bioconjugates for imaging, labelling and sensing. Nat. Mater. 4, 435 (2005).
W.U. Huynh, J.J. Dittmer, and A.P. Alivisatos: Hybrid nanorod-polymer solar cells. Science 295, 2425 (2002).
W.M.H. Sachtler, G.J.H. Dorgelo, and A.A. Holscher: The work function of gold. Surf. Sci.: 5, 221 (1966).
T. Oku, A. Takeda, A. Nagata, T. Noma, A. Suzuki, and K. Kikuchi: Fabrication and characterization of fullerene-based bulk heterojunction solar cells with porphyrin, CuInS2, diamond and exciton-diffusion blocking layer. Energies 3, 671 (2010).
S. Tongay, T. Schumann, and A.F. Hebard: Graphite based Schottky diodes formed on Si, GaAs, and 4H-SiC substrates. Appl. Phys. Lett. 95, 222103 (2009).
Y.J. Yu, Y. Zhao, S. Ryu, L.E. Brus, K.S. Kim, and P. Kim: Tuning the graphene work function by electric field effect. Nano Lett. 9, 3430 (2009).
Y. Ye, L. Gan, L. Dai, Y. Dai, X. Guo, H. Meng, B. Yu, Z. Shi, K. Shang, and G. Qin: A simple and scalable graphene patterning method and its application in CdSe nanobelt/graphene Schottky junction solar cells. Nanoscale 3, 1477 (2011).
V.V. Brus, P.D. Maryanchuk, M.I. Ilashchuk, J. Rappich, I.S. Babichuk, and Z.D. Kovalyuk: Graphitic carbon/n-CdTe Schottky-type heterojunction solar cells prepared by electron-beam evaporation. Sol. Energy 112, 78 (2015).
G.A. Giovannetti, P.A. Khomyakov, G. Brocks, V.M. Karpan, J. van den Brink, and P.J. Kelly: Doping graphene with metal contacts. Phys. Rev. Lett. 101, 026803 (2008).
P.A. Khomyakov, G. Giovannetti, P.C. Rusu, G. Brocks, J. van den Brink, and P.J. Kelly: First-principles study of the interaction and charge transfer between graphene and metals. Phys. Rev. B: Condens. Matter Mater. Phys. 79, 195425 (2009).
A. Kyas, J. Fleischhauer, E. Steinmetz, and H. Wilhelmi: Investigations concerning the work function of doped graphite. Plasma Chem. Plasma Process. 13, 223 (1993).
J. Hölzl and F.K. Schulte: Work function of metals. In Solid Surface Physics, Vol. 85, G. Holer, ed. (Springer-Verlag, Berlin, 1979); p. 126.
H. Kautsky: Quenching of luminescence by oxygen. Trans. Faraday Soc. 35, 216 (1939).
R. Martel, V. Derycke, C. Lavoie, J. Appenzeller, K.K. Chan, J. Tersoff, and Ph. Avouris: Ambipolar electrical transport in semiconducting single-wall carbon nanotubes. Phys. Rev. Lett. 87, 256805 (2001).
M. Ikai, S. Tokito, Y. Sakamoto, T. Suzuki, and Y. Taga: Highly efficient phosphorescence from organic light-emitting devices with an exciton-block layer. Appl. Phys. Lett. 79, 156 (2001).
We would like to acknowledge National Science Foundation (CHE 0748676), Office of Vice-Chancellor of Research, and Office of Sponsored Projects Administration (OSPA) at the Southern Illinois University at Carbondale (SIUC), and NIH (GM 106364) for partial financial support of this research. The Scanning Electron Microscope used in this work was purchased through a grant from National Science Foundation (CHE 0959568).
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Dasari, M., Rajasekaran, P.R., Iyer, R. et al. Calligraphic solar cells: acknowledging paper and pencil. Journal of Materials Research 31, 2578–2589 (2016). https://doi.org/10.1557/jmr.2016.281