Anomalous band gap behavior in mixed Sn and Pb perovskites enables broadening of absorption spectrum in solar cells.

Perovskite-based solar cells have recently been catapulted to the cutting edge of thin-film photovoltaic research and development because of their promise for high-power conversion efficiencies and ease of fabrication. Two types of generic perovskites compounds have been used in cell fabrication: either Pb- or Sn-based. Here, we describe the performance of perovskite solar cells based on alloyed perovskite solid solutions of methylammonium tin iodide and its lead analogue (CH3NH3Sn(1-x)Pb(x)I3). We exploit the fact that, the energy band gaps of the mixed Pb/Sn compounds do not follow a linear trend (the Vegard's law) in between these two extremes of 1.55 and 1.35 eV, respectively, but have narrower bandgap (<1.3 eV), thus extending the light absorption into the near-infrared (~1,050 nm). A series of solution-processed solid-state photovoltaic devices using a mixture of organic spiro-OMeTAD/lithium bis(trifluoromethylsulfonyl)imide/pyridinium additives as hole transport layer were fabricated and studied as a function of Sn to Pb ratio. Our results show that CH3NH3Sn(0.5)Pb(0.5)I3 has the broadest light absorption and highest short-circuit photocurrent density ~20 mA cm(-2) (obtained under simulated full sunlight of 100 mW cm(-2)).

[1]  Sandeep Kumar Pathak,et al.  Lead-free organic–inorganic tin halide perovskites for photovoltaic applications , 2014 .

[2]  Mercouri G Kanatzidis,et al.  Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities, and near-infrared photoluminescent properties. , 2013, Inorganic chemistry.

[3]  Guillermo C Bazan,et al.  Design and synthesis of molecular donors for solution-processed high-efficiency organic solar cells. , 2014, Accounts of chemical research.

[4]  Nigel Pickett,et al.  Nanocrystalline semiconductors: Synthesis, properties, and perspectives , 2001 .

[5]  M. Grätzel,et al.  Title: Long-Range Balanced Electron and Hole Transport Lengths in Organic-Inorganic CH3NH3PbI3 , 2017 .

[6]  Cherie R. Kagan,et al.  Organic-inorganic hybrid materials as semiconducting channels in thin-film field-effect transistors , 1999, Science.

[7]  H. Queisser,et al.  Detailed Balance Limit of Efficiency of p‐n Junction Solar Cells , 1961 .

[8]  M. Kanatzidis,et al.  All-solid-state dye-sensitized solar cells with high efficiency , 2012, Nature.

[9]  Jan C. Hummelen,et al.  Perovskites under the Sun , 2013, Nature Materials.

[10]  M. Johnston,et al.  Formamidinium lead trihalide: a broadly tunable perovskite for efficient planar heterojunction solar cells , 2014 .

[11]  Kiyoyuki Terakura,et al.  Charge-transport in tin-iodide perovskite CH3NH3SnI3: origin of high conductivity. , 2011, Dalton transactions.

[12]  L F Gate Comparison of the photon diffusion model and kubelka-munk equation with the exact solution of the radiative transport equation. , 1974, Applied optics.

[13]  J. Teuscher,et al.  Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites , 2012, Science.

[14]  宁北芳,et al.  疟原虫var基因转换速率变化导致抗原变异[英]/Paul H, Robert P, Christodoulou Z, et al//Proc Natl Acad Sci U S A , 2005 .

[15]  Josef Salbeck,et al.  Solid-state dye-sensitized mesoporous TiO2 solar cells with high photon-to-electron conversion efficiencies , 1998, Nature.

[16]  Tsutomu Miyasaka,et al.  Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. , 2009, Journal of the American Chemical Society.

[17]  Peng Gao,et al.  Mesoscopic CH3NH3PbI3/TiO2 heterojunction solar cells. , 2012, Journal of the American Chemical Society.

[18]  T. Moore,et al.  Mimicking photosynthetic solar energy transduction. , 2001, Accounts of chemical research.

[19]  Nam-Gyu Park,et al.  Organometal Perovskite Light Absorbers Toward a 20% Efficiency Low-Cost Solid-State Mesoscopic Solar Cell , 2013 .

[20]  Wei Wang,et al.  Optical designs that improve the efficiency of Cu2ZnSn(S,Se)4 solar cells , 2014 .

[21]  N. Park,et al.  Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9% , 2012, Scientific Reports.

[22]  David B. Mitzi,et al.  Thin-Film Deposition of Organic−Inorganic Hybrid Materials , 2001 .

[23]  J. Noh,et al.  Chemical management for colorful, efficient, and stable inorganic-organic hybrid nanostructured solar cells. , 2013, Nano letters.

[24]  Lioz Etgar,et al.  Depleted hole conductor-free lead halide iodide heterojunction solar cells , 2013 .

[25]  Prashant V Kamat,et al.  Beyond photovoltaics: semiconductor nanoarchitectures for liquid-junction solar cells. , 2010, Chemical reviews.

[26]  Atul K. Jain,et al.  Stability: Energy for a Greenhouse Planet Advanced Technology Paths to Global Climate , 2008 .

[27]  N. Lewis,et al.  Powering the planet: Chemical challenges in solar energy utilization , 2006, Proceedings of the National Academy of Sciences.

[28]  Hao Li,et al.  CsSnI3: Semiconductor or metal? High electrical conductivity and strong near-infrared photoluminescence from a single material. High hole mobility and phase-transitions. , 2012, Journal of the American Chemical Society.

[29]  Gary Hodes,et al.  Perovskite-Based Solar Cells , 2013, Science.

[30]  R. Tscharner,et al.  Photovoltaic technology: the case for thin-film solar cells , 1999, Science.

[31]  Juan Bisquert,et al.  Mechanism of carrier accumulation in perovskite thin-absorber solar cells , 2013, Nature Communications.

[32]  Hiroyuki Hasegawa,et al.  Hall mobility in tin iodide perovskite CH{sub 3}NH{sub 3}SnI{sub 3}: Evidence for a doped semiconductor , 2013 .

[33]  Edward H. Sargent,et al.  Materials interface engineering for solution-processed photovoltaics , 2012, Nature.

[34]  H. Snaith Perovskites: The Emergence of a New Era for Low-Cost, High-Efficiency Solar Cells , 2013 .

[35]  G. Cantele,et al.  Ab initio investigation of hybrid organic-inorganic perovskites based on tin halides , 2008 .

[36]  Arvind Shah,et al.  Efficiency limits for single-junction and tandem solar cells , 2006 .

[37]  Murray S. Daw,et al.  Investigation of band inversion in (Pb,Sn)Te alloys using ab initio calculations , 2008 .

[38]  Alex K.-Y. Jen,et al.  High-performance perovskite-polymer hybrid solar cells via electronic coupling with fullerene monolayers. , 2013, Nano letters.

[39]  Nripan Mathews,et al.  Formamidinium-Containing Metal-Halide: An Alternative Material for Near-IR Absorption Perovskite Solar Cells , 2014 .

[40]  Kangning Liang,et al.  Synthesis and Characterization of Organic−Inorganic Perovskite Thin Films Prepared Using a Versatile Two-Step Dipping Technique , 1998 .

[41]  H. Snaith,et al.  Low-temperature processed meso-superstructured to thin-film perovskite solar cells , 2013 .

[42]  Laura M. Herz,et al.  Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber , 2013, Science.

[43]  Arthur J. Nozik,et al.  Photoelectrochemistry: Applications to Solar Energy Conversion , 1978 .

[44]  R. Rosenfeld Nature , 2009, Otolaryngology--head and neck surgery : official journal of American Academy of Otolaryngology-Head and Neck Surgery.

[45]  Nam-Gyu Park,et al.  High efficiency solid-state sensitized solar cell-based on submicrometer rutile TiO2 nanorod and CH3NH3PbI3 perovskite sensitizer. , 2013, Nano letters.

[46]  M. Grätzel,et al.  Sequential deposition as a route to high-performance perovskite-sensitized solar cells , 2013, Nature.

[47]  J. Bisquert The Swift Surge of Perovskite Photovoltaics , 2013 .

[48]  Henry J. Snaith,et al.  Efficient planar heterojunction perovskite solar cells by vapour deposition , 2013, Nature.

[49]  T. Ma,et al.  CH3NH3SnxPb(1-x)I3 Perovskite Solar Cells Covering up to 1060 nm. , 2014, The journal of physical chemistry letters.

[50]  Illan J. Kramer,et al.  The architecture of colloidal quantum dot solar cells: materials to devices. , 2014, Chemical reviews.