Formation of Corrugated n = 1 2D Tin Iodide Perovskites and Their Use as Lead-Free Solar Absorbers

Major strides have been made in the development of materials and devices based around low-dimensional hybrid group 14 metal halide perovskites. Thus far, this work has mostly focused upon compounds containing highly toxic Pb, with the analogous less toxic Sn materials being comparatively poorly evolved. In response, the study herein aims to (i) provide insight into the impact of templating cation upon the structure of n = 1 2D tin iodide perovskites (where n refers to the number of contiguous two-dimensional (2D) inorganic layers, i.e., not separated by organic cations), and (ii) examine their potential as light absorbers for photovoltaic (PV) cells. It was discovered through systematic tuning of organic dications, that imidazolium rings are able to induce formation of (110)-oriented materials, including the examples of “3 × 3” corrugated Sn-I perovskites. This structural outcome is a consequence of a combination of supramolecular interactions of the two endocyclic N-atoms in the imidazolium functionalities with the Sn-I framework and the higher tendency of Sn2+ ions to stereochemically express their 5s2 lone pairs relative to the 6s2 electrons of Pb2+. More importantly, the resulting materials feature very short separations between their 2D inorganic layers with iodide–iodide (I···I) contacts as small as 4.174 Å, which is amongst the shortest ever recorded for 2D tin iodide perovskites. The proximate inorganic distances, combined with the polarizable nature of the imidazolium moiety, eases the separation of photogenerated charge within the materials. This is evident from the excitonic activation energies as low as 83(10) meV, measured for ImEA[SnI4]. When combined with superior light absorption capabilities relative to their lead congeners, this allowed fabrication of lead-free solar cells with incident photon-to-current and power conversion efficiencies of up to 70 % and 2.26 %, respectively, which are amongst the highest values reported for pure n = 1 2D group 14 metal halide perovskites. In fact, these values are superior to the corresponding lead iodide material, which demonstrates that 2D Sn-based materials have significant potential as less toxic alternatives to their Pb counterparts

Direct Band Gap Mixed-Valence Organic-inorganic Gold Perovskite as Visible Light Absorbers

Lead-free halide perovskite semiconductors are necessary due to the atmospheric instability and lead toxicity associated with the 3D lead halide perovskites. However, a stable lead-free perovskite with an ideal band gap (1.2-1.4 eV) for photovoltaics is still missing. In this work, we synthesized organic-inorganic gold halide double perovskites ((CH3NH3)2[Au2X6], X = Br, I) through a solution-processed route that offers an ideal direct band gap for photovoltaic applications. Density functional theory calculations confirm the direct nature of the band gap with reasonable absorption coefficients in the visible range and excellent charge transport properties. In addition, the Au-halide perovskites show high chemical stability and photoresponse. These combined properties demonstrate that Au-based halide perovskites can be a promising group of compounds for optoelectronic applications

Cubic NaSbS2 as an Ionic-Electronic Coupled Semiconductor for Switchable Photovoltaic and Neuromorphic Device Applications

Just Accepted - Advanced Material

Doping and Switchable Photovoltaic Effect in Lead Free Perovskites Enabled by Metal Cation Transmutation

Published in Advanced Materials : https://doi.org/10.1002/adma.20180208

Rb as an Alternative Cation for Templating Inorganic Lead-Free Perovskites for Solution Processed Photovoltaics

Published in Chemistry of Materials : https://doi.org/10.1021/acs.chemmater.6b0331