Tang Jiao Huang

(CH3NH3)2PdCl4: A Compound with Two‐Dimensional Organic–Inorganic Layered Perovskite Structure

The synthesis of previously unknown perovskite (CH3 NH3 )2 PdCl4 is reported. Despite using an organic cation with the smallest possible alkyl group, a 2D organic-inorganic layered Pd-based perovskites was still formed. This demonstrates that Pd-based 2D perovskites can be obtained even if the size of the organic cation is below the size limit predicted by the Goldschmidt tolerance-factor formula. The (CH3 NH3 )2 PdCl4 phase has a bulk resistivity of 1.4 Ω cm, a direct optical gap of 2.22 eV, and an absorption coefficient on the order of 104  cm-1 . XRD measurements suggest that the compound is moderately stable in air, an important advantage over several existing organic-inorganic perovskites that are prone to phase degradation problems when exposed to the atmosphere. Given the recent interest in organic-inorganic perovskites, the synthesis of this new Pd-based organic-inorganic perovskite may be helpful in the preparation and understanding of other organic-inorganic perovskites.

A low-cost, ligand exchange-free strategy to synthesize large-grained Cu2ZnSnS4 thin-films without a fine-grain underlayer from nanocrystals

The first direct synthesis of CZTS nanocrystals in a formamide solvent system without using long hydrocarbon chain organic ligands is reported. The kesterite CZTS nanocrystals possess a mean size of 5.2 ± 1.2 nm. No secondary phases have been detected within the known limitations of XRD and Raman measurements. Experimental evidence suggests that excess S2− is present on the surface of the nanocrystals, accounting for their dispersibility in polar solvents. The nanocrystals also exhibit a smaller weight loss of 8.7% at 500 °C compared to 24.4% for those capped by oleylamine. A description of the formation of CZTS FA nanocrystals and the role of formamide during synthesis is proposed. Annealing of spin-coated nanocrystal thin-films highlighted the difficulty of forming dense films from loose nanocrystal films. This work shows that this can be overcome using compaction with a combination of a reasonably soft metal and silicone. A means to compact the film uniformly on a centimeter scale with reduced delamination is thus demonstrated. Annealed compacted films possess crystal grains with a favorable size on the order of microns. More significantly, a large-grain layer is formed without an unwanted residual fine-grain underlayer. The absence of a fine-grain underlayer shows that this ligand exchange-free strategy is effective in resolving a key challenge associated with the nanocrystal approach of making CZTS thin-films while simultaneously being low-cost and having a smaller environmental footprint. The strategy presented here is equally applicable to other nanocrystal approaches requiring the synthesis of dense thin-films from nanocrystal films.

Influence of Ligands on the Formation of Kesterite Thin Films for Solar Cells: A Comparative Study.

The preparation of solar-cell-grade Cu2 ZnSnS4 (CZTS) thin films from ligand-capped small-grained CZTS particles remains hindered by problems of phase segregation, composition non-uniformity, and in particular carbon-layer formation. Herein, through a systematic comparative study of annealed films of CZTS nanocrystals prepared using conventional oleylamine and those prepared using formamide, these problems are found to be mainly attributable to the influence of the ligands, and mechanisms are proposed. Importantly, the origin of the carbon layer in oleylamine-capped CZTS films is revealed to be the reaction between oleylamine and sulfur. This carbon layer has a very poor electrical conductivity, which can be the reason for the limited performance of such films. Fortunately, these problems can almost all be avoided by replacing oleylamine with formamide to form CZTS films.

Highly Stable, New, Organic-Inorganic Perovskite (CH3NH3)2PdBr4: Synthesis, Structure, and Physical Properties

Lead halide perovskites have attracted striking attention recently, due to their appealing properties. However, toxicity and stability are two main factors restricting their application. In this work, a less toxic and highly stable Pd-based hybrid perovskite was experimentally synthesized, after exploring different experimental conditions. This new hybrid organic-inorganic perovskite (CH3 NH3 )2 PdBr4 was found to be an orthorhombic crystal (Cmce, Z=4) with lattice parameters a=8.00, b=7.99, c=18.89 Å. The Cmce symmetry and lattice parameters were confirmed using Pawley refinement and the atoms positions were confirmed based on DFT calculation. This perovskite compound was determined to be a p-type semiconductor, with a resistivity of 102.9 kΩ cm, a carrier concentration of 3.4 ×1012  cm-3 , and a mobility of 23.4 cm2  (V s)-1 . Interestingly, XRD and UV/Vis measurements indicated that the phase of this new perovskite was maintained with an optical gap of 1.91 eV after leaving in air with a high humidity of 60 % for 4 days, and unchanged for months in N2 atmosphere; much more stable than most existing organic-inorganic perovskites. The synthesis and various characterizations of this work further the understanding of this (CH3 NH3 )2 PdBr4 organic-inorganic hybrid perovskite material.