Binary lead and tin perovskites offer the benefits of narrower band gaps for broader adsorption of solar spectrum and better charge transport for higher photocurrent density. Here, we report the growth of large, smooth crystalline grains of bianry lead and tin triiodide perovskite films via a two-step solution process with thermal plus solvent vapor-assisted thermal annealing. The crystalline SnxPb1-xI2 films formed in the first step served as the templates for the formation of crystalline CH3NH3SnxPb1-xI3 films during the second step interdiffusion of methylammonium iodide (MAI). Followed by dimethylsulfoxide (DMSO) vapor-assisted thermal annealing, small, faceted perovskite grains grew into large, smooth grains via the possible mechanism involving bond breaking and reforming mediated by DMSO solvent molecules. The absorption onset was extended to 950 and 1010 nm for the CH3NH3SnxPb1-xI3 perovskites with x = 0.1 and 0.25, respectively. The highest PCE of 10.25% was achieved from the planar perovskite solar cell with the CH3NH3Sn0.1Pb0.9I3 layer prepared via the thermal plus DMSO vapor-assisted thermal annealing. This research provides a way to control and manipulate film morphology, grain size, and especially the distribution of metal cations in binary metal perovskite layers, which opens an avenue to grow perovskite materials with desired properties to enhance device performance.

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Pyrite (FeS2) material is attractive for applications in solar cells, lithium batteries, and hydrogen production because of its abundant, nontoxic features as well as the extraordinary electrical and optical properties. Pyrite (FeS2) nanocrystals (NCs) were synthesized via hot injection method, and the crystalline structure and morphologic evolution of pyrite NCs were investigated. We found that pyrite (FeS2) NCs were generated from a mackinawite FeS0.94 nanosheets template. The initial anisotropic growth of NCs was dominated by oriented attachment mechanism. Ostwald ripening growth became obvious as time progressed, resulting in faceted NCs. In accordance with the analysis of high-resolution transmission electron microscopy (HRTEM) images and surface free energies, we found that the attachment occurs between the opposite facets with high surface free energies including (210)-Fe and (210)-2S as well as (001)-Fe and (001)-2S. The attachment could also happen through a “point-contact” followed by interparticle growth. This study sheds light on a better understanding of the growth mechanism of anisotropic pyrite FeS2 NCs and provides a means to rationally manipulate the morphology of pyrite FeS2 NCs in order to achieve desired physical properties for efficient photovoltaic conversions.

Pyrite FeS 2 hierarchical microparticles consisting of cubic-like crystals with well defined {100} faceted cubic textures were successfully synthesized using a simple hydrothermal method with the presence of ethylenediamine (en) and polyvinylpyrrolidone (PVP). The roles of PVP and en in the synthesis process were elucidated by the investigation of morphology and crystalline phases of the products under different reaction conditions and by the analysis of atomic structures of the pyrite ( 100) and ( 111) surfaces with different termination layers. While en chelates with Fe 2+ and reacts with S 8 of the reaction agents to help with dispersion and nucleation as well as the role of reducing agent, PVP acts as both a phase regulator due to its reducing ability and a surface capping agent to bind the iron atoms at the FeS 2 (111) surface and direct the formation of {100} facets. It was found that the oxidation state of iron ions and the species of anions in the iron reagents also played important roles in the formation of crystalline phase and morphology of the products. The pyrite hierarchical microparticles could be utilized as a new semiconductor ink for solution processing of photovoltaic devices and photodetectors as well as cathode materials for lithium batteries.

Earth-abundant and nontoxic pyrite iron disulfide (FeS2) is very promising for photovoltaic applications but the phase purity and the morphology of iron pyrite nanocrystals (NCs) have a significant impact on the solar cell performance. In this work, we systematically investigated reaction conditions and the local chemical environment on the phase purity and morphology of iron pyrite NCs synthesized via the hot injection method. By using different solvents to dissolve iron and sulfur agents, varying reactant concentrations, and adding trioctylphosphine oxide (TOPO) or 1,2-hexadecanediol (Diol) into the reaction solution, iron pyrite short, branched and chromosome-like rods were obtained with a diameter of ~10 nm and a length of ~20-30 nm as well as quasi-cubic NC agglomerates with a size of ~200 nm. Our experimental results show that the molar ratio of sulfur to iron and the reaction temperature are two critical factors in determining the crystalline phase of the synthesized materials. A mechanism involving the generation of H2S is proposed to explain the phase purity observed. The as-synthesized iron pyrite NCs can be dispersed well in chloroform, chlorobenzene, toluene, and hexane and thus are promising in solution-processable photovoltaic applications.