Metal Chalcohalides: Next Generation Photovoltaic Materials?

Metal chalcohalides have recently been highlighted as so-far overlooked semiconductors that could play an important role in the future of photovoltaics (PV). Indeed, the blooming field of emergent PV technologies is still in search for stable, efficient, and environmentally-friendly light-harvesting materials to be used either in single-junction solar cells or multijunction devices in combination with silicon or another absorbers. Under the broad terms of metal chalcohalides, there exists a plethora of semiconductor materials with different chemical, structural, and optoelectronic characteristics. While some have already been implemented in solar cells with power conversion efficiencies up to 4-5%, others are only theoretically described. This perspective article offers a general overview of these materials as potential next-generation absorbers in PV and also discusses possible limitations, not only related to intrinsic materials' properties but also to processing conditions

Making by Grinding: Mechanochemistry Boosts the Development of Halide Perovskites and Other Multinary Metal Halides

Mechanochemical synthesis has recently emerged as a promising route for the synthesis of functional lead halide perovskites as well as other (lead‐free) metal halides. Mechanochemical synthesis presents several advantages with regards to more commonly used solution‐based processes such as an inherent lower toxicity by avoiding organic solvents and a finer control over stoichiometry of the final products. The ease of implementation, either through the use of a simple mortar and pestle or with an electrically powered ball‐mill, and low amount of side products make mechanochemical synthesis appealing for upscaling the production of halide perovskites. Due to the defect tolerance of lead halide perovskites, they are ideally suited to be prepared by this solvent‐free method. However, the implementation of these semiconductors in high‐efficiency optoelectronic devices requires the transformation of synthesized powder into smooth thin films where still some hurdles remain to be cleared

Low Temperature, Vacuum-Processed Bismuth Triiodide Solar Cells with Organic Small-Molecule Hole Transport Bilayer

Herein, the preparation of fully vacuum-processed bismuth triiodide solar cells with low annealing temperature is reported. Planar n-i-p devices are prepared using a thin compact SnO2 layer as the electron extraction layer and an electron blocking/hole extraction bilayer consisting of an intrinsic and doped organic hole-transport molecule. Using this configuration, herein, higher fill-factors and overall power conversion efficiencies than with conventional solution-processed hole transport materials are achieved

Dry Mechanochemical Synthesis of Highly Luminescent, Blue and Green Hybrid Perovskite Solids

A simple method to obtain bright photoluminescent wide bandgap mixed‐halide 3D perovskites is reported. The materials are prepared by dry mechanochemical synthesis (ball‐milling) starting from neat binary precursors, and show enhanced photoluminescence upon the addition of an adamantane derivative in the precursors' mixture. The structural characterization suggests that the additive does not participate in the crystal structure of the perovskite, which remains unvaried even with high loading of amantadine hydrochloride. By simple stoichiometric control of the halide precursors, the photoluminescence can be finely tuned from the UV to the green part of the visible spectrum. Photoluminescence quantum yields as high as 29% and 5% have been obtained for green‐ and blue‐emitting perovskite solids, even at very low excitation densities

Single-Source Vacuum Deposition of Mechanosynthesized Inorganic Halide Perovskites

Fully inorganic cesium lead halide perovskite thin films were prepared by an easy, fast and dry process based on single-source vacuum deposition. We investigated the structural and optical characteristics of the so-formed films as a function of chemical composition (chloride, bromide and iodide films were formed), post-deposition thermal annealing, as well as previous mechanosynthesis of perovskite powders. We found out that the CsPbX3 perovskite was preferentially formed for the smaller halides and favored by previous ball-milling of CsX and PbX2 precursors. When bigger halides were used and/or CsX and PbX2 precursors were simply mixed without previous mechanosynthesis, PbX2-rich compounds such as CsPb2X5 were preferentially formed in the thin films

Dimensionality Controls Anion Intermixing in Electroluminescent Perovskite Heterojunctions

Metal halide perovskites have emerged as a promising group of materials for optoelectronic applications such as photovoltaics, light emission, and photodetectors. So-far, in particular, the stability of light-emitting devices is limited, which is in part attributed to the intrinsic ionic conductivity of these materials. High-performance devices inevitably contain heterojunctions similar to other optoelectronic devices based on oxide perovskites, II-VI, or III-V group semiconductors. To enable efficient heterojunctions, ion exchange at the interface between different layers should be controlled. Herein, we report a method that enables to control and monitor the extent of anion intermixing between solution-processed lead bromide and vacuum-deposited lead chloride perovskite films. Taking advantage of the ability to fine tune the layer thicknesses of the vacuum-deposited films, we systematically study the effect of film thickness on anionic intermixing. Using these multiple layers, we prepare proof of principle light-emitting devices exhibiting green and blue electroluminescence

Quadruple-Cation Wide-Bandgap Perovskite Solar Cells with Enhanced Thermal Stability Enabled by Vacuum Deposition

Vacuum processing of multicomponent perovskites is not straightforward, because the number of precursors is in principle limited by the number of available thermal sources. Herein, we present a process which allows increasing the complexity of the formulation of vacuum-deposited lead halide perovskite films by multisource deposition and premixing both inorganic and organic components. We apply it to the preparation of wide-bandgap CsMAFA triple-cation perovskite solar cells, which are found to be efficient but not thermally stable. With the aim of stabilizing the perovskite phase, we add guanidinium (GA+) to the material formulation and obtained CsMAFAGA quadruple-cation perovskite films with enhanced thermal stability, as observed by X-ray diffraction and rationalized by microstructural analysis. The corresponding solar cells showed similar performance with improved thermal stability. This work paves the way toward the vacuum processing of complex perovskite formulations, with important implications not only for photovoltaics but also for other fields of application

Solvent-Free Synthesis and Thin-Film Deposition of Cesium Copper Halides with Bright Blue Photoluminescence

Non-toxic alternatives to lead halide perovskites are highly sought after for applications in optoelectronics. Blue-luminescent materials are especially demanded as they could be used to prepare white light-emitting diodes, with important potential applications in lighting systems. However, wide bandgap blue emitters with high photoluminescence quantum yields (PLQY) are typically more difficult to obtain as compared to green- or red-emitting ones. Here, we prepared two series of inorganic cesium copper halides, with the general formulas Cs3Cu2X5 and CsCu2X3 (X = Cl, Br, I, and mixtures thereof) by dry mechanochemical synthesis at room temperature. X-ray diffraction demonstrates quantitative conversion of binary precursors into the desired ternary structures and good halide mixing in single-phase compounds. We identified Cs3Cu2I5 as the most promising material as it maintains blue luminescence centered at 442 nm with high PLQY (>40%) after several days in air (Cs3Cu2Cl5 shows significantly higher PLQY over 80% but is unstable in air). Based on this, we fabricated homogeneous and pinhole-free Cs3Cu2I5 thin films by thermal single-source vacuum deposition. Crystalline phase and photoluminescence are maintained in the thin films, validating that these low-toxicity materials can be synthesized and processed by fully solvent-free routes for a widespread implementation in optoelectronic devices

Efficient Photo- and Electroluminescence by Trap States Passivation in Vacuum-Deposited Hybrid Perovskite Thin Films

Methylammonium lead iodide (MAPI) has excellent properties for photovoltaic applications, although it typically shows low photoluminescence quantum yield (PLQY). Here we report on vacuum-deposited MAPI perovskites obtained by modifying the MAI to PbI2 ratio during vacuum deposition. By studying the excitation density dependence of the photoluminescence lifetime, a large concentration of trap states was deduced for the stoichiometric MAPI films. The use of excess MAI during vacuum processing is capable of passivating these traps, resulting in luminescent films which can be used to fabricate planar LEDs with quantum efficiency approaching 2%

Effects of Oxygen Plasma on the Chemical, Light-emitting, and Electrical Transport Properties of Inorganic and Hybrid Lead Bromide Perovskite Nanocrystal Films

We show that oxygen plasma affects in different ways the structural, chemical, optical, and electrical properties of methylammonium and cesium lead bromide nanocrystals. Hybrid organic-inorganic nanocrystals were severely and quickly degraded by oxygen plasma at 50 W. Their photoluminescence was quenched with almost 100% loss of the initial quantum yield, which is linked to decomposition of the nanocrystals. Inorganic nanocrystals were more resistant to oxygen plasma in the same conditions. Despite a moderate loss of photoluminescence and electrical conductivity, oxygen plasma had a positive impact, removing unbound ligands and resulting in more ohmic behavior of the film. This paves the way for the application of oxygen plasma in the development of perovskite-based optoelectronic devices