Potential and limitations of CsBi3I10 as a photovoltaic material
Herein we demonstrate the dry synthesis of CsBi3I10 both as a free-standing material and in the form of homogeneous thin films, deposited by thermal vacuum deposition. Chemical and optical characterization shows high thermal stability, phase purity, and photoluminescence centered at 700 nm, corresponding to a bandgap of 1.77 eV. These characteristics make CsBi3I10 a promising low-toxicity material for wide bandgap photovoltaics. Nevertheless, the performance of this material as a semiconductor in solar cells remains rather limited, which can be at least partially ascribed to a low charge carrier mobility, as determined from pulsed-radiolysis time-resolved microwave conductivity. Further dev…
Vacuum-Deposited Cesium Tin Iodide Thin Films with Tunable Thermoelectric Properties
Most current thermoelectric materials have important drawbacks, such as toxicity, scarceness, and peak operating temperatures above 300 °C. Herein, we report the thermoelectric properties of different crystalline phases of Sn-based perovskite thin films. The 2D phase, Cs2SnI4, is obtained through vacuum thermal deposition and easily converted into the black β phase of CsSnI3(B-β CsSnI3) by annealing at 150 °C. B-β CsSnI3is a p-type semiconductor with a figure of merit (ZT) ranging from 0.021 to 0.033 for temperatures below 100 °C, which makes it a promising candidate to power small electronic devices such as wearable sensors which may be interconnected in the so-called Internet of Things. T…
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…
Mechanochemical synthesis of inorganic halide perovskites: evolution of phase-purity, morphology, and photoluminescence
Dry mechanochemical ball-milling of halide precursor salts is a promising route for the synthesis of high-purity halide perovskites in a fast and solvent-free manner. However, there is a lack of information on the process mechanisms, kinetics, and possible side-effects. Here, we investigated in detail the mechanochemical synthesis of fully-inorganic CsPbBr3 by ball-milling of stoichiometric CsBr and PbBr2. Detailed structural, morphological and optical analyses reveal several beneficial and detrimental effects of milling as a function of time. Three stages are identified during the process: (i) at short milling times (t < 5 min) different ternary compounds are formed, including stoichiometr…
Highly Luminescent Transparent Cs 2 Ag x Na 1– x Bi y In 1– y Cl 6 Perovskite Films Produced by Single-Source Vacuum Deposition
Thermal deposition of halide perovskites as a universal and scalable route to transparent thin films becomes highly challenging in the case of lead-free double perovskites, requiring the evaporation dynamics of multiple metal halide sources to be balanced or a single-phase precursor preliminary synthesized to achieve a reliable control over the composition and the phase of the final films. In the present Letter, the feasibility of the single-source vacuum deposition of microcrystalline Cs2AgxNa1-xBiyIn1-yCl6 double perovskites into corresponding transparent nanocrystalline films while preserving the bulk spectral and structural properties is shown. The perovskite films produced from the mos…
Pulsed Laser Deposition of Cs 2 AgBiBr 6 : from Mechanochemically Synthesized Powders to Dry, Single-Step Deposition
Cs2AgBiBr6 has been proposed as a promising lead-free and stable double perovskite alternative to hybrid and lead-based perovskites. However, the low solubility of precursors during wet synthesis, or the distinct volatility of components during evaporation, results in complex multistep synthesis approaches, hampering the widespread employment of Cs2AgBiBr6 films. Here, we present pulsed laser deposition of Cs2AgBiBr6 films as a dry, single-step and single-source deposition approach for high-quality film formation. Cs2AgBiBr6 powders were prepared by mechanochemical synthesis and pressed into a solid target maintaining phase purity. Controlled laser ablation of the double perovskite target i…
Tuning the Optical Absorption of Sn-, Ge-, and Zn-Substituted Cs2AgBiBr6 Double Perovskites: Structural and Electronic Effects
Lead-free halide double perovskites (DPs) are highly tunable materials in terms of chemical composition and optical properties. One of the most widely reported DPs is Cs2AgBiBr6, which is envisaged as a promising absorber for photovoltaics. Nevertheless, its bandgap (around 1.9−2.3 eV) remains too large for common tandem solar cells. In this work, we report the mechanochemical synthesis of Sn-, Ge-, and Zn-substituted Cs2AgBiBr6 in powder form; their bandgaps reach 1.55, 1.80, and 2.02 eV, respectively. These differences are rationalized through density functional theory calculations, demonstrating combined electronic and structural (disorder) effects introduced by the divalent metal-cation…
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.