Perovskite solar cells (PSCs) are currently under vigorous research and development, owing to their compelling power conversion efficiencies. PSCs are solution-processed and, therefore, are fabricated using casting and printing methods, such as spin, spray and blade coating. The coating characteristics significantly depend on the physical and rheological properties of the solutions. Thus, due to the scarcity of such properties, in this work, we report the surface tension, viscosity, density, and contact angle of selected methylammonium lead halide perovskite solutions, in order to gain insight into the behavior of the perovskite solutions and the range of such physical properties. The contact angles were measured on PEDOT:PSS and compact TiO2 (c-TiO2) substrates, commonly used as the underneath layers of the perovskite film. In total, 12 solutions of CH3NH3PbI3 and CH3NH3PbI3-xClx dissolved in common solvents, as well as solutions of PbI2, PbCl2, and CH3NH3I were tested. Among the results, it is shown that the tested perovskite solutions are Newtonian, the apparent contact angles on the mesoporous TiO2 (m-TiO2) are close to zero, on the PEDOT:PSS are around 10°, and on the c-TiO2 are around 30°. Also, contact angle hysteresis is observed in the case of the c-TiO2 substrates. Representative impact dynamics and spreading of perovskite solution droplets are also studied, to demonstrate the importance of the solution properties and process parameters on the coating process.

Abstract:In this work, we report on reproducible fabrication of defect-free large-area mixed halide perovskite (CH 3 NH 3 PbI 3−x Cl x ) thin films by scalable spray coating with the area of 25 cm 2 . This is essential for the commercialization of the perovskite solar cell technology. Using an automated spray coater, the film thickness and roughness were optimized by controlling the solution concentration and substrate temperature. For the first time, the surface tension, contact angle, and viscosity of mixed halide perovskite dissolved in dimethylformamide (DMF) are reported as a function of the solution concentration. A low perovskite solution concentration of 10% was selected as an acceptable value to avoid crystallization dewetting. The determined optimum substrate temperature of 150 • C, followed by annealing at 100 • C render the highest perovskite precursor conversion, as well as the highest possible droplet spreading, desired to achieve a continuous thin film. The number of spray passes was also tuned to achieve a fully-covered film, for the condition of the spray nozzle used in this work. This work demonstrates that applying the optimum substrate temperature decreases the standard deviation of the film thickness and roughness, leading to an increase in the quality and reproducibility of the large-area spray-on films. The optimum perovskite solution concentration and the substrate temperature are universally applicable to other spray coating systems.

Drying and crystallization of a thin liquid film of an ionic or a similar solution can cause dewetting in the resulting thin solid film. This paper aims at investigating this type of dewetting, herein termed "crystallization dewetting", using PbI2 dissolved in organic solvents as the model solution. PbI2 solid films are usually used in X-ray detection and lead halide perovskite solar cells. In this work, PbI2 films are fabricated using spin coating and the effect of major parameters influencing the crystallization dewetting, including the type of the solvent, solution concentration, drying temperature, spin speed, as well as imposed vibration on the substrate are studied on dewetting, surface profile and coverage, using confocal scanning laser microscopy. Simplified hydrodynamic governing equations of crystallization in thin films are presented and using a mathematical representation of the process, it is phenomenologically demonstrated that crystallization dewetting occurs due to the absorption and consumption of the solution surrounding a growing crystal. Among the results, it is found that a low spin speed (high thickness), a high solution concentration and a low drying temperature promote crystal growth, and therefore crystallization dewetting. It is also shown that imposed vibration on the substrate can affect the crystal size and crystallization dewetting.

A key step of inexpensive and scalable perovskite thin-film formation is defect-free fabrication through low-cost and facile post-treatment processes. Methods using high annealing temperatures are not favorable for the scale-up of solution-processed thin-film solar cells, particularly on plastic/flexible substrates. This contribution analyzes the effect of ultrasonic vibrations, a recently developed low-cost post-treatment process, on thin-film quality. Ultrasonic vibrations were applied to as-spun CH3NH3PbI3 perovskite thin films prepared with various solvents and antisolvents deposited on substrates with compact and mesoporous textures. Then, mechanisms of solvent evaporation, nucleation, and crystallization of perovskite grains were characterized during ultrasonic vibration. These studies demonstrate that ultrasonic vibration at low temperature facilitates heterogeneous crystallization of perovskite grains with a higher conversion of nuclei into crystal, compared with the conventional annealing process. Topographic scanning electron microscopy images confirm the dense and fully covered thin films after the evaporation of solvent. Furthermore, it is shown that crystal orientation does not change with the choice of solvent, eliminating the effect of solvent on the deposition of thin-film perovskites with this method. Therefore, this ultrasonic vibration post-treatment method is applicable to any solution-processed material and deposition technique, and it can be used to fabricate a range of thin-film devices and printed electronics.

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