High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization

Abstract

Single crystals of methylammonium lead trihalide perovskites (MAPbX3; MA=CH3NH3+, X=Br− or I−) have shown remarkably low trap density and charge transport properties; however, growth of such high-quality semiconductors is a time-consuming process. Here we present a rapid crystal growth process to obtain MAPbX3 single crystals, an order of magnitude faster than previous reports. The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures. The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters. Despite the rapidity of the method, the grown crystals exhibit transport properties and trap densities comparable to the highest quality MAPbX3 reported to date. The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.

Recent Progress in Single‐Crystalline Perovskite Research Including Crystal Preparation, Property Evaluation, and Applications

“…Furthermore, additional optoelectronic properties have been discovered, including long balanced hole–electron diffusion length,19, 20, 21, 22, 23 high carrier mobility,21, 24 high absorption coefficient in visible region,25, 26 and long carrier lifetime 21, 22, 25, 27, 28, 29. These optoelectronic properties make hybrid perovskites ideal candidates for solar cell applications,22, 25, 30, 31, 32, 33, 34, 35, 36, 37, 38 LEDs,39, 40, 41 lasers,42, 43 etc.…”

“…Over the last 2 years, an increasing number of researchers have begun studying single‐crystalline perovskites, including crystal preparations,21, 27, 28, 43, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65 property studies,21, 27, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80 and applications 56, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91. For example, an extremely long carrier lifetime (up to 20 µs) and carrier diffusion length (175 µm) have been found,21 which has received a great deal of attention.…”

“…To date, all reported perovskite crystals have been prepared with the liquid growth method 21, 27, 28, 55, 61. Generally, crystals will form by slowly reducing the solubility of the target samples in a precursor solution.…”

Periodic Organic–Inorganic Halide Perovskite Microplatelet Arrays on Silicon Substrates for Room‐Temperature Lasing

“…Organic–inorganic halide perovskites (CH 3 NH 3 PbX 3 where X = Cl, Br, I) have recently emerged as one of the most promising materials for photovoltaics with certified power conversion efficiencies exceeding 20.1% 1, 2, 3, 4, 5, 6, 7, 8. This outstanding performance can be traced to their long carrier lifetimes, long diffusion length, and low trap densities 9, 10, 11, 12.…”

Solution‐Grown Monocrystalline Hybrid Perovskite Films for Hole‐Transporter‐Free Solar Cells

“…[14] A simpler device architecture based on a monocrystalline film may provide a potential solution for overcoming the challenges in the development of PSCs. Unfortunately, single crystal perovskites are mostly grown in bulk and have yet to be realized in the form of films, [6][7][8] which is an essential prerequisite for practical device applications. The hybrid nature of organometal halide perovskites, i.e.…”