Perovskite Single Crystals by Vacuum Evaporation Crystallization

Abstract Perovskite single crystals have attracted tremendous attention owing to their excellent optoelectronic properties and stability compared to typical multicrystal structures. However, the growth of high‐quality perovskite single crystals (PSCs) generally relies on temperature gradients or the introduction of additives to promote crystal growth. In this study, a vacuum evaporation crystallization technique is developed that allows PSCs to be grown under extremely stable conditions at constant temperature and without requiring additives to promote crystal growth. The new method enables the growth of PSCs of unprecedented quality, that is, MAPbBr3 single crystals that exhibit an ultranarrow full width at half maximum of 0.00701°, which surpasses that of all previously reported values. In addition, the MAPbBr3 single crystals deliver exceptional optoelectronic performance, including a long carrier lifetime of 1006 ns, an ultralow trap‐state density of 3.67 × 109 cm−3, and an ultrahigh carrier mobility of 185.86 cm2 V−1 s−1. This method is applicable to various types of PSCs, including organic–inorganic hybrids, fully inorganic structures, and low‐dimensional structures.


Equation S1
To determine the temperature dependence of the saturated pressure (P) of a fluid along the liquid-vapor coexistence curve, most chemistry and physics textbooks employ the Clausius-Clapeyron equation: [1][2][3][4] where  0 and  0 are the vapor pressure and absolute temperature of a reference point on the coexistence curve, respectively, and A is a constant characteristic of the substance.Equation ( 1) is typically derived from the integration of the Clapeyron equation for vaporization [5] under the following assumptions: (i) the volume occupied by one mole of liquid under its saturated-pressure is negligible compared to the volume occupied by one mole of vapor,   ≪   , (ii) the vapor behaves as an ideal gas,   = / , and (iii) ∆ of vaporization does not change with temperature, ∆ ≈ constant.These are reasonably good approximations at low temperatures where the vapor pressure is small.

S-15
Table S2.Sizes of the MHP single crystals in Figure 2c and Figure S4.

Table S3 .
Additional details of the growth processes for each type of MHP single crystal.

Table S4 .
FWHM values and calculated lattice strain corresponding to different XRD reflections for both the VEC-MAPbBr3 and HT-MAPbBr3 single crystals.

Table S5 .
Trap density and carrier mobility of MAPbBr3 single crystals with different crystal thickness.

Table S6 .
Performance metrics of MAPbBr3 single crystals with different growth methods.
a) Measurement by transient absorption spectroscopy; b) measurement by time-resolved PL spectroscopy.