Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films
Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH 3 NH 3 I) and methylammonium bromide (CH 3 NH 3 Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH 3 NH 3 PbX 3 with X = I, Br, Cl and their mixture) films with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH 3 NH 3 PbI 3-x Br x by exposing the substrate to vapors of a mixture of CH 3 NH 3 I and CH 3 NH 3 Br at reduced pressure and 120 °C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH 3 NH 3 PbI 3-x Br x with 0 ≤ x ≤ 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV ≤ E g ≤ 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH 3 NH 3 PbI 3-x Cl x . Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.