Mechano-optical Modulation of Excitons and Carrier Recombination in Self-Assembled Halide Perovskite Quantum Dots

• Published in: ACS nano 2022-01, Vol.16 (1), p.160-168
• Main Authors: Zhang, Zhijing, Ghimire, Sushant, Okamoto, Takuya, Sachith, Bhagyashree Mahesha, Sobhanan, Jeladhara, Subrahmanyam, Challapalli, Biju, Vasudevanpillai
• Format: Article
• Language: English
• ISSN: 1936-0851; 1936-086X
• DOI: 10.1021/acsnano.1c04944

Mechanically modulating optical properties of semiconductor nanocrystals and organic molecules are valuable for mechano-optical and optomechanical devices. Halide perovskites with excellent optical and electronic properties are promising for such applications. We report the mechanically changing excitons and photoluminescence of self-assembled formamidinium lead bromide (FAPbBr3) quantum dots. The as-synthesized quantum dots (3.6 nm diameter), showing blue emission and a short photoluminescence lifetime (2.6 ns), form 20–300 nm 2D and 3D self-assemblies with intense green emission in a solution or a film. The blue emission and short photoluminescence lifetime of the quantum dots are different from the delayed (ca. 550 ns) green emission from the assemblies. Thus, we consider the structure and excitonic properties of individual quantum dots differently from the self-assemblies. The blue emission and short lifetime of individual quantum dots are consistent with a weak dielectric screening of excitons or strong quantum confinement. The red-shifted emission and a long photoluminescence lifetime of the assemblies suggest a strong dielectric screening that weakens the quantum confinement, allowing excitons to split into free carriers, diffuse, and trap. The delayed emission suggests nongeminate recombination of diffusing and detrapped carriers. Interestingly, the green emission of the self-assembly blueshifts by applying a lateral mechanical force (ca. 4.65 N). Correspondingly, the photoluminescence lifetime decreases by 1 order of magnitude. These photoluminescence changes suggest the mechanical dissociation of the quantum dot self-assemblies and mechanically controlled exciton splitting and recombination. The mechanically changing emission color and lifetime of halide perovskite are promising for mechano-optical and optomechanical switches and sensors.