RESUMEN
Bandgap-engineered inorganic and hybrid halide perovskite (HP) films, nanocrystals, and quantum dots (PQDs) are promising for solar cells. Fluctuations of photoinduced electron transfer (PET) rates affect the interfacial charge separation efficiencies of such solar cells. Electron donor- or acceptor-doped perovskite samples help analyze PET and harvest photogenerated charge carriers efficiently. Therefore, PET in perovskite-based donor-acceptor (D-A) systems has received considerable attention. We analyzed the fluctuations of interfacial PET from MAPbBr3 or CsPbBr3 PQDs to classical electron acceptors such as 7,7,8,8-tetracyanoquinodimethane (TCNQ) and 1,2,4,5-tetracyanobenzene (TCNB) at single-particle and ensemble levels. The significantly negative Gibbs free energy changes of PET estimated from the donor-acceptor redox potentials, the donor-acceptor sizes, and the solvent dielectric properties help us clarify the PET in the above D-A systems. The dynamic nature of PET is apparent from the decrease in photoluminescence (PL) lifetimes and PL photocounts of PQDs with an increase in the acceptor concentrations. Also, the acceptor radical anion spectrum helps us characterize the charge-separated states. Furthermore, the PL blinking time and PET rate fluctuations (108 to 107 s-1) provide us with single-molecule level information about interfacial PET in perovskites.
RESUMEN
Halide perovskites are materials for future optical displays and solar cells. Electron donor-acceptor perovskite heterostructures with distinguishing halide compositions are promising for transporting and harvesting photogenerated charge carriers. Combined e-beam lithography and anion exchange are promising to develop such heterostructures but challenging to prepare multiple heterojunctions at desired locations in single crystals. We demonstrate swift laser trapping-assisted band gap engineering at the desired locations in MAPbBr3 microrods, microplates, or nanocrystal thin films. The built-in donor-acceptor double and multi-heterojunction structures let us transport and trap photogenerated charge carriers from wide-band gap bromide to narrow-band gap iodide domains. We discuss the charge carrier transport and trapping mechanisms from the viewpoints of engineered bands and band continuity. This work offers a convenient method for designing single-, double- and multi-heterojunction donor-acceptor halide perovskites for photovoltaic, photonic, and electronic applications.
RESUMEN
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.
RESUMEN
Interfacial electron transfer across perovskite-electron acceptor heterojunctions plays a significant role in the power-conversion efficiency of perovskite solar cells. Thus, electron donor-acceptor thin films of halide perovskite nanocrystals receive considerable attention. Nevertheless, understanding and optimizing distance- and thickness-dependent electron transfer in perovskite-electron acceptor heterojunctions are important. We reveal the distance-dependent and diffusion-controlled interfacial electron transfer across donor-acceptor heterojunction films formed by formamidinium or cesium lead bromide (FAPbBr3/CsPbBr3) perovskite nanocrystals with TiO2/C60. Self-assembled nanocrystal films prepared from FAPbBr3 show a longer photoluminescence lifetime than a solution, showing a long-range carrier migration. The acceptors quench the photoluminescence intensity but not the lifetime in a solution, revealing a static electron transfer. Conversely, the electron transfer in the films changes from dynamic to static by moving toward the donor-acceptor interface. While radiative recombination dominates the electron transfer at 800 µm or farther, the acceptors scavenge the photogenerated carriers within 100 µm. This research highlights the significance of interfacial electron transfer in perovskite films.