Lead-free double perovskites hold promise for stable and environmentally benign solar cells; however, they exhibit low efficiencies because defects act as charge recombination centers. Identifying trap-assisted loss mechanisms and developing defect passivation strategies constitute an urgent goal. Applying unsupervised machine learning to density functional theory and nonadiabatic molecular dynamics, we demonstrate that negatively charged Br vacancies in Cs 2 AgBiBr 6 create deep hole traps through charge redistribution between the adjacent Ag and Bi atoms. Vacancy electrons are first accepted by Bi and then shared with Ag, as the trap transforms from shallow to deep. Subsequent charge losses are promoted by Ag and Bi motions perpendicular to rather than along the Ag−Bi axis, as can be expected. In contrast, charge recombination in pristine Cs 2 AgBiBr 6 correlates most with displacements of Cs atoms and Br−Br−Br angles. Doping with In to replace Ag at the vacancy maintains the electrons at Bi and keeps the trap shallow.

CsPbBr3 quantum dots (QDs) have been recently suggested for their application as bright green light-emitting diodes (LEDs); however, their optical properties are yet to be fully understood and characterized. In this work, we utilize time-dependent density functional theory to analyze the ground and excited states of the CsPbBr3 clusters in the presence of various low formation energy vacancy defects. Our study finds that the QD perovskites retain their defect tolerance with limited perturbance to the simulated UV–vis spectra. The exception to this general trend is that Br vacancies must be avoided, as they cause molecular orbital localization, resulting in trap states and lower LED performance. Blinking will likely still plague CsPbBr3 QDs, given that the charged defects critically perturb the spectra via red-shifting and lower absorbance. Our study provides insight into the tunability of CsPbBr3 QDs optical properties by understanding the nature of the electronic excitations and guiding improved development for high-performance LEDs.

The hot phonon bottleneck has been under intense investigation in perovskites. In the case of perovskite nanocrystals, there may be hot phonon bottlenecks as well as quantum phonon bottlenecks. While they are widely assumed to exist, evidence is growing for the breaking of potential phonon bottlenecks of both forms. Here, we perform state-resolved pump/probe spectroscopy (SRPP) and time-resolved photoluminescence spectroscopy (t-PL) to unravel hot exciton relaxation dynamics in model systems of bulk-like 15 nm nanocrystals of CsPbBr 3 and FAPbBr 3 , with FA being formamidinium. The SRPP data can be misinterpreted to reveal a phonon bottleneck even at low exciton concentrations, where there should be none. We circumvent that spectroscopic problem with a state-resolved method that reveals an order of magnitude faster cooling and breaking of the quantum phonon bottleneck that might be expected in nanocrystals. Since the prior pump/probe methods of analysis are shown to be ambiguous, we perform t-PL experiments to unambiguously confirm the existence of hot phonon bottlenecks as well. The t-PL experiments reveal there is no hot phonon bottleneck in these perovskite nanocrystals. Ab initio molecular dynamics simulations reproduce experiments by inclusion of efficient Auger processes. This experimental and theoretical work reveals insight on hot exciton dynamics, how they are precisely measured, and ultimately how they may be exploited in these materials.

The drive to develop new organic materials for use in optoelectronic devices has created the need to understand the fundamental role functionalization plays concerning the electronic properties of conjugated molecules. Here density functional theory (DFT) is used to investigate how the HOMO-LUMO gaps of halogenobenzenes are affected as a function of substituent size, position, electronegativity, ionization potential, and polarizability. A detailed molecular orbital analysis is also provided. It is shown that the molecular static polarizability and ionization potential of the bound halogens are the primary physical descriptors governing the HOMO-LUMO gap within halogenobenzenes. Two secondary descriptors controlling the HOMO-LUMO gap in these materials are the aromaticity of the halogen substituted benzene rings (as monitored via the harmonic oscillator method of aromaticity index [HOMA]) and the reduced population of the halogen atomic orbitals in the frontier MOs (%X or %X). The molecular polarizability and aromaticity, as well as %X and %X, are shown to be a function of halogen electronegativity and size, as well as number and position on the ring. It is ultimately demonstrated that halogenobenzenes which are most polarizable and are either least aromatic and/or exhibit the smallest %X (or largest %X) values, have the smallest HOMO-LUMO gaps.