ABSTRACT
Bismuth-based double perovskite Cs2AgBiBr6 is regarded as a potential candidate for low-toxicity, high-stability perovskite solar cells. However, its performance is far from satisfactory. Albeit being an indirect bandgap semiconductor, we observe bright emission with large bimolecular recombination coefficient (reaching 4.5 ± 0.1 × 10-11 cm3 s-1) and low charge carrier mobility (around 0.05 cm2 s-1 V-1). Besides intermediate Fröhlich couplings present in both Pb-based perovskites and Cs2AgBiBr6, we uncover evidence of strong deformation potential by acoustic phonons in the latter through transient reflection, time-resolved terahertz measurements, and density functional theory calculations. The Fröhlich and deformation potentials synergistically lead to ultrafast self-trapping of free carriers forming polarons highly localized on a few units of the lattice within a few picoseconds, which also breaks down the electronic band picture, leading to efficient radiative recombination. The strong self-trapping in Cs2AgBiBr6 could impose intrinsic limitations for its application in photovoltaics.
ABSTRACT
Amongst the many spectacular properties of hybrid lead halide perovskites, their defect tolerance is regarded as the key enabler for a spectrum of high-performance optoelectronic devices that propel perovskites to prominence. However, the plateauing efficiency enhancement of perovskite devices calls into question the extent of this defect tolerance in perovskite systems; an opportunity for perovskite nanocrystals to fill. Through optical spectroscopy and phenomenological modeling based on the Marcus theory of charge transfer, we uncover the detrimental effect of hot carriers trapping in methylammonium lead iodide and bromide nanocrystals. Higher excess energies induce faster carrier trapping rates, ascribed to interactions with shallow traps and ligands, turning these into potent defects. Passivating these traps with the introduction of phosphine oxide ligands can help mitigate hot carrier trapping. Importantly, our findings extend beyond photovoltaics and are relevant for low threshold lasers, light-emitting devices and multi-exciton generation devices.
ABSTRACT
Mechanochemistry is a green, solid-state, re-emerging synthetic technique that can rapidly form complex molecules and materials without exogenous heat or solvent(s). Herein, we report the application of solvent-free mechanochemical ball milling for the synthesis of metal halide perovskites, to overcome problems with solution-based syntheses. We prepared phase-pure, air-sensitive CsSnX3 (X = I, Br, Cl) and its mixed halide perovskites by mechanochemistry for the first time by reactions between cesium and tin(II) halides. Notably, we report the sole examples where metastable, high-temperature phases like cubic CsSnCl3, cubic CsPbI3, and trigonal FAPbI3 were accessible at ambient temperatures and pressures without post-synthetic processing. The perovskites can be prepared up to "kilogram scales." Lead-free, all-inorganic photodetector devices were fabricated using the mechanosynthesized CsSnBr1.5Cl1.5 under solvent-free conditions and showed 10-fold differences between on-off currents. We highlight an essentially solvent-free, general approach to synthesize metastable compounds and fabricate photodetectors from commercially available precursors.
ABSTRACT
We report the high yield synthesis of about 11 nm sized CH3NH3PbBr3 nanocrystals with near-unity photoluminescence quantum yield. The nanocrystals are formed in the presence of surface-binding ligands through their direct precipitation in a benzyl alcohol/toluene phase. The benzyl alcohol plays a pivotal role in steering the surface ligands binding motifs on the NC surface, resulting in enhanced surface-trap passivation and near-unity PLQY values. We further demonstrate that thin films from purified CH3NH3PbBr3 nanocrystals are stable >4 months in air, exhibit high optical gain (about 520 cm-1), and display stable, ultralow amplified spontaneous emission thresholds of 13.9 ± 1.3 and 569.7 ± 6 µJ cm-2 at one-photon (400 nm) and two-photon (800 nm) absorption, respectively. To the best of our knowledge, the latter signifies a 5-fold reduction of the lowest reported threshold value for halide perovskite nanocrystals to date, which makes them ideal candidates for light-emitting and low-threshold lasing applications.
ABSTRACT
Formamidinium lead halide (FAPbX3) has attracted greater attention and is more prominent recently in photovoltaic devices due to its broad absorption and higher thermal stability in comparison to more popular methylammonium lead halide MAPbX3. Herein, a simple and highly reproducible room temperature synthesis of device grade high quality formamidinium lead bromide CH(NH2)2PbBr3 (FAPbBr3) colloidal nanocrystals (NC) having high photoluminescence quantum efficiency (PLQE) of 55-65% is reported. In addition, we demonstrate high brightness perovskite light emitting device (Pe-LED) with these FAPbBr3 perovskite NC thin film using 2,2',2â³-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) commonly known as TPBi and 4,6-Bis(3,5-di(pyridin-3-yl)phenyl)-2-methylpyrimidine (B3PYMPM) as electron transport layers (ETL). The Pe-LED device with B3PYMPM as ETL has bright electroluminescence of up to 2714 cd/m2, while the Pe-LED device with TPBi as ETL has higher peak luminous efficiency of 6.4 cd/A and peak luminous power efficiency of 5.7 lm/W. To our knowledge this is the first report on high brightness light emitting device based on CH(NH2)2PbBr3 widely known as FAPbBr3 nanocrystals in literature.
