Strong self-trapping by deformation potential limits photovoltaic performance in bismuth double perovskite.

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.

Grain Size Modulation and Interfacial Engineering of CH3 NH3 PbBr3 Emitter Films through Incorporation of Tetraethylammonium Bromide.

Metal halide perovskites have demonstrated breakthrough performances as absorber and emitter materials for photovoltaic and display applications respectively. However, despite the low manufacturing cost associated with solution-based processing, the propensity for defect formation with this technique has led to an increasing need for defect passivation. Here, we present an inexpensive and facile method to remedy surface defects through a postdeposition treatment process using branched alkylammonium cation species. The simultaneous realignment of interfacial energy levels upon incorporation of tetraethylammonium bromide onto the surface of CH3 NH3 PbBr3 films contributes favorably toward the enhancement in overall light-emitting diode characteristics, achieving maximum luminance, current efficiency, and external quantum efficiency values of 11 000 cd m-2 , 0.68 cd A-1 , and 0.16 %, respectively.

Broadband-Emitting 2 D Hybrid Organic-Inorganic Perovskite Based on Cyclohexane-bis(methylamonium) Cation.

A new broadband-emitting 2 D hybrid organic-inorganic perovskite (CyBMA)PbBr4 based on highly flexible cis-1,3-bis(methylaminohydrobromide)cyclohexane (CyBMABr) core has been designed, synthesized, and investigated, highlighting the effects of stereoisomerism of the templating cation on the formation and properties of the resulting perovskite. The new 2 D material has high exciton binding energy of 340 meV and a broad emission spanning from 380 to 750 nm, incorporating a prominent excitonic band and a less intense broad peak at room temperature. Significant changes in the photoluminescence (PL) spectrum were observed at lower temperatures, showing remarkable enhancement in the intensity of the broadband at the cost of excitonic emission. Temperature-dependent PL mapping indicates the effective role of only a narrow band of excitonic absorption in the generation of the active channel for emission. Based on the evidences obtained from the photophysical investigations, we attributed the evolution of the broad B-band of (CyBMA)PbBr4 to excitonic self-trapped states.

Facile Method to Reduce Surface Defects and Trap Densities in Perovskite Photovoltaics.

Owing to improvements in film morphology, crystallization process optimization, and compositional design, the power conversion efficiency of perovskite solar cells has increased from 3.8 to 22.1% in a period of 5 years. Nearly defect-free crystalline films and slow recombination rates enable polycrystalline perovskite to boast efficiencies comparable to those of multicrystalline silicon solar cells. However, volatile low melting point components and antisolvent treatments essential for the processing of dense and smooth films often lead to surface defects that hamper charge extraction. In this study, we investigate methylammonium bromide (MABr) surface treatments on perovskite films to compensate for the loss of volatile cation during the annealing process for surface defect passivation, grain growth, and a bromide-rich top layer. This facile method did not change the phase or bandgap of perovskite films yet resulted in a significant increase in the open circuit voltages of devices. The devices with 10 mM MABr treatment show 2% improvement in absolute power conversion efficiency over the control sample.

Corrigendum: Slow cooling and highly efficient extraction of hot carriers in colloidal perovskite nanocrystals.

This corrects the article DOI: 10.1038/ncomms14350.

Slow cooling and highly efficient extraction of hot carriers in colloidal perovskite nanocrystals.

Hot-carrier solar cells can overcome the Schottky-Queisser limit by harvesting excess energy from hot carriers. Inorganic semiconductor nanocrystals are considered prime candidates. However, hot-carrier harvesting is compromised by competitive relaxation pathways (for example, intraband Auger process and defects) that overwhelm their phonon bottlenecks. Here we show colloidal halide perovskite nanocrystals transcend these limitations and exhibit around two orders slower hot-carrier cooling times and around four times larger hot-carrier temperatures than their bulk-film counterparts. Under low pump excitation, hot-carrier cooling mediated by a phonon bottleneck is surprisingly slower in smaller nanocrystals (contrasting with conventional nanocrystals). At high pump fluence, Auger heating dominates hot-carrier cooling, which is slower in larger nanocrystals (hitherto unobserved in conventional nanocrystals). Importantly, we demonstrate efficient room temperature hot-electrons extraction (up to ∼83%) by an energy-selective electron acceptor layer within 1 ps from surface-treated perovskite NCs thin films. These insights enable fresh approaches for extremely thin absorber and concentrator-type hot-carrier solar cells.

Dominant factors limiting the optical gain in layered two-dimensional halide perovskite thin films.

Semiconductors are ubiquitous gain media for coherent light sources. Solution-processed three-dimensional (3D) halide perovskites (e.g., CH3NH3PbI3) with their outstanding room temperature optical gain properties are the latest members of this family. Their two-dimensional (2D) layered perovskite counterparts with natural multiple quantum well structures exhibit strong light-matter interactions and intense excitonic luminescence. However, despite such promising traits, there have been no reports on room temperature optical gain in 2D layered perovskites. Herein, we reveal the challenges towards achieving amplified spontaneous emission (ASE) in the archetypal (C6H5C2H4NH3)2PbI4 (or PEPI) system. Temperature-dependent transient spectroscopy uncovers the dominant free exciton trapping and bound biexciton formation pathways that compete effectively with biexcitonic gain. Phenomenological rate equation modeling predicts a large biexciton ASE threshold of ∼1.4 mJ cm(-2), which is beyond the damage threshold of these materials. Importantly, these findings would rationalize the difficulties in achieving optical gain in 2D perovskites and provide new insights and suggestions for overcoming these challenges.

Structural Evolution in Methylammonium Lead Iodide CH3NH3PbI3.

The organic-inorganic hybrid perovskite, in particular, methylammonium lead iodide (MAPbI3), is currently a subject of intense study due to its desirability in making efficient photovoltaic devices economically. It is known that MAPbI3 undergoes structural phase transitions from orthorhombic Pnma to tetragonal I4/mcm at ∼170 K and then to cubic Pm3̅m at ∼330 K. A tetragonal P4mm phase is also reported at 400 K considering total cation disorder is not appealing due to its hydrogen-bonding capabilities. Resolving this ambiguity of phase transition necessitates the study of the structural evolution across these phases in our work using ab initio methods. In this work, we show that the structural phase evolves from Pnma to I4/mcm to P4mm to Pm3̅m with increasing volume. The P4mm phase is a quasi-cubic one with slight distortion in one direction from cubic Pm3̅m due to the rotation of MA cations. Biaxial strain on MAPbI3 reveals that only the Pnma and P4mm phases are energetically stable at a < 9.14 Å and a > 9.14 Å, respectively. The Pnma, I4/mcm, P4mm, and Pm3̅m phases can be stable under various uniaxial strain conditions. Our study provides a clear understanding of the structural phase transitions that occur in MAPbI3 and provides a guide for the epitaxial growth of specific phases under various strain conditions.

Mechanical Origin of the Structural Phase Transition in Methylammonium Lead Iodide CH3NH3PbI3.

The methylammonium lead iodide perovskite (MAPbI3) is presently a desirable material for photovoltaic application. Its structure is orthorhombic at low temperature and tetragonal at room temperature. Most theoretical works have focused on either tetragonal or orthorhombic phase alone leaving a gap in the understanding of the structural phase transition in between. In this work, by ab initio calculations, we elucidate the origin of structural phase transition between these two phases. We show that there exists a critical ratio of out-of-plane to in-plane lattice constants, c/a ∼ 1.45, where at low c/a the orthorhombic Pnma phase is stable while the tetragonal I4/mcm phase is stable at high c/a. Varying the c/a ratio leads to a change of PbI6 octahedral tilting with the rotation of CH3NH3(+) cations about the NH3 component in and out of the Oxy plane. The origin of this rotation is identified. We propose that under epitaxial conditions a gradual change in structural phase of the MAPbI3 perovskite may exist and understanding its electronic properties will be beneficial toward the solar cell community.