Cubic NaSbS2 as an Ionic-Electronic Coupled Semiconductor for Switchable Photovoltaic and Neuromorphic Device Applications.

The recent emergence of lead halide perovskites as ionic-electronic coupled semiconductors motivates the investigation of alternative solution-processable materials with similar modulatable ionic and electronic transport properties. Here, a novel semiconductor-cubic NaSbS2 -for ionic-electronic coupled transport is investigated through a combined theoretical and experimental approach. The material exhibits mixed ionic-electronic conductivity in inert atmosphere and superionic conductivity in humid air. It is shown that post deposition electronic reconfigurability in this material enabled by an electric field induces ionic segregation enabling a switchable photovoltaic effect. Utilizing post-perturbation of the ionic composition of the material via electrical biasing and persistent photoconductivity, multistate memristive synapses with higher-order weight modulations are realized for neuromorphic computing, opening up novel applications with such ionic-electronic coupled materials.

Doping and Switchable Photovoltaic Effect in Lead-Free Perovskites Enabled by Metal Cation Transmutation.

Creating defect tolerant lead-free halide perovskites is the major challenge for development of high-performance photovoltaics with nontoxic absorbers. Few compounds of Sn, Sb, or Bi possess ns2 electronic configuration similar to lead, but their poor photovoltaic performances inspire us to evaluate other factors influencing defect tolerance properties. The effect of heavy metal cation (Bi) transmutation and ionic migration on the defects and carrier properties in a 2D layered perovskite (NH4 )3 (Sb(1-x) Bix )2 I9 system is investigated. It is shown, for the first time, the possibility of engineering the carriers in halide perovskites via metal cation transmutation to successfully form intrinsic p- and n-type materials. It is also shown that this material possesses a direct-indirect bandgap enabling high absorption coefficient, extended carrier lifetimes >100 ns, and low trap densities similar to lead halide perovskites. This study also demonstrates the possibility of electrical poling to induce switchable photovoltaic effect without additional electron and hole transport layers.

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.

Multidimensional Perovskites: A Mixed Cation Approach Towards Ambient Stable and Tunable Perovskite Photovoltaics.

Although halide perovskites are able to deliver high power conversion efficiencies, their ambient stability still remains an obstacle for commercialization. Thus, promoting the ambient stability of perovskites has become a key research focus. In this review, we highlight the sources of instability in conventional 3 D perovskites, including water intercalation, ion migration, and thermal decomposition. Recently, the multidimensional perovskites approach has become one of the most promising strategies to enhance the stability of perovskites. As compared to pure 2 D perovskites, multidimensional perovskites typically possess more ideal band gaps, better charge transport, and lower exciton binding energy, which are essential for photovoltaic applications. The larger organic cations in multidimensional perovskites could also be more chemically stable at higher temperatures than the commonly used methylammonium cation. By combining 3 D and 2 D perovskites to form multidimensional perovskites, halide perovskite photovoltaics can attain both high efficiency and increased stability.

Tunable room-temperature spin-selective optical Stark effect in solution-processed layered halide perovskites.

Ultrafast spin manipulation for opto-spin logic applications requires material systems that have strong spin-selective light-matter interaction. Conventional inorganic semiconductor nanostructures [for example, epitaxial II to VI quantum dots and III to V multiple quantum wells (MQWs)] are considered forerunners but encounter challenges such as lattice matching and cryogenic cooling requirements. Two-dimensional halide perovskite semiconductors, combining intrinsic tunable MQW structures and large oscillator strengths with facile solution processability, can offer breakthroughs in this area. We demonstrate novel room-temperature, strong ultrafast spin-selective optical Stark effect in solution-processed (C6H4FC2H4NH3)2PbI4 perovskite thin films. Exciton spin states are selectively tuned by ~6.3 meV using circularly polarized optical pulses without any external photonic cavity (that is, corresponding to a Rabi energy of ~55 meV and equivalent to applying a 70 T magnetic field), which is much larger than any conventional system. The facile halide and organic replacement in these perovskites affords control of the dielectric confinement and thus presents a straightforward strategy for tuning light-matter coupling strength.

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.