Self-trapped excitons in two-dimensional perovskites

With strong electron-phonon coupling,the self-trapped excitons are usually formed in materials,which leads to the local lattice distortion and localized excitons.The self-trapping strongly depends on the dimensionality of the materials.In the three dimensional case,there is a potential barrier for self-trapping,whereas no such barrier is present for quasi-one-dimensional systems.Two-dimensional(2D)systems are marginal cases with a much lower potential barrier or nonex istent potential barrier for the self-trapping,leading to the easier formation of self-trapped states.Self-trapped excitons emission exhibits a broadband emission with a large Stokes shift below the bandgap.2D perovskites are a class of layered structure material with unique optical properties and would find potential promising optoelectronic.In particular,self-trapped excitons are present in 2D per-ovskites and can significantly influence the optical and electrical properties of 2D perovskites due to the soft characteristic and strong electron-phonon interaction.Here,we summarized the luminescence characteristics,origins,and characterizations of self-trapped excitons in 2D perovskites and finally gave an introduction to their applications in optoelectronics.

Identifying self-trapped excitons in 2D perovskites by Raman spectroscopy[Invited]

Two-dimensional(2D)perovskites exhibit broadband emission due to strong exciton–phonon coupling-induced self-trapped excitons and thus would find important applications in the field of white-light emitting devices.However,the available identifying methods for self-trapped excitons are currently rather limited and complex.Here,we identify the existence of self-trapped excitons by Raman spectroscopy in both excited and non-excited states.Under excited states,the shifting of the Raman peak indicates the presence of the lattice distortion,which together with the extra Raman scattering peak reveals the presence of self-trapped excitons.Our work provides an alternative simple method to study self-trapped excitons in 2 D perovskites.

Surface depletion field in 2D perovskite microplates: Structural phase transition, quantum confinement and Stark effect

Surface depletion field would introduce the depletion region near surface and thus could significantly alter the optical,electronic and optoelectronic properties of the materials,especially low-dimensional materials.Two-dimensional(2D)organic—inorganic hybrid perovskites with van der Waals bonds in the out-of-plane direction are expected to have less influence from the surface depletion field;nevertheless,studies on this remain elusive.Here we report on how the surface depletion field affects the structural phase transition,quantum confinement and Stark effect in 2D(BA)2PbI4 perovskite microplates by the thickness-,temperature-and power-dependent photoluminescence(PL)spectroscopy.Power dependent PL studies suggest that high-temperature phase(HTP)and low-temperature phase(LTP)can coexist in a wider temperature range depending on the thickness of the 2D perovskite microplates.With the decrease of the microplate thickness,the structural phase transition temperature first gradually decreases and then increases below 25 nm,in striking contrast to the conventional size dependent structural phase transition.Based on the thickness evolution of the emission peaks for both high-temperature phase and low-temperature phase,the anomalous size dependent phase transition could probably be ascribed to the surface depletion field and the surface energy difference between polymorphs.This explanation was further supported by the temperature dependent PL studies of the suspended microplates and encapsulated microplates with graphene and boron nitride flakes.Along with the thickness dependent phase transition,the emission energies of free excitons for both HTP and LTP with thickness can be ascribed to the surface depletion induced confinement and Stark effect.

Nonvolatile electrical switching of optical and valleytronic properties of interlayer excitons

Long-lived interlayer excitons(IXs)in van der Waals heterostructures(HSs)stacked by monolayer transition metal dichalcogenides(TMDs)carry valley-polarized information and thus could find promising applications in valleytronic devices.Current manipulation approaches for valley polarization of IXs are mainly limited in electrical field/doping,magnetic field or twist-angle engineering.Here,we demonstrate an electrochemical-doping method,which is efficient,in-situ and nonvolatile.We find the emission characteristics of IXs in WS2/WSe2 HSs exhibit a large excitonic/valley-polarized hysteresis upon cyclic-voltage sweeping,which is ascribed to the chemical-doping of O2/H2O redox couple trapped between WSe2 and substrate.Taking advantage of the large hysteresis,a nonvolatile valley-addressable memory is successfully demonstrated.The valley-polarized information can be non-volatilely switched by electrical gating with retention time exceeding 60 min.These findings open up an avenue for nonvolatile valley-addressable memory and could stimulate more investigations on valleytronic devices.

A chain-type diamine strategy towards strongly anisotropic triiodide of DMEDA·I6

Linearly bonded triiodide chains with fairly small distance between the adjacent iodine ions feature a facile electron transfer and highly anisotropic properties.Here,we demonstrate a novel strategy towards a new one-dimensional linear triiodide DMEDA·I6,using chain-type N,N'-dimethylethanediamine(DMEDA)cation to coordinate triiodine ions.This triiodide has the shortest distance between adjacent I3^- and good linearity.An estimated electronic band gap of1.36 e V indicates its semiconducting properties.100 fold differences both in polarization-sensitive absorption and effective mass were achieved by simulation,with directions parallel and perpendicular to the a-axis of DMEDA·I6.The DMEDA·I6 single crystal-based photodetectors show a good switching characteristic and a distinct polarization-sensitive photoresponse with linear dichroic photodetection ratio of about 1.9.Strongly anisotropic features and semiconducting properties of DMEDA·I6 make this triiodide system an interesting candidate for polarization related applications.