A chiral switchable photovoltaic ferroelectric 1D perovskite.

Spin and valley degrees of freedom in materials without inversion symmetry promise previously unknown device functionalities, such as spin-valleytronics. Control of material symmetry with electric fields (ferroelectricity), while breaking additional symmetries, including mirror symmetry, could yield phenomena where chirality, spin, valley, and crystal potential are strongly coupled. Here we report the synthesis of a halide perovskite semiconductor that is simultaneously photoferroelectricity switchable and chiral. Spectroscopic and structural analysis, and first-principles calculations, determine the material to be a previously unknown low-dimensional hybrid perovskite (R)-(-)-1-cyclohexylethylammonium/(S)-(+)-1 cyclohexylethylammonium) PbI3. Optical and electrical measurements characterize its semiconducting, ferroelectric, switchable pyroelectricity and switchable photoferroelectric properties. Temperature dependent structural, dielectric and transport measurements reveal a ferroelectric-paraelectric phase transition. Circular dichroism spectroscopy confirms its chirality. The development of a material with such a combination of these properties will facilitate the exploration of phenomena such as electric field and chiral enantiomer-dependent Rashba-Dresselhaus splitting and circular photogalvanic effects.

A Reconfigurable Remotely Epitaxial VO2 Electrical Heterostructure.

The reconfigurability of the electrical heterostructure featured with external variables, such as temperature, voltage, and strain, enabled electronic/optical phase transition in functional layers has great potential for future photonics, computing, and adaptive circuits. VO2 has been regarded as an archetypal phase transition building block with superior metal-insulator transition characteristics. However, the reconfigurable VO2-based heterostructure and the associated devices are rare due to the fundamental challenge in integrating high-quality VO2 in technologically important substrates. In this report, for the first time, we show the remote epitaxy of VO2 and the demonstration of a vertical diode device in a graphene/epitaxial VO2/single-crystalline BN/graphite structure with VO2 as a reconfigurable phase-change material and hexagonal boron nitride (h-BN) as an insulating layer. By diffraction and electrical transport studies, we show that the remote epitaxial VO2 films exhibit higher structural and electrical quality than direct epitaxial ones. By high-resolution transmission electron microscopy and Cs-corrected scanning transmission electron microscopy, we show that a graphene buffered substrate leads to a less strained VO2 film than the bare substrate. In the reconfigurable diode, we find that the Fermi level change and spectral weight shift along with the metal-insulator transition of VO2 could modify the transport characteristics. The work suggests the feasibility of developing a single-crystalline VO2-based reconfigurable heterostructure with arbitrary substrates and sheds light on designing novel adaptive photonics and electrical devices and circuits.

Publisher Correction: Carrier lifetime enhancement in halide perovskite via remote epitaxy.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Carrier lifetime enhancement in halide perovskite via remote epitaxy.

Crystallographic dislocation has been well-known to be one of the major causes responsible for the unfavorable carrier dynamics in conventional semiconductor devices. Halide perovskite has exhibited promising applications in optoelectronic devices. However, how dislocation impacts its carrier dynamics in the 'defects-tolerant' halide perovskite is largely unknown. Here, via a remote epitaxy approach using polar substrates coated with graphene, we synthesize epitaxial halide perovskite with controlled dislocation density. First-principle calculations and molecular-dynamics simulations reveal weak film-substrate interaction and low density dislocation mechanism in remote epitaxy, respectively. High-resolution transmission electron microscopy, high-resolution atomic force microscopy and Cs-corrected scanning transmission electron microscopy unveil the lattice/atomic and dislocation structure of the remote epitaxial film. The controlling of dislocation density enables the unveiling of the dislocation-carrier dynamic relation in halide perovskite. The study provides an avenue to develop free-standing halide perovskite film with low dislocation density and improved carried dynamics.

Merits and Challenges of Ruddlesden-Popper Soft Halide Perovskites in Electro-Optics and Optoelectronics.

Following the rejuvenation of 3D organic-inorganic hybrid perovskites, like CH3 NH3 PbI3 , (quasi)-2D Ruddlesden-Popper soft halide perovskites R2 An -1 Pbn X3 n +1 have recently become another focus in the optoelectronic and photovoltaic device community. Although quasi-2D perovskites were first introduced to stabilize optoelectronic/photovoltaic devices against moisture, more interesting properties and device applications, such as solar cells, light-emitting diodes, white-light emitters, lasers, and polaritonic emission, have followed. While delicate engineering design has pushed the performance of various devices forward remarkably, understanding of the fundamental properties, especially the charge-transfer process, electron-phonon interactions, and the growth mechanism in (quasi)-2D halide perovskites, remains limited and even controversial. Here, after reviewing the current understanding and the nexus between optoelectronic/photovoltaic properties of 2D and 3D halide perovskites, the growth mechanisms, charge-transfer processes, vibrational properties, and electron-phonon interactions of soft halide perovskites, mainly in quasi-2D systems, are discussed. It is suggested that single-crystal-based studies are needed to deepen the understanding of the aforementioned fundamental properties, and will eventually contribute to device performance.

Remote Phononic Effects in Epitaxial Ruddlesden-Popper Halide Perovskites.

Despite their weak nature, van der Waals (vdW) interactions have been shown to effectively control the optoelectronic and vibrational properties of layered materials. However, how vdW effects exist in Ruddlesden-Popper layered halide perovskites remains unclear. Here we reveal the role of interlayer vdW force in Ruddlesden-Popper perovskite in regulating phase-transition kinetics and carrier dynamics based on high-quality epitaxial single-crystalline (C4H9NH3)2PbI4 flakes with controlled dimensions. Both substrate-perovskite epitaxial interaction and interlayer vdW interaction play significant roles in suppressing the structural phase transition. With reducing flake thickness from ∼100 to ∼20 nm, electron-phonon coupling strength decreases by ∼30%, suggesting the ineffectiveness of phonon confinement of the natural quantum wells. Therefore, the conventional understanding that vdW perovskite is equivalent to a multiple quantum well has to be substantially amended due to significant nonlocal phononic effects in the layered crystal, where intralayer interaction is not drastically different from the interlayer force.

High-Temperature Ionic Epitaxy of Halide Perovskite Thin Film and the Hidden Carrier Dynamics.

High-temperature vapor phase epitaxy (VPE) has been proved ubiquitously powerful in enabling high-performance electro-optic devices in III-V semiconductor field. A typical example is the successful growth of p-type GaN by VPE for blue light-emitting diodes. VPE excels as it controls film defects such as point/interface defects and grain boundary, thanks to its high-temperature processing condition and controllable deposition rate. For the first time, single-crystalline high-temperature VPE halide perovskite thin film has been demonstrated-a unique platform on unveiling previously uncovered carrier dynamics in inorganic halide perovskites. Toward wafer-scale epitaxial and grain boundary-free film is grown with alkali halides as substrates. It is shown the metal alkali halides could be used as universal substrates for VPE growth of perovskite due to their similar material chemistry and lattice constant. With VPE, hot photoluminescence and nanosecond photo-Dember effect are revealed in inorganic halide perovskite. These two phenomena suggest that inorganic halide perovskite could be as compelling as its organic-inorganic counterpart regarding optoelectronic properties and help explain the long carrier lifetime in halide perovskite. The findings suggest a new avenue on developing high-quality large-scale single-crystalline halide perovskite films requiring precise control of defects and morphology.

Epitaxial Halide Perovskite Lateral Double Heterostructure.

Epitaxial III-V semiconductor heterostructures are key components in modern microelectronics, electro-optics, and optoelectronics. With superior semiconducting properties, halide perovskite materials are rising as promising candidates for coherent heterostructure devices. In this report, spinodal decomposition is proposed and experimentally implemented to produce epitaxial double heterostructures in halide perovskite system. Pristine epitaxial mixed halide perovskites rods and films were synthesized via van der Waals epitaxy by chemical vapor deposition method. At room temperature, photon was applied as a knob to regulate the kinetics of spinodal decomposition and classic coarsening. By this approach, halide perovskite double heterostructures were created carrying epitaxial interfaces and outstanding optical properties. Reduced Fröhlich electron-phonon coupling was discovered in coherent halide double heterostructure, which is hypothetically attributed to the classic phonon confinement effect widely existing in III-V double heterostructures. As a proof-of-concept, our results suggest that halide perovskite-based epitaxial heterostructures may be promising for high-performance and low-cost optoelectronics, electro-optics, and microelectronics. Thus, ultimately, for practical device applications, it may be worthy to pursue these heterostructures via conventional vapor phase epitaxy approaches widely practised in III-V field.

Photon Transport in One-Dimensional Incommensurately Epitaxial CsPbX3 Arrays.

One-dimensional nanoscale epitaxial arrays serve as a great model in studying fundamental physics and for emerging applications. With an increasing focus laid on the Cs-based inorganic halide perovskite out of its outstanding material stability, we have applied vapor phase epitaxy to grow well aligned horizontal CsPbX3 (X: Cl, Br, or I or their mixed) nanowire arrays in large scale on mica substrate. The as-grown nanowire features a triangular prism morphology with typical length ranging from a few tens of micrometers to a few millimeters. Structural analysis reveals that the wire arrays follow the symmetry of mica substrate through incommensurate epitaxy, paving a way for a universally applicable method to grow a broad family of halide perovskite materials. The unique photon transport in the one-dimensional structure has been studied in the all-inorganic Cs-based perovskite wires via temperature dependent and spatially resolved photoluminescence. Epitaxy of well oriented wire arrays in halide perovskite would be a promising direction for enabling the circuit-level applications of halide perovskite in high-performance electro-optics and optoelectronics.

Single-molecule super-resolution microscopy reveals how light couples to a plasmonic nanoantenna on the nanometer scale.

The greatly enhanced fields near metal nanoparticles have demonstrated remarkable optical properties and are promising for applications from solar energy to biosensing. However, direct experimental study of these light-matter interactions at the nanoscale has remained difficult due to the limitations of optical microscopy. Here, we use single-molecule fluorescence imaging to probe how a plasmonic nanoantenna modifies the fluorescence emission from a dipole emitter. We show that the apparent fluorophore emission position is strongly shifted upon coupling to an antenna and that the emission of dyes located up to 90 nm away is affected by this coupling. To predict this long-ranged effect, we present a framework based on a distance-dependent partial coupling of the dye emission to the antenna. Our direct interpretation of these light-matter interactions will enable more predictably optimized, designed, and controlled plasmonic devices and will permit reliable plasmon-enhanced single-molecule nanoscopy.

Polariton condensation in photonic molecules.

We report on polariton condensation in photonic molecules formed by two coupled micropillars. We show that the condensation process is strongly affected by the interaction with the cloud of uncondensed excitons and thus strongly depends on the exact localization of these excitons within the molecule. Under symmetric excitation conditions, condensation is triggered on both binding and antibinding polariton states of the molecule. On the opposite, when the excitonic cloud is injected in one of the two pillars, condensation on a metastable state is observed and a total transfer of the condensate into one of the micropillars can be achieved. Our results highlight the crucial role played by relaxation kinetics in the condensation process.

Interactions in confined polariton condensates.

We investigate the effect of interactions in zero-dimensional polariton condensates. The shape of the condensate wave function is shown to be modified by repulsive interactions with the reservoir of uncondensed excitons. In large micropillar cavities, when uncondensed excitons are located at the center, the condensate is ejected toward the pillar edges. The same effect results in the generation of optical traps in wire cavities. Once polariton condensates are spatially separated from the excitonic reservoir, spectral signatures of polariton-polariton interactions within the condensate are evidenced.

Optical bistability in a GaAs-based polariton diode.

We report on a new type of optical nonlinearity in a polariton p-i-n microcavity. Abrupt switching between the strong and weak coupling regime is induced by controlling the electric field within the cavity. As a consequence, bistable cycles are observed for low optical powers (2-3 orders of magnitude less than for Kerr induced bistability). Signatures of switching fronts propagating through the whole 300 x 300 microm2 mesa surface are evidenced.

Polariton laser using single micropillar GaAs-GaAlAs semiconductor cavities.

Polariton lasing is demonstrated on the zero-dimensional states of single GaAs/GaAlAs micropillar cavities. Under nonresonant excitation, the measured polariton ground-state occupancy is found as large as 10(4). Changing the spatial excitation conditions, competition between several polariton lasing modes is observed, ruling out Bose-Einstein condensation. When the polariton state occupancy increases, the emission blueshift is the signature of self-interaction within the half-light half-matter polariton lasing mode.