From Heterostructures to Solid-Solutions: Structural Tunability in Mixed Halide Perovskites.

The stability, reliability, and performance of halide-perovskite-based devices depend upon the structure, composition, and particle size of the device-enabling materials. Indeed, the degree of ion mixing in multicomponent perovskite crystals, although challenging to control, is a key factor in determining properties. Herein, an emerging method termed evaporation-crystallization polymer pen lithography is used to synthesize and systematically study the degree of ionic mixing of Cs FA PbX (FA = formamidinium; X = halide anion, ABX ) crystals, as a function of size, temperature, and composition.

Combinatorial Synthesis and Screening of Mixed Halide Perovskite Megalibraries.

A significant bottleneck in the discovery of new mixed halide perovskite (MHP) compositions and structures is the time-consuming and low-throughput nature of current synthesis and screening methods. Here, a high-throughput strategy is presented that can be used to synthesize combinatorial libraries of MHPs with deliberate control over the halide mixing ratio and particle size (for example, CsPb(BrCl) (0 < < 1) with sizes between ∼100 and 400 nm). This strategy combines evaporation-crystallization polymer pen lithography (EC-PPL) and defect-engineered anion exchange to spatially encode particle size and composition, respectively.

Solid-State Ionic Rectification in Perovskite Nanowire Heterostructures.

Halide perovskites have attracted increasing research attention with regard to their potential for optoelectronic applications. Because of its low activation energy, ion migration is implicated in the long-term stability and many unusual transport behaviors of halide perovskite devices. However, direct observation and precise control of the ionic transport in halide perovskite crystals remain challenging.

Halide perovskite nanocrystal arrays: Multiplexed synthesis and size-dependent emission.

Halide perovskites have exceptional optoelectronic properties, but a poor understanding of the relationship between crystal dimensions, composition, and properties limits their use in integrated devices. We report a new multiplexed cantilever-free scanning probe method for synthesizing compositionally diverse and size-controlled halide perovskite nanocrystals spanning square centimeter areas. Single-particle photoluminescence studies reveal multiple independent emission modes due to defect-defined band edges with relative intensities that depend on crystal size at a fixed composition.

Two-dimensional halide perovskite lateral epitaxial heterostructures.

Epitaxial heterostructures based on oxide perovskites and III-V, II-VI and transition metal dichalcogenide semiconductors form the foundation of modern electronics and optoelectronics. Halide perovskites-an emerging family of tunable semiconductors with desirable properties-are attractive for applications such as solution-processed solar cells, light-emitting diodes, detectors and lasers. Their inherently soft crystal lattice allows greater tolerance to lattice mismatch, making them promising for heterostructure formation and semiconductor integration.

Effect of Anisotropic Confinement on Electronic Structure and Dynamics of Band Edge Excitons in Inorganic Perovskite Nanowires.

Inorganic lead halide perovskite nanostructures show promise as the active layers in photovoltaics, light emitting diodes, and other optoelectronic devices. They are robust in the presence of oxygen and water, and the electronic structure and dynamics of these nanostructures can be tuned through quantum confinement. Here we create aligned bundles of CsPbBr nanowires with widths resulting in quantum confinement of the electronic wave functions and subject them to ultrafast microscopy.

Two-Step Patterning of Scalable All-Inorganic Halide Perovskite Arrays.

Halide perovskites have many important optoelectronic properties, including high emission efficiency, high absorption coefficients, color purity, and tunable emission wavelength, which makes these materials promising for optoelectronic applications. However, the inability to precisely control large-scale patterned growth of halide perovskites limits their potential toward various device applications. Here, we report a patterning method for the growth of a cesium lead halide perovskite single crystal array.

Structural and spectral dynamics of single-crystalline Ruddlesden-Popper phase halide perovskite blue light-emitting diodes.

Achieving perovskite-based high-color purity blue-emitting light-emitting diodes (LEDs) is still challenging. Here, we report successful synthesis of a series of blue-emissive two-dimensional Ruddlesden-Popper phase single crystals and their high-color purity blue-emitting LED demonstrations. Although this approach successfully achieves a series of bandgap emissions based on the different layer thicknesses, it still suffers from a conventional temperature-induced device degradation mechanism during high-voltage operations.

Self-Assembly of Two-Dimensional Perovskite Nanosheet Building Blocks into Ordered Ruddlesden-Popper Perovskite Phase.

The self-assembly of nanoparticles, a process whereby nanocrystal building blocks organize into even more ordered superstructures, is of great interest to nanoscience. Here we report the layer-by-layer assembly of 2D perovskite nanosheet building blocks. Structural analysis reveals that the assembled superlattice nanocrystals match with the layered Ruddlesden-Popper perovskite phase.

Quantitative imaging of anion exchange kinetics in halide perovskites.

Ion exchange, as a postsynthetic transformation strategy, offers more flexibilities in controlling material compositions and structures beyond direct synthetic methodology. Observation of such transformation kinetics on the single-particle level with rich spatial and spectroscopic information has never been achieved. We report the quantitative imaging of anion exchange kinetics in individual single-crystalline halide perovskite nanoplates using confocal photoluminescence microscopy.

Intrinsic anion diffusivity in lead halide perovskites is facilitated by a soft lattice.

Facile ionic transport in lead halide perovskites plays a critical role in device performance. Understanding the microscopic origins of high ionic conductivities has been complicated by indirect measurements and sample microstructural heterogeneities. Here, we report the direct visualization of halide anion interdiffusion in CsPbCl-CsPbBr single crystalline perovskite nanowire heterojunctions using wide-field and confocal photoluminescence measurements.

Giant Light-Emission Enhancement in Lead Halide Perovskites by Surface Oxygen Passivation.

Surface condition plays an important role in the optical performance of semiconductor materials. As new types of semiconductors, the emerging metal-halide perovskites are promising for next-generation optoelectronic devices. We discover significantly improved light-emission efficiencies in lead halide perovskites due to surface oxygen passivation.

Rich Chemistry in Inorganic Halide Perovskite Nanostructures.

Halide perovskites have emerged as a class of promising semiconductor materials owing to their remarkable optoelectronic properties exhibiting in solar cells, light-emitting diodes, semiconductor lasers, etc. Inorganic halide perovskites are attracting increasing attention because of the higher stability toward moisture, light, and heat as compared with their organic-inorganic hybrid counterparts. In particular, inorganic halide perovskite nanomaterials provide controllable morphology, tunable optoelectronic properties, and improved quantum efficiency.

Phase-transition-induced p-n junction in single halide perovskite nanowire.

Semiconductor p-n junctions are fundamental building blocks for modern optical and electronic devices. The p- and n-type regions are typically created by chemical doping process. Here we show that in the new class of halide perovskite semiconductors, the p-n junctions can be readily induced through a localized thermal-driven phase transition.

Effects of Catalyst Processing on the Activity and Stability of Pt-Ni Nanoframe Electrocatalysts.

Pt-based alloys have shown great promise as cathodic catalysts for cost-effective proton-exchange membrane fuel cells. Post-synthesis treatment has been recognized as a critical step to improve the catalytic performance of Pt-based alloys. Here, we present the effects of catalyst processing on the catalytic behavior of Pt-Ni nanoframe electrocatalysts in oxygen reduction reaction.

Excited-state vibrational dynamics toward the polaron in methylammonium lead iodide perovskite.

Hybrid organic-inorganic perovskites have attractive optoelectronic properties including exceptional solar cell performance. The improved properties of perovskites have been attributed to polaronic effects involving stabilization of localized charge character by structural deformations and polarizations. Here we examine the Pb-I structural dynamics leading to polaron formation in methylammonium lead iodide perovskite by transient absorption, time-domain Raman spectroscopy, and density functional theory.

Electrical and Optical Tunability in All-Inorganic Halide Perovskite Alloy Nanowires.

Alloying different semiconductors is a powerful approach to tuning the optical and electronic properties of semiconductor materials. In halide perovskites (ABX), alloys with different anions have been widely studied, and great band gap tunability in the visible range has been achieved. However, perovskite alloys with different cations at the "B" site are less understood due to the synthetic challenges.

Thermochromic halide perovskite solar cells.

Smart photovoltaic windows represent a promising green technology featuring tunable transparency and electrical power generation under external stimuli to control the light transmission and manage the solar energy. Here, we demonstrate a thermochromic solar cell for smart photovoltaic window applications utilizing the structural phase transitions in inorganic halide perovskite caesium lead iodide/bromide. The solar cells undergo thermally-driven, moisture-mediated reversible transitions between a transparent non-perovskite phase (81.

Ultralow thermal conductivity in all-inorganic halide perovskites.

Controlling the flow of thermal energy is crucial to numerous applications ranging from microelectronic devices to energy storage and energy conversion devices. Here, we report ultralow lattice thermal conductivities of solution-synthesized, single-crystalline all-inorganic halide perovskite nanowires composed of CsPbI (0.45 ± 0.

Spatially resolved multicolor CsPbX nanowire heterojunctions via anion exchange.

Halide perovskites are promising semiconductor materials for solution-processed optoelectronic devices. Their strong ionic bonding nature results in highly dynamic crystal lattices, inherently allowing rapid ion exchange at the solid-vapor and solid-liquid interface. Here, we show that the anion-exchange chemistry can be precisely controlled in single-crystalline halide perovskite nanomaterials when combined with nanofabrication techniques.

Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CHNHPbI) Perovskite Photochemistry.

Raman and photoluminescence (PL) spectroscopy are used to investigate dynamic structure-function relationships in methylammonium lead iodide (MAPbI) perovskite. The intensity of the 150 cm methylammonium (MA) librational Raman mode is found to be correlated with PL intensities in microstructures of MAPbI. Because of the strong hydrogen bond between hydrogens in MA and iodine in the PbI perovskite octahedra, the Raman activity of MA is very sensitive to structural distortions of the inorganic framework.

Synthesis of Composition Tunable and Highly Luminescent Cesium Lead Halide Nanowires through Anion-Exchange Reactions.

Here, we demonstrate the successful synthesis of brightly emitting colloidal cesium lead halide (CsPbX3, X = Cl, Br, I) nanowires (NWs) with uniform diameters and tunable compositions. By using highly monodisperse CsPbBr3 NWs as templates, the NW composition can be independently controlled through anion-exchange reactions. CsPbX3 alloy NWs with a wide range of alloy compositions can be achieved with well-preserved morphology and crystal structure.

Lasing in robust cesium lead halide perovskite nanowires.

The rapidly growing field of nanoscale lasers can be advanced through the discovery of new, tunable light sources. The emission wavelength tunability demonstrated in perovskite materials is an attractive property for nanoscale lasers. Whereas organic-inorganic lead halide perovskite materials are known for their instability, cesium lead halides offer a robust alternative without sacrificing emission tunability or ease of synthesis.

Atomically thin two-dimensional organic-inorganic hybrid perovskites.

Organic-inorganic hybrid perovskites, which have proved to be promising semiconductor materials for photovoltaic applications, have been made into atomically thin two-dimensional (2D) sheets. We report the solution-phase growth of single- and few-unit-cell-thick single-crystalline 2D hybrid perovskites of (C4H9NH3)2PbBr4 with well-defined square shape and large size. In contrast to other 2D materials, the hybrid perovskite sheets exhibit an unusual structural relaxation, and this structural change leads to a band gap shift as compared to the bulk crystal.

Growth and Anion Exchange Conversion of CH3NH3PbX3 Nanorod Arrays for Light-Emitting Diodes.

The nanowire and nanorod morphology offers great advantages for application in a range of optoelectronic devices, but these high-quality nanorod arrays are typically based on high temperature growth techniques. Here, we demonstrate the successful room temperature growth of a hybrid perovskite (CH3NH3PbBr3) nanorod array, and we also introduce a new low temperature anion exchange technique to convert the CH3NH3PbBr3 nanorod array into a CH3NH3PbI3 nanorod array while preserving morphology. We demonstrate the application of both these hybrid perovskite nanorod arrays for LEDs.