Minliang Lai

Atomically thin two-dimensional organic-inorganic hybrid perovskites

Flat perovskite crystals Bulk crystals and thick films of inorganic-organic perovskite materials such as CH3NH3PbI3 have shown promise as active material for solar cells. Dou et al. show that thin films—a single unit cell or a few unit cells thick—of a related composition, (C4H9NH3)2PbBr4, form squares with edges several micrometers long. These materials exhibit strong and tunable blue photoluminescence. Science, this issue p. 1518 Several inorganic-organic perovskite materials grown as atomically thin crystals exhibit strong photoluminescence. 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. The high-quality 2D crystals exhibit efficient photoluminescence, and color tuning could be achieved by changing sheet thickness as well as composition via the synthesis of related materials.

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. This work highlights the potential utility of postsynthetic interconversion of hybrid perovskites for nanostructured optoelectronic devices such as LEDs, which enables new strategies for the application of hybrid perovskites.

Lasing in robust cesium lead halide perovskite nanowires

Significance Nanowire lasers are miniaturized light sources with great potential for integration into optoelectronic circuits. Many of the current nanowire lasers either require extreme conditions for synthesis or suffer from poor operational stability. We synthesize nanowires of a promising set of compositions, the cesium lead halides, and accomplish this under near-ambient conditions. These nanowires act as efficient laser cavities and are capable of lasing with relatively low excitation thresholds. They also demonstrate unprecedented stability for a perovskite-based nanowire laser and offer a new nanoscale platform for future study. 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. Here, we report the low-temperature, solution-phase growth of cesium lead halide nanowires exhibiting low-threshold lasing and high stability. The as-grown nanowires are single crystalline with well-formed facets, and act as high-quality laser cavities. The nanowires display excellent stability while stored and handled under ambient conditions over the course of weeks. Upon optical excitation, Fabry–Pérot lasing occurs in CsPbBr3 nanowires with an onset of 5 μJ cm−2 with the nanowire cavity displaying a maximum quality factor of 1,009 ± 5. Lasing under constant, pulsed excitation can be maintained for over 1 h, the equivalent of 109 excitation cycles, and lasing persists upon exposure to ambient atmosphere. Wavelength tunability in the green and blue regions of the spectrum in conjunction with excellent stability makes these nanowire lasers attractive for device fabrication.

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. The NWs are highly luminescent with photoluminescence quantum yields (PLQY) ranging from 20% to 80%. The bright photoluminescence can be tuned over nearly the entire visible spectrum. The high PLQYs together with charge transport measurements exemplify the efficient alloying of the anionic sublattice in a one-dimensional CsPbX3 system. The wires increased functionality in the form of fast photoresponse rates and the low defect density suggest CsPbX3 NWs as prospective materials for optoelectronic applications.

Structural, optical, and electrical properties of phase-controlled cesium lead iodide nanowires

Cesium lead iodide (CsPbI3), in its black perovskite phase, has a suitable bandgap and high quantum efficiency for photovoltaic applications. However, CsPbI3 tends to crystalize into a yellow non-perovskite phase, which has poor optoelectronic properties, at room temperature. Therefore, controlling the phase transition in CsPbI3 is critical for practical application of this material. Here we report a systematic study of the phase transition of one-dimensional CsPbI3 nanowires and their corresponding structural, optical, and electrical properties. We show the formation of perovskite black phase CsPbI3 nanowires from the non-perovskite yellow phase through rapid thermal quenching. Post-transformed black phase CsPbI3 nanowires exhibit increased photoluminescence emission intensity with a shrinking of the bandgap from 2.78 to 1.76 eV. The perovskite nanowires were photoconductive and showed a fast photoresponse and excellent stability at room temperature. These promising optical and electrical properties make the perovskite CsPbI3 nanowires attractive for a variety of nanoscale optoelectronic devices.

Spatially resolved multicolor CsPbX3 nanowire heterojunctions via anion exchange

Significance Semiconductor heterojunction is a key building block in modern electronics and optoelectronics. The accurate control over the composition, band gap, energy level (band bending), and doping level is the foundation of ideal functional heterojunctions. We demonstrate highly spatially resolved heterojunctions in a type of semiconductor, halide perovskites, which show great potential in photovoltaic and solid-state lighting applications. We accomplish this through the combination of facile anion-exchange chemistry with nanofabrication techniques. The halide perovskite nanowire heterojunction provides an ideal platform for fundamental studies and technological applications. For example, multicolor lasers or LEDs could be made using such localized heterojunctions; quantitative interdiffusion and ion migration dynamics could be examined at elevated temperatures, etc. 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. We demonstrate spatially resolved multicolor CsPbX3 (X = Cl, Br, I, or alloy of two halides) nanowire heterojunctions with a pixel size down to 500 nm with the photoluminescence tunable over the entire visible spectrum. In addition, the heterojunctions show distinct electronic states across the interface, as revealed by Kelvin probe force microscopy. These perovskite heterojunctions represent key building blocks for high-resolution multicolor displays beyond current state-of-the-art technology as well as high-density diode/transistor arrays.

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 (81.7% visible transparency) with low power output and a deeply coloured perovskite phase (35.4% visible transparency) with high power output. The inorganic perovskites exhibit tunable colours and transparencies, a peak device efficiency above 7%, and a phase transition temperature as low as 105 °C. We demonstrate excellent device stability over repeated phase transition cycles without colour fade or performance degradation. The photovoltaic windows showing both photoactivity and thermochromic features represent key stepping-stones for integration with buildings, automobiles, information displays, and potentially many other technologies.CsPbI3–xBrx solar cells, which undergo temperature- and moisture-driven reversible transitions between a non-perovskite transparent phase and a perovskite light-absorbing phase, are used as thermochromic photovoltaic devices integrated in windows.

Ultralow thermal conductivity in all-inorganic halide perovskites

Significance Discovery of materials with low thermal conductivity in simple, fully dense, and single-crystalline solids has proven extremely challenging. This paper reports the discovery of ultralow thermal conductivity (∼0.4 W⋅m−1⋅K−1) in single-crystalline, all-inorganic halide perovskite nanowires, which is comparable to their amorphous limit value. We attribute ultralow thermal conductivity to a cluster rattling mechanism, based on strong phonon–phonon scattering via the coexistence of collective motions involving various atom groups. These results call attention to the vital thermal transport processes and thermal management strategies for applications with all-inorganic halide perovskites. Further, CsSnI3 shows a rare combination of ultralow thermal conductivity and high electrical conductivity, so it can be a promising material for unique applications as an electrically conductive thermal insulator. 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 CsPbI3 (0.45 ± 0.05 W·m−1·K−1), CsPbBr3 (0.42 ± 0.04 W·m−1·K−1), and CsSnI3 (0.38 ± 0.04 W·m−1·K−1). We attribute this ultralow thermal conductivity to the cluster rattling mechanism, wherein strong optical–acoustic phonon scatterings are driven by a mixture of 0D/1D/2D collective motions. Remarkably, CsSnI3 possesses a rare combination of ultralow thermal conductivity, high electrical conductivity (282 S·cm−1), and high hole mobility (394 cm2·V−1·s−1). The unique thermal transport properties in all-inorganic halide perovskites hold promise for diverse applications such as phononic and thermoelectric devices. Furthermore, the insights obtained from this work suggest an opportunity to discover low thermal conductivity materials among unexplored inorganic crystals beyond caged and layered structures.

Critical Role of Methylammonium Librational Motion in Methylammonium Lead Iodide (CH3NH3PbI3) Perovskite Photochemistry

Raman and photoluminescence (PL) spectroscopy are used to investigate dynamic structure-function relationships in methylammonium lead iodide (MAPbI3) perovskite. The intensity of the 150 cm-1 methylammonium (MA) librational Raman mode is found to be correlated with PL intensities in microstructures of MAPbI3. Because of the strong hydrogen bond between hydrogens in MA and iodine in the PbI6 perovskite octahedra, the Raman activity of MA is very sensitive to structural distortions of the inorganic framework. The structural distortions directly influence PL intensities, which in turn have been correlated with microstructure quality. Our measurements, supported with first-principles calculations, indicate how excited-state MA librational displacements mechanistically control PL efficiency and lifetime in MAPbI3-material parameters that are likely important for efficient photovoltaic devices.

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. Methylammonium lead iodide perovskite exhibits excited-state coherent nuclear wave packets oscillating at ~20, ~43, and ~75 cm−1 which involve skeletal bending, in-plane bending, and c-axis stretching of the I–Pb–I bonds, respectively. The amplitudes of these wave packet motions report on the magnitude of the excited-state structural changes, in particular, the formation of a bent and elongated octahedral PbI64− geometry. We have predicted the excited-state geometry and structural changes between the neutral and polaron states using a normal-mode projection method, which supports and rationalizes the experimental results. This study reveals the polaron formation via nuclear dynamics that may be important for efficient charge separation.Elucidating electron-phonon coupling in hybrid organic-inorganic perovskites may help us to understand the high photovoltaic efficiency. Here, the authors observe low-frequency Raman modes and related nuclear displacements of the Pb–I framework, indicating how these vibrational motions lead to polaron formation in perovskites.