Halide Perovskite Nanowires Research Articles

Controlled Synthesis and Photonics Applications of Metal Halide Perovskite Nanowires

AbstractMetal halide perovskite nanowires (NW)s have recently demonstrated potential applications in integrated photonics devices such as lasers and photodetectors due to their unique physical and chemical characteristics. Here, the rapid progress in the synthesis methods and photonics applications of organic–inorganic hybrid and all‐inorganic halide perovskite NWs are reviewed systematically. The controlled synthesis methods are mainly classified into solution‐phase synthesis, vapor‐phase synthesis, and other synthesis methods. The photonics applications of the halide perovskite NWs, including lasers, photodetectors, solar cells, and other applications, are also introduced and discussed. Finally, the summary and perspectives for halide perovskite NWs are provided.

Self-powered CsPbBr3 nanowire photodetector with a vertical structure

Single crystal halide perovskite nanowires (NWs) have attracted much attention for use in high-performance photodetectors (PDs) due to their high photoluminescence quantum yields, large carrier mobilities, and long carrier diffusion lengths. So far, most high-performance NW PDs are fabricated based on individual or aligned NWs which require complicated preparation processing. Furthermore, it is challenging for these NW PDs to possess self-powered operation characteristics. Here, we report self-powered perovskite NW PDs with a vertical p-i-n structure in which the CsPbBr3 NWs are grown by a combination of solution-phase and halide exchange processes. Before depositing the hole selective layer, poly(methyl methacrylate) is coated on perovskite NW film to fill the internal voids, which passivates surfaces of perovskite NWs and reduces the dark current. Our optimized CsPbBr3 NW PDs show dark current density as low as 4.0 nA cm−2 and photocurrent density as high as 22.9 mA cm−2 under a 473 nm laser illumination with intensity of 641 mW cm−2, leading to a high linear dynamic range of 135 dB. In addition, our perovskite NW PDs display highly self-powered performance with ultrohigh on/off ratios of above 106, responsivity of up to 0.3 A W−1 and detectivity of up to 1 × 1013 Jones at 0 V.

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. We demonstrate this p-n junction formation in a single-crystalline halide perovskite CsSnI3 nanowire (NW). This material undergoes a phase transition from a double-chain yellow (Y) phase to an orthorhombic black (B) phase. The formation energies of the cation and anion vacancies in these two phases are significantly different, which leads to n- and p- type electrical characteristics for Y and B phases, respectively. Interface formation between these two phases and directional interface propagation within a single NW are directly observed under cathodoluminescence (CL) microscopy. Current rectification is demonstrated for the p-n junction formed with this localized thermal-driven phase transition.

Inorganic Ions Assisted the Anisotropic Growth of CsPbCl3 Nanowires with Surface Passivation Effect.

All-inorganic halide perovskite nanowires (NWs) exhibit improved thermal and hydrolysis stability and could thus play a vital role in nanoscale optoelectronics. Among them, blue-light-based devices are extremely limited because of the lack of a facile method to obtain high-purity CsPbCl3 NWs. Herein, we report a direct and facile method for the synthesis of CsPbCl3 NWs assisted by inorganic ions that served both as a morphology controlling agent for the anisotropic growth of nanomaterials and a surface passivation species modulating the surface of nanomaterials. This new approach allows us to obtain high-purity and size-uniform NWs as long as 500 nm in length and 20 nm in diameter with high reproducibility. X-ray photoelectron spectroscopy and ultrafast spectroscopic measurements confirmed that a reduced band gap caused by the surface species of NWs relative to nanocubes (NCs) was achieved at the photon energy of 160 eV because of the hybrid surface passivation contributed by adsorbed inorganic ions. The resulting NWs demonstrate significantly enhanced photoelectrochemical performances, 3.5-fold increase in the photocurrent generation, and notably improved stability compared to their NC counterparts. Our results suggest that the newly designed NWs could be a promising material for the development of nanoscale optoelectronic devices.

High-performance pseudo-halide perovskite nanowire networks for stable and fast-response photodetector

Perovskite-based photodetectors show a great promise thanks to the material's excellent photogeneration and broadband device operation. Amongst the fundamental limitations of halide perovskites, humidity-induced degradation arises as the main impediment towards viable commercial-grade perovskite-based technologies. Here, we report a stable, reproducible and reliable pseudo halide perovskite nanowire network-based photodetector with superior performances. The perovskite nanowire network is deposited using a two-step spin-coating process atop patterned substrates under ambient conditions with relative humidity (RH%), higher than 50%. Because of the particular 1D perovskite nanowire morphology, our devices require no charge collectors, which reduces fabrication steps and costs. Most importantly, we demonstrate that incorporation of lead thiocyanate (Pb(SCN)2) directly in the precursor solution promotes the synthesis of stable hybrid perovskite nanowire networks in ambient conditions. These devices exhibit response time as fast as 50 µs and responsivities up-to ~0.23 A W−1 at 2 V bias. Also, the optimum photodetector exhibited high specific detectivity of 7.1 × 1011 cm Hz1/2 W−1. This novel and yet simple device architecture brings fabrication challenges to a minimum by allowing synthesis of perovskite nanowires under high humidity conditions.

High-Quality In-Plane Aligned CsPbX3 Perovskite Nanowire Lasers with Composition-Dependent Strong Exciton-Photon Coupling.

Cesium lead halide perovskite nanowires have emerged as promising low-dimensional semiconductor structures for integrated photonic applications. Understanding light-matter interactions in a nanowire cavity is of both fundamental and practical interest in designing low-power-consumption nanoscale light sources. In this work, high-quality in-plane aligned halide perovskite CsPbX3 (X = Cl, Br, I) nanowires are synthesized by a vapor growth method on an annealed M-plane sapphire substrate. Large-area nanowire laser arrays have been achieved based on the as-grown aligned CsPbX3 nanowires at room temperature with quite low pumping thresholds, very high quality factors, and a high degree of linear polarization. More importantly, it is found that exciton-polaritons are formed in the nanowires under the excitation of a pulsed laser, indicating a strong exciton-photon coupling in the optical microcavities made of cesium lead halide perovskites. The coupling strength in these CsPbX3 nanowires is dependent on the atomic composition, where the obtained room-temperature Rabi splitting energy is ∼210 ± 13, 146 ± 9, and 103 ± 5 meV for the CsPbCl3, CsPbBr3, and CsPbI3 nanowires, respectively. This work provides fundamental insights for the practical applications of all-inorganic perovskite CsPbX3 nanowires in designing light-emitting devices and integrated nanophotonic systems.

Composition-Graded Cesium Lead Halide Perovskite Nanowires with Tunable Dual-Color Lasing Performance.

Cesium lead halide (CsPbX3 ) perovskite has emerged as a promising low-threshold multicolor laser material; however, realizing wavelength-tunable lasing output from a single CsPbX3 nanostructure is still constrained by integrating different composition. Here, the direct synthesis of composition-graded CsPbBrx I3-x nanowires (NWs) is reported through vapor-phase epitaxial growth on mica. The graded composition along the NW, with an increased Br/I from the center to the ends, comes from desynchronized deposition of cesium lead halides and temperature-controlled anion-exchange reaction. The graded composition results in varied bandgaps along the NW, which induce a blueshifted emission from the center to the ends. As an efficient gain media, the nanowire exerts position-dependent lasing performance, with a different color at the ends and center respectively above the threshold. Meanwhile, dual-color lasing with a wavelength separation of 35 nm is activated simultaneously at a site with an intermediate composition. This position-dependent dual-color lasing from a single nanowire makes these metal halide perovskites promising for applications in nanoscale optical devices.

Cation Dynamics Governed Thermal Properties of Lead Halide Perovskite Nanowires.

Metal halide perovskite (MHP) nanowires such as hybrid organic-inorganic CH3NH3PbX3 (X = Cl, Br, I) have drawn significant attention as promising building blocks for high-performance solar cells, light-emitting devices, and semiconductor lasers. However, the physics of thermal transport in MHP nanowires is still elusive even though it is highly relevant to the device thermal stability and optoelectronic performance. Through combined experimental measurements and theoretical analyses, here we disclose the underlying mechanisms governing thermal transport in three different kinds of lead halide perovskite nanowires (CH3NH3PbI3, CH3NH3PbBr3 and CsPbBr3). It is shown that the thermal conductivity of CH3NH3PbBr3 nanowires is significantly suppressed as compared to that of CsPbBr3 nanowires, which is attributed to the cation dynamic disorder. Furthermore, we observed different temperature-dependent thermal conductivities of hybrid perovskites CH3NH3PbBr3 and CH3NH3PbI3, which can be attributed to accelerated cation dynamics in CH3NH3PbBr3 at low temperature and the combined effects of lower phonon group velocity and higher Umklapp scattering rate in CH3NH3PbI3 at high temperature. These data and understanding should shed light on the design of high-performance MHP based thermal and optoelectronic devices.

Shape-, Size-, and Composition-Controlled Thallium Lead Halide Perovskite Nanowires and Nanocrystals with Tunable Band Gaps

Perovskite nanocrystals have shown themselves to be useful for both absorption- and emission-based applications, including solar cells, photodetectors, and LEDs. Here we present a new class of size-, composition-, and shape-tunable nanocrystals made from Tl3PbX5 (X= Cl, Br, I). These can be synthesized via colloidal methods to produce faceted spheroidal nanocrystals, and perovskite TlPbI3 nanowires. Crystal structures for the orthorhombic and tetragonal phase materials, for both pure and mixed halide species, are compared to the literature and also calculated from first-principles in VASP. We show the ability to tune the band gap by halide substitution to create materials that can absorb strongly between 250 and 450 nm. In addition, we show evidence of the confinement effect in pure halide Tl3PbBr5 nanocrystals suggesting size-tuning is possible as well. By tuning the band gap we can create materials with specific absorption spectra suitable for photodetection that display conduction and photoresponse pro...

Mechanical response of CH3NH3PbI3 nanowires

We report a systematic study of the mechanical response of methylammonium lead triiodide CH3NH3PbI3 nanowires by employing bending measurements using atomic force microscope on suspended wires over photo-lithographically patterned channels. Force-deflection curves measured at room temperature give a Young's modulus between 2 and 14 GPa. This broad range of values is attributed to the variations in the microcrystalline texture of halide perovskite nanowires. The mechanical response of a highly crystalline nanowire is linear with force and has a brittle character. The braking modulus of 48 ± 20 MPa corresponds to 100 μm of radius of curvature of the nanowires, rendering them much better structures for flexible devices than spin coated films. The measured moduli decrease rapidly if the NW is exposed to water vapor.

Influence of Charge Transport Layers on Open-Circuit Voltage and Hysteresis in Perovskite Solar Cells

Summary Perovskite materials have experienced an impressive improvement in photovoltaic performance due to their unique combination of optoelectronic properties. Their remarkable progression, facilitated by the use of different device architectures, compositional engineering, and processing methodologies, contrasts with the lack of understanding of the materials properties and interface phenomena. Here we directly target the interplay between the charge-transporting layers (CTLs) and open-circuit potential ( V OC ) in the operation mechanism of the state-of-the-art CH 3 NH 3 PbI 3 solar cells. Our results suggest that the V OC is controlled by the splitting of quasi-Fermi levels and recombination inside the perovskite, rather than being governed by any internal electric field established by the difference in the CTL work functions. In addition, we provide novel insights into the hysteretic origin in perovskite solar cells, identifying the nature of the contacts as a critical factor in defining the charge accumulation at its interface, leading to either ionic, electronic, or mixed ionic-electronic accumulation.

Solvothermal synthesis of cesium lead halide perovskite nanowires with ultra-high aspect ratios for high-performance photodetectors.

One-dimensional (1D) inorganic perovskite nanowires (NWs) have attracted promising attention for application in the fields of photodetection, lasers and lighting due to their outstanding optoelectronic properties. However the direct synthesis of highly pure all-inorganic perovskite NWs with well-defined morphologies and compositions still remains challenging. Here we report the controllable synthesis of brightly emitting cesium lead halide CsPbX3 (X = Cl, Br) NWs and their assembly into high-performance photodetector nanodevices. High quality CsPbX3 NWs have been directly synthesized via a solvothermal method without using post-synthetic anion-exchange reactions. The NWs are single-crystalline, with uniform diameters of ∼10 nm and lengths of up to tens of microns, showing ultra-high aspect ratios. Both CsPbCl3 and CsPbBr3 NWs show excellent photoluminescence (PL) characteristics with narrow emission spectra and high PL quantum yields (PLQYs). The photodetectors constructed on the CsPbX3 NWs and interdigital electrodes (with interdigitation widths up to 100 μm) exhibit promising photoelectric properties, achieving high switching ratios (5.8 × 103 for CsPbCl3 NW devices and 1.1 × 103 for CsPbBr3 NW devices) and fast response time. The present solvothermal approach is controllable, convenient, and is easily realized for quantifiable preparation, and can further promote the application of the all-inorganic perovskite NWs in the optoelectronic field.

Surface recombination velocity of methylammonium lead bromide nanowires in anodic aluminium oxide templates

Here we present successful surface passivation of halide perovskite nanowires with anodic aluminum oxide templates.

Continuous‐Wave Lasing in Cesium Lead Bromide Perovskite Nanowires

AbstractLead halide perovskite nanowires (NWs) have been demonstrated in pulsed lasing with high quantum yields, low thresholds, and broad tunability. However, continuous‐wave (CW) lasing, necessary for many optoelectronic applications, has not been achieved to date. This is thought to be due to many‐body screening, which reduces the excitonic resonance enhancement of the oscillator strength at high excitation densities necessary for population inversion. Here CW lasing in CsPbBr3 perovskite NWs is reported. Analysis of the cavity modes and their temperature dependence reveals that both CW and pulsed lasing originate from polariton modes near the bottleneck region on the lower polariton branch, with a vacuum Rabi splitting of 0.20 ± 0.03 eV. These findings suggest that lead halide perovskite NWs may serve as low‐power CW coherent light sources and as model systems for polaritonics in the strong‐coupling regime.

Surface-Guided CsPbBr3 Perovskite Nanowires on Flat and Faceted Sapphire with Size-Dependent Photoluminescence and Fast Photoconductive Response.

All-inorganic lead halide perovskite nanowires have been the focus of increasing interest since they exhibit improved stability compared to their hybrid organic-inorganic counterparts, while retaining their interesting optical and optoelectronic properties. Arrays of surface-guided nanowires with controlled orientations and morphology are promising as building blocks for various applications and for systematic research. We report the horizontal and aligned growth of CsPbBr3 nanowires with a uniform crystallographic orientation on flat and faceted sapphire surfaces to form arrays with 6-fold and 2-fold symmetries, respectively, along specific directions of the sapphire substrate. We observed waveguiding behavior and diameter-dependent photoluminescence emission well beyond the quantum confinement regime. The arrays were easily integrated into multiple devices, displaying p-type behavior and photoconductivity. Photodetectors based on those nanowires exhibit the fastest rise and decay times for any CsPbBr3-based photodetectors reported so far. One-dimensional arrays of halide perovskite nanowires are a promising platform for investigating the intriguing properties and potential applications of these unique materials.

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 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.

Solution-phase growth of organolead halide perovskite nanowires and nanoplates assisted by long-chain alkylammonium and solvent polarity

The solution-phase synthesis of organolead halide perovskite nanowires, nanoplates, and nanoparticles at room temperature is controlled by varying the amount of polar solvent dimethylformamide (DMF) in the presence of long-chain hexadecylammonium (HA). The products exhibit tunable bright emission in the entire visible region (408–733nm).

Controlled Synthesis of Composition Tunable Formamidinium Cesium Double Cation Lead Halide Perovskite Nanowires and Nanosheets with Improved Stability

Lead halide perovskites with well-defined morphology have attracted attention for their unique properties as a promising new class of semiconductor materials in photovoltaics and optoelectronics. However, controlling morphologies and compositions of perovskite nanostructures with improved stability, especially for double cation lead halide perovskite, still remains a challenge. Here, we demonstrate a colloidal synthetic approach for direct synthesis of stable single-crystal formamidinium (FA) cesium double cation lead halide FA0.33Cs0.67PbBr3–xIx (0 ≤ x ≤ 3) perovskite nanostructures with controllable morphology over a wide range of halide compositions, without using a previous anion-exchange process. The presence of FA alloyed in the A site for the pure cesium lead halide perovskite structure can stabilize the nanocrystals while delivering a better balance between structure and composition. On the basis of the FA0.33Cs0.67PbBr3–xIx alloy perovskite system, we achieved nanowires and nanosheets with high y...

Ultrahigh-Responsivity Photodetectors from Perovskite Nanowire Arrays for Sequentially Tunable Spectral Measurement.

Compared with polycrystalline films, single-crystalline methylammonium lead halide (MAPbX3, X = halogen) perovskite nanowires (NWs) with well-defined structure possess superior optoelectronic properties for optoelectronic applications. However, most of the prepared perovskite NWs exhibit properties below expectations due to poor crystalline quality and rough surfaces. It also remains a challenge to achieve aligned growth of single-crystalline perovskite NWs for integrated device applications. Here, we report a facile fluid-guided antisolvent vapor-assisted crystallization (FGAVC) method for large-scale fabrication of high-quality single-crystalline MAPb(I1-xBrx)3 (x = 0, 0.1, 0.2, 0.3, 0.4) NW arrays. The resultant perovskite NWs showed smooth surfaces due to slow crystallization process and moisture-isolated growth environment. Significantly, photodetectors made from the NW arrays exhibited outstanding performance in respect of ultrahigh responsivity of 12 500 A W-1, broad linear dynamic rang (LDR) of 150 dB, and robust stability. The responsivity represents the best value ever reported for perovskite-based photodetectors. Moreover, the spectral response of the MAPb(I1-xBrx)3 NW arrays could be sequentially tuned by varying the content of x = 0-0.4. On the basis of this feature, the NW arrays were monolithically integrated to form a unique system for directly measuring light wavelength. Our work would open a new avenue for the fabrication of high-performance, integrated optoelectronic devices from the perovskite NW arrays.

A non-catalytic vapor growth regime for organohalide perovskite nanowires using anodic aluminum oxide templates.

In this work, a novel and facile synthesis process to fabricate single crystalline organometal halide perovskite nanowires has been successfully developed. Nanowires were grown in a high density ordered array from metal nanoclusters inside anodic aluminum oxide templates using a non-catalytic chemical vapor deposition method. Specifically, perovskite NWs were grown as a result of the reaction between methylammonium iodide (MAI) and the Pb/Sn (Pb or Sn) metal in anodic aluminum oxide templates under optimal conditions. The characterization results show that there is a reaction zone at the interface between the perovskite material and metal, at the bottom of the anodic aluminum oxide nanochannels. In order to sustain perovskite NW growth, MAI molecules have to diffuse downward through the perovskite NWs to reach the reaction zone. In fact, the reaction is facilitated by the formation of an intermediate product of the metal iodide compound. This suggests that the Pb/Sn metal is converted to PbI2/SnI2 first and then perovskite NWs are formed as a result of the reaction between MAI and PbI2/SnI2 through a vapor-solid-solid process. The optical characterization results demonstrate that the as-synthesized NWs with an ultra-high nanostructure density can serve as ideal candidates for optoelectronic devices, such as solar cells, light-emitting didoes, photodetectors, etc. And the reported growth approach here is highly versatile combining the merits of excellent controllability, cost-effectiveness and tunability on material composition and physical properties.