All-inorganic halide-perovskite polymer-fiber-photodetector for high-speed optical wireless communication.

The use of optical carrier frequencies will enable seamless data connection for future terrestrial and underwater internet uses and will resolve the technological gap faced by other communication modalities. However, several issues must be solved to propel this technological shift, which include the limitations in designing optical receivers with large detection areas, omnidirectionality, and high modulation bandwidth, mimicking antennas operating in the radio-frequency spectrum. To address this technological gap, herein, we demonstrate halide-perovskite-polymer-based scintillating fibers as a near-omnidirectional detection platform for several tens-to-hundreds of Mbit/s optical communication in both free space and underwater links. The incorporation of all-inorganic CsPbBr3 nanocrystals by engineering the nanocrystal concentration in an ultraviolet-curable polymer matrix ensures a high photoluminescence quantum yield, Mega-Hertz modulation bandwidth and Mbit/s data rate suitable to be used as a high-speed fibers-based receiver. The resultant perovskite polymer-based scintillating fibers offer flexibility in terms of shape and near-omnidirectional detection features. Such fiber properties also introduce a scalable detection area which can resolve the resistance-capacitance and angle-of-acceptance limits in planar-based detectors, which conventionally impose a trade-off between the modulation bandwidth, detection area, and angle of view. A high bit rate of 23 Mbit/s and 152.5 Mbit/s was achieved using an intensity-modulated laser for non-return-to-zero on-off-keying (NRZ-OOK) modulation scheme in free-space and quadrature amplitude modulation orthogonal frequency-division multiplexing (QAM-OFDM) modulation scheme in an underwater environment, respectively. Our near-omnidirectional optical-based antenna based on perovskite-polymer-based scintillating fibers sheds light on the immense possibilities of incorporating functional nanomaterials for empowering light-based terrestrial- and underwater-internet systems.

Low-Temperature Molten Salts Synthesis: CsPbBr3 Nanocrystals with High Photoluminescence Emission Buried in Mesoporous SiO2.

Using mesoporous SiO2 to encapsulate CsPbBr3 nanocrystals is one of the best strategies to exploit such materials in devices. However, the CsPbBr3/SiO2 composites produced so far do not exhibit strong photoluminescence emission and, simultaneously, high stability against heat and water. We demonstrate a molten-salts-based approach delivering CsPbBr3/mesoporous-SiO2 composites with high PLQY (89 ± 10%) and high stability against heat, water, and aqua regia. The molten salts enable the formation of perovskite nanocrystals and other inorganic salts (KNO3-NaNO3-KBr) inside silica and the sealing of SiO2 pores at temperatures as low as 350 °C, representing an important technological advancement (analogous sealing was observed only above 700 °C in previous reports). Our CsPbBr3/mesoporous-SiO2 composites are attractive for different applications: as a proof-of-concept, we prepared a white-light emitting diode exhibiting a correlated color temperature of 7692K. Our composites are also stable after immersion in saline water at high temperatures (a typical underground environment of oil wells), therefore holding promise as oil tracers.

Engineering Band-Type Alignment in CsPbBr3 Perovskite-Based Artificial Multiple Quantum Wells.

Semiconductor heterostructures of multiple quantum wells (MQWs) have major applications in optoelectronics. However, for halide perovskites-the leading class of emerging semiconductors-building a variety of bandgap alignments (i.e., band-types) in MQWs is not yet realized owing to the limitations of the current set of used barrier materials. Here, artificial perovskite-based MQWs using 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole), tris-(8-hydroxyquinoline)aluminum, and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline as quantum barrier materials are introduced. The structures of three different five-stacked perovskite-based MQWs each exhibiting a different band offset with CsPbBr3 in the conduction and valence bands, resulting in a variety of MQW band alignments, i.e., type-I or type-II structures, are shown. Transient absorption spectroscopy reveals the disparity in charge carrier dynamics between type-I and type-II MQWs. Photodiodes of each type of perovskite artificial MQWs show entirely different carrier behaviors and photoresponse characteristics. Compared with bulk perovskite devices, type-II MQW photodiodes demonstrate a more than tenfold increase in the rectification ratio. The findings open new opportunities for producing halide-perovskite-based quantum devices by bandgap engineering using simple quantum barrier considerations.

Delayed Photoluminescence and Modified Blinking Statistics in Alumina-Encapsulated Zero-Dimensional Inorganic Perovskite Nanocrystals.

We demonstrate enhancement of the photoluminescence (PL) properties of individual zero-dimensional (0D) Cs4PbBr6 perovskite nanocrystals (PNCs) upon encapsulation by alumina using an appropriately modified atomic layer deposition method. In addition to the increased PL intensity and improved long-term stability of encapsulated PNCs, our single-particle studies reveal substantial changes in the PL blinking statistics and the persistent appearance of the long-lived, "delayed" PL components. The blinking patterns exhibit a modification from the fast switching between fluorescent ON and OFF states found in bare PNCs to a behavior with longer ON states and more isolated OFF states in alumina-encapsulated PNCs. Controlled exposure of 0D nanocrystals to moisture suggests that the observed PL lifetime changes may be related to water-induced "reservoir" states that allow for longer-lived charge storage with subsequent back-feeding into the emissive states. Viable encapsulation of PNCs with metal oxides that can preserve and even enhance their PL properties can be utilized in the fabrication of extended structures on their basis for optoelectronic and photonic applications.

High-speed colour-converting photodetector with all-inorganic CsPbBr3 perovskite nanocrystals for ultraviolet light communication.

Optical wireless communication (OWC) using the ultra-broad spectrum of the visible-to-ultraviolet (UV) wavelength region remains a vital field of research for mitigating the saturated bandwidth of radio-frequency (RF) communication. However, the lack of an efficient UV photodetection methodology hinders the development of UV-based communication. The key technological impediment is related to the low UV-photon absorption in existing silicon photodetectors, which offer low-cost and mature platforms. To address this technology gap, we report a hybrid Si-based photodetection scheme by incorporating CsPbBr3 perovskite nanocrystals (NCs) with a high photoluminescence quantum yield (PLQY) and a fast photoluminescence (PL) decay time as a UV-to-visible colour-converting layer for high-speed solar-blind UV communication. The facile formation of drop-cast CsPbBr3 perovskite NCs leads to a high PLQY of up to ~73% and strong absorption in the UV region. With the addition of the NC layer, a nearly threefold improvement in the responsivity and an increase of ~25% in the external quantum efficiency (EQE) of the solar-blind region compared to a commercial silicon-based photodetector were observed. Moreover, time-resolved photoluminescence measurements demonstrated a decay time of 4.5 ns under a 372-nm UV excitation source, thus elucidating the potential of this layer as a fast colour-converting layer. A high data rate of up to 34 Mbps in solar-blind communication was achieved using the hybrid CsPbBr3-silicon photodetection scheme in conjunction with a 278-nm UVC light-emitting diode (LED). These findings demonstrate the feasibility of an integrated high-speed photoreceiver design of a composition-tuneable perovskite-based phosphor and a low-cost silicon-based photodetector for UV communication.

Halogen Vacancies Enable Ligand-Assisted Self-Assembly of Perovskite Quantum Dots into Nanowires.

Interest has been growing in defects of halide perovskites in view of their intimate connection with key material optoelectronic properties. In perovskite quantum dots (PQDs), the influence of defects is even more apparent than in their bulk counterparts. By combining experiment and theory, we report herein a halide-vacancy-driven, ligand-directed self-assembly process of CsPbBr3 PQDs. With the assistance of oleic acid and didodecyldimethylammonium sulfide, surface-Br-vacancy-rich CsPbBr3 PQDs self-assemble into nanowires (NWs) that are 20-60 nm in width and several millimeters in length. The NWs exhibit a sharp photoluminescence profile (≈18 nm full-width at-half-maximum) that peaks at 525 nm. Our findings provide insight into the defect-correlated dynamics of PQDs and defect-assisted fabrication of perovskite materials and devices.

Perovskite-Based Artificial Multiple Quantum Wells.

Semiconductor quantum well structures have been critical to the development of modern photonics and solid-state optoelectronics. Quantum level tunable structures have introduced new transformative device applications and afforded a myriad of groundbreaking studies of fundamental quantum phenomena. However, noncolloidal, III-V compound quantum well structures are limited to traditional semiconductor materials fabricated by stringent epitaxial growth processes. This report introduces artificial multiple quantum wells (MQWs) built from CsPbBr3 perovskite materials using commonly available thermal evaporator systems. These perovskite-based MQWs are spatially aligned on a large-area substrate with multiple stacking and systematic control over well/barrier thicknesses, resulting in tunable optical properties and a carrier confinement effect. The fabricated CsPbBr3 artificial MQWs can be designed to display a variety of photoluminescence (PL) characteristics, such as a PL peak shift commensurate with the well/barrier thickness, multiwavelength emissions from asymmetric quantum wells, the quantum tunneling effect, and long-lived hot-carrier states. These new artificial MQWs pave the way toward widely available semiconductor heterostructures for light-conversion applications that are not restricted by periodicity or a narrow set of dimensions.

Bidentate Ligand-Passivated CsPbI3 Perovskite Nanocrystals for Stable Near-Unity Photoluminescence Quantum Yield and Efficient Red Light-Emitting Diodes.

Although halide perovskite nanocrystals (NCs) are promising materials for optoelectronic devices, they suffer severely from chemical and phase instabilities. Moreover, the common capping ligands like oleic acid and oleylamine that encapsulate the NCs will form an insulating layer, precluding their utility in optoelectronic devices. To overcome these limitations, we develop a postsynthesis passivation process for CsPbI3 NCs by using a bidentate ligand, namely 2,2'-iminodibenzoic acid. Our passivated NCs exhibit narrow red photoluminescence with exceptional quantum yield (close to unity) and substantially improved stability. The passivated NCs enabled us to realize red light-emitting diodes (LEDs) with 5.02% external quantum efficiency and 748 cd/m2 luminance, surpassing by far LEDs made from the nonpassivated NCs.

Pure crystal orientation and anisotropic charge transport in large-area hybrid perovskite films.

Controlling crystal orientations and macroscopic morphology is vital to develop the electronic properties of hybrid perovskites. Here we show that a large-area, orientationally pure crystalline (OPC) methylammonium lead iodide (MAPbI3) hybrid perovskite film can be fabricated using a thermal-gradient-assisted directional crystallization method that relies on the sharp liquid-to-solid transition of MAPbI3 from ionic liquid solution. We find that the OPC films spontaneously form periodic microarrays that are distinguishable from general polycrystalline perovskite materials in terms of their crystal orientation, film morphology and electronic properties. X-ray diffraction patterns reveal that the film is strongly oriented in the (112) and (200) planes parallel to the substrate. This film is structurally confined by directional crystal growth, inducing intense anisotropy in charge transport. In addition, the low trap-state density (7.9 × 1013 cm-3) leads to strong amplified stimulated emission. This ability to control crystal orientation and morphology could be widely adopted in optoelectronic devices.

Distinct metal-exchange pathways of doped Ag25 nanoclusters.

Atomically precise metal nanoclusters (NCs) containing more than one type of metal atom (i.e., doped or alloyed), due to synergistic effects, open new avenues for engineering the catalytic and optical properties of NCs in a manner that homometal NCs cannot. Unfortunately, it is still a major challenge to controllably introduce multimetallic dopants in NCs, understanding the dopants' positions, mechanism, and synergistic effects. To overcome these challenges, we designed a metal-exchange approach involving NCs as molecular templates and metal ions as the source of the incoming dopant. In particular, two structurally similar monodoped silver-rich NCs, [MAg24(SR)18]2- (M = Pd/Pt and SR: thiolate), were synthesized as templates to study their mechanistic transformation in response to the introduction of gold atoms. The controllable incorporation of Au atoms into the MAg24 framework facilitated the elucidation of distinct doping pathways through high-resolution mass spectrometry, optical spectroscopy and elemental analysis. Interestingly, gold replaced the central Pd atom of [PdAg24(SR)18]2- clusters to produce predominantly bimetallic [AuAg24(SR)18]- clusters along with a minor product of an [Au2Ag23(SR)18]- cluster. In contrast, the central Pt atom remained intact in [PtAg24(SR)18]2- clusters, and gold replaced the non-central Ag atoms to form trimetallic [AuxPtAg24-x(SR)18]2- NCs, where x = 1-2, with a portion of the starting [PtAg24(SR)18]2- NCs remaining. This study reveals some of the unusual metal-exchange pathways of doped NCs and the important role played by the initial metal dopant in directing the position of a second dopant in the final product.

Highly Efficient Perovskite-Quantum-Dot Light-Emitting Diodes by Surface Engineering.

A two-step ligand-exchange strategy is developed, in which the long-carbon- chain ligands on all-inorganic perovskite (CsPbX3 , X = Br, Cl) quantum dots (QDs) are replaced with halide-ion-pair ligands. Green and blue light-emitting diodes made from the halide-ion-pair-capped quantum dots exhibit high external quantum efficiencies compared with the untreated QDs.

Tailoring ruthenium exposure to enhance the performance of fcc platinum@ruthenium core-shell electrocatalysts in the oxygen evolution reaction.

The catalytic properties of noble metal nanocrystals are a function of their size, structure, and surface composition. In particular, achieving high activity without sacrificing stability is essential for designing commercially viable catalysts. A major challenge in designing state-of-the-art Ru-based catalysts for the oxygen evolution reaction (OER), which is a key step in water splitting, is the poor stability and surface tailorability of these catalysts. In this study, we designed rapidly synthesizable size-controlled, morphology-selective, and surface-tailored platinum-ruthenium core-shell (Pt@Ru) and alloy (PtRu) nanocatalysts in a scalable continuous-flow reactor. These core-shell nanoparticles with atomically precise shells were produced in a single synthetic step with carbon monoxide as the reducing agent. By varying the metal precursor concentration, a dendritic or layer-by-layer ruthenium shell can be grown. The synthesized Pt@Ru and PtRu nanoparticles exhibit noticeably higher electrocatalytic activity in the OER compared to that of pure Pt and Ru nanoparticles. Promisingly, Pt@Ru nanocrystals with a ∼2-3 atomic layer Ru cuboctahedral shell surpass conventional Ru nanoparticles in terms of both durability and activity.

Atomically monodisperse nickel nanoclusters as highly active electrocatalysts for water oxidation.

Achieving water splitting at low overpotential with high oxygen evolution efficiency and stability is important for realizing solar to chemical energy conversion devices. Herein we report the synthesis, characterization and electrochemical evaluation of highly active nickel nanoclusters (Ni NCs) for water oxidation at low overpotential. These atomically precise and monodisperse Ni NCs are characterized by using UV-visible absorption spectroscopy, single crystal X-ray diffraction and mass spectrometry. The molecular formulae of these Ni NCs are found to be Ni4(PET)8 and Ni6(PET)12 and are highly active electrocatalysts for oxygen evolution without any pre-conditioning. Ni4(PET)8 are slightly better catalysts than Ni6(PET)12 which initiate oxygen evolution at an amazingly low overpotential of ∼1.51 V (vs. RHE; η≈ 280 mV). The peak oxygen evolution current density (J) of ∼150 mA cm(-2) at 2.0 V (vs. RHE) with a Tafel slope of 38 mV dec(-1) is observed using Ni4(PET)8. These results are comparable to the state-of-the-art RuO2 electrocatalyst, which is highly expensive and rare compared to Ni-based materials. Sustained oxygen generation for several hours with an applied current density of 20 mA cm(-2) demonstrates the long-term stability and activity of these Ni NCs towards electrocatalytic water oxidation. This unique approach provides a facile method to prepare cost-effective, nanoscale and highly efficient electrocatalysts for water oxidation.

Solution-Grown Monocrystalline Hybrid Perovskite Films for Hole-Transporter-Free Solar Cells.

High-quality perovskite monocrystalline films are successfully grown through cavitation-triggered asymmetric crystallization. These films enable a simple cell structure, ITO/CH3 NH3 PbBr3 /Au, with near 100% internal quantum efficiency, promising power conversion efficiencies (PCEs) >5%, and superior stability for prototype cells. Furthermore, the monocrystalline devices using a hole-transporter-free structure yield PCEs ≈6.5%, the highest among other similar-structured CH3 NH3 PbBr3 solar cells to date.

Heterovalent Dopant Incorporation for Bandgap and Type Engineering of Perovskite Crystals.

Controllable doping of semiconductors is a fundamental technological requirement for electronic and optoelectronic devices. As intrinsic semiconductors, hybrid perovskites have so far been a phenomenal success in photovoltaics. The inability to dope these materials heterovalently (or aliovalently) has greatly limited their wider utilizations in electronics. Here we show an efficient in situ chemical route that achieves the controlled incorporation of trivalent cations (Bi(3+), Au(3+), or In(3+)) by exploiting the retrograde solubility behavior of perovskites. We term the new method dopant incorporation in the retrograde regime. We achieve Bi(3+) incorporation that leads to bandgap tuning (∼300 meV), 10(4) fold enhancement in electrical conductivity, and a change in the sign of majority charge carriers from positive to negative. This work demonstrates the successful incorporation of dopants into perovskite crystals while preserving the host lattice structure, opening new avenues to tailor the electronic and optoelectronic properties of this rapidly emerging class of solution-processed semiconductors.

Air-Stable Surface-Passivated Perovskite Quantum Dots for Ultra-Robust, Single- and Two-Photon-Induced Amplified Spontaneous Emission.

We demonstrate ultra-air- and photostable CsPbBr3 quantum dots (QDs) by using an inorganic-organic hybrid ion pair as the capping ligand. This passivation approach to perovskite QDs yields high photoluminescence quantum yield with unprecedented operational stability in ambient conditions (60 ± 5% lab humidity) and high pump fluences, thus overcoming one of the greatest challenges impeding the development of perovskite-based applications. Due to the robustness of passivated perovskite QDs, we were able to induce ultrastable amplified spontaneous emission (ASE) in solution processed QD films not only through one photon but also through two-photon absorption processes. The latter has not been observed before in the family of perovskite materials. More importantly, passivated perovskite QD films showed remarkable photostability under continuous pulsed laser excitation in ambient conditions for at least 34 h (corresponds to 1.2 × 10(8) laser shots), substantially exceeding the stability of other colloidal QD systems in which ASE has been observed.

Neat and complete: thiolate-ligand exchange on a silver molecular nanoparticle.

Atomically precise thiolate-protected noble metal molecular nanoparticles are a promising class of model nanomaterials for catalysis, optoelectronics, and the bottom-up assembly of true molecular crystals. However, these applications have not fully materialized due to a lack of ligand exchange strategies that add functionality, but preserve the properties of these remarkable particles. Here we present a method for the rapid (<30 s) and complete thiolate-for-thiolate exchange of the highly sought after silver molecular nanoparticle [Ag44(SR)30](-4). Only by using this method were we able to preserve the precise nature of the particles and simultaneously replace the native ligands with ligands containing a variety of functional groups. Crucially, as a result of our method we were able to process the particles into smooth thin films, paving the way for their integration into solution-processed devices.