Exciton diffusion exceeding 1 µm: run, exciton, run!

Exciton diffusion lengths reaching the micrometer length scale have long been desired in solution-processed semiconductors but have remained unattainable using conventional materials to date. Now halide perovskite nanocrystal films show unprecedented exciton migration with diffusion lengths approaching 1 µm owing to the efficient combination of radiative and nonradiative energy transfer.

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.

Molecular behavior of zero-dimensional perovskites.

Low-dimensional perovskites offer a rare opportunity to investigate lattice dynamics and charge carrier behavior in bulk quantum-confined solids, in addition to them being the leading materials in optoelectronic applications. In particular, zero-dimensional (0D) inorganic perovskites of the Cs4PbX6 (X = Cl, Br, or I) kind have crystal structures with isolated lead halide octahedra [PbX6]4- surrounded by Cs+ cations, allowing the 0D crystals to exhibit the intrinsic properties of an individual octahedron. Using both experimental and theoretical approaches, we studied the electronic and optical properties of the prototypical 0D perovskite Cs4PbBr6. Our results underline that this 0D perovskite behaves akin to a molecule, demonstrating low electrical conductivity and mobility as well as large polaron binding energy. Density functional theory calculations and transient absorption measurements of Cs4PbBr6 perovskite films reveal the polaron band absorption and strong polaron localization features of the material. A short polaron lifetime of ~2 ps is observed in femtosecond transient absorption experiments, which can be attributed to the fast lattice relaxation of the octahedra and the weak interactions among them.

CsPb2 Br5 Single Crystals: Synthesis and Characterization.

CsPb2 Br5 is a ternary halogen-plumbate material with close characteristics to the well-reported halide perovskites. Owing to its unconventional two-dimensional structure, CsPb2 Br5 is being looked at broadly for potential applications in optoelectronics. CsPb2 Br5 investigations are currently limited to nanostructures and powder forms of the material, which present unclear and conflicting optical properties. In this study, we present the synthesis and characterization of CsPb2 Br5 bulk single crystals, which enabled us to finally clarify the material's optical features. Our CsPb2 Br5 crystal has a two-dimensional structure with Pb2 Br5- layers spaced by Cs+ cations, and exhibits approximately 3.1 eV indirect band gap with no emission in the visible spectrum.

Zero-Dimensional Cs4PbBr6 Perovskite Nanocrystals.

Perovskite nanocrystals (NCs) have become leading candidates for solution-processed optoelectronics applications. While substantial work has been published on 3-D perovskite phases, the NC form of the zero-dimensional (0-D) phase of this promising class of materials remains elusive. Here we report the synthesis of a new class of colloidal semiconductor NCs based on Cs4PbBr6, the 0-D perovskite, enabled through the design of a novel low-temperature reverse microemulsion method with 85% reaction yield. These 0-D perovskite NCs exhibit high photoluminescence quantum yield (PLQY) in the colloidal form (PLQY: 65%), and, more importantly, in the form of thin film (PLQY: 54%). Notably, the latter is among the highest values reported so far for perovskite NCs in the solid form. Our work brings the 0-D phase of perovskite into the realm of colloidal NCs with appealingly high PLQY in the film form, which paves the way for their practical application in real devices.

Survival and prognostic factors in patients with brain metastasis: Single center experience.

PURPOSE: The purpose of this study was to evaluate the clinical status, prognostic factors and treatment modalities affecting survival in patients with brain metastasis. We aimed to evaluate the whole brain radiation therapy (WBRT) outcomes of patients with brain metastasis in our center. METHODS: Clinical data of 315 patients referred to our center between 2004 and 2014 with metastatic brain cancers were collected and analysed for possible relationships between survival time, age, gender, Karnofsky performance status (KPS), recursive partitioning analysis (RPA), primary tumor, number of brain lesions, surgery, radiation therapy scheme, extracranial metastatic status and primary disease control status. RESULTS: The average patient age of onset was 58 years. The primary tumor site was lung (68%), breast (12%), melanoma (4%), colorectal (1.6%), sarcoma (1.3%) and unknown primary disease (4.4%). The rest of the patients had other primary sites. Eighty four (26.6%) patients had single brain metastasis, 71 (22.5%) had 2 or 3 lesions, and 159 (50.4%) patients had more than 3 lesions. Leptomeningeal involvement was seen in combination of paranchymal involvement in 11 (3.5%) patients. Fifty patients had undergone surgical resection. WBRT was delivered to all of the patients. Median overall survival was 6.7 months (95% CI, 5.80-7.74). Median overall survival of patients treated with combination of surgery and WBRT was significantly better compared with those treated with WBRT alone (13.5 vs 5.5 months, p=0.0001). One- and 2- year survival was 17 and 4.7%, respectively. CONCLUSIONS: The present study concludes that brain metastasis is common in cancer patients. The best overall survival was obtained by surgery+NBRT in good-condition patients. Treatment should be tailored on an individual basis to all these patients.

Perovskite Photodetectors Operating in Both Narrowband and Broadband Regimes.

Photodetectors are designed, which operate in the broadband regime upon bottom illumination (from the indium tin oxide (ITO) side) and in the narrowband regime upon top illumination (from the air/perovskite side). The narrowband photodetectors show high external quantum efficiency of above 104 %. The operational spectrum of the photodetectors can also be tuned by adjusting the halide composition in the active material.

Optical constants of CH3NH3PbBr3 perovskite thin films measured by spectroscopic ellipsometry.

The lack of optical constants information for hybrid perovskite of CH3NH3PbBr3 in thin films form can delay the progress of efficient LED or laser demonstration. Here, we report on the optical constants (complex refractive index and dielectric function) of CH3NH3PbBr3 perovskite thin films using spectroscopic ellipsometry. Due to the existence of voids, the refractive index of the thin films is around 8% less than the single crystals counterpart. The energy bandgap is around 2.309 eV as obtained from photoluminescence and spectrophotometry spectra, and calculated from the SE analysis. The precise measurement of optical constants will be useful in designing optical devices using CH3NH3PbBr3 thin films.

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.

Enhanced Etching, Surface Damage Recovery, and Submicron Patterning of Hybrid Perovskites using a Chemically Gas-Assisted Focused-Ion Beam for Subwavelength Grating Photonic Applications.

The high optical gain and absorption of organic-inorganic hybrid perovskites have attracted attention for photonic device applications. However, owing to the sensitivity of organic moieties to solvents and temperature, device processing is challenging, particularly for patterning. Here, we report the direct patterning of perovskites using chemically gas-assisted focused-ion beam (GAFIB) etching with XeF2 and I2 precursors. We demonstrate etching enhancement in addition to controllability and marginal surface damage compared to focused-ion beam (FIB) etching without precursors. Utilizing the GAFIB etching, we fabricated a uniform and periodic submicron perovskite subwavelength grating (SWG) absorber with broadband absorption and nanoscale precision. Our results demonstrate the use of FIB as a submicron patterning tool and a means of providing surface treatment (after FIB patterning to minimize optical loss) for perovskite photonic nanostructures. The SWG absorber can be patterned on perovskite solar cells to enhance the device efficiency through increasing light trapping and absorption.

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.

Planar-integrated single-crystalline perovskite photodetectors.

Hybrid perovskites are promising semiconductors for optoelectronic applications. However, they suffer from morphological disorder that limits their optoelectronic properties and, ultimately, device performance. Recently, perovskite single crystals have been shown to overcome this problem and exhibit impressive improvements: low trap density, low intrinsic carrier concentration, high mobility, and long diffusion length that outperform perovskite-based thin films. These characteristics make the material ideal for realizing photodetection that is simultaneously fast and sensitive; unfortunately, these macroscopic single crystals cannot be grown on a planar substrate, curtailing their potential for optoelectronic integration. Here we produce large-area planar-integrated films made up of large perovskite single crystals. These crystalline films exhibit mobility and diffusion length comparable with those of single crystals. Using this technique, we produced a high-performance light detector showing high gain (above 10(4) electrons per photon) and high gain-bandwidth product (above 10(8) Hz) relative to other perovskite-based optical sensors.

High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization.

Single crystals of methylammonium lead trihalide perovskites (MAPbX3; MA = CH3NH3(+), X = Br(-) or I(-)) have shown remarkably low trap density and charge transport properties; however, growth of such high-quality semiconductors is a time-consuming process. Here we present a rapid crystal growth process to obtain MAPbX3 single crystals, an order of magnitude faster than previous reports. The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures. The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters. Despite the rapidity of the method, the grown crystals exhibit transport properties and trap densities comparable to the highest quality MAPbX3 reported to date. The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.