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Copper thiocyanate (CuSCN) is a p-type semiconductor that exhibits hole-transport and wide-band gap (∼3.9 eV) characteristics. However, the conductivity of CuSCN is not sufficiently high, which limits its potential application in optoelectronic devices. Herein, CuSCN thin films were exposed to chlorine using a dry etching system to enhance their electrical properties, yielding a maximum hole concentration of 3 × 10

Utilizing four-dimensional scanning ultrafast electron microscopy (4D-SUEM) is a powerful tool to monitor charge dynamics at material surfaces and interfaces especially for the application in renewable energy field. Herein, we uncover unique physical features for 4D-SUEM upon reducing the acceleration of probed primary electrons to 1 keV, for wide range of materials including various single crystals, thin films and quantum dots upon the presence of oxidized and neat surfaces. Working at 1 keV helps to uncover the migration of photogenerated carriers originating from both sub-surface and bulk layers, under the influence of the carriers scattering and the band-bending phenomena. This approach provides a new avenue for the spatial and temporal access to the surface exclusive dynamics in renewable energy materials to unlock their interfacial behaviors at the nanoscale level.

Lead halide perovskites (LHPs) have attracted a tremendous amount of attention because of their applications in solar cells, lighting, and optoelectronics. However, the atomistic principles underlying their decomposition processes remain in large part obscure, likely due to the lack of precise information about their local structures and composition along regions with dimensions on the angstrom scale, such as crystal interfaces. Aberration-corrected scanning transmission electron microscopy combined with X-ray energy dispersive spectroscopy (EDS) is an ideal tool, in principle, for probing such information. However, atomic-resolution EDS has not been achieved for LHPs because of their instability under electron-beam irradiation. We report the fabrication of CsPbBr

Precise identification and in-depth understanding of defects in nanomaterials can aid in rationally modulating defect-induced functionalities. However, few studies have explored vacancy defects in ligand-stabilized metal nanoclusters with well-defined structures, owing to the substantial challenge of synthesizing and isolating such defective metal nanoclusters. Herein, a novel defective copper hydride nanocluster, [Cu36H10(PET)24(PPh3)6Cl2] (Cu36; PET: phenylethanethiolate; PPh3: triphenylphosphine), is successfully synthesized at the gram scale via a simple one-pot reduction method. Structural analysis reveals that Cu36 is a distorted half cubic nanocluster, evolved from the perfect Nichol's half cube. The two surface copper vacancies in Cu36 are found to be the principal imperfections, which result in some structural adjustments, including copper atom reconstruction near the vacancies as well as ligand modifications (e.g., substitution, migration, and exfoliation). Density functional theory calculations imply that the above-mentioned defects have a considerable influence on the electronic structure and properties. The modeling suggests that the formation of defective Cu36 rather than the perfect half cube is driven by the enlargement of the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital of the nanocluster. The structural evolution induced by the surface copper atom vacancies provides atomically precise insights into the defect-induced readjustment of the local structure and introduces new avenues for understanding the chemistry of defects in nanomaterials.

We would like to acknowledge King Abdullah University of Science and Technology for funding. We also acknowledge KAUST NMR core lab for their continuous help. We acknowledge as well the KAUST Imaging Core Lab, particularly Dr. Alessandro Genovese.

Graphite has become a critical material because of its essential role in the lithium-ion battery (LIB) industry. However, the synthesis of graphite requires an energy-intensive thermal treatment. Also, when used in sodium-ion and potassium-ion batteries (SIBs and PIBs), the graphite anode shows poor capacities and cycling stability, which hinders the development of next-generation battery technologies. Finding suitable anode materials for commercial alkali metal-ion batteries is not only urgent for the energy storage industry, but is also important for economic and sustainable development. In this work, we use fly ash carbon (FAC), a residue of crude oil combustion, as an anode material for alkali metal-ion batteries. The FAC anodes show relatively high capacities and excellent cycling stability. The charge storage mechanism of FAC anode is shown to be intercalation coupled with redox reactions of oxygen functional groups. This work shows that FAC is a promising scalable anode material for alkali metal-ion batteries.

Polyhydrido copper nanoclusters are an emerging class of nanomaterials. Unfortunately, insights into the structural evolution and structure–property relationship of such copper nanoclusters are sca...

Recent advancements in gallium oxide (Ga2O3)-based heterostructures have allowed optoelectronic devices to be used extensively in the fields of power electronics and deep-ultraviolet photodetection. While most previous research has involved realizing single-crystalline Ga2O3 layers on native substrates for high conductivity and visible-light transparency, presented and investigated herein is a single-crystalline β-Ga2O3 layer grown on an α-Al2O3 substrate through an interfacial γ-In2O3 layer. The single-crystalline transparent conductive oxide layer made of wafer-scalable γ-In2O3 provides high carrier transport, visible-light transparency, and antioxidation properties that are critical for realizing vertically oriented heterostructures for transparent oxide photonic platforms. Physical characterization based on X-ray diffraction and high-resolution transmission electron microscopy imaging confirms the single-crystalline nature of the grown films and the crystallographic orientation relationships among the monoclinic β-Ga2O3, cubic γ-In2O3, and trigonal α-Al2O3, while the elemental composition and sharp interfaces across the heterostructure are confirmed by Rutherford backscattering spectrometry. Furthermore, the energy-band offsets are determined by X-ray photoelectron spectroscopy at the β-Ga2O3/γ-In2O3 interface, elucidating a type-II heterojunction with conduction- and valence-band offsets of 0.16 and 1.38 eV, respectively. Based on the single-crystalline β-Ga2O3/γ-In2O3/α-Al2O3 all-oxide heterostructure, a vertically oriented DUV photodetector is fabricated that exhibits a high photoresponsivity of 94.3 A/W, an external quantum efficiency of 4.6 × 104%, and a specific detectivity of 3.09 × 1012 Jones at 250 nm. The present demonstration lays a strong foundation for and paves the way to future all-oxide-based transparent photonic platforms.

A popular practice in Li-S battery research is to utilize highly nanostructured hosts and excessive electrolytes to enhance sulfur-specific capacities. However, from the perspective of commercialization, this is a less meaningful approach in the pursuit of high-energy Li-S batteries. Herein, we report the fabrication of a nanoskin composed of a conjugated microporous polymer by electropolymerization to create a closed system for a sulfur cathode. The nanoskin is ultrathin, conductive, continuous, and contains uniform micropores of approximately 0.8 nm. The nanoskin sealing prevents the shuttling of polysulfide species without using the absorption effect, enhances the utilization of electrolytes, and allows a fast transport of lithium ions. As a result, the Li-S batteries comprising the cathode with nanoskin exhibit superior stability (∼86% capacity retention) under lean electrolyte conditions and a prolonged lifetime (1000 cycles). At a low electrolyte/sulfur ratio of 4 μL mg-1, the designed cathode delivered a practical energy density of over 300 Wh kg-1 without using any sophisticated hosts.

Cesium lead halide perovskite nanocrystals (PNCs), while possessing facile chemical synthesis routes and high photoluminescence (PL) properties, are still challenged by issues of instability and de...

The electrochemical performance of aluminum-sulfur batteries is beset by poor stability and sluggish charge-storage properties. To address these issues, carbon allotropes have been used as electrod...

Copper-based nanomaterials have attracted tremendous interest due to their unique properties in the fields of photoluminescence and catalysis. As a result, studies on the correlation between their molecular structure and their properties are of great importance. Copper nanoclusters are a new class of nanomaterials that can provide an atomic-level view of the crystal structure of copper nanoparticles. Herein, a high-nuclearity copper nanocluster with 81 copper atoms, formulated as [Cu81(PhS)46(tBuNH2)10(H)32]3+ (Cu81), was successfully synthesized and fully studied by X-ray crystallography, X-ray photoelectron spectroscopy, hydrogen evolution experiments, electrospray ionization mass spectrometry, nuclear magnetic resonance spectroscopy, and density functional theory calculations. Cu81 exhibits extraordinary structural characteristics, including (i) three types of novel epitaxial surface-protecting motifs; (ii) an unusual planar Cu17 core; (iii) a hemispherical shell, comprised of a curved surface layer and a planar surface layer; and (iv) two distinct, self-organized arrangements of protective ligands on the curved and planar surfaces. The present study sheds light on structurally unexplored copper nanomaterials and paves the way for the synthesis of high-nuclearity copper nanoclusters.

Blue-emitting perovskites can be easily attained by precisely tuning the halide ratio of mixed halide (Br/Cl) perovskites (MHPs). However, the adjustable halide ratio hinders the passivation of Cl ...

In recent years, β-Ga2O3/NiO heterojunction diodes have been studied, but reports in the literature lack an investigation of an epitaxial growth process of high-quality single-crystalline β-Ga2O3/NiO thin films via electron microscopy analysis and the fabrication and characterization of an optoelectronic device based on the resulting heterojunction stack. This work investigates the thin-film growth of a heterostructure stack comprising n-type β-Ga2O3 and p-type cubic NiO layers grown consecutively on c-plane sapphire using pulsed laser deposition, as well as the fabrication of solar-blind ultraviolet-C photodetectors based on the resulting p-n junction heterodiodes. Several characterization techniques were employed to investigate the heterostructure, including X-ray crystallography, ion beam analysis, and high-resolution electron microscopy imaging. X-ray diffraction analysis confirmed the single-crystalline nature of the grown monoclinic and cubic (201) β-Ga2O3 and (111) NiO films, respectively, whereas electron microscopy analysis confirmed the sharp layer transitions and high interface qualities in the NiO/β-Ga2O3/sapphire double-heterostructure stack. The photodetectors exhibited a peak spectral responsivity of 415 mA/W at 7 V reverse-bias voltage for a 260 nm incident-light wavelength and 46.5 pW/μm2 illuminating power density. Furthermore, we also determined the band offset parameters at the thermodynamically stable heterointerface between NiO and β-Ga2O3 using high-resolution X-ray photoelectron spectroscopy. The valence and conduction band offsets values were found to be 1.15 ± 0.10 and 0.19 ± 0.10 eV, respectively, with a type-I energy band alignment.

Although core–shell copper metal nanoclusters are important emerging materials for practical applications and fundamental scientific research, their synthesis lags behind that of gold and silver na...

We report a strong effect of the MXene flake size and surface termination on the dielectric permittivity of MXene polymer composites. Specifically, poly(vinylidene fluoride-trifluoro-ethylene-chlor...

The direct hydrogenation of CO2 to methanol using hydrogen is regarded as a potential technology to reduce greenhouse gas emissions and the dependence on fossil fuels. For this technology to become...

Here, we demonstrate an approach to synthesizing and structurally characterizing three atomically precise anion-templated silver thiolate nanoclusters, two of which form one- and two-dimensional structural frameworks composed of bipyridine-linked nanocluster nodes (referred to as nanocluster-based frameworks, NCFs). We describe the critical role of the chloride (Cl

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/ba...

The rapid development of halide perovskite synthesis offers the opportunity to fabricate high-quality perovskite nanocrystals (NCs), whose structural uniformity can lead to assembled supra-structur...

The achievement of H2 detection, up to 25 ppm, at room temperature using sulfur-treated, platinum (Pt)-decorated porous GaN is reported in this study. This achievement is attributed to the large lateral pore size, Pt catalyst, and surface treatment using organic sulfide. The performance of H2-gas sensors is studied as a function of the operating temperature by providing an adsorption activation energy of 22 meV at 30 ppm H2, confirming the higher sensitivity of the sulfide-treated Pt–porous GaN sensor. Furthermore, the sensing response of the sulfide-treated Pt–porous GaN gas sensor increases with the increase in porosity (surface-to-volume ratio) and pore radii. Using the Knudsen diffusion–surface reaction equation, the H2 gas concentration profile is simulated and fitted within the porous GaN layer, revealing that H2 diffusion is limited by small pore radii because of its low diffusion rate. The simulated gas sensor responses to H2 versus the pore diameter show the same trend as observed for the experimental data. The sulfide-treated Pt–porous GaN sensor achieves ultrasensitive H2 detection at room temperature for 125 nm pore radii.

The presence of localized trap states on the surface of CsPbCl3 perovskite nanocrystals (NCs) is one of the greatest challenges precluding the development of optoelectronic applications of these NCs. Passivation of these defect sites provides a promising pathway to remediating their electronic and optical properties, such as the photoluminescence quantum yield (PLQY). Herein, we demonstrate a postsynthetic dual-surface treatment using trivalent metal ion salts, i.e., YCl3, as a new passivation approach that enhances the PLQY up to 60% while preserving the NC size and crystal structure. Such remarkable enhancement of the PLQY along with prolongation of the average PL lifetimes of treated NCs samples indicates effective passivation of the surface defects and subsequent suppression of the formation of surface nonradiative recombination centers. As a segue toward optoelectronic applications, we probed the photoelectric performance of the NCs using ultraflexible devices; we found that YCl3-treated CsPbCl3 NC f...

Insertion of alkali metal ions, especially Na, is a well-established method to significantly increase the power conversion efficiency of copper indium gallium selenide (CIGSe)-based photovoltaic devices. However, although it is known that Na ions mostly reside on the surface of CIGSe layer following diffusion, the exact mechanism of how Na affects the carrier dynamics of CIGSe still remains ambiguous. This is mainly due to the unavailability of suitable surface-sensitive techniques. Herein, we employ four-dimensional scanning ultrafast electron microscopy (4D S-UEM), which has the unique capability of mapping the charge carrier dynamics in real time and space selectively on the materials surfaces, to directly observe the effect of Na insertion on the carrier dynamics of shelled CIGSe film. It is found that an additional layer of NaF to the thin film of ZnS-shelled CIGSe nanocrystals not only increases the grain size and improves the texture of the film but, more importantly, reduces fast electron trap cha...

Graphite anodes are not stable in most noncarbonate solvents (e.g., ether, sulfoxide, sulfone) upon Li ion intercalation, known as an urgent issue in present Li ions and next-generation Li–S and Li–O2 batteries for storage of Li ions within the anode for safety features. The solid electrolyte interphase (SEI) is commonly believed to be decisive for stabilizing the graphite anode. However, here we find that the solvation structure of the Li ions, determined by the electrolyte composition including lithium salts, solvents, and additives, plays a more dominant role than SEI in graphite anode stability. The Li ion intercalation desired for battery operation competes with the undesired Li+–solvent co-insertion, leading to graphite exfoliation. The increase in organic lithium salt LiN(SO2CF3)2 concentration or, more effectively, the addition of LiNO3 lowers the interaction strength between Li+ and solvents, suppressing the graphite exfoliation caused by Li+–solvent co-insertion. Our findings refresh the knowled...

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.

The use of physicochemical preparation techniques of metal clusters in the ultrahigh vacuum (UHV) allows for high control of cluster nuclearity and size distribution for fundamental studies in catalysis. Surprisingly, the potential of these systems as catalysts for organic chemistry transformations in solution has not been explored. To this end, single Pt atoms and Pt clusters with two narrow size distributions were prepared in the UHV and applied for the hydrogenation of p-chloronitrobenzene to p-chloroaniline in ethanol. Following the observation of very high catalytic turnovers (approaching the million molecules of p-nitroaniline formed per Pt cluster) and of size-dependent activity, this work addresses fundamental questions with respect to the suitability of these systems as heterogeneous catalysts for the conversion of solution-phase reagents. For this purpose, we employ scanning transmission electron microscopy (STEM) and X-ray photoelectron spectroscopy (XPS) characterization before and after react...