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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

It is very challenging to employ solution-processed conducting films in large-area ultrathin nanoelectronics. Here, spray-coated Ti

In this article, we determine the band alignment at the thermodynamically stable heterointerface between a ( 2 ¯ 01 )-oriented single-domain β-(In0.072Ga0.928)2O3 crystal and bulk c-plane sapphire, namely, (0001)-oriented α-Al2O3. The β-(In0.072Ga0.928)2O3 layer was deposited on the bulk sapphire crystal using pulsed laser deposition. The β-(In0.072Ga0.928)2O3 and α-Al2O3 valence and conduction band offsets (VBO and CBO, respectively) were found to be 0 ± 0.1 and 4.87 ± 0.1 eV, respectively. Accordingly, we identified a type-I α-Al2O3/β-(In0.072Ga0.928)2O3 heterojunction. X-ray diffraction measurements confirmed ( 2 ¯ 01 )-oriented single-domain β-(In0.072Ga0.928)2O3 high-quality films with in-plane rotations of every 120 ∘ , whereas Rutherford backscattering spectrometry was employed to verify the bulk composition. We employed high-resolution X-ray photoelectron spectroscopy to measure the core level binding energies of Al 2p and Ga 2p3/2 with respect to the valence band maxima of the β-(In0.072Ga0.928)2O3 and α-Al2O3 layers, respectively. Then, we measured the energy separation between the Al 2p and Ga 2p3/2 core levels at the interface of the heterojunction. β-(InGa)2O3 is a wide-bandgap semiconductor, while α-Al2O3 is a well-known dielectric. Together, they can be employed to fabricate reliable and efficient power electronic devices. We also combined high-resolution transmission electron microscopy, X-ray diffraction, and fast Fourier transform algorithms to characterize the dislocations at the interface.

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, [Cu

Due to their atomically precise structure, photoluminescent copper nanoclusters (Cu NCs) have emerged as promising materials in both fundamental studies and technological applications, such as bio-imaging, cell labeling, phototherapy, and photo-activated catalysis. In this work, a facile strategy is reported for the synthesis of a novel Cu NCs coprotected by thiolate and phosphine ligands, formulated as [Cu

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 degradation. Although atomic layer deposition (ALD) of metal oxides has been one of the common encapsulation approaches for longer term stability, its application inevitably resulted in severe loss of emission efficiency and at times partial loss of structural integrity of perovskites, creating a bottleneck in its practical viability. We demonstrate a nondestructive modified gas-phase technique with codeposition of both precursors trimethylaluminum and water to dramatically enhance the PL emission in zero-dimensional (0D) Cs

Two-dimensional transition metal carbides and/or nitrides (MXenes) have shown promise in developing electrochemical storage of metal ions within conductive galleries due to redox reactions with transition metal atoms. Here, effect of surface chemistry on electrochemical storage of sodium ions within MXene interlayers is investigated by etching Ti

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 [Cu

In recent years, β-Ga

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-chlorofluoroehylene) or P(VDF-TrFE-CFE) polymer embedded with large (ca. 4.5 μm) Ti

Thiols and phosphines are the most widely used organic ligands to attain atomically precise metal nanoclusters (NCs). Here, we used simple hydrides (e.g., H–) as ligands along with phosphines, such as triphenylphosphine (TPP), 1,2-bis(diphenylphosphino)ethane [DPPE], and tris(4-fluorophenyl)phosphine [TFPP] to design and synthesize a new class of hydride-rich silver NCs. This class includes [Ag18H16(TPP)10]2+, [Ag25H22(DPPE)8]3+, and [Ag26H22(TFPP)13]2+. Our work reveals a new family of atomically precise NCs protected by H– ligands and labile phosphines, with potentially more accessible active metal sites for functionalization and provides a new set of stable NC sizes with simpler ligand–metal bonding for researchers to explore both experimentally and computationally.

We report the effect of the Ti3C2Tx MXene flake thickness on its inherent electrochemistry and heterogeneous charge transfer characteristics. It is shown that Ti3C2Tx undergoes irreversible oxidation in a positive potential window, which strongly depends on the flake thickness and pH of the electrolyte. Few-layered Ti3C2Tx exhibits faster electron transfer kinetics (k0 = 0.09533 cm s-1) with a [Fe(CN)6]4-/3- redox mediator compared to multi-layered Ti3C2Tx (k0 = 0.00503 cm s-1). In addition, the few-layered free standing Ti3C2Tx film electrode remains intact after enduring irreversible oxidation.

Recent experimental and theoretical studies have demonstrated that two-dimensional (2D) transition metal dichalcogenide (TMDC) nanoflakes are one of the most promising candidates for non-noblemetal electrocatalysts for hydrogen evolution reaction (HER). However, it is still challenging to optimize their conductivity and enrich active sites for highly efficient electrochemical performance. Herein, we report a chemical vapor deposition (CVD) and thermal annealing two-step strategy to controllably synthesize hybrid electrocatalysts consisting of metallic NbS

There exists a strong demand to replace expensive noble metal catalysts with cheap metal sulfides or phosphides for hydrogen evolution reaction (HER). Recently metal phosphides such as NixP, FeP and CoP have been considered as promising candidates to replace Pt cathodes. Here we report that the nanocrystalline CoP nanosheet assembly on carbon cloth can be formed by a two-step process: electrochemical deposition of Co species followed by gas phase phosphidation. The CoP catalyst in this report exhibits a Tafel slope of 30.1 mV/dec in 0.5 M H2SO4 and 42.6 mV/dec in 1 M KOH. The high HER performance of our CoP catalysts is attributed to the rugae-like morphology which results in a high double-layer capacitance and high density of active sites, estimated as 7.77×1017 sites/cm2.

Efficient photocatalytic hydrogen generation in a suspension system requires a sophisticated nano-device that combines a photon absorber with effective redox catalysts. This study demonstrates an innovative molecular linking strategy for fabricating photocatalytic materials that allow effective charge separation of excited carriers, followed by efficient hydrogen evolution. The method for the sequential replacement of ligands with appropriate molecules developed in this study tethers both quantum dots (QDs), as photosensitizers, and metal nanoparticles, as hydrogen evolution catalysts, to TiO2 surfaces in a controlled manner at the nano-level. Combining hydrophobic and hydrophilic interactions on the surface, CdSe-ZnS core-shell QDs and an Au-Pt alloy were attached to TiO2 without overlapping during the synthesis. The resultant nano-photocatalysts achieved substantially high-performance visible-light-driven photocatalysis for hydrogen evolution. All syntheses were conducted at room temperature and in ambient air, providing a promising route for fabricating visible-light-responsive photocatalysts.

There is a strong demand to replace expensive Pt catalysts with cheap metal sulfides or phosphides for hydrogen generation in water electrolysis. Earth-abundant Fe can be electroplated on carbon cloth (CC) to form high surface area rugae-like FeOOH assembly. Subsequent gas phase phosphidation converts the FeOOH to FeP or FeP2 and the morphology of the crystal assembly is controlled by the phosphidation temperature. FeP prepared at 250 °C presents lower crystallinity and that prepared at higher temperatures of 400 °C and 500 °C possesses higher crystallinity, but lower surface area. The phosphidation at 300 °C produces nanocrystalline FeP and preserves the high-surface area morphology; thus, it exhibits the highest HER efficiency in 0.5 M H2SO4, i.e., the required overpotential to reach 10 and 20 mA cm(-2) is 34 and 43 mV, respectively. These values are lowest among the reported non-precious metal phosphides on CC. The Tafel slope for FeP prepared at 300 °C is around 29.2 mV dec(-1), which is comparable to that of Pt/CC; this indicates that the hydrogen evolution for our best FeP is limited by the Tafel reaction (same as Pt). Importantly, the FeP/CC catalyst exhibits much better stability in a wide-range working current density (up to 1 V cm(-2)), suggesting that it is a promising replacement of Pt for HER.

75 Mo–V–Nb mixed oxide catalysts with a broad range of compositions were prepared by a simple evaporation method, and were screened for the ethane oxidative dehydrogenation (ODH) reaction. The compositions of these 75 catalysts were systematically changed by varying the Nb loading, and the Mo/V molar ratio. Characterization by XRD, XPS, H2-TPR and SEM revealed that an intimate structure is formed among the 3 components. The strong interaction among different components leads to the formation of a new phase or an “intimate structure”. The dependency of conversion and selectivity on the catalyst composition was clearly demonstrated from the results of high-throughput testing. The optimized Mo–V–Nb molar composition was confirmed to be composed of a Nb content of 4–8%, a Mo content of 70–83%, and a V content of 12–25%. The enhanced catalytic performance of the mixed oxides is obviously due to the synergistic effects of the different components. The optimized compositions for ethane ODH revealed in our high-throughput tests and the structural information provided by our characterization studies can serve as the starting point for future efforts to improve the catalytic performance of Mo–V–Nb oxides.

Non-precious metal (NPM) catalysts are synthesized by polymerizing aniline salt using an aqueous Fe 3+ /H 2 O 2 coupled catalytic system on a carbon matrix with a porous creating agent. The sulfur containing compunds such as ammonium peroxydisulfate, are eliminated in this method resulting in a much simpler process. The catalysts’ porous structures are enhanced with ammonium carbonate as a sacrificial material that yields voids when decomposed during the heat treatment at 900 °C in N 2 atmosphere. Two catalysts Fe-N-C/Vu and Fe-N-C/KB (Vu = Vulcan and KB = Ketjen black) were synthesized and characterized. Their oxygen reduction reaction (ORR) activities were investigated using a rotating ring-disk electrode (RRDE) in both 0.1 M KOH and 0.1 M HClO 4 . The catalysts show improved ORR activities close to that of Pt-based catalysts, low H 2 O 2 formation and also demonstrated a remarkable tolerance towards methanol oxidation.

We study the band discontinuity at the GaN/single-layer (SL) WSe

Since compelling device efficiencies of perovskite solar cells have been achieved, investigative efforts have turned to understand other key challenges in these systems, such as engineering interfacial energy-level alignment and charge transfer (CT). However, these types of studies on perovskite thin-film devices are impeded by the morphological and compositional heterogeneity of the films and their ill-defined surfaces. Here, we use well-defined ligand-protected perovskite nanocrystals (NCs) as model systems to elucidate the role of heterovalent doping on charge-carrier dynamics and energy level alignment at the interface of perovskite NCs with molecular acceptors. More specifically, we develop an in situ doping approach for colloidal CsPbBr

The growth of TiO2 films by plasma enhanced atomic layer deposition using Star-Ti as a precursor has been systematically studied. The conversion from amorphous to crystalline TiO2 was observed either during high temperature growth or annealing process of the films. The refractive index and bandgap of TiO2 films changed with the growth and annealing temperatures. The optimization of the annealing conditions for TiO2 films was also done by morphology and density studies.

The Suzuki–Miyaura coupling reaction is one of the most important synthetic catalytic reactions developed in the 20th century. However, the use of toxic organic solvents for this reaction still poses a scientific challenge and is an aspect of economical and ecological relevance. The use of water as a reaction medium overcomes this issue. In the present work, we described efficient Suzuki coupling reactions in water, without any phase transfer reagents and it is possible to couple challenging substrates like aryl chlorides. Notably, this protocol also works with ultra-low loading of catalyst with high turnover numbers.

The interaction of low energy electrons (0–18 eV) with C2F4Cl2 molecules condensed in multilayer amounts on a cryogenically cooled Au substrate generates Cl2, as can be seen from the energy and temperature dependence of the Cl− desorption signal. The cross section for Cl2 formation exhibits two pronounced resonant features with maxima near 0 and 10 eV, dropping to essentially zero in the energy range between the resonances (near 3 eV). The energy dependence of the reaction cross section qualitatively follows that of Cl− desorption, which itself can be correlated to dissociative electron attachment (DA) processes in the gas phase. While at 10 eV excited negative ion resonances and electronically excited states of neutral C2F4Cl2 may be involved in the process, in the low energy region (

Correlation of charge state of Mn with the increase in resistivity with Mn concentration is demonstrated in Mn-doped indium tin oxide films. Bonding analysis shows that Mn 2p3/2 core level can be deconvoluted into three components corresponding to Mn2+ and Mn4+ with binding energies 640.8 eV and 642.7 eV, respectively, and a Mn2+ satellite at ?5.4 eV away from the Mn2+ peak. The presence of the satellite peak unambiguously proves that Mn exists in the +2 charge state. The ratio of concentration of Mn2+ to Mn4+ of ?4:1 suggests that charge compensation occurs in the n-type films causing the resistivity increase. � 2010 American Institute of Physics.

Arsenic trisulfide (As 2 S 3 ) glass is an interesting material for photonic integrated circuits (PICs) as infrared (IR) or nonlinear optical components. In this paper, direct laser writing was applied to engineer the refractive index of As 2 S 3 thin film. Film samples were exposed to focused above bandgap light with wavelength at 405nm using different fluence adjusted by laser power and exposure time. The index of refraction before and after laser irradiation was calculated by fitting the experimental data obtained from Spectroscopic Ellipsometer (SE) measurement to Tauc-Lorenz dispersion formula. A positive change in refractive index (Δn=0.19 at 1.55μm) as well as an enhancement in anisotropy was achieved in As 2 S 3 film by using 10mW, 0.3μs laser irradiation. With further increasing the fluence, refractive index increased while anisotropic property weakened. Due to the rapid and large photo-induced modification of refractive index obtainable with high spatial resolution, this process is promising for integrated optic device fabrication.

Porous activated nanocarbons with well-controlled dimensionality and morphology (i.e. 0D activated carbon nanoparticles, 1D activated carbon nanotubes, and 2D activated carbon nanosheets) were derived successfully from different template-induced polyaniline nanostructures by facile carbonization and activation processes. The obtained nanocarbons show large specific surface areas (1332–2005 m2 g−1), good conductivities, and highly porous nanoscale architectures. The supercapacitors fabricated using the shape-controlled nanocarbons exhibit high specific capacitance, excellent rate capability, and superior long-term cycling stability in both aqueous and ionic liquid electrolytes. More importantly, a very high energy density of 50.5 W h kg−1 with a power density of 17.4 kW kg−1 can be obtained from the activated carbon nanotube based supercapacitors in an ionic liquid electrolyte (with a charge time of ∼10 s), making the shape-controlled nanocarbons promising candidates for high-performance energy storage devices.

Hetero-element doping (e.g., N, F, C) of TiO2 is inevitably accompanied by significantly increased structural defects due to the dopants' nature being foreign impurities. Very recently, in situ self-doping with homo-species (e.g., Ti(3+)) has been emerging as a rational solution to enhance TiO2 photoactivity within both UV and visible light regions. Herein we demonstrate that conventional electrochemical reduction is indeed a facile and effective strategy to induce in situ self-doping of Ti(3+) into TiO2 and the self-doped TiO2 photoelectrodes showed remarkably improved and very stable water splitting performance. In this study, hierarchical TiO2 nanotube arrays (TiO2 NTs) were chosen as TiO2 substrates and then electrochemically reduced under varying conditions to produce Ti(3+) self-doped TiO2 NTs (ECR-TiO2 NTs). The optimized saturation photocurrent density and photoconversion efficiency on the ECR-TiO2 NTs under simulated AM 1.5G illumination were identified to be 2.8 mA cm(-2) at 1.23 V vs. RHE and 1.27% respectively, which are the highest values ever reported for TiO2 based photoelectrodes. The electrochemical impedance spectra measurement confirms that the electrochemical induced Ti(3+) self-doping improved the electrical conductivity of the ECR-TiO2 NTs. The versatility and effectiveness of the electrochemical reduction method for Ti(3+) self-doping in P25 based TiO2 was also examined and confirmed.

A detailed study of the role of oxygen vacancies in determining the effective mass and high temperature (300–1000 K) thermoelectric properties of La-doped epitaxial SrTiO3 thin films is presented. It is observed that at intermediate temperatures, a transition from degenerate to non-degenerate behavior is observed in the Seebeck coefficient, but not electrical conductivity, which is attributed to heterogeneous oxygen non-stoichiometry. Heikes formula is found to be invalid for the films with oxygen vacancies. By fitting the spectroscopic ellipsometry (SE) data, obtained in the range 300–2100 nm, using a Drude-Lorentz dispersion relation with two Lorentz oscillators, the electrical and optical properties of the films are extracted. Using the excellent agreement between the transport properties extracted from SE modeling and direct electrical measurements, we demonstrate that an increase in concentration of oxygen vacancies results in a simultaneous increase of both carrier concentration and electron effecti...

The influence of oxygen vacancies on the transport properties of epitaxial thermoelectric (Sr,La)TiO3 thin films is determined using electrical and spectroscopic ellipsometry (SE) measurements. Oxygen vacancy concentration was varied by ex-situ annealing in Ar and Ar/H2. All films exhibited degenerate semiconducting behavior, and electrical conductivity decreased (258–133 S cm−1) with increasing oxygen content. Similar decrease in the Seebeck coefficient is observed and attributed to a decrease in effective mass (7.8–3.2 me), as determined by SE. Excellent agreement between transport properties deduced from SE and direct electrical measurements suggests that SE is an effective tool for studying oxide thin film thermoelectrics.