Tailoring the surface-oxygen defects of a tin dioxide support towards an enhanced electrocatalytic performance of platinum nanoparticles.

Tin-dioxide nanofacets (SnO2 NFs) are crystal-engineered so that oxygen defects on the maximal {113} surface are long-range ordered to give rise to a non-occupied defect band (DB) in the bandgap. SnO2 NFs-supported platinum-nanoparticles exhibit an enhanced ethanol-electrooxidation activity due to the promoted charge-transport via the DB at the metal-semiconductor interface.

Role of glutamine-169 in the substrate recognition of human aminopeptidase B.

BACKGROUND: Aminopeptidase B (EC 3.4.11.6, APB) preferentially hydrolyzes N-terminal basic amino acids of synthetic and peptide substrates. APB is involved in the production and maturation of peptide hormones and neurotransmitters such as miniglucagon, cholecystokinin and enkephalin by cleaving N-terminal basic amino acids in extended precursor proteins. Therefore, the specificity for basic amino acids is crucial for the biological function of APB. METHODS: Site-directed mutagenesis and molecular modeling of the S1 site were used to identify amino acid residues of the human APB responsible for the basic amino acid preference and enzymatic efficiency. RESULTS: Substitution of Gln169 with Asn caused a significant decrease in hydrolytic activity toward the fluorescent substrate Lys-4-methylcoumaryl-7-amide (MCA). Substantial retardation of enzyme activity was observed toward Arg-MCA and substitution with Glu caused complete loss of enzymatic activity of APB. Substitution with Asn led to an increase in IC50 values of inhibitors that interact with the catalytic pocket of APB. The EC50 value of chloride ion binding was also found to increase with the Asn mutant. Gln169 was required for maximal cleavage of the peptide substrates. Molecular modeling suggested that interaction of Gln169 with the N-terminal Arg residue of the substrate could be bridged by a chloride anion. CONCLUSION: Gln169 is crucial for obtaining optimal enzymatic activity and the unique basic amino acid preference of APB via maintaining the appropriate catalytic pocket structure and thus for its function as a processing enzyme of peptide hormones and neurotransmitters.

Low Dark Current Operation in InAs/GaAs(111)A Infrared Photodetectors: Role of Misfit Dislocations at the Interface.

We demonstrate an extended short-wave infrared (e-SWIR) photodetector composed of an InAs/GaAs(111)A heterostructure with interface misfit dislocations. The layer structure of the photodetector consists simply of an n-InAs optical absorption layer directly grown with a thin undoped-GaAs spacer layer on n-GaAs by molecular beam epitaxy. The lattice mismatch was abruptly relaxed by forming a misfit dislocation network at the initial stage of the InAs growth. We found high-density threading dislocations (1.5 × 109 cm-2) in the InAs layer. The current-voltage characteristics of the photodetector at 77 K had a very low dark current density (<1 × 10-9 A cm-2) at a positive applied voltage (electrons flow from n-GaAs to n-InAs) of up to ∼+1 V. Simulation of the band structure revealed that the direct connection of GaAs and InAs and the formation of interfacial states by the misfit dislocations play significant positive roles in suppressing dark current. Under illumination with e-SWIR light at 77 K, a clear photocurrent signal was observed with a 2.6 µm cutoff wavelength, which is consistent with the bandgap of InAs. We also demonstrated e-SWIR detection at room temperature with a 3.2 µm cutoff wavelength. The maximum detectivity at 294 K exceeds 2 × 108 cm Hz0.5 W-1 for the detection of e-SWIR light at 2 µm.

Highly Efficient Deposition of Centimeter-Scale MoS2 Monolayer Film on Dragontrail Glass with Large Single-Crystalline Domains.

Highly efficient growth of a centimeter-scale MoS2 monolayer film by oxide scale sublimation chemical vapor deposition (OSSCVD) in a time as short as 60 s is reported. Benefiting from the superior catalytic ability of Dragontrail glass (DT-glass) substrate and the controlled large vapor supersaturation of the molybdenum source, the ultrafast deposition of MoS2 is realized with maintaining large-sized single-crystalline domains over 20 µm at maximum in the film. It is comparable to those reported for MoS2 grown in tens of minutes and even hours. Similar to the face-to-face precursor feed route, the gas-controlled OSSCVD with a showerhead configuration facilitates a homogeneous and controllable source supply. It enables high-quality monolayer MoS2 film deposition on 2 × 2 cm2 DT-glass with centimeter-scale uniformity confirmed by microscopic, spectroscopic, and electrical characterizations. Back-gate MoS2 field-effect transistors fabricated on polycrystalline continuous film exhibit the maximum field-effect mobility of 5.1 cm2 V-1 s-1 and a peak Ion /Ioff ratio of 5 × 108 . They reach 40 cm2  V-1  s-1 and 1.2 × 109 , respectively, on single-crystalline domains. These results are even greater than those for MoS2 grown using 1-2 orders of magnitude longer deposition time and higher temperatures. This study highlights the opportunities for low-cost high-throughput production of large-area high-quality monolayer MoS2 .

Oxide Scale Sublimation Chemical Vapor Deposition for Controllable Growth of Monolayer MoS2 Crystals.

A newly developed oxide scale sublimation chemical vapor deposition (OSSCVD) technique for 2D MoS2 growth is reported. Gaseous MoO3 , which is supplied separately from H2 S, can be generated in situ by flowing O2 over Mo metal with oxidation and sublimation processes. In this method, particularly, controllably and abruptly modulating the supply of MoO3 is achievable by precisely tuning O2 flow. Having appropriate conditions, where the generation rate of MoO3 on the Mo metal surface is not larger than its sublimation rate, is critical to enable stable growth. Otherwise, MoS2 deposition can be caused by accumulated MoO3 on the metal surface, regardless of oxygen supply. Proof-of-concept experiments with varied process parameters are conducted, confirming OSSCVD enables MoS2 growth with significantly improved flexibility, controllability, and reproducibility relative to conventional powder-source CVD. By utilizing alkali-aluminosilicate glass, Dragontrail, as catalytic substrate, single-crystalline MoS2 triangular domains as large as 25 µm are obtained, followed by a fully covered monolayer on Dragontrail in 25 min. Substrate pretreatment by H2 S yields enlarged domain size and reduced domain density, owning to the extracted alkali metals from Dragontrail into the growth zone. The study opens new avenues for the controllable growth of high-quality MoS2 and other transition metal dichalcogenides.

Experimental study of near-field light collection efficiency of aperture fiber probe at near-infrared wavelengths.

We examined the near-field collection efficiency of near-infrared radiation for an aperture probe. We used InAs quantum dots as ideal point light sources with emission wavelengths ranging from 1.1 to 1.6 µm. We experimentally investigated the wavelength dependence of the collection efficiency and compared the results with computational simulations that modeled the actual probe structure. The observed degradation in the collection efficiency is attributed to the cutoff characteristics of the gold-clad tapered waveguide, which approaches an ideal conductor at near-infrared wavelengths.

Tunable Doping of Rhenium and Vanadium into Transition Metal Dichalcogenides for Two-Dimensional Electronics.

Two-dimensional (2D) transition metal dichalcogenides (TMDCs) with unique electrical properties are fascinating materials used for future electronics. However, the strong Fermi level pinning effect at the interface of TMDCs and metal electrodes always leads to high contact resistance, which seriously hinders their application in 2D electronics. One effective way to overcome this is to use metallic TMDCs or transferred metal electrodes as van der Waals (vdW) contacts. Alternatively, using highly conductive doped TMDCs will have a profound impact on the contact engineering of 2D electronics. Here, a novel chemical vapor deposition (CVD) using mixed molten salts is established for vapor-liquid-solid growth of high-quality rhenium (Re) and vanadium (V) doped TMDC monolayers with high controllability and reproducibility. A tunable semiconductor to metal transition is observed in the Re- and V-doped TMDCs. Electrical conductivity increases up to a factor of 108 in the degenerate V-doped WS2 and WSe2 . Using V-doped WSe2 as vdW contact, the on-state current and on/off ratio of WSe2 -based field-effect transistors have been substantially improved (from ≈10-8 to 10-5 A; ≈104 to 108 ), compared to metal contacts. Future studies on lateral contacts and interconnects using doped TMDCs will pave the way for 2D integrated circuits and flexible electronics.

Strain relaxation in InAs heteroepitaxy on lattice-mismatched substrates.

Strain relaxation processes in InAs heteroepitaxy have been studied. While InAs grows in a layer-by-layer mode on lattice-mismatched substrates of GaAs(111)A, Si(111), and GaSb(111)A, the strain relaxation process strongly depends on the lattice mismatch. The density of threading defects in the InAs film increases with lattice mismatch. We found that the peak width in x-ray diffraction is insensitive to the defect density, but critically depends on the residual lattice strain in InAs films.

Double-Sided Nonalloyed Ohmic Contacts to Si-doped GaAs for Plasmoelectronic Devices.

There is increasing demand for the ability to form ohmic contacts without lossy intermediate layers on both the top and bottom sides of metal-semiconductor-metal plasmoelectronic devices such as quantum cascade lasers and metasurface photodetectors. Although highly Si-doped n-GaAs surfaces can allow an ohmic contact without alloying, conditions for realizing nonalloyed ohmic contacts to other n-GaAs surfaces, originally buried inside but exposed by removing the substrate, have yet to be studied. We discovered that nonalloyed ohmic contacts to initially buried surfaces with a practically low contact resistivity down to 77 K can be realized by fulfilling certain requirements, specifically keeping the Si-doping concentration within a narrow range of 7.5 × 1018 to 1.25 × 1019 cm-3 and setting the growth temperature of the succeeding upper layers to a low value of 530 °C.

Wafer-scale and deterministic patterned growth of monolayer MoS2via vapor-liquid-solid method.

Vapor transportation is the core process in growing transition-metal dichalcogenides (TMDCs) by chemical vapor deposition (CVD). One inevitable problem is the spatial inhomogeneity of vapors. The non-stoichiometric supply of transition-metal precursors and chalcogens leads to poor control in the products' location, morphology, crystallinity, uniformity and batch to batch reproducibility. The vapor-liquid-solid (VLS) growth method often involves molten precursors (e.g., non-volatile Na2MoO4) at growth temperatures higher than their melting points. The liquid Na2MoO4 can precipitate out solid MoS2 monolayers when saturated with sulfur vapor. Taking advantage of the VLS growth, we attained three kinds of important achievements: (i) a 4-inch-wafer-scale uniform growth of MoS2 flakes on SiO2/Si substrates, (ii) a 2-inch-wafer-scale growth of continuous MoS2 film with the grain size exceeding 100 µm on sapphire substrates, and (iii) a patterned (site-controlled) growth of MoS2 flakes and films. We clarified that the VLS growth thus paves a new way for the high-efficient and scalable synthesis of two-dimensional TMDC monolayers.

Strain Relaxation in GaSb/GaAs(111)A Heteroepitaxy Using Thin InAs Interlayers.

We have systematically studied the strain relaxation processes in GaSb heteroepitaxy on GaAs(111)A using thin InAs interlayers. The growth with 1 ML- and 2 ML-InAs leads to formation of an InAsSb-like layer, which induces tensile strain in GaSb films, whereas the GaSb films grown with thicker InAs layers (≥3 ML) are under compressive strain. As the InAs thickness is increased above 5 ML, the insertion of the InAs layer becomes less effective in the strain relaxation, leaving residual strain in GaSb films. This leads to the elastic deformation of the GaSb lattice, giving rise to the increase in the peak width of X-ray rocking curves.

Direct visualization of the N impurity state in dilute GaNAs using scanning tunneling microscopy.

The interaction between nitrogen (N) impurity states in III-V compounds plays a key role in controlling optoelectronic properties of the host materials. Here, we use scanning tunneling microscopy to characterize the spatial distribution and electronic properties of N impurity states in dilute GaNAs. We demonstrated that the N impurity states can be directly visualized by taking empty state current images using the multipass scanning method. The N impurity states broadened over several nanometers and exhibited a highly anisotropic distribution with a bowtie-like shape on the GaAs(110) surface, which can be explained by anisotropic propagation of strain along the zigzag chains of Ga and As atoms in the {110} plane. Our experimental findings provide strong insights into a possible role of N impurity states in modifying properties of the host materials.

Quantum key distribution over 120 km using ultrahigh purity single-photon source and superconducting single-photon detectors.

Advances in single-photon sources (SPSs) and single-photon detectors (SPDs) promise unique applications in the field of quantum information technology. In this paper, we report long-distance quantum key distribution (QKD) by using state-of-the-art devices: a quantum-dot SPS (QD SPS) emitting a photon in the telecom band of 1.5 µm and a superconducting nanowire SPD (SNSPD). At the distance of 100 km, we obtained the maximal secure key rate of 27.6 bps without using decoy states, which is at least threefold larger than the rate obtained in the previously reported 50-km-long QKD experiment. We also succeeded in transmitting secure keys at the rate of 0.307 bps over 120 km. This is the longest QKD distance yet reported by using known true SPSs. The ultralow multiphoton emissions of our SPS and ultralow dark count of the SNSPD contributed to this result. The experimental results demonstrate the potential applicability of QD SPSs to practical telecom QKD networks.

Visible-light photodecomposition of acetaldehyde by TiO2-coated gold nanocages: plasmon-mediated hot electron transport via defect states.

Skeletal gold nanocages (Au NCs) are synthesized and coated with TiO2 layers (TiO2-Au NCs). The TiO2-Au NCs exhibit enhanced photodecomposition activity toward acetaldehyde under visible light (>400 nm) illumination because hot electrons are generated over the Au NCs by local surface plasmon resonance (LSPR) and efficiently transported across the metal/semiconductor interface via the defect states of TiO2.

Cathodoluminescence study of AlGaAs/GaAs multilayers grown on ridge-type triangles on GaAs (111)A substrates.

We have studied the cathodoluminescence of AlxGa1-xAs/GaAs multilayers grown on ridge-type triangles by molecular beam epitaxy. The compositional variation of Al, as well as the distribution of impurity and/or defect, was revealed by variations in the cathodoluminescence spectra and images. The Al composition in an AlxGa1-xAs layer was highest in the (111)A facet and decreased in the order (100), (411)A, (111)-delta and (110) facets. On the other hand, the carbon concentration was highest in the (411)A facet and decreased in the order (111)A, (111)-delta, (100) and (110) facets. It should be noted that the (111)-delta facet has a significant effect on the redistribution of Al. Although our ridge-type triangles are rather large for the quantum structures, these data have elucidated the self-organization mechanism of the AlxGa1-xAs/GaAs system and have yielded information on the design of quantum structures. We conclude that cathodoluminescence observation is a powerful tool for studying the compositional variation or band structure of three-dimensional microscale or nanoscale construction.