{[In2S7]8-}∞ Chain and Isolated HgS4 Planar Unit Constructed One-Dimensional Pentanary Sulfide K2Ba7HgIn4S16 Exhibiting Nonlinear-Optical Activity.

Hg-based chalcogenides possess diverse structures, large nonlinear-optical (NLO) responses, and suitable birefringences, making them potentially suitable for numerous crucial criteria of practical application as infrared (IR) NLO crystals. Here, a new pentanary Hg-based sulfide K2Ba7HgIn4S16 has been discovered by a high-temperature solid-state method. It crystallizes in the orthorhombic P21212 space group, and its one-dimensional structure is constructed by {[In2S7]8-}∞ chains and isolated [HgS4]6- planar quadrilateral units located bewteeen the chains, representing a novel type of chalcogenide. K2Ba7HgIn4S16 exhibits a moderate NLO effect of 0.5 × AGS at 2.1 µm and a high laser-induced damage threshold of ∼5.8 × AGS, as well as a band gap of 2.98 eV, demonstrating that K2Ba7HgIn4S16 is a potential IR NLO material. This work enriches the structural chemistry of chalcogenides and the family of Hg-based IR NLO chalcogenides.

Sciatic nerve block downregulates the BDNF pathway to alleviate the neonatal incision-induced exaggeration of incisional pain via decreasing microglial activation.

Sciatic nerve block is under investigation as a possible therapeutic strategy for neonatal injury-induced exaggeration of pain responses to reinjury. Spinal microglial priming, brain-derived neurotrophic factor (BDNF) and Src homology-2 domain-containing protein tyrosine phosphatase-2 (SHP2) participate in exaggerated incisional pain induced by neonatal incision. However, effects of sciatic nerve block on exacerbated incisional pain and underlying mechanisms remain unclear. Here, we demonstrated that sciatic nerve block alleviates pain hypersensitivity and microglial activation in rats subjected to neonatal incision and adult incision (nIN-IN). Chemogenetic activation or inhibition of spinal microglia attenuates or mimics effects of sciatic nerve block on pain hypersensitivity, respectively. Moreover, α-amino-3-hydroxy- 5-methy- 4-isoxazole propionate (AMPA) receptor subunit GluA1 contributes to the exaggeration of incisional pain. The inhibition of BDNF or SHP2 blocks upregulations of downstream molecules in nIN-IN rats. Knockdown of SHP2 attenuates the increase of GluA1 induced by injection of BDNF in adult rats with only neonatal incision. The inhibition of microglia or ablation of microglial BDNF attenuates upregulations of SHP2 and GluA1. Additionally, sciatic nerve block downregulates the expression of these three molecules. Upregulation of BDNF, SHP2 or AMPA receptor attenuates sciatic nerve block-induced reductions of downstream molecules and pain hypersensitivity. Microglial activation abrogates reductions of these three molecules induced by sciatic nerve block. These results suggest that decreased activation of spinal microglia contributes to beneficial effects of sciatic nerve block on the neonatal incision-induced exaggeration of incisional pain via downregulating BDNF/SHP2/GluA1-containing AMPA receptor signaling. Thus, sciatic nerve block may be a promising therapy.

Phase evolution of ultra-thin Ni silicide films on CF4 plasma immersion ion implanted Si.

We present a systematic study on the effects of CF4 plasma immersion ion implantation (PIII) in Si on the phase evolution of ultra-thin Ni silicides. For 3 nm Ni, NiSi2 was formed on Si substrates with and without CF4 PIII at temperature as low as 400 °C. For 6 nm Ni, NiSi was formed on pure Si, while epitaxial NiSi2 was obtained on CF4 PIII Si. The incorporation of C and F atoms in the thin epitaxial NiSi2 significantly reduces the layer resistivity. Increasing the Ni thickness to 8 nm results in the formation of NiSi, where the thermal stability of NiSi, the NiSi/Si interface and Schottky contacts are significantly improved with CF4 PIII. We suggest that the interface energy is lowered by the F and C dopants present in the layer and at the interface, leading to phase evolution of the thin Ni silicide.

Improved Ferroelectric Performance of Mg-Doped LiNbO3 Films by an Ideal Atomic Layer Deposited Al2O3 Tunnel Switch Layer.

Bilayer structures composed of 5% Mg-doped LiNbO3 single-crystal films and ultrathin Al2O3 layers with thickness ranging from 2 to 6 nm have been fabricated by using ion slicing technique combined with atomic layer deposition method. The transient domain switching current measurement results reveal that the P-V hysteresis loops are symmetry in type II mode with single voltage pulse per cycle, which may be attributed to the built-in electric field formed by asymmetric electrodes and compensation of an internal imprint field. Besides, the inlaid Al2O3, as an ideal tunnel switch layer, turns on during ferroelectric switching, but closes during the post-switching or non-switching under the applied pulse voltage. The Al2O3 layer blocks the adverse effects such as by-electrode charge injection and improves the fatigue endurance properties of Mg-doped LiNbO3 ferroelectric capacitors. This study provides a possible way to improve the reliability properties of ferroelectric devices in the non-volatile memory application.

Atomic Layer Deposition of Nickel on ZnO Nanowire Arrays for High-Performance Supercapacitors.

A novel hybrid core-shell structure of ZnO nanowires (NWs)/Ni as a pseudocapacitor electrode was successfully fabricated by atomic layer deposition of a nickel shell, and its capacitive performance was systemically investigated. Transmission electron microscopy and X-ray photoelectron spectroscopy results indicated that the NiO was formed at the interface between ZnO and Ni where the Ni was oxidized by ZnO during the ALD of the Ni layer. Electrochemical measurement results revealed that the Ti/ZnO NWs/Ni (1500 cycles) electrode with a 30 nm thick Ni-NiO shell layer had the best supercapacitor properties including ultrahigh specific capacitance (∼2440 F g-1), good rate capability (80.5%) under high current charge-discharge conditions, and a relatively better cycling stability (86.7% of the initial value remained after 750 cycles at 10 A g-1). These attractive capacitive behaviors are mainly attributed to the unique core-shell structure and the combined effect of ZnO NW arrays as short charge transfer pathways for ion diffusion and electron transfer as well as conductive Ni serving as channel for the fast electron transport to Ti substrate. This high-performance Ti/ZnO NWs/Ni hybrid structure is expected to be one of a promising electrodes for high-performance supercapacitor applications.

Realizing a facile and environmental-friendly fabrication of high-performance multi-crystalline silicon solar cells by employing ZnO nanostructures and an Al2O3 passivation layer.

Nowadays, the multi-crystalline silicon (mc-Si) solar cells dominate the photovoltaic industry. However, the current acid etching method on mc-Si surface used by firms can hardly suppress the average reflectance value below 25% in the visible light spectrum. Meanwhile, the nitric acid and the hydrofluoric contained in the etching solution is both environmental unfriendly and highly toxic to human. Here, a mc-Si solar cell based on ZnO nanostructures and an Al2O3 spacer layer is demonstrated. The eco-friendly fabrication is realized by low temperature atomic layer deposition of Al2O3 layer as well as ZnO seed layer. Moreover, the ZnO nanostructures are prepared by nontoxic and low cost hydro-thermal growth process. Results show that the best passivation quality of the n+ -type mc-Si surface can be achieved by balancing the Si dangling bond saturation level and the negative charge concentration in the Al2O3 film. Moreover, the average reflectance on cell surface can be suppressed to 8.2% in 400-900 nm range by controlling the thickness of ZnO seed layer. With these two combined refinements, a maximum solar cell efficiency of 15.8% is obtained eventually. This work offer a facile way to realize the environmental friendly fabrication of high performance mc-Si solar cells.

Photoluminescence enhancement of ZnO nanowire arrays by atomic layer deposition of ZrO2 layers and thermal annealing.

The effects of shell thickness and rapid thermal annealing on photoluminescence properties of one-dimensional ZnO/ZrO2 core/shell nanowires (NWs) are studied in this work. The ZnO/ZrO2 core/shell structures were synthesized by coating thin ZrO2 layers on the surface of ZnO NWs using atomic layer deposition. The morphological and structural characterization studies reveal that the ZrO2 shells have a polycrystalline structure, which are uniformly and conformally coated on the high quality single-crystal ZnO NWs. As compared with bare ZnO NWs, the ZnO/ZrO2 core/shell structures show a remarkable and continuous enhancement of ultraviolet (UV) emission in intensity with increasing ZrO2 shell thickness up to 10 nm. The great improvement mechanism of the UV emission arises from the surface passivation and the efficient carrier confinement effect of the type-I core/shell system. Moreover, it is observed that the UV emission of ZnO/ZrO2 core/shell structures after thermal annealing increases with increasing annealing temperature. The dominant surface exciton (SX) emission in the bare ZnO NWs and the ZnO/ZrO2 core/shell nanostructures has been detected in the low temperature photoluminescence spectra. A blue shift of the NBE emission peak as well as the varied decay rate of the SX emission intensity are also found in the ZnO NWs after the growth of ZrO2 shells and further thermal treatment. Our results suggest that the ZnO/ZrO2 core/shell nanostructures could be widely implemented in the optical and electronic devices in the future.

Surface-plasmon mediated photoluminescence enhancement of Pt-coated ZnO nanowires by inserting an atomic-layer-deposited Al2O3 spacer layer.

Surface-plasmon mediated photoluminescence emission enhancement has been investigated for ZnO nanowire (NW)/Pt nanoparticle (NP) nanostructures by inserting an Al2O3 spacer layer. The thickness of the Al2O3 spacer layer and of the Pt NPs capped on the ZnO NWs are well controlled by atomic layer deposition. It is found that the photoluminescence property of the ZnO NW/Al2O3/Pt hybrid structure is highly tunable with respect to the thickness of the inserted Al2O3 spacer layer. The highest enhancement (∼14 times) of the near band emission of ZnO NWs is obtained with an optimized Al2O3 spacer layer thickness of 10 nm leading to a ultraviolet-visible emission ratio of 271.2 compared to 18.8 for bare ZnO NWs. The enhancement of emission is influenced by a Förster-type non-radiative energy transfer process of the exciton energy from ZnO NWs to Pt NPs as well as the coupling effect between excitons of ZnO NWs and surface plasmons of Pt NPs. The highly versatile and tunable photoluminescence properties of Pt-coated ZnO NWs achieved by introducing an Al2O3 spacer layer demonstrate their potential application in highly efficient optoelectronic devices.

Facile synthesis and enhanced luminescent properties of ZnO/HfO2 core-shell nanowires.

The morphological, structural and photoluminescence properties of one-dimensional ZnO/HfO2 core-shell nanowires (NWs) with various thicknesses of HfO2 shell layers are studied in detail in this work. The ZnO NWs have been fabricated by a simple hydrothermal method, which are then coated by thin HfO2 shell layers using atomic layer deposition (ALD). The morphological and structural characterization demonstrates that the HfO2 shells with polycrystalline structures grow on the single-crystalline ZnO NWs conformally. Moreover, the ZnO/HfO2 core/shell NWs show remarkable enhanced ultraviolet (UV) emission with increasing thickness of the HfO2 shell layer compared with bare ZnO NWs. The UV emission intensity for the sample with HfO2 shell thickness of ∼16 nm is about 9 times higher than that of bare ZnO NWs. It mainly results from the decreased surface states by surface passivation of the HfO2 shell layer as well as a typical type-I band alignment in the ZnO/HfO2 core/shell structure. A model is also proposed to explain the evolution of the wide visible emission band with the relatively low intensity of the core/shell structures. Our results suggest that the ZnO/HfO2 core/shell structures have potential applications for high-efficiency optoelectronic devices such as UV light-emitting diodes and lasers.

Enhanced photovoltaic performance of inverted pyramid-based nanostructured black-silicon solar cells passivated by an atomic-layer-deposited Al2O3 layer.

Inverted pyramid-based nanostructured black-silicon (BS) solar cells with an Al2O3 passivation layer grown by atomic layer deposition (ALD) have been demonstrated. A multi-scale textured BS surface combining silicon nanowires (SiNWs) and inverted pyramids was obtained for the first time by lithography and metal catalyzed wet etching. The reflectance of the as-prepared BS surface was about 2% lower than that of the more commonly reported upright pyramid-based SiNW BS surface over the whole of the visible light spectrum, which led to a 1.7 mA cm(-2) increase in short circuit current density. Moreover, the as-prepared solar cells were further passivated by an ALD-Al2O3 layer. The effect of annealing temperature on the photovoltaic performance of the solar cells was investigated. It was found that the values of all solar cell parameters including short circuit current, open circuit voltage, and fill factor exhibit a further increase under an optimized annealing temperature. Minority carrier lifetime measurements indicate that the enhanced cell performance is due to the improved passivation quality of the Al2O3 layer after thermal annealing treatments. By combining these two refinements, the optimized SiNW BS solar cells achieved a maximum conversion efficiency enhancement of 7.6% compared to the cells with an upright pyramid-based SiNWs surface and conventional SiNx passivation.

Diastereomeric resolution of racemic o-chloromandelic acid.

The separation of rac-o-chloromandelic acid 1 with enantiopure aryloxypropylamine via diastereomeric salt formation was investigated. (R)-o-chloromandelic acid (R)-1, a key intermediate for the antithrombotic agent clopidogrel, was obtained in 65% yield and 98% ee by Dutch resolution of rac-1 with (S)-2-hydroxyl-3-(p-chlorophenoxy) propylamine (S)-5 as resolving agent and (S)-2-hydroxyl-3-(o-nitrophenoxy) propylamine (S)-4 as nucleation inhibitor.