Ultrathin ZnS single crystal nanowires: controlled synthesis and room-temperature ferromagnetism properties

Highly uniform single crystal ultrathin ZnS nanowires (NWs) with 2 nm diameter and up to 10 μm length were fabricated using a catalyst-free colloidal chemistry strategy. The nanowires crystallized in hexagonal phase structure with preferential growth along the direction of the (001) basal plane. The strong polarity of the (001) plane composed of Zn cations or S anions drives the oriented attachment of ZnS nanocrystals (NCs) along this direction via electrostatic (or dipole) interaction. The ultrathin ZnS nanowires show intrinsic ferromagnetism at room temperature and other unusual properties related to its unique nature, such as large anisotropic lattice expansion, large blue-shift of UV-vis absorption band of the excition, and photoluminescence spectrum of the exciton band edge. First-principles DFT computation results show that Zn vacancies can induce intrinsic ferromagnetism in these undoped ZnS NWs. The main source of the magnetic moment arises from the unpaired 3p electrons at S sites surrounding the Zn vacancies carrying the magnetic moment ranging from 0.26 to 0.66 μ(B). Calculated results indicate that the magnetic moment of the ultrathin ZnS NWs can be increased by increasing the Zn vacancy concentration without significant energy cost. The calculated magnetization value (1.96 or 0.40 emu/g for Zn vacancies on the surface of NWs or inside, respectively) by Zn(53)S(54) supercell model is larger than our experimental value (0.12 emu/g at 1.8 K and 0.05 emu/g at 300 K), but the ferromagnetic result is qualitatively in agreement.     

硫化锌与硫化锌/氧化锌异质结纳米线的化学气相沉积法制备与表征

介绍一种利用石墨还原快速制备大量硫化锌纳米线的方法,并分别合成了超晶格型、双轴型、核/壳型的硫化锌/氧化锌异质结纳米线。所合成的硫化锌纳米线存在六方纤锌矿和立方闪锌矿两种晶型,纳米线长度达几十微米,直径在20-50 nm,直径均匀且产量很高。在具有双轴型的硫化锌/氧化锌异质结中,首次发现具有超结构特征的氧化锌。HRTEM分析表明,硫化锌/氧化锌超晶格异质结界面为ZB-ZnS(111)∥ZnO(0001),而核/壳型异质结界面为W-ZnS(0001)∥ZnO(0001),这三个晶面分别为各自晶体的极性面,即所合成的硫化锌/氧化锌异质结中极性面相互平行。对ZnS 和ZnS/ZnO 异质结的生长机制进行了探讨,并对硫化锌纳米线与硫化锌/氧化锌异质结的光学性质进行了分析。     

Crystal orientation-ordered ZnS nanowire bundles

We report a novel approach for growing aligned and orientation-ordered ZnS nanowires. Our method relies on a buffer layer of CdSe grown on a Si(111) substrate, on which ZnS nanowires are grown. The growth process of the nanowire bundles is presented. The technique demonstrated could be an effective pathway for growing patterned, aligned, size-controlled, and orientation-ordered ZnS nanowires.     

Carbon-coated single-crystalline zinc sulfide nanowires

Single-crystalline ZnS nanowires coated with graphitic carbon shells were synthesized by thermal evaporation of a mixture of ZnS and SnS powders in a graphite crucible. As-synthesized ZnS/C nanostructures were characterized using X-ray diffraction, scanning electron microscope, and transmission electron microscopy equipped with an energy-dispersive X-ray spectrometer. The ZnS core nanowires were formed by a Sn-catalytic vapor-liquid-solid process and grew along the [210] directions. Photoluminescence spectrum reveals that the carbon-coated ZnS nanowires have a strong emission band centered at 586 nm and a shoulder band at 645 nm.     

Epitaxial heterostructures: side-to-side Si-ZnS, Si-ZnSe biaxial nanowires, and sandwichlike ZnS-Si-ZnS triaxial nanowires

Epitaxial semiconducting heterostructures: side-to-side Si-ZnS, Si-ZnSe biaxial nanowires, and sandwichlike ZnS-Si-ZnS triaxial nanowires were grown via a simple two-stage thermal evaporation of mixed SiO and ZnS or SiO and ZnSe powders under a precise temperature control. Each nanowire had a uniform diameter of 40-120 nm and length ranging from several to several tens of micrometers. Subnanowires of Si, ZnS, and ZnSe within them had a diameter of 20-50, 40-60, and 20-50 nm, respectively. The optical property (nanoscale cathodoluminescence) was also investigated from these new structures. It is proposed that the Si nanowires formed through disproportionation of SiO to Si in the first evaporation stage and then served as one-dimensional nanoscale substrates (or templates) for an epitaxial growth of ZnS or ZnSe nanowires in the following thermal evaporation of ZnS or ZnSe powders. The present results suggest that the simple method might be useful for the synthesis of many other heterostructures containing Si and II-VI or III-V semiconducting composite nanowires to meet the growing demands of nanoscale science and technology.     

Self-organized hierarchical ZnS/SiO(2) nanowire heterostructures

Novel hierarchical heterostructures formed by wrapping ZnS nanowires with highly dense SiO(2) nanowires were successfully synthesized by a vapor-liquid-solid process. The as-synthesized products were characterized using X-ray diffraction, scanning electron microscopy and transmission electron microscopy equipped with an energy-dispersive X-ray spectrometer. Studies indicate that a typical hierarchical ZnS/SiO(2) heterostructure consists of a single-crystalline ZnS nanowire (core) with diameter gradually decreasing from several hundred nanometers to 20 nm and adjacent amorphous SiO(2) nanowires (branches) with diameters of about 20 nm. A possible growth mechanism was also proposed for the growth of the hierarchical heterostructures.     

超细Pd纳米线表层富Pt作为耐久性氧还原催化剂研究

本文控制合成一维方向生长的直径为1.5 nm,长度为11.8 nm的超细Pd纳米线,结合欠电位沉积方法在其表面制备了不同Pt原子层的Pd@Pt核壳结构纳米电催化剂. 高分辨透射电镜和光电子能谱结果证实了这种核壳结构及Pt在Pd纳米线上的均匀分布. 相比于商业化Pt黑催化剂,该核壳结构电催化剂对酸性介质中的氧气还原反应呈现了较高的电催化活性和增强的耐久性. 显著增强的耐久性可归属于催化剂一维结构的稳定性.     

大长径比ZnS纳米线的制备、结构和生长机理

通过碳热辅助化学气相沉积法, 以Au作为催化剂, 在较低温度(800 益)制备了ZnS纳米线, 其尺寸均匀, 表面光滑, 直径约为40 nm, 具有很大的长径比, 是典型的单晶纤锌矿六方结构. 高分辨透射电镜和选区电子衍射分析表明, 纳米线的生长方向为[1100], 与已报道的生长方向不同. 纳米线的生长是由气-液-固(vapor-liquid-solid)机理控制的.     

Molecular Template Assisted Growth of Ultrathin Silicon Carbide Nanowires with Strong Green Light Emission and Excellent Field‐Emission Properties

A novel molecule template assisted chemical co‐reduction method has been successfully developed for the controlled synthesis of ultrathin β‐SiC single‐crystalline nanowires on a large scale. The ultrathin β‐SiC single‐crystalline nanowires are about 8 nm in diameter and 200–800 nm in length. The resulting thin β‐SiC single‐crystalline nanowire is new in the family of β‐SiC one‐dimensional (1D) nanostructures. A synergistic action of π‐stacking and steric hindrance result from the 1,10‐phenanthroline molecule template are proposed to explain the growth mechanism of the ultrathin β‐SiC single‐crystalline nanowires based on the experimental observation. Importantly, such ultrathin β‐SiC nanowire has shown a strong structure‐induced enhancement of photoluminescence properties and has exhibited a very strong green light emission, which can be seen by naked eye. Furthermore, the unique β‐SiC ultrathin nanowire structure exhibits a low turn‐on field (3.57 V μm^?1) and a large field‐emission current density (20 mA cm^?2). These results suggest that the ultrathin β‐SiC nanowires can be expected to find promising applications as field emitters and photoelectronic devices.     

Controlled synthesis and photoluminescence properties of ZnS nanowires and nanoribbons

Rapid synthesis of wurtzite ZnS nanowires and nanoribbons has been achieved by a simple thermal evaporation of ZnS powder onto Si substrate in the presence of Au catalyst. A vapor-liquid-solid process is proposed for the formation of the ZnS nanostructures. The flow rate of the inert carrier Ar gas along with the temperature play an important role in defining the morphology of the ZnS nanostructures. The morphological change of the ZnS nanostructures and their growth sequence were studied through scanning electron microscopy. Room-temperature photoluminescence measurements showed intense blue emission at approximately 398 nm from both the nanowires and the nanoribbons.     

Laser Assisted Catalytic Growth of ZnS/CdSe Core‐Shell and Wire‐Coil Nanowire Heterostructures

ZnS/CdSe core‐shell and wire‐coil nanowire heterostructures have been synthesized by chemical vapor deposition assisted with pulsed laser ablation. Measurements from high‐resolution transmission electron microscopy and selected area electron diffraction have revealed that both ZnS/CdSe core‐shell and wire‐coil nanowires are of single‐crystalline hexagonal wurtzite structures and grow along the [0001] direction. While the lattice parameters of ZnS and CdSe in the core‐shell nanowires are nearly equal to those of bulk ZnS and CdSe, change of the lattice parameters in the CdSe‐coil is attributed to the doping of Zn into CdSe, resulting in the relaxation of compressive strain at the interface between CdSe‐coil and ZnS‐wire. Composition variation across the interfacial regions in the ZnS/CdSe nanowire heterostructures ranges only 10–15 nm despite the pronounced lattice mismatch between ZnS and CdSe by ?11%. Growth mechanisms of the ZnS/CdSe nanowire heterostructures are discussed.     

The role of oxidative etching in the synthesis of ultrathin single-crystalline Au nanowires

The fabrication of ultrathin single-crystal Au nanowires with high aspect ratio and that are stable in air is challenging. Recently, a simple wet-chemical approach using oleylamine has been reported for the synthesis of Au nanowires with micrometer length and 2 nm in diameter. Despite efforts to understand the mechanism of the reaction, an ultimate question about the role of oxygen (O(2)) during the synthesis remained unclear. Here we report that the synthesis of ultrathin Au nanowires employing oleylamine is strongly affected by the amount of O(2) absorbed in the reaction solution. Saturating the solution with O(2) leads to both a high-yield production of nanowires and an increase in their length. Nanowires with diameters of about 2 nm and lengths of 8 μm, which corresponds to an aspect ratio of approximately 4000, were produced. The role of oxygen is attributed to the enhanced oxidation of twin defects on Au nanoparticles formed in the first stage of the reaction. Understanding the role of oxidative etching is crucial to significantly increasing the yield and the length of ultrathin Au nanowires.     

Solvothermal synthesis and photoluminescent properties of ZnS/cyclohexylamine: inorganic-organic hybrid semiconductor nanowires

An inorganic-organic hybrid semiconductor, ZnS/CHA (CHA = cyclohexylamine) nanocomposites was successfully synthesized via a solvothermal method using CHA as solvent, which yielded uniform and ultralong nanowires with widths of 100-1000 nm and lengths of 5-20 microm. Changing the reaction conditions could alter the morphology and optical properties of the nanocomposites. The periodic layer subnanometer structures were identified by high-resolution transmission electron microscopy (HR-TEM) images, with thickness of approximately 2 nm. The composites exhibited a very large blue-shift in their optical absorption edge as well as an exciton excitation band due to a strong quantum confinement effect caused by the internal subnanometer-scale structures. The pure hexagonal wurtzite ZnS nanowires were also obtained by extracting the ZnS/CHA nanocomposites with dimethyl formamide (DMF). In addition, the luminescent properties of exciton and defect-related transitions in different samples of ZnS/CHA were discussed in detail.     

Hierarchical saw-like ZnO nanobelt/ZnS nanowire heterostructures induced by polar surfaces

Saw-like nanostructures composed of single-crystalline ZnO nanobelts and single-crystalline ZnS nanowires have been successfully synthesized by a vapor-solid process. Several techniques, including scanning electron microscope, transmission electron microscopy, and photoluminescence spectroscopy, were used to investigate the structures, morphology, and photoluminescence properties of the products. Due to the similar crystal habits of wurtzite ZnO and ZnS with chemically active Zn-terminated (0001) and chemically inactive O-terminated (or S-terminated) (000) polar surfaces, hierarchical saw-like nanostructures were considered to be formed by the initiation of a chemically active Zn-terminated ZnO (0001) polar surface. Photoluminescence properties of the heterostructures, different from pure ZnO nanobelts or ZnS nanowires, were also studied at room temperature.     

Growth of Cu2S ultrathin nanowires in a binary surfactant solvent

We demonstrate a facile solution-phase method for the synthesis of single-crystal, high aspect ratio, and ultrathin nanowires of hexagonal-phase Cu2S by thermal decomposition of CuS2CNEt2 in a mixed surfactant solvent of dodecanethiol and oleic acid at 160 degrees C. Cu2S nanowires can be controllably synthesized with a diameter as thin as 1.7 nm and length up to tens of micrometers; they are usually aligned in the form of bundles with a thickness of hundreds of nanometers. Based on the experimental results, the formation mechanism of the ultrathin nanowires has been properly proposed. Some key synthetic parameters, which have a significant effect on the sizes and shapes of the products, have also been investigated in detail. UV-vis spectroscopy measurement reveals that the resultant ultrathin nanowires show a strong quantum size effect.     

Synthesis, Structure and Growth Mechanism of ZnS Nanowires with High Aspect Ratio

ZnS nanowires were successfully synthesized through the direct reaction of Zn and S vapor via carbon-assisted chemical evaporation deposition method with Au catalyst. The investigations indicated that the size of ZnS nanowires with a diameter of approximately 40 nm was uniform along the axis of the wire and the surfaces were slick. The ZnS nanowire with a hexagonal wurtzite structure was a typical single crystalline structure. HRTEM and SEAD results demonstrated that the nanowire grew along [100] direction, which was different from the common direction reported in literatures. The growth of nanowires was controlled by vapor-liquid-solid (VLS) mechanism.     

One-step preparation of coaxial CdS-ZnS nanowires

A new approach was developed to prepare coaxial (core-shell) CdS-ZnS nanowires via a one-step metallo-organic chemical vapor deposition (MOCVD) process with co-fed single source precursors of CdS and ZnS. Single source precursors of CdS and ZnS with sufficiently different reactivity were prepared and paired up to form the coaxial heterostructure in a one-step process.     

Facile hydrothermal synthesis of zinc sulfide nanowires for high-performance asymmetric supercapacitor

A facile, single-step hydrothermal route is followed to prepare ZnS nanowires with large aspect ratios. The obtained ZnS nanowires deposited on nickel foam (ZnS/Ni-foam) exhibit a specific capacitance of 781 F/g at a current density of 0.5 A/g. An asymmetric supercapacitor fabricated from ZnS/Ni-foam as a positive electrode and jute derived activated carbon coated on Ni-foam (JAC/Ni-foam) as a negative electrode attains a high specific capacitance of 573 F/g at a current density of 0.5 A/g, with an accompanying high energy density of 51 Wh/kg at a power density of 200 W/kg in an extensive operating potential window of 1.2 V. In addition, the ZnS//JAC asymmetric supercapacitor reveals long-term cyclic stability, after 10,000 GCD cycles the device sustain around ～87 % of the initial specific capacitance. These results shed enlighten a new opportunity for promising electrode materials in supercapacitors.     

Insulating tubular BN sheathing on semiconducting nanowires

An effective method was developed for generation of insulating tubular boron nitride (BN)-sheathed nanostructures. ZnS nanowires and multilayered Si-SiO2 nanowires were successfully sheathed with insulating tubular BN-forming nanocables. Both the semiconductor nanowire cores and the BN sheaths are crystalline with well-uniform morphologies.     

High-quality luminescent tellurium nanowires of several nanometers in diameter and high aspect ratio synthesized by a poly (vinyl pyrrolidone)-assisted hydrothermal process

Large-scale selective synthesis of uniform single crystalline tellurium nanowires with a diameter of 4-9 nm, and microbelts with a width of 250-800 nm and tens of micrometers in length, can be realized by a poly (vinyl pyrrolidone) (PVP)-assisted hydrothermal process. The formation of tellurium nanowires and nanobelts in the presence of PVP is strongly dependent on the reaction conditions such as temperature, the amount of PVP, and reaction time. The results demonstrated that the keys for selective synthesis of Te nanobelts and nanowires are to modulate the growth rates of (100), (101), and (110) planes in the presence of PVP and to precisely control the reaction kinetics. High-quality luminescent ultrathin t-Te nanowires with a diameter of 4-9 nm display strong luminescent emission in the blue-violet region. This approach provides a facile route for the production of high-quality tellurium nanostructures with an interesting optical property. Furthermore, the synthesized ultrathin nanowires with deep blue color and nanobelts in gray color by this approach can be well dispersed in water or ethanol, making it possible for further engineering of their surfaces to prepare other hybrid core-shell nanostructures.