Characterization and Field‐Emission Properties of Needle‐like Zinc Oxide Nanowires Grown Vertically on Conductive Zinc Oxide Films

Needle‐like ZnO nanowires with high density are grown uniformly and vertically over an entire Ga‐doped conductive ZnO film at 550 °C. The nanowires are grown preferentially in the c‐axis direction. The X‐ray diffraction (XRD) θ‐scan curve shows a full width at half maximum (FWHM) value of 2°. This indicates that the c‐axes of the nanorods are along the normal direction of the substrate surface. The investigation using high‐resolution transmission electron microscopy (HRTEM) confirmed that each nanowire is a single crystal. A room‐temperature photoluminescence (PL) spectrum of the wires consists of a strong and sharp UV emission band at 380 nm and a weak and broad green–yellow band. It reveals a low concentration of oxygen vacancies in the ZnO nanowires and their high optical quality. Field electron emission from the wires was also investigated. The turn‐on field for the ZnO nanowires was found to be about 18 V μm^–1 at a current density of 0.01 μA cm^–2. The emission current density from the ZnO nanowires reached 0.1 mA cm^–2 at a bias field of 24 V μm^–1.     

Tunable Near‐Infrared Organic Nanowire Nanolasers

Organic semiconductor nanowires have inherent advantages, such as amenability to low‐cost, low‐temperature processing, and inherent four‐level energy systems, which will significantly contribute to the organic solid‐state lasers (OSSLs) and miniaturized laser devices. However, the realization of near‐infrared (NIR) organic nanowire lasers is always a big challenge due to the difficultly in fabrication of organic nanowires with diameters of ≈100 nm and material issues such as low photoluminescence quantum efficiency in the red‐NIR region. What is more, the achievement of wavelength‐tunable OSSLs has also encountered enormous challenge. This study first demonstrates the 720 nm NIR lasing with a low lasing threshold of ≈1.4 µJ cm^?2 from the organic single‐crystalline nanowires, which are self‐assembled from small organic molecules of (E )‐3‐(4‐(dimethylamino)‐2‐methoxyphenyl)‐1‐(1‐hydroxynaphthalen‐2‐yl)prop‐2‐en‐1‐one through a facile solution‐phase growth method. Notably, these individual nanowires' Fabry–Pérot cavity can alternatively provide the red‐NIR lasing action at 660 or 720 nm from the 0–1 or 0–2 radiative transition channels, and the single (660 or 720 nm)/dual‐wavelength (660 and 720 nm) laser action can be achieved by modulating the length of these organic nanowires due to the intrinsic self‐absorption. These easily‐fabricated organic nanowires are natural laser sources, which offer considerable promise for coherent light devices integrated on the optics microchip.     

Development of a Seedless Floating Growth Process in Solution for Synthesis of Crystalline ZnO Micro/Nanowire Arrays on Graphene: Towards High‐Performance Nanohybrid Ultraviolet Photodetectors

A seedless solution process is developed for controllable growth of crystalline ZnO micro/nanowire arrays directly on single‐layer graphene sheets made in chemical vapor deposition (CVD). In particular, the alignment of the ZnO micro/nanowires correlates well with the density of the wires, which is determined by both the sample configuration in solution and the graphene surface cleaning. With increasing wire density, the ZnO micro/nanowire array alignment may be varied from horizontal to vertical by increasing the physical confinement. Ultraviolet photodetectors based on the vertically aligned ZnO micro/nanowires on graphene show high responsivity of 1.62 A W^?1 per volt, a 500% improvement over epitxial ZnO sensors, a 300% improvement over ZnO nanoparticle sensors, and a 40% improvement over the previous best results for nanowire/graphene hybrid sensors. This seedless, floating growth process could be scaled up for large scale growth of oriented ZnO micro/nanowires on graphene at low costs.     

Atom Probe Tomography of Zinc Oxide Nanowires

Wide-bandgap zinc oxide (ZnO) semiconductors and nanowires have become important materials for electronic and photonic device applications. In this work, we report the growth of well-aligned single-crystal ZnO nanowire arrays on sapphire substrates by chemical vapor deposition and the development of atom probe tomography, an emerging nanoscale characterization method capable of providing deeper insight into the three-dimensional distribution of atoms and impurities within its structure. Using a metal-catalyst-free approach, the influence of the growth parameters on the orientation and density of the nanowires were studied. The resulting ZnO nanowires were determined to be single crystalline, with diameter on the order of 50 nm to 150 nm and length that could be controlled between 0.5 μm to 20 μm. Their density was on the order of high 10⁸ cm⁻² to low 10⁹ cm⁻². In addition to routine characterizations using scanning and transmission electron microscopy, x-ray diffraction, photoluminescence, and Raman spectroscopy, we developed the atom probe tomography technique for ZnO nanowires, comparing the voltage pulse and laser pulse modes. In-depth analysis of the data was carried out to determine the accurate chemical composition of the nanowires and reveal the incorporation of nitrogen impurities. The current–voltage characteristics of individual nanowires were measured to determine their electrical properties.     

Metastable Copper‐Phthalocyanine Single‐Crystal Nanowires and Their Use in Fabricating High‐Performance Field‐Effect Transistors

This paper describes a simple, vapor‐phase route for the synthesis of metastable α‐phase copper‐phthalocyanine (CuPc) single‐crystal nanowires through control of the growth temperature. The influence of the growth temperature on the crystal structures, morphology, and size of the CuPc nanostructures is explored using X‐ray diffraction (XRD), optical absorption, and transmission electron microscopy (TEM). α‐CuPc nanowires are successfully incorporated as active semiconductors in field‐effect transistors (FETs). Single nanowire devices exhibit carrier mobilities and current on/off ratios as high as 0.4 cm² V^?1 s^?1 and >10⁴, respectively.     

Manipulable and Hybridized,Ultralow‐Threshold Lasing in a Plasmonic Laser Using Elliptical InGaN/GaN Nanorods

Manipulating stimulated‐emission light in nanophotonic devices on scales smaller than their emission wavelengths to meet the requirements for optoelectronic integrations is a challenging but important step. Surface plasmon polaritons (SPPs) are one of the most promising candidates for sub‐wavelength optical confinement. In this study, based on the principle of surface plasmon amplification by the stimulated emission of radiation (SPASER), III‐Nitride‐based plasmonic nanolaser with hybrid metal–oxide–semiconductor (MOS) structures is designed. Using geometrically elliptical nanostructures fabricated by nanoimprint lithography, elliptical nanolasers able to demonstrate single‐mode and multimode lasing with an optical pumping power density as low as 0.3 kW cm^?2 at room temperature and a quality Q factor of up to 123 at a wavelength of ≈490 nm are achieved. The ultralow lasing threshold is attributed to the SPP‐coupling‐induced strong electric‐field‐confinement in the elliptical MOS structures. In accordance with the theoretical and experimental results, the size and shape of the nanorod are the keys for manipulating hybridization of the plasmonic and photonic lasing modes in the SPASER. This finding provides innovative insight that will contribute to realizing a new generation of optoelectronic and information devices.     

Selective Patterned Growth of Single‐Crystal Ag–TCNQ Nanowires for Devices by Vapor–Solid Chemical Reaction

We report the deterministic growth of individual single‐crystal organic semiconductor nanowires of silver–tetracyanoquinodimethane (Ag–TCNQ) with high yield (>90%) by a vapor–solid chemical reaction process. Ag–metal films or patterned dots deposited onto substrates serve as chemical reaction centers and are completely consumed during the growth of the individual or multiple nanowires. Selective‐area electron diffraction (SAED) revealed that the Ag–TCNQ nanowires grow preferentially along the strong π–π stacking direction of Ag–TCNQ molecules. The vapor–solid chemical reaction process described here permits the growth of organic nanowires at lower temperatures than chemical vapor deposition (CVD) of inorganic nanowires. The single‐crystal Ag–TCNQ nanowires are shown to act as memory switches with high on/off ratios, making them potentially useful in optical storage, ultrahigh‐density nanoscale memory, and logic devices.     

ZnO近紫外波长纳米激光器的研究

随着纳米科技的兴起,纳米激光的研究成为了又一个新的重要课题.ZnO纳米微晶有两种结构可以产生随机激光,一是六角柱形蜂窝状微晶结构,二是颗粒粉末状结构,产生的近紫外激光波长是387.5 nm,光泵浦阈值是50 kW/cm2.采用气相输运的催化外延晶体生长过程来制备ZnO纳米线阵列构成的光致纳米激光器,激光波长383 nm,线宽仅为0.3 nm,光泵浦阈值是40 kW/cm2.     

A Roadmap for Controlled and Efficient n‐Type Doping of Self‐Assisted GaAs Nanowires Grown by Molecular Beam Epitaxy

N‐type doping of GaAs nanowires has proven to be difficult because the amphoteric character of silicon impurities is enhanced by the nanowire growth mechanism and growth conditions. The controllable growth of n‐type GaAs nanowires with carrier density as high as 10²⁰ electron cm^?3 by self‐assisted molecular beam epitaxy using Te donors is demonstrated here. Carrier density and electron mobility of highly doped nanowires are extracted through a combination of transport measurement and Kelvin probe force microscopy analysis in single‐wire field‐effect devices. Low‐temperature photoluminescence is used to characterize the Te‐doped nanowires over several orders of magnitude of the impurity concentration. The combined use of those techniques allows the precise definition of the growth conditions required for effective Te incorporation.     

Long K‐Doped Titania and Titanate Nanowires on Ti Foil and FTO/Quartz Substrates for Solar‐Cell Applications

Potassium‐doped titania and titanate nanowires are fabricated by moisture‐assisted direct oxidation of titanium. The influence of the fabrication conditions on nanowire structure and morphology is investigated. It is shown that the presence of potassium is essential for nanowire formation, while the nanowire structure and morphology are strongly dependent on the fabrication temperature. The longest nanowires (ca. 10 μm) are obtained at 650 °C. At this substrate temperature, nanowires could be produced over a large substrate area both by oxidation of the Ti foil as well as by depositing a Ti film on the substrate (quartz or fluorine‐doped tin oxide (FTO)/quartz). Photovoltaic cells based on these nanowires are fabricated. The cell performance is dependent on the nanowire fabrication temperature and the substrate used, as well as on the annealing environment. Short‐circuit current densities of I_sc = 3.05 mA cm^–2 and I_sc = 4.97 mA cm^–2 could be obtained for Ti foil and FTO/quartz substrates, respectively, while the corresponding power‐conversion efficiencies are η = 0.93 % and η = 1.88 % (under AM 1.5 illumination, 100 mW cm^–2; AM: air mass).     

Epitaxial Growth of Aligned Semiconductor Nanowire Metamaterials for Photonic Applications

A novel class of optical metamaterials is presented consisting of high densities of aligned gallium phosphide (GaP) nanowires fabricated using metal‐organic vapor phase‐epitaxy. Starting from a gold island film as a catalyst for nanowire growth, a sequential combination of vapor–liquid–solid and lateral growth modes is employed to obtain a continuous tunability of the nanowire volume fraction from 7% to over 35%. By choosing different crystallographic orientations of the GaP substrate, metamaterials are designed with different nanowire orientations. The anisotropy of the nanowire building blocks results in strong optical birefringence. Polarization interferometry demonstrates a very large polarization extinction contrast of 4 × 10³ combined with a sharp angular resonance which holds promise for optical sensing. Nanowire metamaterials may find applications in photonics, optoelectronics, non‐linear and quantum optics, microfluidics, bio‐, and gas sensing.     

ZnSe–Si Bi‐coaxial Nanowire Heterostructures

We report on the fabrication, structural characterization, and luminescence properties of ZnSe/Si bi‐coaxial nanowire heterostructures. Uniform ZnSe/Si bi‐coaxial nanowire heterostructures are grown on silicon substrates by the simple one‐step thermal evaporation of ZnSe powder in the presence of hydrogen. Both ZnSe and silicon are single‐crystalline in the bi‐coaxial nanowire heterostructures, and there is a sharp interface along the nanowire axial direction. Furthermore, secondary nanostructures of either ZnSe nanobrushes or a SiO_x sheath are also grown on the primary bi‐coaxial nanowires, depending on the ratio of the source materials. The experimental evidence strongly suggests that bi‐coaxial nanowires are formed via a co‐growth mechanism, that is, ZnSe terminates specific surfaces of silicon and leads to anisotropic, one‐dimensional silicon growth, which simultaneously serves as preferential nucleation sites for ZnSe, resulting in the bi‐coaxial nanowire heterostructures. In addition, the optical properties of ZnSe/Si nanowires are investigated using low‐temperature photoluminescence spectroscopy.     

Sn‐catalyzed silicon nanowire solar cells with 4.9% efficiency grown on glass

We present a single pump‐down process to texture hydrogenated amorphous silicon solar cells. Mats of p‐type crystalline silicon nanowires were grown to lengths of 1 µm on glass covered with flat ZnO using a plasma‐assisted Sn‐catalyzed vapor‐liquid‐solid process. The nanowires were covered with conformal layers of intrinsic and n‐type hydrogenated amorphous silicon and a sputtered layer of indium tin oxide. Each cell connects in excess of 10⁷ radial junctions over areas of 0.126 cm². Devices reach open‐circuit voltages of 0.8 V and short‐circuit current densities of 12.4 mA cm⁻², matching those of hydrogenated amorphous silicon cells deposited on textured substrates. Copyright © 2012 John Wiley & Sons, Ltd.     

Wavelength‐Emission Tuning of ZnO Nanowire‐Based Light‐Emitting Diodes by Cu Doping: Experimental and Computational Insights

The band‐gap engineering of doped ZnO nanowires is of the utmost importance for tunable light‐emitting‐diode (LED) applications. A combined experimental and density‐functional theory (DFT) study of ZnO doping by copper (Zn²⁺ substitution by Cu²⁺) is presented. ZnO:Cu nanowires are epitaxially grown on magnesium‐doped p‐GaN by electrochemical deposition. The heterojunction is integrated into a LED structure. Efficient charge injection and radiative recombination in the Cu‐doped ZnO nanowires are demonstrated. In the devices, the nanowires act as the light emitters. At room temperature, Cu‐doped ZnO LEDs exhibit low‐threshold emission voltage and electroluminescence emission shifted from the ultraviolet to violet–blue spectral region compared to pure ZnO LEDs. The emission wavelength can be tuned by changing the copper content in the ZnO nanoemitters. The shift is explained by DFT calculations with the appearance of copper d states in the ZnO band‐gap and subsequent gap reduction upon doping. The presented data demonstrate the possibility to tune the band‐gap of ZnO nanowire emitters by copper doping for nano‐LEDs.     

High‐efficiency µc‐Si solar cells made by very high‐frequency plasma‐enhanced chemical vapor deposition

Microcrystalline silicon‐based single‐junction p–i–n solar cells have been fabricated by very high‐frequency plasma enhanced chemical vapor deposition using a showerhead cathode at high pressures and under silane depletion conditions. The i‐layers are made near the transition from amorphous to crystalline. It was found that, especially at high crystalline fractions, the open‐circuit voltage and fill factor are very sensitive to the morphology of the substrate. At an i‐layer deposition rate 0·45 nm/s, we have measured a stabilised efficiency of 10% (V_oc = 0·52 V, FF = 0·74) for a cell made on texture‐etched ZnO:Al. The performance is stable under light soaking. The defect density of the absorber layer is in the 10¹⁵ cm⁻³ range. In spite of the presence of oxygen contamination, good electrical properties and good infrared cell response are obtained. Copyright © 2006 John Wiley & Sons, Ltd.     

Vertically Aligned Hybrid Core/Shell Semiconductor Nanowires for Photonics Applications

A family of 1D organic/inorganic core/shell materials formed by an inner organic nanowire (ONW) conformally covered with an inorganic wide band gap semiconductor (ZnO or TiO₂) layer is presented. The developed procedure is a two‐steps vacuum methodology involving the formation of supported single crystal small‐molecule nanowires by physical vapor deposition and plasma enhance chemical vapor deposition (PECVD) of the inorganic shell. Critical characteristics of the last technique are the possibilities of low temperature and remote configuration deposition. Additionally, an initial step has to be included in order to create nucleation centers for the growth of the ONWs. The procedure and its general character in terms of the variability in organic core and inorganic shells composition and the applicability of the technique to different substrates are presented. The formation of the inorganic shell with no damage of the organic core single‐crystalline structure is demonstrated by high resolution transmission electron microscopy. The vertical alignment of the hybrid nanostructure is achieved thanks to the interaction of the 1D organic nanostructured surfaces and the glow discharge during the deposition of the inorganic shell by PECVD. The optical properties of these core/shell NWs are studied by fluorescence spectroscopy and microscopy, and their application as nanoscale waveguides in the 550–750 nm range addressed.     

Study of the Piezoelectric Power Generation of ZnO Nanowire Arrays Grown by Different Methods

The piezoelectric power generation from ZnO nanowire arrays grown on different substrates using different methods is investigated. ZnO nanowires were grown on n‐SiC and n‐Si substrates using both the high‐temperature vapor liquid solid (VLS) and the low‐temperature aqueous chemical growth (ACG) methods. A conductive atomic force microscope (AFM) is used in contact mode to deflect the ZnO nanowire arrays. No substrate effect was observed but the growth method, crystal quality, density, length, and diameter (aspect ratio) of the nanowires are found to affect the piezoelectric behavior. During the AFM scanning in contact mode without biasing voltage, the ZnO nanowire arrays grown by the VLS method produced higher and larger output voltage signal of 35 mV compared to those grown by the ACG method, which produce smaller output voltage signal of only 5 mV. The finite element (FE) method was used to investigate the output voltage for different aspect ratio of the ZnO nanowires. From the FE results it was found that the output voltage increases as the aspect ratio increases and starts to decreases above an aspect ratio of 80 for ZnO nanowires.     

ZnO Hemisphere Pits Nanowire/CdS Photoelectrode for High-Efficiency Photoelectrochemical Water Splitting

In this paper, a ZnO hemisphere pits nanowire (HPW) photoelectrode is fabricated by using polystyrene (PS) nanospheres as templates, and CdS is deposited on ZnO nanowires to improve further its photoelectrochemical performance. Firstly, PS nanospheres are deposited on ZnO seed layers by air–liquid interface self-assembling method. Subsequently, ZnO HPWs are grown which effected by PS nanospheres. Finally, CdS nanoparticles were deposited on the ZnO HPWs to construct ZnO/CdS heterojunction photoanodes by successive ionic layer adsorption and reaction method. This hemisphere pits nanowires composite structure demonstrated a highly efficient photoelectrocatalytic performance with a remarkable photocurrent density of 2.27 mA cm^?2 determined at 0.8 V versus Ag/AgCl. The enhanced performance of ZnO hemisphere pits nanowires/CdS nanoparticles (ZnO/CdS) composite photoanodes originated from the enhanced light absorption in the visible region and reduced photogenerated charges recombination rate. Furthermore, compared with ordinary nanowire arrays, hemisphere pits nanowire structure can reflect light more times to facilitate light harvesting. This work exhibits the important significance in constructing photoelectrodes for photoelectrochemical water splitting and other photoelectric devices.     

Light‐Emitting Rubrene Nanowire Arrays: A Comparison with Rubrene Single Crystals

This is a report on a new method of growth of a light‐emitting rubrene nanowires array with diameters of 200 ± 10 nm by using organic vapor transport through Al₂O₃ nanoporous templates. Nanometer‐scale laser confocal microscope (LCM) photoluminescence (PL) spectra and crystalline structures of the rubrene nanowires are compared with those of rubrene single crystals prepared with the same experimental conditions without the template. In the LCM PL spectra it is observed that the PL spectra and intensity varies with the detecting positions because of the crystal growth characteristics of the rubrene molecules. A single rubrene nanowire has a wider LCM PL band width than that of the rubrene single crystal. This may originate from the light emissions of the mixed polarized bands due to additional new crystallinity in the formation of the nanowires. From the current–voltage characteristic curves, the semiconducting nature of both the rubrene nanowires and single crystals is observed.     

Large‐Size Bulk and Thin‐Film Stilbazolium‐Salt Single Crystals for Nonlinear Optics and THz Generation

We present new stilbazolium salt DSTMS (4‐N,N‐dimethylamino‐4′‐N′‐methyl‐stilbazolium 2,4,6‐trimethylbenzenesulfonate) with both high second‐order nonlinear optical properties and very favorable crystal growth characteristics. We are able to obtain very large area bulk single crystals of more than 3 × 3 × 0.2 cm³ with a high optical quality without using seed crystals by using low‐temperature solution growth. We also demonstrate the growth of single crystalline thin films of DSTMS with an area of up to 6 × 5 mm² and a thickness between 5–30 μm. Nonlinear optical measurements reveal that DSTMS possesses large nonlinear optical susceptibilities with χ₁₁₁⁽²⁾ = (430 ± 40) pm V^–1 at 1.9 μm. Highly efficient generation of broadband THz waves with THz electric field strengths of more than 4 kV cm^–1 using 160 fs laser pump pulses at a wavelength λ = 1.45 μm and DSTMS crystals has been demonstrated.