Rapid,One‐Step,Digital Selective Growth of ZnO Nanowires on 3D Structures Using Laser Induced Hydrothermal Growth

For functional nanowire based electronics fabrication, conventionally, combination of complex multiple steps, such as (1) chemical vapor deposition (CVD) growth of nanowire, (2) harvesting of nanowire, (3) manipulation and placement of individual nanowires, and (4) integration of nanowire to circuit are necessary. Each step is very time consuming, expensive, and environmentally unfriendly, and only a very low yield is achieved through the multiple steps. As an alternative to conventional complex multistep approach, original findings are presented on the first demonstration of rapid, one step, digital selective growth of nanowires directly on 3D micro/nanostructures by developing a novel approach; laser induced hydrothermal growth (LIHG) without any complex integration of series of multiple process steps such as using any conventional photolithography process or CVD. The LIHG process can grow nanowires by scanning a focused laser beam as a local heat source in a fully digital manner to grow nanowires on arbitrary patterns and even on the non‐flat, 3D micro/nano structures in a safer liquid environment, as opposed to a gas environment. The LIHG process can greatly reduce the processing lead time and simplify the nanowire‐based nanofabrication process by removing multiple steps for growth, harvest, manipulation/placement, and integration of the nanowires. LIHG process can grow nanowire directly on 3D micro/nano structures, which will be extremely challenging even for the conventional nanowire integration processes. LIHG does not need a vacuum environment to grow nanowires but can be performed in a solution environment which is safer and cheaper. LIHG can also be used for flexible substrates such as temperature‐sensitive polymers due to the low processing temperature. Most of all, the LIHG process is a digital process that does not require conventional vacuum deposition or a photolithography mask.     

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.     

Title: Using Alignment and 2D Network Simulations to Study Charge Transport Through Doped ZnO Nanowire Thin Film Electrodes

Factors affecting charge transport through ZnO nanowire mat films were studied by aligning ZnO nanowires on substrates and coupling experimental measurements with 2D nanowire network simulations. Gallium doped ZnO nanowires were aligned on thermally oxidized silicon wafer by shearing a nanowire dispersion in ethanol. Sheet resistances of nanowire thin films that had current flowing parallel to nanowire alignment direction were compared to thin films that had current flowing perpendicular to nanowire alignment direction. Perpendicular devices showed ～5 fold greater sheet resistance than parallel devices supporting the hypothesis that aligning nanowires would increase conductivity of ZnO nanowire electrodes. 2‐D nanowire network simulations of thin films showed that the device sheet resistance was dominated by inter‐wire contact resistance. For a given resistivity of ZnO nanowires, the thin film electrodes would have the lowest possible sheet resistance if the inter‐wire contact resistance was one order of magnitude lower than the single nanowire resistance. Simulations suggest that the conductivity of such thin film devices could be further enhanced by using longer nanowires.     

Controlled Growth of ZnO Nanowires and Their Optical Properties

This article surveys recent developments in the rational synthesis of single‐crystalline zinc oxide nanowires and their unique optical properties. The growth of ZnO nanowires was carried out in a simple chemical vapor transport and condensation (CVTC) system. Based on our fundamental understanding of the vapor–liquid–solid (VLS) nanowire growth mechanism, different levels of growth controls (including positional, orientational, diameter, and density control) have been achieved. Power‐dependent emission has been examined and lasing action was observed in these ZnO nanowires when the excitation intensity exceeds a threshold (∼40 kW cm^–2). These short‐wavelength nanolasers operate at room temperature and the areal density of these nanolasers on substrate readily reaches 1 × 10¹⁰ cm^–2. The observation of lasing action in these nanowire arrays without any fabricated mirrors indicates these single‐crystalline, well‐facetted nanowires can function as self‐contained optical resonance cavities. This argument is further supported by our recent near‐field scanning optical microscopy (NSOM) studies on single nanowires.     

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.     

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.     

石墨烯上生长GaN纳米线

采用金属Ga升华法在石墨烯/蓝宝石衬底上生长了高质量GaN纳米线,研究了不同的生长条件,如NH3流量、反应时间、催化剂和缓冲层等对GaN纳米线形貌的影响,采用扫描电子显微镜(SEM)对GaN纳米线进行表征.研究发现,在适当的NH3流量且无催化剂时,衬底上可以生长出粗细均匀的GaN纳米线.反应时间为5 min时,纳米线密集分布在衬底上,表面光滑.在石墨烯/蓝宝石上预先低温生长GaN缓冲层,然后升温至1 100℃进行GaN纳米线生长,获得了具有择优取向的GaN纳米线结构.研究表明,石墨烯和缓冲层对获得GaN纳米线结构有序阵列具有重要的作用.     

Highly sensitive near infrared organic phototransistors based on conjugated polymer nanowire networks

Highly sensitive near-infrared (NIR) organic phototransistors (OPTs) were fabricated using nanowire network based on a narrow bandgap donor-acceptor (D-A) polymer as the photoactive channel. The D-A polymer nanowire network-based NIR-OPTs exhibit high responsivity of ∼246 A/W under an NIR illumination source (850 nm) with a light intensity of ∼0.1 mW/cm². This value is over one order of magnitude higher than that of the structurally identical planar D-A polymer thin film OPTs. The high performance of the nanowire network-based phototransistors is attributed to the excellent hole transport ability, reduced density of the structural defects in the polymer nanowires, and improved contact at the channel layer/electrode interfaces. The high sensitivity and low cost solution-fabrication process render this OPT technology appealing and practically viable for application in large area NIR sensors.     

Insulator‐Conductor Type Transitions in Graphene‐Modified Silver Nanowire Networks: A Route to Inexpensive Transparent Conductors

Silver nanowire coatings are an attractive alternative to indium tin oxide for producing transparent conductors. To fabricate coatings with low sheet resistance required for touchscreen displays, a multi‐layer network of silver nanowires must be produced that may not be cost effective. This problem is counteracted here by modifying the electrical properties of an ultra‐low‐density nanowire network through local deposition of conducting graphene platelets. Unlike other solution‐processed materials, such as graphene oxide, our pristine graphene is free of oxygen functional groups, resulting in it being electrically conducting without the need for further chemical treatment. Graphene adsorption at inter‐wire junctions as well as graphene connecting adjacent wires contributes to a marked enhancement in electrical properties. Using our approach, the amount of nanowires needed to produce viable transparent electrodes could be more than 50 times less than the equivalent pristine high density nanowire networks, thus having major commercial implications. Using a laser ablation process, it is shown that the resulting films can be patterned into individual electrode structures, which is a pre‐requisite to touchscreen sensor fabrication.     

ZnO纳米线的快速生长机理及其场发射性能研究

为了快速制备具有优良场发射性能的ZnO纳米线,对ZnO纳米线的生长机理及场发射性能进行研究。首先采用优化的两步法制备出高长径比的ZnO纳米线,其次采用SEM对ZnO的微观形貌进行表征,然后,在分析形貌特点的基础上,说明了强碱体系下ZnO纳米线薄膜的快速生长机理。最后,对典型样品的场发射性能进行了测试。测试果表明,优化后的两步法,只需3h即可获得直径为40~50nm,长度为2.2~2.7μm,长径比高达54的纳米线。薄膜的开启电场为3.6V/μm,阈值场强为9.1V/um,场增强因子β高达3 391。研究表明,高pH值溶液可以加快ZnO纳米线沿C轴方向的择优生长,获得高长径比的ZnO纳米线,进而获得优良的场发射性能。     

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.     

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.     

Catalyst-free growth of ZnO nanowires on various-oriented sapphire substrates by pulsed-laser deposition

Catalyst-free growth of one-dimensional zinc oxide (ZnO) nanowires is reported. ZnO nanowires were synthesized on ZnO buffer layers deposited on various-oriented sapphire substrates. Syntheses of ZnO buffer layers and nanowires were performed by ultraviolet pulsed-laser deposition. ZnO nanowire's number density was the lowest in the case of using m-cut sapphire substrates. ZnO nanowires grown on a-cut sapphire substrates had vertical alignment with distances of tens to hundreds of nanometers. On the other hand, ZnO nanowires grown on c-cut sapphire substrates had the biggest nucleation rate. The dependence of crystalline orientation of ZnO buffer layers on the orientation of sapphire substrates were investigated by electron back scatter diffraction measurement. From their results, the growth models of ZnO buffer layers were suggested and the variations in morphological properties of ZnO nanowires were discussed.     

Three‐Dimensional Branched Nanowire Heterostructures as Efficient Light‐Extraction Layer in Light‐Emitting Diodes

A facile method to fabricate three‐dimensional branched ZnO/MgO nanowire heterostructures and their application as the efficient light‐extraction layer in light‐emitting diodes are reported. The branched MgO nanowires are produced on the hydrothermally‐grown ZnO nanowires with a small tapering angle towards the tip (≈6°), by the oblique angle flux incidence of MgO. The structural evolution during the growth verifies the formation of the MgO nanoscale islands with strong (111) preferred orientation on very thin (5–7 nm) MgO (110) layer. The MgO nanobranches, then grown on the islands, are polycrystalline consisting of many grains oriented in specific directions of <200> and <220>, supported by the nucleation theory. The LEDs with the branched ZnO/MgO nanowire arrays show a remarkable enhancement in the light output power by 21% compared with that of LEDs with pristine ZnO nanowires. Theoretical calculations using a finite‐difference time‐domain method reveal that the nanostructure is very effective in breaking the wave‐guiding mode inside the ZnO nanowires, extracting more light especially in radial direction through the MgO nanobranches.     

ZnO纳米线的低温生长及其发光特性

采用电场辅助电化学沉积的方法在阳极氧化铝模板中沉积出ZnO纳米线阵列.透射电子显微镜和X射线衍射测试结果表明,制备的纳米线是单晶ZnO纳米线,形貌均匀,直径大约为60nm,并且择优于(101)晶面.对生长过程中所加的辅助电场的作用给出了初步解释.光致发光谱表明,在350～650nm范围内存在一个很宽的发光峰.     

Stable α‐CsPbI3 Perovskite Nanowire Arrays with Preferential Crystallographic Orientation for Highly Sensitive Photodetectors

All‐inorganic metal‐halide perovskites CsPbX₃ (X = Cl, Br, I) exhibit higher stability than their organic–inorganic hybrid counterparts, but the thermodynamically instable perovskite α phase at room temperature of CsPbI₃ restricts the practical optoelectronic applications. Although the stabilization of α‐CsPbI₃ polycrystalline thin films is extensively studied, the creation of highly crystalline micro/nanostructures of α‐CsPbI₃ with large grain size and suppressed grain boundary remains challenging, which impedes the implementations of α‐CsPbI₃ for lateral devices, such as photoconductor‐type photodetectors. In this work, stable α‐CsPbI₃ perovskite nanowire arrays are demonstrated with large grain size, high crystallinity, regulated alignment, and position by controlling the dewetting dynamics of precursor solution on an asymmetric‐wettability topographical template. The correlation between the higher photoluminescence (PL) intensity and longer PL lifetime indicates the nanowires exhibit stable α phase and suppressed trap density. The preferential (100) orientation is characterized by discrete diffraction spots in grazing incidence wide‐angle scattering patterns, suggesting the long‐range crystallographic order of these nanowires. Based on these high‐quality nanowire arrays, highly sensitive photodetectors are realized with a responsivity of 1294 A W^?1 and long‐term stability with 90% performance retention after 30‐day ambient storage.     

ZnO纳米线的低温生长及其发光特性

采用电场辅助电化学沉积的方法在阳极氧化铝模板中沉积出ZnO纳米线阵列.透射电子显微镜和X射线衍射测试结果表明,制备的纳米线是单晶ZnO纳米线,形貌均匀,直径大约为60nm,并且择优于(101)晶面.对生长过程中所加的辅助电场的作用给出了初步解释.光致发光谱表明,在350～650nm范围内存在一个很宽的发光峰.     

Sputtered ZnO seed layer enhances photovoltaic behavior in hybrid ZnO/P3HT solar cells

We investigated the characteristics of inverted solar cells comprising bulk-heterojunction active layers of ZnO nanowire arrays and poly(3-hexylthiophene), P3HT. By utilizing a sputtered ZnO seed layer, we are able to grow vertically oriented ZnO nanowire arrays homoepitaxially. Unlike the ZnO nanowires that are grown on sol–gel derived seed layers, our nanowires are more uniform in their dimensions and spatial distribution. This sputtered seed layer also acts as the hole-blocking layer when these nanowire arrays are incorporated in solar cells; hybrid solar cells comprising these nanowires and P3HT exhibit power conversion efficiencies of 1.6%. To date, this is the highest efficiency observed for ZnO nanowire arrays:P3HT hybrid solar cells.     

A Fully Transparent and Flexible Ultraviolet–Visible Photodetector Based on Controlled Electrospun ZnO‐CdO Heterojunction Nanofiber Arrays

It is essential for novel photodetectors to show good photoresponses, high stability, and have facile fabrication methods. Herein, an optimized electrospinning method to fabricate a photodetector based on nanowire arrays that has a wide spectral response range is demonstrated. Arrays of ZnO‐CdO hybrid nanowires are carefully fabricated fusing ZnO and CdO portions into the same nanowires and subsequently assembling those nanowires into a regular structure. Compared to pure ZnO or CdO nanowire arrays, the hybrid arrays show comparable photocurrent/dark current ratios and response speeds, but they possess a much wider spectral response range from ultraviolet to visible light. The optoelectronic and electronic properties of the ZnO‐CdO hybrid nanowire arrays are systematically explored. Based on this, a transparent and flexible photodetector made of ZnO‐CdO hybrid nanowire arrays is fabricated. It shows a high transparency of around 95% in the spectral range of 400–800 nm and maintains its properties even after 200 bending cycles. Importantly, the developed, simple method can be directly applied to many types of substrates and a transfer of the nanowires becomes unnecessary, which guarantees a high quality of the devices.     

An Evanescent Coupling Approach for Optical Characterization of ZnO Nanowires

使用纳米氧化硅光纤探针,利用倏逝波耦合方法,将紫外到红外的激光成功地耦合进单根ZnO纳米线,耦合效率可达25%.实验观测了单根纳米线的荧光特性,发现ZnO纳米线光传输损耗很低.研究证明:采用透镜聚焦激发纳米线发光的传统耦合方法,只能使用特殊激发波长的光;而倏逝波耦合方法具有高效、适用性强的特点,在半导体纳米线和纳米带的光学特性研究中有广泛的应用前景.