Polymer‐Templated Hydrothermal Growth of Vertically Aligned Single‐Crystal ZnO Nanorods and Morphological Transformations Using Structural Polarity

Position‐configurable, vertical, single‐crystalline ZnO nanorod arrays are fabricated via a polymer‐templated hydrothermal growth method at a low temperature of 93 °C. A sol‐gel processed dense c‐oriented ZnO seed layer film is employed to grow nanorods along the c‐axis direction [0001] regardless of any substrate crystal mismatches. Here, one‐beam laser‐interference lithography is utilized to fabricate nanoscale holes over an entire 2‐in. wafer during the preparation of the polymer template. As such, vertically aligned ZnO nanorods can be grown from the seed layer exposed at the bottom of each hole. Furthermore, morphological transformations of the ZnO nanorods into pencil‐like, needle‐like, tubular, tree‐like, and spherical shapes are obtained by controlling the growth conditions and utilizing the structural polarity of the ZnO nanorods.     

Aligned Growth of Semiconductor Nanowires on Scratched Amorphous Substrates

Aligned growth of planar semiconductor nanowires (NWs) on crystalline substrates has been widely demonstrated during the past two decades and was used for the fabrication of a large variety of devices. However, the dependence on single-crystal substrates is a major obstacle in the way of implementing NW-based applications in today's silicon- and glass-based technologies. Here, the guided growth of semiconductor NWs is demonstrated along nanoscale-depth scratches, created in a nonlithographic process on amorphous oxidized silicon wafers and soda-lime glass. Scratches are created on the substrates in a few seconds using a robust and scalable mechanical polishing process. Growth of planar NWs of different materials (CdS, CdSe, ZnSe, and ZnO) guided by scratches on Si/SiO₂ wafers and glass is demonstrated and studied. Photoluminescence measurements from individual NWs grown along scratches show that the interaction with the substrate preserves the optical properties of the material. Crystallographic analysis indicates that all materials grow as single crystals, and the influence of the scratches on the different materials is discussed in terms of morphology, crystallinity, and crystallographic orientations. This process opens the way to large-scale integration of NWs into functional devices by guided growth for various applications including displays, polarized light sensors, and smart windows.     

Hydrothermal Growth: Polymer‐Templated Hydrothermal Growth of Vertically Aligned Single‐Crystal ZnO Nanorods and Morphological Transformations Using Structural Polarity (Adv. Funct. Mater. 18/2010)

Position‐configurable, vertical, single‐crystalline ZnO nanorod arrays are fabricated via a polymer‐templated hydrothermal growth method at a low temperature of 93 °C. A sol‐gel processed dense c‐oriented ZnO seed layer film is employed to grow nanorods along the c‐axis direction [0001] regardless of any substrate crystal mismatches. Here, one‐beam laser‐interference lithography is utilized to fabricate nanoscale holes over an entire 2‐in. wafer during the preparation of the polymer template. As such, vertically aligned ZnO nanorods can be grown from the seed layer exposed at the bottom of each hole. Furthermore, morphological transformations of the ZnO nanorods into pencil‐like, needle‐like, tubular, tree‐like, and spherical shapes are obtained by controlling the growth conditions and utilizing the structural polarity of the ZnO nanorods.     

石墨烯上生长GaN纳米线的研究

在常压条件下采用化学气相淀积(CVD)技术在有石墨烯插入层的衬底上生长GaN纳米线,研究了生长温度、石墨烯插入层、催化剂等因素对GaN纳米线的形貌、光学特性以及结构的影响.通过扫描电子显微镜(SEM)、光致发光(PL)谱、拉曼(Raman)谱和透射电子显微镜(TEM)等表征手段对GaN纳米线的形貌、光学特性以及结构进行表征.结果表明,在1 100℃条件下,同时有石墨烯插层和催化剂的衬底表面能够获得低应力单晶GaN纳米线.石墨烯、催化剂对于获得低应力单晶GaN纳米线有重要的作用.     

SAM Functionalized ZnO Nanowires for Selective Acetone Detection: Optimized Surface Specific Interaction Using APTMS and GLYMO Monolayers

In modern days, self‐assembled monolayer (SAM) functionalized surfaces represent an interesting tool for the development of ultrasensitive and selective sensing platforms for the detection of chemical substances such as biomolecules and gases. The ability of SAM to generate different functional groups on a single surface such as zinc oxide (ZnO) can be used to immobilize biomolecules and detect different analytes such as gases, proteins, etc. Herein, SAM functionalized ZnO NW‐based sensors are developed for acetone exhaled breath analysis. ZnO NWs are synthesized using a vapor–liquid–solid mechanism and their functionalization is done with two different SAMs, i.e., (3‐aminopropyl)trimethoxysilane (APTMS) and 3‐glycidoxypropyltrimethoxysilane (GLYMO). The enhancement in the electron depletion layer resistance (and also width) due to the capturing of electrons from the ZnO NWs surface by APTMS and GLYMO molecules is found to be the major reason in their superior sensing performances. The amine (–NH₂) groups of APTMS monolayer enhance the sensors selectivity toward acetone due to their reactions with acetone molecules, which produce imine in addition to water molecules. Moreover, after the functionalization with APTMS SAMs, the detection limits of the sensors are improved from 6 to 0.5 ppm, which makes these devices potential candidates for acetone exhaled breath analysis.     

Growth and characterization of ZnO thin films on GaN epilayers

Dense ZnO(0001) films formed at 500°C via coalescence of islands grown via metalorganic vapor phase epitaxy (MOVPE) either on GaN/AlN/SiC(0001) substrates or on initial, coherent ZnO layers. Conical crystallites formed due to thermal expansion-induced stresses between the ZnO and the substrate. Interfaces between the ZnO films on GaN epilayers exposed either simultaneously to diethylzinc and oxygen or only to diethylzinc at the initiation of growth were sharp and epitaxial. Interfaces formed after the exposure of the GaN to O₂ were less coherent, though an interfacial oxide was not observed by cross-sectional transmission electron microscopy (TEM). Threading dislocations and stacking faults were observed in all films.     

Vertically Well‐Aligned ZnO Nanowires on c‐Al2O3 and GaN Substrates by Au Catalyst

In this letter, we report that vertically well‐aligned ZnO nanowires were grown on GaN epilayers and c‐plane sapphire via a vapor‐liquid‐solid process by introducing a 3 nm Au thin film as a catalyst. In our experiments, epitaxially grown ZnO nanowires on Au‐coated GaN were vertically well‐aligned, while nanowires normally tilted from the surface when grown on Au‐coated c‐Al₂O₃ substrates. However, pre‐growth annealing of the Au thin layer on c‐Al₂O₃ resulted in the growth of well‐aligned nanowires in a normal surface direction. High‐resolution transmission electron microscopy measurements showed that the grown nanowires have a hexagonal c‐axis orientation with a single‐crystalline structure.     

电化学方法生长有序纳米柱阵列的发光性质

采用电化学方法在磁控溅射方法生长的ZnO薄膜上生长垂直于衬底排列的ZnO纳米柱.ZnO薄膜的作用主要是为ZnO纳米柱的生长提供同质外延层.电化学生长的ZnO纳米柱具有良好的晶体质量和发光性能.通过研究其变温发光光谱可以确定其紫外发光峰来自于带边激子的辐射复合.此种方法生长的ZnO纳米柱在场发射显示、蓝紫色和白光发光二极管方面有潜在的应用前景.     

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.     

蓝宝石衬底上水平生长ZnO纳米线及紫外敏感性能研究

在无催化剂条件下,采用化学气相沉积(CVD)方法在蓝宝石(110)衬底上制备了ZnO纳米线.X射线衍射(XRD)图谱上只有ZnO的(100)衍射峰和(110)衍射峰.扫描电子显微镜分析表明,ZnO纳米线在蓝宝石衬底上水平生长.在样品上蒸镀了金叉指电极,以256nm的紫外光作为光源,测试了样品的紫外光敏感性能,研究表明水平生长的ZnO纳米线对紫外光具有较快的响应,在5V偏压下,光电流与暗电流比为30;当波长为354nm时光响应度达到最大值为0.56A/W.     

蓝宝石衬底上水平生长ZnO纳米线及紫外敏感性能研究

在无催化剂条件下,采用化学气相沉积(CVD)方法在蓝宝石(110)衬底上制备了ZnO纳米线.X射线衍射(XRD)图谱上只有ZnO的(100)衍射峰和(110)衍射峰.扫描电子显微镜分析表明,ZnO纳米线在蓝宝石衬底上水平生长.在样品上蒸镀了金叉指电极,以256nm的紫外光作为光源,测试了样品的紫外光敏感性能,研究表明水平生长的ZnO纳米线对紫外光具有较快的响应,在5V偏压下,光电流与暗电流比为30;当波长为354nm时光响应度达到最大值为0.56A/W.     

Observation of a 2D Electron Gas and the Tuning of the Electrical Conductance of ZnO Nanowires by Controllable Surface Band‐Bending

Direct experimental evidence for the existence of a 2D electron gas in devices based on ZnO nanowires (NWs) is presented. A two‐channel core/shell model is proposed for the interpretation of the temperature‐dependent current–voltage (I–V) characteristics of the ZnO NW, where a mixed metallic–semiconducting behavior is observed. The experimental results are quantitatively analyzed using a weak‐localization theory, and suggest that the NW is composed of a “bulk” semiconducting core with a metallic surface accumulation layer, which is basically a 2D electron gas in which the electron–phonon inelastic scattering is much weaker than the electron–electron inelastic scattering. A series of I–V measurements on a single NW device are carried out by alternating the atmosphere (vacuum, H₂, vacuum, O₂), and a reversible change in the conductance from metallic to semiconducting is achieved, indicating the surface accumulation layer is likely hydroxide‐induced. Such results strongly support the two‐channel model and demonstrate the controllable tuning of the ZnO NW electrical behavior via surface band‐bending.     

一维氧化锌纳米线生长技术及潜在应用

详细综述了一维ZnO纳米线的制备方法,包括气–液–固催化反应生长法、模板限制辅助生长法、金属有机气相外延生长法、自组织生长法等,介绍了其在微电子及光电子领域的潜在应用。并报道了作者采用热氧化射频磁控共溅射Zn/SiO2复合膜,金属锌从SiO2基质中析出合成了六方纤锌矿结构ZnO纳米线。     

Arrays of Inorganic Nanodots and Nanowires Using Nanotemplates Based on Switchable Block Copolymer Supramolecular Assemblies

Here, a novel and simple route to fabricate highly dense arrays of palladium nanodots and nanowires with sub‐30 nm periodicity using nanoporous templates fabricated from supramolecular assemblies of a block copolymer, polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) and a low molecular weight additive, 2‐(4′‐hydroxybenzeneazo) benzoic acid (HABA) is demonstrated. The palladium nanoparticles, which are directly deposited in the nanoporous templates from an aqueous solution, selectively migrate in the pores mainly due to their preferential attraction to the P4VP block covering the pore wall. The polymer template is then removed by oxygen plasma etching or pyrolysis in air resulting in palladium nanostructures whose large scale morphology mirrors that of the original template. The method adopted in this work is general and versatile so that it could easily be extended for patterning a variety of metallic materials into dot and wire arrays.     

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.     

Si基氨化ZnO／Ga2O3薄膜制备GaN纳米线

利用射频磁控溅射法在Si(111)衬底上溅射ZnO中间层和Ga2O3薄膜，然后在管式炉中常压下通氨气对ZnO/Ga2O3薄膜进行氨化，高温下ZnO层在氨气气氛中挥发，而Ga2O3薄膜和氨气反应合成出GaN纳米线．X射线衍射测量结果表明利用该方法制备的GaN纳米线具有沿c轴方向择优生长的六角纤锌矿结构．利用扫描电子显微镜、透射电子显微镜、傅里叶红外透射谱、能量弥散谱及选区电子衍射观测并分析了样品的形貌、成分和晶格结构．研究发现ZnO层的挥发有利于Ga2O3和NH3反应合成GaN纳米线．     

图形化氧化锌纳米线的合成和场发射性能研究

通过简单的热蒸发在ITO电极上合成图形化氧化锌纳米线,利用SEM,XRD,EDX和PL光谱分析氧化锌纳米线的表面形貌、微观结构和光学特性,并测试其场发射性能。SEM表明,ZnO纳米线的直径约为100-200nm,长度大于5um,且均匀长在ITO电极表面。场发射测试表明,图形化ZnO纳米线的开启电场和阈值电场分别为1.6 V/m和4.92 V/m,在电场强度为5.38 V/m时发射电流高达 2.26 mA/cm2,经4.5h场发射测试后发射电流的浮动低于5%。低的开启电场、高的发射电流和好的稳定性表明图形化氧化锌纳米线是一种应用前景广阔的场发射材料。     

Growth and characterization of ZnO nanowires on p-type GaN

ZnO nanowires were grown by catalyst-free metal-organic vapour-phase epitaxy on top of a p-type GaN buffer. The optical properties of the ZnO nanowires were investigated by temperature-dependent and time-resolved photoluminescence and compared to those of ZnO nanowires directly grown on sapphire. The luminescence intensity decrease with temperature of the nanowires grown on GaN reveals an original behavior since it is constant over 120 K, showing the existence of strong localization centers. In addition, the temperature-dependent decay time measurements indicate a lower density of non-radiative channels for the nanowires grown on GaN.     

不同晶种上ZnO纳米线的生长及紫外光电导特性

采用射频磁控溅射法在石英衬底上沉积了AZO和ITO透明导电膜,然后采用溶液化学法以两种导电膜为晶种分别生长ZnO纳米线。利用扫描电镜和X射线衍射等测试手段对样品进行表征,进而通过一种垂直测试结构,研究其紫外光电导特性的差异。结果表明:晶种对纳米线的生长起决定性作用,只有在结晶良好并且择优取向的AZO膜上才能生长出垂直于衬底且取向一致的ZnO纳米阵列,而在ITO膜上,ZnO纳米线的取向具有很大的随机性。AZO上垂直生长的纳米线紫外响应速度较快,且呈现良好的欧姆接触特性,但两种样品恢复时间都较长,分析认为是纳米线曝光面积不同和内部的缺陷、表面态等原因造成的。