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1、AlignedAligned ZnOZnO NanorodNanorod ArraysArrays GrownGrown DirectlyDirectly onon ZincZinc FoilsFoils andand ZincZinc SpheresSpheres byby a a Low-TemperatureLow-Temperature OxidizationOxidization MethodMethod用低温氧化方法直接在锌箔和锌用低温氧化方法直接在锌箔和锌颗粒培养排列有序的氧化锌纳米颗粒培养排列有序的氧化锌纳米棒阵列棒阵列ABSTRACTABSTRACT Vertically a
2、ligned, dense ZnO nanorod arrays were grown directly on zinc foils by a catalyst-free,low-temperature (450_500 C) oxidization method. The zinc foils remain conductive even after the growth of ZnOnanorods on its surface. The success of this synthesis largely relies on the level of control over oxygen
3、 introduction.By replacing zinc foils with zinc microspheres, unique and sophisticated urchin-like ZnO nanorod assemblies can be readily obtained. 摘要摘要 垂直有序密排的氧化锌纳米棒阵列直接通垂直有序密排的氧化锌纳米棒阵列直接通 过无催化剂，低温（过无催化剂，低温（450500 C）氧化法在）氧化法在 锌箔上生长。在氧化锌纳米棒生长在它表锌箔上生长。在氧化锌纳米棒生长在它表 面上后，锌箔仍然具有导电性。合成能够面上后，锌箔仍然具有导电性。合成能够
4、成功在很大程度上依赖于对引导氧气控制成功在很大程度上依赖于对引导氧气控制 程度。程度。 通过将锌箔更换成锌微球，独特和复杂的通过将锌箔更换成锌微球，独特和复杂的 海胆样氧化锌纳米棒组件很容易获得。海胆样氧化锌纳米棒组件很容易获得。Z Zinc oxide (ZnO) is recognized as oneof the most important photonic materials for applications in the blue_ultraviolet region owing to its direct wide band gap (_3.37 eV) and large ex
5、citation binding energy (60 meV at room temperature).Stimulated by the recent discovery of belt like morphology and the realization of room-temperature UV lasing from ZnO nanowires,ZnO nanostructures in the form of nanorods, nanowires, and nanobelts have attracted a great deal of attention from the
6、research community. Especially, substantial effort has been devoted to the fabrication of vertically aligned ZnO nanowire arrays because these arrays demonstrated superior optical and field emission properties that make them promising candidates for applications in UV lasers, light-emitting diodes (
7、LED),solar cells, and field emission displays. To fabricate vertically aligned ZnO nanorod arrays, three main techniques were usually used so far. The first technique is based on the well-known vapor_liquid_solid (VLS) growth mechanism,10 in which gold nanoparticles were used as the catalyst to dire
8、ct the nanowire growth, a-plane sapphire which has perfect lattice matchup with ZnO c plane was used as the growth substrates, and the growth was conducted at relatively high temperatures of 由于其直宽禁带和大的激励结合能，氧化锌是公认的由于其直宽禁带和大的激励结合能，氧化锌是公认的应用于蓝紫外地区最重要的光子材料之一应用于蓝紫外地区最重要的光子材料之一,由于带状由于带状形态发现的促进和室温紫外激光发射的实
9、现，氧化锌形态发现的促进和室温紫外激光发射的实现，氧化锌纳米线，以纳米棒，纳米线，和纳米带形式存在的纳纳米线，以纳米棒，纳米线，和纳米带形式存在的纳米氧化锌吸引了研究机构大量的注意力。尤其是，大米氧化锌吸引了研究机构大量的注意力。尤其是，大量努力已投入垂直有序排列的氧化锌纳米线阵列的制量努力已投入垂直有序排列的氧化锌纳米线阵列的制备中，因为这些阵列显示优越的光学和场发射性能，备中，因为这些阵列显示优越的光学和场发射性能，使他们有望应用于紫外激光器，发光二极管（发光二使他们有望应用于紫外激光器，发光二极管（发光二极管），太阳能电池，和极管），太阳能电池，和led。为了制造垂直有序排。为了制造垂直
10、有序排列氧化锌纳米棒阵列，至今为止三个主要的技术通常列氧化锌纳米棒阵列，至今为止三个主要的技术通常被被使用。第一种技术是在著名的气液固增长机制，其中使用。第一种技术是在著名的气液固增长机制，其中黄金纳米粒子被用作催化剂引导纳米线的生长，蓝宝黄金纳米粒子被用作催化剂引导纳米线的生长，蓝宝石状晶面具有完美的晶格匹配，它用氧化锌晶面被用石状晶面具有完美的晶格匹配，它用氧化锌晶面被用作生长基质，并且生长在相对温度高作生长基质，并且生长在相对温度高850_1000c的的情况下进行情况下进行The second techniqueis metal_organic chemical vapordeposit
11、ion(MOCVD), in whichmetal_organic zincprecursor (diethyl zinc,Et2Zn) was used as thezinc source andaligned ZnO nanowireswere epitaxiallysubstrates (or silicon wafers) at 400_500 C in a lowpressure MOCVD syste m.13_15第二种方法是金属有机化学气相沉积，其第二种方法是金属有机化学气相沉积，其中金属有机锌前体被用作锌源，有序排列的纳米氧化中金属有机锌前体被用作锌源，有序排列的纳米氧化锌锌
12、在在400500 时在低压有机金属化学气相时在低压有机金属化学气相 沉积技术培养基（或硅晶片）沉积技术培养基（或硅晶片）外延生长外延生长The third technique isbased on solution method, in which ZnO nanocrystals(5_10 nm in diameter) were coated on a substrate (e.g.,silicon wafer) to act as the seeds followed by hydrothermalZnO growth in an aqueous solution of zinc nit
13、ratehydrate at 90 C.The solution process is favored forits low cost and the ease of scale-up (arrays on four inchsilicon wafer and two-inch plastic substrates werereported17) but suffers from the low crystalline qualitycompared with the VLS- and MOCVD-grown nanowires.In addition, some electrical and
14、 optical applications ofthe above-mentioned ZnO nanowires remain constrainedby the expensive and/or nonconducting substrates(such as sapphire).In this paper, we report the controlled growth of verticallyaligned ZnO nanorod arrays on metal zinc foils(10 cm long by 1 cm wide) by a catalyst-free, lowte
15、mperature(450_500 C) oxidization method. Moreamazingly, by substituting the flat zinc foils with highlycurved zinc microspheres, sophisticated urchin-likeZnO nanorod superstructures, such as ZnO nanorodballs/bowls whose surfaces were covered with dense,uniform ZnO nanorods, can be readily obtained.
16、第三种是基于溶液的方法，其中纳米氧化第三种是基于溶液的方法，其中纳米氧化 锌（锌（5_10纳米直径）被涂覆在衬底（例如，纳米直径）被涂覆在衬底（例如， 硅晶片）来充当种子，随后在硅晶片）来充当种子，随后在90 c时将水时将水 热氧化锌生长在锌盐水合物溶液中热氧化锌生长在锌盐水合物溶液中.溶液生溶液生 长过程成本低，易于规模化（报道的四英长过程成本低，易于规模化（报道的四英 寸硅晶片阵列和寸硅晶片阵列和2寸塑料衬底）备受青睐，寸塑料衬底）备受青睐， 但与气液固和金属有机化学沉积法制造的但与气液固和金属有机化学沉积法制造的纳米线相比，其结晶度低。纳米线相比，其结晶度低。 此外，上述提及的的氧化锌纳米线一些在此外，上述提及的的氧化锌纳米线一些在 电光学上的应用仍然是受昂贵和电光学上的应用仍然是受昂贵和/或不导电或不导电 衬底制约（如蓝宝石）。在本文中，我们衬底制约（如蓝宝石）。在本文中，我们 报告了，通过无催化剂，低温（报告了，通过无催化剂，低温（450_500 丙）氧化法，在金属锌箔（丙）氧化法，在金属锌箔（1
