气-液-固法在半导体纳米线生长中的应用

气-液-固法(VLS)是目前生长各种准一维纳米结构的主要工艺技术.本文首先介绍了VLS的生长原理,然后以生长机制为主线,着重评论了近3-5年内它在ZnO、GaN、Si以及SiC等纳米线及其阵列合成中应用的某些新进展.最后提出了改进VLS方法的几项措施,并展望了它的今后发展趋势.     

硅纳米线的制备技术

硅纳米线作为一种新型的一维纳米材料,在纳米电子器件、光电器件及集成电路方面具有很好的应用前景.介绍了硅纳米线在制备方面的国内外研究现状与进展,重点讨论了基于金属催化气-液-固(VLS)生长机理、氧化物辅助生长机理的硅纳米线制备及模板法等制备硅纳米线的研究成果、特点及生长机理.与金属催化VLS生长机理相比,氧化物辅助生长硅纳米线不需要金属催化剂,能避免金属污染,保证了硅纳米线的纯度,因而是今后深入研究的方向.     

Si纳米线的生长机制及其研究进展

si纳米线及其阵列是近年内新发展起来的准一维半导体光电信息材料,在场效应器件、单电子存储器件、光探测器件、场发射器件、纳米传感器件和高效率发光器件以及集成技术中具有潜在的应用.本文以气-液-固(VLS)生长机制为主线,介绍与评论了近5年来Si纳米线在制备与合成技术方面所取得的一些最新进展.其主要内容包括Si纳米线的各种金属催化生长和氧化物辅助生长,最后指出了今后该研究的发展方向.     

气-固反应法合成准一维纳米结构材料的研究

综述了利用气-固反应法合成准一维纳米结构材料的研究进展,简要介绍了气-固反应法与气相法的不同点,重点讨论了用气-固反应法直接热氧化或硫化铜、铁、锌等金属以合成准一维纳米结构氧化物、硫化物的过程以及气-固反应法的生长机理,并介绍了准一维纳米结构材料的潜在应用.     

一维纳米碳在碳基体上生长的研究进展

综述了采用化学气相沉积法在各种碳质基体上生长一维纳米碳的制备方法,阐述了基体的预处理、催化剂、碳源、生长温度等各种因素对产物的影响,简要介绍了在碳基体上生长一维纳米碳的性能和应用.     

氧化铝一维纳米材料制备方法的研究进展

氧化铝一维纳米材料由于其独特的结构成为材料研究的热点之一,近年来国内外有关其制备方法的报道也相对较多.较全面地介绍了氧化铝一维纳米材料的制备方法,包括VLS法、VS法、水热法、溶胶-凝胶法和模板法等.分析了各类方法的特点,指出了制备氧化铝一维纳米材料存在的问题,并展望了其未来的发展.     

碳纳米纤维在纳米催化剂上的不同生长形态

利用纳米镍、酒石酸铜催化剂,通过碳的化学气相沉积法(CVD)分别制备出并列形态和"V"形态生长的碳纳米纤维,并通过透射电子显微镜(TEM)、扫描电子显微镜(SEM)对其进行了观察研究,发现生长在催化剂粒子上的碳纳米纤维在初始生长时的生长方向与催化剂粒子形状之间有密切关系.我们分析认为,在碳纳米纤维的生长过程中,碳在催化剂粒子中的扩散速度是控制步骤,并且决定催化剂粒子晶面上不同生长点的纤维生长速度.     

催化裂解甲烷制备-维纳米网状碳材料

通过沉淀法和相转移法的结合制备纳米催化剂.采用该催化剂催化裂解甲烷反应制备出了一维纳米网状碳材料,此类碳材料的比表面积为286m2/g.预计该材料具有良好的储氢、吸附性能.     

一维Si3N4合成的研究进展

纤维、晶须、纳米线等一维Si_3N_4材料及纳米带、纳米管、纳米环、纳米电缆等准一维Si_3N_4材料是具有优异的力学和热学性质的宽禁带半导体,在复合材料、催化、微纳器件和机电系统等方面有重要的应用价值。按形貌特征对一维Si_3N_4进行分类,概括了直接氮化法、碳热还原法、化学气相沉积法和先驱体热解法等合成方法,阐述了气-液-固、气-固、固-液-固等生长机制,详述并总结了一维Si_3N_4的研究现状,进而对其存在的问题和研究方向进行了分析和展望。     

用VLS机制制备硅纳米线的生长阶段研究

在镀Ni的Si衬底上用硅烷高温分解的方法由VLS机制制备了硅纳米线，在不同的实验条件下研究了VLS机制生长的三个阶段：结晶阶段、共熔阶段和生长阶段，特殊条件下制备的处于结晶阶段的长度仅几十纳米的硅纳米线显示硅纳米线是从催化剂颗粒中长出来的，观察到的硅纳米线的生长过程说明VLS机制在纳米尺度仍然有效，可用于各种材料纳米线的制备。     

A vapor-liquid-solid model for chemical vapor deposition growth of carbon nanotubes

Although carbon nanotubes (CNTs) with a variety of morphologies have been successfully synthesized, there is no clear physical picture of the growth process. Correspondingly, the growth mechanism is still not clear up to now. Here we suggest a VLS model for the growth process of CNTs, which involves a liquid or liquid-like state catalyst. The basic idea is that, due to the high thermal conductivity and nanometer size of the catalyst and the fast diffusion of carbon atoms in it, both the temperature and the carbon atom distribution across it are uniform. The supersaturation level can be expressed as a function of the carbon concentration and temperature, which determines the nucleation dynamics and growth kinetics. Based on this model, the growth rate equation was obtained to describe the growth kinetics of carbon nanotubes, which shows good accordance with the experimental results.     

Periodically twinned nanowires and polytypic nanobelts of ZnS: The role of mass diffusion in vapor-liquid-solid growth

There are two mass diffusion processes regarding the vapor-liquid-solid (VLS) growth of nanostructures: one is inside the catalyst droplet toward the liquid-solid interface; the other is along the side surface planes of the growing nanostructures. In this letter, microscale, modulated mass diffusion scenarios are exhibited through the synthesis of two types of ZnS nanostructures in an Au-catalyzed VLS process: periodically twinned nanowires originated from periodical fluctuation between diffusion rate inside the catalytic droplet and the growth rate on the liquid-solid interface; the formation of asymmetrically polytypic nanobelts is related to one certain side surface bounded by high surface-energy plane, which serves as a preferential diffusion direction of reactant adatoms. The results may have important impact on the understanding of the physical and chemical process of the VLS mechanism. These longitudinally and latitudinally tunable crystalline structures enrich the family of one-dimensional nano-building blocks, and may find potential applications in nanotechnology.     

On the formation of voids, etched holes, and GaO particles configuration during the nanowires growth by VLS method on GaAs substrate

The nanowires grown on GaAs semiconductor substrate play very important roles in nanoelectronics, optoelectronics, and sensors. The nanowires can be produced by many methods among the existing methods of nanowires growth on GaAs semiconductor, the vapor–liquid–solid (VLS) method appears to be simple, low cost, and popular. However, this method in practice requires further investigations concerning the growth mechanisms, size effects, and the role of Au catalyst metal diffusion, as well as the effect of technological conditions. Several undesired phenomena, which strongly influence the morphologies, features, and applications of the grown nanowires, can occur as the result of using thick Au catalyst layers, high growth temperatures, and/or small vapor volume in the closed ampoule. This paper aims to examine simultaneous formation of voids, etched holes, and GaO particles along with the nanowires grown by VLS method on GaAs substrate. As the result, typical technological conditions for the nanowires growth with better characterizations are proposed.     

气相生长纳米碳纤维的形态控制

报道了在浮动催化系统中,催化剂、促进剂以及苯/氢气比例等因素对气相生长纳米碳纤维形态的决定性作用和不同结构形态纳米碳纤维的选择生长.利用控制催化剂前体和促进剂的含量以及苯与氢气的比例等因素,制备了平直碳纳米管、弯曲碳纳米管、碳珠/纳米碳纤维、纳米碳纤维等不同结构的气相生长纳米碳纤维.实验结果表明,在浮动催化系统中,调节催化剂和促进剂的含量以及苯与氢气的摩尔比等关键性因素可以实现对气相生长纳米碳纤维形态结构的控制.     

碳热还原法合成AIN晶须及其生长机理

以Al2O3和石墨为原料，采用碳热还原法制备AIN晶须.研究了矿化剂的种类及温度等工艺对AIN晶须合成的影响结果表明，以CaF2和B2O3为矿化剂的AIN品须是以VLS机制生长的，高温下VLS机制可以转变为VS机制，同时存在两维成核及螺位错生长过程，晶须生长方向大多呈{101n}，（n=0，1，2，3）及{121m}，（m=0，1；2）的晶面生长     

用不同催化剂制备纳米炭纤维的生长机理

研究了以Fe或Ni的催化剂采用有机物催化热解法制备的纳米炭纤维的形貌和结构。发现在两种情况下纳米炭纤维的生长机理安全不同;以Fe为催化剂纳米炭纤维基本符合气-液-固（VLS）催化生长机制（也称溶解扩散机制）,而以Ni为催化剂纳米炭纤维则符合固相催化生长机制。     

合成陨硫铁表面的炭丝和炭球

采用电弧放电蒸发和沉淀技术，使用石墨和黄铁矿为原料，在合成的陨硫铁球粒表面发现有空心球体和丝状物质。经ＳＥＭ、ＴＥＭ和ＥＤＸ的研究，证实它们是纳米级的炭球和炭丝。讨论了用电弧放电法合成陨硫铁过程中，天然矿物黄铁矿对炭丝、炭球和纳米碳管形成的催化作用及其关系     

Control of lateral dimension in metal-catalyzed germanium nanowire growth: usage of carbon sheath

We report on the catalytic growth of thin carbon sheathed single crystal germanium nanowires (GeNWs), which can solve the obstacles that have disturbed a wide range of applications of GeNWs. Single crystal Ge NW core and amorphous carbon sheath are simultaneously grown via vapor-liquid-solid (VLS) process. The carbon sheath completely blocks unintentional vapor deposition on NW surface, thus ensuring highly uniform diameter, dopant distribution, and electrical conductivity along the entire NW length. Furthermore, the sheath not only inhibits metal diffusion but also improves the chemical stability of GeNWs at even high temperatures.     

Controlling heterojunction abruptness in VLS-grown semiconductor nanowires via in situ catalyst alloying

For advanced device applications, increasing the compositional abruptness of axial heterostructured and modulation doped nanowires is critical for optimizing performance. For nanowires grown from metal catalysts, the transition region width is dictated by the solute solubility within the catalyst. For example, as a result of the relatively high solubility of Si and Ge in liquid Au for vapor-liquid-solid (VLS) grown nanowires, the transition region width between an axial Si-Ge heterojunction is typically on the order of the nanowire diameter. When the solute solubility in the catalyst is lowered, the heterojunction width can be made sharper. Here we show for the first time the systematic increase in interface sharpness between axial Ge-Si heterojunction nanowires grown by the VLS growth method using a Au-Ga alloy catalyst. Through in situ tailoring of the catalyst composition using trimethylgallium, the Ge-Si heterojunction width is systematically controlled by tuning the semiconductor solubility within a metal Au-Ga alloy catalyst. The present approach of alloying to control solute solubilities in the liquid catalyst may be extended to increasing the sharpness of axial dopant profiles, for example, in Si-Ge pn-heterojunction nanowires which is important for such applications as nanowire tunnel field effect transistors or in Si pn-junction nanowires.     

Vapor-solid-solid growth of crystalline silicon nanowires using anodic aluminum oxide template

Silicon nanowires (SiNWs) were grown at low temperatures close to metal silicon eutectic point on a silicon substrate using gold catalyst coupled with assistance of the aluminum anodic oxide template. Either a vapor-solid-solid (VSS) growth process below metal silicon eutectic temperature or a vapor-liquid-solid (VLS) process at slightly higher temperatures was observed. The transmission electron microscopy coupled with both the X-ray energy dispersive spectroscopy and the selected area electron diffraction was adopted to characterize the SiNWs. Although the mechanism triggering the VSS process is still not clear, both the geometric and morphological characteristics of the SiNWs grown by the VSS process are discussed and compared with the SiNWs grown by the VLS process. The VSS SiNWs have a much slower growth rate (less than 100 nm/h), a smaller and more uniform diameter (in the range of 15.22 nm) due to a much slower rate of silicon diffusion and much smaller amount of silicon (6.8 wt.%) dissolved in the solid nanocatalyst.