真空镀膜法制备纳米银颗粒膜局域表面等离激元共振特性的研究

本文研究用真空蒸发和真空溅射镀膜方法制备的纳米银颗粒膜的局域表面等离激元特性,并根据不同方法制备的纳米银颗粒局域表面等离激元特性的差异,研究其增强分子对可见光的吸收,增强拉曼散射和增强光催化的作用。本研究将真空镀膜应用到纳米技术和表面等离激元领域,拓展了真空镀膜的应用范围,同时为纳米颗粒的制备及其局域表面等离激元特性的研究提供了一种独特的方法。     

一种太阳电池纳米陷光结构的制备方法

提出了一种利用石墨纳米颗粒作为掩膜,通过金属辅助刻蚀来制备具有低反射率的太阳电池纳米陷光结构的方法。用该方法制得了一种表面覆盖有纳米线和纳米孔的太阳电池纳米陷光结构。结合金属辅助刻蚀的机制和这种陷光结构的形成原理,分析了石墨纳米颗粒和H2O2浓度对陷光结构形貌的影响,并讨论了陷光结构的形貌对样品陷光性能的影响。最后,制得了在300～1100nm波长范围内平均反射率仅为3.6%的太阳电池陷光层。     

纳米孔氮化镓材料的制备和研究

介绍了一种在氮化镓外延片表面制备得到孔径为纳米量级的多孔结构的工艺.用电化学方法制备出孔径为纳米量级的多孔阳极氧化铝模板作为掩模,经过电感耦合等离子体(ICP)刻蚀制备得到纳米孔氮化镓材料.孔的大小和孔间距可以通过改变阳极氧化条件来控制,改变刻蚀时间可以控制孔深.刻蚀所用气体为氯气和惰性气体的混合物.扫描电镜照片显示,掩模图形能够很好地转移到GaN材料上.刻蚀后的材料经光荧光谱(PL Spectra)谱和Raman散射谱测试,显示出良好的光学特性,并在一定程度上释放了应力.     

金属辅助化学刻蚀法制备硅纳米线的研究进展

硅纳米线(Si NWs)由于具有独特的一维结构、热电导率、光电性质、电化学性能等特点,被广泛应用于热电与传感器件、光电子元器件、太阳能电池、锂离子电池等领域。金属辅助化学刻蚀法(MACE)是制备Si NWs的常用方法之一,具有操作简便、设备简单、成本低廉和高效等优点,可大规模商业化应用,因而近年来被广泛研究。金属辅助化学刻蚀制备硅纳米线的过程可以分为两步:首先在洁净的硅衬底表面沉积一层金属(Ag、Au、Pt等)纳米颗粒,以催化、氧化它附近的硅原子;然后利用HF溶解氧化层,从而对硅晶片进行刻蚀,形成纳米线阵列。然而,这种简单高效的制备硅纳米线的方法存在一些难以控制的缺点:(1)金属纳米颗粒聚集、相连后造成Si NWs之间的缝隙比较大,从而导致Si NWs密度较低;(2)由于金属纳米颗粒沉积的随机性,在硅晶片表面分布不均匀,不仅导致刻蚀出的纳米线直径范围(50～200 nm)较宽,而且使制得的纳米线阵列排列无序且间距不易调控;(3)当刻蚀出的硅纳米线太长时,范德华力等作用会造成纳米线顶端出现严重的团簇现象。针对常规法存在的一些问题以及不同的器件对硅纳米线的形貌、类型和直径等的要求,近年来的研究主要集中在如何减少纳米线顶端团簇、调控纳米表面粗糙度和直径、低成本制备有序硅纳米线等方面。目前一些改进常规金属辅助化学刻蚀的方法取得了进展,比如:(1)用酸溶液或UV/Ozone对硅晶片预处理,在表面形成氧化层,可以使纳米线的均匀性得到改善并增大其密度(从18%提高到38%);(2)使用物理气相沉积法在硅晶片表面沉积一层金属纳米薄膜,然后再刻蚀,这种方法能够减少纳米线顶端团簇和有效调控纳米线直径;(3)利用模板法(聚苯乙烯小球模板、氧化铝模板、二氧化硅模板和光刻胶模板等)可以制备出有序的硅纳米线阵列。本课题组用离子束刻蚀的方法制备了直径范围可以控制在30～90 nm的聚苯乙烯小球模板,为小尺寸有序硅纳米线的制备打下了坚实的基础。本文简要介绍了常规MACE的原理和制备流程,总结了硅晶片的类型、刻蚀溶液的浓度、温度和刻蚀时间等因素对Si NWs形貌、尺度、表面粗糙度、刻蚀方向以及刻蚀速率的影响,用相关的机制解释了H2O2过量时刻蚀路径偏离垂直方向的机理以及刻蚀速率随溶液浓度变化的原因,重点综述了氧化层预处理、物理法沉积贵金属纳米薄膜、退火处理和模板法等改进方法在减少纳米线顶部团簇、改善均匀性、制备有序且直径和间距可控纳米线中的研究进展。     

银纳米颗粒的化学还原法制备简介及其应用

银纳米颗粒的光学性能,如局域表面等离子体共振(Localized Surface Plasmon Resonance,LSPR)特性可通过其形貌、尺寸、外部介电环境的调控而实现变化。不同形貌的银纳米颗粒具有强弱不同的局域表面等离子体共振效应,从而表现出独特的光学性质。综述了利用化学还原法制备不同形貌的银纳米颗粒,主要包括柠檬酸钠还原法、多元醇法以及种子介导生长法,分析了这3种合成方法的机理和特点,将近年来不同形貌银纳米颗粒的研究进展进行了综述。最后介绍了不同形貌银纳米颗粒在表面增强拉曼散射(Surface-Enhanced Roman scattering,SERS)基底、催化、抗菌领域上的应用研究,并总结和展望了银纳米颗粒在合成和相关应用领域的发展前景。     

Ag/石墨烯复合材料的制备及其对邻氨基苯甲酸甲酯的SERS效应

以还原的氧化石墨烯(r-GO)为前驱物,采用紫外光照还原和水合肼还原两个不同的合成过程,简单制得了没有有机分子存在的Ag沉积r-GO纳米复合材料,其中被还原的Ag呈颗粒状沉积在r-GO片层表面。由于紫外光照还原反应速率较慢,制得的Ag颗粒分散性相对较好,尺寸分布较窄,粒径主要处在25~80 nm间;而用水合肼还原,因反应速率较快,获得的Ag颗粒团聚较严重,尺寸分布较宽,粒径主要处在20~130 nm间。在此基础上,以一种香料邻氨基苯甲酸甲酯为标记分子,在波长为785 nm激光激发下,对获得的一系列含Ag复合材料进行了表面增强Raman散射光谱(SERS)测试,结果表明,它们具有非常高的SERS效应,增强因子在108附近,其中,用水合肼还原制得的复合材料SERS效应更加明显。     

银纳米球阵列的局域表面等离子体特性研究北大核心CSCD

基于金属纳米颗粒的光散射理论,利用时域有限差分法计算了Ag纳米球阵列不同结构参数下的散射光谱、吸收光谱及散射效率,分析了Ag纳米球阵列在共振波长下的极化电场和极化电荷分布情况,讨论了Ag纳米球阵列的局域表面等离子体(LSP)对GaN基LED发光效率增加的机理。结果表明,随着间距的减小,Ag纳米球阵列LSP的散射峰逐渐呈双模分布,且位于长波段的散射峰蓝移;随着Ag纳米球直径的增大,LSP的共振波长红移且散射效率增大。当LSP的共振波长与LED辐射光波长相匹配时,Ag纳米球阵列的LSP与LED辐射光发生耦合作用,在一定条件下,部分耦合的能量辐射到自由空间,增大LED的内量子效率。     

基于柔性掩膜的高可靠性玻璃喷砂微加工工艺

喷砂是一种高效率的表面加工技术,将其应用于微加工领域可以实现对玻璃、硅和陶瓷等脆性材料的选择性刻蚀.本文着重探讨了掩膜性质及刻蚀条件对喷砂微加工刻蚀效率及刻蚀形貌的影响.实验中对柔性聚二甲基硅氧烷(PDMS)掩膜微结构的制备方法进行了改良,即借助精密切削工艺实现PDMS/SU-8微结构边界精确互补成形,制备了可以满足选择性刻蚀要求的掩膜结构.同时改变实验条件,研究了掩膜开口尺寸、压缩空气压强以及砂材粒径对喷砂速率及刻蚀形貌的影响.结果表明:适当增大压缩空气气压有助于待刻蚀材料从塑性到脆性的转变,刻蚀速率有明显提高.而将砂材粒径从30μm减小至20μm,可以改善成形形貌.初步研究结果表明,文中提出的玻璃喷砂微加工方法能够满足深度为500μm的玻璃通孔阵列的刻蚀要求.     

分子动力学模拟样品温度对F刻蚀SiC的影响

利用分子动力学模拟方法研究了在低能F原子刻蚀SiC表面过程中样品温度对刻蚀的影响。由模拟结果可知,随着温度的升高,F在样品表面的沉积量和散射量均呈下降趋势,而发生溅射的F的量和与样品作用生成挥发物质的F的量逐渐增加。Si的刻蚀量均随着温度的升高而升高。样品中Si原子的刻蚀主要是通过生成SiF4得以实现的,C原子的刻蚀主要是通过生成CFx(x=1～3)等挥发性物质实现的。     

Ag-TiO_2纳米纤维的制备及其光电转换性能研究

利用静电纺丝技术制备尺寸均一、性能稳定的Ag-TiO_2复合纳米纤维。结合了纳米银颗粒的表面等离激元共振效应,克服了TiO_2材料比表面积小、光生电子与空穴复合几率高以及对光生载流子量子化效率低的缺点,并且Ag纳米颗粒在复合材料中有很好的可调节性,同时这种材料的制备工艺简单、易重复。采用扫描电子显微镜(SEM),X射线衍射(XRD)对Ag-TiO_2复合纤维进行了表征,结果证明产物为Ag-TiO_2复合纳米纤维,且纤维分散性好、长径比大,同时掺杂均匀。相比较于TiO_2纳米纤维,Ag-TiO_2纳米纤维的光电转换性能明显提高。此外研究了Ag掺杂量对复合材料光电转换效果的影响,结果表明,掺杂10wt%Ag的Ag-TiO_2复合纳米纤维光电转换效率最高。     

Fabrication and optical property of vertically-aligned ZnO/Si double nanostructures

We fabricated the vertically-aligned zinc oxide (ZnO)/silicon (Si) double nanostructures by simple processes using the metal-assisted chemical etching and a subsequent hydrothermal synthesis, and their optical property was investigated. For efficient antireflection characteristics, Si nanostructures were optimized by changing the size of the dewetted silver (Ag) at different etching times. The thermally dewetted Ag nanoparticles or semi-island films as metal catalysts were controlled by the Ag film thickness and dewetting temperature. To form the ZnO/Si double nanostructures, ZnO nanorods were synthesized on the chemically etched Si nanostructures using a thin sputtered ZnO seed layer. The grown ZnO nanorod arrays (NRAs) exhibited good crystallinity and further reduced the surface reflection due to their antireflective property. The ZnO/Si double nanostructures showed the increased peak intensity of X-ray diffraction as well as the significantly reduced solar weight reflectance of 6.05% compared to 11.71% in the ZnO NRAs on the flat Si substrate. Also, the enhanced antireflection property of ZnO/Si double nanostructures was theoretically analyzed by performing the rigorous coupled wave analysis simulation.     

直流电化学腐蚀法制备多孔硅的表面形貌研究

采用正交实验，直流电化学腐蚀法制备多孔硅。用原子力显微镜对表面进行观察，研究电化学腐蚀参数对其表面形貌的影响。氢氟酸浓度（CHF）升高，使临界电流密度（JPS）增大，有利于多孔硅的形成。电流密度（J）增大，多孔硅的孔隙率和孔径随之变大，而其纳米粒径将变小。腐蚀时间（t）越长，孔径越大，孔越深。     

二氧化硅纳米颗粒的反应离子刻蚀及其在硅纳米针尖制备中的应用

系统地研究了硅衬底上二氧化硅纳米颗粒的反应离子刻蚀（R IE）过程,并在此基础上制备了可用于场发射的硅纳米针尖阵列.首先,采用改进的蒸发法在硅衬底上实现二氧化硅纳米颗粒的单层密排结构,再采用典型的刻蚀二氧化硅的RIE技术同时刻蚀硅衬底和二氧化硅纳米颗粒,在对纳米颗粒尺寸随刻蚀进行而改变的电镜照片分析的基础上,获得了相应的二氧化硅纳米颗粒刻蚀模型,计算得到横向和纵向的刻蚀速率;当刻蚀后的二氧化硅纳米颗粒从衬底上脱落后,进一步对硅衬底的刻蚀可以得到锐利的硅纳米针尖阵列,初步的实验结果表明,所制备的硅纳米针尖具有较好的场发射特性.     

Broadband and wide-angle antireflection subwavelength structures of Si by inductively coupled plasma etching using dewetted nanopatterns of Au thin films as masks

We report the broadband and wide-angle antireflection subwavelength structures (SWSs) on silicon (Si) substrate by inductively coupled plasma (ICP) etching using gold (Au) nanopatterns as etch masks. The reflectance depends strongly on the etched profile of Si SWSs which is influenced by both thermal dewetting and etching conditions. The size, shape, and array geometry of nano-sized patterns, which are produced via the thermal dewetting of Au thin films, are optimized under proper heat treatment. The etched depth and shape of Si nano tips are controlled additionally by ICP power, thus achieving the efficient antireflection characteristics. The optimized Si SWS with the tapered structure and sharp tips at high ICP power leads to a significantly low reflectance value of < 1% at wavelengths of 350-1100 nm. Furthermore, it exhibits a wide-angle antireflection property of < 7.5% at incident angles of 8-70° over a wide wavelength range of 300-1100 nm.     

Formation and mechanism of silicon nanostructures by Ni-assisted etching

Instead of noble metal like Pt, Au and Ag, cheap Ni nanoparticles (Ni NPs) were used to fabricate silicon nanostructures. Ni was found to be etched off during the etching process, while forming silicon nanostructures with very low reflectance of 1.59 % from 400 to 900 nm. The formation mechanism of silicon nanostructures by Ni-assisted etching was presented from the point of view of the low electronegativity of Ni. The Ni NPs were found being etched off during the assisted etching process, which implies that the transfer rate of electrons from Si to Ni is slower than that from Ni to O^? in the case of using Ni as assisted metal. The reason of sparser and deeper silicon nanostructures etched in lower H₂O₂ concentration solution is that the Ni NPs can be lasted for longer time in the etching solution with lower H₂O₂ concentration so that more silicon atoms will be oxidized and then removed for those under Ni NPs due to the hole transfer and those where uncovered by Ni NPs due to the hole diffusion.     

Simultaneous Fabrication of Very High Aspect Ratio Positive Nano‐ to Milliscale Structures

A simple and inexpensive technique for the simultaneous fabrication of positive (i.e., protruding), very high aspect (>10) ratio nanostructures together with micro‐ or millistructures is developed. The method involves using residual patterns of thin‐film over‐etching (RPTO) to produce sub‐micro‐/nanoscale features. The residual thin‐film nanopattern is used as an etching mask for Si deep reactive ion etching. The etched Si structures are further reduced in size by Si thermal oxidation to produce amorphous SiO₂, which is subsequently etched away by HF. Two arrays of positive Si nanowalls are demonstrated with this combined RPTO‐SiO₂‐HF technique. One array has a feature size of 150 nm and an aspect ratio of 26.7 and another has a feature size of 50 nm and an aspect ratio of 15. No other parallel reduction technique can achieve such a very high aspect ratio for 50‐nm‐wide nanowalls. As a demonstration of the technique to simultaneously achieve nano‐ and milliscale features, a simple Si nanofluidic master mold with positive features with dimensions varying continuously from 1 mm to 200 nm and a highest aspect ratio of 6.75 is fabricated; the narrow 200‐nm section is 4.5 mm long. This Si master mold is then used as a mold for UV embossing. The embossed open channels are then closed by a cover with glue bonding. A high aspect ratio is necessary to produce unblocked closed channels after the cover bonding process of the nanofluidic chip. The combined method of RPTO, Si thermal oxidation, and HF etching can be used to make complex nanofluidic systems and nano‐/micro‐/millistructures for diverse applications.     

Bulk Micromachining of Si by Metal‐assisted Chemical Etching

Bulk micromachining of Si is demonstrated by the well‐known metal‐assisted chemical etching (MaCE). Si microstructures, having lateral dimension from 5 μm up to millimeters, are successfully sculpted deeply into Si substrate, as deep as >100 μm. The key ingredient of this success is found to be the optimizations of catalyst metal type and its morphology. Combining the respective advantages of Ag and Au in the MaCE as a Ag/Au bilayer configuration leads to quite stable etch reaction upon a prolonged etch duration up to >5 h. Further, the permeable nature of the optimized Ag/Au bilayer metal catalyst enables the etching of pattern features having very large lateral dimension. Problems such as the generation of micro/nanostructures and chemical attacks on the top of pattern surface are successfully overcome by process optimizations such as post‐partum sonication treatment and etchant formulation control. The method can also be successful to vertical micromachining of Si substrate having other crystal orientations than Si(100), such as Si(110) and Si(111). The simple, easy, and low‐cost nature of present approach may be a great help in bulk micromachining of Si for various applications such as microelectromechanical system (MEMS), micro total analysis system (μTAS), and so forth.     

Blue luminescence from porous layers produced by metal-assisted chemical etching on low-doped silicon

Photoluminescent porous layers were formed on highly resistive p-type silicon by a metal-assisted chemical etching method using K₂Cr₂O₇ as an oxidizing agent. A thin layer of Ag is deposited on the (1 0 0) Si surface prior to immersion in a solution of HF and K₂Cr₂O₇. The morphology of the porous silicon (PS) layer formed by this method as a function of etching time was investigated by scanning electron microscopy (SEM). It shows that the surface is formed by macropores filled with microporous silicon. The porous layers were characterized by backscattering spectrometry (BS) as a function of etching time in random and channelling mode. Channelling spectra show that the porous layer remains crystalline after etching. On the other hand, random and channelling spectra show that the deposited silver diffuses into the pore. Luminescence from metal-assisted chemically etched layers was measured. It was found that the PL intensity increases with increasing etching time. This behaviour is attributed to increase of the density of the silicon nanostructure. Finally, the PL spectra show two peaks of emission at 450 and 600 nm.     

Hybrid Anodic and Metal‐Assisted Chemical Etching Method Enabling Fabrication of Silicon Carbide Nanowires

Silicon carbide (SiC) is one of the most important third‐generation semiconductor materials. However, the chemical robustness of SiC makes it very difficult to process, and only very limited methods are available to fabricate nanostructures on SiC. In this work, a hybrid anodic and metal‐assisted chemical etching (MACE) method is proposed to fabricate SiC nanowires based on wet etching approaches at room temperature and under atmospheric pressure. Through investigations of the etching mechanism and optimal etching conditions, it is found that the metal component plays at least two key roles in the process, i.e., acting as a catalyst to produce hole carriers and introducing band bending in SiC to accumulate sufficient holes for etching. Through the combined anodic and MACE process the required electrical bias is greatly lowered (3.5 V for etching SiC and 7.5 V for creating SiC nanowires) while enhancing the etching efficiency. Furthermore, it is demonstrated that by tuning the etching electrical bias and time, various nanostructures can be obtained and the diameters of the obtained pores and nanowires can range from tens to hundreds of nanometers. This facile method may provide a feasible and economical way to fabricate SiC nanowires and nanostructures for broad applications.     

MEMS压印模板制作的刻蚀机理及尺寸控制方法

为了提高基于湿法刻蚀压印模板制作工艺中刻蚀图形尺寸的控制精度,研究了玻璃湿法刻蚀的反应动力学过程,得到刻蚀剂中（HF）2为决定反应速率的主要活性成分的结论;结合实验建立了合理的刻蚀速率模型．采用不同氢氟酸浓度的刻蚀液进行了实验,实测刻蚀速率与理论计算数值的对比结果表明模型预测精度达到96％以上．基于该模型刻蚀深度确定刻蚀时间进行了压印模板制作的实验,制作了图形特征尺寸为15μm、刻蚀深度为8μm的压印模板．对模板图形的测量结果表明,通过该模型预测的尺寸误差仅为0．05μm．