多孔硅纳向分辨拉曼及光致发光研究

运用高灵敏度的共焦显微拉曼系统研究了多孔硅在纵的拉曼效应和光致发光的性质。研究结果表明多孔硅在形成的初期和后的反应机制不相同。反应初期,外表面的颗粒尺寸比内同大,而经过长时间刻蚀而获得得的多孔硅,其相表面颗粒尺寸比 小。我们认为反应的初期主要表面不均匀电场的影响,而随着表面多孔层的增厚和颗粒的细化,刻蚀反应逐渐变成受传质过程和量子尺寸约束的控制。     

多孔硅的拉曼光谱研究

本文研究了多孔硅的拉曼光谱随激发激光功率的变化 ,发现当激发光的功率较低时 ,多孔硅的拉曼光谱在 5 2 0cm- 1附近为一单峰。随着激光功率的增加 ,该单峰向低波数移动且半高宽增大 ,当继续增大激光功率时 ,该单峰分裂为双峰 ,位于低波数一侧的拉曼峰随着激光功率的增大而进一步向低波数移动。多孔硅的拉曼光谱随着激光功率的变化是一个可逆的过程。这一结果表明 ,低波数拉曼峰的位置既不能作为多孔硅颗粒尺寸的量度 ,也不能只把低波数的拉曼峰作为多孔硅的特征。我们认为激光诱导多孔硅中LO和TO声子模的简并解除是观察到双峰的主要原因。     

硅刻蚀现场研究的表面拉曼光谱技术

通过对拉曼谱仪和电极粗糙方法的优化,本文将表面拉曼光谱技术拓宽到了半导体硅电极表面的现场研究,文中观测了不同粗糙时间对硅刻蚀的影响,并实时考察了硅氢表面在开路电位下的氧化过程,实验结果表明,在以ＨＦ为主的湿法刻蚀中,硅表面的悬挂键主要被Ｈ而不是被Ｆ取代。     

多孔硅表面Ag层对吸附其上的若丹明B染料分子表面增强Raman散射的影响

采用溶液电镀方法在多孔硅表面制备纳米尺寸的银颗粒,测量了不同镀银多孔硅表面吸附的ＲｈＢ染料分子以及固态的ＲｈＢ染料的Ｒａｍａｎ散射谱。在相同的激发强度下,固态ＲｈＢ染料的Ｒａｍａｎ散射最弱,而镀银的多孔硅表面具有明显的增强效果（～１０＾４）。     

制备集成微通道的表面增强拉曼基底

本文介绍一种集成微通道的表面增强拉曼基底。采用湿法刻蚀方法在硅片上形成微通道,然后电子束蒸发沉积金薄膜,最后在300℃温度下高真空退火30分钟,使微通道内形成均匀且高密度的金纳米颗粒结构。用场发射扫描电子显微镜(SEM)对基底表面进行表征发现:金膜厚度对基底的表面形貌影响很大,5nm厚的金膜在退火后形成了均匀的高密度的纳米颗粒结构,而10nm厚的金膜退火后没有得到高密度纳米颗粒结构。用10-6 M的罗丹明6G作为探测分子进行拉曼实验测试结果同样表明:5nm厚的金膜退火后形成高密度的金纳米颗粒显著地增强了R6G拉曼信号。同时,对比了宽度分别为25、60、110!m三种尺寸的微通道的基底表面形貌和拉曼增强效应,微通道尺寸对表面形貌和拉曼增强效应影响均很小。     

不同退火温度的ZrO_2 纳米颗粒光学声子和表面吸附分子的拉曼散射研究(英文)

本文对晶粒尺寸在5nm 1 μm范围的纯ZrO2 纳米颗粒进行了拉曼散射研究。除了ZrO2 本征拉曼振动峰外,还有几个新的拉曼振动模式被观察到。我们的结果显示当纳米颗粒尺寸减少时,纳米ZrO2 颗粒的体相特征拉曼峰变弱,而由缺陷,表面和颗粒尺寸引起的相关效应呈强势。晶粒尺寸在1 5纳米左右是引起体相拉曼光谱变化的临界尺寸。晶粒尺寸在1 5纳米以下,其体相拉曼峰发生宽化和峰位移动,以及分别出现在位于1 0 40cm- 1的表面振动峰和1 4个较弱的二阶振动模式。这些结果反映了纳米颗粒的微结构变化与颗粒尺寸和表面效应以及它们之间相互作用的信息     

基于直接胶体晶体刻蚀技术的高度有序纳米硅阵列的尺寸及形貌控制

以自组装单层胶体小球阵列为掩模，采用直接胶体晶体刻蚀技术在硅表面制备二维有序尺寸可控的纳米结构.在样品制备过程中，首先通过自组装法在硅表面制备了直径200nm的单层聚苯乙烯(PS)胶体小球的二维有序阵列；然后对样品直接进行反应离子刻蚀(RIE)，以氧气为气源，利用氧等离子体对聚苯乙烯小球和对硅的选择性刻蚀作用，通过改变刻蚀时间，制备出不同尺寸的PS胶体小球的有序单层阵列；接着以此二维PS胶体单层膜为掩模，以四氟化碳为气源对样品进行刻蚀；最后去除胶体球后得到二维有序的硅柱阵列.SEM和AFM的测量结果表明：改变氧等离子体对胶体球的刻蚀时间和四氟化碳对硅的刻蚀时间，可以控制硅柱的尺寸以及形貌，而硅柱阵列的周期取决于原始胶体球的直径. 关键词： 胶体晶体刻蚀 纳米硅柱阵列     

多孔硅银淀积表面RhB染料分子的表面增强Raman散射

我们采用多孔硅和多孔硅银淀积表面作为衬底研究了ＲｈＢ染料分子的表面增强Ｒａ ｍａｎ散射。在多孔硅表面,ＲｈＢ染料分子的Ｒａｍａｎ散射有大约１０倍的表面增强效果;而在多孔硅的银淀积表面,表现出超过１０４表面增强。通过多孔硅表面银颗粒对ＲｈＢ染料分子荧光的抑制和对Ｒａｍａｎ散射的表面增强,我们获得了谱峰清晰的ＲｈＢ染料分子Ｒａｍａｎ散射谱     

不同晶粒尺寸SnO2纳米粒子的拉曼光谱研究

对晶粒尺寸在4-80 nm范围的纯SnO2纳米颗粒进行了拉曼散射研究.除了SnO2 本征拉曼振动峰外,还有几个新的拉曼振动峰和波长在700 nm左右的一个发光很强而且峰宽很大的荧光峰被观察到.结果所示,当纳米颗粒尺寸减小时,纳米SnO2 颗粒的体相特征拉曼峰变弱,而由缺陷,表面和颗粒尺寸引起的相关效应呈强势.晶粒尺寸在20 nm左右是引起体相拉曼光谱变化的临界尺寸. 晶粒尺寸在20 nm以下,其体相拉曼峰的发生宽化和峰位移动, 以及分别出现在位于571 cm-1 的表面振动峰,位于351 cm-1 处的界面峰和与表面吸附水分子及氢氧基团的N系列拉曼峰是纳米SnO颗粒的主要特征.这些结果反映了纳米颗粒的微结构变化与颗粒尺寸和表面效应以及它们之间相互作用的信息.     

发光多孔硅表面微结构及其晶格畸变的实验研究

用电化学方法制备了不发光多孔硅和发光多孔硅,用X射线双晶衍射对两类多孔硅表面进行了微结构分析和晶体质量表征,实验表明两类多孔硅的微结构间存在着很大差别。不发光多孔硅表面对X射线的双晶衍射摇摆曲线可解叠成两个峰,它们分别来自样品多孔层和单晶硅衬底,而发光多孔硅对X射线的双晶衍射摇摆曲线呈高斯对称分布,不可解叠。发光多孔硅比不发光多孔硅表面晶体质量差,且电化学腐蚀越严重,表面晶体质量下降也越严重。     

A novel method of fabricating porous silicon material: ultrasonically enhanced anodic electrochemical etching

Ultrasonically enhanced anodic electrochemical etching is developed to fabricate luminescent porous silicon (PS) material. The samples prepared by the new etching method exhibit superior characteristics to those prepared by conventional direct current etching. By applying ultrasonically enhanced etching, PS microcavities with much higher quality factors can be fabricated. The improved quality induced by ultrasonic etching can be ascribed to increased rates of escape of hydrogen bubbles and other etched chemical species from the porous silicon pillars' surface. This process will cause the reaction between the etchant and the silicon wafer to proceed more rapidly along the vertical direction in the silicon pores than laterally.     

The effects of chemical etching of porous silicon on Raman spectra

We have investigated the effects of chemical etching on Raman spectra of porous silicon. The as-anodized porous silicon consisted mainly of crystalline silicon, as indicated by the Raman spectra. The background in the spectrum was strong, indicating that the porous silicon surface was rough due to the presence of pores. When chemical etching was performed five times, the Raman spectrum revealed the presence of spherically shaped nanocrystalline silicon whose diameter was around 3.5 nm. Further chemical etching, however, extinguished the nanocrystallites, in addition to smoothing the surface morphology.     

Optimization of porous silicon preparation technology for SERS applications

A series of porous silicon samples prepared at different etching parameters, namely etchant composition, etching time and current density, was investigated as substrates for surface-enhanced Raman scattering (SERS). Silver nanostructures were deposited on porous silicon by immersion plating method and Rhodamine 6G was used as analyte. The relation between the etching parameters, morphology of porous silicon surface and its SERS efficiency after silver deposition is examined. We show that a high HF content in the etchant allows the formation of a film with close-packed silver nanocrystals, which possess strong surface enhancement properties.     

Fabrication and characterization of porous silicon layers for applications in optoelectronics

In the present paper, several samples of porous silicon monolayers and multilayers were prepared at different anodization conditions with fixed HF concentration. The room temperature photoluminescence wavelength observed to be increased with increased etching time and current density respectively. By Raman measurement it has been observed that as the size of silicon crystallites decreased with increased etching time, the silicon optical phonon line shifted somewhat to lower frequency from 520.5 cm⁻¹ and became broader asymmetrically. The surface roughness and pyramid like hillocks surface was confirmed by AFM measurement. In SEM images, the porous silicon layers were clearly observed by white and black strips. It was also observed that the reflectivity increased as the number of porous silicon layers was increased.     

Surface and bulk structural properties of nanostructured porous silicon prepared by electrochemical etching at different etching time

Nanostructured porous silicon (NPSi) is versatile nanomaterials, and attractive area in device application after visible luminescence was observed from NPSi by Canham (1990). NPSi has been prepared by electrochemical techniques with silicon wafer as a based material. The electrolyte solution consists of ethanol and hydrofluoric acid at volume ratio of 1:1. The etching time was varied while other preparation parameters were fixed to produce different porosity of NPSi samples. The structural properties of samples were measured using field emission scanning electron microscope and Raman spectrometer. The surface structural study has shown the surface roughness increase at inertial stage but decrease gradually with longer etching time. However, nanostructured surface was decreased with increasing of etching time. From side view measurement, the nanopillar of NPSi becomes smaller size while increase of etching time. The crystallinity of PSi is observed by Raman scattering varied with different etching time. The photoluminescence measurement will be carried out to study the correlation between optical and structural properties.     

Applications of porous silicon formed by electrochemical etching using an electrolyte based on HF:formaldehyde

In this work, we report the experimental results on the formation of porous silicon (PSi) monolayers by electrochemical etching using a formaldehyde based electrolyte. The results were compared with PSi monolayers obtained with the traditional electrolyte (HF:ethanol). Both electrolytes facilitate the removal of H₂ generated as a subproduct during the electrochemical etching process in the surface of the c-Si substrate. Formaldehyde presents a good affinity to surfaces and interfaces and the excess of water in the electrolyte reduces the pore sizes of PSi samples. The porosity and etching rate values are similar than those obtained using HF:et solutions. The refractive index values are the same in both cases at the same porosity in the visible range. The results have shown that the chemical characteristics of the ethanol and formaldehyde can give some different advantages to the PSi process and its applications.     

多孔硅光致发光峰半峰全宽的压缩

硅发光对于在单一硅片上实现光电集成是至关重要的.目前已有的使硅产生发光的方法有:掺杂深能级杂质、掺稀土离子、多孔硅、纳米硅以及Si/SiO₂超晶格.声空化所引发的特殊的物理、化学环境为制备光致发光多孔硅薄膜提供了一条重要的途径.实验表明,声化学处理对于改善多孔硅的微结构,提高发光效率和发光稳定性都是一项非常有效的技术.超声波加强阳极电化学腐蚀制备发光多孔硅薄膜,比目前通用的常规方法制备的样品显示出更优良的性质.这种超声波的化学效应源于声空化,即腐蚀液中气泡的形成、生长和急剧崩溃.在多孔硅的腐蚀过程中,由于超声波的作用增加了孔中氢气泡的逸出比率和塌缩,有利于孔沿垂直方向的腐蚀,使多孔硅光致发光峰的半峰全宽压缩到了3.8nm.     

多孔硅拉曼光谱的研究

采用电化学腐蚀的方法制备多孔硅。对不同实验条件下所得到的多孔硅的拉曼光谱进行了分析，确认多孔硅是具有纳米晶结构特征的材料，肯定了量子限制效应在多孔硅光致发光中的作用。     

Study of porous silicon structure by Raman scattering

In this paper, the effect of etching time on light emitting porous silicon has been studied by using Raman scattering. Enhancement of Raman intensity by increasing the porosity is observed. Also there is a red shift, about 4 cm⁻¹, from the Raman peak of crystalline silicon to that of porous silicon. The phonon confinement model suggests the existence of spherical nanocrystalline silicon with diameter around 7 nm. But SEM images show that the samples have a sheetlike structure that confines phonons in one dimension. This should not cause any shift in their Raman spectra. It is suggested that the observed Raman peak shift is due to the spherical nanocrystals on the surface of these sheets.