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.     

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.     

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。     

多孔硅纵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向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期的反应机制不相同。反应初期,外表面的颗粒尺寸比内表面的大,而经过长时间刻蚀而获得的多孔硅,其外表面颗粒尺寸比内表面的小。我们认为反应的初期主要受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。     

少子寿命和表面形貌与多孔硅发光性能的关系

研究了不同时间腐蚀的多孔硅的光致发光性能与多孔硅的表面形貌和少子寿命之间的关系。结果表明,多孔硅的发光来自与氧空位有关的缺陷,而多孔硅表面的氢原子能够钝化多孔硅表面的非辐射中心从而提高多孔硅的发光效率。多孔硅的空隙度随腐蚀时间的延长而增大,这也导致了多孔硅的少子寿命的降低,从而造成多孔硅的光致发光效率随多孔硅空隙度的增大以及少子寿命的降低而提高。另外,原子力显微照片表明长时间的腐蚀使多孔硅表面层被化学腐蚀,从而降低了多孔硅表面的粗糙度。     

Morphological and optical properties changes in nanocrystalline Si (nc-Si) deposited on porous aluminum nanostructures by plasma enhanced chemical vapor deposition for Solar energy applications

Photoluminescence (PL) spectroscopy was used to determine the electrical band gap of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous alumina structure by fitting the experimental spectra using a model based on the quantum confinement of electrons in Si nanocrystallites having spherical and cylindrical forms. This model permits to correlate the PL spectra to the microstructure of the porous aluminum silicon layer (PASL) structure. The microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that the structure of the nanocrystalline silicon layer (NSL) is dependent of the porosity (void) of the porous alumina layer (PAL) substrate. This structure was performed in two steps, namely the PAL substrate was prepared using sulfuric acid solution attack on an Al foil and then the silicon was deposited by plasma enhanced chemical vapor deposition (PECVD) on it. The optical constants (n and k as a function of wavelength) of the deposited films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The SE spectrum of the porous aluminum silicon layer (PASL) was modeled as a mixture of void, crystalline silicon and aluminum using the Cauchy model approximation. The specific surface area (SSA) was estimated and was found to decrease linearly when porosity increases. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural 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.     

Silicon Porosification: State of the Art

This review is devoted to the analysis of the problems related to fabrication of the Si porous layers. The review was motivated by a great interest to Si-based porous materials from nano- to macro-scale for various applications in electronics, optoelectronics, photonics, chemical sensors, biosensors, etc. The peculiarities of the silicon porosification and the principles of preparing porous layers are considered in the present article. Various methods used for Si porosification such as chemical stain etching, chemical vapor etching, laser-induced etching, metal-assisted etching, spark processing and reactive ion (plasma) etching were analyzed. However, the main attention was focused on electrochemical porosification of Si. The review discusses in detail the influence of parameters such as electrolyte composition and pH, current density, etching time, temperature, wafer doping and orientation, lighting, magnetic field, and ultrasonic agitation on the process of Si porosification. It was shown that the structure of porous silicon strongly depends on both technological parameters of electrochemical etching and the parameters of the semiconductor subject to treatment. This review also addresses the main properties of porous silicon, porous multilayer and 3D structure formation, oxidation of porous Si, release of the porous layer, drying, storage, etching, filling and surface functionalizing of porous Si. Features of III-V compound porosification are also briefly analyzed.     

Electroluminescence from a current-emitting nanostructured silicon device

A three-dimensional silicon based nanodevice mainly consisting of two conductive silicon cantilevers was fabricated out of silicon-on-insulator material by electron beam lithography, reactive ion etching, and fluoride based wet chemical etching. One of the cantilevers is bent and sticks to the silicon substrate while the other one is freely suspended. We observed electroluminescence in the visible range when a voltage of any polarity is dropped across both levers. The measured spectra covered the range 400–950 nm peaking at about 650 nm. The current applied to the device could tune the intensity of the electroluminescence spectrum. Light powers ranging from 160 fW to some pW were measured at frequencies up to 17 kHz. The origin of the electroluminescence is discussed in comparison to porous silicon and spark-processed silicon.     

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.     

有机吸附物对多孔硅微腔发光的影响

理论上,采用Bruggeman有效介质近似,研究了有机吸附物对多孔硅微腔的折射率及其光致发光谱的影响.实验上,采用计算机控制的电化学腐蚀法制备了多孔硅微腔样品,并利用机械泵油的蒸气分子与该微腔样品进行相互作用.研究发现,多孔硅微腔发射的窄化光致发光谱对泵油蒸气分子的吸附与脱附很敏感,与之伴随的是该窄化光致发光谱发生明显的峰位移动(可达71nm)和强度变化.结合Bruggeman近似和表面态对多孔硅发光的影响,对实验结果进行了定性解释.实验结果与理论模拟结果符合较好. 关键词： Bruggeman近似 吸附物 多孔硅微腔 光致发光谱     

Effect of surface modification by thermally oxidization and HF etching on UV photoluminescence emission of porous silicon

Photoluminescence of porous silicon (PS) is instable due perhaps to the nanostructure modification in air. The controllable structure modification processes on the as-prepared PS were conducted by thermal oxidization and/or HF etching. The PL spectra taken from thermally oxidized PS showed a stable photoluminescence emission of 355 nm. The photoluminescence emission taken from both of PS and oxidized porous silicon (OPS) samples etched with HF were instable, which can be reversibly recovered by the HF etching procedure. The mechanism of UV photoluminescence is discussed and attributed to the transformation of luminescence centers from oxygen deficient defects to the oxygen excess defects in the thermal oxidized PS sample and surface absorbed silanol groups on PS samples during the chemical etched procedure.     

稀氢氟酸中硅表面氢终端的原位拉曼光谱研究

本文用共焦显微拉曼系统原位观察了Ｓｉ（１００）表面氢终端原子在稀氢氟酸中的变化过程。研究表明：在硅片浸入氢氟酸溶液的初期,表面主要被硅和三个氢原子的结合体（Ｓｉ Ｈ３）以及硅和两个氢原子的结合体（Ｓｉ Ｈ２）所覆盖。随着腐蚀过程的延长,Ｓｉ Ｈ３越来越少,Ｓｉ Ｈ２的信号不断增强,并且,硅和单个氢原子的结合体（Ｓｉ Ｈ）的信号也开始出现。最终,硅表面主要被Ｓｉ Ｈ２所覆盖,有少量Ｓｉ Ｈ３和Ｓｉ Ｈ键。本文还表明,拉曼光谱用来原位观察半导体材料表面终端原子键在溶液中的变化是很有用的工具     

空间限制与应变对发光多孔硅喇曼光谱的影响

发光多孔硅的喇曼光谱在５２０ｃｍ^－１附近呈现一锐峰，峰位的红移随多孔度的增大而增大采用微晶模型拟合喇曼谱的线形，发现除了光学声子的空间限制效应，硅单晶的应变对峰位的移动也有显著贡献。通过谱形的拟合估算了硅微粒的应变，与已报道的Ｘ射线衍射结果相一致。在多孔硅的喇曼光诸中没有观察到起源于非晶硅的光散射信号。 关键词：     

Structural and optical features of nanoporous silicon prepared by electrochemical anodic etching

Nanoporous silicon (NPS) samples were prepared by electrochemical anodic etching of p-type (0 0 1) silicon wafers in HF solution, and some of them were aged in air. The nanostructural, optical and chemical features of the NPS were investigated in terms of etching and aging conditions. The surface of the porous Si exhibits an etched layer with a thickness of 30–40 nm; this layer appears to consist of aggregates of 5–10 nm size nano-crystallites. The NPS exhibited broad photoluminescence (PL) spectra with its peak in the red light region (740 nm). After aging the porous samples for 4 weeks in air, we observed the PL intensity became approximately a fifth of that of the as-prepared one, along with a blue shift. It is very likely that the blue shift of the PL peak was caused by the shrinkage of the Si nano-crystallites due to the oxidation in the surface of the nano-crystallites.     

Comparative investigation of photoluminescence of silicon wire structures and silicon oxide films

Photoluminescence spectra and their dependence on temperature as well as Raman scattering spectra and Atomic Force Microscopy investigations have been used to study the peculiarities of the red photoluminescence band in low-dimensional Si structures, such as porous silicon and silicon oxide films. It has been shown that the red photoluminescence band of porous silicon is complex and can be decomposed into two elementary bands. It was discovered that elementary band intensities depend very much on surface morphology of porous silicon. The same positions of the photoluminescence bands are also observed in silicon oxide films for different oxide composition. Comparative investigation of the PL temperature dependences in porous silicon and silicon oxide films indicates that silicon-oxide defect related mechanisms of some elementary photoluminescence bands are involved.     

Raman spectra of tetrapyrrole photosensitizer chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript> and their interpretation

The resonance and surface enhanced Raman scattering (SERS) spectra of chlorin e 6 trisodium salt in aqueous solutions, solid films, and adsorbed on the silver-coated surface of porous silicon are presented. Using the quantum-mechanical density functional method, the geometric structure and vibrational frequencies of the chlorin e ₆ molecule are calculated and the Raman spectrum of this molecule is interpreted for the first time. The geometry of sorption of chlorin e ₆ on the surface of a nanostructured silver film is considered based on a comparative analysis of the resonance Raman and SERS Raman spectra in the approximation of a short-range mechanism of Raman scattering enhancement.     

Etching of silicon in fluoride solutions

The development and status of what is commonly called the Gerischer mechanism of silicon etching in fluoride solutions is reviewed. The two most widely used and studied wet etchants of silicon are F^? and OH^?. Their mechanisms of atom removal share many things in common; in particular, chemical passivation by a hydrogen-terminated surface plays an important role in both. Crucially, however, their initiation steps are different, and this leads to important differences in the structures of the materials produced by the etchants. The initiation of etching by F^? is electrochemical in nature, responding to the electronic structure of the Si, and is, therefore, a self-limiting reaction that can produce nanocrystalline porous silicon. Hydroxide etching destroys porous silicon because its initiation step is a catalytic chemical reaction and not a self-limiting process. A number of unanswered questions regarding the dynamics of fluoride etching are highlighted.     

Annealing and amorphous silicon passivation of porous silicon with blue light emission

The photoluminescence (PL) of the annealed and amorphous silicon passivated porous silicon with blue emission has been investigated. The N-type and P-type porous silicon fabricated by electrochemical etching was annealed in the temperature range of 700-900 °C, and was coated with amorphous silicon formed in a plasma-enhanced chemical vapor deposition (PECVD) process. After annealing, the variation of PL intensity of N-type porous silicon was different from that of P-type porous silicon, depending on their structure. It was also found that during annealing at 900 °C, the coated amorphous silicon crystallized into polycrystalline silicon, which passivated the irradiative centers on the surface of porous silicon so as to increase the intensity of the blue emission.     

Optical Analysis of Nanocrystalline ZnO Films Coated on Porous Silicon by Radio Frequency (RF) Magnetron Sputtering

Zinc oxide thin films have been deposited onto porous silicon (PSi) substrates at high growth rates by radio frequency (RF) sputtering using a ZnO target. The advantages of the porous Si template are economical and it provides a rigid structural material. Porous silicon is applied as an intermediate layer between silicon and ZnO films and it contributed a large area composed of an array of voids. The nanoporous silicon samples were adapted by photo electrochemical (PEC) etching technique on n-type silicon wafer with (111) and (100) orientation. Micro-Raman and photoluminescence (PL) spectroscopy are powerful and non-destructive optical tools to study vibrational and optical properties of ZnO nanostructures. Both the Raman and PL measurements were also operated at room temperature. Micro-Raman results showed that the A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at around 522 and 530 cm^–1, re- spectively. PL spectra peaks are distinctly apparent at 366 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The peak luminescence energy in nanocrystalline ZnO on porous silicon is blue-shifted with regard to that in bulk ZnO (381 nm). The Raman and PL spectra pointed to oxygen vacancies or Zn interstitials which are responsible for the green emission in the nanocrystalline ZnO.