Theory of Raman Scattering by Phonons in Germanium Nanostructures

Within the linear response theory, a local bond-polarization model based on the displacement–displacement Green’s function and the Born potential including central and non-central interatomic forces is used to investigate the Raman response and the phonon band structure of Ge nanostructures. In particular, a supercell model is employed, in which along the [001] direction empty-column pores and nanowires are constructed preserving the crystalline Ge atomic structure. An advantage of this model is the interconnection between Ge nanocrystals in porous Ge and then, all the phonon states are delocalized. The results of both porous Ge and nanowires show a shift of the highest-energy Raman peak toward lower frequencies with respect to the Raman response of bulk crystalline Ge. This fact could be related to the confinement of phonons and is in good agreement with the experimental data. Finally, a detailed discussion of the dynamical matrix is given in the appendix section.     

Study on the Si–Si Vibrational States of the Near Surface Region of Porous Silicon

The Si–Si vibrational states near the surface region of porous silicon has been characterized using Fourier Transform Infrared Spectroscopy (FTIR) due to its enlarged surface area. By means of anodic etch and oxidization experiments, two Si–Si vibration modes of porous silicon have been identified as near the surface regions and in the bulk, respectively. The intensity of absorption peak at 620 cm^–1, which originates from the Si–Si bonds vibrations on the surface and near surface regions of porous silicon, is found to vary depending on the length of etch and degree of oxidation of porous silicon, which exists before etching and is recovered again after fully oxidation. The peak of 610 cm^–1 doesn't change throughout the oxidation experiment, and to be assigned for Si–Si bond vibrations in the bulk. With an extra irradiation of Nd:Yag laser on the PS sample the Raman and FTIR spectra reveal a red shift. These results can give an interpretation to explain the different phenomenon of Si–Si vibrations of Raman and FTIR spectroscopy.     

Optical Characterization of Free-Standing Porous Silicon Films

We report here the optical characterization of two free-standing porous silicon (PS) films of porosity 70% and 85%, grown on a p- and a n-type Si. We determine the optical band gap in these films from the excitation wavelength dependence of the photoluminescence band. As the excitation wavelength is changed from red (800 nm) to UV (355 nm), a blue shift of the photoluminescence (PL) band is observed. We attribute the observed blue shift of the PL band to the emission due to the distribution of bandgap in PS. Both samples are oxidized in air and we believe that the observed bandgap in these films arises from the inhomogeneous distribution of Si particle sizes. However, we find that intrinsic defects play a dominant role in the process of luminescence. Electron spin resonance measurement indicates the presence of defects leading to the saturation of the optical absorption spectra and a decrease in intensity of the PL band. The lineshape of the PL band is modeled using a weighted asymmetric Gaussian that selects a gap distribution function at each excitation wavelength. From Raman measurements in these two films, the quantum confinement effect in Si nanostructures is clearly observed in both films.     

Radiative and nonradiative relaxation phenomena in hydrogen- and oxygen-terminated porous silicon

Abstract

Using time-resolved photoluminescence spectroscopy over a wide range of temperatures, we were able to probe both radiative and nonradiative relaxation processes in luminescent porous silicon. By comparing the photoluminescence decay times from freshly prepared and oxidized porous silicon, we show that radiative processes should be linked with quantum confinement in small Si nanocrystallites and are not affected by oxidation. In contrast, nonradiative relaxation processes are associated with the state of oxidation where slower relaxation times characterize hydrogen-terminated porous silicon. These results are in a good agreement with the extended vibron model for small Si nanocrystallites.

PACS

78.55.Mb; 78.67.Rb; 78.47.jd     

Silicon and Germanium Nanostructures for Photovoltaic Applications: Ab-Initio Results

Actually, most of the electric energy is being produced by fossil fuels and great is the search for viable alternatives. The most appealing and promising technology is photovoltaics. It will become truly mainstream when its cost will be comparable to other energy sources. One way is to significantly enhance device efficiencies, for example by increasing the number of band gaps in multijunction solar cells or by favoring charge separation in the devices. This can be done by using cells based on nanostructured semiconductors. In this paper, we will present ab-initio results of the structural, electronic and optical properties of (1) silicon and germanium nanoparticles embedded in wide band gap materials and (2) mixed silicon-germanium nanowires. We show that theory can help in understanding the microscopic processes important for devices performances. In particular, we calculated for embedded Si and Ge nanoparticles the dependence of the absorption threshold on size and oxidation, the role of crystallinity and, in some cases, the recombination rates, and we demonstrated that in the case of mixed nanowires, those with a clear interface between Si and Ge show not only a reduced quantum confinement effect but display also a natural geometrical separation between electron and hole.     

Porous silicon nanowires

In this mini-review, we summarize recent progress in the synthesis, properties and applications of a new type of one-dimensional nanostructures-single crystalline porous silicon nanowires. The growth of porous silicon nanowires starting from both p- and n-type Si wafers with a variety of dopant concentrations can be achieved through either one-step or two-step reactions. The mechanistic studies indicate the dopant concentration of Si wafers, oxidizer concentration, etching time and temperature can affect the morphology of the as-etched silicon nanowires. The porous silicon nanowires are both optically and electronically active and have been explored for potential applications in diverse areas including photocatalysis, lithium ion batteries, gas sensors and drug delivery.     

Spectroscopic characterization of thin SiC films

The electrical, structural and optical properties of thin SiC films were investigated. A new approach based on high temperature annealing of layered carbon–silicon structures was used for the formation of the films. The SiC films were prepared by deposition of 30 nm thick carbon films on crystalline silicon (c-Si) and on porous silicon layers grown on c-Si. The layers were annealed to temperatures between 800 and 1400°C for different annealing times ranging between 15 and 180 s. The structure of the resulting SiC films was analyzed by Raman spectroscopy. The Raman spectra of as-deposited films consist of two broad bands at 1350 and 1580 cm⁻¹ characteristic of the presence of amorphous carbon. These bands were shifted to lower frequencies in the spectra of annealed layers and were assigned to the hexagonal and cubic SiC phases. The photoluminescence spectra of the studied layers show a broad band at 550 nm. The most intense photoluminescence was observed from non-annealed porous silicon layers covered with thin carbon films. A degradation of the luminescence and a simultaneous increase of the conductivity of the layers with increasing annealing temperature and/or duration of annealing was observed. This behavior strongly suggests the creation of defect states which determine the conductivity of the layers and at the same time act as non-radiative centers. The increase of defect states was explained as originating from the dehydrogenation of the silicon carbide layers by annealing.     

Microscopic and Spectroscopic Characterization of Stacking‐Sequence Disordered SiC

Nanometric silicon carbide (SiC) powder (~5 nm) with a stacking‐sequence disordered structure (SD‐SiC), synthesized from elemental powders of Si and C, was investigated by microscopic and several spectroscopic methods. The structure of SD‐SiC was characterized by transmission electron microscopy (TEM), ¹³C, and ²⁹Si‐NMR, and by infrared (IR), Raman, and X‐ray photoelectron spectroscopy (XPS) methods. TEM characterizations showed relatively large deviations of the lattice parameters in the as‐synthesized SiC, indicative of the presence of stacking‐sequence disorder. IR analysis showed a weaker Si‐C bond in the SD‐SiC than in the 3C‐SiC. XPS determinations showed that C and Si in SD‐SiC are similar to those in 3C‐SiC. Broader peaks of ²⁹Si and ¹³C MAS‐NMR also indicate that the structure of SD‐SiC is different from that of 3C‐SiC. Raman spectroscopy exhibited activities for the crystalline polytypes and the amorphous of SiC but lack of them for the SD‐SiC. The inactivity of Raman spectroscopy for the SD‐SiC along with large deviation of the lattice constant and the extremely broad X‐ray diffraction peaks would indicate that SD‐SiC is a possible intermediate state between conventional polytype SiC and amorphous SiC, that is, a possible new type of SiC.     

Effects of Low-Thermal-Budget Treatments on the Porous Si Material Properties

Our interest in porous silicon is due to its potential benefits in crystalline Si solar cells. Besides the use as an anti-reflection coating, the porous layer also acts as a light-diffusor. However major drawbacks are the significant light absorption within the porous layer and both insufficient as well as unstable surface passivating capabilities. The unstable nature of the porous Si is also reflected in the presence of suboxides after storage in ambient. In this work we focus on rapid-thermal-oxidation (RTO) and plasma-nitridation as low-thermal-budget chemical modification techniques in order to obtain a surface layer with a controlled and stable structure and composition. RTO of porous Si converts the material into SiO₂ in conjunction with a drastically decreased porosity. Both a remote- and a direct-plasma nitridation of porous Si are able to incorporate nitrogen uniformly throughout the porous layer while preserving the porous character.     

Nanostructures formed by displacement of porous silicon with copper: from nanoparticles to porous membranes

ABSTRACT: The application of porous silicon as a template for the fabrication of nanosized copper objects is reported. Three different types of nanostructures were formed by displacement deposition of copper on porous silicon from hydrofluoric acid-based solutions of copper sulphate: (1) copper nanoparticles, (2) quasi-continuous copper films, and (3) free porous copper membranes. Managing the parameters of porous silicon (pore sizes, porosity), deposition time, and wettability of the copper sulphate solution has allowed to achieve such variety of the copper structures. Elemental and structural analyses of the obtained structures are presented. Young modulus measurements of the porous copper membrane have been carried out and its modest activity in surface enhanced Raman spectroscopy is declared.     

Nature of the Silicon-Animal Cell Interface

The paper reports the results of the study of cell culture growth at the surface of porous silicon. They show that porous and poly(nano)crystalline Si offer significant advantages over bulk Si surfaces for cell adherence and viability: these materials do not require coating with substances such as polylysine to support cell growth; porous Si is light-addressable because of photoluminescence and photovoltaic effects noted [Unal and Bayliss, J. Appl. Phys. 80, 3532 (1996)], allowing the potential for optical data transfer and less susceptibility to interference from external electronic equipment; finally nanostructured coatings can be applied to most object shapes, giving flexibility in their application.     

Efficient PL Emission from p-type Porous Silicon: A Comparative Study for Selection of Effective Anodization Parameters

The physical mechanism of highly efficient photoluminescence (PL) emission from p-type silicon is described by a comparative study of the effectiveness of the etching parameters in an electrochemical anodization technique. Two series of porous silicon samples were prepared in a combination of anodization current and time, to maintain the total amount of anodic charge transfer constant. Photoluminescence studies show that irrespective of the amount of charge transfer, the samples prepared with comparatively higher current density show an efficient PL as well as stronger blueshift in the emission energy vis-à-vis the samples prepared for longer durations. An overall decrease in crystallite size, as estimated by Raman spectral analysis, was observed for both series of samples with the progress of charge transfer. Comparative analysis shows a marginal difference in crystallite size for both series of samples in the initial state of charge transfer, whereas major differences arise at higher values. This is explained with the formation of silicon suboxide on the porous surface at higher current density, leading to initiation of side wall reaction, and higher reduction rate in crystallite size as well as strong luminescence due to the carrier quantum confinement effect.     

Porous silicon nanocrystals in a silica aerogel matrix

ABSTRACT: Silicon nanoparticles of three types (oxide-terminated silicon nanospheres, micron-sized hydrogen-terminated porous silicon grains and micron-size oxide-terminated porous silicon grains) were incorporated into silica aerogels at the gel preparation stage. Samples with a wide range of concentrations were prepared, resulting in aerogels that were translucent (but weakly coloured) through to completely opaque for visible light over sample thicknesses of several millimetres. The photoluminescence of these composite materials and of silica aerogel without silicon inclusions was studied in vacuum and in the presence of molecular oxygen in order to determine whether there is any evidence for non-radiative energy transfer from the silicon triplet exciton state to molecular oxygen adsorbed at the silicon surface. No sensitivity to oxygen was observed from the nanoparticles which had partially H-terminated surfaces before incorporation and so we conclude that the silicon surface has become substantially oxidised. Finally, the FTIR and Raman scattering spectra of the composites were studied in order to establish the presence of crystalline silicon; by taking the ratio of intensities of the silicon and aerogel Raman bands, we were able to obtain a quantitative measure of the silicon nanoparticle concentration independent of the degree of optical attenuation.     

Raman Scattering and Backscattering Studies of Silicon Nanocrystals Formed Using Sequential Ion Implantation

Silicon nanocrystals were produced using a two-stage gold ion implantation technique. The first stage implantation using low energy ions led to the formation of an amorphous Si (a-Si) layer. A subsequent high energy Au irradiation in the second stage was found to produce strained Si NCs. An annealing step at a temperature as low as 500 °C was seen to result in strain free NCs. Higher temperature annealing of the samples was found to result in a growth in size from recrystallization of the a-Si matrix. Raman Scattering, X-Ray diffraction and Rutherford Backscattering Spectrometry have been used to study the effect of annealing on the samples and the size of the Si NCs formed. The data can be well explained using a phonon confinement model with an extremely narrow size distribution. The XRD results are in line with the Raman analysis.     

碳纤维微观结构表征： Raman光谱

Raman光谱作为材料微观结构表征的重要方法,其对碳材料的结构具有相当的敏感性,在0～3300cm^-1的波数范围内都有相当显著的谱峰响应。其中,理想石墨晶格面内CC键伸缩振动的G线和由无序结构引起的D线是认识碳材料纳米尺度结构特征的关键切入点。基于上述特征指标可以获得碳结构微观应力、晶态结构、石墨化度及结构不均匀性等一系列结构特征,是研究碳纤维微观结构及其形成、演变过程的重要技术手段。近年来,随着以“Mapping”技术为代表的系列新技术的成功应用,针对碳纤维微观结构的Raman光谱应用技术出现了一系列新的进展。本文以Raman光谱的碳纤维微观、介观层面的应用技术为切入点,综述了近年来Raman光谱在碳纤维微观应力/应变、晶态结构、石墨化度及结构不均匀性等方面的进展情况。     

Size-dependent visible absorption and fast photoluminescence decay dynamics from freestanding strained silicon nanocrystals

In this article, we report on the visible absorption, photoluminescence (PL), and fast PL decay dynamics from freestanding Si nanocrystals (NCs) that are anisotropically strained. Direct evidence of strain-induced dislocations is shown from high-resolution transmission electron microscopy images. Si NCs with sizes in the range of approximately 5-40 nm show size-dependent visible absorption in the range of 575-722 nm, while NCs of average size <10 nm exhibit strong PL emission at 580-585 nm. The PL decay shows an exponential decay in the nanosecond time scale. The Raman scattering studies show non-monotonic shift of the TO phonon modes as a function of size because of competing effect of strain and phonon confinement. Our studies rule out the influence of defects in the PL emission, and we propose that owing to the combined effect of strain and quantum confinement, the strained Si NCs exhibit direct band gap-like behavior.     

Application of the chemical vapor infiltration and reaction (CVI-R) technique for the preparation of highly porous biomorphic SiC ceramics derived from paper

Chemical vapor infiltration and reaction (CVI-R) is used to produce biomorphic high porous SiC ceramics based on biological structures such as paper. The paper fibers are first converted into a biocarbon (C_b) template by a carbonization step. In a second step methyltrichlorosilane (MTS) in excess of hydrogen is infiltrated into the C_b-template by CVI technique, depositing a Si/SiC layer around each fiber. The reaction (R) between biocarbon and excess silicon to form additional silicon carbide occurs during a subsequent thermal treatment as a third step of the ceramization process. Due to the mild infiltration conditions (850–900 °C) the initial micro- and macrostructure of the carbon preform is retained in the final ceramics. The applied characterization methods after every step of the ceramization process are X-ray Photoelectron Spectroscopy (XPS), Raman spectroscopy, Thermal Gravimetric Analysis (TGA), and Scanning Electron Microscopy (SEM). The bending strength of the resulting porous ceramics is measured by the double ring bending test. It is found that a slight excess of free Si in relation to the amount of carbon from the C_b-template must be deposited in the Si/SiC layer to achieve a nearly complete conversion of the C_b-templates into SiC ceramic. The weight gain after infiltration has to be at least 400 wt.%. Varying the infiltration conditions such as temperature, MTS concentration and infiltration time, ceramics in a wide range of porosity (55–80%) and mechanical properties (5–40 MPa) can be produced. A thermal treatment temperature of 1400 °C is found to be optimal for the reaction between the deposited Si and the biocarbon.     

Raman Scattering from Metal-Deposited Porous Silicon

Raman scattering from porous silicon layer into which silver is immersion-plated was studied. Ag-deposited samples show extra Raman bands. Heat treatment of the Ag-deposited samples results in a great decrease in such Raman bands. Also dipping in hydrofluoric acid solution causes a spectral change. Some comments on the assignment of the Raman peaks of the Ag-deposited porous silicon are given, and the structure of porous silicon on which metal is immersion-plated is discussed.     

Fabrication and characterization of silicon nanostructures based on metal-assisted chemical etching

We present a facile method to fabricate one-dimensional Si nanostructures based on Ag-induced selective etching of silicon wafers. To obtain evenly distributed Si nanowires (SiNWs), the fabrication parameters have been optimized. As a result, a maximum of average growth rate of 0.15 μm/min could be reached. Then, the fabricated samples were characterized by water contact angle (CA) experiments. As expected, the as-etched silicon samples exhibited a contact angle in the range of 132°–136.5°, whereas a higher contact angle (145°) could be obtained by chemical modification of the SiNWs with octadecyltrichlorosilane (OTS). Additionally, Raman spectra experiments have been carried out on as-prepared nanostructures, showing a typical decreasing from 520.9 cm^?1 to 512.4 cm^?1 and an asymmetric broadening, which might be associated with the phonon quantum confinement effect of Si nanostructures.     

Photochemical Etching of Silicon

Silicon that was immersed in hydrofluoric acid can be etched photochemically by laser, and it was found to produce long and regular columnar structure, if the laser power density is greater than 10 mW/mm². Another criterion is that the laser wavelength should be at the blue end of visible spectrum. Fine wires with diameter 300–200 nm were also observed at the top of these columns. The dimension of these fine wires is near to quantum confinement dimension, thus can be taken as supporting evidence for quantum confinement. The photoluminescence spectra full width half maximum was narrower than that from porous silicon fabricated from conventional anodisation method. The narrower full width was attributed to the uniformity of the porous silicon structure. A physical model is proposed to explain the observed strong directional etching. The model showed that once the etch sites have randomly initiated, the etching rate becomes directional under the influence of laser. The intensity of laser controls the etching direction such that silicon columns are formed if the intensity of the laser is strong enough.