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.     

Structural and optical properties study of nanocrystalline Si (nc-Si) thin films deposited on porous aluminum by plasma enhanced chemical vapor deposition

In this paper we report detail investigation and correlation between micro-structural and optical properties of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous aluminum structure. The influence of the microstructure of the nc-Si thin films on their optical properties was investigated through an extensive characterization. The effect of anodisation currents on the microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM) and transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). The optical constants (n and k as a function of wavelength) of the films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The silicon layer (SL) was modeled as a mixture of void, crystalline silicon and aluminum using the Bruggeman approximation. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties. A very bright photoluminescence (PL) was obtained and find to depend on anodisation current.     

Optical and electrical characterization of aluminium doped ZnO layers

Al doped ZnO (ZAO) thin films (with Al-doping levels 2 at.%) were deposited at different deposition parameters on silicon substrate by reactive magnetron sputtering for solar cell contacts, and samples were investigated by transmission electron microscopy (TEM), electron energy loss spectroscopy (EELS) and spectroscopic ellipsometry (SE). Specific resistances were measured by the well known 4-pin method. Well visible columnar structure and in most cases voided other regions were observed at the grain boundaries by TEM. EELS measurements were carried out to characterize the grain boundaries, and the results show spacing voids between columnar grains at samples with high specific resistance, while no spacing voids were observed at highly conductive samples. SE measurements were evaluated by using the analytical expression suggested by Yoshikawa and Adachi [H. Yoshikawa, S. Adachi, Japanese Journal of Applied Physics 36 (1997) 6237], and the results show correlation between specific resistance and band gap energy and direct exciton strength parameter.     

In situ ellipsometric study of electrodeposition of manganese films on copper

Electrodeposition of manganese film on copper substrate in a chloride-based solution was investigated by cyclic voltammetry (CV) in combination with in situ spectroscopic ellipsometry (SE). The SE results at different polarization potentials show that the hydrogen evolution has no influence on the SE measurement. The CV results, confirmed by SE data, indicate the starting reduction and oxidation potentials of manganese. The potential for electrodeposition of manganese film with the maximum thickness was determined based on the SE measurements. The SE results show that the manganese film is relatively loose, which is consistent with the observation by scanning electron microscopy (SEM). The growth kinetics of manganese electrodeposition was proposed according to the SE measurements.     

Realisation and metrological characterisation of thickness standards below 100 nm

High-accuracy film thickness measurements in the range below 100 nm can be made by various complex methods like spectral ellipsometry (SE), scanning force microscopy (SFM), grazing incidence X-ray reflectometry (GIXR), or X-ray fluorescence analysis (XRF). The measurement results achieved with these methods are based on different interactions between the film and the probe. A key question in nanotechnology is how to achieve consistent results on a level of uncertainty below one nanometre with different techniques.Two different types of thickness standards are realised. Metal film standards for X-ray techniques in the thickness range 10 to 50 nm are calibrated by GIXR with monochromatised synchrotron radiation of 8048 eV. The results obtained at four different facilities show excellent agreement. SiO₂ on Si standards for SE and SFM in the thickness range 6 to 1000 nm are calibrated by GIXR with monochromatised synchrotron radiation of 1841 eV and with a metrological SFM. Consistent results within the combined uncertainties are obtained with the two methods. Surfaces and interfaces of both types of standards are additionally investigated by transmission electron microscopy (TEM). PACS 61.10.Kw; 68.55.Jk; 06.20.Fn; 06.60.Mr; 07.79.Lh     

Comparative study of the oxidation of thin porous silicon layers studied by reflectometry, spectroscopic ellipsometry and secondary ion mass spectroscopy

We present a systematic study on ultrathin porous silicon (PS) layers (40–120 nm) of different porosities, formed by electrochemical etching and followed by thermal oxidation treatment (300°C and 600°C) and by electrochemical oxidation. The oxidised and non-oxidised PS layers have been analysed by spectroscopic reflectometry (SR), spectroscopic ellipsometry (SE) and secondary ion mass spectroscopy (SIMS). The SR and SE spectra were fitted by a multiparameter fit program and the composition and the thickness of the PS layers were evaluated by different optical models. PS layers, formed electrochemically in the outermost layer of a p/n⁺ monocrystalline silicon junction were successfully evaluated using a gradient porosity optical model. The non-oxidised PS, formed in p-type silicon, can be well described by a simple optical model (one-layer of two-components, silicon and voids). The spectra of the oxidised PS layers can be fitted better using an optical model with three interdependent components (crystalline-silicon, silicon-dioxide, voids). The SIMS results give a strong support for the optical model used for SR and SE.     

Electronic properties of electrolyte/anodic alumina junction during porous anodizing

The growth of porous oxide films on aluminum (99.99% purity), formed in 4% phosphoric acid was studied as a function of the anodizing voltage (23-53 V) using a re-anodizing technique and transmission electron microscopy (TEM) study. The chemical dissolution behavior of freshly anodized and annealed at 200 °C porous alumina films was studied. The obtained results indicate that porous alumina has n-type semiconductive behavior during anodizing in 4% phosphoric acid. During anodising, up to 39 V in the barrier layer of porous films, one obtains an accumulation layer (the thickness does not exceed 1 nm) where the excess electrons have been injected into the solid producing a downward bending of the conductive and valence band towards the interface. The charge on the surface of anodic oxide is negative and decreases with growing anodizing voltage. At the anodizing voltage of about 39 V, the charge on the surface of anodic oxide equals to zero. Above 39 V, anodic alumina/electrolyte junction injects protons from the electrolyte. These immobile positive charges in the surface layer of oxide together with an ionic layer of hydroxyl ions concentrated near the interface create a field, which produces an upward bending of the bands.     

Structural characterization of AlN films synthesized by pulsed laser deposition

We obtained AlN thin films by pulsed laser deposition (PLD) from a polycrystalline AlN target using a pulsed KrF* excimer laser source (248 nm, 25 ns, intensity of ∼4 × 10⁸ W/cm², repetition rate 3 Hz, 10 J/cm² laser fluence). The target-Si substrate distance was 5 cm. Films were grown either in vacuum (10⁻⁴ Pa residual pressure) or in nitrogen at a dynamic pressure of 0.1 and 10 Pa, using a total of 20,000 subsequent pulses. The films structure was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and spectral ellipsometry (SE). Our TEM and XRD studies showed a strong dependence of the film structure on the nitrogen content in the ambient gas. The films deposited in vacuum exhibited a high quality polycrystalline structure with a hexagonal phase. The crystallite growth proceeds along the c-axis, perpendicular to the substrate surface, resulting in a columnar and strongly textured structure. The films grown at low nitrogen pressure (0.1 Pa) were amorphous as seen by TEM and XRD, but SE data analysis revealed ∼1.7 vol.% crystallites embedded in the amorphous AlN matrix. Increasing the nitrogen pressure to 10 Pa promotes the formation of cubic (≤10 nm) crystallites as seen by TEM but their density was still low to be detected by XRD. SE data analysis confirmed the results obtained from the TEM and XRD observations.     

Interaction of acoustic waves with porous layer

Interaction of sound impulse with porous layer is investigated. The presence of a barrier shielded by the layer and the gap between the porous layer and the barrier is possible. Method of calculation in linear approximation of pressures and tensions in the porous layer, gap, and on the barrier has been proposed. The method serves to interpret data on acoustic waves interaction with porous layer obtained experimentally or with the use of finite-difference methods. Specifics of acoustic wave propagation into the porous layer and further reflection from the barrier has been studied. Comparison of calculation data with experimental data of other authors on impulse propagation through the porous plate submerged in water has been carried out.     

椭圆偏振光谱实时在线监测与离线分析微晶硅薄膜的生长

采用甚高频等离子体增强化学气相沉积技术高速沉积了有无籽晶层两个系列微晶硅薄膜,通过椭圆偏振光谱、拉曼光谱和XRD对薄膜进行了分析,发现采用籽晶层后,在薄膜沉积初期有促进晶化的作用;由于籽晶层减少了薄膜的诱导成核时间,提高了薄膜的沉积速率,对比了实时在线和离线椭圆偏振光谱两种测量状态对分析微晶硅薄膜的影响,研究发现,当薄膜较薄时,实时在线测量得到的薄膜厚度小于离线下的数值;当薄膜较厚时,两种测量条件下得到的薄膜厚度差异较小;实时在线条件下得到的表面粗糙度要大于离线条件下得到的数值,这是由于薄膜暴露在大气中后表面有硅氧化物生成,对表面有平滑作用.     

Mixed polarization in determining the film thickness of a silicon sphere by spectroscopic ellipsometry

The effect of a spherical shape on the measurement result of spectroscopic ellipsometry (SE) is analyzed, and a method to eliminate this effect is proposed. Based on the simulation result of the SE measurement on a silicon sphere by ray tracking, we find that the sphere makes the parallel incident beam of the SE be divergent after reflection, and the measurement error of the SE caused by this phenomenon is explained by the mixed polarization theory. By settling an aperture in front of the detector of the SE, we can almost eliminate the error. For the silicon sphere with a diameter of 94 mm used in the Avogadro project, the thickness error of the oxide layer caused by the spherical shape can be reduced from 0.73 nm to 0.04 nm by using the proposed method. The principle of the method and the results of the experimental verification are presented.     

Optical and X-ray characterization of ferroelectric strontium-bismuth-tantalate (SBT) thin films

Metal-organic chemical vapor deposition (MOCVD) made layers of strontium-bismuth-tantalate (SBT) were characterized by spectroscopic ellipsometry (SE) using the Adachi model [S. Adachi, Phys. Rev. B 35 (1987) 7454-7463]. The evaluated optical parameters were correlated with the physical and chemical behavior examined by X-ray diffraction (XRD).As a result, it was possible to fit the measured spectra with the Adachi model in a wide range covering the region of the band gap. The Adachi model provides electronic layer parameters like the transition energy E₀ and broadening Γ. Our investigations established a correlation between XRD-determined average grain size and the electronic layer parameters.     

Investigation of the hemoglobin adsorption in porous silicon by the ellipsometry method

The hemoglobin adsorption in porous silicon is studied by the method of spectroscopic ellipsometry. The layer-by-layer component distribution in the porous silicon-hemoglobin system shows that hemoglobin molecules penetrate through the porous layer with a slight gradient of the protein volume fraction.     

Electrical conductivity and electromagnetic interference shielding characteristics of multiwalled carbon nanotube filled polyacrylate composite films

Multiwalled carbon nanotubes (MWCNTs) were homogeneously dispersed in pure acrylic emulsion by ultrasonication to prepare MWCNT/polyacrylate composites applied on building interior wall for electromagnetic interference (EMI) shielding applications. The structure and surface morphology of the MWCNTs and MWCNT/polyacrylate composites were studied by field emission scanning microscopy (FESEM) and transmission electron microscopy (TEM). The electrical conductivity at room temperature and EMI shielding effectiveness (SE) of the composite films on concrete substrate with different MWCNT loadings were investigated and the measurement of EMI SE was carried out in two different frequency ranges of 100-1000 MHz (radio frequency range) and 8.2-12.4 GHz (X-band). The experimental results show that a low mass concentration of MWCNTs could achieve a high conductivity and the EMI SE of the MWCNT/polyacrylate composite films has a strong dependence on MWCNTs content in both two frequency ranges. The SE is higher in X-band than that in radio frequency range. For the composite films with 10 wt.% MWCNTs, the EMI SE of experiment agrees well with that of theoretical prediction in far field.     

椭圆偏振光谱表征单晶硅衬底上生长的非晶硅和外延硅薄膜

本文采用射频等离子体增强化学气相沉积(rf-PECVD)技术在单晶硅衬底上沉积了两个系列的硅薄膜. 通过对样品进行固定角度椭圆偏振测试, 结果表明第一个系列硅薄膜为非晶硅, 形成了突变的a-Si:H/c-Si异质结构, 此结构在HIT电池中有利于形成好的界面特性, 对于非晶硅薄膜采用通常的Tauc-Lorentz摇摆模型(Genosc)拟合结果很好; 第二个系列硅薄膜为外延硅, 对于外延硅薄膜, 随着膜厚增加晶化率降低, 当外延硅薄膜厚度为46 nm时开始非晶硅生长. 对于外延硅通常采用EMA模型(即将硅薄膜体层看成由非晶硅和c-Si构成的混合层)拟合结果较好, 当硅薄膜中出现非晶硅生长时, 将体层分成混合层和非晶硅两层, 采用三层模型拟合结果很好. 本文证实了椭偏光谱分析采用不同的模型可对单晶硅衬底上不同结构的硅薄膜进行有效表征.     

多量子势垒双阻挡层结构对AlGaN 基深紫外激光二极管的性能优化

为提高AlGaN基深紫外激光二极管(Deep Ultraviolet Laser Diodes,DUV-LD)有源区内载流子浓度,减少载流子泄露,提出一种DUV-LD双阻挡层结构,相对于传统的单一电子阻挡层(Electron Blocking Layer, EBL)结构,又引入一空穴阻挡层(Hole Blocking Layer, HBL),仿真结果证明空穴阻挡层的应用能很好地减少空穴泄漏.同时又对双阻挡层改用五周期Al_0.98Ga_0.02N/Al_0.9Ga_0.1N多量子势垒层结构,结果显示与矩形EBL和HBL激光二极管相比,多量子势垒EBL和HBL激光二极管有更好的斜率效率,并且有源区内电子和空穴载流子浓度以及辐射复合速率都有效提高,其中多量子势垒EBL在阻挡电子泄露方面效果更显著.     

离子注入硅片快速退火后的红外椭偏光谱研究

离子注入硅片经高温退火后晶体结构缺陷会被修复,其在可见光波段下的光学性质趋于单晶硅,常规的可见光椭偏光谱法对掺杂影响的测量不再有效.本研究将测量波段扩展到红外区域(2—20μm),报道了利用红外椭偏光谱法测量经离子注入掺杂并高温退火的硅片掺杂层光学和电学性质的方法和结果.通过建立基于Drude自由载流子吸收的等效光学模型,得到了杂质激活后掺杂层的杂质浓度分布、电阻率和载流子迁移率等电学参数,以及掺杂层的红外光学常数色散关系,分析了这些参数随注入剂量的关系并对其物理机理给予了解释.研究表明,中远红外椭偏测量是表征退火硅片的有效方法,且测量波长越长,所能分辨的掺杂浓度越低.     

Local chemical states and microstructure of photoluminescent porous silicon studied by means of EELS and TEM

Photoluminescent porous Si (PS) layers were formed on low resistivity p-type Si(100) wafers by anodization at a current density (Ia) of 100-350 mA cm(-2) at room temperature. The local chemical states and the microstructures of the PS layers were studied by means of electron energy loss spectroscopy (EELS) and transmission electron microscopy (TEM), and were correlated to the red photoluminescence (PL). The PS layer consists of sponge-like and tree-like structures. The tree-like structure becomes finer with increase of Ia. The fine tree-like structure is shown to be favorable for intensive PL. The EELS analysis reveals that the Si-4O structure, namely the basic structure of SiO2, and Si crystals coexist in the PS layers. The relative content of SiO2 to Si crystallites (R) increases with increase in Ia and decreases with the depth from the top surface of the PS layer. High R corresponds to intensive PL. These results suggest that PL may be connected with some kind of defects in SiO2 and/or defects in the boundary between Si crystallites and SiO2 structure in anodized PS layers, and that PL may be mainly emitted from the layer near the top surface of the PS layers.     

Quantitative TEM analysis of Al/Cu multilayer systems prepared by pulsed laser deposition

Thin films composed of alternating Al/Cu/Al layers were deposited on a (111) Si substrate using pulsed laser deposition (PLD). The thicknesses of the film and the individual layers, and the detailed internal structure within the layers were characterized by means of transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and energy-filtered TEM (EFTEM). Each Al or Cu layer consists of a single layer of nano-sized grains of different orientations. EFTEM results revealed a layer of oxide about 2 nm thick on the surface of the Si substrate, which is considered to be the reason for the formation of the first layer of nano-sized Al grains. The results demonstrate that the PLD technique is a powerful tool to produce nano-scale multilayered metal films with controllable thickness and grain sizes.     

Deposition behavior on the barrier layer of porous anodic alumina

This work is trying to fabricate nanostructure, for the first time, on the porous anodic alumina’s (PAA) barrier layer, which has smooth half-sphere structure. The deposition of indium oxide confirms that the materials can completely cover the surface area of the barrier layer. Both chemical dissolving the PAA or mechanical peel-off can bring free-standing indium oxide thin layer. Morphology study on both sides of deposited layer verifies that the ordered indium oxide nanorods can self-arrange well and form a half-sphere front surface and nanohole-array rear surface. This work confirms that we can get some special nanostructures with the help of the barrier layer of PAAs.