An application of Raman spectroscopy on the measurement of residual stress in porous silicon

The porous silicon film, at micron level, and the bulk silicon substrate is a basic structure in MEMS components. The residual stress, due to the lattice mismatch between the film and the substrate, exists on the interface and may cause cracking and damaging on the component. Micro-Raman spectroscopy is an optical measurement method that was rapidly applied into the fields of chemistry, physics, material science and mechanics. In this paper, the method is introduced and applied to the study of the stress problems in porous silicon as follows. (1) In the electrochemical etching technique for porous silicon preparation, the distribution of the tensile residual stress along the transitional region between etched and un-etched area is experimentally studied and the result reveals the stress is continuous across the region. In the etched region it reaches GPa level, and in the transition region the gradient of the stress is high. (2) In chemical etching preparation of porous silicon, the residual stress rises up seriously in the cracked area, up to 0.92 GPa. With the porosity increasing, the tensile stress on the porous silicon film increases accordingly. The appearance of the porous silicon film surface is also given by metalloscope and atomic force microscope. The structure of the micro-pores is expected to have a close relation with the distribution of the residual stress.     

基片曲率法在多孔硅薄膜残余应力检测中的应用

通过基底曲率法设计和制作了一种测量薄膜应力的装置，它具有全场性、非接触性、高分辨率、无破坏、数据获取速度快等特点.使用该装置测量了电化学腐蚀法制作的多孔硅薄膜的残余应力，并研究了孔隙率和基底掺杂浓度对残余应力的影响，结果表明随着孔隙率的增加和硼离子掺杂浓度的提高，多孔硅表面的拉伸应力逐渐加大，由此表明多孔硅薄膜的微观结构与残余应力的大小有着密切的联系. 关键词： 薄膜 残余应力 孔隙率 多孔硅     

Effect of temperature on residual stress and mechanical properties of Ti films prepared by both ion implantation and ion beam assisted deposition

Ti films with a thickness of 1.6 μm (group A) and 4.6 μm (group B) were prepared on surface of silicon crystal by metal vapor vacuum arc (MEVVA) ion implantation combined with ion beam assisted deposition (IBAD). Different anneal temperatures ranging from 100 to 500 °C were used to investigate effect of temperature on residual stress and mechanical properties of the Ti films. X-ray diffraction (XRD) was used to measure residual stress of the Ti films. The morphology, depth profile, roughness, nanohardness, and modulus of the Ti films were measured by scanning electron microscopy (SEM), scanning Auger nanoprobe (SAN), atomic force microscopy (AFM), and nanoindentation, respectively. The experimental results suggest that residual stress was sensitive to film thickness and anneal temperature. The critical temperatures of the sample groups A and B that residual stress changed from compressive to tensile were 404 and 428 °C, respectively. The mean surface roughness and grain size of the annealed Ti films increased with increasing anneal temperature. The values of nanohardness and modulus of the Ti films reached their maximum values near the surface, then, reached corresponding values with increasing depth of the indentation. The mechanism of stress relaxation of the Ti films is discussed in terms of re-crystallization and difference of coefficient of thermal expansion between Ti film and Si substrate.     

Ellipsometric studies of porous silicon

Multiple-angle-of-incidence (MAI) ellipsometry at 632.8 nm is used to characterize P and P⁺ porous silicon of high porosity. Complex dielectric constants are obtained, from which the porosity can be estimated qualitatively. The properties of the imaginary part of the dielectric constants are studied and the possible causes are discussed. Two dielectric constants, perpendicular and parallel to the interface, respectively, are measured based on a semi-infinite anisotropic model. Ellipsometric studies demonstrate a larger difference between the two dielectric constants in P⁺ porous silicon, but both P and P⁺ samples only show weak anisotropy, i.e., a network-like structure, which tends towards isotropy, is more suitable for porous silicon than a column-like one, which shows strong anisotropy.     

Effect of porosity on the laser induced damage threshold of porous anodic alumina films

Thermal stress of porous alumina films has been simulated by finite element method based on thermal transfer equation and thermal stress formulas. The influence of equivalent thermal conductivity and elastic modulus on laser induced damage threshold (LIDT) has been studied. It was found that the biggest circumferential tensile stress will be small with the porosity from 15% to 35%, and it effectively improves the LIDT. The equivalent thermal conductivity and LIDT decreases with the increase of porosity. The equivalent elastic modulus decreases and LIDT increase with the increase of porosity.     

Effect of spraying power on the microstructure and mechanical properties of supersonic plasma-sprayed Ni-based alloy coatings

The aim of this paper was to investigate the microstructure and mechanical properties of the supersonic plasma-sprayed Ni-Cr-B-Si-C coatings prepared at different spraying powers. The microstructure, phase composition, porosity, Young's modulus, micro-hardness, and residual stresses of the coatings were investigated and determined. The variations of the porosity, Young's modulus and micro-hardness of the coatings were evaluated by using statistical method. Results showed that the variations of porosity, Young's modulus and micro-hardness of the coatings followed the Weibull distributions. With increasing the porosity, the micro-hardness and Young's modulus of the coating decreased. The mean value of the Young's modulus of the coating calculated from Weibull plot was almost proportional to the square root of the micro-hardness of the coating. With increasing the power, Young's modulus of the coating increased, which, in turn, resulted in the increment of the residual stress at the coating surface.     

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。     

Characterization of thermal, optical and carrier transport properties of porous silicon using the photoacoustic technique

In this work, the porous silicon layer was prepared by the electrochemical anodization etching process on n-type and p-type silicon wafers. The formation of the porous layer has been identified by photoluminescence and SEM measurements. The optical absorption, energy gap, carrier transport and thermal properties of n-type and p-type porous silicon layers were investigated by analyzing the experimental data from photoacoustic measurements. The values of thermal diffusivity, energy gap and carrier transport properties have been found to be porosity-dependent. The energy band gap of n-type and p-type porous silicon layers was higher than the energy band gap obtained for silicon substrate (1.11 eV). In the range of porosity (50-76%) of the studies, our results found that the optical band-gap energy of p-type porous silicon (1.80-2.00 eV) was higher than that of the n-type porous silicon layer (1.70-1.86 eV). The thermal diffusivity value of the n-type porous layer was found to be higher than that of the p-type and both were observed to increase linearly with increasing layer porosity.     

Audible vibration diagnostics of thermo-elastic residual stress in multi-crystalline silicon wafers

This paper presents audible vibratory mode data obtained by mechanically exciting acoustic modes in multi-crystalline silicon wafers with various levels and distributions of residual stress. Natural frequency data from the silicon wafers is found to correlate with residual stress optical polariscopy measurements. The data is fit with both linear and quadratic models with correlation coefficients of 0.8. The results reveal a dependence of wafer audible mode frequencies on residual stress level that may be useful for solar cell mechanical quality control and breakage inspection.     

Porosity, mechanical properties, residual stresses of supersonic plasma-sprayed Ni-based alloy coatings prepared at different powder feed rates

The aim of this paper was to investigate the effect of powder feed rate (PFR) on the microstructure and mechanical properties of the supersonic plasma-sprayed Ni-Cr-B-Si-C coatings. The microstructure, porosity and mechanical properties of the coatings and the residual stresses at the coating surfaces were experimentally determined. Results showed that the variations of porosity, elastic moduli and micro-hardness of the coatings followed Weibull distribution. From the statistical trend, the porosity of the coating increased with increasing PFR. However, the elastic modulus and the micro-hardness of the coating decreased and reached local minima and then increased with increasing PFR. Elastic modulus could be generally considered to be an increasing function of micro-hardness. The mean value of the elastic modulus of the coating calculated from Weibull plot was almost proportional to the square root of the mean value of the micro-hardness of the coating. Moreover, with increasing PFR, the residual stress at the coating surface, which was mainly governed by the elastic modulus of the coating, decreased to a local minimum and then increased.     

Modeling the influence of the porosity of laser-ablated silicon films on their photoluminescence properties

Nanostructured porous Si-based films produced by pulsed laser ablation (PLA) from a silicon target in residual helium gas can exhibit both size-dependent (1.6-3.2 eV) and fixed photoluminescent (PL) bands (1.6 and 2.2 eV) with their relative contributions depending on the film porosity. We study the influence of prolonged oxidation in ambient air on properties of the fixed PL bands, associated with oxidation phenomena, and their correlation with structural properties of the films. In addition, we propose a model describing the appearance of surface radiation states for oxidized films of various porosities. Our experiments and numerical simulations led to a conclusion that the 1.6 eV PL is due to a mechanism involving a recombination through the interfacial layer between Si core and an upper oxide of nanocrystals. This mechanism gives the optimal porosity of 73% for the most efficient production of 1.6 eV PL centers that is in excellent agreement with our experimental results.     

Tensile strength of aluminium nitride films

Two-layered aluminium nitride (AlN)/silicon nitride microbridges were fabricated for microbridge tests to evaluate the elastic modulus, residual stress and tensile strength of the AlN films. The silicon nitride layer was added to increase the robustness of the structure. In a microbridge test, load was applied to the centre of a microbridge and was gradually increased by a nano-indenter equipped with a wedge tip until the sample was broken, while displacement was recorded coherently. Measurements were performed on single-layered silicon nitride microbridges and two-layered AlN/silicon nitride microbridges respectively. The data were fitted to a theory to derive the elastic modulus, residual stress and tensile strength of the silicon nitride films and AlN films. For the AlN films, the three parameters were determined to be 200, 0.06 and 0.3?GPa, respectively. The values of elastic modulus obtained were consistent with those measured by conventional nano-indentation method. The tensile strength value can be used as a reference to reflect the maximum tolerable tensile stress of AlN films when they are used in micro-electromechanical devices.     

AFM investigation of nanoparticles formed on silicon surface by femtosecond laser pulses

It is shown by atomic force microscopy that nanoparticles formed upon ablation of surface of single-crystal and porous silicon by femtosecond laser pulses have a lateral size from several tens to 200 nm and a height from 2 to 30 nm. Dependences of the nanoparticle sizes and surface concentrations on the residual pressure, which demonstrate the gas atmosphere influence on the nanoparticle formation, are obtained.     

Estimating the extent of surface oxidation by measuring the porosity dependent dielectrics of oxygenated porous silicon

Surface oxidation and porosity variation play significant roles in the dielectric performance of porous silicon (PS) yet discriminating the contribution of these events is a challenge. Here we present an analytical solution that covers contributions from the components of silicon oxide surface, silicon backbone and voids using a serial–parallel capacitance structure. Agreement between modeling predictions and measurement has been realized, which turns out an effective method that enables us to estimate the extent of surface oxidation of a specimen by measuring the porosity dependent dielectric response of the chemically passivated PS, and provides guidelines that could be useful for designing dielectric porous structures with surface oxidation.     

Influence of experimental parameters on physical properties of porous silicon and oxidized porous silicon layers

This paper reports physical properties of porous silicon and oxidized porous silicon, manufactured by anodisation from heavily p-type doped silicon wafers as a function of experimental parameters. The growth rate and refractive index of the layers were studied at different applied current densities and glycerol concentrations in electrolyte. When the current density varied from 5 to 100 mA/cm², the refractive index was between 1.2 and 2.4 which corresponded to a porosity range from 42 to 85%. After oxidation, the porosity decreased and was between 2 and 45% for a refractive index range from 1.22 to 1.46. The thermal processing also induced an increase in thickness which was dependent on the initial porosity. This increase in thickness was more important for the lowest porosities. Lastly, the roughness of the porous layer/silicon substrate interface was studied at different applied current densities and glycerol concentrations in solution. Roughness decreased when the current density or glycerol concentration increased. Moreover, roughness was also reduced by thermal oxidation.     

Investigation of silicon structures with periodically varying porosity by x-ray diffractometry methods

The features of formation of silicon structures with a periodically varying porosity are investigated by X-ray diffractometry. It is revealed that the magnitude of anode current density corresponding to the formation of a layer with higher porosity that is part of a multilayer porous structure also affects the porosity of a second, less porous layer. As time elapses, the single-crystalline matrix of which porous layers consist is amorphized and a structure consisting of amorphous layers with a periodically varying density arises.     

Spatial versus quantum confinement in porous amorphous silicon nanostructures

Light-emitting porous amorphous silicon has been produced by anodization in HF of hydrogenated amorphous silicon films. The maximal thickness of the porous films is limited by the onset of an instability which results in the formation of large channels short-circuiting the amorphous layer. This is due to the high resistivity of the amorphous silicon films as compared to that of the electrolyte. Confinement effects on the electron wavefunction are analyzed in situ using photoluminescence measurements in hydrofluoric acid and compared to those observed in porous crystalline silicon. For crystalline silicon, a huge blue shift of the photoluminescence is observable upon reducing the size of the structures by photo-etch, showing clear evidence of quantum confinement effects in this material. No shift has been observed when carrying out the same experiment with amorphous silicon. This indicates that the extent of the wavefunction in the bandtail states involved in luminescence is too small to be sensitive to confinement down to the minimum sizes of our porous material ( 3 nm). Measurements of the width and the temperature dependence of the photoluminescence demonstrate that the Urbach energy does not change upon increasing the porosity, i.e., upon decreasing the size of the a-Si:H nanostructures, in contradiction with what has been reported in ultrathin a-Si:H multilayers. Received: 3 August 1998     

Size Control of Porous Silicon Nanoparticles by Electrochemical Perforation Etching

Size‐controlled porous silicon‐based nanoparticles are prepared by pulsed electrochemical etching of single crystal silicon wafers, followed by ultrasonic fracture of the freestanding porous layer. When high‐current density pulses are applied periodically during the porous layer etching process, a porous multilayer results in which porous layers are separated by thin layers of much higher porosity. Ultrasonic fracture selectively cleaves the porous film along these high‐porosity perforations, providing greater size control and improved yields (by 5x) of the resulting porous nanoparticles. The effect of pulse width and repetition rate is systematically studied: tunability of the average nanoparticle size in the range 160–350 nm is demonstrated.     

嵌入多孔硅中的C60分子的发光行为

1990年团簇C60分子分离的成功[1],立即引起了科学界的极大重视,有关C60分子的超导电性、光谱特性以及电子能级结构的研究报道与日俱增,由于单个C60分子是直径为7.1Å的球形分子,因而在某种程度上对于由C60分子聚集而成的具有几个纳米尺寸的CBO微晶的体系应该也具有类似于半导体超微粒低维量子限域的物理特性.     

Mechanical properties of sol-gel derived lead zirconate titanate thin films by nanoindentation

Lead zirconate titanate (PZT) thin films are deposited on platinized silicon substrate by sol-gel process. The crystal structure and surface morphology of PZT thin films are characterized by X-ray diffraction and atomic force microscopy. Depth-sensing nanoindentation system is used to measure mechanical characteristics of PZT thin films. X-ray diffraction analyses confirm the single-phase perovskite structures of all PZT thin films. Nanoindentation measurements reveal that the indentation modulus and hardness of PZT thin films are related with the grain size and crystalline orientation. The increases of the indentation modulus and hardness with grain size are observed, indicating the reverse Hall-Petch effect. Furthermore, the indentation modulus of (1 1 1)-oriented PZT thin film is higher than those of (1 0 0)- and random-oriented films. The consistency between experimental data and numerical results of the effective indentation moduli for fiber-textured PZT thin films using Voigt-Reuss-Hill model is obtained.