Capacitance method for determination of basic parameters of porous silicon

Microstructure and physical characteristics of porous silicon (PS), such as thickness, bulk porosity, dielectric permittivity, and refractive index depend directly on the production conditions, e.g., on the electrolyte composition, anodizing current density, duration of etching, etc. Various possibilities of applications of PS generate high interest towards elaboration of new or modified operative nondestructive methods for testing the microstructure characteristics of PS layer for the adjustment of its processing regimes.According to the mechanism of formation of PS and experimental data on the morphology of PS layers, a porous layer is represented as a structure with cylindrical pores of equal lengths piercing the silicon frame. This approximation allows considering the structure using the parallel plate model within parallel-connected capacitances of the silicon frame and the air or liquid dielectric-filled pores.A method for obtaining information on the volume porosity, thickness, and dielectric permittivity of a PS layer by means of two measurements of the structure capacitance—in dry air and when the pores are filled by a condensed medium having a dielectric permittivity strongly differing from that of air (e.g., methanol)—is described.Sufficiently good agreement has been revealed between the data calculated from the capacitance measurements and obtained by other methods.     

Low-porosity porous silicon nanostructures on monocrystalline silicon solar cells

In this work we present a study of low-porosity porous silicon (PS) nanostructures stain etched on monocrystalline silicon solar cells. The PS layers reduce the reflectance, improve the diffusion of dopants by rapid thermal processes, and increase the homogeneity of the sheet resistance. Some samples were subjected to chemical oxidation in HNO₃ to reduce the porosity of the surface layer. After the diffusion process, deposition of a SiN_x antireflection layer, and screen printing of the samples, an efficiency of 15.5% is obtained for low-porosity PS solar cells, compared with an efficiency of 10.0% for standard PS cells and 14.9% for the reference Cz cells.     

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。     

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.     

The light-enhanced NO₂ sensing properties of porous silicon gas sensors at room temperature

The NO2 gas sensing behavior of porous silicon(PS) is studied at room temperature with and without ultraviolet(UV) light radiation.The PS layer is fabricated by electrochemical etching in an HF-based solution on a p +-type silicon substrate.Then,Pt electrodes are deposited on the surface of the PS to obtain the PS gas sensor.The NO2 sensing properties of the PS with different porosities are investigated under UV light radiation at room temperature.The measurement results show that the PS gas sensor has a much higher response sensitivity and faster response-recovery characteristics than NO2 under the illumination.The sensitivity of the PS sample with the largest porosity to 1 ppm NO2 is 9.9 with UV light radiation,while it is 2.4 without UV light radiation.We find that the ability to absorb UV light is enhanced with the increase in porosity.The PS sample with the highest porosity has a larger change than the other samples.Therefore,the effect of UV radiation on the NO2 sensing properties of PS is closely related to the porosity.     

Growth of ZnO Nanostructures on Porous Silicon and Oxidized Porous Silicon Substrates

We have investigated an oxidation of substrate effect on structural morphology of zinc oxide (ZnO) rods. ZnO rods are grown on porous silicon (PS) and on thermally oxidized porous silicon substrates by carbothermal reduction of ZnO powder through chemical vapour transport and condensation. Porous silicon is fabricated by electrochemical etching of silicon in hydrofluoric acid solution. The effects of substrates on morphology and structure of ZnO nanostructures have been studied. The morphology of substrates is studied by atomic force microscopy in contact mode. The texture coefficient of each sample is calculated from X-ray diffraction data that demonstrate random orientation of ZnO rods on oxidized porous silicon substrate. The morphology of structures is investigated by scanning electron microscopy that confirms the surface roughness tends to increase the growth rate of ZnO rods on oxidized PS compared with porous silicon substrate. A green emission has been observed in ZnO structures grown on oxidized PS substrates by photoluminescence measurements.     

The light-enhanced NO2 sensing properties of porous silicon gas sensors at room temperature

The NO2 gas sensing behavior of porous silicon（PS） is studied at room temperature with and without ultraviolet（UV） light radiation.The PS layer is fabricated by electrochemical etching in an HF-based solution on a p ＋-type silicon substrate.Then,Pt electrodes are deposited on the surface of the PS to obtain the PS gas sensor.The NO2 sensing properties of the PS with different porosities are investigated under UV light radiation at room temperature.The measurement results show that the PS gas sensor has a much higher response sensitivity and faster response-recovery characteristics than NO2 under the illumination.The sensitivity of the PS sample with the largest porosity to 1 ppm NO2 is 9.9 with UV light radiation,while it is 2.4 without UV light radiation.We find that the ability to absorb UV light is enhanced with the increase in porosity.The PS sample with the highest porosity has a larger change than the other samples.Therefore,the effect of UV radiation on the NO2 sensing properties of PS is closely related to the porosity.     

On the morphology of stain-etched porous silicon films

Morphology of stain-etched porous silicon films was investigated by a non-destructive technique, based on reflectance spectrometry: dielectric function profiles were computed by spectral reflectance via a finite difference model, and porosity was deduced by the effective medium approximation. Theoretical calculations were supported by high-resolution electron microscopy observations. The relations among oxidising species concentration in the etching solution, porosity profile and surface reflectance of the films were investigated.     

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.     

Structure and photoluminescence properties of ZnS films grown on porous Si substrates

ZnS films were deposited on porous silicon (PS) substrates with different porosities. With the increase of PS substrate porosity, the XRD diffraction peak intensity decreases and the surface morphology of the ZnS films becomes rougher. Voids appear in the films, due to the increased roughness of PS structure. The photoluminescence (PL) spectra of the samples before and after deposition of ZnS were measured to study the effect of substrate porosity on the luminescence properties of ZnS/PS composites. As-prepared PS substrates emit strong red light. The red PL peak of PS after deposition of ZnS shows an obvious blueshift. As PS substrate porosity increases, the trend of blueshift increases. A green emission at about 550 nm was also observed when the porosity of PS increased, which is ascribed to the defect-center luminescence of ZnS. The effect of annealing time on the structural and luminescence properties of ZnS/PS composites were also studied. With the increase of annealing time, the XRD diffraction peak intensity and the self-activated luminescence intensity of ZnS increase, and, the surface morphology of the ZnS films becomes smooth and compact. However, the red emission intensity of PS decreases, which was associated with a redshift. White light emission was obtained by combining the luminescence of ZnS with the luminescence of PS.     

Enhanced physical properties of porous silicon for improved hydrogen gas sensing

In the current communication, porous silicon samples were prepared by pulsed photoelectrochemical etching using a hydrofluoric acid-based solution. The structural and gas-sensing properties of the samples were studied. Apart from the cycle time T and pause time T_off of the pulsed current, a novel parameter, in the shape of the current named ‘delay time T_d’ was introduced. Our results showed that by optimization of delay time, the porosity of samples can be controlled due to the chemical preparation of silicon surface prior to electrochemical anodization. The fourier-transform infrared measurements of porous silicon (PS) layers on Si substrate showed that the typical PS surface was characterized by chemical species like Si–H and Si–O–Si terminations. The two-minute delay before applying electrical current was considered sufficient for the fabrication of higher porosity (83%), more uniform, and more stable structures. The photoluminescence (PL) peak of the optimized sample showed higher intensity than the other samples. An obvious PL blue shift also revealed a change in the crystallographic characteristics of silicon due to quantum confinement effects. Metal–semiconductor–metal diodes with Schottky contacts of nickel were fabricated on PS samples and the potential application of optimized substrates for the improved sensitivity, stability, response time and recovery time of hydrogen gas sensors was subsequently studied.     

The effect of PS porosity on the structure,optical and electrical properties of ZnS/PS

ZnS films were deposited on porous silicon (PS) substrates with different porosities by pulsed laser deposition (PLD). The crystalline structure, surface morphology of ZnS films on PS substrates and optical, electrical properties of ZnS/PS composites were studied. The results show that, ZnS films deposited on PS substrates were grown in preferred orientation along β-ZnS (111) direction corresponding to crystalline structure of cubic phase. With the increase of PS porosity, the XRD diffraction peak intensity of ZnS films decreases. Some voids and cracks appear in the films. Compared with as-prepared PS, the PL peak of PS for ZnS/PS has a blueshift. The larger the porosity of PS, the greater the blueshift is. A new green light emission located around 550 nm is observed with increasing PS porosity, which is ascribed to defect-center luminescence of ZnS. The blue, green emission of ZnS combined with the red emission of PS, a broad photoluminescence band (450–750 nm) is formed. ZnS/PS composites exhibited intense white light emission. The I–V characteristics of ZnS/PS heterojunctions showed rectifying behavior. Under forward bias conditions, the current density is large. Under reverse bias conditions, the current density nearly to be zero. The forward current increases with increasing PS porosity. This work lay a foundation for the realization of electroluminescence of ZnS/PS and solid white light emission devices.     

Influence of alkali metallization (Li, Na and K) on photoluminescence properties of porous silicon

We present results for alkali metallization effects on photoluminescence (PL) properties of porous silicon (PS). The metallization of PS was realized by immersion plating in solutions containing 3 mM LiNO₃, KNO₃ and NaNO₃ metal salts. The surface bond configuration of PS was monitored by Fourier transmission infrared spectroscopy (FTIR) and it was found that the PS surface was oxidized after metallization. Surface properties of PS were investigated by field emission scanning electron microscopy (FE-SEM) and it was found that the PS surface was covered by alkali metals for short immersion times. The PL intensity increased for critical immersion times and PL spectrum shifted to high energy region with the metallization. The experimental results suggest a possibility that the metallization provides a relatively easy way to achieve an increase in the PL intensity and oxidation of the PS surface.     

金属/多孔硅/单晶硅(M/PS/Si)微结构的电学特性

采用双槽电化学腐蚀法制备多孔硅层,然后在多孔硅表面沉积形成金属电极,制备出M/PS/Si微结构.利用SEM分析多孔硅的表面形貌,通过测试其I-V特性分析M/PS/Si微结构的电学特性.结果表明:由Pt做电极形成的M/PS/Si结构,表现出非整流特性.M/PS/Si结构的I-V曲线由线性区和非线性区组成,多孔硅孔隙率越高的M/PS/Si结构的I-V特性曲线线性区越宽.由Cu做电极形成的M/PS/Si结构,表现出整流特性.其整流比随多孔硅孔隙率增加而减小. 关键词： M/PS/Si微结构 孔隙率 I-V特性')" href="#">I-V特性 欧姆接触     

多孔硅后处理对其镶嵌染料光学特性的影响

对多孔硅进行真空退火处理和暴露大气快速退火处理,将有机染料香豆素102(C102)镶嵌其中,研究镶嵌复合膜发光特性的变化。通过比较多孔硅退火处理前、后傅立叶红外(FT-IR)吸收光谱的变化,从多孔硅与镶嵌染料分子间的能量传递方式角度出发,解释了PS表面态氧化能改善镶嵌复合膜发光特性的原因。实验通过改变多孔硅表面态,提高了复合膜的发光效率和多孔硅基体的透明程度,证明了多孔硅是一种良好的载体,在发展固体激光器方面有一定的应用,同时为实现硅基蓝绿发光开辟一条新的途径。     

The role of surface oxidation on luminescence degradation of porous silicon

This study reports a comparative analysis on time dependent degradation of photoluminescence (PL) spectra of porous silicon (PS) during dark-aging (DA) and photo-aging (PA). Fourier Transform Infrared (FTIR) spectroscopy studies have been performed to get an insight on possible chemical changes in the PS surface. It has been found that SiH_x bonds decrease progressively while SiO_x bonds increase. FTIR and PL measurements revealed presence of blue shifts in the PL spectra during the aging stages (PA and DA). While the PL intensity of dark aged PS shows a decrease during the first 3 weeks and an increase afterwards, the PL intensity decreases continuously for photo-aged PS. The change in the PL spectra has been investigated by overlapping of two different PL bands which are reflective of oxidation of PS surface and size of Si naonocrystallites. A possible bond configuration model about the oxidation of PS surface has also been proposed. The results are interpreted in terms of quantum size effects in PS and the influence of the surface composition.     

An investigation of natural oxidation process on stain-etched nanoporous silicon by micro-Raman spectroscopy

Micro-Raman spectra of porous silicon (PS) samples as-formed, from stain etching process using heavily doped silicon wafers, and after 750 days storage in air were analyzed around Si peak (300-600 cm⁻¹) and at photoluminescence (PL) range (300-8000 cm⁻¹). The first-order Raman spectra in the vicinity of Si peak were fitted from phonon confinement model including a term taking into account the amorphous phase. This analysis allowed the determination of the correlation length, which corresponds to the crystallite size, also considering the PS natural oxidation process. The photoluminescence band, generated by Si crystallites located on the outermost part of the PS layer, was also fitted with a Gaussian distribution. In order to investigate the porous silicon nanostructure, the micro-Raman spectra were measured for different sets of porous silicon samples. These spectra showed good reproducibility and the effects of the natural oxidation at different periods. A slight decrease in the crystallite size was observed for all samples sets studied, while the spectral part related to the amorphous phase did not describe significant changes. The central position of PL band, analyzed after the oxidation process, exhibited consistently a shift to higher energies. In addition, top view high resolution scanning electron microscopy (HRSEM) images also confirmed a reasonable reproducibility and homogeneity. The results showed that after storing in air, natural oxidation can modify the Si crystallites size at the surface but not increase the amorphous phase.     

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.     

Anodic oxidation of porous silicon bilayers

This paper focuses on the study of the effect of anodic oxidation in porous silicon bilayers composed of two porous layers of different porosities. The order of the two types of layers has been alternated, and the thicknesses and refractive indices have been optically characterized by Fourier transform infrared spectroscopy. The results show that the refractive index of anodic oxidized porous silicon is reduced significantly with respect to just formed porous silicon. It is also observed that the quality of the oxidation is related to the porosity of the inner porous layer of the silicon bilayer structure. This effect is interpreted in terms of quantum size effects.     

Surface analysis of thermally annealed porous silicon

Quasi-monocrystalline porous silicon (QMPS) has high potential for photovoltaic application for its enhanced optical absorption compared to bulk silicon in the visible range of solar spectrum. In this study, QMPS was formed from low porosity (∼20-30%) porous silicon (PS) produced by electrochemical anodization, and thermal annealing in the temperature range 1050-1100 °C under pure hydrogen ambient for a duration of 30 min. We analyzed the material surface by grazing incidence X-ray diffraction (GIXRD), field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM) and dynamic secondary ion mass spectroscopy (SIMS) study. The crystallinity was confirmed by GIXRD while FESEM studies revealed that the surface layer is pore free with voids embedded inside the body. AFM studies indicated relatively smooth and uniform surface and the dynamic SIMS study showed the depth profiles of impurities present in the material.