Ag Deposition Forms and Uniformity on Porous Silicon by Electrochemical Method

The electrochemical deposition technique was applied to achieve porous silicon (PS) surface passivated with Ag deposition for improving the properties of PS photoluminescence. The relation of Ag depositing forms to current density and the effect of PS hydrophilic surface on deposition uniformity were investigated. The experimental results indicated that there were two critical current densities (maximum and minimum) in which Ag was absent and electroplated on PS surface correspondingly, and the range of current density for deposition of Ag on porous silicon was from 50 μA/cm² to 400 μA/cm². The process of changing PS surface from hydrophobic into hydrophilic had positive effect on Ag deposition uniformity. Under the same experimental conditions, PS hydrophobic surface presented uneven Ag deposition.However, hydrophilic surface treated with SC-1 solution was even. Finally, the effect of PS surface passivation with Ag even deposition on photoluminescence intensity and stabilization of PS was studied. It was discovered that Ag passivation inhibited the degradation of PL intensity effectively. In addition, excessive Ag deposition had a quenching effect on room-temperature visible photoluminescence of PS.     

Hydrogen bubbles and formation of nanoporous silicon during electrochemical etching

Many nanoporous Si structures, including those formed by common electrochemical etching procedures, produce a uniformly etched nanoporous surface. If the electrochemical etch rate is slowed down, details of the etch process can be explored and process parameters may be varied to test hypotheses and obtain controlled nanoporous and defect structures. For example, after electrochemical etching of heavily n‐doped (R = 0.05–0.5 Ω·cm) silicon 〈100〉 single crystals at a current density of 10 mA cm^?2 in buffer oxide etch (BOE) electrolyte solution, defect craters containing textured nanopores were observed to occur in ring‐shaped patterns. The defect craters apparently originate at the hydrogen/BOE bubble interface, which forms during hydrogen evolution in the reaction. The slower hydrogen evolution due to low current density and high BOE viscosity allows sufficient bubble residence time so that a high defect density appears at the bubble edges where local reaction rates are highest. Current‐carrying Si? OH species are most likely responsible for the widening of the craters. Reducing the defect/doping density in silicon lowers the defect concentration and thereby the density of nanopores. Measurements of photoluminescence lifetime and intensity show a distinct feature when the few nanopores formed at the ring edges are isolated from each other. Overall features observed in the photoluminescence intensity by XPS strongly emphasize the role of surface oxide that influences these properties. Copyright © 2005 John Wiley & Sons, Ltd.     

Enhancement and stabilization of the photoluminescence from porous silicon prepared by Ag‐assisted electrochemical etching

In this paper, we present the results of studies on the photoluminescence (PL) of porous silicon (PSi) samples obtained by etching with the assistance of silver metal in different ways. If the Si sample, after being coated with a layer of silver nanoparticles, is electrochemically etched, its PL intensity becomes hundreds of times stronger than the PL intensity when it is chemically etched in the similar conditions. The difference in the PL intensities is explained partly by the anodic oxidation of silicon which occurs during the electrochemical etching process. The most obvious evidence that silicon had been oxidized anodically in the electrochemical etching process is the disappearance of the PSi layer and the appearance of the silicon oxide layer with mosaic structure when the anodization current density is large enough. The anodic oxidation has the effect of PSi surface passivation. Because of that, the PL of obtained PSi becomes stronger and more stable with time. Copyright © 2012 John Wiley & Sons, Ltd.     

化学氧化对多孔硅表面态和光致发光的影响

自1990年英国科学家Canham发现室温下多孔老（poroussilicon缩写为PS）的可见光区光致发光以来，在世界范围内迅速形成了一股强大的多孔硅研究热．硅是间接禁带半导体．禁带宽度为1．11eV，不可能在可见区发光．对于多孔硅在可见区的强烈荧光发射及其形成，Canham和Lehamm等分别建议可用量子线的尺寸限制效应未解释[1,2]．但Tsai和Hance等用FTIR研究经过后处理的多孔老样品[3]，认为多孔硅的发光与表面的硅氢化物相关，并提出硅的二氢化物SiH2的浓度与荧光强度相关．关于多孔硅的发光机制，还有非晶态发光[4]等说法．因止匕多孔硅的发…     

钇对掺饵多孔硅体系1.54μm发光的增强作用

首次报道了用恒电位电解法将饵、钇共掺入多孔硅（porous silicons, PS） 中，经高温退火处理后，观察到了在近红外区（1.54 μm）室温下较强的光致发光 （photoluminescence, PL），并与掺饵多孔硅（erbium-doped porous silicon, PS:Er）做了比较，发现钇的共掺入对掺饵多孔硅体系1.54 μm发射起了增强作用 。研究了饵、钇共掺杂多孔硅（erbium and yttrium co-doped porous silicon, PS:Er, Y）光致发光强度随温度的变化，发现PS:Er与Si:Er材料相似，有较强的 温度猝灭效应，而PS:Er，Y体系的PL强度随温度升高趋于平稳，且有增强的趋势， 受温度影响不明显，并初步探讨了其发光机制。     

Dipole polarizabilities of germanium clusters

Dipole polarizabilities of Ge_n clusters with 2–25 atoms are calculated using finite field (FF) method within density functional theory. The dipole moments and polarizabilities of clusters are sensitively dependent on the cluster geometries and electronic structures. The clusters with low symmetry and large HOMO–LUMO gap prefer to large dipole moments. The polarizabilities of the Ge_n clusters increase rapidly in the size range of 2–5 atoms and then fluctuate around the bulk value. The larger HOMO–LUMO gap may lead to smaller polarizability. As compared with the compact structure and diamond structure, the prolate cluster structure corresponds to a larger polarizability.     

纳晶稀土复合氧化物Dy1-xSrxCoO3-y I. 荧光特性及其机理研究

研究了在紫外(UV)激发下纳晶Dy1-xSrxCoO3-y(0.0≤x≤1.0)的荧光特性及其发光机理。结果表明, 纳晶Dy1-xSrxCoO3-y的荧光为量子限域型光致发光, 这源于纳晶的尺寸量子化效应, 其发光机理为量子限域模型。Dy^3^+的自身浓度猝灭机理为电隅极-电四极相互作用。纳晶电偶极跃迁的振子强度为3.256×10^-^6～41.00×10^-^6, 摩尔消光系数为0.8581-10.82。     

An X-ray spectroscopy study of CdS nanoparticles formed by the Langmuir–Blodgett technique on the surface of carbon nanotube arrays

The composition and electronic structure of cadmium sulfide (CdS) nanoparticles formed by the Langmuir–Blodgett (LB) technique on clean silicon wafers and the surface of vertically aligned carbon nanotube (CNT) arrays are studied by X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The samples were annealed in a vacuum at 175 °C and 225 °C to remove the organic matrix of the LB film. From the analysis of the XPS data the increased concentration of sulfate groups on the surface of CdS nanoparticles formed on CNTs and the electron density transfer from CdS to CNTs are determined. An increase in the LB film annealing temperature causes an increase in the degree of crystallinity and the CdS crystallite size and a decrease in the photoluminescence intensity of a CdS–CNT hybrid.     

Photoluminescence study of silicon solar cells irradiated with large fluence electrons or protons

In order to investigate the anomalous degradation of space silicon solar cells which was found in large fluence region, photoluminescence measurements are carried out for the cells irradiated with 1 MeV electrons with a fluence exceeding 1×10¹⁶ e/cm² and 10 MeV protons with a fluence exceeding 1×10¹³ p/cm². For both irradiation, the intensity of boron-related bound exiton line decreases with fluence and it disappears at the fluences where the anomalous degradation occurs. The dominant defect is a complex of an interstitial carbon and an interstitial oxygen (C_I–O_I). The generation of five-vacancy-defects was also observed for the proton irradiation. Variations of photoluminescence line intensity are discussed in terms of displacement damage dose calculated based on non-ionizing energy loss (NIEL).     

Surface passivated silicon nanocrystals with stable luminescence synthesized by femtosecond laser ablation in solution

We report the synthesis of silicon nanocrystals via a one-step route, namely, femtosecond laser ablation in 1-hexene under ambient conditions. The size of these silicon nanocrystals is 2.37 ± 0.56 nm as determined by transmission electron microscopy. Fourier transform infrared spectra and X-ray photoelectron spectra indicate that the surface of the silicon nanocrystals is passivated by organic molecules and is also partially oxidized by O(2) and H(2)O dissolved in the solution. These silicon nanocrystals emit stable and bright blue photoluminescence. We suggest that the photoluminescence originates from the radiative recombination of electron-hole pairs through the oxide-related centers on the surface of the silicon nanocrystals. The decay rate of the oxide-related surface recombination can be comparable to that of the direct band gap transition. In the excitation and emission spectra, a vibrational structure with nearly constant spacings (0.18 eV) is observed. We propose that the strong electron-phonon coupling between excitons and the longitudinal optical (LO) phonons of the Si-C vibration is responsible for this vibrational structure. The fluctuations in the peak resolution, about ±0.01 eV, are ascribed to the size distribution and presence of Si-O vibrations. These silicon nanocrystals offer stable luminescence and are synthesized through a "green" and simple route. They may find important applications in many fields, such as bioimaging and environmental science.     

Influence of Hydrogen and Oxygen on Porous Silicon Light Emission

The effect of oxygen and hydrogen on the photoluminescence intensity of porous silicon was examined. The results indicate that the presence of oxygen is necessary for visible light emission. In contrast, high hydrogen passivation is unfavorable for visible light emission.     

CdS:Mn nanocrystals passivated by ZnS: synthesis and luminescent properties

Synthesis and characterization of highly luminescent ZnS-passivated CdS:Mn (CdS:Mn/ZnS) core/shell structured nanocrystals are reported. Mn-doped CdS core nanocrystals are produced ranging from 1.5 to 2.3 nm in diameter with epitaxial ZnS shell of wider band gap via a reverse micelle process. UV irradiation-stimulated photo-oxidation of the ZnS shell results in formation of sulfate (ZnSO(4)) as determined by x-ray photoelectron spectroscopy, which increases the photoluminescence emission intensity and subsequent photostability. Luminescent relaxation lifetime data present two different decay components, consisting of slow decay emission from the Mn center and a fast decay emission from a defect-related center. The impact of the density of surface defect states upon the emission spectra is discussed.     

DNA/CdS纳米粒子复合体系的光谱和光电化学性质

在水溶液中以DNA作为模板和稳定剂, 构筑了DNA与CdS纳米粒子复合体系(DNA/CdS NPC), 研究DNA的含量, 单双链等对复合体系光电响应的影响, 并综合TEM, UV-Vis, IR和荧光光谱等对其形貌和光谱性质进行表征. 结果表明, CdS纳米粒子(CdS NPs)与DNA链之间主要通过静电作用结合; DNA模板对CdS NPs的禁带宽度没有影响; 以DNA模板合成的CdS NPs具有较高的表面态密度, 其对CdS NPs的荧光有增强作用, 而对光电流响应有抑制作用, 并且DNA在复合体系中的含量影响荧光增强和光电流减弱的程度. 该复合体系在荧光标记检测和DNA的定量分析方面可能具有应用前景.     

Exciton-mediated hydrosilylation on photoluminescent nanocrystalline silicon

A novel white light-promoted reaction using photoluminescent nanocrystalline silicon enables the hydrosilylation of alkenes and alkynes, providing stabilization of the porous silicon without significant loss of the photoemissive qualities of the material. Photopatterning and lithographic fabrication of isolated porous silicon structures are made possible. Experiments and observations are presented which indicate that the light promoted hydrosilylation reaction is unique to photoluminescent silicon, and does not function on nonemissive material. Hydrosilylation using a reactive center generated from a surface-localized exciton is proposed based upon experimental evidence, explaining the photoluminescence requirement. Indirect excitons formed by light absorption mediate the formation of localized electrophilic surface states which are attacked by incoming alkene or alkyne nucleophiles. Supra-band gap charge carriers have sufficient energy to react with nucleophilic alkenes and alkynes, thereupon causing Si-C bond formation, an irreversible event. The light-promoted hydrosilylation reaction is quenched by reagents that quench the light emission from porous silicon, via both charge transfer and energy transfer pathways.     

含时密度泛函理论研究低带隙的中性和带电的交替共聚芴的光学特性

用含时的密度泛函（TD—DFT）方法研究了低带隙的中性和带电的交替共聚芴Green 1）,该化合物是由烷染取代芴和（1,2,5-噻吩基-3,4-硫重氮基）喹喔啉噻吩（T—TDQ—T）单元交替重复组成,对他们的激发态特性用二维（2D）和三维（3D）实空间分析方法做了进一步分析．对于中性的Green 1,分别得到其带隙、键能、激子结合能和核驰豫能．用3D跃迁密度方法对中性和带电的Green 1的跃迁偶极矩进行比较可显示出跃迁偶极矩的取向和强度;用3D电荷差异密度方法显示出激发后的中性和带电的Green 1电荷重新分布和比较,用2D实空间分析方法（跃迁密度矩阵）来研究中性和带电的Green 1处于激发态时的电子空穴相干性．中性Green 1的激发态特性分别用TD—DFT和ZINDO两种方法进行了计算,比较得出电子-电子相互作用（在TD—DFT中）对激发态性质的重要影响．     

Light-emitting properties of amorphous Si:C:O:H layers fabricated by oxidation of carbon-rich a-Si:C:H films

Amorphous hydrogenated carbon-rich silicon–carbon alloy film (a-Si_0.3C_0.7:H) was deposited by reactive dc-magnetron sputtering of silicon target in argon–methane gas mixture. As-deposited film exhibits white photoluminescence at room temperature. After the deposition the samples were thermally annealed in dry Ar, wet Ar, or dry O₂ flow at 450 °C for 30 minutes that resulted in the enhancement of the photoluminescence intensity by a factor of about 5, 8 and 12 respectively. Spectral distribution of light emission was almost unchanged at the annealing in dry and wet argon while the oxidation in pure oxygen resulted in strong enhancement of a “blue” shoulder in the spectrum. EPR measurements at room temperature showed the decrease of spin concentration after thermal treatment in dry and wet argon and no EPR signal was detected after annealing in oxygen. FTIR and XPS measurements evidenced the formation of a-Si:O:C:H composite material after dry oxidation. Based on the measurements of photoluminescence in the temperature range 7–300 K it is suggested that light-emitting efficiency of a-Si_0.3C_0.7:H is determined by migration of the photo-excited carriers to non-radiative recombination centers. The physical mechanisms that can be involved in the strong enhancement of visible photoluminescence in Si:C:O:H layers are discussed.     

Optical gap and excitation energies of small Ge nanocrystals

Using the density functional theory (DFT) with the hybrid nonlocal exchange correlation functional of Becke and Lee, Yang and Parr (B3LYP), we have calculated the optical gap and the oscillator strengths for several of the lowest, spin and symmetry allowed, electronic transitions of small Ge nanocrystals passivated by hydrogen. The largest nanoparticle has an approximate diameter of 2 nm. Our results show that the optical gap exhibits size dependence (due to quantum confinement) roughly similar to silicon nanoparticles. However, for this range of diameters, there is an indirect-to-direct transition in the spectra of Ge as the size of the nanocrystals decrease. The first allowed excitation (fundamental optical gap) of each germanium nanoparticle has relatively larger oscillator strengths compared to silicon. The diameter of the smallest Ge nanocrystal capable to emit in the visible region of the spectrum, is approximately 1.9 nm, compared to 2.2 nm for silicon nanocrystals.     

Through‐Space Conjugated Molecular Wire Comprising Three π‐Electron Systems

A [2.2]paracyclophane‐based through‐space conjugated oligomer comprising three π‐electron systems was designed and synthesized. The arrangement of three π‐conjugated systems in an appropriate order according to the energy band gap resulted in efficient unidirectional photoexcited energy transfer by the Förster mechanism. The energy transfer efficiency and rate constants were estimated to be >0.999 and >10¹² s^?1, respectively. The key point for the efficient energy transfer is the orientation of the transition dipole moments. The time‐dependent density functional theory (TD‐DFT) studies revealed the transition dipole moments of each stacked π‐electron system; each dipole moment was located on the long axis of each stacked π‐electron system. This alignment of the dipole moments is favorable for fluorescence resonance energy transfer (FRET).     

电场中B2分子特性研究

利用密度泛函理论(DFT)B3LYP/6-3l1＋G(2d)方法研究在不同方向电场(0～＋0.02 a.u.)作用下的B2分子的基态键长、总能量、偶极矩、最高占据轨道(HOMO)能量、最低空轨道(LUMO)能量、能隙及势能曲线的变化规律. 结果表明: 在一定外加电场范围内, 随电场强度的增大, 分子键长变大; 总能量降低; 偶极矩增大; HOMO能级、LUMO能级均降低; 能隙依赖外电场方向, 平行分子轴(Z)方向电场使能隙递减, 垂直分子轴(X)方向电场使能隙递增; 分子势能降低, 平行分子轴线(Z)方向电场对分子势能的影响随着核间距的增大而增大, 原有的“势能平台”遭到破坏.     

Er3+、In3+等金属离子对多孔硅光致发光性质的影响

用阳极腐蚀的方法制备了多孔硅样品,用电化学方法在多孔硅中注入Er3+、In3+等金属离子,并对注入离子后多孔硅的光致荧光光谱进行了研究,结果表明：注入Er3+及In3+后的多孔硅在588nm处的发光峰强度大大增加,同时发光峰稍有展宽。随着离子注入时间的增长,强度继续增加,但当离子溶液浓度一定时,这种增强对时间具有饱和性。