硅纳米针及其光致发光特性(英文)

pacc:7855C Theusageofhydrofluoricacid(HF)orfluo ridewasbelievedtobeindispensableinthefabri cationofporoussilicon(PSi)sinceitsdiscovery. Herewereportanovelmethod,metal-assisted -chemical-reaction-etching(MACRE) method,topreparePSiwithoutHFacidorfluo rid…     

Formation mechanism of Si(1 0 0) surface morphology in alkaline fluoride solutions

Formation mechanism of Si(1 0 0) surface morphology in alkaline fluoride solutions was investigated both theoretically and experimentally. By analysis of Raman spectra of silicon wafer surfaces and three kinds of etching solutions (NaOH, NaOH/NH₄F, and NaOH/NH₄F/Na₂CO₃) with and without addition of Na₂SiO₃·9H₂O, no Si-F bond is formed, F⁻ and CO₃²⁻ ions accelerate the condensation of Si-OH groups. Based on experimental results, it is proposed that bare silicon and silicon oxide coexist at the wafer surface during etching process and silicon oxide of different structure, size, and site at the surface manufacture different surface morphology in alkaline fluoride solution.     

Optical characteristics of porous silicon structures

Morphology, composition, and optical properties of porous silicon on single-crystal-silicon substrates and p-n junctions are studied. Substrate orientation, type of conduction, and composition of etching agent are varied to obtain nano-, meso-, and microporous silicon and multilayer porous structures. A correlation of the photoluminescence intensity and intensity of the IR absorption band peaking at 616 cm^?1 is related to the presence of Si-Si bonds.     

Mechanism of primary self-organization in porous silicon with a regular structure

A mechanism for self-organization of a regular system of pores in porous silicon is proposed. According to this mechanism, the self-organization obeys the general kinetic laws for a system of charge carriers. The mean interpore spacing in porous silicon prepared from p-Si and the anodizing current density required for synthesizing porous silicon through anodic etching are evaluated in terms of the proposed mechanism. The results obtained are in good agreement with the available experimental data. The dependence of the mean interpore spacing on the carrier concentration in the initial silicon is predicted to be similar to the function L(n) ～ n^?1/2. The validity of the proposed mechanism is confirmed by computer simulation.     

IR study on the effect of chloride ion on porous silicon

Infrared (IR) studies have been carried out on porous silicon samples to infer on the changes in the surface bonding in the porous silicon (PS) layer due to chloride (Cl⁻) and subsequent fluoride (F⁻) ion exposures with respect to time. It is observed that silicon hydride linkages decreases and silicon oxide linkages increases with time of exposure to HCl, suggesting a possible oxidation of the porous layer. IR study revealed the formation of SiO (silanones) bonds. A possible mechanism for the formation of silanones from SiOH species has been proposed to explain the observation. We also observed a saturation of silicon oxide groups with complete disappearance of silicon hydride peaks indicating the complete conversion of silicon hydride to oxides. Furthermore on exposure to F⁻, the IR spectrum showed a rapid destruction of silicon oxygen linkages.     

X-ray photoelectron spectroscopic studies of black silicon for solar cell

The black silicon has been produced by plasma immersion ion implantation (PIII) process. The microstructure and optical reflectance are characterized by field emission scanning electron microscope and spectrophotometer. Results show that the black silicon appears porous or needle-like microstructure with the average reflectance of 4.87% and 2.12%, respectively. The surface state is investigated by X-ray photoelectron spectroscopy (XPS) technique. The surface of the black silicon is composed of silicon, carbon, oxygen and fluorine element. The formation of Si_xO_yF_z in the surface of black silicon can be proved clearly by the O 1s, F 1s and Si 2p XPS spectra. The formation mechanism of the black silicon produced by PIII process can be obtained from XPS results. The porous or needle-like structure of the black silicon will be formed under the competition of SF_x⁺ (x ≤ 5) and F⁺ ions etching effect, Si_xO_yF_z passivation and ion bombardment.     

Coupled chemical reactions in dynamic nanometric confinement: V. The influence of Li+ and F− ions on etching of nuclear tracks in polymers

Etching of continuous nuclear tracks in thin polymer foils from both sides is known to lead to the formation of double-conical nanopores. In this work and related ones we try to find out how this etching kinetics is modified when materials are added which react with each other upon their contact towards some new product that influences the etching. For that purpose we have chosen here Li⁺ and F^? ions as the additions, which react with each other to form LiF precipitations. The coupled etching and precipitation kinetics is recorded by measuring the electrical current that is transmitted through the foils upon application of a low-frequency alternating sinusoidal voltage. Depending on the etchant concentrations, the etching temperature and the time of Li⁺ and F^? addition, different effects are found that range from (a) no alteration of the transmitted current at all, via (b) the emergence of an alternating current with a temperature-dependent amplitude, and (c) the complete vanishing of any transmitted current at all, towards (d) chaotic transmitted current histories with phases with strong current spike emission and (e) rather quiet phases, alternating with each other in a rather unsystematic way. The observed effects are ascribed to (a) the enhanced penetration efficiency of both the Li⁺ and F^? ions through the polymeric bulk and/or latent ion tracks after the removal of the polymer's protective surface layer by the etchant, (b) the high mobility of preferentially the F^? ions within the polymer, (c) the LiF precipitation within the polymer or on its surface upon encounter of Li⁺ and F^? ions, (d) the nanofluidic properties of narrow etched tracks covered with Li⁺ ions on the wall surfaces and F^? ions beyond, and/or (e) the formation of LiF membranes within the etched tracks.     

Realization of silicon quantum wires by selective chemical etching and thermal oxidation

Ultra-fine silicon quantum wires with SiO₂ boundaries were successfully fabricated by combining SiGe/Si heteroepitaxy, selective chemical etching and subsequent thermal oxidation. The results are observed by scanning electron microscopy. The present method provides a very controllable way to fabricate ultra-fine silicon quantum wires, which is fully compatible with silicon microelectronic technology. As one of the key processes of controlling the lateral dimensions of silicon quantum wires, the wet oxidation of silicon wires has been investigated, self-limiting wet oxidation phenomenon in silicon wires is observed. The characteristic of the oxidation retardation of silicon wires is discussed.     

Porous Silicon@Polythiophene Core–Shell Nanospheres for Lithium‐Ion Batteries

Polythiophene‐coated porous silicon core–shell nanospheres (Si@PTh) composite are synthesized by a simple chemical oxidative polymerization approach. The polythiophene acts as a flexible layer to hold silicon grains when they are repeatedly alloying/dealloying with lithium during the discharge/charge process. The long lifespan and high‐current‐density rate ­capability (at a current of 8 A g^?1) of the Si@PTh composite are vastly improved compared with as‐prepared Si spheres. Typically, these Si@PTh composite electrodes achieve a reversible capacity of 1130.5 mA h g^?1 at 1 A g^?1 current density after 500 cycles, and can even possess a discharge capacity up to 451.8 mA h g^?1 at 8 A g^?1. The improved electrochemical performance can be ascribed to the synergy effects of the flexible PTh coating and the distinctive core–shell nanospheres with porous structure, which can largely alleviate the volume expansion of the Si during alloying with lithium.     

稀土（Tb，Gd）掺杂多孔硅的光致发光性能研究

用电化学方法对多孔硅薄膜进行了稀土（Tb，Gd）离子的化学掺杂.利用荧光分光光度计测试了样品的光致发光特性.用扫描电子显微镜研究了薄膜的表面形貌.用卢瑟福背散射谱分析了稀土离子在多孔硅薄膜中的分布情况.结果表明，Tb的掺入显著增强了多孔硅的发光强度，并且发光峰位出现蓝移.这是由于Tb³⁺的4f能级⁵D_{4—⁷F3，⁵D4—⁷F关键词： 多孔硅 稀土掺杂 光致发光}     

Surface wave photonic device based on porous silicon multilayers

Porous silicon is widely studied in the field of photonics due to its interesting optical properties. In this work, we present theoretical and first experimental studies of a new kind of porous silicon photonic device based on optical surface wave. A theoretical analysis of the device is presented using plane-wave approximation. The porous silicon multilayered structures are realized using electrochemical etching of p⁺-type silicon. Morphological and optical characterizations of the realized structures are reported.     

Electroluminescence from a current-emitting nanostructured silicon device

A three-dimensional silicon based nanodevice mainly consisting of two conductive silicon cantilevers was fabricated out of silicon-on-insulator material by electron beam lithography, reactive ion etching, and fluoride based wet chemical etching. One of the cantilevers is bent and sticks to the silicon substrate while the other one is freely suspended. We observed electroluminescence in the visible range when a voltage of any polarity is dropped across both levers. The measured spectra covered the range 400–950 nm peaking at about 650 nm. The current applied to the device could tune the intensity of the electroluminescence spectrum. Light powers ranging from 160 fW to some pW were measured at frequencies up to 17 kHz. The origin of the electroluminescence is discussed in comparison to porous silicon and spark-processed silicon.     

Peculiarities of the capacitance-voltage characteristic of a photoelectric solar energy convertor based on a silicon p-n junction with a porous silicon antireflection coating

Experimental results on the high-frequency capacitance-voltage characteristic of a photoelectric solar energy converter based on the n ⁺-p junction with a thin porous silicon film on the frontal surface are considered. It is shown that the capacitance-voltage characteristic is determined by the surface metal-insulator-semiconductor (MIS) structure formed as a result of growing of a porous silicon layer by electrochemical anode etching. The effective thickness of the insulator layer of the MIS structure, the impurity concentration in its semiconductor region, and the density of surface states are determined.     

Patterning of porous silicon by metal-assisted chemical etching under open circuit potential conditions

Porous silicon is the most studied Si-based light-emitting material. The potential for the application of porous silicon in optoelectronics and also for chemical or biochemical sensing is high. Therefore, the successful patterning of porous silicon on Si wafers is of great interest. HF-based aqueous solutions containing H₂O₂ as oxidizing agent, in combination with appropriate metal deposition, can supply the necessary current in order to sustain the electrochemical etching of single crystalline Si under no external anodic bias. The H₂O₂ concentration can tune the etching rate of the Si wafers as well as the observed photoluminescence intensity and photon energy. We demonstrate that porous silicon growth can be preferentially initiated at sites where metal (Pt) has been deposited and effectively be confined there, in order to form a well-defined pattern of desired geometry. Conventional DC sputtering using stainless-steel masks was applied in order to test various patterning geometries and lengthscales. Photoluminescence spectroscopy, atomic force and optical microscopy were used in order to characterize the produced porous silicon patterns. This method could be a simple, cost-effective way for the production of porous silicon patterns on Si wafers, which could be used in various fields of application.     

Photoluminescence of porous silicon coated by SILD method with LaF3 nanolayers

The method of lanthanum fluoride passivating layer synthesis in the matrix of porous silicon by successive ionic layer deposition was elaborated and optimized. Luminescence and FTIR of obtained structures demonstrate the crucial role of the chemical composition of silicon nanocrystallite surface in the formation of radiative recombination channels and in the stability of porous silicon photoluminescence. The combination of high optical transparency of LaF₃ layers and low recombination losses in silicon covered with such layers allows to recommend the lanthanum fluoride film as an effective passivating coating for silicon optoelectronics devices.     

Synthesis and characterization of porous silicon layers for 1D photonic crystal application

In this paper, we studied the optical and physical properties of electrochemically prepared porous silicon layers. The atomic force microscopy analysis showed that the etching depth, pore diameter and surface roughness increase as the etching time increased from 30 to 50 mA/cm². By tuning two current densities J₁ = 50 mA/cm² and J₂ = 30 mA/cm², two samples of 1D porous silicon photonic crystals were fabricated. The layered structure of 1D photonic crystals has been confirmed by scanning electron microscopy measurement which showed white and black strips of two distinct refractive index layers. Finally, the measured reflectance spectra of 1D porous silicon photonic crystals were compared with simulated results.     

Photoluminescence activity of Yang and Secco etched multicrystalline silicon material

Ultraviolet and blue-green photoluminescence (PL) was investigated on multicrystalline silicon (mc-Si) samples chemically etched by Secco and Yang solutions. The samples were characterized by dislocation density (10⁵-10⁶ cm⁻²). The form of etched pits is triangular with Yang etch and like a honeycomb with Secco etch as observed with a scanning electron microscope (SEM). These textures of mc-Si wafers give a PL activity similar to that obtained with nanostructures of porous silicon (PS) as reported in the literature. The ultraviolet PL spectra observed with Yang etch shift to the blue-green spectrum range when applying Secco etch. In our experiments we have observed 3-5 μm diameter macro pores separated by a high density of nanowalls. These observations suggest that the origin of the PL activity are quantum dots resulting from the silicon nanocrystallites obtained after few minutes of chemical etching.     

Thermal depolarization in crystals of calcium fluoride doped with oxygen

The study of thermally induced depolarization (TD) in crystals of calcium fluoride doped with oxygen reveals the existence of nearest-neighbour (nn) dipolar complexes comprising substitutional oxide ions (O_s^2?) and fluoride ion vacancies (F_v^?) on nn sites. Evidence for this relaxation is seen in TD experiments both on pure calcium fluoride doped with oxygen and on Na⁺ doped CaF₂ crystals that had been heated in air. Similar measurements on CaF₂: Y³⁺, O^2? reveal six separate relaxations, two of which are due to Y_s^3??F_i^? complexes that do not involve oxygen, one is due to O_s^2??F_v^? dipoles, and one is t the T₁ complex, Y_s³⁺ (O^2?)₄(F_v^?)₃. The remaining two relaxations were not identified but are probably d larger defect clusters.     

Silicon Porosification: State of the Art

This review is devoted to the analysis of the problems related to fabrication of the Si porous layers. The review was motivated by a great interest to Si-based porous materials from nano- to macro-scale for various applications in electronics, optoelectronics, photonics, chemical sensors, biosensors, etc. The peculiarities of the silicon porosification and the principles of preparing porous layers are considered in the present article. Various methods used for Si porosification such as chemical stain etching, chemical vapor etching, laser-induced etching, metal-assisted etching, spark processing and reactive ion (plasma) etching were analyzed. However, the main attention was focused on electrochemical porosification of Si. The review discusses in detail the influence of parameters such as electrolyte composition and pH, current density, etching time, temperature, wafer doping and orientation, lighting, magnetic field, and ultrasonic agitation on the process of Si porosification. It was shown that the structure of porous silicon strongly depends on both technological parameters of electrochemical etching and the parameters of the semiconductor subject to treatment. This review also addresses the main properties of porous silicon, porous multilayer and 3D structure formation, oxidation of porous Si, release of the porous layer, drying, storage, etching, filling and surface functionalizing of porous Si. Features of III-V compound porosification are also briefly analyzed.     

Fabrication and characterization of porous silicon layers for applications in optoelectronics

In the present paper, several samples of porous silicon monolayers and multilayers were prepared at different anodization conditions with fixed HF concentration. The room temperature photoluminescence wavelength observed to be increased with increased etching time and current density respectively. By Raman measurement it has been observed that as the size of silicon crystallites decreased with increased etching time, the silicon optical phonon line shifted somewhat to lower frequency from 520.5 cm⁻¹ and became broader asymmetrically. The surface roughness and pyramid like hillocks surface was confirmed by AFM measurement. In SEM images, the porous silicon layers were clearly observed by white and black strips. It was also observed that the reflectivity increased as the number of porous silicon layers was increased.