氢等离子体气氛中退火多孔硅的表面和光荧光特性

用电化学腐蚀法制备了多孔硅(PS),在氢等离子体气氛中不同温度下对多孔硅样品进行了退火处理,并进行了光致发光(PL)谱和原子力显微镜(AFM)表面形貌的测量。不同退火温度给PS表面形态带来较大变化,也影响了其PL谱特性。在退火的样品中观察到的PL谱高效蓝光和紫光谱带,我们认为主要源于量子限制发光峰和非平衡载流子被带隙中浅杂质能级所俘获而引起的辐射复合所产生的。在420—450℃退火处理的多孔硅的PL谱上观察到了一个未见诸于报道的紫光新谱带(3．24eV,382nm),其发光机理有待于进一步研究。     

多孔硅发光与量子尺寸效应的实验研究

利用电化学阳极腐蚀的方法制备了多孔硅膜,实验发现多孔硅膜为多层结构,表面层为纳米结构,其余为微米结构,多孔硅的物理及化学结构的研究表明多孔硅是一种表面上含硅、氧、氢、氟元素组成的化合物包覆着的纳米晶硅粒和微米硅丝.多孔硅的发光主要来自表面纳米结构层,亚微米结构层并未见发光,从实验上证实了多孔硅的发光与量子尺寸效应紧密关联.     

多孔硅光致发光的非线性光学特性

采用电化学腐蚀法制备多孔硅（ＰＳ）,测量了多孔硅在近红外光（８００ｎｍ）激光下的光致发光（ＰＬ）谱和光致发光激光（ＰＬＥ）谱;结果表明多孔硅具有良好的上转换荧光特性光学特性并存存放时间 长,在一定期内峰值强度有明显的增。这种非线性光学响应的增强,被认为与空间量子限制效应作用下局域束缚关,光致发光谱的多峰结构表明多孔硅中存在多种发光中心。用量子限制／发光中心模型可以解释本实验结果。     

多孔硅的微结构与发光特性研究

利用原子力显微镜（AFM）和光致荧光（PL）光谱对一系列直流腐蚀和脉冲腐蚀的多孔硅的微结构及发光特性进行了对比研究．表面和侧面的AFM结果表明，多孔硅表面呈“小山”状，有许多小的、突出的硅颗粒．在相同的腐蚀条件（等效）下，脉冲腐蚀的样品表面Si颗粒更加尖锐、突出，侧面的线状结构更明显，多孔硅层更厚．对应的PL谱，脉冲腐蚀的样品发光更强．量子限制效应的理论可以比较成功地解释这个结果 关键词：     

多孔硅的光致发光和红外吸收光谱研究

用电化学腐蚀法制备出多孔硅系列样品.室温下具有明亮可见的光致发光.增大电解电流或延长腐蚀时间,发光光谱明显地“蓝移”;提高样品测量温度,发光光谱也明显地“蓝移”。红外吸收光谱表明多孔硅中除了硅丝骨架以外,还含有H、F及O等元素,随着腐蚀时间的增加,F和O原子的相对含量增加.实验结果表明,多孔硅在可见光区的发光现象是一种量子尺寸效应.     

声空化物理化学综合法制备发光多孔硅薄膜的微结构与发光特性

声空化所引发的特殊的物理、化学环境为制备高效发光的多孔硅薄膜提供了一条重要的途径.实验结果表明，声化学处理对于改善多孔硅的微结构，提高发光效率和发光稳定性都是一项非常有效的技术.超声波加强阳极电化学腐蚀制备发光多孔硅薄膜，比目前通用的常规方法制备的样品显示出更优良的性质.这种超声的化学效应源于声空化，即腐蚀液中气泡的形成、生长和急剧崩溃，在多孔硅的腐蚀过程中，孔中的氢气泡，由于超声波的作用增加了逸出比率和塌缩，有利于孔沿垂直方向的腐蚀. 关键词： 声空化方法 微结构 发光特性 多孔硅     

发光多孔硅表面微结构及其晶格畸变的实验研究

用电化学方法制备了不发光多孔硅和发光多孔硅,用X射线双晶衍射对两类多孔硅表面进行了微结构分析和晶体质量表征,实验表明两类多孔硅的微结构间存在着很大差别。不发光多孔硅表面对X射线的双晶衍射摇摆曲线可解叠成两个峰,它们分别来自样品多孔层和单晶硅衬底,而发光多孔硅对X射线的双晶衍射摇摆曲线呈高斯对称分布,不可解叠。发光多孔硅比不发光多孔硅表面晶体质量差,且电化学腐蚀越严重,表面晶体质量下降也越严重。     

Eu~(2+)/Dy~(3+)共掺高硅氧发光玻璃发光性质的影响因素分析

高硅氧发光玻璃因具有较好的热稳定性、化学稳定性等优点,成为极具潜力的荧光材料。针对其仍存在发光强度较弱的问题,从与发光性质紧密相关的制备工艺出发,分析各关键工艺参数对高硅氧玻璃发光性质的影响具有重要的意义。本文制备了关键工艺参数不同的Eu2+/Dy3+共掺高硅氧发光玻璃,通过测试微孔表面结构参数、发射光谱和红外吸收光谱等,研究了分相温度、溶液离子浓度和烧结温度等制备关键工艺参数对高硅氧发光玻璃光致发光性质的影响。当分相温度不同时,多孔玻璃微孔表面结构参数和高硅氧玻璃的发射光谱表明,分相温度通过影响多孔玻璃的比表面积间接的影响高硅氧玻璃的发光性质,多孔玻璃比表面积数值越大,高硅氧玻璃发光强度越大。当溶液离子浓度不同时,高硅氧玻璃的发射光谱表明,当溶液中Dy3+浓度增加,高硅氧玻璃中Dy3+和Eu2+发光增强;当Dy3+浓度大于0.1mol·L-1时,由于Dy3+的发光出现浓度猝灭效应,高硅氧玻璃整体发光强度减弱。当烧结温度不同时,高硅氧玻璃的发射光谱和红外吸收光谱表明,随着烧结温度升高,高硅氧玻璃中—OH残留量减少,发光强度增强;当烧结温度大于1 000℃时,高硅氧玻璃出现析晶,发光强度减弱。     

多孔硅光致发光峰半峰全宽的压缩

硅发光对于在单一硅片上实现光电集成是至关重要的.目前已有的使硅产生发光的方法有:掺杂深能级杂质、掺稀土离子、多孔硅、纳米硅以及Si/SiO₂超晶格.声空化所引发的特殊的物理、化学环境为制备光致发光多孔硅薄膜提供了一条重要的途径.实验表明,声化学处理对于改善多孔硅的微结构,提高发光效率和发光稳定性都是一项非常有效的技术.超声波加强阳极电化学腐蚀制备发光多孔硅薄膜,比目前通用的常规方法制备的样品显示出更优良的性质.这种超声波的化学效应源于声空化,即腐蚀液中气泡的形成、生长和急剧崩溃.在多孔硅的腐蚀过程中,由于超声波的作用增加了孔中氢气泡的逸出比率和塌缩,有利于孔沿垂直方向的腐蚀,使多孔硅光致发光峰的半峰全宽压缩到了3.8nm.     

发光不衰减的多孔硅

用一种新的方法制备出了具有不同衰减的光致发光特性的多孔硅。如此制备的多孔硅新鲜样品,其发光峰位强度比普通多孔硅高２￣２．５倍,将样品在室温下暴露于空气中,其发光强度在前４个月中单调增加,然后达到饱和。在随后的８个月中,没有观察到发光衰减,发光峰位也没有发生变化,这种发光稳定性被归因子于多孔硅表面所形成的稳定的Ｆｅ－Ｓｉ键。文章探讨了发光不衰减、峰位不蓝移的机理,并为多孔硅发光的量子限域模型提供了强     

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。     

Morphological changes in porous silicon nanostructures: non-conventional photoluminescence shifts and correlation with optical absorption

In this paper, we show that the photoluminescence (PL) shifts of p-type porous silicon (PS) are mainly attributed to some morphological changes related to anodisation conditions. We discuss how differences in the stirring and nature of the electrolytic solution can lead to morphological changes of the PS layers. It has been found that when PS is formed in pure aqueous HF solution, it can exhibit a non-conventional and reproducible “porosity – PL peak relationship”. By correlating the PL spectral behaviour and PS morphology throughout a quantum-confinement model, we explain both conventional and non-conventional PL shifts. Correlation of PL and optical absorption (OA) shows that the PL peak energy and the optical absorption edge of PS exhibit the same trend with size effect. The spectral behaviour of OA with regard to that of PL is well analysed within the quantum-confinement model throughout the sizes and shapes of the nanocrystallites forming PS. The value of the effective band gap energy determined from the calculated lowest PL energy almost corresponds to that estimated from the optical absorption coefficient. These results suggest that the lowest radiative transition between the valence band and the conduction band corresponds to the largest luminescent wires, and that the radiative recombination process leading to the PL emission occurs in the c-Si crystallite core.     

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.     

Decay processes of photoluminescence in a nanocrystalline SiC thin film

Nanocrystalline (nc)-SiC film has been deposited by helicon wave plasma enhanced chemical vapor deposition technique and intense blue-white light emission is obtained. Microstructure analyses show that the 3C–SiC particles are embed in amorphous SiC matrix, and the average size of the nc-SiC is 3.96 nm. The photon energy of the main photoluminescence (PL) band is higher than the band gap of bulk SiC, which indicates that the optical emission mainly occurs in quantum states of 3C–SiC nanocrystals. In addition, the band tail states of amorphous SiC also contribute to the optical emission. Three decay processes are obtained from time-resolved PL spectra by deconvolution treatment, and the decay components correspond to the quantum confinement effect (QCE), surface states of nc-SiC particles, and band tail of amorphous SiC, respectively. The fractional integrated PL intensity of QCE related decay process decreases dramatically in the lower PL photon energy, indicating that the QCE mainly contributes to the short wavelength optical emission.     

Multipeak-structured photoluminescence mechanisms of as-prepared and oxidized Si nanoporous pillar arrays

Silicon dominates the electronic industry, but its poor optical properties mean that it is not preferred for photonic applications. Visible photoluminescence (PL) was observed from porous Si at room temperature in 1990, but the origin of these light emissions is still not fully understood. This paper reports that an Si nanocrystal, silicon nanoporous pillar array (Si-NPA) with strong visible PL has been prepared on a Si wafer substrate by the hydrothermal etching method. After annealing in O₂ atmosphere, the hydride coverage of the Si pillar internal surface is replaced by an oxide layer, which comprises of a great quantity of Si nanocrystal (nc-Si) particles and each of them are encapsulated by an Si oxide layer. Meanwhile a transition from efficient triple-peak PL bands from blue to red before annealing to strong double-peak blue PL bands after annealing is observed. Comparison of the structural, absorption and luminescence characteristics of the as-prepared and oxidized samples provides evidence for two competitive transition processes, the band-to-band recombination of the quantum confinement effect of nc-Si and the radiative recombination of excitons from the luminescent centres located at the surface of nc-Si units or in the Si oxide layers that cover the nc-Si units because of the different oxidation degrees. The sizes of nc-Si and the quality of the Si oxide surface are two major factors affecting two competitive processes. The smaller the size of nc-Si is and the stronger the oxidation degree of Si oxide layer is, the more beneficial for the luminescent centre recombination process to surpass the quantum confinement process is. The clarification on the origin of the photons may be important for the Si nanoporous pillar array to control both the PL band positions and the relative intensities according to future device requirements and further fabrication of optoelectronic nanodevices.     

A novel method of fabricating porous silicon material: ultrasonically enhanced anodic electrochemical etching

Ultrasonically enhanced anodic electrochemical etching is developed to fabricate luminescent porous silicon (PS) material. The samples prepared by the new etching method exhibit superior characteristics to those prepared by conventional direct current etching. By applying ultrasonically enhanced etching, PS microcavities with much higher quality factors can be fabricated. The improved quality induced by ultrasonic etching can be ascribed to increased rates of escape of hydrogen bubbles and other etched chemical species from the porous silicon pillars' surface. This process will cause the reaction between the etchant and the silicon wafer to proceed more rapidly along the vertical direction in the silicon pores than laterally.     

Characterization of nanostructured CuO–porous silicon matrix formed on copper-coated silicon substrate via electrochemical etching

A pulsed anodic etching method has been utilized for nanostructuring of a copper-coated p-type (100) silicon substrate, using HF-based solution as electrolyte. Scanning electron microscopy reveals the formation of a nanostructured matrix that consists of island-like textures with nanosize grains grown onto fiber-like columnar structures separated with etch pits of grooved porous structures. Spatial micro-Raman scattering analysis indicates that the island-like texture is composed of single-phase cupric oxide (CuO) nanocrystals, while the grooved porous structure is barely related to formation of porous silicon (PS). X-ray diffraction shows that both the grown CuO nanostructures and the etched silicon layer have the same preferred (220) orientation. Chemical composition obtained by means of X-ray photoelectron spectroscopic (XPS) analysis confirms the presence of the single-phase CuO on the surface of the patterned CuO–PS matrix. As compared to PS formed on the bare silicon substrate, the room-temperature photoluminescence (PL) from the CuO–PS matrix exhibits an additional weak ‘blue’ PL band as well as a blue shift in the PL band of PS (S-band). This has been revealed from XPS analysis to be associated with the enhancement in the SiO₂ content as well as formation of the carbonyl group on the surface in the case of the CuO–PS matrix.     

生长温度对6H-SiC上SiCGe薄膜发光特性的影响

利用低压化学气相淀积工艺在6H-SiC衬底成功制备了SiCGe薄膜。通过光致发光(PL)谱研究了生长温度对SiCGe薄膜发光特性的影响。结果表明:生长温度为980,1030,1060℃的SiCGe薄膜的室温光致发光峰分别位于2.13,2.18,2.31eV处;通过组分分析和带隙计算,认定该发光峰来自于带间辐射复合,证实了改变生长温度对SiCGe薄膜带隙的调节作用。同时,对SiCGe薄膜进行了变温PL测试,发现当测试温度高于200K时,发光峰呈现出蓝移现象。认为这是不同机制参与发光所造成的。