阴极还原和酸处理对多孔硅稳定性和发光特性的改善

采用两种简单的多孔硅后处理方法,即阴极还原和酸处理来提高多孔硅的发光特性。结果表明,对多孔硅进行阴极还原处理,能明显改善多孔硅的稳定性;对多孔硅进行酸处理,能有效提高多孔硅的发光强度。结合阴极还原和酸处理两实验技术的特点,对所制备的多孔硅先进行阴极还原处理,再进行酸处理,结果表明该方法能较好地提高多孔硅的发光效率和发光稳定性。     

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。     

Ag Deposition Forms and Uniformity on Porous Silicon by Electrochemical Method

采用电化学沉积Ag的方法对多孔硅表面进行钝化改善其发光性能,探讨了沉积电流密度大小与沉积Ag的形式以及多孔硅表面亲水性处理对沉积Ag均匀性的影响. 结果表明,改变沉积电流密度大小后出现了两个临界电流密度,即不发生Ag沉积和在PS表层形成Ag电镀,深入PS孔道内沉积Ag的电流密度范围为50～400 A/cm²;多孔硅表面亲水性处理对沉积Ag均匀性有积极作用,在相同的实验条件下,未经表面亲水性处理的疏水多孔硅表面沉积Ag不均匀,而经过SC-1溶液处理后的亲水多孔硅表面上沉积Ag分布较均匀. 进一步研究了均匀沉积Ag钝化处理对PS的光致发光强度和稳定性的影响,证明采用Ag钝化处理能有效地抑制发光强度的衰减;而过量的Ag沉积会使PS发生荧光猝灭现象.     

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。     

多孔硅的一种新的后处理方法──微波等离子体辅助钝化处理

报道了对多孔硅进行后处理的一种新方法，即真空中微波等离子体辅助的钝化处理．傅里叶变换红外吸收谱表明，经处理的样品表面主要是被SiS_x和SiO_y所覆盖．与未经处理的样品相比，其发光强度增加约3.5倍，PL峰位蓝移了40nm，而且在空气条件下存放60d后发光强度没有变化．表明这种方法是增加多孔硅发光强度和提高稳定性的有效方法之一．     

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     

多孔硅表面钝化对其发光性能的影响

报道多孔硅（ＰＳ）的表面钝化对其光致发光（ＰＬ）和电致发光（ＥＬ）的影响,ＰＬ和ＥＬ谱表明,经钝化处理的ＰＳ的ＰＬ和ＥＬ强度明显增强,且发光峰位较大蓝移;存放实验表明,经钝化处理的ＰＳ的ＰＬ和ＥＬ发光强度和发光峰位具较好的稳定性;Ｉ～Ｖ曲线显示,经钝化处理的ＰＳ发光器件具有较低的劝电压,结结果表明：用钝化处理的方法是几ＰＬ和ＥＬ强度和稳定性及改善器件性能的有效途径。     

多孔硅的表面碳膜钝化

报道对多孔硅（ＰＳ）进行碳膜（ＣＦ）钝化处理的结果。红外吸收光谱表明,经钝化处理样品的表面由Ｓｉ－Ｃ、Ｓｉ－Ｎ和Ｓｉ－Ｏ键所覆盖;荧光我谱表明,经钝化处理的样品较未处理的样品发光强度提高４￣４．５倍,且发光峰位明显蓝移;存放实验显示,经钝化处理的样品发光强度稳定、发光峰位不变。这些结果表明正丁胺可以在多孔硅表面形成优良的钝化碳膜,是一种十分有效的多孔硅后处理途径。     

一种新型阳极氧化多孔硅技术

在适当条件下氧化多孔硅是提高多孔硅发光强度的良好途径,提出了一种新型阳极氧化方法,并探讨了该方法所涉及的阳极氧化条件。采用含CH3CSNH2的HF酸水溶液作为氧化剂对初始多孔硅进行了湿法阳极氧化,发现氧化使多孔硅光致发光性质得到极大改善,进而研究了氧化电流、氧化温度、氧化时间等一系列因素对氧化多孔硅光致发光强度的影响,并给出了合理解释。实验发现,在1mA,10min,60℃的氧化条件下,采用阳极氧化技术使多孔硅发光强度增强了18倍。     

多孔硅-导电聚酯材料复合发光器的光学特性研究

poly-4-dicyanomethylene-4H-cyclopenta[2,1-b:3,4-b]dithiophene monolayer(PCDM)是一种导电,低导带聚酯材料。如果在多孔硅纳米结构中附上一层以自组方式生成的PCDM单分子层,就可以制成能够产生稳定电致发光的器件。发光器的结构是金／PCDM／多孔硅／硅／铝,发光器的电致发光,在白天可用肉眼观察到。有很宽的发光波长,几乎覆盖了整个可见光区域且峰值位于650nm,发光器的面积为1cm^2,启动正向电压在14－30V,电流约300mA。经长时间测试,发光器的稳定性很好,在空气中放置3个月,在输入功率不变的情况下,发光强度也不发生变化,当施以反向电压时,样品仍可以发光而且稳定性较高,在250h内I－V未发生明显变化,扫描电镜图像显示PCDM覆盖的表面要比多孔硅表面平整,而PCDM分子有可能进入到多孔硅纳米孔径当中去,起到了提高发光器稳定性和延长其寿命的作用。     

Regularities of the photoluminescence of porous silicon after chemical etching in HF

The effect of chemical treatment of porous silicon samples by HF on its photoluminescence and its evolution with time in sample aging in air is investigated. It is shown that the effect of HF on the luminescence parameters depends on the duration of the treatment and the initial photoluminescence intensity of the sample. It is found that chemical etching in HF accelerates the growth of the total luminescence intensity in aging of the sample in air. The evolution of the photoluminescence spectrum in aging of the sample in air after chemical etching can be explained within the framework of the quantum-size model of the luminescence of porous silicon. Presented at the Fall Meeting of the Material Research Society, December 1–5, 1997, Boston, USA Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 3, pp. 423–427, May–June, 1999.     

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     

Photoluminescence and electroluminescence from porous silicon

The properties and origins of the red, blue and infrared photoluminescence bands of porous silicon are reviewed and discussed in the light of the models that have been proposed to explain the experimental and theoretical results. The red band is due to quantum confinement possibly supplemented by surface states; the blue band is linked to the presence of silicon dioxide; the infrared band is correlated with dangling bonds and bandgap luminescence in large crystallites. The fabrication and characterization of light-emitting devices made of porous silicon are reported and discussed with respect to critical issues such as the device stability, efficiency, modulation speed, emission wavelength, and compatibility with microelectronic processing.     

Effects of selenium treatment on composition and photoluminescence properties of porous silicon

In this work, an ultrasonically enhanced anodic electrochemical etching is developed to fabricate light-emitting porous silicon material. Porous silicon layer is fabricated in n-type (1 0 0) oriented silicon using HF solution and treated in selenious acid to increase the photoluminescence intensity. It is found that the increase of photoluminescence intensity after selenious acid treatment is higher in the intact zones and lower in the detached zones of ultrasonic excitation. The photoluminescence appears as a non-monotonous function of time exposure of selenious acid treatment. Surface chemical composition analysis by X-ray photoelectron spectroscopy shows formation of Si-Se_x and Si-Se_x-O_y on the surface of porous silicon treated with the selenious acid.     

Electrochemical deposition of cerium on porous silicon to improve photoluminescence properties

In this work, we present results for Cerium (Ce) doping effects on photoluminescence (PL) properties of porous silicon (PS). Cerium was deposited using electrochemical deposition on porous silicon prepared by electrochemical anodization of P-type (100) Si. From the photoluminescence spectroscopy, it was shown that porous silicon treated with cerium can lead to an increase of photoluminescence when they are irradiated by light compared to the porous silicon layer without cerium. In order to understand the contribution of cerium to the enhanced photoluminescence, energy dispersive X-ray (EDX) spectroscopy, Fourier transmission infrared spectroscopy (FTIR), X-ray diffraction (XRD) and atomic force microscopy (AFM) were performed, and it was shown that the improved photoluminescence may be attributed to the change of Si–H bonds into Si–O–Ce bonds and to a newly formed PS layer during electrochemical Ce coating.     

Influence of preparation and storage conditions on photoluminescence of porous silicon powder with embedded Si nanocrystals

The time changes of photoluminescence (PL) characteristics of porous silicon (porSi) powder during storing in different ambients have been reported. A porous silicon material with embedded Si nanocrystals of size of few nanometers was prepared by an electrochemical method from 10 to 20 Ωcm p-type Si wafers, and both constant and pulse current anodization regimes were used. A powder with a submicron average particle size was obtained by simple mechanical lift-off of the porous layer followed by additional manual milling. The air, hexane, and water as storage media were used, and modification by a nonionic surfactant (undecylenic acid) of the porSi surface was applied in the latter case. Dependence of PL characteristics on preparation and storage conditions was then studied. A remarkable blue shift of a position of PL maximum was observed in time for porSi powders in each storage media. In water suspension a many-fold build-up (10–30) of PL intensity in a time scale of few days was accompanied by an observed blue shift. Photoluminescence time behavior of porSi powders was described by a known mechanism of the change of porSi PL from free exciton emission of Si nanocrystals to luminescence of localized oxidized states on the Si nanocrystal surface.     

大气中长期存放与长时间热氧化后多孔硅光致发光峰能量的会聚

改变阳极氧化的工艺条件,制备出光致发光峰能量位于1.4—2.0eV范围内的大量多孔硅样品,其中45块样品在大气中存放一年,102块样品在200℃下热氧化(累计达200小时).在上述两种情况下,光致发光峰能量在氧化后都会聚到1.70—1.75eV能量范围.假设在充分氧化的多孔硅中包裹纳米硅的氧化层中,存在发光能量处于～1.70—1.75eV的发光中心,上述实验结果可以用量子限制/发光中心模型解释. 关键词：     

Luminescence centers in porous silicon

Photoluminescence studies on porous silicon show that there are luminescence centers present in the surface states. By taking photoluminescence spectra of porous silicon with respect to temperature, a distinct peak can be observed in the temperature range 100–150 K. Both linear and nonlinear relationships were observed between excitation laser power and the photoluminescence intensity within this temperature range. In addition, there was a tendency for the photoluminescence peak to red shift at low temperature as well as at low excitation power. This is interpreted as indicating that the lower energy transition becomes dominant at low temperature and excitation power. The presence of these luminescence centers can be explained in terms of porous silicon as a mixture of silicon clusters and wires in which quantum confinement along with surface passivation would cause a mixing of andX band structure between the surface states and the bulk. This mixing would allow the formation of luminescence centers.