恒电位电解法制备光致发光掺钬多孔硅

研究了一种新的多孔硅掺稀土的电化学方法———恒电位电解，以及稀土硝酸盐支持电解质有机溶剂的新电解体系。这一方法和体系的特点是通过采用适当外加电压来控制电解产物，提高掺入的稀土浓度，提高发光强度，同时避免生成导致发光不稳定的产物，提高发光稳定性。优化了阳极氧化制备多孔硅的条件和阴极还原制备掺钬多孔硅的条件（钬化合物浓度、溶剂、离子强度、电解电压、时间），获得光致发光强度高于多孔硅的掺钬多孔硅。对多孔硅和掺钬多孔硅的光致发光机制进行了讨论。     

掺铕多孔硅的恒电位电解法制备及其光致发光

首次报道掺稀土多孔硅的恒电位电解法和稀土硝酸盐－支持电解质－非乙醇有机溶剂的电解体系,这一新方法和新体系具有易于控制电解产物,可掺入高浓度稀土（１０＾２１／ｃｍ＾３以上）,自主控制掺人稀土的浓度并显著增强多孔硅室温光致发光的优点。研究了溶剂、外加电压、Ｅｕ（ＮＯ３）３浓度及电解时间对多孔硅（ＰＳ）室温光致发光的影响,优化了恒电位电解法制备掺铕多孔硅的条件,获得了室温光致发光强度高于多孔硅的ＰＳ：Ｅ     

多孔硅跃迁特征的研究

采用表面光电压谱和光致荧光激发谱对多孔硅的能带结构和跃迁特性进行了系统研究，结果表明，多孔硅泊带隙明显大于单晶硅的带隙，在３００－５００ｎｍ区产观察到几个与制备条件有关的精细结构带，此构带为多孔硅中不同尺寸的硅线能级，这一发现恰与理论计算结果一致，从实验上支持了多孔硅的量子限域模型。     

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。     

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。     

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。     

多孔硅的光电化学特性研究

研究了多孔硅的光电化学特性和溶液中的光致电荷转移机一，由Ｐ型单晶硅制备的多孔硅具有Ｐ型半导体的光电性质，且光电流响应高于单晶硅，由于多孔硅表面态能级对光致电荷的陷阱作用，多孔硅呈现了独特的光电流响应和光致电荷转移性质。     

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650 nm.发光器的面积为1 cm2,启动正向电压在14～30 V,电流约300 mA.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250 h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.     

用STM研究电化学阳极氧化制备的多孔硅

本文利用扫描遂道显微镜(STM)并辅以快速富立叶变换(FFT)和数据拟合等数学方法对电化学阳极氧化法制备的多孔硅(PS)的微结构及形貌进行了研究。同时研究了多孔硅的微结构与其发光性质和电化学性质的相互关系。研究表明,在其他条件不变情况下,随阳极氧化电流密度的增大,所形成的多孔硅的微孔向纵深延伸,多孔硅层增厚,微孔相连后形成的硅柱变细,发光强度增大,发光峰位明显蓝移,与单晶硅相比,多孔硅电极的平带电位明显负移,而电极电流在两极区内均增大。     

多孔硅制备条件对其电致发光特性的影响

应用蒸镀-阳极氧化法制备结构为ITO/PS/p-S i/A l的多孔硅电致发光器件,在7.5V电压下实现了数小时连续电致发光.实验表明,多孔硅电致发光峰位会随着阳极氧化电流密度的增大、腐蚀时间的延长以及HF酸浓度的降低而蓝移.欲制备工作电压较低、发光时间较长、发光效率较高的电致发光样品,则多孔硅制备时的阳极氧化应使用较低电流密度和较短的腐蚀时间.     

发光多孔硅表面的STM研究

自从Canham首次报道了室温下多孔硅的光致发光现象以来^[1],多孔硅已成为半导体光电化学及材料领域内最为热门的研究课题^[2].     

发光多孔硅的光谱及电化学研究

单晶硅是E_g为1.1eV的间接带隙半导体材料,在可见光区不发光,不能应用于光电子领域.但是,Canham 1990年首次发现^[1],适当条件下形成的多孔硅在室温下就可发出强度能与Ⅲ-Ⅴ族半导体发光二极管相媲美的可见光。     

Atomic Force Microscopic Studies of Light-Emitting Porous Silicon

The surface morphologies of porous silicon (PS), fabricated under various anodic etching conditions and on different typvs of silicon substrates, were studied using atomic force microscopy (AFM). The typical sizes of silicon crystallites of PS were found to be 4-10 nanome-ters,an expected for quantum confinement effect. The results suggested the doping concentration of silicon substrate plays an important role compared with the doping type in determining the surface microstructures. On p^- PS samples, a step-like dependence of the PS crystallite size of HF etching concentration was observed for the first time,in nice agreement with the,tep-like photo-luminescence (PL) phenomenon. which strongly supported the quantum confinement model.     

Oscillations of open-circuit potential during immersion plating of silicon in CuSO4/HF solutions

The paper analyzes the nature of oscillations of open-circuit potential (OCP) during immersion plating of copper on silicon wafers. The oscillations are observed within well-determined interval of experimental conditions (composition of the electrolyte, doping level of silicon wafers, temperature, viscosity of electrolyte, etc.). Different to other known cases of the electrochemical oscillations, in the present case, there is no external source of the electrical current. We summarize here experimental findings relevant to this phenomenon and analyze possible reasons for the occurrence of the OCP oscillations. The effect is well fit by the general phenomenology of chaos-order transitions in complex chemical systems. We present a model for the oscillatory behavior which involves simultaneous reactions of Cu deposition and oxidation of silicon wafer, generation of local mechanical stress in the system, nonlinear electrochemical etching of silicon, localization of the electric field at the etched surface, etc. Published in Russian in Elektrokhimiya, 2006, Vol. 42, No. 5, pp. 574–585. The text was submitted by the author in English. Deceased.     

HETEROJUNCTION DIODES OF POROUS SILICON WITH SOLUBLE POLYANILINE*

Two kinds of heterojunction diodes of porous silicon (PS) with soluble polyaniline (PANI) werefabricated. One is a heterojunction diode of PS with water-soluble copolymer of polyaniline (PAOABSA),Al/PS-PAOABSA/Au cell as rectifying diode. Another is a heterojunction diode of PS with solublepolyaniline doped with DBSA, Al/PS-PANI (DBSA)/Au cell as light emitting diode (LED). The rectifyingcharacteristics of the rectifying diodes were measured as a function of the degree of sulfonation and thicknessof the copolymers, as well as oxidation of PS. The rectifying ratio of the heterojunction can reach 5.0×10~4 at±3 V bias. For the LED, the photoluminescence (PL) and electroluminescence (EL) spectra were measuredand discussed.     

硅在HF溶液中阳极溶解的研究

Uhlir及Turner早在50年代就已发现^[1,2],硅在HF溶液中阳极极化时,阳极电流大于某一特定值硅表面会发生电抛光反应,而低于这个值硅表面则会形成一层不同颜色的多孔硅层.1990年Canham发现多孔硅层在室温下有光致发光现象^[3],受到科学界的高度重视,在世界范围内掀起了研究多孔硅的热潮^[4].众多的研究表明,多孔硅的发光性能与其微孔的多少、大小和分布密切相关.但多孔硅要发展成为可实用的光电子材料,首先必须制备出微孔分布均匀,孔径及孔深可控的多孔硅材料.这就有必要弄清多孔硅的形成机理^[5],了解硅在HF溶液中的溶解过程及机理.为此,本文对不同掺杂浓度不同导电类型的(111)晶面单晶硅在HF溶液中的电流-电压(I-V)、电容-电压(C-V)特性进行了研究,并对这些特性进行了分析.     

Quantum confinement effect in electroluminescent porous silicon

Ｖｉｓｉｂｌｅｐｈｏｔｏｌｕｍｉｎｅｓｃｅｎｃｅ(ＰＬ)ｏｎｈｉｇｈｌｙｐｏｒｏｕｓｓｉｌｉｃｏｎｌａｙｅｒｓｂｙｅｌｅｃｔｒｏｃｈｅｍｉｃａｌｌｙｅｔｃｈｉｎｇｃｒｙｓｔａｌｌｉｎｅｓｕｂｓｔｒａｔｅｓｗａｓｒｅｐｏｒｔｅｄｉｎ1990[1].Ｔｈｉｓｓｕｒｐｒｉｓｉｎｇｏｐｔｉｃａｌｐｒｏｐｅｒｔｙｏｆｐｏｒｏｕｓｓｉｌｉｃｏｎ(ＰＳ)ｉｓｅｘｐｌａｉｎｅｄａｓｆｏｌｌｏｗｓ:ｔｈｅｐｏｒｏｕｓｌａｙｅｒｉｓｃｏｍｐｏｓｅｄｏｆｑｕａｎｔｕｍｓｉｚｅｅｎｔｉｔｉｅｓ,ｗｈｅｒｅａｑｕａｎｔｕｍｃｏｎｆｉｎ…     

Fabrication and chemical surface modification of nanoporous silicon for biosensing applications

In this work, porous silicon (PS) films with varied porosity (68–82%) were formed on the p-type, boron-doped silicon wafer (100) by the electrochemical anodisation in an aqueous hydrofluoric acid and isopropyl alcohol solution at different current densities (I _d) ranging from 20–70 mA cm^?2, respectively. Biofunctionalisation of the PS surface was carried out by chemically modifying the surface of PS by the deposition of 3-aminopropyltriethoxysilane thermally leading to high density of amine groups covering the PS surface. This further promotes the immobilisation of immunoglobulin (human IgG and goat anti-human IgG binding) on to the PS surface. Formation of nanostructured PS and the attachment of antibody–antigen to its surface were characterised using photoluminescence (PL), Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy techniques, respectively. The possibility of using these structures as biosensors has been explored based on the significant changes in the PL spectra before and after exposing the PS optical structures to biomolecules. These experimental results open the possibility of developing optical biosensors based on the variation of the PL position of the PL spectra of PS-based devices.     

阳极氧化与超临界干燥结合制备多孔硅

多孔硅（PS）在室温下发射强可见光，这一发现在国际上引起极大关注，成为材料科学、半导体物理和化学以及信息科学领域研究的热点［1，2］．最近三、四年，国内外对PS制备工艺、影响PS发光的因素、PS发光机制、PS应用前景等方面进行了广泛的研究［2］，但有一些基本问题仍待解决，如关于PS发光机制尚存在分歧；PS电致发光效率低，离应用差距甚远；高多孔度PS微孔结构不稳定等．PS微孔内溶剂蒸发过程中，由于毛细管张力的存在，造成微孔骨架受力不匀．强的应力使PS骨架脆弱，甚至微孔结构坍缩，从而导致PS结构不稳定．对于高多孔度…