Size Separation and Photochemical Properties of Quantized Semiconductor Microcrystals

量子化半导体微晶的尺寸分离和光化学性质

基本信息

批准号：
04650733
负责人：
UCHIDA Hiroyuki
金额：
$ 1.09万
依托单位：
Yamanashi University (1993)Osaka University (1992)
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1992
资助国家：
日本
起止时间：
1992 至 1993
项目状态：
已结题

项目摘要

Photochemical and photophysical properties of semiconductor microcrystals depend greatly on their size due to the quantum size effects. Bisides the size effect, properties of microcrystals must be greatly influenced by their surface conditions, i.e.nonstoichiometry in the surface composition and kinds of stabilizers. Therefore, in order to clarify their size-dependent properties, it is desirable to employ microcrystals having almost identical surface conditions except their particle size. A fractionation of CdS microcrystals with the use of gel electrophoresis is one of the promising techniques to allow such conditions. In the present research, effective methods for size-separation of quantized semiconductor microcrystals were developed and photoinduced electron transfer on size-separated CdS microcrystals were examined. Major achievements are as follows ;1. Efficient size-separation of quantized CdS by means of improved electrophoresis.First, the gel electrophoresis of quantized CdS ( … More Q-CdS, stabilized with HMP, diameter=3-9nm)) was carried out employing a polyacrylamide gel column with application of 100V.A thermal diffusion of CdS particles in the gel was inhibited by cooling of the elctrophoresis cell with ice bath. The resulting CdS-gel layr of 6cm length was cut into 6 slices. It was found that the second electrophoresis of each gel slice resulted in very efficient and prompt extraction of CdS particles from the slice of the gel. With the size-separation, the absorption spectrum of Q-CdS blue-shifted and became steep, the degree being more marked with an increase in the fraction number. It was confirmed by TEM observation that the size-separation gave narrow size distribution and particles of 5.02 nm and 3.58 nm average diameter were present in the fraction 1 and 6, respectively.2. Photoinduced electron transfer on size-separated CdS microcrystals.The rate of reduction of methylviologen on CdS microcrystals prepared by fractionation with the use of gel electrophoresis increased with decreasing the particle size. The observed results were successfully analyzed in terms of shifts in the conduction bandedge due to the size-quantization. The potential of the conduction bandedge of the microcrystals of various sizes relative to that of crystalline bulk CdS is derived based on the flat band potential of the bulk CdS and the shifts of the conduction band expected by the size-quantization. By assuming that the potential difference between the derived potential of the conduction bandedge and the redox potential of methylviologen is the overvoltage for the reduction reaction, Tafel relation with the transfer coefficient of ca. 0.3 was observed between the reduction rate and the overvoltage. Less

由于量子尺寸效应，半导体微晶的光化学和光物理性质很大程度上取决于它们的尺寸，除了尺寸效应之外，微晶的性能还必须很大程度上受到其表面条件的影响，即表面组成和稳定剂种类的非化学计量。为了阐明它们与尺寸相关的特性，需要采用除了颗粒尺寸之外具有几乎相同的表面条件的微晶。使用凝胶电泳是实现这种条件的有前途的技术之一。在本研究中，开发了量子化半导体微晶体尺寸分离的有效方法，并检查了尺寸分离的 CdS 微晶体上的光诱导电子转移。如下；1. 通过改进的电泳对量子化 CdS 进行有效的尺寸分离。首先，量子化 CdS 的凝胶电泳（……更多Q-CdS，用HMP稳定，直径＝3-9nm))使用聚丙烯酰胺凝胶柱并施加100V进行。通过用冰浴冷却电泳池来抑制凝胶中CdS颗粒的热扩散。将6cm长的CdS-凝胶层切成6片，发现每个凝胶片的第二次电泳都可以非常有效且快速地提取CdS。随着尺寸分离，Q-CdS的吸收光谱发生蓝移并变得陡峭，并且随着级分数的增加，该程度更加明显，通过TEM观察证实了尺寸。 - 分离得到窄的尺寸分布，并且级分 1 和 6 中分别存在平均直径为 5.02 nm 和 3.58 nm 的颗粒。 2. 尺寸分离的 CdS 微晶上的光诱导电子转移。使用凝胶电泳分级分离制备的 CdS 微晶上甲基紫精的还原率随着粒径的减小而增加，根据尺寸量子化引起的导带边缘的变化成功地分析了观察到的结果。不同尺寸的微晶相对于晶体块状 CdS 的带边是根据块状 CdS 的平带电势和预期的导带偏移得出的。通过假设导带边缘的导出电势和甲基紫精的氧化还原电势之间的电势差是还原反应的过电压，在还原速率和尺寸量子化之间观察到约0.3的塔菲尔关系。过电压.更少