本文選題：半導體納米線 + 溶液法��； 參考：《北京理工大學》2015年博士論文

【摘要】：自二十世紀八十年代以來,納米科學逐漸發(fā)展成為一門跨領域、多學科交叉的前沿學科。作為一類經典的納米材料體系,半導體納米線因其一維結構所帶來的獨特偏振光學特性、低激光激發(fā)閾值、增強的壓電特性等性質,一直倍受關注。半導體納米線的制備方法可簡單的分為氣相法和液相法,與氣相制備法相比,溶液法制備的半導體納米線具有尺寸小(可表現量子限域效應)、反應溫度低、有機配體包覆、可連續(xù)制備等特點,是這一領域的重要研究方向。然而,溶液法制備的納米線存在熒光量子產率低下、光譜調控范圍窄、性能單一、發(fā)光理論研究滯后等問題,阻礙了相關研究的進一步發(fā)展。針對上述問題,本論文開展了II-VI族半導體納米線的研究,發(fā)展了溶液-液滴-固體法(Solution-Liquid-Solid,SLS)合成技術,通過摻雜、合金化等策略實現了膠體納米線發(fā)光性質的調控,開發(fā)了多種多功能半導體納米線,利用低溫穩(wěn)態(tài)熒光光譜和時間分辨光譜,初步闡明了所制備的半導體納米線的發(fā)光機制。所取得的主要進展如下:(1)合金化是調控半導體材料發(fā)光光譜的有效策略,合金半導體材料的制備必須克服反應前驅體活性差別的難題,與零維納米晶相比,半導體納米線的合金化過程不僅需要在橫截面方向實現,還需在長軸方向完成均勻合金,生長條件要求更加苛刻。本論文發(fā)展了SLS的制備技術,通過前驅體、催化劑、反應溫度的調控,以原位生成的Bi納米液滴為微反應容器,制備了波長范圍可調(508 nm-628 nm)的CdSe_xS_(1-x)合金納米線,其熒光量子產率高達8.8%,比單純的CdSe或CdS納米線的熒光量子產率(1%)提高了一個數量級。另外,未經排列的納米線已經顯示出明顯的偏振發(fā)光特性,偏振度(polarization ratio)可達0.6。為了理解激子在合金半導體中的運動過程以及合金化提高納米線熒光量子效率的機理,利用低溫穩(wěn)態(tài)熒光光譜和時間分辨光譜對CdSe_xS_(1-x)合金納米線的激發(fā)態(tài)復合過程進行了深入的研究和分析,通過了解低溫下合金納米線熒光光譜的變化,并進一步結合時間分辨光譜和熒光壽命的結果,提出了合金半導體納米線中激子的遷移和限域競爭復合發(fā)光機制:即半導體納米線的熒光量子產率是由輻射復合速率和界面缺陷的捕獲速率共同決定的,在合金納米線中,由于成分導致的勢能谷的存在,光生激子一旦產生會被勢能谷局域束縛,大大降低了其向表面的遷移,這就使激子有效輻射復合的幾率大大增加,熒光量子產率也相應增高。(2)摻雜是現在半導體技術中控制材料性質的主要策略之一,尤其是同時具備多種功能的半導體材料是現代半導體技術和應用的重要方向。但是,由于納米晶體本身的“自清潔”效應(Self-Purification),如何實現半導體納米材料的摻雜一直是納米材料制備的挑戰(zhàn)之一,特別是對納米線來說,如何保證摻雜離子在納米線長軸方向的均勻性是不可忽視的一大挑戰(zhàn)。我們以Bi納米液滴為微反應容器,以Cd(S_2CNEt_2)_2為單前驅體,發(fā)展了一種簡單的SLS單源前驅體摻雜法,制備了Mn~(2+)和Eu~(3+)摻雜的CdS一維半導體納米線,并提出了SLS單源前軀體摻雜法制備膠體稀磁半導體納米線的成核及生長機理。另外,通過改變摻雜所用的Mn~(2+)含量(0.18%-0.81%),可以調控Mn~(2+)摻雜的CdS稀磁半導體納米線的雙色發(fā)光峰中藍光和橙光的比例,實現白光發(fā)射。該摻雜策略具有兩大突出特點:簡單通用、摻雜均勻。
[Abstract]:Since 1980s, nanoscience has gradually developed into a cross field and interdisciplinary frontier. As a class of classic nanomaterials, semiconductor nanowires have been attracting more and more attention because of their unique polarization optical properties, low laser excitation threshold, and enhanced piezoelectric properties. The preparation method of conductor nanowires can be easily divided into gas phase method and liquid phase method. Compared with the gas phase preparation method, the semiconductor nanowires prepared by solution method have the characteristics of small size (which can show quantum confinement effect), low reaction temperature, organic ligand encapsulation, continuous preparation, etc., which is an important research direction in this field. However, solution method has been used to prepare the nanowires. The nanowires have low fluorescence quantum yield, narrow spectrum control range, single performance and delayed luminescence theory, which hinders the further development of the related research. In this paper, the research of II-VI semiconductor nanowires is carried out in this paper, and the solution liquid drop solid method (Solution-Liquid-Solid, SLS) synthesis technology is developed. A variety of multifunctional semiconductor nanowires have been developed by over doping and alloying, and a variety of multi-functional semiconductor nanowires have been developed. The luminescence mechanism of the semiconductor nanowires has been preliminarily clarified by the low temperature steady-state fluorescence spectrum and time resolved spectrum. The main progress is as follows: (1) alloying is the regulation of semiconductor materials. The effective strategy of the luminescence spectrum is that the preparation of the alloy semiconductor material must overcome the problem of the difference in the activity of the precursor. Compared with the zero dimension nanocrystalline, the alloying process of the semiconductor nanowires needs not only to be realized in the direction of cross section, but also to complete the uniform alloy in the direction of the long axis, and the requirement for the growth condition is more demanding. This paper develops the SLS By controlling the precursors, catalysts and reaction temperature, the Bi nanowires with tunable wavelength range (508 nm-628 nm) are prepared by the precursor, catalyst, and reaction temperature. The fluorescence quantum yield of the nanowires is up to 8.8%, which is more than the fluorescence quantum yield (1%) of the pure CdSe or CdS nanowires. In addition, the unarranged nanowires have shown obvious polarization luminescence properties. The degree of polarization (polarization ratio) is up to 0.6. in order to understand the movement of the exciton in the alloy semiconductor and the mechanism of improving the fluorescence quantum efficiency of the nanowire by alloying. The low temperature stable fluorescence spectrum and the time resolved spectrum are used for the combination of CdSe_xS_ (1-x). The excited state complex process of the nanowires is deeply studied and analyzed. By understanding the changes in the fluorescence spectra of the alloy nanowires at low temperature and further combining the time resolved spectra and the fluorescence lifetime, the mechanism of the migration of excitons and the limited domain competitive composite luminescence mechanism in the alloy semiconductor nanowires, that is, semiconductor nanowires, is proposed. The fluorescence quantum yield is determined by the radiation recombination rate and the capture rate of the interfacial defects. In the alloy nanowires, the potential energy valley, due to the presence of the composition, will be bound by the potential energy valley locally, greatly reducing the migration of the exciton to the surface, which greatly increases the probability of the effective radiation recombination of the exciton. The yield of light quantum is also higher. (2) doping is one of the main strategies to control the properties of semiconductors, especially the semiconductor materials with multiple functions at the same time are the important direction of modern semiconductor technology and applications. However, the "self cleaning" effect (Self-Purification) of the nanocrystalline itself can be realized half. The doping of conducting nanomaterials has been one of the challenges for nanomaterials. Especially for nanowires, how to ensure the uniformity of the doped ions in the long axis of nanowires is an unnegligible challenge. We developed a simple SLS single source with Bi nano droplets as microreactor and Cd (S_2CNEt_2) _2 as a single precursor. Mn~ (2+) and Eu~ (3+) doped CdS one-dimensional semiconductor nanowires were prepared by precursor doping, and the nucleation and growth mechanism of colloidal diluted magnetic semiconductor nanowires prepared by SLS single source precursor doping method were proposed. In addition, the Mn~ (2+) doped CdS dilute semiconductor nanowires could be regulated by changing the content of Mn~ (2+) (0.18% -0.81%) used in doping. The white light emission is achieved by the ratio of blue light and orange light in the two-color emission peak. The doping strategy has two outstanding characteristics: simple and universal, and uniform doping.

【學位授予單位】：北京理工大學
【學位級別】：博士
【學位授予年份】：2015
【分類號】：TB383.1

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