本文關(guān)鍵詞： 氧化鋅 本征缺陷 間隙鋅 鋅空位 一維納米結(jié)構(gòu) 摻雜　出處：《南京大學(xué)》2016年博士論文　論文類型：學(xué)位論文

【摘要】：氧化鋅(ZnO)是一種直接帶隙Ⅱ-Ⅵ族化合物半導(dǎo)體材料,禁帶寬度約為3.37 eV,其室溫下的激子束縛能高達(dá)60 meV,在短波長光電器件領(lǐng)域有著廣闊的應(yīng)用前景。但ZnO中的p型摻雜具有較高的形成能和嚴(yán)重的自補(bǔ)償效應(yīng),并導(dǎo)致大量的施主型本征缺陷與雜質(zhì),已成為制約ZnO材料發(fā)展的重大科學(xué)問題與技術(shù)困難,嚴(yán)重阻礙了ZnO材料優(yōu)異光電性能的發(fā)揮與器件應(yīng)用。與此同時(shí),ZnO材料具有一個(gè)非常重要的特點(diǎn),即可以通過多種技術(shù)與方法制備出形貌豐富的納米結(jié)構(gòu)。相比于薄膜材料,這種具有較大表體比的ZnO納米材料的表面態(tài)密度較高,具有很高的化學(xué)活性從而降低p型摻雜或相關(guān)缺陷的形成能,可顯著提高摻雜效率,有助于改善ZnO中p型摻雜的技術(shù)困難。針對ZnO材料發(fā)展中p型摻雜這一重大技術(shù)難題,本論文將ZnO的p型摻雜與納米結(jié)構(gòu)相結(jié)合,圍繞一維ZnO納米結(jié)構(gòu)的制備和摻雜等相關(guān)問題,系統(tǒng)研究了本征和氮(N)摻雜ZnO微納米柱陣列的結(jié)構(gòu)、組態(tài)、光學(xué)等性質(zhì),以此為基礎(chǔ)重點(diǎn)分析了ZnO微納米柱內(nèi)部主要的本征缺陷,如間隙鋅(Zni)和鋅空位(Vzn)的行為特征,并著重探討了對相關(guān)的本征施主和受主進(jìn)行有效調(diào)控的技術(shù)與方法。論文取得的研究成果主要如下：(1) 開展了本征和N摻雜ZnO微納米柱的生長控制研究。采用基于碳熱還原反應(yīng)的化學(xué)氣相沉積法,進(jìn)行了ZnO微納米柱的生長實(shí)驗(yàn),總結(jié)得到了最優(yōu)的生長條件,在ZnO模板襯底上成功制備了ZnO微納米柱陣列。引入一氧化二氮(N20)氣體同時(shí)作為N源和O源,實(shí)現(xiàn)了N的有效摻雜。研究表明,本征和N摻雜的ZnO微納米柱陣列都具有很高的晶格質(zhì)量,取向一致,相互平行,垂直于襯底沿c軸外延生長。(2) 深入研究了N摻雜ZnO微納米柱的結(jié)構(gòu)、晶格振動(dòng)與光學(xué)等性質(zhì),掌握了本征缺陷Zni和Vzn的行為特征,揭示了它們與ZnO材料復(fù)合發(fā)光行為的內(nèi)在關(guān)聯(lián),建立了研究其基本性質(zhì)的綜合表征手段。在N摻雜ZnO微納米柱陣列樣品的光致發(fā)光譜中指認(rèn)出了和淺受主Vzn團(tuán)簇相關(guān)的復(fù)合發(fā)光峰,表明N的摻雜有利于在ZnO材料中形成淺受主Vzn團(tuán)簇；而具有精細(xì)雙峰結(jié)構(gòu)的綠帶發(fā)光正是從淺施主Zni的基態(tài)及其激發(fā)態(tài)到深受主單一Vzn的輻射躍遷。(3) 研究并獲得了N摻雜ZnO微納米柱中本征缺陷的調(diào)控方法,包括對本征施主的抑制,以及引入本征受主的思路與途徑。系統(tǒng)的研究了生長過程中不同的Ⅵ/Ⅱ比對N摻雜ZnO微納米柱陣列樣品的晶格振動(dòng)、元素組態(tài)、順磁共振以及光學(xué)等性質(zhì)的影響,提出通過調(diào)控Ⅵ/Ⅱ比這一關(guān)鍵技術(shù)參數(shù),在實(shí)現(xiàn)抑制本征施主缺陷的同時(shí),促使淺受主Vzn團(tuán)簇的穩(wěn)定形成。(4) 研究了N摻雜ZnO微米柱發(fā)光光譜的空間精細(xì)分布,掌握了與VZn相關(guān)的本征受主型缺陷在微米柱內(nèi)部的局域性空間分布特征,建立了N摻雜ZnO微米柱發(fā)光和缺陷分布的核殼結(jié)構(gòu)模型。研究顯示,自由激子發(fā)射主要來源于微米柱的核心區(qū)域,而和淺受主Vzn團(tuán)簇相關(guān)的復(fù)合發(fā)光、以及和深受主單一Vzn相關(guān)的綠帶發(fā)光均主要來自于微米柱的表面區(qū)域；由此表明,和Vzn相關(guān)的本征受主型缺陷主要分布在N摻雜ZnO微米柱的表面。(5) 開展ZnO微納米柱中等價(jià)態(tài)元素和受主元素共摻雜的技術(shù)研究。采用化學(xué)氣相沉積法制備了碲(Te)和N共摻雜的ZnO微納米柱陣列,重點(diǎn)揭示了一維ZnO納米結(jié)構(gòu)中的Te元素在調(diào)控施主和受主方面所起到的作用。研究發(fā)現(xiàn)通過對Te摻雜組份的調(diào)控,既能實(shí)現(xiàn)對淺施主缺陷Zni的有效抑制,又能有效提升N在ZnO微納米柱內(nèi)的固溶度,為未來解決ZnO材料中p型摻雜的技術(shù)困難提供了一條可能的技術(shù)途徑。
[Abstract]:Zinc Oxide (ZnO) is a kind of direct band gap II-VI compound semiconductor material, the band gap is about 3.37 eV, the exciton binding energy at room temperature up to 60 meV, has a wide application prospect in the field of short wavelength devices. But the P doped ZnO with the formation energy and the serious self the compensation effect is high, and lead to the intrinsic defects and impurities in a large number of donor type, has become a major scientific issues and technical difficulties of ZnO material development, seriously hindered the play and application of ZnO materials with excellent optical properties. At the same time, the ZnO material has a very important feature, which can be through a variety of techniques and methods preparation of nanostructures rich. Compared to the film material, the surface state density is higher than the ZnO that has a bigger body of nanometer materials, has high chemical activity so as to reduce the formation of P type doping or related defects Can, can significantly improve the doping efficiency, technical difficulties contribute to the improvement of P doped in ZnO. In order to solve the major technical problems in the development of P type ZnO doped materials, this dissertation combines P doped and nano structure of ZnO, focuses on the problem of one-dimensional ZnO nanostructures were prepared and doped with other related systems study on the intrinsic and nitrogen (N) structure, doped ZnO micro nano column array configuration, optical properties, based on the analysis of ZnO micro nano column internal main intrinsic defects, such as interstitial zinc (Zni) and zinc vacancy (Vzn) behavior, and discusses the technology and method the effective control of the donor and acceptor related. The main research achievements of this article are as follows: (1) to carry out the intrinsic and N doped ZnO micro nano column growth control research. Through chemical vapor carbon thermal reduction reaction based on phase deposition method, the ZnO micro nano column growth The optimal growth conditions, summed up the successful preparation of ZnO micro nano column array was prepared on ZnO template substrates. By introducing a two nitrogen oxide (N20) gas at the same time as the N source and O source, realize the effective doping of N. The results show that the intrinsic and N doped ZnO micro nano column array with lattice quality, high orientation, parallel to each other along the c axis perpendicular to the substrate epitaxial growth. (2) studied N doped ZnO micro nano structure column, lattice vibration and optical properties. The behavior of the intrinsic defects of Zni and Vzn, reveals the inherent correlation between them and ZnO the composite material luminescence behavior, the establishment of a comprehensive characterization methods to study its basic properties. In N doped ZnO micro nano column array samples in the photoluminescence spectra of the peaks and identified the composite shallow acceptor Vzn clusters related, shows that N doping is conducive to the formation of shallow acceptor Vzn group in the ZnO. Shuangfeng has a fine structure of clusters; and the green light is from the ground state and the excited states of shallow donor Zni to the radiation transition of single Vzn by the Lord. (3) research and the control method of N doped ZnO micro nano column of intrinsic defects, including inhibition of intrinsic donor, and the introduction of ideas and ways the acceptor. Systematic study on the growth process of different VI / II ratio of N doped ZnO micro nano column array sample lattice vibration, element configuration, effect of CIS magnetic resonance and optical properties, put forward through the regulation of VI / II ratio of the key technical parameters in suppression of intrinsic donor defects at the same time, the shallow acceptor Vzn clusters formed stable. (4) study of N doped ZnO micro column luminescence spectrum space fine local spatial distribution, grasp the intrinsic defects in the micro column internal acceptor type distribution characteristics associated with VZn, built with N Miscellaneous ZnO micron column luminescence and core-shell structure of the defect distribution model. Research shows that the core area of free exciton emission mainly comes from the micro column, and shallow acceptor Vzn clusters related recombination, and by the surface area of the main single Vzn related green luminescence were mainly from micro pillars; this shows that Vzn and the intrinsic acceptor defects mainly distributed on the surface of N doped ZnO micro column. (5) technology research of ZnO micro nano medium column element valence and acceptor co doping. Tellurium was prepared by chemical vapor deposition (Te) and N Co doped ZnO micro nano column array. It reveals the Te element of one dimensional ZnO nanostructures in play in regulating the role of donor and acceptor. The study found that through the regulation of Te dopant composition, which can effectively suppress the shallow donor defects of Zni, and can effectively improve the N in ZnO micro nano The solid solubility in the rice column provides a possible technical way to solve the technical difficulties of P type doping in ZnO materials in the future.

【學(xué)位授予單位】：南京大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2016
【分類號】：TN304.21

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