本文選題：氧化鋅　切入點(diǎn)：復(fù)合納米結(jié)構(gòu)　出處：《北京科技大學(xué)》2016年博士論文

【摘要】：ZnO是一種n型直接寬帶隙Ⅱ-Ⅵ族金屬氧化物半導(dǎo)體材料,具有一系列獨(dú)特的物理、化學(xué)性能。其中,ZnO的一維納米結(jié)構(gòu)極大改善了其光電及電輸運(yùn)等性能,并被廣泛應(yīng)用于太陽能電池、光電化學(xué)(PEC)電池等能量轉(zhuǎn)換器件或是紫外探測(cè)、生物傳感等信息傳感器件。本文采用簡(jiǎn)單的水熱法,較低溫、無催化、高產(chǎn)量地制備了高質(zhì)量ZnO納米棒陣列�；诖瞬牧�,先后與二維石墨烯薄膜、三維空間網(wǎng)絡(luò)狀石墨烯材料、金納米顆粒以及載流子濃度可調(diào)的Cu20窄帶隙p型半導(dǎo)體材料相結(jié)合構(gòu)建性能相互彌補(bǔ)、作用相互協(xié)同的ZnO基復(fù)合納米結(jié)構(gòu),實(shí)現(xiàn)了ZnO/rGO、ZnO/3DGF、Au@ZnO 以及ZnO/Cu2O四種異質(zhì)結(jié)光陽極的設(shè)計(jì)與構(gòu)建。系統(tǒng)研究了它們對(duì)光電化學(xué)性能的提升效果以及相應(yīng)的陽極結(jié)構(gòu)優(yōu)化、表面等離激元共振效應(yīng)、p-n結(jié)構(gòu)建及界面調(diào)控等一系列增強(qiáng)機(jī)制。并進(jìn)一步將所構(gòu)建光陽極應(yīng)用至光電化學(xué)型生物傳感器,實(shí)現(xiàn)了對(duì)谷胱甘肽(GSH)生物分子的高性能探測(cè)。此外,亦發(fā)現(xiàn)了復(fù)合納米結(jié)構(gòu)光陽極的PEC性能對(duì)其PEC生物傳感性能影響的基本規(guī)律。針對(duì)電極結(jié)構(gòu)設(shè)計(jì)與優(yōu)化,在還原氧化石墨烯(rGO)薄膜表面實(shí)現(xiàn)了ZnO納米棒陣列的原位生長。紫外光輻照下,由于rGO層極強(qiáng)的電子提取性能促進(jìn)了光陽極內(nèi)部的電子輸運(yùn),ZnO/rGO相較于純ZnO光陽極具有提升的PEC性能。在OV (vs.Ag/AgC 1)工作偏壓下,所構(gòu)建的ZnO/rGO基PEC型生物傳感器對(duì)GSH實(shí)現(xiàn)了2.17μM(n=3)的探測(cè)下限以及10-2OOμM(R2=0.997)的線性范圍。對(duì)電極結(jié)構(gòu)進(jìn)行進(jìn)一步優(yōu)化,在3D空間網(wǎng)絡(luò)狀石墨烯泡沫的表面實(shí)現(xiàn)了ZnO納米棒陣列的原位生長。紫外光輻照下,由于3D石墨烯的大表面積及高電子傳輸效率等優(yōu)勢(shì),ZnO/3D石墨烯的PEC性能相較于ZnO/rGO或純ZnO光陽極均有明顯的增強(qiáng)。在0V(vs. Ag/AgCl)工作偏壓下,所構(gòu)建的ZnO/3D石墨烯基PEC型生物傳感器對(duì)GSH實(shí)現(xiàn)了1.79 μM(n=3)的探測(cè)下限以及10-300 μM (R2=0.991)的線性范圍。針對(duì)表面等離激元共振效應(yīng),利用紫外還原法在ZnO納米棒陣列表面合成了Au納米顆粒。太陽光輻照下, Au納米顆粒的表面等離激元共振效應(yīng)增強(qiáng)了光陽極在可見光部分的吸收并在Au表面產(chǎn)生了大量熱電子,隨后注入至ZnO的導(dǎo)帶,從而獲得了提升的PEC性能。在OV(vs.Ag/AgCl)工作偏壓下,所構(gòu)建的Au@ZnO基PEC型生物傳感器對(duì)GSH實(shí)現(xiàn)了3.29 μM(n=3)的探測(cè)下限以及20～1000 μM(R2=0.996)的線性范圍。針對(duì)p-n結(jié)的構(gòu)建與界面調(diào)控,利用電化學(xué)沉積法在ZnO納米棒陣列表面合成了p型Cu2O薄膜。通過改變沉積生長時(shí)間實(shí)現(xiàn)了對(duì)Cu2O薄膜厚度及結(jié)區(qū)面積的調(diào)控,并通過改變Cu2O中載流子濃度實(shí)現(xiàn)了對(duì)ZnO/Cu2O異質(zhì)結(jié)界面處電子結(jié)構(gòu)的調(diào)控。優(yōu)化獲得的具有最佳光捕獲能力及最大內(nèi)建電場(chǎng)強(qiáng)度的Zn0/Cu2O p-n異質(zhì)結(jié)從光吸收與光生電荷分離兩個(gè)角度貢獻(xiàn)于提升的PEC性能。在0 V(vs.Ag/AgCl)工作偏壓以及太陽光輻照下,所構(gòu)建的ZnO/Cu2O基PEC型生物傳感器對(duì)GSH實(shí)現(xiàn)了0.42 μM(n=3)的探測(cè)下限以及10-1000 μM(R2=0.991)的線性范圍。此外,通過對(duì)所構(gòu)建的ZnO基復(fù)合納米結(jié)構(gòu)PEC型生物傳感器的探測(cè)性能進(jìn)行比較,發(fā)現(xiàn)隨著光陽極PEC性能的提升,其PEC生物傳感性能得到了極大的改善。本研究以功能器件的構(gòu)建為導(dǎo)向,在獲得高性能光電化學(xué)型生物傳感器的同時(shí),深入研究了不同形式ZnO基復(fù)合納米結(jié)構(gòu)光陽極的光電化學(xué)性能及其相對(duì)應(yīng)性能增強(qiáng)手段的工作機(jī)制。通過該研究,力爭(zhēng)對(duì)ZnO基復(fù)合納米材料的性能有進(jìn)一步的理解,以推動(dòng)其在光電化學(xué)以及相關(guān)太陽能光伏領(lǐng)域當(dāng)中的應(yīng)用與發(fā)展。
[Abstract]:ZnO is a n type direct wide band gap II-VI metal oxide semiconductor materials, has a series of unique physical and chemical properties. Among them, one-dimensional nano structure of ZnO has greatly improved the optical and electrical transport properties, and is widely used in solar cell, photoelectrochemical (PEC) battery energy converter or is the ultraviolet detection, biological sensing information sensor. This paper uses the simple hydrothermal method, low temperature, non catalytic, high quality ZnO nanorod arrays were prepared in high yield. Based on this material, and has a two-dimensional graphene film, three-dimensional space network like graphene materials, Cu20 narrow band gap P type of semiconductor material of gold nanoparticles and the carrier concentration can be adjusted by combining construction performance of mutual complement, ZnO based nano composite structure interaction, the realization of the ZnO/rGO, ZnO/3DGF, Au@ZnO and ZnO/Cu2O four kinds of heterojunction light anode design With the construction of them. To enhance the effect of the photoelectrochemical properties of the anode and the corresponding structure optimization system to study the surface plasmon resonance effect, p-n structure and interface control and a series of enhancement mechanism. And further the application to Gou Jianguang anode photoelectric chemical biological sensor, the glutathione (GSH) high performance detection of biological molecules. In addition, also found that the basic laws affecting the properties of PEC composite nano structured light anode on the PEC biosensor performance. According to the design and optimization of the electrode structure, the reduction of graphene oxide (rGO) thin film on the surface of the in situ growth of ZnO nanorod arrays. Under UV irradiation, due to electron rGO layer strong extraction performance facilitates the electron transport within the light anode, ZnO/rGO compared with pure ZnO photoanode with PEC to improve the performance. In OV (vs.Ag/AgC 1) work bias, constructed by ZnO/rG O based PEC biosensor to achieve 2.17 M of GSH (n=3) and the detection limit 10-2OO M (R2=0.997). The linear range for further optimization of the electrode structure on the surface of the 3D space network like graphene foam realized in situ ZnO nanorod arrays growth. Under ultraviolet light radiation, the 3D graphite by the large surface area and high electron transfer efficiency and other advantages, the performance of PEC ZnO/3D graphene compared to ZnO/rGO or pure ZnO photoanode was significantly enhanced in 0V (vs. Ag/AgCl) work bias, the ZnO/3D graphene based PEC biosensor has been 1.79 M of GSH (n=3). The detection limit of 10-300 M (R2=0.991). The linear range for surface plasmon resonance effect, using the UV reduction synthesis of Au nanoparticles in the ZnO nanorod array surface. The sun light irradiation, Au nanoparticles surface plasmon resonance effect Strengthen the light anode in the visible part of the absorption and generate a large number of hot electrons on the surface of Au, then injected into the conduction band of ZnO, which was PEC to improve the performance. In OV (vs.Ag/AgCl) bias, Au@ZnO based PEC biosensor constructed realizes 3.29 M of GSH (n=3). The detection limit of 20~1000 M (R2=0.996) and the linear range. According to the regulation of construction and interface of the p-n junction, was synthesized by electrochemical deposition of P type Cu2O thin film on the surface of ZnO nanorod arrays. By changing the deposition time to achieve the control of the thickness and area of junction area of Cu2O film, and by changing the carrier concentration in Cu2O implementation the ZnO/Cu2O heterojunction interface control electronic structure. Optimization has the best ability to capture light and maximum internal electric field strength Zn0/Cu2O p-n heterojunction absorption and photoinduced charge separation from two aspects contribute to the light To improve the performance of PEC. In 0 V (vs.Ag/AgCl) bias and solar light irradiation, ZnO/Cu2O based PEC biosensor constructed realizes 0.42 M of GSH (n=3) and the detection limit of 10-1000 M (R2=0.991) of the linear range. In addition, through the comparison of detection performance of ZnO base construction the composite nano structure of PEC biosensor, with light anode PEC to enhance the performance of PEC, the biosensor performance has been greatly improved. This research is to build a functional device for guidance in obtaining high performance of Photoelectrochemical biosensor and studied the photoelectrochemical properties of different forms of ZnO composite nano structured light anode and the corresponding performance enhancement mechanism means. Through this study, to the performance of ZnO based composite nano materials have further understanding, to promote the photoelectric chemical and related too The application and development of solar energy in the field of photovoltaic.

【學(xué)位授予單位】：北京科技大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TB383.1;TP212

【參考文獻(xiàn)】

相關(guān)期刊論文 前1條

1 張躍;康卓;閆小琴;廖慶亮;;納米氧化鋅基酶生物傳感器（英文）[J];Science China Materials;2015年01期

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本文編號(hào)：1728819