本文關鍵詞： 超薄銅薄膜 柔性透明電極 太陽能電池　出處：《山東大學》2016年博士論文　論文類型：學位論文

【摘要】：先進柔性光電以及光伏器件的迅猛發(fā)展對透明導電電極的開發(fā)提出了更苛刻的要求,高光電性能、高柔性、高穩(wěn)定性同時成本低廉、制備工藝簡單、易實現(xiàn)大規(guī)模生產(chǎn)的柔性透明導電電極的開發(fā)迫在眉睫。傳統(tǒng)的單層透明導電氧化物(主要是ITO)由于價格昂貴、機械柔韌性差及不可避免的高溫制備過程等不能滿足相關產(chǎn)業(yè)的需求。目前,基于金屬納米線、納米網(wǎng)格、碳納米管以及石墨烯開發(fā)出的透明電極被認為是最有希望的ITO替代產(chǎn)品并得到了廣泛的研究。然而上述電極仍面臨各自不同的技術難題,例如：金屬納米線及納米網(wǎng)格電極氧化失效問題嚴重,碳材料電極制備工藝不成熟光電性能遠低于理論預測值。因此上述電極在短期內難以實現(xiàn)大面積產(chǎn)業(yè)化從而替代ITO。氧化物-金屬-氧化物(Oxide-Metal-Oxide, OMO)多層膜結構復合電極因其簡單穩(wěn)定的結構、優(yōu)良的機械柔性、成熟的大規(guī)模制備工藝等成為一種潛在的替代者。但受制于金屬層厚度與形貌,金屬基復合電極的光學性能的提高往往伴隨著電學性能的損失,獲得理想超薄連續(xù)金屬層成為提高光電性能的唯一途徑。然而由于金屬與氧化物界面間潤濕性較差,金屬在氧化物襯底上的島狀生長模式導致很難制備超薄連續(xù)的金屬薄膜。迄今為止仍未有提高Cu在氧化物襯底潤濕性的相關報道。Cu基多層膜結構透明電極因其透過率較差并未得到廣泛的關注。本文通過在濺射過程中引入微量02、N2來改變薄膜生長模式從而獲得超薄連續(xù)的微摻雜銅(Cu(O)、Cu(N))薄膜：同時將氧摻雜銅Cu(O)薄膜用作Cu薄膜生長的潤濕層制備出超薄連續(xù)的Cu薄膜�；谝陨铣∵B續(xù)Cu薄膜成功開發(fā)出具有優(yōu)異光電性能的Cu基多層膜結構透明電極,采用上述新型Cu薄膜透明電極替代傳統(tǒng)Cu基電極以及單層ITO電極作窗口電極的柔性有機太陽能電池的光電轉換效率顯著提高。主要研究內容如下：(1)通過微量的02摻雜沉積得到厚度低至2.5nm的超薄連續(xù)Cu(O)薄膜。研究證實微氧化對Cu薄膜生長初期納米團簇在ZnO襯底上遷移運動的抑制是導致更早形成超薄連續(xù)薄膜的原因。采用Cu(O)作為中間金屬層的ZnO/Cu(O=5.0%)/ZnO電極光電性能優(yōu)異(可見光區(qū)平均透過率達到83%,面電阻低至13Ωsq-1)及抗氧化性。采用Cu(O)基多層膜結構電極為窗口電極的有機太陽能電池轉化率高達7.5%,高于采用傳統(tǒng)Cu薄膜電極和ITO電極的電池效率。(2)為了避免Cu靶材在02環(huán)境中因氧化導致的靶中毒問題以及大面積樣品制備過程中氧濃度不易控制等技術難題,采用相對惰性的N2代替O2研究了氮摻雜對Cu薄膜生長模式的影響。研究發(fā)現(xiàn)低于1at.%的氮摻雜足以引起Cu薄膜形貌發(fā)生顯著變化。N原子在Cu納米團簇表面的吸附削弱了Cu原子間的內聚能,抑制其三維島狀生長,較早地形成連續(xù)的氮摻雜銅Cu(N)薄膜�；诖私Y果開發(fā)出一種價格低廉、制備工藝簡單可行,同時光電性能優(yōu)于傳統(tǒng)采用Cu薄膜作為中間金屬層的多層膜結構電極的ZnO/Cu(N)/ZnO電極。采用該電極制備得到光電轉換效率為7.1%的柔性有機太陽能電池。(3)利用1nm-Cu(O)薄膜作為Cu薄膜沉積的潤濕層,制備得到完全連續(xù)的Cu(O)/Cu復合薄膜,發(fā)現(xiàn)Cu在Cu(O)表面以一種類外延的二維層狀模式生長。由于降低了中間金屬層中的雜質濃度,基于此開發(fā)出的ZnO/Cu(O)/Cu/ZnO電極光電性能得到進一步提高,表現(xiàn)出優(yōu)于ITO電極的光電性能,其可見光區(qū)平均透過率高于85%,面電阻低至11Ωsq-1。采用該電極為窗口電極的柔性有機太陽能電池光電轉化效率高達7.72%。綜上,本文提供了一種在氧化物襯底上制備超薄連續(xù)金屬薄膜的有效方法,并對金屬潤濕性改善的深層機理進行了初步探討�；诟倪M后的超薄連續(xù)Cu膜制備得到光電性能優(yōu)異的Cu基多層膜結構電極,解決了柔性襯底上制備高品質透明導電薄膜的技術難題,同時采用該電極制備得到高光電轉化效率的有機光伏器件。
[Abstract]:More stringent requirements for the development of the advanced photoelectric flexible transparent conductive electrode and the rapid development of photovoltaic devices, high optical performance, high flexibility, high stability and low cost, simple preparation process, easy to realize the development of mass production of flexible transparent conductive electrode is imminent. The traditional single layer transparent conductive oxide (ITO) because the price is high, not high temperature preparation process such as poor mechanical flexibility and the inevitable to meet the needs of industry. At present, the metal nanowires based on nano grid, carbon nanotubes and graphene transparent electrode developed is considered the most promising ITO alternative products and has been extensively studied. However, the electrode still faces different technical problems, such as: metal nanowires and nano grid electrode oxidation failure problems of carbon electrode preparation technology not mature photoelectric The performance is far lower than the predicted values. So the electrode in the short term is difficult to achieve a large area of industrialization as an alternative to the ITO. oxide metal oxides (Oxide-Metal-Oxide, OMO) multilayer structure composite electrode due to its simple structure and stability, excellent mechanical flexibility, mature large-scale preparation process as a potential replacement. But subject to the metal layer thickness and morphology, optical properties of metal matrix composite electrode to improve the electrical properties often accompanied by loss, obtain the ideal thin continuous metal layer has become the only way to improve the photoelectric performance. However due to the metal and oxide interface between poor wettability of metal oxide in the substrate leads to island growth mode to prepare ultrathin continuous metal films. So far there is no relevant reports in Cu to improve the wettability of.Cu based oxide substrate layer structure because of its transparent electrode The poor rate has not been widely concerned. Through the introduction of trace in the sputtering process 02, N2 to change the film growth model to obtain ultrathin continuous micro copper doped (Cu (O), Cu (N)) and oxygen doped copper film: Cu (O) thin film was used as a wetting layer of Cu thin film growth system preparation of ultra-thin continuous Cu films. Above ultrathin continuous Cu films successfully developed a Cu based multi layer structure of transparent electrode has excellent photoelectric properties based on the photoelectric conversion efficiency of the new Cu thin film transparent electrode to replace the traditional Cu based electrode and ITO electrode as the single window electrode of flexible organic solar cells increased significantly. The main research the contents are as follows: (1) get thin continuous Cu thicknesses as low as 02 2.5nm through doping deposition trace (O) films. Studies have confirmed that micro oxidation initial growth of nanoclusters on ZnO substrate inhibited migration movement is on Cu thin film The cause of formation of thin continuous film. Earlier by Cu (O) as an intermediate metal layer ZnO/Cu (O=5.0%) /ZnO electrode with excellent photoelectric performance (average visible transmittance reaches 83%, the surface resistance as low as 13 SQ-1) and antioxidant activity. Using Cu (O) based layer structure electrode for organic solar cell window the electrode conversion rate as high as 7.5%, higher than that of the conventional Cu electrode and ITO electrode film battery efficiency. (2) in order to avoid the problems caused by the target poisoning Cu target in the 02 oxidation environment and a large area in the sample preparation process of oxygen concentration is not easy to control and other technical problems, using relatively inert N2 instead of O2 research the effect of nitrogen doping on the growth mode of Cu thin film. The study found that lower nitrogen doped 1at.% cause Cu thin film morphology change of.N atom in Cu nanoclusters adsorption weakens the Cu interatomic cohesive energy, suppression of the 3D Island growth, early formation of nitrogen doped copper continuous Cu (N) thin film. The results to develop a low price based on the preparation process is simple and feasible, and better than the traditional photoelectric properties of Cu thin films as electrode structure with intermediate metal layers of multilayer films of ZnO/Cu (N) /ZnO electrode using the electrode preparation. Get the photoelectric conversion efficiency of flexible organic solar cell 7.1%. (3) using 1nm-Cu (O) film as a wetting layer deposited Cu films, prepared by continuous Cu (O) /Cu composite films were found in the Cu Cu (O) surface growth in two dimensional layered model a kind of extension. Due to the reduction of the concentration of impurities in the intermediate metal layer, the development of ZnO/Cu (O) based on the photoelectric properties of /Cu/ZnO electrode has been further improved, showing the photoelectric performance is better than that of ITO electrode, the average visible transmittance is higher than 85%, as the window of the electrode by surface resistance as low as 11 sq-1. Flexible organic solar cell photoelectric conversion efficiency and electrode up to 7.72%. in summary, this paper provides an effective method for preparation of ultra-thin continuous metal films in the oxide substrate, and the underlying mechanism of metal wettability improvement were discussed. Ultra thin continuous Cu membrane modified by Cu based multi layer structure the electrode based on excellent optoelectronic properties, to solve the technical problems of high quality transparent conductive film prepared on flexible substrate, and the electrode prepared by high photoelectric conversion efficiency of organic photovoltaic devices.

【學位授予單位】：山東大學
【學位級別】：博士
【學位授予年份】：2016
【分類號】：TB383.2;TM914.4
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本文編號：1510161