臺灣博碩士論文加值系統

中 文 摘 要
本研究使用反應性非平衡磁控濺鍍製程合成三氧化鎢/五氧化二釩（WO3/V2O5）多層膜（multi-layers）及VWOx三元合金單層薄膜。在合成多層膜及多成分薄膜前，首先要先確定V2O5、WO3單層膜之最佳製程參數，先設定最佳之氧流量，再改變製程參數（如基材轉速、濺鍍時間與基材溫度），以探討製程參數對於薄膜的微結構、著色性質、薄膜表面型態之間的關係。
由Field emission SEM及AFM表面形態分析，WOX、V2O5、WO3/V2O5多層膜及VWOx三元合金薄膜表面為50至200nm大小的奈米顆粒，且VWOx三元薄膜隨著釩靶功率的提高，粒徑有變大的現象；而V2O5則是隨著氧流量變大，粒徑有縮小的現象。
由EPMA分析薄膜化學計量，當WOx薄膜在氧氣流量達到11 sccm之後，化學計量維持最終穩定態（WO3）。在VOx薄膜方面，氧氣流量達到8 sccm之後呈現最終穩定態（V2O5）。XRD繞射分析方面，WO3薄膜都是非晶質（amorphous）薄膜；而VOx薄膜則是隨著氧氣流量增加造成V2O5結構有從優取向的改變，由（110）轉變成（200）。而WO3/V2O5多層膜與VWOx三元合金薄膜在分析後都是非晶質薄膜。
由UV光譜分析穿透率變化，WO3薄膜最佳著色能力在可見光之穿透率變化達到最大值（為77.7％），光學密度為0.66，著色性質隨著氧流量增加導致著色效率下降。而V2O5薄膜最佳著色能力在可見光之穿透率變化最大到36％，其光學密度為0.22，由於 V2O5薄膜氧氣流量增加造成其結晶結構有從優取向的改變，進而影響著色能力。多成分VWOx薄膜隨著釩添加量增大導致著色效率下降，最佳著色能力在釩添加2.6at%，可見光穿透率變化達到最大57％，光學密度為0.35。

Abstract
The aim of this research is to synthesize electrochromic films of the W-V-O system the single layer and multilayer of WO3 and V2O5 using a reactively unbalanced DC magnetron sputtering technique. Before synthesizing multilayer and ternary films, the processing parameters of monolithic V2O5 and WO3 films are optimized by adjusting mainly the oxygen flow. Then, the processing parameters such as the rotating speeding of the substrate, sputtering time, and the substrate temperature are tuning to establish the relations among the processing parameters, the microstructure, the morphology and the electrochromic behaviors.
From the results of FE-SEM (Field Emission Scanning Electron Microscopy) and AFM (Atomic Force Microscope) images, we find that the morphologies of WOX, V2O5, WO3/V2O5 multilayer and VWOx films are composed of nanograins with size of 50 ~ 200 nm. The grain size of VWOx films increases as the power of vanadium target increases and declined as the oxygen flow increases.
The stoichiometry of the films is analyzed using EPMA (Electron Probe X-ray Microanalyzer). The WOx film has the stoichiometry of WO3 when the oxygen flow exceeds 11 sccm. The stoichiometry of VOx is V2O5 when the oxygen flow exceeds 8 sccm. The WO3 films are amorphous to XRD. The VOx films are crystalline phase of V2O5 and then the preferred orientation change from (110) to (200) as the oxygen flow rate increases. The WO3/V2O5 multilayer and ternary VWOx films are all amorphous.
The electrochromic property of the films is measured by the transmittance variation (ΔT) in UV-VIS spectrometer bleaching and coloring of the films. Accordingly, the optical density is calculated from the transmittance variation. The transmittance variation at the WO3 films at 550 nm band reaches its maximum about 77.7％, and the optical density is 0.66. The V2O5 film gets to its maximum about 36%, and the optical density is 0.22. The VyWOx films become less coloring efficient as the addition of the vanadium increases. When the addition of the vanadium is 2.6 at%, the transmittance variation the VyWOx attains its maximum about 57％ with the optical density of 0.35.For monolithic WO3 films, then ΔT increase as the film thickness increases. The ΔT of all the films studies are related to film thickness.

目 錄
致謝（Acknowledge）…………………..…..……….…………..….…...i
中文摘要（Abstract）…………………..……..…..….……………..…..ii
英文摘要（Abstract）……………………….………………………..…iv
目錄（Table of Contents）………………..…..…….…………………...vi
圖目錄（List of Figures）…………………..…..….…….…..………….ix
表目錄（List of Table） ………….………..…....……….….………….xii

第一章 前言
1.1概述 …………….………………………………………….. 1
1.2研究動機…….…….….……………………………..……… 3

第二章 文獻回顧
2.1電致色變發展歷史………..….……….…...…………..…… 6
2.2電致色變材料總類………....…………………….………… 7
2.3成長WO3相關文獻..………......…..………….….………... 9
2.4成長V2O5相關文獻……….……..………………...………11
2.5混合金屬氧化物…………...….……………..…….……….12
2.6變色機制……………..….…….………………….………...15

第三章 濺鍍原理及薄膜成長機制
3.1濺鍍原理 ………….……………………………………….20
3.2非平衡磁控濺鍍……………..……………………………..21
3.3反應性磁控濺鍍…………….………..…………………….23
3.4反應濺鍍不同濺鍍源…….……..………………………….25
3.5薄膜沈積原理………………………………………………27
3.6薄膜微觀結構………………………………………………29

第四章 實驗方法
4.1實驗系統介紹………………….……………………………31
4.2材料準備…………….………………………………………33
4.2.1 試片前處理…………………………………………..34
4.3設定實驗條件…………………………………………….…34
4.3.1 WOx單層膜……….………………………………….35
4.3.2 VOx單層膜………….………………………………..36
4.3.3VWOx單層膜…….………………………………...…36
4.3.4 WO3/V2O5 多層膜……………………………………37
4.4鍍膜程序………………………………………….……37
4.5分析儀器..………...……….…….……………….……..39

第五章 結果與討論
5.1WO3單層膜..………….……………………………....…..…43
5.1.1 WOx氧氣流量對WOx薄膜的影響….….….………..43
5.1.2 WOx薄膜表面形態..………………………...………..48
5.1.3 WOx材料結構分析..…..…………………….………..51
5.1.4 WOx薄膜光學性質.....…………………….………….53
5.2 V2O5單層膜 …………….…………….…………..……….. 58
5.2.1氧氣流量對VOx薄膜的影響..…………....….……... 58
5.2.2 VOX薄膜表面形態…………………….……………..62
5.2.3VOX薄膜材料結構分析……………….…………….. 65
5.2.4VOX薄膜光學性質…………………….…………….. 68
5.3 VWOx單層膜 …………………………….………….…….71
5.3.1釩靶材功率對VWOx薄膜的影響……...………...… 71
5.3.2 VWOx薄膜表面型態..…………....………..…….….. 73
5.3.3 VWOx材料結構分析…..……....…..………….…….. 77
5.3.4 VWOx薄膜光學性質...……....……..………….……..78
5.4多層膜 ………………..…………………..……………...…83
5.4.1 WO3/V2O5 雙層薄膜…………………………...……..83
5.4.2 WO3/V2O5 多層膜……….……………….……..….…88
5.5綜合討論 ………………………….…………………………93

第六章 結論與未來工作..……………...………………..………..…...97

參考文獻 …………………..….……………………………………….99

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