臺灣博碩士論文加值系統

本研究使用一種可簡化製程調控的合金靶材，結合濺鍍生長CIG薄膜前驅層、蒸鍍硒化層的創新性製程，在Mo下電極薄膜上沉積CIGS太陽能電池吸收層薄膜。
室溫及高溫濺鍍的CIG前驅層薄膜為含Ga之Cu7In3、Cu16In9。隨著溫度升高，會產生另一相對富In的Cu11In9相。SEM表面形態分析發現：這些富Cu與富In的相會呈現明顯不同的晶粒尺度與分布狀態，前者之晶粒尺寸為400 nm並構成基地，後者之晶粒尺寸高達1.5 μm並呈現凸起狀態。這種差異歸因於富In相具有較高的流動性。
前驅層硒化計採用Mo/CIG/Se、Mo/CIG/Se（夾層）/ CIG、Mo/Se（底層）/CIG/Se三種結構。為了促進Se的均質化並防止高溫硒化時Se的快速流失，先進行低溫（100~150℃）擴散處理，並利用RBS確認擴散的均勻性，再對其進行高溫（450~550℃）硒化處理。然而，這些研究發現Se仍有補充不足的問題，故高溫硒化後，會產生In-Se及Cu-Se二元化合物與CIGS黃銅礦（Chalcopyrite）的混合物，並無法得到CIGS單相薄膜。但是，高溫硒化時若進行硒蒸氣的臨場補充，不但可消除雜相，而且能產生表面平整，晶粒粗大且為單相黃銅礦的CIGS薄膜。

The research uses alloy target for innovative process which can simplify the process control. It combines sputtering CIG thin film precursor layer and evaporation selenium layer, and deposit CIGS solar cell thin film absorber on Mo back contact layer.
Sputtering CIG precursor layer in room and high temperature are Cu7In3 and Cu16In9 structures with gallium substituent. As temperature rises up, a relatively In-rich Cu11In9 phase will be in appearance. The analysis of SEM surface morphology figures that these In-rich and Cu-rich phases present obviously different grain size and distribution. The size of Cu-rich grains is 400 nm constructed matrix grain layer and In-rich grains is 1.5μm with bulge type. The differences refer to higher fluidness of In-rich phases.
Precursor selenization adopt Mo/CIG/Se, CIG/Se/CIG and Se/CIG/Se three structures. In order to improve the selenium homogenization and prevent rapid selenium loss in high temperature, low temperature (100~150℃) diffusion process is proceeded first and ensure the diffusion uniformity by RBS, and then proceed the selenization process in high temperature. However, the studies indicate that selenium under supply is still the problems, so In-Se, Cu-Se bi-element compounds and CIGS chalcopyrite phase mixture are grown, and single phase CIGS can not be get. Otherwise, in-situ selenium vapor resupply in high temperature selenization not only cancels the mixed phases but grows the single phase CIGS chalcopyrite structure with smooth surface and large grain.

中文摘要…………………………………………………………………i
英文摘要…………………………………………………………………ii
總目錄……………………………………………………………………iii
圖目錄……………………………………………………………………vi
表目錄……………………………………………………………………x
第一章 前言……………………………………………………………..1
第二章 實驗研究之動機與文獻回顧…………………………………..5
2.1 CIGS薄膜太陽能電池背景………………………………………5
2.2 CIGS薄膜太陽能電池製程………………………………………11
2.3 CIGS薄膜太陽能電池待改進之問題……………………………16
2.4 研究目標…………………………………………………………17
第三章 實驗設備與方法……………………………………………….18
3.1 製程設備…………………………………………………………18
3.1.1 超高真空磁控濺鍍系統…………………………………….18
3.1.2 高真空濺、蒸鍍系統……………………………………….20
3.2 分析設備…………………………………………………………22
3.2.1超微細表面型態階梯輪廓儀………………………………..22
3.2.2 四點探針片電組量測系統………………………………….23
3.2.3 掠角X光繞射儀（GI-XRD）……………………………. 24
3.2.4 掃描式電子顯微鏡（SEM）……………………………….26
3.2.5 拉賽福背向散射能譜儀（RBS）…………………………..28
3.2.6 離子耦合電漿-原子發散能譜儀（ICP-AES）…………….30
3.3 薄膜製備………………………………………………………...贞31
3.3.1 CIG三元合金靶材製備……………………………………..31
3.3.2 濺鍍Mo背接觸層…………………………………………..32
3.3.3 濺鍍CIG前驅物薄膜……………………………………….32
3.3.4 蒸鍍Se薄膜…………………………………………………34
3.3.5 CIG-Se疊層設計……………………………………………..34
3.3.6硒化條件控制………………………………………………...34
3.3.7 實驗流程…………………………………………………….35
第四章 實驗結果與討論……………………………………………….36
4.1 Mo背接觸層結構與特性………………………………………...36
4.2 CIG薄膜前驅物結構分析………………………………………..39
4.3 CIG/Se/CIG三層結構硒化製程結構分析……………………….43
4.4 Se/CIG/Se三層結構硒化製程結構分析…………………………44
4.5『三元合金前驅層堆疊硒化』雙層結構分析……………………46
4.5.1 擴散處理…………………………………………………….46
4.5.2 硒化氣氛……………………………………………..……..49
4.6 片電阻變化分析………………………………………..….…52
第五章 結論……………………………………………………..……. 53
參考文獻……………………………………………………….………111
附錄………………………………………………………….…………116
一、超微細表面型態輪廓儀操作……………………………….…116
二、相圖……………………………………….………….………...118
三、CIGS晶體結構………………………………………………...121

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