臺灣博碩士論文加值系統

本論文研究以硒薄膜層與硒蒸氣硒化銅銦鎵(1:0.5:0.5)金屬前驅層製備銅銦鎵硒薄膜，探討在不同的堆疊結構(Glass/Mo/Se/CIG、Glass/Mo/CIG/Se)與硒化退火參數下對銅銦鎵硒薄膜的影響，並進一步的在退火製程中加入硒氣氛，觀察對硒化後薄膜的影響，最後根據前期的研究成果設計製備低鎵與低氧元素的金屬前驅層進行硒化退火，觀察鎵與氧元素在硒化退火過程中所佔的重要地位。

實驗分析結果中發現薄膜在不同的堆疊方式與退火參數下對薄膜的影響，其中Glass/Mo/CIG/Se結構在較短的擴散處理下會阻礙氧元素的脫離而產生銦氧相，藉由較長的擴散處理可使表層的氧脫離得到較佳的銅銦鎵硒結晶形貌，而在Glass/Mo/Se/CIG結構退火後發現底層硒元素皆往表面偏移現象，並在薄膜表層形成銅銦鎵硒的結晶，而當在Glass/Mo/Se/CIG結構退火在充滿硒氣氛的環境下，分析結果顯示在此條件下會使表面產生富銅的結晶，並可使表面高含量的硒原子朝薄膜底部擴散，使薄膜表面硒原子濃度高於底部，避免了硒原子朝表面偏移。

在改變CIG前驅層鎵與氧含量的分析結果中發現，在降低鎵元素含量的條件下，薄膜內部的氧分子較容易偏移至表面，致使表面銦與氧的氧化相。而製備低氧前驅層對於硒化反應則有很明顯的改善，硒原子的擴散不再受到氧原子的阻礙而使硒化深度明顯增加，達到整層薄膜完全硒化的目的。

In this study, CuInGaSe2 films were prepared by Se film and Se vapor hybrid selenization of Cu-In-Ga metallic precursor film, with structures of glass/Mo/Se/CIG and glass/Mo/CIG/Se. Effects of selenization parameters on the CIGS film properties were investigated. The influences of the selenization with and without Se vapor were also analyzed. According to these results, a low Ga-content and low O-content precursor film was used to evaluate the roles that Ga and O played during the selenization process.

Among the testing samples, the sample with the structure of glass/Mo/CIG/Se showed In2O3 phase due to the obstruction of oxygen out-diffusion from the film when a short selenization time was used. Long selenization duration can reduce the surface oxygen content and thus obtain better crystalline morphology. If selenized without Se vapor, the precursor film with structure of glass/Mo/Se/CIG showed that Se content at the bottom almost totally diffused to top region, and the CIGS crystals were formed only at the surface. Supplement by Se vapor when selenization leads to Cu-rich crystals and high Se concentration on the sample surface layer to avoid absence of Se at the bottom of the sample.

Regarding different Ga- and O-content precursor films, the results showed that oxygen in the low Ga-content precursors significantly moved to surface, and thus leaded to InO3 phase. On the other hand, applying low O-content precursors improved the selenization process, in which Se diffused into the film without obstruction from oxygen, and finally the completely selenized CIGS film could be obtained.

中文摘要................................................i
Abstract...............................................iii
誌謝....................................................v
目錄....................................................vi
表目錄..................................................x
圖目錄..................................................xi
第一章 緒論..............................................1
1.1 前言.................................................1
1.2 CIGS薄膜太陽電池的發展背景[1]........................3
1.3 CIGS薄膜的製程.......................................8
1.3.1 真空濺鍍法製備CIGS薄膜.............................9
1.4 研究動機與目的.......................................11
第二章 太陽能電池原理與文獻回顧..........................13
2.1 太陽能電池原理[19-20]................................13
2.1.1 太陽能電池等效電路.................................15
2.1.2 太陽電池轉換效率...................................16
2.2 太陽電池的種類.......................................18
2.2.1 單晶矽太陽電池簡介.................................20
2.2.2 多晶矽太陽能電池簡介...............................21
2.2.3 非晶矽薄膜太陽能電池簡介...........................21
2.2.4 碲化鎘薄膜太陽能電池概述...........................22
2.3銅銦鎵硒(CIGS)薄膜太陽能電池..........................23
2.3.1銅銦鎵硒薄膜太陽電池的工作原理與複合機制............25
2.3.2 銅銦鎵硒薄膜太陽電池的製程與結構...................26
第三章 實驗規畫與設備...................................36
3.1實驗流程與規劃........................................36
3.1.1實驗流程............................................36
3.1.2實驗設計............................................38
3.1.3實驗材料準備與試片的前處理..........................42
3.1.3.1試片的前處理......................................42
3.1.3.2實驗靶材..........................................43
3.1.3.3硒粉..............................................43
3.2 實驗設備.............................................44
3.2.1 射頻磁控濺鍍系統...................................44
3.2.2 連續式多腔體濺鍍系統...............................45
3.2.3 硒化退火系統.......................................47
3.3 分析儀器.............................................49
3.3.1 場發式電子顯微鏡...................................49
3.3.2 X光繞射分析儀......................................51
3.3.3 霍爾量測儀.........................................52
3.3.4 X光電子能譜儀......................................53
第四章 結果與討論........................................56
4.1不同低溫擴散時間對上層硒薄膜硒化退火的影響............56
4.1.1 材料結構形貌分析...................................56
4.1.2 XRD結晶繞射分析....................................60
4.1.2 XPS成份縱深分析....................................61
4.2高溫退火時間對上層硒薄膜硒化的影響....................62
4.2.1 材料結構形貌分析...................................62
4.2.2 XRD結晶繞射分析....................................66
4.2.3 XPS成份縱深分析....................................67
4.3高溫退火時間對下層硒薄膜硒化的影響....................68
4.3.1 材料結構形貌分析...................................68
4.3.2 XRD結晶繞射分析....................................75
4.3.3 XPS成份縱深分析....................................76
4.4氣體與下層硒薄膜複合式硒化在不同退火時間下的影響......79
4.4.1 材料結構形貌分析...................................79
4.4.2 XRD結晶繞射分析....................................82
4.4.3 XPS成份縱深分析....................................83
4.5低Ga含量前驅層複合式硒化在不同退火時間下的影響........84
4.5.1 材料結構形貌分析...................................84
4.5.2 XRD結晶繞射分析....................................87
4.5.3 XPS成份縱深分析....................................88
4.6低氧前驅層在不同結構下硒化退火之影響..................89
4.6.1 Mo/CIG/Se結構下硒化退火之影響......................89
4.6.2 Mo/Se(600 nm)/CIG結構下硒化退火之影響..............92
4.6.3 Mo/Se(600 nm)/CIG結構以複合式硒化退火之影響........94
4.6.4 Mo/Se(600 nm)/CIG/Se(1.2 μm)結構下硒化退火之影響..96
4.7 Hall電性量測.........................................98
第五章 結論..............................................99
參考文獻................................................101
Extended Abstract.......................................107
簡歷(CV)................................................110

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