本研究中利用P型氧化亞銅與N型矽晶圓製作異質接面太陽能電池，首先利用氫氧化鉀鹼性水溶液對單晶矽的非等向性蝕刻特性，在矽晶圓表面製作金字塔結構以降低表面光反射；同時利用熱氧法氧化矽晶圓表面再以濕蝕刻移除表面氧化膜，這樣做的目的有二，首先是可以降低金字塔結構的銳利度，其次則在於清除製程中矽晶圓表面所吸附的雜質。接下來使用超臨界流體製程對矽晶圓作表面鈍化，以修補矽晶圓表面由於斷鍵所形成的缺陷。最後利用溶液製成與反應式濺鍍兩種方式沉積氧化亞銅薄膜，並以熱蒸鍍的方式沉積銀電極完成元件。 矽晶圓經非等向性蝕刻後表面的金字塔結構能將基板反射率從29.6%降至15.3%，同時由SEM證實熱氧法與氧化層蝕刻也能有效降低結構銳利度，但也會造成反射率上升，成長0.5μm二氧化矽的矽晶圓經蝕刻後的基板反射率增加為17.7%。最後以反應式濺鍍沉積氧化亞銅薄膜的太陽能電池元件有最好的元件表現，其開路電壓為0.3V、短路電流密度為1.03mA/cm2、填充因子(Full Factor, FF)為0.37、元件效率為0.11%。在表面鈍化部分，矽晶圓晶經超臨界流體處理1小時候的載子生命週期為94.1μs，未來想提升元件表現需先克服載子生命週期太短的問題。

In this study, we fabricate heteorjunction solar cells which are composed of P-type cuprous oxide on N-type silicon wafer. First, the silicon wafer was textured with KOH alkaline solution to lower the weighted reflection. In the following, we used thermal oxidation to grow silicon oxide on the surface of silicon wafer, and removed the grown oxide with wet etching. There are two reasons to do so. One is to lower the sharpness of pyramid structure, and another is to remove particles which could attach to the silicon surface during fabricating process. Moreover, we do the surface passivation of silicon using supercritical fluid to repair defects. Finally, we deposited P-type cuprous oxide on silicon substrate with both solution process and reactive sputtering and completed the devices by fabricating the metal electrodes. The reflectivity of silicon substrate was reduced from 29.6% to 15.3% by texturizing the Si surface. The SEM pictures also showed that the sharpness of pyramid structure was successfully reduced with thermal oxidation and etching. However, this led to an increase of reflectivity. The reflectivity increased from 15.3% to 17.7% after removing 0.5μm thermal oxide on the Si surface. Finally, the performance of devices was measured by solar simulator at AM1.5. The best devices showed an open circuit voltage (VOC ) of 0.3V、a short circuit current density (JSC) of 1.03mA/cm2、a full factor (FF) of 0.37 and an energy conversion efficiency (η) of 0.11%. The carrier lifetime of the textured silicon wafer which is passivated with supercritical fluid is only 94.1μs. The carrier lifetime must be improved before a high performance Cu2O/n-Si heterojunction solar call can be obtained.

第一章 導論 1
1-1 太陽能電池簡介 1
1-2 影響效率的關鍵 1
1-3 太陽能電池基本原理 2
1-4 太陽能電池的電性參數 3
1-1-1 短路電流 5
1-1-2 開路電壓 5
1-1-3 填充因子 6
1-1-4 轉換效率 6
1-5 HIT solar cells 7
1-6 超臨界製程 8
1-6-1 清洗晶圓表面 9
1-6-2 製造產生微米及奈米粒子 9
1-6-3 超臨界流體沉積(Supercritical Fluid Deposition, SCFD) 9
1-7 異質接面太陽能電池(Heterojunction Solar Cells) 10
1-8 矽晶圓表面抗反射結構 10
1-9 矽晶圓表面鈍化(Surface Passivation)的方法 11
1-9-1 熱氧法 11
1-9-2 化學氣相沉積(Chemical Vapor Deposition, CVD) 11
1-9-3化學處理法 12
1-9-4 超臨界流體製程 12
1-10 動機 12
第二章 製程材料與儀器介紹 14
2-1 銅氧化物 14
2-2 反應性濺鍍 15
2-3 氫氧化鉀蝕刻 17
2-4 RCA洗淨製程 17
2-5 濕氧熱氧法 17
2-6 超臨界流體製程 18
2-7 高真空熱蒸鍍系統 18
2-8 量測設備 19
2-8-1 場發射型掃描式電子顯微鏡 19
2-8-2 紫外光-可見光光譜儀 19
2-8-3 四點探針 20
2-8-4 表面輪廓儀 21
2-8-5 雙晶薄膜X光繞射儀 21
2-8-6 太陽光模擬器 23
2-8-7 載子生命週期量測儀 23
第三章 實驗步驟 25
3-1 清洗矽晶圓 25
3-2 表面結構蝕刻 25
3-3 RCA清洗製程 26
3-4 熱氧法氧化製程 26
3-5 超臨界流體製程 27
3-6 氧化銅沉積 27
3-7 鍍電極 28
第四章 結果與討論 29
4-1 矽晶圓基板處理結果分析 29
4-1-1 鹼蝕刻與表面結構分析 29
4-1-2 熱氧法改善結構圓潤角分析 32
4-1-3 矽基板反射率結果分析 34
4-2 超臨界表面鈍化結果 35
4-3 太陽能電池元件結果分析 36
4-3-1 Sol-gel氧化亞銅薄膜太陽能電池元件分析 36
4-3-2 Sputtered氧化銅薄膜太陽能電池元件分析 38
4-4 載子生命週期量測 42
第五章 結論 46
參考文獻 47

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