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本論文研究摻雜銅之氧化銦錫堆疊層對具氧化鉬電洞選擇性層及鋁背表面電場之單晶矽太陽能電池光電特性研究，透過改變銅的RF 和 DC 電漿源，探討各種銅摻雜 ITO 堆疊中 Cu 的位置效應，找到結果趨勢圖。因為氧化銦錫穿透率良好，故常作為透明導電電極材料，摻雜一定比例的銅，可以有效降低電阻率，因此藉由改變濺鍍銅的直流功率，增強矽基板與摻雜銅之氧化銦錫連接層的特性，並有效提升太陽能電池的光電轉換效率，且摻雜厚度越薄的銅可以使穿透率提升，其次，在同一功率下，探討氧化銦錫堆疊各種雙層摻雜銅之氧化銦錫對單晶矽太陽能電池光電換效率之影響，另外利用霍爾效應分析儀、紫外光/可見光/紅外光光譜分析儀、掃描式電子顯微鏡和紫外光電子能譜儀，觀察各種氧化銦錫堆疊摻雜銅之氧化銦錫的薄膜特性，後續實驗，以最佳參數探討比較對具蒸鍍氧化鉬電洞選擇性層及鋁背表面電場之單晶矽太陽能電池的光電轉換效率衰減百分比。
實驗結果顯示，網印式單晶矽太陽能電池的正面鍍上摻雜銅之氧化銦錫，然後再堆疊一層氧化銦錫，在銅的直流功率為7W的情況下，其光電轉換效率衰減百分比最小，僅衰減-2.69%。經由紫外光/可見光/紅外光光譜儀量測得知，平均穿透率是85.13%，經由霍爾量測得知，移動率是32.67 cm2 V-1 S-1、電阻率是0.318 mΩ – cm，經由掃描式電子顯微鏡觀察得知，薄膜厚度大約是60 nm，經由紫外光電子能譜儀量測得知，功函數是4.44 eV。後續實驗以最佳參數在具蒸鍍氧化鉬電洞選擇性層之單晶矽太陽能電池，其實驗結果得知，背面蒸鍍氧化鉬/銀之元件的光電轉換換效率衰減百分比最小，僅衰減-2.07%。

Effects of copper-doped indium tin oxide (ITO) stack layers on photovoltaic properties of monocrystalline silicon solar cells (MSSCs) with molybdenum oxides (MoOx) as hole-selective layers (HSLs) and Al back surface field (Al-BSF) were studied. The position effect of Cu in various copper-doped ITO stacks was explored by varying the RF and DC plasma sources of copper, and a trend plot of the results was found. Since ITO has good transmittance, ITO is often used as a transparent conductive electrode material. The resistivity can be reduced by doping a certain proportion of copper. Therefore, by changing the DC power of sputtering copper, the characteristics of the silicon substrate and the copper-doped ITO connection layer are enhanced, and the conversion efficiency (CE) of the solar cell is effectively improved. The penetration rate can be improved by the thinner the doping thickness of copper. Secondly, under the same power, the influence of ITO stacked with various double-layer copper-doped ITO on the CE of MSSCs was discussed. In addition, the Hall effect analyzer, UV/visible/infrared (UV/VIS/IR) spectrometer, scanning electron microscope (SEM) and UV photoelectron spectrometer (UPS) were used to observe the thin film characteristics of various ITO stacked with copper doped ITO. In follow-up experiments, the optimal parameters were used to discuss and compare the percentage of CE decay of MSSCs with evaporated MoOx HSL and Al-BSF. The experimental results show that the front side of the MSSCs was plated with copper-doped ITO and ITO stacked layers. The percentage of CE attenuation with -2.69% was demonstrated the smallest by the DC power of copper at 7 W. The average transmittance is 85.13% by UV/VIS/IR spectrometer. According to the Hall measurement, the mobility and resistivity were to be 32.67 cm2 V-1 S-1, and 0.318 mΩ–cm, respectively. The ITO of 60 nm and the work function of 4.44 eV were measured by SEM and UPS, respectively. The percentage of CE decay of the MSSC with MoOx/Ag is the smallest, only -2.07%.

摘要... i
Abstract....... ii
誌謝... iii
目錄... iv
表目錄.. ix
圖目錄.. x
第一章 緒論..... 1
1.1透明導電氧化銦錫(ITO)應用於太陽能光電元件之文獻回顧..... 1
1.2摻雜銅(Cu)之氧化銦錫應用於光電元件之文獻回顧.... 1
1.3氧化鉬(MoO2)電洞選擇性接觸層應用於光電元件之文獻回顧.... 3
1.4研究動機..... 4
1.5論文架構..... 4
第二章 實驗流程與特性測量........ 5
2.1 摻雜銅之氧化銦錫堆疊層對元件之前段實驗製程..... 5
2.1.1 透過(Radio Corporation of America：RCA)的方式清洗矽晶片，去除矽晶片表面的自然氧化層和微粒子.. 5
2.1.2 藉由濕式蝕刻的方式，將異丙醇、去離子水、及氫氧化鉀的混合液對矽晶片進行糙化(Textured)..... 6
2.1.3 使用高溫爐管進行磷擴散(Diffusion)，在矽晶片形成射極層(n+).... 7
2.1.4 使用熱退火的方式，將晶粒釋放應力.... 7
2.1.5 使用酸性的混合液將矽晶片清洗擴散完產生的磷玻璃(PSG)、邊緣隔絕(Edge isolation)..... 7
2.1.6 透過電漿增強化學氣相沉積法(Plasma Enhanced Chemical Vapor Deposition：PECVD)，在矽晶片正面上沉積氮化矽(SiNx)，並且作為抗反射層... 7
2.1.7 藉由網印機將銀(Ag)膠網印(Screen print)在矽晶片上，並且烤乾... 7
2.2 比較直流和射頻電漿源在各種ITO : Cu / ITO堆疊層效應對具鋁(Al)背表面電場之單晶矽太陽能電池之光電特性影響... 8
2.2.1 藉由網印機將鋁膠網印在矽晶片上，並且烤乾..... 8
2.2.2 透過燒結(Fired)製程，將銀膠刺穿氮化矽形成銀電極...... 8
2.2.3 使用雷射切割機(Laser cutting)將矽晶片切割成2 × 2 cm2........ 8
2.2.4 太陽能光伏元件的電流-電壓特性量測系統(I-V measurement)...... 9
2.2.5 改變銅靶材的直流和射頻電漿源在矽晶片的正面上濺鍍各種ITO : Cu / ITO堆疊層薄膜 ...........................................................................9
2.2.6 比較直流和射頻電漿源在各種摻雜銅之氧化銦錫堆疊層效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響..... 9
2.3 比較直流和射頻電漿源在各種ITO : Cu / ITO堆疊層效應對元件光電特性之材料分析............. 10
2.3.1 霍爾效應(Hall Effect)量測分析 : 電阻率(Resistivity)、片電阻(Sheet resistance)、移動率(Mobility)、載子濃度(Concentration)... 10
2.3.2 紫外光/可見光/紅外光光譜儀(UV/VIS/IR)量測分析 : 穿透率(Transmittance)、萃取其能隙(Hv)....... 10
2.3.3 掃描式電子顯微鏡(SEM)量測分析 : 銅靶材的直流和射頻電漿源在ITO : Cu / ITO堆疊層之元件的薄膜厚度........ 10
2.4 改變銅的直流功率在ITO : Cu / ITO堆疊層效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響........ 10
2.4.1 藉由網印機將鋁膠網印在矽晶片上，並且烤乾..... 11
2.4.2 透過燒結製程，將銀膠刺穿氮化矽形成銀電極..... 11
2.4.3 使用雷射切割機將矽晶片切割成2 × 2 cm2....... 11
2.4.4 太陽能光伏元件的電流-電壓特性量測系統....... 11
2.4.5 改變銅的直流功率在矽晶片的正面上濺鍍ITO : Cu / ITO堆疊層薄膜....12
2.4.6 改變銅的直流功率在摻雜銅之氧化銦錫堆疊層效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響.... 12
2.5 改變銅的直流功率在ITO : Cu / ITO堆疊層效應對元件光電特性之材料分析...... 12
2.5.1 霍爾量測分析 : 電阻率、片電阻、移動率、載子濃度...... 13
2.5.2 紫外光/可見光/紅外光光譜儀量測分析 : 穿透率、萃取其能隙....... 13
2.5.3 掃描式電子顯微鏡量測分析 : 不同的銅的直流功率在ITO : Cu / ITO堆疊層之元件的薄膜厚度... 13
2.6 雙層ITO : Cu在ITO : Cu / ITO堆疊層之位置效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響.... 13
2.6.1 藉由網印機將鋁膠網印在矽晶片上，並且烤乾..... 13
2.6.2 透過燒結製程，將銀膠刺穿氮化矽形成銀電極..... 14
2.6.3 使用雷射切割機將矽晶片切割成2 × 2 cm2....... 14
2.6.4 太陽能光伏元件的電流-電壓特性量測系統....... 14
2.6.5 矽晶片的正面上濺鍍雙層ITO : Cu在各種ITO : Cu / ITO堆疊層薄膜........ 14
2.6.6各種雙層摻雜銅之氧化銦錫其堆疊一層氧化銦錫連接層之位置效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響......... 15
2.7 雙層ITO : Cu在ITO : Cu / ITO堆疊層之位置效應對元件光電特性之材料分析... 15
2.7.1 霍爾效應量測分析 : 電阻率、片電阻、移動率、載子濃度.. 15
2.7.2 紫外光/可見光/紅外光光譜儀量測分析 : 穿透率、萃取其能隙....... 15
2.8 ITO : Cu / ITO堆疊層對具氧化鉬電洞選擇性層與鋁背表面電場之單晶矽太陽能電池之光電特性影響.. 16
2.8.1 透過燒結製程，將銀膠刺穿氮化矽形成銀電極..... 16
2.8.2 使用雷射切割機將矽晶片切割成2 × 2 cm2....... 16
2.8.3 矽晶片的正面使用樹脂(Polymer)旋塗兩層抗蝕刻阻擋層，並烤乾.... 17
2.8.4 使用氫氟酸(DHF)混合液蝕刻矽晶片背表面的自然氧化層.... 17
2.8.5 矽晶片的背面蒸鍍氧化鉬/銀顆粒....... 17
2.8.6 太陽能光伏元件的電流-電壓特性量測系統....... 18
2.8.7 矽晶片的正面上濺鍍ITO : Cu / ITO堆疊層薄膜.. 18
2.8.8 比較摻雜銅之氧化銦錫堆疊層對具氧化鉬電洞選擇性層與鋁背表面電場之單晶矽太陽能電池之光電特性...... 18
2.9 ITO : Cu / ITO堆疊層對具氧化鉬電洞選擇性層與鋁背表面電場對元件光電特性之材料分析 ............................................................................19
2.9.1 紫外光電子能譜儀(UPS)量測分析 : ITO : Cu薄膜對元件之價帶偏移(EF – EV)、功函數(WF)... 19
第三章 摻雜銅之氧化銦錫堆疊層對單晶矽太陽能電池光電特性研究......... 38
3.1 比較直流和射頻電漿源在各種ITO : Cu / ITO堆疊層效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響........ 38
3.1.1 比較直流和射頻電漿源在各種摻雜銅之氧化銦錫堆疊層效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響..... 38
3.1.2 結論..... 39
3.2 比較直流和射頻電漿源在各種ITO : Cu / ITO堆疊層效應對元件光電特性之材料分析............. 39
3.2.1 霍爾效應量測分析 : 電阻率、片電阻、移動率、載子濃度.......... 39
3.2.2 紫外光/可見光/紅外光光譜儀量測分析 : 穿透率、萃取其能隙....... 40
3.2.3 掃描式電子顯微鏡量測分析 : 銅靶材的直流和射頻電漿源在ITO : Cu / ITO堆疊層之元件的薄膜厚度...... 40
3.2.4 結論..... 40
3.3 改變銅的直流功率在ITO : Cu / ITO堆疊層效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響........ 40
3.3.1 改變銅的直流功率在摻雜銅之氧化銦錫堆疊層效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響.... 41
3.3.2 結論..... 41
3.4 改變銅的直流功率在ITO : Cu / ITO堆疊層效應對元件光電特性之材料分析...... 41
3.4.1 霍爾效應量測分析 : 電阻率、片電阻、移動率、載子濃度.. 41
3.4.2 紫外光/可見光/紅外光光譜儀量測分析 : 穿透率、萃取其能隙....... 42
3.4.3 掃描式電子顯微鏡量測分析 : 不同的銅的直流功率在ITO : Cu / ITO堆疊層之元件的薄膜厚度... 42
3.4.4 結論..... 42
3.5 雙層ITO : Cu在ITO : Cu / ITO堆疊層之位置效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響.... 42
3.5.1 各種雙層摻雜銅之氧化銦錫其堆疊一層氧化銦錫連接層之位置效應對具鋁背表面電場之單晶矽太陽能電池之光電特性影響....... 43
3.5.2 結論..... 43
3.6 雙層ITO : Cu在ITO : Cu / ITO堆疊層之位置效應對元件光電特性之材料分析... 43
3.6.1 霍爾效應量測分析 : 電阻率、片電阻、移動率、載子濃度.. 43
3.6.2 紫外光/可見光/紅外光光譜儀量測分析 : 穿透率、萃取其能隙....... 44
3.6.3 結論..... 44
3.7 ITO : Cu / ITO堆疊層對具氧化鉬電洞選擇性層與鋁背表面電場之單晶矽太陽能電池之光電特性影響.. 44
3.7.1 比較摻雜銅之氧化銦錫堆疊層對具氧化鉬電洞選擇性層與鋁背表面電場之單晶矽太陽能電池之光電特性...... 44
3.7.2 結論..... 45
3.8 ITO : Cu / ITO堆疊層對具氧化鉬電洞選擇性層與鋁背表面電場對元件光電特性之材料分析 ................45
3.8.1 紫外光光電子光譜儀量測分析 : ITO : Cu薄膜對元件之價帶偏移、功函數..... 45
3.8.2 結論..... 45
第四章 總結論與未來展望.. 67
4.1 總結論...... 67
4.2 未來展望.... 67
參考文獻........ 68
Extended Abstract...... 71
Abstract....... 71
Introduction... 72
Experimental... 73
Results and discussion......... 73
Conclusions............ 74
Results and Discussion......... 74

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