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研究生：	楊久慶 Yang, Chiu-Ching
論文名稱：	利用噴墨技術製作熱電薄膜應用於矽太陽能電池之研究 A study of thermoelectric thin-film by ink-jet printing for silicon solar cell application
指導教授：	李文熙 Lee, Wen-Hsi
學位類別：	碩士 Master
系所名稱：	電機資訊學院 - 電機工程學系 Department of Electrical Engineering
論文出版年：	2010
畢業學年度：	98
語文別：	中文
論文頁數：	137
中文關鍵詞：	水熱法、噴印塗佈、鉍碲、鉍銻碲
外文關鍵詞：	hydrothermal process, ink-jet printing, Bi2Te3, Bi0.5Sb1.5Te3
相關次數：	點閱：76 下載：2
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本實驗利用水熱法製備鉍碲和鉍銻碲粉末，藉由分散實驗比對中，於粉末添加適當溶劑後用來塗佈成膜，並利用不同成膜方式比較其熱電特性，其材料分析上利用EDS對於粉末與薄膜進行成分分析；使用X光粉末繞射儀針對其結構及結晶性進行分析並觀察是否有雜相的存在；使用掃描式電子顯微鏡觀察微結構及緻密性；原子力顯微鏡分析在不同熱處理持溫時間下之粗糙度。
實驗結果得知粉末在180℃且NaBH4加入為Te莫耳數的4倍後，即可發現EDS比例相當接近所要的組成比，從XRD中發現無雜相的存在。藉由溫度180℃與時間48小時合成條件下，有助於主peak強度的提升與結晶性較好。接著由沉降實驗中可對比出粉末於水中分散效果較佳，且其加入分散劑後差異不大。後續利用粉末加入水後塗佈成膜，藉由旋轉塗佈與噴印塗佈不同方式比較其熱電特性，並且調整噴印機台之參數以求得較穩定的液滴現象去塗佈成膜。運用旋轉塗佈成膜方式鉍碲薄膜經熱處理500℃ 7分鐘下，功率因子為0.055，鉍銻碲在同樣熱處理條件下功率因子為1.868。後來由噴印塗佈成膜方式鉍碲薄膜經熱處理500℃ 9分鐘下，功率因子改善為1.576，鉍銻碲在同樣熱處理條件下功率因子也提升至4.05，且其薄膜也較為平坦。最後將熱電薄膜整合於矽太陽能電池提升0.577發電效率。

The experiment applied hydrothermal process to synthesize Bi2Te3 and Bi0.5Sb1.5Te3 powders. By dispersing the powders in different kinds of solvents, we could observe the precipitation phenomenon, and then chose the solvent suitable for thin film coating by spin coating and ink-jet printing. Finally, we compared the two coating processes and studied the influence on the thermoelectric property. Energy dispersive spectroscopy (EDS) was used to estimate the composition of the powders and thin films. The crystal structure and second phases of the powders and thin films were identified by powder x-ray diffraction (XRD). The microstructure was observed by scanning electron microscope (SEM) and atomic force microscope (AFM), and the compactness of the films was also characterized at different annealing temperature.
Based on the EDS results, when the concentration of NaBH4 was four times the concentration of Te, the composition of powders would be close to the stoichiometry of Bi2Te3 and Bi0.5Sb1.5Te3 at the synthesizing temperature of 180℃. The XRD data showed no second phase existed. Annealing at the temperature of 180℃ for 48 hours, could improve the crystallinity of the powders. Through dispersing the powders into different kind of solvents, we found that water was the most suitable solvent for Bi2Te3 and Bi0.5Sb1.5Te3 powders. The influence of adding dispersing agent into the solvent for assisting dispersion was not apparent. By adjusting the parameters of the ink-jet printer, the thin films can be coated in a stable condition and thus having a better quality. The power factor of Bi2Te3 and Bi0.5Sb1.5Te3 thin films coated by spin coating at 500℃ for 7 minutes was 0.055 and 1.868, respectively. However, the power factor of Bi2Te3 and Bi0.5Sb1.5Te3 thin films coated by ink-jet printing at 500℃ for 9 minutes were 1.576 and 4.05, respectively. From the AFM analysis, the thin films coated by ink-jet printing is much flatter than that by spin coating. Finally, we combine the thermoelectric generator with silicon solar cell and get a 0.577% raise in the efficiency.

第一章 緒論	1
1-1 背景	1
1-2 研究目的	3
1-3 論文架構	3
第二章 文獻回顧	4
2-1 熱電致冷器及熱電發電機之原理	4
2-2 Z值的探討	7
2-3 熱電材料介紹	10
2-4 晶體結構	11
2-5 相圖	14
2-6 水熱法	18
2-7 奈米粉體分散理論	19
2-8 燒結理論[39]	21
第三章 實驗方法與步驟	24
3-1 實驗材料	24
3-1.1 實驗靶材(Sputtering Target)	24
3-1.2 基材(Substrates)	24
3-1.3 濺鍍及退火使用氣氛(Gas Ambient)	24
3-1.4 實驗相關藥品	24
3-2 實驗設備	25
3-2.1 薄膜濺鍍系統(Sputtering System)	25
3-2.2 磁石攪拌平台	26
3-2.3 烘箱	26
3-2.4 高溫爐	27
3-2.5 快速退火爐(Rapid Thermal Annealing)	28
3-2.6 旋轉塗佈機(Spin Coater)	29
3-2.7 噴墨式塗佈機(Ink-Jet Printing)	30
3-3 實驗流程	35
3-3.1 水熱法溶液的配製進行粉末合成	35
3-3.2 沉降實驗	36
3-3.3 旋轉塗佈成膜	36
3-3.4 噴墨塗佈成膜	36
3-3.5 RTA熱處理	37
3-3.6 鉬電極製作	37
3-4 鍍層分析儀器	38
3-4.1 α-step 膜厚計	38
3-4.2 四點探針	38
3-4.3 掃描式電子顯微鏡(Scanning Electron Microscope；SEM) [46]	39
3-4.4 能量分散光譜儀(Energy Dispersive Spectroscopy；EDS) [46]	40
3-4.5 X-Ray粉墨繞射儀 (Powder X-ray Diffraction)[47]	41
3-4.6 原子力顯微鏡 (Atomic Force Microscopy；AFM)	41
3-4.7 霍爾量測( Hall Effect Measurement)	42
3-4.8 熱電力量測( Seebeck Measurement)	46
第四章 實驗結果與討論	47
4-1 水熱法製備Bi2Te3與Bi0.5Sb1.5Te3粉末	47
4-1.1 添加不同濃度NaBH4對合成Bi2Te3之影響	47
4-1.2 改變不同溫度對合成Bi2Te3之影響	54
4-1.3 改變不同時間對合成Bi2Te3之影響	57
4-1.4 改變不同溫度對合成Bi0.5Sb1.5Te3之影響	59
4-1.5 改變不同時間對合成Bi0.5Sb1.5Te3之影響	62
4-2 沉降實驗	65
4-2.1 溶劑差異對分散Bi2Te3粉末之影響	65
4-2.2 溶劑差異對分散Bi0.5Sb1.5Te3粉末之影響	66
4-2.3 分散劑比例不同對分散Bi2Te3粉末之影響	68
4-2.4 分散劑比例不同對分散Bi0.5Sb1.5Te3粉末之影響	69
4-3 噴印塗佈液滴之不同參數變化	71
4-3.1 電壓參數變化	71
4-3.2 頻率參數變化	73
4-3.3 波形參數變化	74
4-4 燒結成膜	80
4-4.1 Bi2Te3旋轉塗佈高溫爐熱處理之溫度變化	80
4-4.2 Bi2Te3旋轉塗佈RTA熱處理之溫度變化	83
4-4.3 Bi2Te3旋轉塗佈RTA熱處理之時間變化	86
4-4.4 Bi2Te3噴印塗佈RTA熱處理之溫度變化	89
4-4.5 Bi2Te3噴印塗佈RTA熱處理之時間變化	92
4-4.6 Bi0.5Sb1.5Te3旋轉塗佈高溫爐熱處理之溫度變化	96
4-4.7 Bi0.5Sb1.5Te3旋轉塗佈RTA熱處理之溫度變化	98
4-4.8 Bi0.5Sb1.5Te3旋轉塗佈RTA熱處理之時間變化	101
4-4.9 Bi0.5Sb1.5Te3噴印塗佈RTA熱處理之溫度變化	104
4-4.10 Bi0.5Sb1.5Te3噴印塗佈RTA熱處理之時間變化	107
4-5 熱電薄膜之特性量測	112
4-5.1 Bi2Te3旋轉塗佈熱處理溫度不同之特性量測	113
4-5.2 Bi2Te3旋轉塗佈熱處理持溫時間不同之特性量測	115
4-5.3 Bi2Te3噴印塗佈熱處理溫度不同之特性量測	117
4-5.4 Bi2Te3噴印塗佈熱處理持溫時間不同之特性量測	118
4-5.5 Bi0.5Sb1.5Te3旋轉塗佈熱處理溫度不同之特性量測	120
4-5.6 Bi0.5Sb1.5Te3旋轉塗佈熱處理持溫時間不同之特性量測	122
4-5.7 Bi0.5Sb1.5Te3噴印塗佈熱處理溫度不同之特性量測	124
4-5.8 Bi0.5Sb1.5Te3噴印塗佈熱處理持溫時間不同之特性量測	126
4-6 應用於矽太陽能電池	128
第五章 結論	133
第六章 參考文獻	135


                                    

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