臺灣博碩士論文加值系統

本研究以噴霧熱解法鍍膜系統，將含有錫離子的前驅物之溶液以氣體攜帶至加熱的玻璃基材，使溶劑瞬間受熱蒸發，同時前驅物的錫離子在大氣環境下進行氧化反應，形成氟摻雜的錫氧化物結晶薄膜(FTO)沈積在玻璃基材上。本實驗使用SnCl4為前驅物，並採用乙醇與水的混合共溶劑，並以氬氣為攜帶氣體。主要目標在找出基材沈積溫度、共溶劑比例、錫離子的濃度、氟摻雜比例、攜帶氣體、噴霧壓力、噴嘴到基材距離、噴霧時間等程序參數對光學穿透性與導電度的最佳化條件。實驗結果，證實基材沈積溫度在350℃以上薄膜即呈現二氧化錫結晶。隨著不同共溶劑的比例，薄膜粗糙度會有相當明顯的改變，進而影響薄膜的光學穿透性，變化幅度在80％∼90％之間，並影響電阻率，從5.5×10-3 Ω-cm降低至1.8×10-3 Ω-cm。錫離子的濃度將會影響薄膜的緻密性以及晶粒尺寸，晶粒大約為200nm~300nm。氟摻雜比例並不會明顯改變薄膜的結晶微結構；但由霍爾效應的量測，導致載子濃度的增加致使電阻率降至6×10-4 Ω-cm。本實驗工作，可以得到最佳化條件之攜帶氣體壓力為2 kg/cm2、噴霧距離為25公分、單次噴塗時間為0.5秒、共溶劑比例為3 / 7、錫濃度為0.8M、摻雜比例為10v%、沈積溫度為400℃。在最佳化條件下得到的透明導電薄膜光學穿透性在85％以上，電阻率能夠低於10-3 Ω-cm。經進一步在最佳化條件下製作的透明導電薄膜上塗佈多孔性TiO2薄膜後，吸附D149染料組成染料敏化太陽能電池，獲得效率為3.6%(市售FTO所得結果為3.9％）。

Spray pyrolysis technique was used to prepare a conducting fluorine-doped tin oxide (FTO) thin film on glass substrate in this study. Spray solution containing Sn+4 ions precursor was sprayed onto the heated substrate in which a FTO deposition was obtained by the pyrolysis process. Tin ions were oxidized in air atmosphere and formed fluorine-doped tin oxide thin film on glass substrate. In the process, argon was used to carry the precursor solution. Ethanol and water were mixed to use as a co-solvent. The main purpose is to search the optimum process parameters of transmittance and resistivity of FTO by varying process parameters, such as carrier gas, spray pressure, the distance between nozzle and substrate, spray time interval, concentration of tin cation, co-solvent ratio, doping level, and substrate temperature. From the experimental results, tin oxide crystals can be observed when the deposited temperature was above 300℃. The roughness of FTO thin film was obviously influenced with different co-solvent (H2O/EtOH) ratios, whereas the transmittance of FTO film ranged from around 80 to 90%. The resistivity of FTO thin film can be lowered from 5.5×10-3 to 1.8×10-3 Ω-cm. Concentration of tin cation affected the grain size ranging from 150 to 300 nm and the uniformity of FTO film. The optimum parameter conditions could be obtained as follows: 2 kg/cm2 of spray pressure, 25 cm distance between nozzle to substrate, 0.5s of spray time interval, 3/7 of co-solvent (H2O/EtOH) ratio, 0.8M tin ion concentration, 10v% of CF3COOH doping level (vs. precursor solution), and 400℃deposited substrate temperature. At optimum conditions, the transparent conductive oxide FTO film possesses a transmittance ~ 90% and low resistivity below 10-3 Ω-cm. This optimal FTO-coated glass was used as a substrate for further application in a dye-sensitized solar cell. TiO2 nano-particle film was deposited on the FTO substrate and then adsorbed D149 dye to assemble a dye-sensitized solar cell with efficiency of 3.6% (as compared to 3.9% efficiency of Hartford FTO substrate).

目錄
致謝...............................................................................................................Ⅰ
目錄...............................................................................................................Ⅱ
表目錄...........................................................................................................Ⅶ
圖目錄...........................................................................................................Ⅸ
中文摘要.........................................................................................................1
英文摘要.........................................................................................................2
第一章 緒論...................................................................................................4
1.1 前言...................................................................................................4
1.2 染料敏化太陽能電池（Dye-sensitized solar cells，DSSC）之研究發展..................................................................................................5
1.3 研究動機和目的...............................................................................8
1.4 二氧化錫之透明導電薄膜與應用...................................................8
1.5 二氧化錫薄膜之製備方式...............................................................9
1.6 研究架構..........................................................................................11
第二章 文獻回顧.....................................................................12
2.1 染料敏化太陽能電池結構與工作原理.........................................12
2.2 二氧化鈦簡介.................................................................................13
2.3染料/敏化劑.....................................................................................14
2.3.1釕金屬錯合物染料光敏化劑................................................15
2.3.2 量子點無機染料...................................................................17
2.4 電解質.............................................................................................18
2.5 金屬/導電玻璃對電極....................................................................19
2.6 二氧化錫結構與特性.....................................................................20
2.7 二氧化錫之導電機制.....................................................................21
2.8 二氧化錫之鍍膜方法.....................................................................22
第三章 實驗方法與步驟.............................................................................25
3.1 Precurse solution 準備..................................................................27
3.1.1 前驅物溶液的配製................................................................27
3.1.2 起始溶液................................................................................27
3.2 玻璃基版之準備.............................................................................27
3.3實驗裝置之架構..............................................................................28
34 實驗參數…......................................................................................29
3.4.1 霧壓力(Spray Pressure)系列.................................................29
3.4.2噴霧時間(Spray Time)系列....................................................29
3.4.3噴霧距離(Distance)系列........................................................29
3.4.4共溶劑比例(Solvent Ratio)(酒精/水)系列.............................30
3.4.5錫濃度(Concentration)系列....................................................30
3.4.6氟摻雜比例(Doping Level)系列............................................30
3.4.7沈積溫度(Temperature)系列..................................................30
3.5薄膜分析、量測使用之儀器...........................................................32
3.5.1 X光繞射(X-ray diffraction)分析...........................................32
3.5.2 掃瞄式電子顯微鏡(SEM)分析.............................................32
3.5.2.1 截面(cross-section)觀察..............................................32
3.5.2.2 表面(top-view)觀察.....................................................34
3.5.3 Hall effect量測.......................................................................34
3.5.4 四點探針量測........................................................................35
3.5.5 紫外光-可見光(UV-Visible)分析..........................................36
3.5.6 原子力顯微鏡(AFM) ...........................................................36
第四章 實驗結果.........................................................................................41
4.1 X-ray繞射圖.....................................................................................41
4.1.1噴霧壓力(Spray Pressure)系列...............................................41
4.1.2噴霧時間(Spray Time)系列....................................................42
4.1.3噴霧距離(Distance)系列........................................................43
4.1.4共溶劑比例(Solvent Ratio)(酒精/水)系列.............................44
4.1.5錫濃度(Concentration)系列....................................................45
4.1.6氟摻雜比例(Doping Level)系列............................................46
4.1.7沈積溫度(Temperature)系列..................................................47
4.2 UV-visible光譜.................................................................................48
4.2.1噴霧壓力(Spray Pressure)系列...............................................48
4.2.2噴霧時間(Spray Time)系列....................................................50
4.2.3噴霧距離(Distance)系列........................................................52
4.2.4共溶劑比例(Solvent Ratio)(酒精/水)系列.............................54
4.2.5錫濃度(Concentration)系列....................................................56
4.2.6氟摻雜比例(Doping Level)系列............................................58
4.2.7沈積溫度(Temperature)系列..................................................60
4.3 SEM結果..........................................................................................62
4.3.1 截面觀察................................................................................62
4.3.2 表面觀察................................................................................64
4.3.2.1混合共溶劑比例(Solvent Ratio)(酒精/水)系列...........64
4.3.2.2錫濃度(Concentration)系列..........................................70
4.3.2.3氟摻雜比例(Doping Level)系列...................................76
4.3.2.4沈積溫度(Temperature)系列........................................81
4.4 原子力顯微鏡.................................................................................86
4.4.1混合共溶劑比例(Solvent Ratio)(酒精/水)系列....................86
4.4.2錫濃度(Concentration)系列...................................................90
4.4.3氟摻雜比例(Doping Level)系列............................................94
4.4.4沈積溫度(Temperature)系列..................................................97
4.5導電性量測結果.............................................................................100
4.5.1噴霧壓力(Spray Pressure)系列............................................100
4.5.2噴霧時間(Spray Time)系列..................................................101
4.5.3噴霧距離(Distance)系列......................................................102
4.5.1混合共溶劑比例(Solvent Ratio)(酒精/水)系列...................103
4.5.2錫濃度(Concentration)系列..................................................105
4.5.3氟摻雜比例(Doping Level)系列..........................................107
4.5.4沈積溫度(Temperature)系列................................................109
第五章 討論................................................................................................111
5.1噴霧壓力(Spray Pressure)系列.......................................................111
5.1噴霧時間(Spray Time)系列............................................................112
5.1噴霧距離(Distance)系列................................................................113
5.1共溶劑比例(Solvent Ratio)(酒精/水)系列.....................................114
5.1錫濃度(Concentration)系列............................................................115
5.1氟摻雜比例(Doping Level)系列....................................................116
5.1沈積溫度(Temperature)系列..........................................................117
第六章 結論...............................................................................................118
參考文獻.....................................................................................................119
附錄















表目錄
Table 1-1 DSSC之發展歷史...........................................................................7
Table 3-1實驗藥品表…….….......................................................................26
Table 3-2噴霧熱解沈積法製備的二氧化錫................................................31
Table 4-1不同噴霧壓力之穿透度比較........................................................49
Table 4-2不同噴霧時間之穿透度比較........................................................51
Table 4-3不同噴霧距離之穿透度比較........................................................53
Table 4-4不同混合共溶劑比例之穿透度比較............................................55
Table 4-5不同錫濃度之穿透度比較............................................................57
Table 4-6不同氟摻雜比例之穿透度比較....................................................59
Table 4-7不同沈積溫度之穿透度比較........................................................61
Table 4-8 各系列薄膜之厚度......................................................................62
Table 4-9 不同混合共溶劑比例之平均粒徑大小......................................86
Table 4-10 不同混合共溶劑之粗糙度........................................................86
Table 4-11 不同錫濃度之平均粒徑大小....................................................90
Table 4-12 不同錫濃度之粗糙度................................................................90
Table 4-13 不同氟摻雜濃度平均粒徑大小................................................94
Table 4-14不同氟摻雜濃度之粗糙度..........................................................94
Table 4-15 不同沈積溫度之粒徑大小........................................................97
Table 4-16 不同沈積溫度之粗糙度............................................................97
Table 4-17不同噴霧壓力之片電阻及穿透率比較....................................100
Table 4-18 不同噴塗時間之片電阻及穿透度比較..................................101
Table 4-19 不同噴霧距離之片電阻及穿透度比較..................................102
Table 4-20 不同混合共溶劑比例之片電阻及穿透率比較......................104
Table 4-21 不同混合共溶劑之電阻率及載子濃度、遷移率..................104
Table 4-22 不同錫濃度之片電阻及穿透率..............................................106
Table 4-23 不同錫濃度之電阻率及載子濃度、遷移率...........................106
Table 4-24 不同氟摻雜比例之片電阻及穿透率......................................108
Table 4-25 不同氟摻雜比例之電阻率及載子濃度、遷移率..................108
Table 4-26不同沈積溫度之片電阻及穿透率...........................................110
Table 4-27 不同沈積溫度之電阻率及載子濃度、遷移率......................110













圖目錄
Figure 1-1 實驗研究架構.............................................................................11
Figure 2-1染料敏化太陽能電池(DSSC)之三明治結構.............................12
Figure 2-2各種氧化物相對的能隙圖..........................................................14
Figure 2-3 (a) N3以及(b) N719之化學式結構...........................................16
Figure 2-4 染料透過carboxylate groups與TiO2表面形成ester linkages..16
Figure 2-5 Charge transfer processes between dye and the TiO2 lattice…...17
Figure 2-6二氧化錫的單位晶胞之結晶結構..............................................20
Figure 3-1 實驗流程圖….............................................................................25
Figure 3-2 實驗裝置圖….............................................................................28
Figure 3-3截面試片製作..............................................................................33
Figure 3-4 霍爾量測試片簡圖.....................................................................34
Figure 3-5 (a)四點探針試片，在薄膜上圖四點銀膠；(b) 四點探針量測示意圖.............................................................................................35
Figure 3-6 UV-visible量測示意圖...............................................................36
Figure 3-7 AFM偵測表面起伏的示意圖 (a) 懸臂會隨著試片表面起伏而變形 (b) 由於懸臂的變化，偵測器可依據雷射反射角度不同得到不同的數據。.....................................................................37
Figure 3-8為原子力顯微鏡表面粗糙度量測的示意圖.............................40
Figure 4-1改變噴霧壓力所得到的X光繞射圖。噴霧時間(0.5秒)、噴嘴到基版距離(20 cm)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(5/5)、錫的濃度(0.5 M) .............................................41
Figure 4-2改變噴霧時間所得到的X光繞射圖。噴霧壓力(2 kg/cm2)、噴嘴到基版距離(20 cm)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(5/5)、錫的濃度(0.5 M) ..........................................42
Figure 4-3改變噴霧距離所得到的X光繞射圖。噴霧壓力(2 kg/cm2)、噴塗時間(1秒)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(5/5)、錫的濃度(0.5 M)................ ..........................................43
Figure 4-4改變噴霧時間所得到的X光繞射圖。固定噴霧壓力(2 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒)、摻雜比例(5 v%)、沈積溫度(400 ℃)、錫的濃度(0.5 M) ...........................44
Figure 4-5改變錫濃度所得到的X光繞射圖。固定噴霧壓力(2 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(3/7)..........................................45
Figure 4-6改變氟摻雜濃度所得到的X光繞射圖。噴霧壓力(2 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒)、沈積溫度(400 ℃)、共溶劑比例(3/7)、錫的濃度(0.5 M) ..........................................46
Figure 4-7改變沈積溫度所得到的X光繞射圖。噴霧壓力(2 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒) 、摻雜比例(10 v%)、共溶劑比例(3/7)、錫的濃度(0.5M)..........................................47
Figure 4-8 改變噴霧壓力所得到的UV-visible光譜。噴霧時間(0.5秒)、噴嘴到基版距離(20 cm)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(5/5)、錫的濃度(0.5 M) ..........................................49
Figure 4-9改變噴霧時間所得到的UV-visible光譜。噴霧壓力(3 kg/cm2)、噴嘴到基版距離(20 cm)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(5/5)、錫的濃度(0.5 M) ...................................51
Figure 4-10改變噴霧距離所得到的UV-visible光譜。噴霧壓力(3 kg/cm2)、噴塗時間(1秒)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(5/5)、錫的濃度(0.5 M).................................53
Figure 4-11改變共溶劑比例所得到的UV-visible光譜。噴霧壓力(3 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒)、摻雜比例(5 v%)、沈積溫度(400 ℃)、錫的濃度(0.5 M) ....................55
Figure 4-12改變錫濃度所得到的UV-visible光譜。噴霧壓力(3 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒)、摻雜比例(5 v%)、沈積溫度(400 ℃)、共溶劑比例(3/7).......................................57
Figure 4-13改變氟摻雜濃度所得到的UV-visible光譜。噴霧壓力(3 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒)、沈積溫度(400 ℃)、共溶劑比例(3/7)、錫的濃度(0.5 M).....................59
Figure 4-14改變沈積溫度所得到的UV-visible光譜。噴霧壓力(3 kg/cm2)、噴嘴到基版距離(25 cm)、噴塗時間(1秒) 、摻雜比例(10 v%)、共溶劑比例(3/7)、錫的濃度(0.5 M)......................61
Figure 4-15摻雜氟的SnO2薄膜...................................................................62
Figure 4-16共溶劑比例為0/10之SEM表面形貌(a)3萬倍(b) 5萬倍.....65
Figure 4-17共溶劑比例為3/7之SEM表面形貌(a)3萬倍(b) 5萬倍.....66
Figure 4-18共溶劑比例為5/5之SEM表面形貌(a)3萬倍(b) 5萬倍.....67
Figure 4-19共溶劑比例為7/3之SEM表面形貌(a)3萬倍(b) 5萬倍.....68
Figure 4-20共溶劑比例為10/0之SEM表面形貌(a)3萬倍(b) 5萬倍.....69
Figure 4-21錫濃度為0.2 M之SEM表面形貌(a)3萬倍(b) 5萬倍.............71
Figure 4-22錫濃度為0.4 M之SEM表面形貌(a)3萬倍(b) 5萬倍.............72
Figure 4-23錫濃度為0.6 M之SEM表面形貌(a)3萬倍(b) 5萬倍.............73
Figure 4-24錫濃度為0.8 M之SEM表面形貌(a)3萬倍(b) 5萬倍.............74 Figure 4-25錫濃度為1 M之SEM表面形貌(a)3萬倍(b) 5萬倍................75
Figure 4-26氟摻雜比例為5 v%之SEM表面形貌(a)3萬倍(b) 5萬倍.......77
Figure 4-27氟摻雜比例為10 v%之SEM表面形貌(a)3萬倍(b) 5萬倍.....78
Figure 4-28氟摻雜比例為15 v%之SEM表面形貌(a)3萬倍(b) 5萬倍.....79
Figure 4-29氟摻雜比例為20 v%之SEM表面形貌(a)3萬倍(b) 5萬倍.....80
Figure 4-30沈積溫度為300 ℃之SEM表面形貌(a)3萬倍(b) 5萬倍........82
Figure 4-31沈積溫度為350 ℃之SEM表面形貌(a)3萬倍(b) 5萬倍........83
Figure 4-32沈積溫度為400 ℃之SEM表面形貌(a)3萬倍(b) 5萬倍........84 Figure 4-33沈積溫度為450 ℃之SEM表面形貌(a)3萬倍(b) 5萬倍........85
Figure 4-34不同混合共溶劑比例之AFM掃瞄3D立體圖當(a)比例為0/10；(b) 比例為3/7.................................................................87
Figure 4-35不同混合共溶劑比例之AFM掃瞄3D立體圖當(a)比例為5/5；(b) 比例為7/3.................................................................87
Figure 4-36不同共溶劑比例之AFM掃瞄3D立體圖當比例為5/5...........87
Figure 4-37不同錫濃度之AFM掃瞄3D立體圖當(a)濃度為0.2 M；(b) 濃度為0.4 M.................................................................................91
Figure 4-38不同錫濃度之AFM掃瞄3D立體圖當(a)濃度為0.6 M；(b) 濃度為0.8 M.................................................................................92
Figure 4-39不同錫濃度之AFM掃瞄3D立體圖當濃度為1 M.................93
Figure 4-40不同氟摻雜比例之AFM掃瞄3D立體圖當(a)比例為5 v%；(b) 比例為10 v%。..................................................................95
Figure 4-41不同氟摻雜比例之AFM掃瞄3D立體圖當(a)比例為15 v%；(b) 比例為20 v%。..................................................................96
Figure 4-42不同沈積溫度之AFM掃瞄3D立體圖當(a)溫度為300℃；(b) 比例為350℃............................................................................98
Figure 4-43不同沈積溫度之AFM掃瞄3D立體圖當(a)溫度為400℃；(b) 比例為450℃............................................................................99

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