本研究利用電子槍蒸鍍製程，並配合後退火與氧化程序，成長 Cu-Sn-Mn-O多元氧化物薄膜，並以此應用於光電化學電池與降解有機物之領域。
本研究選用CuO、SnO2、MnO2等地球含量豐富的氧化物，透過不同成份比例之調配，由UV-Vis之量測結果，得到在光波長為400 nm至 700 nm之吸收係數高於104 cm-1的薄膜，接著進行PL、CL、UPS分析，得知薄膜能隙約在2.3 eV，而價帶、導帶之能階位置約在6.7 eV及4.4 eV。本研究透過霍爾效應量測，得知經後退火與氧化程序之薄膜的載子濃度，可被降低到1019 至1021cm-3。透過GIXRD之晶體結構分析得知，此多元氧化物薄膜屬於混和物，存在CuO、Cu2O、SnO2、MnO、Mn3O4等晶相，並以SEM觀察得知薄膜表面形貌粗糙。
本研究將靶材成份為CuO : SnO2 : MnO2 = 3 : 1 : 3，經電子束蒸鍍並以後退火與氧化程序優化過之薄膜，並經製程條件最佳化後，進行LSV (Linear sweep voltammetry)、J-t圖(光電流-時間曲線)之特性測量後，得知薄膜在可見光照射下可得0.042 mA/cm2電流密度，而在太陽光照射下，可提供近0.1 mA/cm2電流密度，但會產生衰減現象；此外，在紫外光區的降解RhB (Rhodamine B) 有機物之速率常數為1.72 x 10-3 min-1，可見光區的降解RhB有機物之速率常數為6.9 x 10-4 min-1，而可見光區的降解MO (Methyl orange) 有機物之速率常數為2.3 x 10-3 min-1；由結果可知，Cu-Sn-Mn-O薄膜在以太陽光分解水方面之應用具有潛力。

In this work, the Cu-Sn-Mn multicomponent oxide thin film deposited from earth-abundant, stable, eco-friendly compound, CuO, SnO2, MnO2, were presented. The applications as an electrode for photoelectrochemical cell and as a material for degradation pollutant were also demonstrated.
The synthesis and characterization of Cu-Sn-Mn-O thin film were investigated in this study. By controlling the composition of target, Cu-Sn-Mn-O thin films showed more than 104 cm-1 absorption coefficient in wavelength of 400 nm to 700 nm, in visible light region by UV-Vis analysis.
The thin films were further investigated by ultraviolet photoelectron spectroscopy (UPS) , photoluminescence (PL) , cathodoluminescene (CL). The Ev (valence band energy), Ec (conduction band energy) band position of thin films, deposited from target composition of Cu : Sn : Mn = 3 : 1 : 3, was characterized as 6.7 eV, 4.4 eV, respectively, and the Eg (band gap) was measured to be 2.3 eV. Carrier concentrations of Cu-Sn-Mn-O thin films could be reduced between 1019 to 1021 cm-3 after annealing and oxidation process. By grazing incident X-ray diffractometer (GIXRD) analyses, Cu-Sn-Mn-O thin film verified as a composite containing CuO, Cu2O, SnO2, MnO, and Mn3O4.
The solar energy applications were investigated by JSV (linear sweep voltammetry), J-t (photocurrent-time curve), and photodegradation experimental tests. The best result showed a current density of 0.042 mA/cm2 under visible light excitation with good stability, and near 0.1 mA/cm2 under solar light excitation but lack of good stability. The rate constant of RhB degradation was 1.72 x 10-3 min-1 under 365 nm UV-light excitation, and 6.9 x 10-4 min-1 under visible light excitation. The rate constant of MO degradation was 2.3 x 10-3 min-1 under visible light excitation. The Cu-Sn-Mn-O thin films developed in this work showed the potential of water splitting under solar light.

目錄
摘要 I
ABSTRACT III
誌謝 V
圖目錄 XV
表目錄 XXII
第一章 緒論 1
第二章 文獻回顧及原理簡介 3
2.1半導體材料性質 3
2.2光觸媒簡介 5
2.2.1光觸媒催化機制 5
2.2.2光觸媒材料特性 7
2.2.3 光電化學電池原理與架構 12
2.2.4現今光觸媒材料表現 15
第三章 實驗流程與儀器簡介 18
3.1 實驗步驟 18
3.1.1 銅錫錳氧化物靶材之製備 21
3.1.2 銅錫錳氧化物薄膜之製備 24
3.1.3 銅錫錳氧化物光電化學電極之製備及電池架構 30
3.1.4 銅錫錳氧化物有機物降解實驗之架構 31
3.2 實驗儀器簡介 35
3.2.1 熱重/熱差分析儀 (TG/DTA) 35
3.2.2 熱機械分析儀 (TMA) 37
3.2.3 紫外光/可見光分光光譜儀 (UV-VIS) 38
3.2.4光激發螢光放光儀 (PL) 及陰極激發螢光放光儀 (CL) 41
3.2.5 紫外光光電子能譜儀 (UPS) 44
3.2.6 霍爾效應量測儀 (HALL EFFECT MEASUREMENT) 47
3.2.7 感應耦合電漿質譜儀 (ICP-MS) 49
3.2.8 薄膜厚度輪廓量測儀 (ALPHA STEP) 51
3.2.9 低掠角X光繞射分析儀 (GIXRD) 52
3.2.10 X光繞射分析儀 (XRD) 54
3.2.11 場發射掃描電子顯微鏡 (SEM) 55
第四章 實驗結果與討論 57
4.1 固態程序製備銅錫錳氧化物靶 59
4.1.1 銅錫錳氧化物靶熱重分析 59
4.1.2 銅錫錳氧化物靶熱機械及結構分析 63
4.2 電子槍蒸鍍法製備銅錫錳氧化物薄膜 67
4.2.1銅錫錳氧化物靶成份比例之影響 67
4.2.1.1不同靶材成份之薄膜光譜分析 67
4.2.1.2不同靶材成份之薄膜電性 71
4.2.1.3 不同靶材成份之薄膜結晶性 72
4.3 後退火與氧化程序對銅錫錳氧化物薄膜之影響 74
4.3.1 後退火溫度對薄膜電性之影響 75
4.3.2 真空腔體中各環境氣氛與加熱持溫時間對薄膜電性之影響 78
4.3.3 爐管真空環境中不同氧分壓對薄膜電性之影響 82
4.3.4爐管中進行不同氧分壓對薄膜光學特性之影響 85
4.3.5 於爐管中進行不同氧分壓後退火與氧化程序之薄膜成份分析 97
4.4 銅錫錳氧化物光觸媒光電流表現 98
4.5 銅錫錳氧化物光觸媒有機物降解表現 101
第五章 結論 111
第六章 未來展望 113
參考文獻 114
本研究產出之論文發表 119
本研究將發表之期刊論文 119

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