本實驗是以反應式直流磁控共濺鍍法於Corning 1737玻璃上製備SnO2與Cr摻雜SnO2 (Cr-doped SnO2)薄膜。Cr-doped SnO2薄膜製備完成後，以X光繞射(X-ray Diffraction)、能量散射光譜儀(Energy Dispersive Spectrometer)、原子力顯微鏡(Atomic Force Microscopy)、紫外光-可見光光譜儀(UV-Visible spectrometer)、超導量子干涉磁量儀(Superconducting Quantum Interference Device Magnetometer)與霍爾效應量測(Hall effect measurement)等儀器分別進行薄膜之晶體結構、化學成分、表面形貌、透光率、磁性、電阻率、載子濃度與載子遷移率等物理特性檢測。另將SnO2和Cr摻雜SnO2試片進行酸化處理測試酸化前後性質的改變；最後再以電鍍方式將Cu2O鍍在SnO2系列的試片上並研究其材料與物理特性。
在Cr含量對SnO2薄膜影響的實驗中，從X光繞射的結果顯示，鍍在Corning 1737玻璃上之Cr-doped SnO2為多晶結構，Cr的含量多寡並不影響SnO2的結構，而隨著Cr的含量增加，薄膜表面變得粗糙、透光率降低、電阻率變大、載子濃度減少，但載子遷移率卻增高；另外當Cr含量增加時，則SnO2薄膜有順磁性現象產生。
將SnO2與Cr摻雜SnO2試片經腐蝕後，會提升其導電性，而薄膜表面影響不大；透光性在腐蝕後約略降低，但在可見光範圍仍維持在80%以上，薄膜會隨著酸液濃度改變而使電性變化不同。
以電鍍將Cu2O鍍在SnO2系列的試片上時，由於純SnO2薄膜本身電性較差，所以導致Cu2O成長不易，所以進一步以Sb摻雜SnO2來提高其電性與業界所用之FTO做比較；實驗結果得知試片導電性愈佳對Cu2O之成形有影響外，其heterojunction也較易具有整流效果。

Undoped and Cr-doped SnO2 thin films were deposited on Corning 1737 glasses by using the reactive DC magnetron co-sputtering technique. The Cr concentration of Cr-doped SnO2 films was modulated by controlling the sputtering power of the Cr target during deposition and determined by energy dispersive x-ray analysis. The influences of Cr concentration on the crystal structure, morphology and topography, optical transmittance, magnetic characteristics and electrical properties of SnO2 films were studied. The results show that the electrical conductivity and optical transmittance decrease with increasing the Cr concentration. Paramagnetic characteristics due to the Cr doping were also observed in the Cr-doped SnO2 films.
The enhancement of electrical conductivity and carrier concentration due to surface treatment on SnO2 films by acid aques solution was observed and ascribed to the reduction reaction of H+ ions with oxygen atoms of SnO2 films which increases oxygen vacancies and then enhances the electrical conductivity of films.
Oxide heterojunctions were fabricated by electrodepositing cuprous oxide (Cu2O) films on F-doped SnO2 (FTO) and Sn-doped SnO2 (ATO) conductive glasses. Nonlinear and rectifying behaviors were observed in current-voltage measurements on Cu2O/ATO and Cu2O/FTO heterojunctions. However, the large turn-on voltage, 4~6 V, which may be correlated to the electron affinity of SnO2 implies the existence of conduction barriers at the interface between Cu2O and FTO/ATO layers. This can be attributed to the poor adhesion of Cu2O layers with FTO and ATO substrates.

明志科技大學碩士學位論文指導教授推薦書 i
明志科技大學碩士學位論文口試委員審定書 ii
明志科技大學學位論文授權書 iii
博碩士論文電子檔案上網授權書 iv
誌謝 v
中文摘要 vi
英文摘要 vii
目錄 viii
表目錄 xi
圖目錄 xii
第一章 前言 1
1-1 二氧化錫的性質與應用 1
1-2 研究目的 2
第二章 文獻回顧 4
2-1二氧化錫結構與特性 4
2-2二氧化錫之導電機制 5
2-3濺鍍原理 6
2-3.1物理氣相沉積(PVD)原理 6
2-3.2電漿產生原理 6
2-3.3電漿產生源 6
2-3.4直流濺鍍 7
2-3.5反應性濺射 8
2-4磁性理論 9
2-4.1磁性的來源與種類 9
2-4.2稀磁性半導體發展 11
2-5 P-N Junction 15
2-6儀器原理與架構 16
2-6.1 XRD 16
2-6.2 AFM 17
2-6.3 EDS 18
2-6.4霍爾量測儀 20
2-6.5紫外光-可見光光譜 21
第三章 實驗步驟與方法 23
3-1 SnO2與摻Cr共濺鍍製程 23
3-1.1實驗材料 23
3-1.2基板之清潔 23
3-1.3實驗系統 25
3-1.4 SnO2與摻Cr共濺鍍成長流程 25
3-1.5 實驗參數 26
3-2酸化處理製程 27
3-2.1實驗材料 27
3-2.2濃度計算 27
3-2.3實驗步驟 27
3-3 Cu2O/SnO2 heterojunctions 28
3-3.1實驗材料 28
3-3.2電鍍Cu2O薄膜實驗步驟 28
3-4薄膜分析與量測技術 29
3-4.1X光繞射(XRD) 29
3-4.2原子力顯微鏡(AFM) 29
3-4.3能量散射光譜儀(EDS) 29
3-4.4霍爾效應量測 (Hall effect measurement) 30
3-4.5紫外光-可見光光譜儀(UV-Visible) 30
3-4.6超導量子干涉磁量儀(SQUID) 30
3-4.7光電導效應 30
第四章 結果與討論 31
4-1 Undoped SnO2與Cr-doped SnO2薄膜 31
4-1.1薄膜晶體結構分析(XRD) 31
4-1.2薄膜成分分析(EDS) 32
4-1.3薄膜表面形貌(AFM) 34
4-1.4電性量測 36
4-1.5透光率量測 39
4-2酸化處理結果 40
4-2.1電性量測 40
4-2.2薄膜表面形貌 42
4-2.3透光率量測 46
4-3 Cu2O/SnO2 heterojunctions 48
4-3.1 晶體結構分析 48
4-3.2電流-電壓特性量測(I-V Characteristics) 49
4-3.3 AFM量測 51
4-3.4穿透率量測 51
4-3.5光激發螢光光譜 52
4-3.6光電流效應 53
第五章 結論 55
第六章 參考文獻 56


表目錄
表3.1、SnO2與Cr-doped SnO2薄膜濺鍍參數表 26
表4.1、改變Cr靶濺鍍功率鍍製而得之Cr-doped SnO2薄膜中Cr含量 33
表4.2、不同Cr濺鍍功率摻雜SnO2薄膜表面粗糙度 34
表4.3、不同Cr功率對電阻率(ρ)、載子濃度(n)、載子遷移率(μ)之數據37
表4.4、SnO2薄膜以不同濃度HCl進行表面酸化前後之電阻率(ρ)與載子濃 度(n) 41
表4.5、Cr-doped SnO2薄膜以1M的HCl溶液進行表面酸化前後之電阻率(ρ)與載子濃度(n)子濃度(n) 42


圖目錄
圖2.1、二氧化錫的單位晶胞之結晶結構圖 4
圖2.2、直流濺鍍系統 7
圖2.3、電漿中電位分佈 8
圖2.4、反應性濺鍍示意圖 9
圖2.5、(A)磁性半導體：半導體內磁性元素為週期性排列 (B)稀磁性半導體：半導體內摻雜少量元素 (C)半導體 (藍色圓點為磁性元素) 13
圖2.6、理論預測DMS的Tc (A)Ditel等人以RKKY理論預測許多p-type稀磁性半導體的居禮溫度，實線標示為室溫(300K) (B)寬能係DMS之能係與居理溫度的關係 14
圖2.7、電子與電洞無法越過接面形成空乏區示意圖 16
圖2.8、多數載子通過PN接面進而能通過能障複合發光示意圖 16
圖2.9、布拉格定律 17
圖2.10、AFM接觸式、非接觸式、輕敲式作用力與距離的關係 18
圖2.11、X光與螢光及歐傑電子放射示意圖 19
圖2.12、霍爾量測原理示意圖 21
圖2.13、UV-Visible透光率量測示意圖 22
圖3.1、實驗流程圖 24
圖4.1、在工作壓力為3.2×10-3 torr、溫度為450℃、氬氣比氧氣流量為17.5:8.5 sccm、鍍膜時間為1hr下，不同Cr功率之SnO2 32
圖4.2、以不同Cr濺鍍功率所製備的Cr-doped SnO2薄膜之EDS分析圖譜 33
圖4-3、不同Cr濺鍍功率摻雜SnO2試片之表面形貌(A)Cr:0W (B)Cr:5W (C)Cr:10W (D)Cr:15W (E)Cr:20W (F)Cr:30W (G)Cr:50W (H)Cr:70W 36
圖4-4、Cr-doped SnO2薄膜之電阻率(ρ)、載子濃度(n)與載子遷移率(μ)對不同Cr濺鍍功率之關係圖 37
圖4-5、不同Cr濺鍍功率製備Cr-doped SnO2薄膜之磁化(M)與溫度(T)關係圖 38
圖4-6、Cr-doped SnO2薄膜之透光率與Cr濺鍍功率(Cr含量)關係圖 39
圖4-7、SnO2浸不同濃度酸前後其表面變化圖情形(A)0.3M前 (B)0.3M後 (C)0.7M前 (D)0.7M後 (E)1M前 (F)1M後 (G)2M前 (H)2M後 (I)3M前 (J)3M後 44
圖4-8、圖4.8 當試片為摻雜Cr的SnO2薄膜時，浸入1M酸時其表面形貌之變化(A)Cr:5W浸酸前 (B)Cr:5W 浸酸後 (C)Cr:15W浸酸前(D)Cr:15W 浸酸後(E)Cr:30W浸酸前(F)Cr:30W 浸酸後(G)Cr:50W浸酸前(H)Cr:50W 浸酸後(I)Cr:70W浸酸前(J)Cr:7W 浸酸後 46
圖4-9、以1M~9M不同濃度HCl腐蝕之SnO2試片之透光性 47
圖4-10、以0.1M~0.9M之HCl酸化SnO2試片之透光性 47
圖4-11、Cu2O在不同基板上之XRD光譜 48
圖4-12、將Cu2O電鍍在(A)FTO與(B)ATO上之I-V Curve 50
圖4-13、Cu2O以(A)FTO (B)ATO為基板之表面形貌 51
圖4-14、不同基板之Cu2O透光性 52
圖4-15、Cu2O之光激發螢光光譜 53
圖4-16、Cu2O-Cu2O和Cu2O-FTO之光電流圖譜 54

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