臺灣博碩士論文加值系統

本研究以異丙醇作為溶劑，用溶膠-凝膠(sol-gel)法塗布在天然雲母基板上，製備氧化鋅的薄膜層(ZnO)，再去使用水熱法成長氧化鋅奈米線(ZnO:NWs)，最後再塗佈鈣鈦礦量子點溶液在表面去做照光量測及濕度量測，並使用SEM、EDS、TEM、XRD、XPS、PL、UV-Vis，進行各種的晶體結構分析。因鈣鈦礦到ZnO的界面電荷轉移，在引入ZnO層之後的光電流增強了一個數量級以上。
在SEM中，可觀察到ZnO及ZnO上的鈣鈦礦量子點溶液，看出在氧化鋅奈米線上有均勻覆蓋，奈米線方面Pure ZnO NWs長度約1.44μm左右和CsPbBr3 QD/ZnO NWS約1.191μm，則從EDS分析中可確認有Cs 0.07%和Pb 0.08%及Br 12.35%，另外透過濕度量測和純ZnO奈米線是屬於N型材料，從PL量測CsPbBr3 QD/ZnO中peak在524nm可顯示出它對綠光有很好的反應。
在光量測部分我們在暗室下，使用綠光照射下，跟純氧化鋅相比有高的響應性，而後在濕度量測部分我們固定溫度在不同環境濕度下的電流響應，且在搭配綠光進行濕度變化量測，有更高響應及縮短響應時間。

關鍵字：溶膠-凝膠，鈣鈦礦量子點，氧化鋅

In this study, isopropyl alcohol was used as a solvent, and a sol-gel method was applied to a natural mica substrate to prepare a thin film layer of zinc oxide (ZnO), and then a hydrothermally grown zinc oxide nanowire was used. ZnO: NWs), finally coated with perovskite quantum dot solution on the surface for illuminance measurement and humidity measurement, and using SEM, EDS, TEM, XRD, XPS, PL, UV-Vis, various crystal structures analysis. Due to the interfacial charge transfer from perovskite to ZnO, the photocurrent after introduction of the ZnO layer is increased by more than an order of magnitude.
In the SEM, the perovskite quantum dot solution on ZnO and ZnO can be observed, and it is seen that there is uniform coverage on the zinc oxide nanowire, and the Pure ZnO NWs in the nanowire is about 1.44 μm in length and about CsPbBr3 QD/ZnO NWS. 1.191μm, it can be confirmed from EDS analysis that there are Cs 0.07% and Pb 0.08% and Br 12.35%. In addition, the moisture permeability measurement and the pure ZnO nanowire are N-type materials, and the CsPbBr3 QD/ZnO peak from the PL measurement. It shows a good response to green light at 524 nm.
In the light measurement section, we have high responsiveness under pure sunlight and green light, and then in the humidity measurement part we fixed the current response under different environmental humidity, and in the green Light is measured for humidity changes, which has higher response and shorter response time.
Keywords: sol-gel, perovskite quantum dots, zinc oxide

目次
中文摘要…………………………………………….……………………………..……. VII
Abstract.………………………………………………………………...……….……......VIII
目次……………………………………………………………………………….…………IX
表目次…………………………………………………………………………….……….XII
圖目次………………………………………………………………………………….…XIII
第一章 緒論 1
1.1前言 1
1.2 雲母 2
第二章、文獻回顧 3
2.1 量子點特性 3
2.2量子點應用 3
2.3量子點特性 5
2.3.1表面效應 5
2.3.2小尺寸效應 6
2.3.3量子效應 6
2.4無機鈣鈦礦量子點 7
2.5氧化鋅介紹 8
2.5.1氧化鋅製備 9
2.5.1.1溶膠-凝膠法(SOL-GEL METHOD) 9
2.5.1.2旋塗法(SPIN COATING) 10
2.5.1.3 水熱法(HYDROTHERMAL METHOD) 12
2.5.2 氧化鋅之發光機制 13
2.5.3氧化鋅之光催化反應原理 15
2.5.4氧化鋅奈米線光響應與濕度影響 17
第三章 實驗步驟與方法 19
3.1 實驗流程與架構 19
3.1.1 雲母片(MICA)之形貌 20
3.1.2雲母片材料處理流程 21
3.1.3經處理過後的雲母片 22
3.2 化學藥品 23
3.2.1 溶膠-凝膠(SOL-GEL)法製備氧化鋅薄膜之材料 23
3.2.2水熱法製備氧化鋅奈米線之材料 23
3.2.3製備鈣鈦礦量子點溶液 24
3.2.4鈣鈦礦量子點溶液 24
3.2.5 LED元件電激發光（ELECTROLUMINESCENCE）量測系統分析 28
3.3 製程方法 29
3.3.1 溶膠-凝膠(SOL-GEL)法製備氧化鋅(ZNO)薄膜 29
3.3.1.1 旋轉塗佈薄膜 30
3.3.3 水熱法成長氧化鋅奈米線 32
3.3.4無機鈣鈦礦量子點溶液於ZNO奈米線表面 33
第四章 儀器介紹 34
4.1分析儀器 34
4.1.1掃描式電子顯微鏡(SCANNING ELECTRONS MICROSCOPE, SEM) 34
4.1.2能量散佈分析儀 (EDS) 35
4.1.3 X光繞射分析儀 (XRD) 36
4.1.4微光激發光譜儀(MICRO-PL SPECTROMETER) 37
4.1.5穿透式電子顯微鏡(TRANSMISSION ELECTRON MICROSCOPE,TEM) 38
4.1.6 X射線光電子能譜學(X-RAY PHOTOELECTRON SPECTROSCOPY , XPS) 39
4.2.1 KEITHLEY-4200 40
4.2.2 KEITHLEY-237 40
5.1 ZNO薄膜之SEM分析 41
5.2氧化鋅奈米線之SEM分析 42
5.3 鈣鈦礦量子點氧化鋅奈米線成長於ZNO薄膜之SEM及EDS分析 43
5.4鈣鈦礦量子點氧化鋅奈米線之TEM分析 45
5.5 氧化鋅奈米線和鈣鈦礦量子點氧化鋅XRD分析 48
5.6鈣鈦礦量子點薄膜與鈣鈦礦量子點氧化鋅之PL分析 50
5.7 雲母片基板光學特性分析 51
5.8氧化鋅奈米線光學特性分析 53
5.9鈣鈦礦量子點氧化鋅奈米線之XPS分析 56
5.10光電測量結果 60
5.10.1 氧化鋅奈米線之光暗電流量測 60
5.10.2鈣鈦礦量子點氧化鋅奈米線之光暗電流量測 62
5.11濕度量測 65
5.11.1不同環境濕度下之響應量測 65
5.11.2不同環境濕度下照光之響應量測 68
第六章 結論與未來展望 74
6.1 結論 74
6.2 未來展望 75
參考文獻 76



表目次
表2-1、近年來有關於鈣鈦礦量子點期刊…………………………………………..11
表3-1、氧化鋅薄膜材料藥品………………………………………………………..23
表3-2、氧化鋅奈米線材料藥品……………………………………………………..23
表3-3、溶膠-凝膠法之溶質、溶劑及穩定劑材料…………………………………29
表4-1、能量散佈光譜儀 (EDS) 之優缺點表………………………………………35
表5-1、鈣鈦礦量子點薄膜與鈣鈦礦量子點氧化鋅之PL分析表…………………..50
表5-2、ZnO之光暗電流……………………………………………………………..61
表5-3、鈣鈦礦量子點氧化鋅之光暗電流…………………………………………..63
表5-4、氧化鋅與鈣鈦礦量子點氧化鋅之光暗電流………………………………..64
表5-5、照射UV光在不同環境濕度之響應量測……………………………………70
表5-6、鈣鈦礦量子點之氧化鋅照射綠光在不同環境濕度之響應量測…………..72
表5-7、滴DI water水照光在不同環境濕度之響應量測…………………………..73




圖目次

圖2-1、六方晶體之纖鋅礦結構……………………………………………………….8
圖2-2、旋轉塗佈過程之步驟…………………………………………………………10
圖2-3、氧化鋅能階與激子激發示意圖(a) band-to-band emission; (b) excition emission………………………………………………………………………………..14
圖2-4、氧化鋅的各種缺陷能階示意圖………………………………………………15
圖2-5、光催化的一般機制……………………………………………………………16
圖2-6 氧化鋅(N-type)濕度感測機制…………………………………………………17
圖2-7 氧化鋅奈米線光響應濕度影響………………………………………………..18
圖3-1、實驗流程圖……………………………………………………………………19
圖3-2、雲母片(Mica)之形貌………………………………………………………….20
圖3-3、雲母片材料處理流程………………………………………………………….21
圖3-4、天然雲母片材料經處理過後………………………………………………….22
圖3-5、鈣鈦礦量子點溶液(CsPbBr3 QD)……………………………………………24
圖3-6、照射UV光在鈣鈦礦量子點試片正面……………………………………….25
圖3-7、照射綠光在鈣鈦礦量子點試片正面………………………………………….25
圖3-8、照射藍光在鈣鈦礦量子點試正面…………………………………………….26
圖3-9、照射UV光在鈣鈦礦量子點試片反面……………………………………….26
圖3-10、照射綠光在鈣鈦礦量子點試片反面…………………………………………27
圖3-11、照射藍光在鈣鈦礦量子點試片反面………………………………………….27
圖3-12、LED的EL曲線(a)Green LED (b)UV LED……………………………….28
圖3-13、水熱法成長氧化鋅奈米線實驗簡易示意圖…………………………………32
圖3-14、(a)氧化鋅薄膜(b)氧化鋅奈米線(c)滴鈣鈦礦量子點溶液於氧化鋅奈米線..33
圖5-1、重複一次薄膜層之SEM (a)(b) Pure ZnO Top、Cross section…………….41
圖5-2、氧化鋅奈米線成長於ZnO薄膜層之SEM (a) Top view (b) Cross section….42
圖5-3、氧化鋅奈米線之EDS分析圖…………………………………………………42
圖5-4、鈣鈦礦量子點氧化鋅奈米線之SEM…………………………………………43
圖5-5、鈣鈦礦量子點氧化鋅奈米線之EDS分析圖…………………………………44
圖5-6、鈣鈦礦量子點氧化鋅奈米線之TEM圖……………………………………..45
圖5-7、鈣鈦礦量子點氧化鋅之HR-TEM與繞射圖…………………………………46
圖5-8、鈣鈦礦量子點氧化鋅EDS-Mapping分析圖………………………………..47
圖5-9、Zinc oxide powder diffraction file (JCPDS 36-1451)……………………….48
圖5-10、氧化鋅奈米線和鈣鈦礦量子點氧化鋅XRD分析…………………………49
圖5-11、鈣鈦礦量子點薄膜與鈣鈦礦量子點氧化鋅之PL分析……………………50
圖5-12、照光在CsPbBr3 QD/ZnO示意圖…………………………………………..51
圖5-13 雲母片基板於各波長之光(a)穿透率(b)吸收率……………………………...52
圖5-14、雲母基板(Mica)於各波長之各波長能帶寬度………………………………52
圖5-15、氧化鋅奈米線於各波長之光(a)穿透率(b)吸收率………………………….54
圖5-16、氧化鋅於各波長之各波長能帶寬度…………………………………………54
圖5-17、鈣鈦礦量子點氧化鋅於各波長之光(a)穿透率(b)吸收率………………….55
圖5-18、鈣鈦礦量子點氧化鋅於各波長之各波長能帶寬度…………………………55
圖5-19、氧化鋅奈米線之XPS分析-鋅………………………………………………56
圖5-20、氧化鋅奈米線之XPS分析-氧………………………………………………57
圖5-21、鈣鈦礦量子點氧化鋅奈米線之XPS分析-銫………………………………57
圖5-22、鈣鈦礦量子點氧化鋅奈米線之XPS分析-鉛………………………………58
圖5-23、鈣鈦礦量子點氧化鋅奈米線之XPS分析-溴……………………………….58
圖5-24、鈣鈦礦量子點氧化鋅奈米線之XPS分析………………………………….59
圖5-25、氧化鋅奈米線圖元件結構之量測示意圖……………………………………60
圖5-26、氧化鋅I-V圖…………………………………………………………………61
圖5-27、氧化鋅I-T圖………………………………………………………………….61
圖5-28、鈣鈦礦量子點氧化鋅奈米線圖元件結構之量測示意圖……………………62
圖5-29、鈣鈦礦量子點氧化鋅奈米線之暗電流及光電流圖………………………….63
圖5-30、鈣鈦礦量子點氧化鋅奈米線之光響應圖……………………………………63
圖5-31、氧化鋅在不同環境濕度之響應量測圖………………………………………66
圖5-32、氧化鋅不同環境濕度之I-V曲線圖…………………………………………66
圖5-33、鈣鈦礦量子點之氧化鋅在不同環境濕度之響應量測圖…………………….67
圖5-34、鈣鈦礦量子點之氧化鋅在不同環境濕度之I-V曲線圖……………………67
圖5-35、ZnO照射UV光在不同環境濕度之響應量測………………………………68
圖5-36、鈣鈦礦量子點之氧化鋅照射UV光在不同環境濕度之響應量測…………69
圖5-37、鈣鈦礦量子點之氧化鋅照射綠光在不同環境濕度之響應量測…………….71
圖5-38、滴DI Water水在鈣鈦礦量子點之氧化鋅照射綠光響應………………….73
圖5-39、滴DI Water水在鈣鈦礦量子點之氧化鋅照射UV光響應………………..73

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