高摻雜之二氧化錫薄膜能隙窄化現象及氧化銦薄膜之應力量測與探討

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林揚益(Yang-Yi Lin) 查詢紙本館藏

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化學工程與材料工程學系

論文名稱

高摻雜之二氧化錫薄膜能隙窄化現象及氧化銦薄膜之應力量測與探討
(Bandgap Narrowing in High Dopant Tin Oxide and Stress Measurement of Flexible ITO Thin Film)

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摘要(中)

此研究主題分成兩大方向來探討透明導電薄膜。首先以四氯化錫(SnCl4)和五氯化銻(SbCl5)作為前驅物，以大氣化學氣相沉積法(APCVD)，通入不同比例之前驅物，製備摻雜銻之二氧化錫(SnO2:Sb)透明導電薄膜於玻璃基板上。希冀在不影響光學穿透為前提，以高濃度摻雜方式降低薄膜電阻率。另外以捲對捲式(roll-to-roll)脈衝濺鍍法製備氧化銦(ITO)透明導電薄膜於PET基板上退火後量測電性，探討脈衝濺鍍法對ITO薄膜在長時間退火過程中的影響與變化。另外，將ITO薄膜製備於可撓式玻璃基板，在不同環境下退火探討其電性及光學性質並找出最低電阻率後，以同步輻射GIXRD結合cos2αsin2Ψ方法量測ITO薄膜受到張應力(tensile stress)和壓應力(compresive stress)下之應力變化。在高濃度摻雜實驗中發現，在光學能隙隨著摻雜濃度提升，出現能隙窄化之現象。此能隙窄化現象是受到摻雜原子之影響，使能隙計算上需考慮帶尾能態(Band tailing)現象。另外還需考慮自身能態(Self energy)，摻雜後電子與電子及電子與摻雜原子之間作用力的影響。在捲對捲脈衝式濺鍍法製備ITO薄膜於PET基板上，調整不同duty ratio比例並進行不同時間退火及量測電性。從實驗結果中發現，在退火後1個小時後，因受到薄膜結晶的影響，載子移動率(mobility)增加幅度遠大於載子濃度(carrier concentration)衰退幅度，使ITO薄膜有最大的電性變化。將ITO薄膜鍍製於可撓式玻璃上，在真空環境下，退火溫度在300 ℃及退火時間一個小時下，其薄膜會有最高的平均穿透率及最低電阻率。量測應力實驗發現ITO薄膜退火後，仍存有很大的張應力。施加外加應力也很難抵消或增加其殘留應力，因此ITO薄膜受到捲對捲式(roll-to-roll)製程的影響，其製程殘留應力為最主要應力來源。

摘要(英)

In order to reduce the resistivity of tin oxide thin film, antimony-doped tin oxide (SnO2:Sb, ATO) films have been deposited on glass substrates using atmospheric pressure chemical vapor deposition (APCVD) method. The precursors are mixed with SnCl4, SbCl5 and O2 to prepare the films. The precursors of chlorine ions involved in doping and reduced the resistivity. This study used synchrotron grazing incidence X-Ray diffraction (GIXRD) to investigate the film microstructure. Our results show that the precursors of chlorine ions were involved in the doping mechanism, causing the microstructure of films to change slightly. The film has an average transmittance between 85.8 % and 74.3 % within a visible spectral range from 400 nm to 800 nm. The minimal resistivity was 5.0 x10-4 Ωcm after doping. Figure of merit suggested that the film deposited at 500 ℃ with R equals to 0.5 has the best quality. The dopant caused a narrowing of bandgap that was due to interaction between electrons and impurities. The synchrotron GIXRD data show that the chlorine ions caused the lattice constant change. The tin doped indium oxide (ITO) thin films were prepared on polyethylene terephthalate (PET) substrate by roll-to-roll pulsed DC sputtering with various duty ratios. The films were ex-situ annealing at 150 ℃ for 0.5 to 15 hour in air. The purpose of this study is to know the pulsed DC effect on conductive and microstructure of the film. It was found that the pulsed DC could affect on conductivity, long time annealing. The ITO film deposited on flexible glass substrate by roll-to-roll DC sputtering. The synchrotron GIXRD was measured residual stress, compressive stress, and tensile stress of the film. In our results, the compressive stress is hard to relaxation after annealing an hour in vacuum at 300 ℃. The external stress is hard to affect the ITO thin film residual stress.

關鍵字(中)

★ 透明導電薄膜
★ 能隙窄化
★ 可撓式基板

關鍵字(英)

★ Transparent conductive oxide
★ Bandgap narrowing
★ Flexible substrate

論文目次

Chapter 1 Introduction 1
1.1 Transparent Conductive Oxide Film (TCO) 4
1.2 Classification of TCO Films 7
1.2.1 P-type and n-type TCO films 7
1.2.2 Classification of n-type TCO films 8
1.2.3 Major TCO films 9
1.3 Deposition Methods 10
1.3.1 Major deposition methods 10
1.3.2 Spray pyrolysis 11
1.3.3 Evaporation 11
1.3.4 Atmospheric pressure chemical vapor deopsition (APCVD) 12
1.3.5 Roll-to-roll and pulsed-DC sputtering 12
1.3.6 Pulsed laser deposition (PLD) 14
1.4 Present Status of TCO Development 15
1.5 Material Property and Physical Theory of TCO Films 17
1.5.1 Electrical property 17
1.5.2 Bandgap theory 18
1.5.3 Annealing property 20
1.5.4 Stress analysis 21
Chapter 2 Motivation 23
2.1 Highly Doped Tin Oxide Thin Film by APCVD 23
2.2 ITO Thin Film Prepared by Roll-to-roll Pulsed-DC Sputtering 24
2.3 ITO Thin Film on Flexible Glass 25
Chapter 3 Experimental 26
3.1 Highly Doped Tin Oxide Thin Film 26
3.2 ITO Thin Film Prepared by Roll-to-roll Pulsed-DC Sputtering 28
3.3 ITO Thin Film on Flexible Glass 31
Chapter 4 Results and Discussion 33
4.1 Highly Doped Tin Oxide Thin Film 33
4.1.1 Electrical property 33
4.1.2 Optical property 37
4.1.3 Material property 38
4.1.4 Theory discussion and material analysis 43
4.1.5 Bandgap narrowing 53
4.2 ITO Thin Film Prepared by Roll-to-roll Pulsed-DC Sputtering 61
4.2.1 Electrical property 61
4.2.2 Mechanism discussion 66
4.3 ITO Thin Film Deposited on Flexible Glass 70
4.3.1 The simulation 70
4.3.2 Electrical property 75
4.3.3 Optical property 83
4.3.4 Material property 85
4.3.5 Stress property 87
Chapter 5 Summary 93
References 94

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指導教授

吳子嘉(Albert T. Wu)

審核日期

2013-8-22

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