成長自組裝單分子膜於透明基板表面以及沉積氧化鋅鋁薄膜於自組裝單分子膜修飾基板之研究

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研究生：	武氏進韶 TIEN - THIEU
論文名稱：	成長自組裝單分子膜於透明基板表面以及沉積氧化鋅鋁薄膜於自組裝單分子膜修飾基板之研究 Study the fabrication of self-assembled monolayers (SAMs) on transparent substrates and the deposition of aluminum doped zinc oxide (AZO) thin films on top of the SAMs modified substrates
指導教授：	戴龑 Yian Tai
口試委員:	蔡大翔 Dah-Shyang Tsai 江志強 Jyh-Chiang Jiang 王澤元 Tse-yuan Wang 陶雨臺 Tao, Yu-Tai
學位類別：	博士 Doctor
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2013
畢業學年度：	101
語文別：	英文
論文頁數：	133
中文關鍵詞：	Self assembled monolayers (SAMs) 、aluminum doped zinc oxide (AZO) 、RF sputtering 、polyethylene terephthalate (PET)
外文關鍵詞：	Self assembled monolayers (SAMs), aluminum doped zinc oxide (AZO), RF sputtering, polyethylene terephthalate (PET)
相關次數：	點閱：333 下載：3
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本研究利用一個簡單的方法成長有機矽烷自組裝單分子薄膜於透明基板上。特別是PET基板表面可經由化學修飾卻不會受到化學破壞，藉由照射紫外光臭氧燈使得PET基板表面產生大量親水基團，也可使自組裝單分子薄膜中的矽烷基分子排列較為緻密。我們在PET與玻璃基板長上有機矽烷的自組裝單分子薄膜以改變基板表面的官能基、濕潤度和表面張力。
室溫下以射頻濺鍍沉積AZO薄膜基板，其參數分別在靶材與基板距離為3~7cm，工作壓力控制在2~8mTorr，另外，我們也探討AZO薄膜在提供電子的官能基與接受電子的官能基之自組裝單分子薄膜的效應。在最佳參數20W，基板與靶材距離6cm，工作壓力5mTorr下，沉積AZO薄膜於自組裝單分子修飾過之PET基板，其電阻可從2.29 x 10-3 Ωcm降低至1.12 x 10-3 Ωcm，並且其穿透值在可見光區可達85%。

自組裝單分子薄膜在透明基板上的性質和azo薄膜的結構、電性與光學性質可藉由接觸角測量儀(CA)、X光光電子能譜儀(XPS)、半接觸式原子力顯微鏡(AFM)、X光繞射儀(XRD)、場發射掃描式電子顯微鏡(SEM)、霍爾量測與紫外光光譜儀來做分析。

A facile, robust and effective method was used to fabricate organosilane self assembled monolayers (SAMs) on transparent substrates. Speciﬁcally, polyethylene terephthalate (PET) substrate surfaces could be chemically modiﬁed while avoiding chemical degradation. The results shown that UV – Ozone pretreatment for PET (uv-PET) substrate surfaces used favours a more densed packing of silane molecules in the self assembled processes due to generating a large surface concentration of hydrophilic moieties by UV irradiation. Various substrate surfaces having different functional groups, wettability, and the surface tension were developed by coating organosilane SAMs on PET and glass substrates.
Aluminium doped zinc oxide (AZO) were deposited on transparent substrates via RF magnetron sputtering at room temperature. The sputtering parameters such as working distance and working pressure were varied from 3 to 7 cm and from 2.0 x 10-3 to 8.0 x 10-3 Torr, respectively. The effects of electron-donating/withdrawing properties of SAM functional groups on property of AZO films have been studied. The resistivity of AZO films deposited on uv-PET was decreased from 2.29 x 10-3 to 1.12 x 10-3 Ωcm by applying SAM modification at optimized conditions of 20W, 6 cm and 5.0 x 10-3 Torr. High optical transmittance of AZO films was also achieved at around 85% in visible wavelength region.
The properties of SAMs on transparent substrate and the structural, electrical and optical properties of AZO films were characterized by contact angle (CA), X-ray photoelectron spectroscopy (XPS), Atomic force microscopy (AFM), X-ray Diffraction (XRD), Field-Emission Scanning electron microscope (FE-SEM), Hall measurement and Ultraviolet–visible spectroscopy (UV-Vis).

Table of contents


Abstract	I
Chinese abstract	II
Acknowledgements	III
Table of Contents	IV
List of Figures	VIII
List of Tables	XIII
List of Abbreviation	XV
Chapter 1. Introduction	4
1 Preface	4
2 Self-assembled monolayers (SAMs)	5
2.1 The advantages of SAMs	6
2.2 Applications of SAMs	6
2.2.1 Protective coatings	7
2.2.2 Wetting and adhesion control	8
2.2.3 SAMs as templates for nucleation growth of crystals	9
2.2.4 SAMs as model systems for surface chemistry	10
2.2.5 Bio-related applications	10
2.2.6 Lateral structuring	11
2.2.7 Electronic properties	11
3 Transparent conductive oxides (TCOs)	12
3.1 Application of TCOs	13
3.1.1 TCO coatings	13
3.1.2 Flat panel displays	14
3.1.3 Solar cells	14
3.2 Trends in the development of TCO materials	15
4 Motivation and Research Objective	16
5 The outline of dissertation	23
Chapter 2 Theory	24
1 Self-assembled monolayers, mechanism and fabrication	24
1.1 SAMs-molecule structure	24
1.1.1 Head group	25
1.1.2 Backbone	25
1.1.3 Terminal Group	26
1.2 Mechanism and Kinectics of SAM	27
1.2.1 Organosufur (thiol) SAMs on gold substrate	27
1.2.2 Organosilane SAMs on Si, glass substrates	27
1.2.3 Carboxylic Acid SAMs on Metal, Metal oxide	28
1.3 SAM fabrication	28
2 AZO thin films, mechanism of thin film growth and fabrication methods	30
2.1 Zinc oxide (ZnO)	30
2.2 AZO structures	31
2.3 Mechanism of thin film growth	32
2.3.1 Nucleation and Island formation	32
2.3.2 Coalescence	35
2.3.3 Thickness Growth	36
2.4 Thin film deposition methods	38
2.4.1 Electron Beam evaporation	39
2.4.2 Sputtering	40
2.4.3 Pulsed Laser Deposition (PLD)	41
2.4.4 Chemical Vapor Deposition (CVD)	42
2.4.5 Chemical Spray Pyrolysis (CSP)	42
2.4.6 Sol-gel	43
Chapter 3 Experimental Section	45
1 Experiment	45
1.1 Materials	45
1.2 Experimental procedure	46
1.2.1 SAM fabrication	46
1.2.2 AZO Thin Film Fabrication	47
1.2.3 Operation procedure of RF-sputtering	48
2 Characterization Tools	50
2.1 Contact Angle Meter	50
Figure 3.6 Contact angle meter.	51
2.2 X-ray Photoelectron Spectroscopy (XPS)	51
2.3 Ultraviolet-visible spectroscopy (UV - Vis)	52
2.4 Atomic Force Microscopy (AFM)	53
2.5 Field Emission Scanning Electron Microscopy (FE-SEM)	54
2.6 X-ray Diffraction (XRD)	55
2.7 Four point probe	56
2.8 Hall effect measurement system	57
2.9 Transmission Electron Microscopy (TEM)	58
2.10 Photoelectron Spectroscopy in Air (AC2)	59
Chapter 4 Results and Discussion	61
1  SAMs on transparent substrates	61
1.1  SAMs on glass substrates	61
1.1.1  Individual SAMs with different functional groups	61
1.1.2 Mix (NH2 and CF3) SAM	69
1.2  SAMs on PET and up-PET substrates	71
1.2.1 PET and uv-PET substrates	71
1.2.2 Individual SAMs with different functional groups	72
1.2.3 Mix (NH2 and CF3) SAM	88
2 AZO films on transparent substrates	91
2.1 AZO thin films at different working distances	91
2.2 AZO films deposited at different working pressures	95
2.2.1 AZO films deposited on PET at different working pressures	95
2.2.2 AZO thin films deposited on glass at different working distance	104
2.3 AZO thin films deposited on SAMs modified substrates	109
2.3.1 AZO films deposited on Silane SAMs modified uv-PET substrates	109
2.3.2 AZO films deposited on SAMs modified PET substrates	121
2.3.3 AZO films deposited on Silane SAMs modified glass substrates	128

                                

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