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研究生：	黃俊閔 Huang, Chun-Min
論文名稱：	利用掃描式熱探針微影技術低溫合成及成像銀奈米粒子之研究 Low-Temperature Scanning Thermal Lithography for Silver Nanoparticle Synthesis and Patterning
指導教授：	郭昌恕 Kuo, Chang-Shu
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2010
畢業學年度：	98
語文別：	英文
論文頁數：	116
中文關鍵詞：	奈米熱分析、定點熱分析、熱探針微影技術、奈米銀粒子、過氧化苯甲醯、高分子薄膜
外文關鍵詞：	Nano-TA, in-situ thermal analysis, SThM, silver nanoparticles, BPO, thermal properties of thin film
相關次數：	點閱：110 下載：0
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本研究以掃描式熱探針微影技術合成及成像銀奈米粒子於高分子薄膜中。掃描式熱探針微影技術將微米熱探針導入掃描探針微影術，此熱探針不僅提供定點加熱，並且同時為熱流感應器，可進行微米級熱分析。利用旋轉塗佈法，聚甲基丙烯酸甲酯與硝酸銀溶液在載玻片或聚亞醯胺基材形成奈米薄膜，當掃描式熱探針微影製程中的基板材料。在掃描式熱探針微影製程中，利用熱探針對銀的先趨物進行熱還原反應，在奈米薄膜中成功地還原出銀奈米粒子。並藉由定點熱分析，分析銀奈米粒子合成所需的反應溫度與熱流量。此外，過氧化苯甲醯為一種過氧化高能材料，高能材料在相對較低的溫度裂解，進一步產生焦耳熱能，此利用此焦耳熱能加速所需的化學或物理反應，高能材料可當另一個熱能來源。
由實驗結果中證實，加入過氧化苯甲醯後，利用掃描式熱探針微影技術合成銀奈米粒子之反應溫度可降至150oC。進一步的熱分析指出，反應溫度的減少是由於高能材料的影響。由暗視野光學顯微鏡與穿透式電子顯微鏡的圖像中，可以確認銀奈米粒子在聚甲基丙烯酸甲酯薄膜中分佈的情形。以微米熱探針進行掃描式熱探針微影製程，其生成圖像線寬的空間解析度約為2微米。

In this research work, scanning thermal lithography (SThL) was demonstrated for the synthesis and patterning of silver nanoparticles in a polymer-based thin film. This SThL technique involved the use of the scanning probe microscope equipped with a micro-scaled thermal probe that provided a localized heating mechanism and simultaneously acted as a temperature sensor. A solution containing poly (methyl methacrylate) and silver nitrate was spin-coated on slide or polyimide substrates. Thermally-induced reduction reaction of silver precursors was successfully achieved by the thermal probe with the formation of embedded silver nanoparticles. In-situ thermal analysis was also investigated for the details of nanoparticle synthesis in terms of the reaction temperature and the required heat flow. In addition, a peroxide-based energetic reagent, Benzoyl Peroxide (BPO), was introduced as the extra energy source. Thermal decomposition of BPO took place at the relatively low temperature, which allowed the localized joule heat to be generated to accelerate the desired chemical or physical reactions. As a result, the synthesis and patterning of silver nanoparticles via the SThL was demonstrated at the temperature as low as about 150oC. Further investigations also indicated the temperature reduction was contributed by the presence of energetic reagents. Dark-field optical microscopy and TEM images confirmed the patterned silver nanoparticles in PMMA films. SThL with micro-scaled thermal probes produced the spatial resolution as small as 2 micrometers.

誌謝	I
中文摘要	II
Abstract	III
Table of contents	V
List of Tables	VIII
List of Illustrations	IX
Chapter 1  Introduction	1
1	Scanning probe microscopy (SPM)	2
1.1	Scanning tunneling microscopy (STM)	2
1.2	Atomic force microscopy (AFM)	3
1.3	Scanning thermal microscopy (SThM)	6
2	Thermal analysis	8
2.1	Conventional thermal analysis: TGA, DTA, DSC, DMA, TMA	8
2.2	Advance thermal analysis: Micro-TA and Nano-TA	13
3	Introduction of thermal probe, in-situ thermal analysis and SThM	17
3.1	Micro-scale thermal probe: Wollaston wire probe	17
3.2	Nano-scale thermal probe: nano-TATM probes	17
3.3	Principle of in-situ TA and SThM	20
4	Scanning probe lithography	25
4.1	Dip-pen lithography (DPL)	25
4.2	Mechanical force lithography (MFL)	26
4.3	Anodization lithography (ANL)	27
4.4	Scanning thermal lithography (SThL)	27
5	Noble metal nanoparticles (NPs)	31
6	Motivation of research	32
Chapter 2  Literature Reviews and Theory	33
1	Theory of micro- and nano-TA	33
1.1	First generation system: micro-TATM	33
1.2	Second generation system: nano-TATM	36
2	Theory of scanning thermal microscopy (SThM)	40
3	Theory of energy absorption by a sample from micro- or nano-probe	42
4	Silver nano-particles	46
4.1	Surface plasmon resonance (SPR)	46
4.2	Synthesis of silver nano-particles	49
Chapter 3  Experiments	51
1	Materials and instruments	51
1.1	Materials	51
1.2	Instruments	53
2	Experiment process	54
2.1	Film preparation	54
2.2	Thermal analysis of BPO	57
2.3	Patterning on PMMA/AgNO3 and PMMA/AgNO3/coumarin 6 films by SThL	58
3	Analysis instrument	59
3.1	Thermal analysis: SThM	59
3.3	Patterns of Ag NPs: TEM、SThM、dark-field optical microscopy	60
3.4	Surface plasmon resonance (SPR): UV-visible、fluorescence spectrophotometer	62
Chapter 4  Result and Discussion	64
1	Preparing PMMA/BPO/AgNO3 films for conduct SThL	64
1.1	Investigation of AgNO3 solution for diffusing	64
1.2	UV-vis spectra of PMMA/AgNO3/BPO films	67
1.3	Removal of unreacted AgNO3 from PMMA films	68
2	Fluorescence-quenched of coumarin 6 by Ag NPs	70
3	Morphology and SThM of patterns fabricated by SThL	73
4	Dark-field optical microscopy images patterned by SThL	77
4.1	Patterning on PMMA-BPO-AgNO3 films	77
4.2	Patterning on PMMA-BPO-AgNO3-C6 films	82
5	Images of transmission electron microscopy	86
6	Discussions of thermal analysis on PMMA/BPO films	90
6.1	Thickness and morphology of different PMMA/BPO films	90
6.2	In-situ thermal analysis on PMMA/BPO films	94
6.3	In-situ isothermal analysis on PMMA/BPO films	98
Chapter 5  Conclusion	108
Reference	109

                                    

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校內：2015-08-23公開
校外：不公開電子論文尚未授權公開，紙本請查館藏目錄

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