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研究生： 陳隆
Chen, Lung
論文名稱： In-Situ熱分析和掃描式熱探針微影技術對光電高分子薄膜之研究
In-Situ Thermal Analysis and Scanning Thermal Microscopy of Optoelectronic Polymer Thin Films
指導教授： 郭昌恕
Cuo, 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： 2009
畢業學年度： 97
語文別： 英文
論文頁數： 109
中文關鍵詞： 奈米熱分析，定點熱分析，熱探針顯微技術，光電有機材料，P3HT/PCBM，高分子薄膜
外文關鍵詞： P3HT/PCBM, optoelectronic organic materials, scanning thermal microscopy, In-situ thermal analysis, Nano-thermal analysis, polymer thin films
相關次數： 點閱：127  下載：1 
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    • 本研究以奈米級熱分析探討光電高分子薄膜的熱性質。此研究，藉由結合掃描探針顯微技術和熱探針的技術，對薄膜材料表面進行in-situ熱分析和掃描式熱顯微分析。
    在有機光電太陽能電池的研究中，以P3HT［Poly(3- hexylthiophene)］和PCBM［[6,6]-phenyl-C61-butyric acid methyl ester］構成的異質接面結構主動層是現今較常被研究及看好的組合。此主動層以旋轉塗佈的方式將P3HT/PCBM的溶液塗佈於ITO玻璃基板上，薄膜的厚度範圍為30至900 nm。研究中顯示薄膜厚度會影響薄膜的熱膨脹係數和熔點。此外，在掃描式熱探針顯微實驗中，藉由改變不同的掃描溫度以及試片表面熱傳導性的顯影，可顯示出熱傳導的波動變化並得知試片表面在何時產生相轉變（或相分離）。
    在純P3HT和P3HT/PCBM的試片中，熱傳導性的差分別在80oC 和120oC有最明顯的變化訊號。在80oC的訊號是表示純P3HT的玻璃轉換溫度，而120oC的訊號指出P3HT/PCBM薄膜正經歷相轉變和形態重排，文獻指出，此溫度為最適合P3HT/PCBM機太陽能電池的退火溫度。

    Nano-scaled thermal analysis of optoelectronic polymer thin films was investigated in this research work. A scanning probe microscopy (SPM) integrated with a scanning thermal probe was employed to perform the in-situ thermal analysis and the scanning thermal microscope (SThM) on the surface of thin film materials.
    Poly(3-hexyl thiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), commonly used in bulk heterojunction photovoltaics, were spin-coated on silicon wafers or ITO-coated glass substrates with film thickness ranged from 30 to 900 nm. Thermal expansion profiles indicated the thermal expansion coefficients and the melting temperatures of P3HT/PCBM samples were both affected by film thicknesses. A series of SThM with various scanning temperatures was conducted for the 2D mapping of surface thermal conductivities.　Fluctuations of these thermal conductivities revealed the thermal transitions and/or the phase separations near the material surfaces. Thermal conductivity differentials were maximized at the mapping temperatures of about 80oC and 120oC for pure P3HT and P3HT/PCBM samples, respectively. The first one represented the 80oC glass transition temperature of P3HT, which was usually undetectable in the conventional differential scanning calorimetry. And, the 120oC temperature recognized the optimized thermal annealing of P3HT/PCBM blends, where the phase separation and morphological rearrangement of P3HT and PCBM domains altered the distribution of surface thermal conductivities.

    Table of contents Acknowledgement-----------------------------------------------------------------I 中文摘要---------------------------------------------------------------------------II Abstract---------------------------------------------------------------------------III Table of Contents-----------------------------------------------------------------V List of Abbreviation-----------------------------------------------------------VIII List of Tables---------------------------------------------------------------------IX List of Illustration-----------------------------------------------------------------X Chapter 1. Introduction-----------------------------------------------------------1 1-1 Methods of thermal analysis-------------------------------------------2 1-1-1 Conventional techniques----------------------------------------2 1-1-2 Advanced techniques--Micro- and Nano-TA ----------------7 1-2 Comparison of novel thermal characterization techniques-------11 1-3 Principals of In-situ thermal analysis and thermal mapping-----17 1-3-1 Micro-scale thermal probe : Wollaston wire probe--------17 1-3-2 Nano-scale thermal probe : nano-TA probe-----------------19 1-3-3 Functions of nano-TATM --------------------------------------21 1-4 Scanning probe lithography ------------------------------------------27 1-4-1 Anodization nanolithography---------------------------------27 1-4-2 Dip-pen nanolithography--------------------------------------27 1-4-3 Scanning thermal lithography --------------------------------28 1-5 Introduction of P3HT/PCBM solar cell system--------------------31 1-6 The motivation of research -------------------------------------------33 Chapter 2. Literature Review --------------------------------------------------35 2-1 Theory of micro- and nano-TA --------------------------------------35 2-1-1 First generation system---micro-TATM ----------------------35 2-1-2 Second generation system---nano-TATM--------------------37 2-2 Theory of thermal mapping-------------------------------------------42 2-3 Calibration of temperature--------------------------------------------44 2-4 Theory of thermal properties of SThM system --------------------46 2-5 Principles of P3HT/PCBM as photovoltaic solar cells-----------48 2-5-1 The mechanism of organic solar cells-----------------------48 2-5-2 Types of active layer of organic donor-acceptor cells-----51 2-5-3 Thermal properties of P3HT/PCBM-------------------------54 Chapter 3. Experiments---------------------------------------------------------55 3-1 Materials and instruments --------------------------------------------55 3-1-1 Materials---------------------------------------------------------55 3-1-2 Instruments------------------------------------------------------57 3-2 Experimental process--------------------------------------------------58 Chapter 4. Result and Discussion----------------------------------------------64 4-1 The relation between heating rate and melting point--------------64 4-2 The relationship between tip force and in-situ TA ----------------66 4-3 The discussion of thermal analyzed result--------------------------71 4-3-1 In-situ TA for pure P3HT thin films -------------------------73 4-3-2 In-situ TA for P3HT-PCBM thin films ----------------------78 4-3-3 Thermal mapping for P3HT/PCBM thin films-------------89 Chapter 5. Conclusion---------------------------------------------------------102 Reference------------------------------------------------------------------------104

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