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完整後設資料紀錄
DC 欄位 | 值 | 語言 |
---|---|---|
dc.contributor.advisor | 陳文章(Wen-Chang Chen) | |
dc.contributor.author | Cheng-Yu Chung | en |
dc.contributor.author | 鍾承佑 | zh_TW |
dc.date.accessioned | 2021-06-15T13:50:12Z | - |
dc.date.available | 2018-12-01 | |
dc.date.copyright | 2015-12-01 | |
dc.date.issued | 2015 | |
dc.date.submitted | 2015-10-20 | |
dc.identifier.citation | [1] Indium Tin Oxide and Alternative Transparent Conductor Markets, NanoMarkets, LC, 2009.
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dc.identifier.uri | http://tdr.lib.ntu.edu.tw/jspui/handle/123456789/51795 | - |
dc.description.abstract | 聚醯亞胺為傳統高性能高分子,已經泛用於各個領領域與產業中。近年來來由於可撓式及穿戴式裝置蓬勃發展,軟性透明基材的需求也日益益漸增,聚醯亞胺以其優異異的性質表現使其為研究開發的重點。然而一般金屬導體於軟性基材的附著力力 極差,使其於軟性電路路板的應用上受限。本論文以兩步升溫閉環製備聚醯亞胺結 合噴塗金金屬導體的方式,使金屬導體均勻塗佈並配位鍵結於聚醯亞胺以及感光型聚醯亞胺,成功製備出具有高導電度度以及良好附著力力的聚醯亞胺金屬導電膜以及 圖案化金屬電極,茲敘述如下:
論文第一部分由分子設計的概念以脂環族雙胺(CHDA)與剛硬芳香族雙酸酐 (BPDA) 以開環聚合成聚醯亞胺前驅物,半脂環族聚醯氨酸, poly[t-1,4-cyclohexyldiamine amic acid]) (CHBPDAPAA), 並將之塗布於基材上。 聚醯胺酸 CHBPDAPAA,可藉由升溫製備局部閉環聚醯亞胺,保留胺基以及羧酸基來來提供足量的孤對電子與奈奈米金金屬做配位鍵結。本實驗以噴塗製程將奈奈米銀顆粒以及奈米銀線均勻塗佈於局部閉環聚醯亞胺,利用局部閉環聚醯亞胺上孤對電子與所使用之奈米銀進行配位鍵結,製備出具有高導電度及良好吸附力之導電薄膜。本實驗可進一步以少量奈米銀線以及奈米銀顆粒以無電鍍方式激發銅還原沈積於奈米銀顆粒以及奈米銀線聚醯亞胺薄膜。最後成功製備出在波長 550nm 下透光度度 64%,且具有片電阻 0.63 Ω/□的高導電度度透光膜。本實驗結果成功以聚醯亞胺兩步閉環法製備出高導電度度以及具有良好吸附力力的聚醯亞胺導電薄膜。 論文第二部分以不同黏度度之聚醯胺酸ﰀHﰁPﰂﰃPﰃﰃ混入光鹼劑,藉由光罩以顯影蝕刻製程製備出圖案化聚醯胺酸。結合曝後烤製程的侷部閉環圖案化聚醯亞胺其表面保有親水表面以及足夠孤對電子使奈米銀線可與表面配位鍵結。 本實驗以噴塗製程將奈米銀線均勻噴塗後再以膠帶將圖案化外奈米銀線剝除,成功製備出厚度度800nm解析度度40 μm之圖案化奈米銀線電極。此外,本實驗將並五苯熱鍍上此圖案化奈米銀線電極製備以並五苯為主動層的場效應電晶體.製備出具有電子遷移率 0.12 cm2/Vs 以及開關比 1.2x 107 的場效應電晶體。本結果成功以奈米銀線溶液噴塗製程結合圖案化聚醯亞胺製備出解析度微米等級的圖案化奈米銀線電極。 | zh_TW |
dc.description.abstract | Polyimides (PIs) have been widely used for high-performance functional materials in electronics. In display and wearable electronics, PIs gradually attracted considerable attention due to their flexibility and transparency. However, the weak adhesion of the metal conductors to the substrate remains challenges. In this study, we deposited metal conductors and their patterned electrodes on PIs and photosensitive polyimides (PSPIs) by spray-coating and two-step condensation of PIs, as described in the following:
In the Chapter 2, a semialicyclic poly( amic acid) (PAA), poly(trans-1,4- cyclohexylenediphenylene amic acid) (CHBPDAPAA), were synthesized from the monomers of tetracarboxylic dianhydride (BPDA) and trans-1,4-cyclohexyldiamine (CHDA) and deposited on glass by spin-coating. In the following, it was then partially imidized to retain the hydrophilic surface and the moieties with enough lone pair electrons for binding with silver nanoparticle (Ag NPs) or silver nanowire (Ag NWs). The highly-dispersed Ag NPs or Ag NWs were deposited on the partially imidized PI surface by solution spray coating and their adhesion on the PI film could be maintained after complete thermal imidization. Furthermore, by the post-treatment of electroless copper plating the highly conductive thin film could be also successfully fabricated on PI film, exhibiting an 64% optical transmittance at 휆 = 550nm with an average sheet resistance of 0.63 Ω/□ for the application of transparent electrodes. Our results provide a new approach for fabricating high conductive film on polyimide substrate by simply combining two-step condensation of PI. In the Chapter 3 of the thesis, we synthesized CHBPDAPAA with different viscosity and patterned with shadow masks and followed by partially imidized to retain the hydrophilic surface and the moieties with enough lone pair electrons for binding with Ag NWs. The highly dispersed Ag NWs solution was deposited on the patterned surface by spray coating. The well-patterned Ag NWs electrodes in 40μm channel length was obtained by cleaning the Ag NWs residue with scotch tapes. The pentacene-based field-effect transistor (FET) was fabricated with well patterned Ag NWs electrodes, which exhibited the charge carrier mobility of 0.12 cm2/Vs with a high ON/OFF ratio up to 1.2x 107. Our results demonstrate that this patterning methodology can provide a new approach for fabricating Ag NW patterns in a high resolution using a solution process. | en |
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dc.description.tableofcontents | 中文摘要 .................................................................................................. I Abstract ................................................................................................ III Contents................................................................................................IV
List of Tables..........................................................................................IX List of Schemes .....................................................................................X List of Figures .......................................................................................XI 1 Chapter1 General Introduction ...........................................................1 1.1 The Next Generation of Transparent Conductors ..............................1 1.1.1 Commonly Used Transparent Conductor........................................1 1.1.2 Conducting Polymers ................................................................... 3 1.1.3 Carbon Material Conductors ......................................................... 4 1.1.4 Metal Conductors ......................................................................... 5 1.2 Introduction of Field-Effect Transistors............................................. 8 1.2.1 Device Structures and Working Principles .................................... 8 1.2.2 Characterizations of Field-Effect Transistors ...............................10 1.3 Metal Conductive Electrode fabrications with Direct Write Coating ............................................................................................................. 12 1.3.1 Inkjet Printing............................................................................... 13 1.3.2 Aerosol-Jet Printing .................................................................... 15 1.3.3 Spray-coating ............................................................................. 16 1.4 Improving Adhesion of Metal Conductors to the Substrate............. 18 1.4.1 Surface Treatment with Polydopamine ........................................ 18 1.4.2 Network by Conducting-Polymer-Assisted Joining.......................20 1.5 High Performance Polymers with Strong Lone Pair Functional Group................................................................................................... 21 1.5.1 Polyimides................................................................................... 22 1.5.2 Photosensitive Polyimides .......................................................... 24 1.5.3.1 Positive-working PSPIs............................................................. 28 1.5.4.2 Negative-working PSPIs .......................................................... 29 1.6 Research Objectives ...................................................................... 30 2 Chapter2 Preparing of Highly Conductive and Well Adhesive Metallic Polyimide Films through Two-step Polycondensation Method.............. 39 2.1 Introduction ................................................................................... 39 2.2 Experimental Section ..................................................................... 41 2.2.1 Materials...................................................................................... 41 2.2.2 Preparing Metal Conductors on Polyimide Film .......................... 42 2.2.2.1 Synthesis of Poly[t-1,4-cyclohexyldiamine-biphenyl amic acid] ............................................................................................................. 42 2.2.2.2 Fabricating Silver Nanoparticle and Silver Nanowire on Polyimide ............................................................................................................. 43 2.2.3.3 Electroless Plated Copper Thin Film on Polyimide Film ............ 44 2.3 Characterization ............................................................................ 44 2.4 Results and Discussion................................................................... 45 2.4.1 Polyimide Surface Properties ...................................................... 45 2.4.1.1 Chemical Structure Characterization & Solubility Test............... 45 2.4.1.2 Water Contact Angle................................................................. 46 2.4.2 Spray Coating Condition toward Conductive Film Thickness and Conductivity ........................................................................................ 48 2.4.2.1 Electrical properties.................................................................. 48 2.4.2.2 Optical properties .................................................................... 49 2.4.3 Electroless Plated Copper on AgNPs and AgNWs Deposited PI Film ............................................................................................................. 50 2.4.3.1 Deposition Time in Electroless Bath.......................................... 51 2.4.3.2 X-ray Diffraction Pattern for Plated Copper Thin Films ............. 52 2.4.3.3 EDX Spectrum Analysis for Plated Copper Thin Films .............. 53 2.4.3.4 SEM Image for Plated Copper Thin Films ................................. 53 2.4.3.5 Optical Properties for Plated Copper Thin Films....................... 54 2.4.3.6 Long-term Stability for Plated Copper Thin Films ..................... 54 2.5. Conclusion.................................................................................... 55 3 Chapter3 Patterned Silver Nanowires Electrode using Photosensitive Polyimides and Their Organic Transistor Device Applications............... 66 3.1 Introduction ................................................................................... 66 3.2 Experimental Section ..................................................................... 69 3.2.1 Materials...................................................................................... 69 3.2.2 Synthesis of Photosensitive Polyimide ........................................ 70 3.2.2.1 Synthesis of CHBPDAPAA with Different Viscosity .................. 70 3.2.2.2 Photosensitivity of Poly( amic acid) CHBPDAPAA .................... 71 3.2.2.3 Water Contact Angle................................................................. 72 3.2.2.4 Degree of Imidization ............................................................... 73 3.2.3 Fabrication of Patterned Silver Nanowire Electrodes .................. 74 3.2.4 Fabricating Pentacene FET using Patterned AgNWs Electrode ... 75 3.3 Characterization ............................................................................ 77 3.4 Results and Discussion................................................................... 78 3.4.1 Chemical Structure Characterization and Its Surface Properties . 78 3.4.2 AgNWs Distribution and Adhesion on PSPI Substrate ................. 80 3.4.3 Transmittance over Sheet Resistance of the spray-coated AgNW electrodes on PSPI/ Glass.................................................................... 82 3.4.4 Fabrication of Patterned AgNWs electrodes on SiO2 .................. 83 3.4.4.1 Optimized PSPI viscosity for Patterned AgNWs Electrode fabrication............................................................................................ 83 3.4.4.2 Versatile Patterned AgNWs Electrode Fabrications .................. 85 3.4.5 Electrical Characteristics of Pentacene FET ................................ 88 3.5. Conclusion.................................................................................... 89 4 Chapter4 Conclusion ...................................................................... 103 5 Reference........................................................................................ 105 List of Table Table 1.1 Comparison of transparent conducting materials in terms of their compatibility with solution coatable processes and performance relative to ITO .......................................................................................33 List of Scheme Scheme 2.1 Synthesis of CHBPDAPI.....................................................57 Scheme 2.2 Fabrication of metal conductive PI film..............................57 Scheme 2.3 Electroless plating of Cu metal conductive PI film .............58 Scheme 3.1 Synthesis of high viscosity and low viscosity CHBPDAPAA.........................................................................................90 Scheme 3.2 Lithographic process of PSPIs ..........................................90 Scheme 3.3 Scheme of patterned silver nanowire electrodes fabrication ..............................................................................................................91 Scheme 3.4 Schematic of fabricating pentacene FET using the patterned AgNWs electrode...................................................................................91 List of Figure Figure 1.1 Schematic structure of (a) the top-contact and (b) the bottom-contact FET...........................................................................................33 Figure 1.2 (a) Transfer characteristics of FETs for the equivalent devices with various Vd. (b) The output characteristics of FETs with various Vg ..............................................................................................................34 Figure 1.3 (a) Schematic diagram showing the inkjet printing process. The right/top image shows an SEM image of an inkjet-printed PEDOT:PSS electrode. (b) PQT-12 transistors prepared with Au nanoparticle source/ drain electrodes. (c) Ag electrode pattern fabricated using a sub-femtoliter inkjet printing system ........................................34 Figure 1.4 (a) Schematic drawing showing the spray-coating process. (b) PEDOT:PSS S/D electrodes fabricated by spray-coating. (c) AFM image and height profile of a P3HT film fabricated by spray-coating(left). Comparison of the field-effect mobilities in P3HT transistors prepared via two different P3HT deposition processes (right)....................................35 Figure 1.5 (a) Schematic representation of the spray-deposited AgNWs on dopamine-modified PDMS films with the lone pair interaction between AgNWs and the PDMS surface, and the binding interaction of the polydopamine and the nanowire............................................................36 Figure 1.6 (a) Schematics of the pentagonal AgNW juntion with nanosoldering by PEDOT:PSS coating (left) and SEM image of AgNWs joined by PEDOT:PSS through nanosoldering(right). (b) Adhesion force test of AgNW electrodes of pristine AgNW network before nanosoldering (left) and after nanosoldering (right). Middle is transient adhesion force test via 90° peel of test with linear stage ..............................................36 Figure 1.7 Requests for PSPIs ..............................................................37 Figure 1.8 Photolithographic processes.................................................38 Figure 2.1 IR spectra of completely imidized PI and partially imidized PI...........................................................................................................58 Figure 2.2 Chemical structure of (a) completely imidized PI, and (b) partially imidized PI...............................................................................59 Figure 2.3 Water contact angle of (a) completely imidized PI and (b) partially imidized PI...............................................................................59 Figure 2.4 OM images with sheet resistance and Ag NWs amount variations of the Ag NWs solution spray-coated on (a) partially imidized PI, (b) completely imidized PI film and the first time taping test of (c) partially imidized PI, (d) completely imidized PI by 3M scotch tape. N/A means not applicable............................................................................60 Figure 2.5 OM images with sheet resistance and amount variations of the 10mg/ ml AgNPs solution spray-coated on partially imidized PI film (a) 10(s), (b) 30(s), (c) and 60(s). OM images with sheet resistance and amount variations of the 1mg/ ml AgNWs solution spray-coated on partially imidized PI film (a) 10(s), (b) 30(s), (c) 60(s)...............................61 Figure 2.6 Optical images with transparency@400nm of (a) AgNPs-10s, (b) AgNPs-30s, (c) AgNPs-60s, (d) AgNWs-10s, (e) AgNWs-30s, and (f) AgNWs-60s...........................................................................................61 Figure 2.7 Thickness and resistivity of plated copper on AgNWs-10s films versus the immersion time in copper plation bath ........................62 Figure 2.8 OM images with sheet resistance and amount variations of electroless plated copper AgNPs spray-coated on partially imidized PI film (a) 10(s), (b) 30(s), and (c) 60(s). OM images with sheet resistance and amount variations of electroless Plated Copper AgNWs spray-coated on partially imidized PI film (a) 10(s), (b) 30(s), and (c) 60(s)........62 Figure 2.9 XRD pattern for plated copper thin films on (a) AgNPs deposited and (b) AgNWs deposited PI film ..........................................63 Figure 2.10 EDS spectrum of (a) AgNPs, (b) AgNWs, (c) CuAgNPs and (d) CuAgNWs deposited PI film...................................................................64 Figure 2.11 SEM image of (a) AgNPs, (b) AgNWs, (c) CuAgNPs and (d) CuAgNWs deposited PI film...................................................................64 Figure 2.12 Optical images with transparency@400nm of (a) CuAgNPs-10s, (b) CuAgNPs-30s, (c) CuAgNPs-60s, (d) CuAgNWs-10s, (e) CuAgNWs-30s, and (f) CuAgNWs-60s ..................................................65 Figure 2.13 The resistance increase ratio (R/ R0) of plated copper tracks under long-term storage test ................................................................65 Figure 3.1 (a) FTIR spectra of PSPI film containing DNCDP at each step: spin-cast on a silicon wafer and pre-baked at 100 oC for 20 min; after exposure to broad-band and PEB at 190 oC for 5 min; cure at 250 oC for 10 min; reference fully-cured PI film at the elevated temperature up to 350 oC for 1 hr under nitrogen. Chemical structure of (b) completely imidized PSPI and (c) partially imidized PSPI ........................................92 Figure 3.2 OM images with sheet resistance and Ag NWs amount variations of the AgNWs solution spray-coated on (a) partially imidized PSPI, (b) completely imidized PSPI film and the first time taping test of (c) partially imidized PSPI, (d) completely imidized PSPI by 3M scotch tape. N/A means not applicable.............................................................93 Figure 3.3 OM images with sheet resistance and Ag NWs amount variations of the Ag NWs solution spray-coat on partially imidized PSPI after (a) five times and (b) ten times taping test by 3M scotch tape, and (c) is the SEM image of the distributed AgNWs......................................94 Figure 3.4 (a) Optical transmittance at λ = 550nm of the completely imidized PSPI film, and (b) is the integrated transmittance at λ = 550nm over sheet resistance of the AgNWs-completely imidized PSPI.............95 Figure 3.5 OM images and surface profiles of the developed CHBPDAPAA negative patterns with different viscosities on the SiO2 substrate: (a) A 1.2-μm-thick CHBPDAPAA with higher inherent viscosity 0.42 dL/g (b) A 1.2-μm-thick CHBPDAPAA with lower inherent viscosity 0.30 dL/g. The prebake, the broad-band exposure, and PEB were fixed to 100 oC for 10 min, 500 mJ/cm2, and at 190 oC for 4.5 min, respectively...........................................................................................95 Figure 3.6 OM images comparation of AgNWs spay-coated on the developed 40-µμmchannelCHBPDAPAA/PBG (80/20 wt/wt) negative patterns with different viscosities on the SiO2 substrate: (a) A 0.8-μm-thick CHBPDAPAA with inherent viscosity 0.42 dL/g (b) A 0.8-μm-thick CHBPDAPAA/PBG (80/20 wt/wt) with inherent viscosity 0.30 dL/g........96 Figure 3.7 Optical images of (a) Inherent viscosity 0.30 dL/g CHBPDAPAA/PBG (80/20 wt/wt) negative patterns on the 2.5x2.5cm SiO2 substrate (b) AgNWs spray-coated on the film and then peeled off by 3M scotch tape, each block was filled clear patterns with 40µμm channel..................................................................................................97 Figure 3.8 Initial state and 3M scotch tape peeling off treatment comparation OM images of five AgNWs/partial PI/ SiO2 electrodes with four 40 µμm channel (a) 1st (b) 2nd (c) 3rd (d) 4th channel ....................97 Figure 3.9 Electrodes conducting test of five AgNWs/partial PI/ SiO2 electrodes with four 40µμm channel......................................................98 Figure 3.10 Optical images of (a) Electrode Mask design of 50µμm channel length with both side 1000 μm connect to 1000x1000 μm2 block (b) CHBPDAPAA/PBG (80/20 wt/wt) negative patterns with channel OM images of (a) mask on the 2.5x2.5cm2 SiO2 substrate (c) Electrode Mask design of 50µμm channel length with both side 7000 µm connect to 1000x1000 µμm block (d) CHBPDAPAA/PBG (80/20 wt/wt) negative patterns with channel OM images of (c) mask on the 2.5x2.5cm2 SiO2 substrate...............................................................................................99 Figure 3.11 Height line profiles of the CHBPDAPAA/PBG (80/20 wt/wt) pattern (a) middle 40μm channel (b) side 1000x1000 μm2 block in the figure3.20 (d).......................................................................................100 Figure 3.12 Optical images of preparation 40µμm channel length AgNWs electrode with different mask design by 3M scotch tape (a) both side 1000 µμm connect to 1000x1000 µμm block on the 2.5x2.5cm SiO2 substrate (b) both side 7000 µμm connect to 1000x1000μm block......100 Figure 3.13 OM image of AgNWs spray-coated on 40µμm channel length CHBPDAPAA/PBG (80/20 wt/wt) negative patterns (a) before 3M scotch tape peel off (b) after 3M scotch tape peel off, and the OM image is focusing on the pattern.101 Figure 3.14 OM image of AgNWs spray-coated on 40µμm channel length CHBPDAPAA/PBG (80/20 wt/wt) negative patterns (a) before 3M scotch tape peel off (b) after 3M scotch tape peel off, and the OM image is focusing on the SiO2 substrate.....101 Figure 3.15 Electrodes conducting test of 40µμm channel length with both side 7000µμm connect to 1000x1000µμm2 block .......................102 Figure 3.16 (a) Transfer curves (b) output curves, measured for the pentacene FETs using the patterned silver nanowire electrode ...........102 | |
dc.language.iso | en | |
dc.title | 以聚醯亞胺高分子基板製備高導電度金屬薄膜及圖案化電極於電子元件應用 | zh_TW |
dc.title | Highly Conductive Metallic Film and Patterned Electrode on Polyimide Substrate for Electrical Device Applications | en |
dc.type | Thesis | |
dc.date.schoolyear | 104-1 | |
dc.description.degree | 碩士 | |
dc.contributor.oralexamcommittee | 劉振良(Cheng-Liang Liu),李文亞(Wen-Ya Lee),郭霽慶(Chi-Ching Kuo) | |
dc.subject.keyword | 感光型聚醯亞胺,聚醯胺酸,孤對電子,圖案化電極,奈米銀線, | zh_TW |
dc.subject.keyword | photosensitive polyimides,Poly(amic acid),lone pair,patterned electrode,?silver nanowires, | en |
dc.relation.page | 115 | |
dc.rights.note | 有償授權 | |
dc.date.accepted | 2015-10-20 | |
dc.contributor.author-college | 工學院 | zh_TW |
dc.contributor.author-dept | 高分子科學與工程學研究所 | zh_TW |
顯示於系所單位: | 高分子科學與工程學研究所 |
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