臺灣博碩士論文加值系統

軟性電子元件因其應用領域，需要整體結構皆具備可拉伸、撓曲之特性。目前常見應用於軟性電子元件之有機材料，載子遷移率相對於傳統固態元件性能較差。因此發展具備拉伸特性且高載子遷移率的材料是目前研究的趨勢。單壁奈米碳管因其堅韌卻又可撓曲的物理性質，與優秀之電子性能，而具備應用於軟性電子元件中的潛力。但單壁奈米碳管會因其結構的改變而擁有不同之導電性質，所以純化單一導電性質之單壁奈米碳管對於後續的應用是非常重要的關鍵。本研究以共軛高分子選擇性分散單壁奈米碳管之方法為基礎，希望能建立一個純化單壁奈米碳管的標準程序，並以不同管徑大小之單壁奈米碳管、不同的共軛高分子作為研究對象。用以探討選擇性分散單壁奈米碳管之機制。
於第二章，較大管徑之單壁奈米碳管具備較高的電子遷移率，但目前之文獻中並無共軛高分子選擇性分散大管徑單壁奈米碳管之紀錄，故我們著重在選擇性分散大管徑之單壁奈米碳管。使用常見用於選擇性分散單壁奈米碳管的共軛高分子聚芴(Polyfluorene)、聚噻吩(Polythiophene) 來分散較大管徑之單壁奈米碳管。針對製程參數、高分子與碳管之比例改良。選擇性分散後得到的單壁奈米碳管其管徑為1.42 nm與1.74 nm。且製備成場效電晶體後，其分析結果呈現半導體性質，得到之電子遷移率為4.21×10-2 cm2/(s×V)。最後與文獻比較並探討選擇性分散之機制，並嘗試說明為何我們可以選擇性分散出較大管徑之單壁奈米碳管。
於第三章，以單壁奈米碳管與共軛高分子之間的凡德瓦爾力作為研究對象。首先確認已建立之製程能否應用於較小管徑之單壁奈米碳管。一樣以聚芴(Polyfluorene)、聚噻吩(Polythiophene) 等共軛高分子來選擇性分散較小管徑之單壁奈米碳管。從光激發光實驗中得到數種掌性之半導體性質單壁奈米碳管。製備之電晶體電流開關比達到104，電子遷移率達到9.95×10-2 cm2/(s×V)。確認製程的可行性後，導入含有凡德瓦爾力之疏水長鏈之嵌段高分子，研究不同凡德瓦爾力強度對於選擇性分散單壁奈米碳管之影響。從UV/VIS/NIR的結果上發現，越長之疏水鏈段對於單壁奈米碳管有越高選擇性分散的特性。從光激發光螢光光譜中也發現，不同的疏水鏈段長度對於同掌性的單壁奈米碳管也具有不同的分散能力。

Soft electronics require not only high electronic performance but also stretchable and flexible properties. Currently used in organic materials for soft electronic components, carrier mobility is poorer than traditional solid-state components. Therefore, the development of materials with tensile properties and high carrier mobility is currently the trend of research. Single-walled carbon nanotubes have the potential to be used in soft electronic components due to their tough but flexible physical properties and excellent electronic properties. However, single-walled carbon nanotubes have different conductive properties due to their structural changes, therefore the purification of single-conductor single-walled carbon nanotubes is very important for subsequent applications. Based on the method of conjugated polymer selective dispersion of single-walled carbon nanotubes, it is hoped that a standard procedure for purifying single-walled carbon nanotubes can be established. Different diameters of single-walled carbon nanotubes and different conjugated polymers were selected as research objects. To explore the mechanism of selective dispersion of single-walled carbon nanotubes.
In Chapter 2, we used the conjugate polymer, polyfluorene and polythiophene, which are commonly used to selectively disperse single-walled carbon nanotubes, For dispersing single-walled carbon nanotubes with larger diameters. The single-walled carbon nanotubes obtained after selective dispersion have diameters of 1.42 nm and 1.74 nm. After the preparation of the field effect transistor, the analysis exhibited semiconducting properties, and the obtained carrier mobility was 4.21×10-2 cm2/(s×V). We tried to explain why PFO can sort relatively larger diameter of single-wall carbon nanotubes which is comparing with the reference.
In Chapter 3, the effect of van der Waals force between single-walled carbon nanotubes and conjugated polymers is the object we want to study. It is first necessary to confirm whether the established process can be applied to single-walled carbon nanotubes with smaller diameters. Similarly, a conjugated polymer such as polyfluorene or polythiophene is used to selectively disperse carbon nanotubes with smaller diameter. Several kinds of chirality of semiconducting single-walled carbon nanotubes were confirmed by the photoluminescence result. The prepared transistor on/off current ratio reached 104, and the carrier mobility reached 9.95×10-2 cm2 /(s×V). After confirming the feasibility of the process, a block polymer containing a long hydrophobic chain was introduced to study the effect of different van der Waals strength on the selective dispersion of single-walled carbon nanotubes. From the results of UV/VIS/NIR, it was found that the longer the hydrophobic segment has higher selectively dispersion of the single-walled carbon nanotube. It has also been found from the photoluminescence result that different hydrophobic segment lengths also have different dispersing ability for the same chirality of carbon nanotubes.

目錄
Chapter 1. Introduction 1
1.1. Fundamentals on Single-wall Carbon Nanotube 2
1.1.1. Mechanical Properties of Single-wall Carbon Nanotube 2
1.1.2. Electrical Properties of Single-wall Carbon Nanotube 2
1.1.3. Selectively Dispersion of Single-wall Carbon Nanotubes by Conjugated-Polymer 5
1.1.4. Fundamentals on Organic Field-Effect Transistors (OFETs) 6
Chapter 2. Sorting Large-diameter Single-wall Carbon Nanotube by Conjugated Polymer. 9
2.1. Introduction 9
2.2. Experiment Sections 9
2.2.1. Materials 9
2.2.2. Polymer-assisted Dispersion of Carbon Nanotubes 10
2.2.3. Device Fabrication 11
2.2.4. Characterization 13
2.3. Result and Discussion 14
2.3.1. Spectroscope Characterization of Sorted SWNT 14
2.3.2. Morphology and Electrical Properties 21
2.4. Conclusion 25
Chapter 3. Sorting Carbon Nanotube by Conjugated-Polymer with Hydrophobic Alkyl Chain 27
3.1. Introduction 27
3.2. Experiment Sections 28
3.2.1. Materials 28
3.2.2. Polymer-assisted Dispersion of Carbon Nanotubes 28
3.2.3. Device Fabrication 29
3.2.4. Characterization 30
3.3. Result and Discussion 31
3.3.1. Spectroscope Characterization of Sorted SWNT 31
3.3.2. Morphology and Electrical Properties 39
3.4. Conclusion 44
Reference 46

Reference
[1] H. Klauk et al., “High-mobility polymer gate dielectric pentacene thin film transistors,” Journal of Applied Physics, vol. 92, no. 9, pp. 5259-5263, 2002.
[2] J. Peet et al., “Efficiency enhancement in low-bandgap polymer solar cells by processing with alkane dithiols,” Nature Materials, vol. 6, no. 7, pp. 497-500, 2007.
[3] S. C. B. Mannsfeld et al., “Highly sensitive flexible pressure sensors with microstructured rubber dielectric layers,” Nature Materials, vol. 9, no. 10, pp. 859-864, 2010.
[4] J.-F. Chang et al., “Enhanced Mobility of Poly(3-hexylthiophene) Transistors by Spin-Coating from High-Boiling-Point Solvents,” Chemistry of Materials, vol. 16, no. 23, pp. 4772-4776, 2004/11/01, 2004.
[5] Y. Li et al., “High mobility diketopyrrolopyrrole (DPP)-based organic semiconductor materials for organic thin film transistors and photovoltaics,” Energy & Environmental Science, vol. 6, no. 6, pp. 1684-1710, 2013.
[6] S. Iijima, “Helical microtubules of graphitic carbon,” Nature, vol. 354, no. 6348, pp. 56-58, 1991/11/01, 1991.
[7] S. M. Bachilo et al., “Structure-assigned optical spectra of single-walled carbon nanotubes,” Science, vol. 298, no. 5602, pp. 2361-6, Dec 20, 2002.
[8] J. P. Lu, “Elastic Properties of Carbon Nanotubes and Nanoropes,” Physical Review Letters, vol. 79, no. 7, pp. 1297-1300, 08/18/, 1997.
[9] Y. H. Yang, and W. Z. Li, “Radial elasticity of single-walled carbon nanotube measured by atomic force microscopy,” Applied Physics Letters, vol. 98, no. 4, 2011.
[10] A. Eatemadi et al., “Carbon nanotubes: properties, synthesis, purification, and medical applications,” vol. 9, no. 1, pp. 393, August 13, 2014.
[11] J. W. G. Wildöer et al., “Electronic structure of atomically resolved carbon nanotubes,” Nature, vol. 391, no. 6662, pp. 59-62, 1998.
[12] Y. Matsuda, J. Tahir-Kheli, and W. A. Goddard Iii, “Definitive band gaps for single-wall carbon nanotubes,” Journal of Physical Chemistry Letters, vol. 1, no. 19, pp. 2946-2950, 2010.
[13] M. J. O'Connell et al., “Band gap fluorescence from individual single-walled carbon nanotubes,” Science, vol. 297, no. 5581, pp. 593-596, 2002.
[14] A. Chortos et al., “Universal Selective Dispersion of Semiconducting Carbon Nanotubes from Commercial Sources Using a Supramolecular Polymer,” ACS Nano, vol. 11, no. 6, pp. 5660-5669, Jun 27, 2017.
[15] J. Ding et al., “Enrichment of large-diameter semiconducting SWCNTs by polyfluorene extraction for high network density thin film transistors,” Nanoscale, vol. 6, no. 4, pp. 2328-39, Feb 21, 2014.
[16] H. W. Lee et al., “Selective dispersion of high purity semiconducting single-walled carbon nanotubes with regioregular poly(3-alkylthiophene)s,” Nat Commun, vol. 2, pp. 541, Nov 15, 2011.
[17] M. Zheng et al., “DNA-assisted dispersion and separation of carbon nanotubes,” Nat Mater, vol. 2, no. 5, pp. 338-42, May, 2003.
[18] M. S. Arnold, S. I. Stupp, and M. C. Hersam, “Enrichment of single-walled carbon nanotubes by diameter in density gradients,” Nano Letters, vol. 5, no. 4, pp. 713-718, 2005.
[19] F. Chen et al., “Toward the extraction of single species of single-walled carbon nanotubes using fluorene-based polymers,” Nano Lett, vol. 7, no. 10, pp. 3013-7, Oct, 2007.
[20] J. Gao et al., “Effectiveness of sorting single-walled carbon nanotubes by diameter using polyfluorene derivatives,” Carbon, vol. 49, no. 1, pp. 333-338, 2011.
[21] T. Lei, I. Pochorovski, and Z. Bao, “Separation of Semiconducting Carbon Nanotubes for Flexible and Stretchable Electronics Using Polymer Removable Method,” Acc Chem Res, vol. 50, no. 4, pp. 1096-1104, Apr 18, 2017.
[22] L. Liang et al., “High-efficiency dispersion and sorting of single-walled carbon nanotubes via non-covalent interactions,” Journal of Materials Chemistry C, vol. 5, no. 44, pp. 11339-11368, 2017.
[23] A. Nish et al., “Highly selective dispersion of single-walled carbon nanotubes using aromatic polymers,” Nat Nanotechnol, vol. 2, no. 10, pp. 640-6, Oct, 2007.
[24] J. Ouyang et al., “Sorting of Semiconducting Single-walled Carbon Nanotubes in Polar Solvents with an Amphiphilic Conjugated Polymer Provides General Guidelines for Enrichment,” ACS Nano, vol. 12, no. 2, pp. 1910-1919, Feb 27, 2018.
[25] I. Pochorovski et al., “H-bonded supramolecular polymer for the selective dispersion and subsequent release of large-diameter semiconducting single-walled carbon nanotubes,” J Am Chem Soc, vol. 137, no. 13, pp. 4328-31, Apr 8, 2015.
[26] M. S. Dresselhaus et al., “Raman spectroscopy of carbon nanotubes,” Physics Reports, vol. 409, no. 2, pp. 47-99, 2005.
[27] D. Fong, and A. Adronov, “Recent developments in the selective dispersion of single-walled carbon nanotubes using conjugated polymers,” Chem Sci, vol. 8, no. 11, pp. 7292-7305, Nov 1, 2017.