表面接枝聚(3-烷基噻吩)於奈米碳管之合成與光電性質研究

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研究生：	黎英芳 Le Anh Phuong
論文名稱：	表面接枝聚(3-烷基噻吩)於奈米碳管之合成與光電性質研究 The Synthesis and Optoelectronic Behaviour of Conjugated Polymer Poly(3-hexylthiophene) P3HT Grafted on the surface of Multi-Walled Carbon Nanotubes
指導教授：	楊長謀 Yang, A.C.-M.
口試委員:
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學工程學系 Materials Science and Engineering
論文出版年：	2010
畢業學年度：	99
語文別：	英文
論文頁數：	69
中文關鍵詞：	poly(3-hexylthiophene) 、multi-walled carbon nanotubes 、a "grafting from" method 、photovoltaic behaviour
相關次數：	點閱：3 下載：0
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A nanocomposite of multi-walled carbon nanotubes (MWCNTs) and poly(3-hexylthiophene) (P3HT) was prepared by grafting P3HT on the surface of CNTs via a “grafting from” method. By using chemical oxidative polymerization with controlling the reaction condition, different coating thickness of P3HT on MWCNTs was obtained. P3HT grafted on the surface of MWCNTs (P3HT-g-CNT) are soluble in common organic solvents. Fourier Transform Infrared (FT-IR) spectra was employed to characterize the change in the surface functionalities. The transmission electron microscopy (TEM) micrographs showed the uniform coating of P3HT on CNTs with the thickness 2.1 nm, 3.6 nm and 8.3 nm. Thermogravimetric analysis (TGA) was used to study the polymer content grafted on the surface of MWCNTs. The wide-angle X-ray scattering (WAXS) presented the disordered structure of P3HT chains grafted on CNTs. The Raman scattering indicated that the polymer conformation is modified by π-π interaction with CNTs which causes a shift of P3HT peak from 1445 cm-1 to 1430 cm-1. Furthermore, although the photoluminescence peak of P3HT remained unchanged when grafted on CNTs, modifications of the energy gap of P3HT was observed, indicating variations of vibronic levels arising from the grafting. Moreover, broadening of the PL emission peaks took place that suggested decreasing of lifetimes of the photo-excited species when grafted on CNTs. The bilayer photovoltaic devices based on pure P3HT blended with P3HT-g-CNT (P3HT/P3HT-g-CNT) as the electron donor and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as the electron-acceptor showed an enhanced photocurrent density and power conversion efficiency compared to photovoltaic devices based on pure P3HT and P3HT/P3HT-g-CNT.

Table of Contents

Chapter 1
Introduction    1
Chapter 2
Literature review    3
2.1 Structures of CNTs    3
2.2 Productions of CNTs    5
2.2.1 The arc-evaporation technique     5
2.2.2 Laser ablation method     6
2.2.3 Catalytic growth     7
2.3 Chemically functionalized carbon nanotubes    8
2.3.1 Oxidation of CNTs     9
2.3.2 The grafting polymer chains on the surface of CNTs    10
2.4 The role of CNTs in electronic materials    11
2.4.1 Organic light emitting diodes (OLEDs)    12
2.4.2 Organic thin film solar cell     13
2.5 Polythiophene and Poly (3-hexylthiophene) (P3HT)     15
Chapter 3
Experimental details    16
3.1 Materials     16
3.2 The process to synthesize P3HT grafted on the surface of MWCNTs     17
3.2.1 Acid treatment of MWCNTs     18
3.2.2 Synthesis of P3HT chains grafted to the surface of MWCNTs     19
3.3 Preparation of P3HT    22
3.4 Defunctionalization of P3HT-g-MWCNTs    22
3.5 Device Fabrication of the Organic Photovoltaic Cell     23
3.6 Characterizations     25
3.7 Instruments     26
3.7.1 Fourier Transform Infrared (FT-IR)    26
3.7.2 Transmission Electron Microscopy (TEM)    27
3.7.3 Thermogravimetric analysis (TGA)    28
3.7.4 Gel Permeation Chromatography (GPC)    29
3.7.5 Raman spectroscopy    30
3.7.6 Photoluminescence (PL)    31
Chapter 4
Results and discussions    32
4.1 Dispersion observation.     32
4.2 The regioregularity of P3HT     33
4.3 FTIR spectra    34
4.4 TEM micrographs    35
4.5 Wide-Angle X-ray Scattering    38
4.6 Thermogravimetry analysis    40
4.7 Raman spectroscopy characterization      42
4.8 Photoluminescence spectra     44
4.8 Current – voltage (I –V) characteristics     52


Chapter 5
Conclusion    65
References    66

List of figures

Figure 2.1 Structures of CNTs    3
Figure 2.2 Possible vectors specified by the pairs of integers [m,n] for general CNTs     4
Figure 2.3 Arc discharge apparatus produced the first carbon nanotubes     5
Figure 2.4 Schematics of a laser ablation set-up     6
Figure 2.5 Schematics of a CVD deposition oven.    7
Figure 2.6 Functionalization possibilities for SWCNTs    8
Figure 2.7 Optimized device structure for bulk heterojunction organic solar cells    14
Figure 2.8 The chemical structure of P3HT     15
Figure 3.1 The flow chart of experiments     17
Figure 3.2 MWCNT acid-treatment    18
Figure 3.3 Monomer 3-thiopheneethanol (3TE) grafted on MWCNTs    19
Figure 3.4 Poly(3-hexylthiophene) grafted on MWCNTs - step I    20
Figure 3.5 Top and side view of the device structure for photovoltage     24
Figure 3.6 Scematic diagram of the proposed structure     24
Figure 3.7 Fourier Transform Infrared instrument    26
Figure 3.8 Schematic of layout of optical components in a basic TEM    27
Figure 3.9 Thermogravimetric analysis instrument     28
Figure 3.10  Schematic of a basic gel permeation chromatography    29

Figure 3.11 Gel permeation chromatography instrument     29
Figure 3.12 Photoluminescence instrument     31
Figure 4.1 The dispersion of CNT-g-monomer HET in (a) CH3Cl and (b) CH3CN    32
Figure 4.2 NMR spectra of P3HT    33
Figure 4.3 FT-IR spectra of MWCNTs-COOH , MWCNTs-COCl, MWCNTs-g-HET    34
Figure 4.4 TEM micrographs of MWCNTs-g-P3HT of step I     36
Figure 4.5 TEM micrographs of MWCNTs-g-P3HT of step II-A    36
Figure 4.6 TEM micrographs of MWCNTs-g-P3HT of step II-B    36
Figure 4.7 WAXS patterns    39
Figure 4.8 TGA analyses of acid treated MWCNTs, defunctionalized P3HT and P3HT-g-MWCNTs with different coating thickness.    40
Figure 4.9 Raman spectra of (a) acid treated MWCNTs, (b)MWCNT-g-P3HT-2, (c) MWCNT-g-P3HT-4, (d) MWCNT-g-P3HT-4 and (e) P3HT     42
Figure 4.10 PL and PLE spectra of MWCNT-g-P3HT-2    44
Figure 4.11 PL and PLE spectra of MWCNT-g-P3HT-4    44
Figure 4.12 PL and PLE spectra of MWCNT-g-P3HT-8    44
Figure 4.13 The intensity comparision of PL spectra of MWCNT-g-P3HT with different coating thickness    45
Figure 4.14 The comparision of PL spectra of P3HT-g-MWCNTs with different coating thickness with the normalized P3HT content.    46
Figure 4.15 PL and PLE spectra of neat P3HT with different molecular weight.    49
Figure 4.16 The PL maximum peak versus the molecular weight    49
Figure 4.17 PL and PLE spectra of MWCNT-g-P3HT-2, defunctionalized P3HT (from the step I with the Mw: 13K) and neat P3HT (Mw: 14K)    50
Figure 4.18 PL and PLE spectra of MWCNT-g-P3HT-4, defunctionalized P3HT (from the step II-A with the Mw: 30K) and neat P3HT (Mw: 32K)    50
Figure 4.19 PL and PLE spectra of MWCNT-g-P3HT-8, defunctionalized P3HT (from step II-B with the Mw: 66K) and neat P3HT (Mw: 70K)    50
Figure 4.20 The PL maximum peak of neat P3HT, defunctionalized P3HT and P3HT-g-MWCNTs versus the molecular weight.    51
Figure 4.21 The I-V curve of acid-treated MWCNTs    52
Figure 4.22 I-V characteristics of the photovoltaic cell where P3HT (Mw:70K) was served as the active layer    53
Figure 4.23  I-V characteristics of the photovoltaic cell where P3HT blending with 1% MWCNTs-COOH was served as the active layer.    53
Figure 4.24 I-V characteristics of the photovoltaic cell, where MWCNTs-g-P3HT-2 was served as the active layer     54
Figure 4.25 I-V characteristics of the photovoltaic cell, where P3HT blending with 50% MWCNTs-g-P3HT-2 was served as the active layer     54
Figure 4.26  I-V characteristics of the photovoltaic cell, where P3HT blending with 10% MWCNTs-g-P3HT-2 was served as the active layer     55
Figure 4.27 I-V characteristics of the photovoltaic cell, where P3HT blending with 5% MWCNTs-g-P3HT-2 was served as the active layer     56
Figure 4.28 I-V characteristics of the photovoltaic cell where P3HT blending with 1% MWCNTs-g-P3HT-2 was served as the active layer.    56
Figure 4.29 I-V characteristics of the photovoltaic cell where P3HT blending with 10% MWCNTs-g-P3HT-4 was served as the active layer    57
Figure 4.30 I-V characteristics of the photovoltaic cell where P3HT blending with 5% MWCNTs-g-P3HT-4 was served as the active layer.    58
Figure 4.31 I-V characteristics of the photovoltaic cell where P3HT blending with 1% MWCNTs-g-P3HT-4 was served as the active layer.    58
Figure 4.32 I-V characteristics of the photovoltaic cell where P3HT blending with 10% MWCNTs-g-P3HT-8 was served as the active layer.     59
Figure 4.33 I-V characteristics of the photovoltaic cell where P3HT blending with 5% MWCNTs-g-P3HT-8 was served as the active layer.    59
Figure 4.34 I-V characteristics of the photovoltaic cell where P3HT blending with 1% MWCNTs-g-P3HT-8 was served as the active layer.    60
Figure 4.35 The open circuit voltage versus the concentration of MWCNT-g-P3HT with different coating thickness in nanocomposite for the active layer.    60
Figure 4.36 The short circuit current versus the concentration of MWCNT-g-P3HT with different coating thickness in nanocomposite for the active layer.     60
Figure 4.37 (a) J-V characteristics for solar cells based on P3HT and P3HT/MWCNT-g-P3HT-2(1%, 5% and 10%), (b) J-V characteristics for bilayer solar cells based on P3HT/PCBM and P3HT/MWCNT-g-P3HT-2(1% and 10%)/PCBM.    61
Figure 4.38 Band gap diagram of the bilayer device.    61

List of Tables

Table 3.1 List of materials     16
Table 3.2 Summary of conditions to synthesize P3HT grafting on MWCNTs    21
Table 4.1 The coating thickness calculated by TEM corresponding to the molecular weight determined by GPC     37
Table 4.2 The comparision of P3HT coating thickness between the results of TEM and TGA    41
Table 4.3 The band gap of MWCNTs-g-P3HT with different coating thickness.    45
Table 4.4 The spacing between 2 neibouring polymers grafted on CNTs.    47
Table 4.5 The overlapping percentage between 2 neibouring polymers grafted on CNTs
.    45
Table 4.6  The performance of photovoltaic cells of P3HT and nanocomposites     62

                                

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