Confinement effect of carbon nanotubes on the chain mobility of conjugated polymer poly(9,9-dioctylfluorenyl-2,7-diyl)

Li Ling-Dong; Ye An-Na; Zhou Sheng-Lin; Zhang Xiao-Hua; Yang Zhao-Hui

doi:10.7498/aps.68.20182008

Abstract

The conjugated polymer polyflourene has been well studied for its strong blue light emission ability and high quantum efficiency behavior. It has wide applications for light emitting diodes, sensors as well as photo-detectors. Therein the $ \beta $ conformation of PFO crystals is more attractive due to its longer conjugation length, higher carrier mobility and better luminous efficiency. Therefore it is great essential to control the formation and stability of $ \beta $ conformation of PFO crystals to develop new kind of photo-electronic devices. As is known, polymeric materials confined in a nanometer-sized space often exhibit unique properties compared with their bulk state, such as abnormal chain mobility, molecular assembly and phase transition behavior. These factors are of great significance to develop new kind of material and applications. Generally the confined condition includes quantum dot (zero-dimensional, 0D), nanowire or nanotube (1D), ultrathin film (2D) and nanoparticle (3D). In this paper, we design a unique 1D nanoconfined environment based on vertically aligned carbon nanotube (CNT) array structure. An ultra-high CNT density is achieved through a solvent-induced contraction process. The adjacent narrow carbon nanotube gap thus forms a quasi-1 confined nano-space with the tunable size ranging from 5 to 50 nm. Then we infiltrate the conjugated polymer poly(9,9-dioctylfluorene-2,7-diyl) (PFO) into those nano-gaps of carbon nanotube arrays through a solvent evaporation method to obtain the PFO infilled CNT array composite film. It is found that the chain mobility of PFO molecules in such a 1D nano-confined space of carbon nanotubes is significantly suppressed compared with the scenario of the spin-coated PFO film. The transition speed between different crystal forms of PFO declines greatly, which meanwhile improves the thermal stability of the $ \beta $ conformation of PFO crystal. Additionally, the aligned carbon nanotubes have great effects on the orientation and distribution of PFO chains. The PFO crystals are confirmed to grow preferentially along the longitudinal direction of CNT array, which is potential to grow PFO crystals with high quality and excellent performance. Thus, such a PFO/CNT array composite film can have great potential to prepare PFO photovoltaic devices with excellent luminescent properties and high stability in the future.

Keywords:

carbon nanotube arrays /
polymer poly(9,9-dioctylfluorene-2,7-diyl) /
confined space /
chain mobility

Authors and contacts

Jiangsu Key Laboratory of Thin Films,Center for Soft Condensed Matter Physics and Interdisciplinary Research, School of Physical Science and Technology, Soochow University, Suzhou 215006, China

Corresponding author: Yang Zhao-Hui, yangzhaohui@suda.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 21204059), the Specially-Appointed Professor Plan in Jiangsu Province, China (Grant Nos. SR10800215, SR10800312), and the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20181430).

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References

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Cited By

图 1 PFO的化学结构式及三种不同的构象结构及其特征内扭角的示意图 (a) R=(CH₂)₇CH₃; (b) $\alpha$构象; (c) $\gamma $构象; (d) $\beta $构象

Figure 1. Chemical structure of PFO and Schematic illustration of three distinct conformational structures and their characteristic intrachain torsional angles: (a) R=(CH₂)₇CH₃; (b) $\alpha$-phase; (c) $\gamma $-phase; (d) $\beta $-phase.

DownLoad: Full-Size Img PowerPoint

图 2 (a) PFO/S-ACNTs样品制备流程图; (b) ACNTs阵列收缩前后的对照图; (c) ACNTs的SEM和TEM图 (插图); (d), (e), (f) 相同放大倍数ACNTs、S-ACNTs和PFO/S-ACNTs的SEM图

Figure 2. (a) Schematic preparation of PFO/S-ACNTs; (b) photographs of ACNTs before and after the densification; (c) SEM and TEM (insets) images of as-grown ACNTs; (d), (e), (f) SEM cross-section images of ACNTs、S-ACNTs and PFO/S-ACNTs in the same magnification.

DownLoad: Full-Size Img PowerPoint

图 3 (a) PFO薄膜的吸收光谱 (蓝色) 与荧光光谱 (红色); (b), (c), (d) 分别对应PFO薄膜、PFO/S-ACNTs和PFO&RCNTs薄膜随退火温度变化的荧光光谱图 (激发波长为380 nm); (e) 三种PFO样品0—0发射峰峰位随退火温度的变化

Figure 3. (a) UV-vis absorption spectra (blue) and PL spectra (red) of PFO film; PL spectra of PFO film, PFO/S-ACNTs and PFO&RCNTs film with different annealing conditions corresponding to (b), (c) and (d), respectively (the excitation wavelength is 380 nm); (e) annealing temperature dependence of the 0—0 emission peak of three PFO based samples.

DownLoad: Full-Size Img PowerPoint

图 4 三种薄膜样品在不同温度下退火后的XRD衍射图 (所有样品在氮气氛围下退火1 h) (a) PFO滴膜样品; (b) PFO/S-ACNTs样品; (c) PFO & RCNTs

Figure 4. XRD diffraction pattern of (a) PFO drop film, (b) PFO/S-ACNTs, and (c) PFO & RCNTs at different annealing temperature (all samples are annealed in nitrogen atmosphere for 1 h).

DownLoad: Full-Size Img PowerPoint

[1]	Cook J H, Santos J, Li H, Al-Attar H A, Bryce M R, Monkman A P 2014 J. Mater. Chem. C 2 5587 Google Scholar
[2]	Schelkle K M, Bender M, Jeltsch K, Buckup T, Mullen K, Hamburger M, Bunz U H 2015 Angew. Chem. Int. Ed. 54 14545 Google Scholar
[3]	Luo J, Zhou Y, Niu Z Q, Zhou Q F, Ma Y G, Pei J 2007 J. Am. Chem. Soc. 129 11314 Google Scholar
[4]	Zhong C, Duan C, Huang F, Wu H, Cao Y 2011 Chem. Mater. 23 326 Google Scholar
[5]	Cingil H E, Storm I M, Yorulmaz Y, Te B D W, De V R, Cohen S M A, Sprakel J 2015 J. Am. Chem. Soc. 137 9800 Google Scholar
[6]	Lv F T, Qiu T, Liu L B, Ying J M, Wang S 2016 Small 12 696 Google Scholar
[7]	Inganas O, Zhang F, Andersson M R 2009 Acc. Chem. Res. 42 1731 Google Scholar
[8]	Wu H, Ying L, Yang W, Cao Y 2009 Chem. Soc. Rev. 38 3391 Google Scholar
[9]	Scherf U, List E J W 2002 Adv. Mater. 14 477 Google Scholar
[10]	Chen S H, Su A C, Su C H, Chen S A 2005 Macromolecules 38 379 Google Scholar
[11]	Chen S H, Chou H L, Su A C, Chen S A 2004 Macromolecules 37 6833 Google Scholar
[12]	Grell M, Bradley D D C, Ungar G, Hill J, Whitehead K S 1999 Macromolecules 32 5810 Google Scholar
[13]	Lee C C, Lai S Y, Su W B, Chen H L, Chung C L, Chen J H 2013 J. Phys. Chem. C 117 20387 Google Scholar
[14]	Chunwaschirasiri W, Tanto B, Huber D L, Winokur M J 2005 Phys. Rev. Lett. 94 107402 Google Scholar
[15]	Arif M, Volz C, Guha S 2006 Phys. Rev. Lett. 96 025503 Google Scholar
[16]	Cadby A J 2000 Phys. Rev. B 62 15604 Google Scholar
[17]	Lu H H, Liu C Y, Chang C H, Chen S A 2007 Adv. Mater. 19 2574 Google Scholar
[18]	Peet J, Brocker E, Xu Y, Bazan G C 2008 Adv. Mater. 20 1882 Google Scholar
[19]	Asada K, Kobayasi T, Naito H 2006 Japanese Journal of Applied Physics Part 2-Letters and Express Letters 45 L247 Google Scholar
[20]	Zhang Q, Chi L, Hai G, Fang Y, Li X, Xia R, Huang W, Gu E 2017 Molecules 22 315 Google Scholar
[21]	Huang L, Huang X, Sun G, Gu C, Lu D, Ma Y 2012 J. Phys. Chem. C 116 7993 Google Scholar
[22]	Li T, Liu B, Zhang H, Ren J, Bai Z, Li X, Ma T, Lu D 2016 Polymer 103 299 Google Scholar
[23]	Li T, Huang L, Bai Z, Li X, Liu B, Lu D 2016 Polymer 88 71 Google Scholar
[24]	O'Carroll D, Lieberwirth I, Redmond G 2007 Nat. Nanotechnol. 2 180 Google Scholar
[25]	Grimm S, Martín J, Rodriguez G, Fernández-Gutierrez M, Mathwig K, Wehrspohn R B, Gösele U, San Roman J, Mijangos C, Steinhart M 2010 J. Mater. Chem. 20 3171 Google Scholar
[26]	Liu C L, Chen H L 2018 Soft Matter 14 5461 Google Scholar
[27]	Li M, Wu H, Huang Y, Su Z 2012 Macromolecules 45 5196 Google Scholar
[28]	Shin K, Woo E, Jeong Y G, Kim C, Huh J, Kim K W 2007 Macromolecules 40 6617 Google Scholar
[29]	Garcia G M C, Linares A, Hernandez J J, Rueda D R, Ezquerra T A, Poza P, Davies R J 2010 Nano Lett. 10 1472 Google Scholar
[30]	Steinhart M, Goring P, Dernaika H, Prabhukaran M, Gosele U, Hempel E, Thurn A T 2006 Phys. Rev. Lett. 97 027801 Google Scholar
[31]	Hui W, Wei W, Huixian Yang A, Su Z 2007 Macromolecules 40 4244 Google Scholar
[32]	Wu H, Wang W, Huang Y, Su Z 2009 Macromol Rapid Commun. 30 194 Google Scholar
[33]	Wu Y, Gu Q, Ding G, Tong F, Hu Z, Jonas A M 2013 ACS Macro Lett. 2 535 Google Scholar
[34]	Ding G, Wu Y, Weng Y, Zhang W, Hu Z 2013 Macromolecules 46 8638 Google Scholar
[35]	O'Brien G A, Quinn A J, Tanner D A, Redmond G 2006 Adv. Mater. 18 2379 Google Scholar
[36]	O'Carroll D, Iacopino D, O'Riordan A, Lovera P, O'Connor É, O'Brien G A, Redmond G 2008 Adv. Mater. 20 42 Google Scholar
[37]	Steinhart M, Wendorff J H, Greiner A, Wehrspohn R B, Nielsch K, Schilling J, Choi J, Gösele U 2002 Science 296 1997 Google Scholar
[38]	Ding G, Li C, Li X, Wu Y, Liu J, Li Y, Hu Z, Li Y 2015 Nanoscale 7 11024 Google Scholar
[39]	Wei S, Zhang Y, Liu J, Li X, Wu Y, Wei H, Weng Y, Gao X, Li Y, Wang S D, Hu Z 2015 Adv. Mater. Interfaces 2 1500153 Google Scholar
[40]	Zhang P, Huang H, He T, Hu Z 2012 ACS Macro Lett. 1 1007 Google Scholar
[41]	Li X H, Shen X Z, Gao X, Weng Y Y 2017 RSC Adv. 7 55885 Google Scholar
[42]	Ajayan P M, Lijima S 1993 Nature 361 333 Google Scholar
[43]	Ugarte D, Stöckli T, Bonard J M, Châtelain A, Heer W A D 1998 Appl. Phys. A 67 101
[44]	Nakamura A, Koyama T, Miyata Y, Shinohara H 2016 J. Phys. Chem. C 120 4647 Google Scholar
[45]	Liu Z, Liao G, Li S, Pan Y, Wang X, Weng Y, Zhang X, Yang Z 2013 J. Mater. Chem. A 1 13321 Google Scholar
[46]	Bai Z, Liu Y, Li T, Li X, Liu B, Liu B, Lu D 2016 J. Phys. Chem. C 120 27820 Google Scholar
[47]	Futaba D N, Hata K, Yamada T, Hiraoka T, Hayamizu Y, Kakudate Y, Tanaike O, Hatori H, Yumura M, Iijima S 2006 Nat. Mater. 5 987 Google Scholar
[48]	Zhou S, Sheng J, Yang Z, Zhang X 2018 J. Mater. Chem. A 6 8763 Google Scholar
[49]	Li X, Bai Z, Liu B, Li T, Lu D 2017 J. Phys. Chem. C 121 14443 Google Scholar
[50]	Jen T H, Wang K K , Chen S A 2012 Polymer 53 5850 Google Scholar
[51]	Chen S H, Su A C, Chen S A 2005 J. Phys. Chem. B 109 10067 Google Scholar
[52]	Torkkeli M, Galbrecht F, Scherf U, Knaapila M 2015 Macromolecules 48 5244 Google Scholar
[53]	Sheng J, Zhou S, Yang Z, Zhang X 2018 Langmuir 34 3678 Google Scholar
[54]	Wang M, Li L, Zhou S, Tang R, Yang Z, Zhang X 2018 Langmuir 34 10702 Google Scholar

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