doi:10.1007/s10118-021-2514-2

Citation: Zuo, H. T.; Gan, F.; Dong, J.; Zhang, P.; Zhao, X.; Zhang, Q. H. Highly transparent and colorless polyimide film with low dielectric constant by introducing meta -substituted structure and trifluoromethyl groups. Chinese J. Polym. Sci. 2021, 39, 455–464 doi: 10.1007/s10118-021-2514-2 shu

Highly Transparent and Colorless Polyimide Film with Low Dielectric Constant by Introducing Meta-substituted Structure and Trifluoromethyl Groups

Hong-Tao Zuo ^a ,
Feng Gan ^a ,
Jie Dong ^a ,
Peng Zhang ^b ,
Xin Zhao ^a,, ,
Qing-Hua Zhang ^a,,

a.
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai 201620, China
b.
Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Xin Zhao, E-mail: xzhao@dhu.edu.cn
Qing-Hua Zhang, E-mail: qhzhang@dhu.edu.cn
Received Date: 2020-08-05
Accepted Date: 2020-10-05
Available Online: 2020-11-10

Figures(9) / Tables(3)

An effective design strategy for preparing highly transparent polyimide film with low dielectric constant is presented. The key to the strategy is to simultaneously introduce meta-substituted structure and trifluoromethyl in polymer chains. By using this design strategy, a highly transparent polyimide film with low-k was synthesized from 3,5-diaminobenzotrifluoride (m-TFPDA) and 4,4′-(hexafluoroisopropylidene) diphthalic anhydride (6FDA) through a two-step method. The obtained m-TFPDA/6FDA (CPI) film (~30 μm) possesses high optical transparency (λ_cutoff=334 nm, T_450nm=85.26%, Haze=0.31) and is close to colorless (L^*=96.03, a^*=−0.34, b^*=2.12, yellow index=3.96). The intrinsic k and dielectric loss value of the film are 2.27 and 0.0013 at 10 kHz, respectively. More importantly, such low dielectric performance could remain stable up to 280 °C, and the film shows a low moisture rate (~0.51%), which helps to maintain the low-k property stability in different humid environments. Meanwhile, the film also shows good thermal stability and mechanical properties, with a glass transition temperature (T_g) of 296 °C and the 5 wt% decomposition temperature (T_d,5%) of 522 °C under N₂. The tensile strength and tensile modulus of the film are 85.1 MPa and 1.96 GPa, respectively. In addition, the film is soluble in common solvents, which allows simple solution processing and low-cost, continuous roll-to-roll processes. This design strategy is beneficial to improving the transparency, lightening yellow color, lowering the dielectric constant and meanwhile maintaining the comprehensive properties of polyimide films, which is mainly due to the introduced meta-substituted and trifluoromethyl structures effectively inhibiting the transfer of charge transfer complex (CTC) effects and increasing the free volume of film. This design strategy could also be extended to other high-performance polymer systems.
- Polyimide film,
- Transparent,
- Colorless,
- Low dielectric constant
1. [1]
  Lee, D. H.; Yun, H. D.; Jung, E. D.; Chu, J. H.; Nam, Y. S. Song, S.; Seok, S. H.; Song, M. H. Kwon, S. Y. Ultrathin graphene intercalation in PEDOT:PSS/colorless polyimide-based transparent electrodes for enhancement of optoelectronic performance and operational stability of organic devices. ACS Appl. Mater. Interfaces 2019, 11, 21069−21077. doi: 10.1021/acsami.9b04118
2. [2]
  Yin, X. D.; Feng, Y. Y.; Zhao, Q.; Li, Y.; Li, S. W.; Dong, H. L.; Hu, W. P.; Feng, W. A. A highly transparent, strong, and flexible fluorographene/fluorinated polyimide nanocomposite film with low dielectric constant. J. Mater. Chem. C 2018, 6, 6378−6384. doi: 10.1039/C8TC00998H
3. [3]
  Kim, S. D.; Lee, B.; Byun, T.; Chung, I. S.; Park, J.; Shin, I.; Ahn, N. Y.; Seo, M.; Lee, Y.; Kim, Y.; Kim, W. Y.; Kwon, H.; Moon, H.; Yoo, S.; Kim, S. Y. Poly(amide-imide) materials for transparent and flexible displays. Sci. Adv. 2018, 4, eaau1956.
4. [4]
  Li, T. L.; Hsu, S. L. C. Preparation and properties of a high temperature, flexible and colorless ITO coated polyimide substrate. Eur. Polym. J. 2007, 43, 3368−3373. doi: 10.1016/j.eurpolymj.2007.04.039
5. [5]
  Kang, S. B.; Kim, H. J.; Noh, Y. J.; Na, S. I.; Kim, H. K. Face-to-face transferred multicrystalline ITO films on colorless polyimide substrates for flexible organic solar cells. Nano Energy 2015, 11, 179−188. doi: 10.1016/j.nanoen.2014.10.030
6. [6]
  Bai, L.; Zhai, L.; Hea, M. H.; Wang, C. O.; Mo, S.; Fan, L. Thermal expansion behavior of poly(amide-imide) films with ultrahigh tensile strength and ultralow CTE. Chinese J. Polym. Sci. 2020, 38, 748−758. doi: 10.1007/s10118-020-2366-1
7. [7]
  Kashiyama, Y.; He, J. H.; Machida, S.; Horie, K. Large photoinduced refractive index change in a polyimide film by charge-transfer complex formation with a polymer-bound phenylazide fragment. Macromol. Rapid Commun. 2001, 22, 185−188. doi: 10.1002/1521-3927(200102)22:3<185::AID-MARC185>3.0.CO;2-C
8. [8]
  Ishida, H.; Wellinghoff, S. T.; Baer, E.; Koenig, J. Spectroscopic studies of poly [N,N′-bis(phenoxyphenyl) pyromellitimide]. 1. Structures of the polyimide and three model compounds. Macromolecules 1980, 13, 826−834. doi: 10.1021/ma60076a011
9. [9]
  Zhang, Q.; Tsai, C. Y.; Li, L. J.; Liaw, D. J. Colorless-to-colorful switching electrochromic polyimides with very high contrast ratio. Nat. Commun. 2019, 10, 1239. doi: 10.1038/s41467-019-09054-8
10. [10]
  Kim, M.; Ryu, T. I.; Ok, K. H.; Kwak, M. G.; Park, S.; Park, N. G.; Han, C. J.; Kim, B. S.; Ko, M. J.; Son, H. J.; Kim, J. W. Transparent electronics: inverted layer-by-layer fabrication of an ultraflexible and transparent Ag nanowire/conductive polymer composite electrode for use in high-performance organic solar cells. Adv. Funct. Mater. 2015, 25, 4580−4589. doi: 10.1002/adfm.201501046
11. [11]
  Jang, J. H.; Cueva, G.; Hoke, W. E.; Lemonias, P. J.; Fay, P.; Adesida, I. Metamorphic graded bandgap InGaAs-InGaAlAs-InAlAs double heterojunction P-i-I-N photodiodes. J. Lightwave. Technol. 2002, 20, 507−514. doi: 10.1109/50.989001
12. [12]
  Ni, H. J.; Liu, J. G.; Wang, Z. H.; Yang, S. Y. A review on colorless and optically transparent polyimide films: chemistry, process and engineering applications. J. Ind. Eng. Chem. 2015, 28, 16−27. doi: 10.1016/j.jiec.2015.03.013
13. [13]
  Mi, Z. M.; Liu, Z. X.; Yao, J. N.; Wang. C. B.; Zhou, C. J.; Wang. D. M.; Zhao, X. G.; Zhou, H. W.; Zhang, Y. M.; Chen, C. H. Transparent and soluble polyimide films from 1,4:3,6-dianhydro-D-mannitol based dianhydride and diamines containing aromatic and semiaromatic units: preparation, characterization, thermal and mechanical properties. Polym. Degrad. Stab. 2018, 151, 80−89. doi: 10.1016/j.polymdegradstab.2018.01.006
14. [14]
  Li, F.; Shen, J. L.; Liu, X. F.; Cao, Z. H.; Cai, X.; Li, J. L.; Ding, K.; Liu, J. K.; Tu, G. L. Flexible QLED and OPV based on transparent polyimide substrate with rigid alicyclic asymmetric isomer. Org. Electron. 2017, 51, 54−61. doi: 10.1016/j.orgel.2017.09.010
15. [15]
  Zhai, L.; Yang, S. Y.; Fan, L. Preparation and characterization of highly transparent and colorless semi-aromatic polyimide films derived from alicyclic dianhydride and aromatic diamines. Polymer 2012, 53, 3529−3539. doi: 10.1016/j.polymer.2012.05.047
16. [16]
  Yeo, H.; Goh, M.; Ku, B. C.; You, N. H. Synthesis and characterization of highly-fluorinated colorless polyimides derived from 4,4′-((perfluoro-[1,1′-biphenyl]-4,4′-diyl)bis(oxy))bis(2,6-dimethylaniline) and aromatic dianhydrides. Polymer 2015, 76, 280−286. doi: 10.1016/j.polymer.2015.09.019
17. [17]
  Jia, M. C.; Zhou, M. T.; Li, Y. J.; Lu, G. L.; Huang, X. Y. Construction of semi-fluorinated polyimides with perfluorocyclobutyl aryl ether-based side chains. Polym. Chem. 2018, 9, 920−930. doi: 10.1039/C8PY00004B
18. [18]
  Sato, S.; Ichikawa, M.; Suzuki, E.; Matsumoto, M.; Nagai, K. Photoelectric properties of ABA-type triblock copolymers designed using fluorine-containing polyimide macroinitiators with polyhedral oligomeric silsesquioxane. Polym. Eng. Sci. 2017, 57, 1207−1213.
19. [19]
  Zhuang, Y. B.; Seong, J. G.; Lee, Y. M. Polyimides containing aliphatic/alicyclic segments in the main chains. Prog. Polym. Sci. 2019, 92, 35−88. doi: 10.1016/j.progpolymsci.2019.01.004
20. [20]
  Nawaz, H.; Akhter, Z.; Iqbal, N. Study of physicochemical properties of meta and ortho trifluoromethyl substituted isomeric aromatic polyimides. Polym. Bull. 2017, 74, 3889−3906. doi: 10.1007/s00289-017-1927-0
21. [21]
  Lee, C. W.; Kwak, S. M.; Yoon, T. H. Synthesis and characterization of polyimides from bis(3-aminophenyl)-2,3,5,6-tetrafluoro-4-trifluoromethylphenyl phosphine oxide (mDA7FPPO). Polymer 2006, 47, 4140−4147. doi: 10.1016/j.polymer.2006.03.002
22. [22]
  Bong, S.; Yeo, H.; Ku, B. C.; Goh, M.; You, N. H. Highly soluble polyimide based on asymmetric diamines containing trifluoromethyl group for high performance dielectric material. Macromol. Res. 2018, 26, 85−91.
23. [23]
  Wang, C. Y.; Zhao, X. Y.; Li, G.; Jiang, J. M. High solubility and optical transparency of novel polyimides containing 3,3′,5,5′-tetramethyl pendant groups and 4-tert-butyltoluene moiety. Polym. Degrad. Stab. 2009, 94, 1526−1532. doi: 10.1016/j.polymdegradstab.2009.04.032
24. [24]
  Qian, C.; Bei, R. X.; Zhu, T. W.; Zheng, W. W.; Liu, S. W.; Chi, Z. G.; Aldred, M. P.; Chen, X. D.; Zhang, Y.; Xu, J. R. Facile strategy for intrinsic Low-k dielectric polymers: molecular design based on secondary relaxation behavior. Macromolecules 2019, 52, 4601−4609. doi: 10.1021/acs.macromol.9b00136
25. [25]
  Li, X. T.; Liu, T.; Jiao, Y. Z.; Dong, J.; Gan, F.; Zhao, X.; Zhang, Q. H. Novel high-performance poly(benzoxazole-co-imide) resins with low dielectric constants and superior thermal stabilities derived from thermal rearrangement of ortho-hydroxy polyimide oligomers. Chem. Eng. J. 2019, 359, 641−651. doi: 10.1016/j.cej.2018.11.175
26. [26]
  Amin, M.; Samy, H.; Küpper, J. Robust and accurate computational estimation of the polarizability tensors of macromolecules. J. Phys. Chem. Lett. 2019, 10, 2938−2943. doi: 10.1021/acs.jpclett.9b00963
27. [27]
  Yu, S. Z.; Wong, T. K. S.; Hu, X.; Pita, K. Synthesis and characterization of porous silsesquioxane dielectric films. Thin Solid Films 2005, 473, 191−195. doi: 10.1016/j.tsf.2004.03.040
28. [28]
  Liu, Y. W.; Qian, C.; Qu, L. J.; Wu, Y. N.; Zhang, Y.; Wu, X. H.; Zou, B. Y.; Chen, W. X.; Chen, Z. Q.; Chi, Z. G.; Liu, S. W.; Oigiviy, L. Y.; Xu, J. R. A bulk dielectric polymer film with intrinsic ultralow dielectric constant and outstanding comprehensive properties. Chem. Mater. 2015, 27, 6543−6549. doi: 10.1021/acs.chemmater.5b01798
29. [29]
  Chern, Y. T.; Tsai, J. Y. Low dielectric constant and high organosolubility of novel polyimide derived from unsymmetric 1,4-bis(4-aminophenoxy)-2,6-di-tert-butylbenzene. Macromolecules 2008, 41, 9556−9564. doi: 10.1021/ma802305q
30. [30]
  Chen, W. X.; Zhou, Z. X.; Yang, T. T.; Bei, R. X.; Zhang, Y.; Liu, S. W.; Chi, Z. G.; Chen, X. D.; Xu, J. R. Synthesis and properties of highly organosoluble and low dielectric constant polyimides containing non-polar bulky triphenyl methane moiety. React. Funct. Polym. 2016, 108, 71−77. doi: 10.1016/j.reactfunctpolym.2016.04.011
31. [31]
  Liu, Y. W.; Tang, L. S.; Qu, L. J.; Liu, S. W.; Chi, Z. G.; Zhang, Y.; Xu, J. R. Synthesis and properties of high-performance functional polyimides containing rigid nonplanar conjugated fluorene moieties. Chinese J. Polym. Sci. 2019, 37, 416−427. doi: 10.1007/s10118-019-2225-0
32. [32]
  Liu, Y. W.; Zhou, Z. X.; Qu, L. J.; Zou, B.; Chen, Z. Q.; Zhang, Y., Liu, S. W.; Chi, Z. G.; Chen, X. D.; Xu, J. R. Exceptionally thermostable and soluble aromatic polyimides with special characteristics: intrinsic ultralow dielectric constant, static random access memory behaviors, transparency and fluorescence. Mater. Chem. Front. 2017, 1, 326−337. doi: 10.1039/C6QM00027D
33. [33]
  Yang, H.; Cheng, X. P.; Cheng, X. X.; Pan, F. S.; Wu, H.; Liu, G. H.; Song, Y. M.; Cao, X. Z.; Jiang, Z. Y. Highly water-selective membranes based on hollow covalent organic frameworks with fast transport pathways. J. Membr. Sci. 2018, 565, 331−341. doi: 10.1016/j.memsci.2018.08.043
34. [34]
  Liu, H.; Zhai, L.; Bai, L.; He, M. H.; Wang, C. O.; Mo, S.; Fan, L. Synthesis and characterization of optically transparent semi-aromatic polyimide films with low fluorine content. Polymer 2019, 163, 106−114. doi: 10.1016/j.polymer.2018.12.045
35. [35]
  Tao, S. J. Positronium annihilation in molecular substances. J. Chem. Phys. 1972, 56, 5499−5510. doi: 10.1063/1.1677067
36. [36]
  Dlubek, G.; Stejny, J.; Alam, M. A. Effect of cross-linking on the free-volume properties of diethylene glycol bis(allyl carbonate) polymer networks: a positron annihilation lifletime study. Macromolecules 1998, 31, 4574−4580. doi: 10.1021/ma971801y
37. [37]
  Eldrup, M. M.; Lightbody, D.; Sherwood, J. N. The temperature dependence of positron lifetimes in solid pivalic acid. Phys. Chem. Chem. Phys. 1981, 63, 51−58.
38. [38]
  Ghaemy, M.; Berenjestanaki, F. R.; Bazzar, M. Organosoluble, thermally stable and low dielectric constant fluorinated polyimides containing 2,4,5-triphenylimidazole moiety in the main chains. Des. Monomers Polym. 2014, 17, 101−110. doi: 10.1080/15685551.2013.840473
1. [1]
  Zhen-He Wang , Xing Chen , Hai-Xia Yang , Jiang Zhao , Shi-Yong Yang . The In-plane Orientation and Thermal Mechanical Properties of the Chemically Imidized Polyimide Films. Chinese J. Polym. Sci, 2019, 37(3): 268-278. doi: 10.1007/s10118-019-2173-8
2. [2]
  Yi-Wu Liu , Li-Shuang Tang , Lun-Jun Qu , Si-Wei Liu , Zhen-Guo Chi , Yi Zhang , Jia-Rui Xu . Synthesis and Properties of High Performance Functional Polyimides Containing Rigid Nonplanar Conjugated Fluorene Moieties. Chinese J. Polym. Sci, 2019, 37(4): 416-427. doi: 10.1007/s10118-019-2225-0
3. [3]
  Chen-yi Wang , Wen-tao Chen , Chang Xu , Xiao-yan Zhao , Jian Li . Fluorinated Polyimide/POSS Hybrid Polymers with High Solubility and Low Dielectric Constant. Chinese J. Polym. Sci, 2016, 34(11): 1363-1372. doi: 10.1007/s10118-016-1845-x
4. [4]
  Xiuting Li , Xiaomeng Zhu , Jie Dong , Xin Zhao , Qinghua Zhang . Preparation of low-dielectric permittivity polyimide resins with high surface activity from chemically bonded hyperbranched polysiloxane. Chinese J. Polym. Sci, 2021, (): -. doi: 10.1007/s10118-021-2585-0
5. [5]
  Xiong-Fa Yang , Jia Liu , Qiong Chen , Yan-Ping Shen , Hong-Zhi Liu , Guo-Qiao Lai . A Low Temperature Vulcanized Transparent Silane Modified Epoxy Resins for LED Filament Bulb Package. Chinese J. Polym. Sci, 2018, 36(5): 649-654. doi: 10.1007/s10118-018-2028-8
6. [6]
  . SYNTHESIS AND PROPERTIES OF TRANSPARENT THIODIGLYCOL DIMETHACRYLATE COPOLYMER RESINS*. Chinese J. Polym. Sci, 2004, 22(1): 25-30.
7. [7]
  ZHANG Xuexin , HONG Huaimao , LI Zhuomei . STUDY ON THE MODIFICATION OF POLY (METHYL METHACRYLATE) TRANSPARENT MATERIAL*. Chinese J. Polym. Sci, 1992, 10(1): 1-7.
8. [8]
  Jia-yu Zhan , Guo-feng Tian , Zhan-peng Wu , Sheng-li Qi , De-zhen Wu . Preparation of Polyimide/BaTiO3/Ag Nanocomposite Films via in situ Technique and Study of Their Dielectric Behavior. Chinese J. Polym. Sci, 2014, 32(4): 424-431. doi: 10.1007/s10118-014-1413-1
9. [9]
  José Antonio Tec-Sánchez , Andrés Iván Oliva Arias , Manuel Aguilar-Vega , Juan Valerio Cauich-Rodríguez , José Luis Santiago-García . Preparation and Characterization of Flexible, Transparent and Thermally Stable Aromatic Co-polyamides. Chinese J. Polym. Sci, 2019, 37(2): 136-141. doi: 10.1007/s10118-019-2190-7
10. [10]
  Wei Chen , Mian Ji , Shi-yong Yang . High Thermal Stable Polyimide Resins Derived from Phenylethynylendcapped Fluorenyl Oligoimides with Low Melt Viscosities. Chinese J. Polym. Sci, 2016, 34(8): 933-948. doi: 10.1007/s10118-016-1813-5
11. [11]
  Chao Qian , Zhen-Guo Fan , Wei-Wen Zheng , Run-Xin Bei , Tian-Wen Zhu , Si-Wei Liu , Zhen-Guo Chi , Matthew P. Aldred , Xu-Dong Chen , Yi Zhang , Jia-Rui Xu . A Facile Strategy for Non-fluorinated Intrinsic Low-k and Low-loss Dielectric Polymers: Valid Exploitation of Secondary Relaxation Behaviors. Chinese J. Polym. Sci, 2020, 38(3): 213-219. doi: 10.1007/s10118-020-2339-4
12. [12]
  Qi Luo , Hong-Ting Pu , Zhi-Hua Zhang , Xiong Zhang , Cheng-Long Yu . Foam/Film Alternating Multilayer Structure with High Toughness and Low Thermal Conductivity Prepared via Microlayer Coextrusion. Chinese J. Polym. Sci, 2021, 39(5): 566-572. doi: 10.1007/s10118-021-2524-0
13. [13]
  Chan-juan Liu , Mei Mei , Xiang-lin Pei , Xiao-hua Huang , Chun Wei . Aromatic Polyimides with Tertbutyl-substituted and Pendent Naphthalene Units: Synthesis and Soluble, Transparent Properties. Chinese J. Polym. Sci, 2015, 33(8): 1074-1085. doi: 10.1007/s10118-015-1658-3
14. [14]
  Kun Xu , Yi-qing Hu . FABRICATION OF TRANSPARENT PU/ZrO2 NANOCOMPOSITE COATINGS WITH HIGH REFRACTIVE INDEX. Chinese J. Polym. Sci, 2010, 28(1): 13-20.
15. [15]
  Hui-Qin Cui , Rui-Xiang Peng , Wei Song , Jian-Feng Zhang , Jia-Ming Huang , Li-Qiang Zhu , Zi-Yi Ge . Optimization of Ethylene Glycol Doped PEDOT:PSS Transparent Electrodes for Flexible Organic Solar Cells by Drop-coating Method. Chinese J. Polym. Sci, 2019, 37(8): 760-766. doi: 10.1007/s10118-019-2257-5
16. [16]
  Yi-fan Zhao , Wen-jun Zou , Huan Li , Kun Lu , Wei Yan , Zhi-xiang Wei . Large-area, Flexible Polymer Solar Cell Based on Silver Nanowires as Transparent Electrode by Roll-to-Roll Printing. Chinese J. Polym. Sci, 2017, 35(2): 261-268. doi: 10.1007/s10118-017-1875-z
17. [17]
  Si-Ting Sun , Hang Wang , Dong Huang , Ying-Li Ding , Yang Zhang , Dong-Po Song , Kun-Yu Zhang , Li Pan , Yue-Sheng Li . Refractive Index Engineering as a Novel Strategy toward Highly Transparent and Tough Sustainable Polymer Blends. Chinese J. Polym. Sci, 2020, 38(12): 1335-1344. doi: 10.1007/s10118-020-2439-1
18. [18]
  WAN Meixiang , CAO Yong , LI Junchao , ZHOU Weixia , LI Suzhen . FREE STANDING FILM OF POLYANILINE. Chinese J. Polym. Sci, 1991, 9(3): 209-219.
19. [19]
  YANG Jiping , SUN Qiushi , HOU Xiaohuai , WAN Meixiang . GAS SEPARATION PROPERTIES OF FREESTANDING FILM OF POLYANILINE. Chinese J. Polym. Sci, 1993, 11(2): 121-124.
20. [20]
  NI Shaoru , YU Fusheng , SHEN Lianfang , QIAN Baogong . DIELECTRIC PROPERTIES OF 1, 2-POLYBUTADIENES. Chinese J. Polym. Sci, 1987, 5(2): 120-124.

Get Citation

PDF

XML

Article Metrics

PDF Downloads(2)
Abstract views(377)
HTML views(307)
Cited By(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142