Journal of Polymer Research

, 25:192 | Cite as

Photo-sensitive bio-based copolymer containing cholic acids: novel functional materials for 248nm photoresist

  • Changwei Ji
  • Jingcheng LiuEmail author
  • Xiangfei Zheng
  • Ren Liu
  • Yan Yuan
  • Xiaoya Liu
  • Qidao Mu


Cholic acid is a class of biological compounds that exhibit valuable properties, and have been applied in many fields due to its special chemical structures for many areas. In this study, poly[(methacrylic acid tert-butyl cholate ester)-co-(acetoxy styrene)] [P(MATC-co-AS)] was synthesized from cholic acid, then the final copolymer poly[(methacrylic acid tert-butyl cholate ester)-co-(p-hydrostyrene)] [P(MATC-co-HS)] was obtained after P(MATC-co-AS) was hydrolysized. The structure and properties of the copolymers were determined through nuclear magnetic resonance, gel permeation chromatography, UV spectrometry, thermogravimetric analysis, and differential scanning calorimetry. The ultraviolet spectra of the copolymers indicate that they exhibit excellent optical transmittance at 248 nm. Moreover, the photolithography performance of a positive-tone photoresist based on the copolymers were evaluated using an KrF laser exposure system. The results indicate that a resolution of 0.25 μm could be achieved at a low exposure dose.


Bio-based Cholic acid Photoresist Resolution 



This work has been financially supported by the Fundamental Research Funds for the Central Universities (No.JUSRP51719A), the China Postdoctoral Foundation Project (No.2016M601712), and Postgraduate Research & Practice Innovation Program of Jiangsu Provence (No.KYCX217-1434, No.SJCX18_0619). Very thanks for Suzhou Rui Hong Electronic Chemicals Co., Ltd. and 13th Research Institute of China Electronics Technology Group Corporation for the Lithographic evaluations.

Supplementary material

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ESM 1 (DOC 1179 kb)


  1. 1.
    Zeng C, Seino H, Ren J, Hatanaka K, Yoshie N (2013) Bio-based furan polymers with self-healing ability. Macromolecules 46(5):1794–1802CrossRefGoogle Scholar
  2. 2.
    Feng Y, Liang H, Yang Z, Yuan T, Luo Y, Li P, Zhang C (2017) A Solvent-Free and Scalable Method To Prepare Soybean-Oil-Based Polyols by Thiol–Ene Photo-Click Reaction and Biobased Polyurethanes Therefrom. ACS Sustain. Chem. Eng. 5(8):7365–7373CrossRefGoogle Scholar
  3. 3.
    Liu R, Zhang X, Gao S, Liu X, Wang Z, Yan J (2016) Bio-based epoxy-anhydride thermosets from six-armed linoleic acid-derived epoxy resin. RSC Adv. 6(58):52549–52555CrossRefGoogle Scholar
  4. 4.
    Tan SQ, Abraham T, Ference D, Macosko CW (2011) Rigidpolyurethane foams from a soybean oil-based Polyol. Polymer 52(13):2840–2846CrossRefGoogle Scholar
  5. 5.
    Liu HH, Chen WT, Wu FC (2002) Characterization of negative tone photoresist based on acid catalyzed dehydration crosslinking of novolac resins having pendant carboxyl groups. J. Polym. Res. 9(4):251–256CrossRefGoogle Scholar
  6. 6.
    S. Chang, J. H. Yang, J. H. Chien, Y. D. Lee, Synthesis of a novel alkaline-developable photosensitive copolymer based on MMA, MAA, SM, and 2-HEMA-grafted GMA copolymer for an innovative photo-imageable dry-peelable temporary protective plastisol. J. Polym. Res. 20 (4) (2013) 115:1-11.Google Scholar
  7. 7.
    Yu J, Xu N, Liu Z, Wang L (2012) Novel one-component positive-tone chemically amplified i-line molecular glass photoresists. ACS Appl. Mater. Interfaces. 4(5):2591–2596CrossRefPubMedGoogle Scholar
  8. 8.
    Wei Q, Wang L (2015) Novel one-component positive-tone chemically amplified i-line molecular glass photoresist based on tannic acid. Chem. Res. Chin. Univ. 31(4):585–589CrossRefGoogle Scholar
  9. 9.
    Kim S, Marelli B, Brenckle MA, Mitropoulos AN, Gil ES, Tsioris K, Omenetto FG (2014) All-water-based electron-beam lithography using silk as a resist. Nat. nanotechnol. 9(4):306–310CrossRefPubMedGoogle Scholar
  10. 10.
    Sun YL, Li Q, Sun SM, Huang JC, Zheng BY, Chen QD, Sun HB (2015) Aqueous multiphoton lithography with multifunctional silk-centred bio-resists. Nat. commun 6(8612):1–10Google Scholar
  11. 11.
    Jiang B, Yang J, Li C, Zhang L, Zhang X, Yang P (2017) Water-Based Photo- and Electron-Beam Lithography Using Egg White as a Resist. Adv. Mater. Interfaces. 4(7):1–9CrossRefGoogle Scholar
  12. 12.
    Zhu XX, Nichifor M (2002) Polymeric materials containing bile acids. Acc. Chem. 35(7):539–546CrossRefGoogle Scholar
  13. 13.
    Thérien-Aubin H, Gautrot JE, Shao Y, Zhang J, Zhu XX (2010) Shape memory properties of main chain bile acids polymers. Polymer 51(1):22–25CrossRefGoogle Scholar
  14. 14.
    Mendonça PV, Serra AC, Silva CL, Simões S, Coelho JF (2013) Polymeric bile acid sequestrants—synthesis using conventional methods and new approaches based on “controlled”/living radical polymerization. Prog. Polym. Sci. 38(3-4):445–461CrossRefGoogle Scholar
  15. 15.
    Shi C, Yuan D, Nangia S, Xu G, Lam KS, Luo J (2014) A structure–property relationship study of the well-defined telodendrimers to improve hemocompatibility of nanocarriers for anticancer drug delivery. Langmuir 30(23):6878–6888CrossRefPubMedPubMedCentralGoogle Scholar
  16. 16.
    Anandkumar D, Rajakumar P (2017) Synthesis and anticancer activity of bile acid dendrimers with triazole as bridging unit through click chemistry. Steroids 125:37–46CrossRefPubMedGoogle Scholar
  17. 17.
    Kim JB, Lee BW, Kang JS (1999) Poly(t-butyl-3a-(5-norbornene-2-carbonyloxy)-7a,12a-dihydroxy-5bcholan-24-oate-co-maleic anhydride) for a 193-nm photoresist. Polymer 40:7423–7426CrossRefGoogle Scholar
  18. 18.
    Kim JB, Lee BW, Yun HJ, Kwon YG (2000) 193-nm Photoresists based on norbornene copolymers with derivatives of bile acid. Chem. Lett. 29(4):414–415CrossRefGoogle Scholar
  19. 19.
    Kim JB, Ko JS, Choi JH, Jang JH, Oh TH, Kim HW, Lee BW (2004) Synthesis and lithographic evaluation of poly [(methacrylic acid tert-butyl cholate ester)-co-(γ-butyrolactone-2-yl methacrylate)]. Polymer 45(16):5397–5401CrossRefGoogle Scholar
  20. 20.
    Wu L, Hu F, Wang Q, Wang J, Wang L (2017) Preparation of a Kind of Positive Chemically Amplified Deep UV Photoresist Material with High Sensitivity. Chem. J. Chin. Univ. 38(5):896–901Google Scholar
  21. 21.
    Li H, Zhou Z, Liu J, Xu W, Liu R, Liu X (2017) One-pot synthesis of molecular glass photoresists based on β-cyclodextrin containing a t-butyloxy carbonyl group for i-line lithography. Polymer. Bull. 74(4):1091–1101CrossRefGoogle Scholar
  22. 22.
    H. Li, J. Liu,; X. Zheng, C. Ji, Q. Mu, R. Liu, X. Liu, Synthesis of chemically amplified photoresist polymer containing four (Meth) acrylate monomers via RAFT polymerization and its application for KrF lithography. J. Polym. Res. 23 (5) (2016) 102 1-7.Google Scholar
  23. 23.
    Bonar-Law RP, Davis AP, Sanders JK (1990) New procedures for selectively protected cholic acid derivatives. Regioselective protection of the 12α-OH group, and t-butyl esterification of the carboxyl group. J. Chem. Soc, Perkin Transactions 1(8):2245–2250CrossRefGoogle Scholar
  24. 24.
    Li H, Liu J, Zheng X, Ji C, Mu Q, Liu R, Liu X (2016) Synthesis of a branched photosensitive copolymer and its application for negative-type photoresists. J. Appl. Polym. Sci. 133(3):1–7Google Scholar
  25. 25.
    Zheng X, Ji C, Zeng Q, Liu J, Liu R, Mu Q, Liu X (2017) Synthesis of novel copolymer based on precipitation polymerization and its application in positive-tone photoresist. J. Polym. Res. 24(11):198–205CrossRefGoogle Scholar
  26. 26.
    Frechet JM, Eichler E, Ito H, Willson CG (1983) Poly (p-tert-butoxycarbonyloxystyrene): a convenient precursor to p-hydroxystyrene resins. Polymer 24(8):995–1000CrossRefGoogle Scholar

Copyright information

© Springer Nature B.V. 2018

Authors and Affiliations

  • Changwei Ji
    • 1
    • 2
  • Jingcheng Liu
    • 1
    • 2
    Email author
  • Xiangfei Zheng
    • 1
    • 2
  • Ren Liu
    • 1
    • 2
  • Yan Yuan
    • 1
    • 2
  • Xiaoya Liu
    • 1
    • 2
  • Qidao Mu
    • 3
  1. 1.The Key Laboratory of synthestic and biological Colloids, Ministry of Education, School of Chemical and Material EngineeringJiangnan UniversityWuxiChina
  2. 2.International Research Centre for Photo responsible Functional Molecules & MaterialsJiangnan UniversityWuxiChina
  3. 3.Suzhou Rui Hong Electronic Chemicals Co., Ltd.SuzhouChina

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