Article
  • Residual Stress Behavior and Characterization of Polyimide Cross-linked Networks via Ring-opening Metathesis Polymerization
  • Nam KH, Seo J, Jang W, Han H
  • 개환 복분해 중합을 통한 가교형 폴리이미드 박막의 잔류응력 거동 및 특성 분석
  • 남기호, 서종철, 장원봉, 한학수
Abstract
Cross-linked polyimides (PIs) were synthesized by reacting 4,4'-(hexafluoroisopropylidene)-diphthalic anhydride (6FDA) and 2,2'-bis(trifluoromethyl)benzidine (TFDB) with various ratios of the cross-linkable, end-capping agent cis-1,2,3,6-tetrahydrophthalic anhydride (CDBA) via ring-opening metathesis polymerization. Residual stress behaviors were investigated in-situ during thermal imidization of the cross-linked PI precursors using a thin film stress analyzer (TFSA) by wafer bending method. The thermal properties were investigated via differential scanning calorimetry (DSC), thermomechanical analysis (TMA), and thermogravimetric analysis (TGA). The optical properties were measured by ultraviolet-visible spectrophotometer (UV-vis) and spectrophotometry. All properties were interpreted with respect to their morphology of cross-linked networks. With increasing the amounts of the end-capping agent, the residual stress decreased from 27.9 to -1.3 MPa, exhibited ultra-low stress and high thermal properties. The minimized residual stress and enhanced thermal properties of the cross-linked PI makes them potential candidates for versatile high-density multi-layer structure applications.

본 연구에서는 미세 전자 소자용 절연박막 및 차세대 플렉시블 디스플레이 기판으로서 사용이 기대되는 폴리이미드(PI)에 개환 복분해 중합(ring-opening metathesis polymerization)이 가능한 환형 말단 캡핑제(end-capping agent)인 cis-1,2,3,6-tetrahydrophthalic anhydride(CDBA)로 사슬 말단에 가교 반응이 된 가교형 폴리이미드를 합성하였다. 말단 캡핑제의 조성비에 따른 가교형 폴리이미드 박막의 잔류응력 거동은 thin film stress analyzer(TFSA)를 이용한 wafer bending mothod로 온도에 따라 연속적인 거동을 in-situ로 측정하였다. 열특성은 시차 주사 열량계(DSC), 열기계 분석기(TMA) 및 열 중량 분석기(TGA)를 이용하여 측정하였고, 광학 특성은 자외선/가시광선 분광광도계(UV-vis)와 색차계(spectrophotometer)를 이용하였으며, 네트워크 구조의 모폴로지(morphology) 변화를 통해 해석하였다. 말단 캡핑제의 조성비가 증가함에 따라 잔류응력은 27.9에서 -1.3 MPa로 초저응력 및 향상된 열 특성을 나타내었으나, 광학 특성은 감소됨을 보였다. 가교형 폴리이미드 박막의 우수한 특성 발현은 고집적도 다층 구조의 안정성 및 신뢰도가 요구되는 분야의 응용성이 확대될 것으로 기대된다.

Keywords: polyimide; ring-opening metathesis polymerization; cross-linked network; residual stress behavior; morphology.

References
  • 1. Ma SL, Kim YS, Lee JH, Kim JS, KIm I, Won JC, Polym. Korea, 29(2), 204 (2005)
  •  
  • 2. Tseng IH, Liao YF, Chiang JC, Tsai MH, Mater. Chem. Phys., 136(1), 247 (2012)
  •  
  • 3. Kovalev MK, Kalinina F, Androsov DA, Cho C, Polymer, 54, 127 (2013)
  •  
  • 4. Shin GJ, Chi JH, Zin WC, Chang T, Ree M, Jung JC, Polym. Korea, 30(2), 97 (2006)
  •  
  • 5. Yu YH, Yeh JM, Liou SJ, Chen CL, Liaw DJ, Lu HY, J. Appl. Polym. Sci., 92(6), 3573 (2004)
  •  
  • 6. Wei H, Fang X, Han Y, Hu B, Yan Q, Eur. Polym. J., 46, 246 (2010)
  •  
  • 7. Kim Y, Chang JH, Macromol. Res., 21(2), 228 (2013)
  •  
  • 8. Wuu DS, Chen TN, Lay E, Liu CH, Chang CH, Wei HF, Jiang LY, Lee HU, Chang YY, J. Electrochem. Soc., 157(2), C47 (2010)
  •  
  • 9. Myung BY, Kim JS, Kim JJ, Yoon TH, J. Polym. Sci. A: Polym. Chem., 41(21), 3361 (2003)
  •  
  • 10. Park JS, Chang JH, Polym. Korea, 32(6), 580 (2008)
  •  
  • 11. Koo M, Bae JS, Shim SE, Kim D, Nam DG, Lee JW, Lee GW, Yeum JH, Oh W, Colloid Polym. Sci., 289, 1503 (2011)
  •  
  • 12. Moghadam F, Moghadam K, Solid State Technol., 27, 149 (1984)
  •  
  • 13. Jeong KU, Kim JJ, Yoon TH, Polymer, 42(14), 6019 (2001)
  •  
  • 14. Liaw DJ, Wang KL, Huang YC, Lee KR, Lai JY, Ha CS, Prog. Polym. Sci, 37, 907 (2012)
  •  
  • 15. Sutthasupa S, Terada K, Sanda F, Masuda T, J. Polym. Sci. A: Polym. Chem., 44(18), 5337 (2006)
  •  
  • 16. Min U, Chang JH, Polym. Korea, 34(6), 495 (2010)
  •  
  • 17. Ree M, Nunes TL, Czornyj G, Volksen W, Polymer, 33, 1228 (1992)
  •  
  • 18. Chung H, Lee J, Hwang J, Han H, Polymer, 42(18), 7893 (2001)
  •  
  • 19. Chung H, Lee C, Han H, Polymer, 42(1), 319 (2001)
  •  
  • 20. Jang W, Seo J, Lee C, Paek SH, Han H, J. Appl. Polym. Sci., 113(2), 976 (2009)
  •  
  • 21. Park MH, Yang SJ, Jang W, Han H, Korean Chem. Eng. Res., 43(2), 305 (2005)
  •  
  • 22. Ree M, Kim K, Woo SH, Chang H, J. Appl. Phys., 81, 698 (1997)
  •  
  • 23. Jang WB, Lee HS, Lee SY, Choi SH, Shin DY, Han HS, Mater. Chem. Phys., 104(2-3), 342 (2007)
  •  
  • 24. Jang W, Shin D, Choi S, Park S, Han H, Polymer, 48(7), 2130 (2007)
  •  
  • 25. Jang W, Seo M, Seo J, Park S, Han H, Polym. Int., 57, 350 (2008)
  •  
  • 26. Bao C, Guo Y, Song L, Hu Y, J. Mater. Chem., 21, 13924 (2011)
  •  
  • 27. Shi J, Wang Y, Liu L, Bai H, Wu J, Jiang C, Zhou Z, Mater. Sci. Eng. A-Struct. Mater. Prop. Microstruct. Process., 512, 109 (2009)
  •  
  • 28. Hu G, Ma Y, Wang B, Mater. Sci. Eng. A-Struct. Mater. Prop. Microstruct. Process., 504, 8 (2009)
  •  
  • 29. Lee JY, Jang JS, Polymer, 47(9), 3036 (2006)
  •  
  • 30. Fan J, Hu X, Yue CY, Polym. Int., 52, 15 (2003)
  •  
  • 31. Sasaki T, Moriuchi H, Yano S, Yokota R, Polymer, 46(18), 6968 (2005)
  •  
  • 32. Liu JG, Zhao XJ, Fan HSL, Yang SY, High Perform. Polym., 18, 851 (2006)
  •  
  • 33. Maier G, Prog. Polym. Sci, 26, 3 (2001)
  •  
  • Polymer(Korea) 폴리머
  • Frequency : Bimonthly(odd)
    ISSN 0379-153X(Print)
    ISSN 2234-8077(Online)
    Abbr. Polym. Korea
  • 2022 Impact Factor : 0.4
  • Indexed in SCIE

This Article

  • 2014; 38(6): 752-759

    Published online Nov 25, 2014

  • Received on Apr 3, 2014
  • Accepted on May 17, 2014