本研究利用Terephthaloyl chloride (TC)、3,3'-Dihydroxybenzidine(DHB)、以及2,2'-Bis(1,3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF)三種單體進行低溫聚縮合(low temperature polycondensation)反應，合成出四種不同結構的可溶性聚苯噁唑前驅物(polyhydroxyamide，PHA)。本實驗藉由改變DHB以及BisAPAF單體的合成比例來降低高分子的熱膨脹係數(CTE)，當此兩單體的添加莫耳比為1：1時，再與TC單體反應，所得到的PHA將其命名為50DHB-PHA，經高溫環化(curing)反應後可得到熱膨脹係數小於20 ppm/℃的聚苯噁唑(Polybenzoxazole，PBO)。且50DHB-PHA在有機溶劑NMP及DMAc中具有不錯的溶解度。由熱機械分析(TMA)可得知CTE隨著DHB單體添加量增加而下降，而玻璃轉移溫度(Tg)則隨DHB單體添加量增加而增加，當DHB添加比例為50%時，PBO的CTE為18 ppm/℃，玻璃轉移溫度為372℃。由熱重損失分析、拉伸測試、紫外-可見光光譜分析可知PBO的熱穩定性以及機械強度隨DHB單體添加量增加而增加，但透光度隨DHB單體添加量增加而降低。

Four kinds of low CTE polybenzoxazole precursors, polyhydroxyamides (PHAs), were synthesized by low temperature polymerization of 3,3'-dihydroxybenzidine (DHB), 2,2'-Bis(1,3-amino-4-hydroxyphenyl)hexafluoropropane (BisAPAF) and terephthaloyl chloride (TC) in NMP. These polymers were characterized by FT-IR, 1H-NMR, XRD, TMA, TGA, UV-Visible and universal testing machine. The inherent viscosities of these precursors were in the range of 0.42–0.89 dL/g. All of these polymers could be solution-cast into flexible and tough films. The cut off wavelength of polyhydroxyamides were in the range of 348–426 nm. After curing, these polybenzoxazoles (PBOs) showed CTE and Tg in the range of 18–41 ppm/℃ and 341–372℃, respectively. The polybenzoxazoles also showed good thermal stability, with 5% weight loss temperature being recorded above 500°C in air or nitrogen atmosphere. The strength of polybenzoxazoles was above 60MPa. The water uptake of these polybenzoxazoles was all below 1%. All polyhydroxyamides and polybenzoxazoles were amorphous.

[1] P. Ganrou, W. B. Rogers, D. M. Scheck, A. J. Strandjord, Y. Ida, and K. Ohba, "Stress-buffer and passivation processes for Si and GaAs IC's and passive components using photosensitive BCB: process technology and reliability data," Advanced Packaging, IEEE Transactions on, vol. 22, pp. 487-498, 1999.
[2] G. Maier, S. Banerjee, J. Haußmann, and R. Sezi, "High-temperature polymers for advanced microelectronics," High Performance Polymers, vol. 13, pp. S107-S115, 2001.
[3] S. L. C. Hsu, C. Y. Lin, and S. W. Chuang, "Positive‐working aqueous base developable photosensitive polybenzoxazole precursor/organoclay nanocomposites," Journal of applied polymer science, vol. 97, pp. 2350-2356, 2005.
[4] T. Hirano, K. Yamamoto, and K. Imamura, "Application for WLP at positive working photosensitive polybenzoxazole," in University/Government/Industry Microelectronics Symposium, 2003. Proceedings of the 15th Biennial, 2003, pp. 246-249.
[5] H.-s. Noh, K.-s. Moon, A. Cannon, P. J. Hesketh, and C. Wong, "Wafer bonding using microwave heating of parylene intermediate layers," Journal of Micromechanics and Microengineering, vol. 14, p. 625, 2004.
[6] J. Yota, H. Ly, R. Ramanathan, H.-C. Sun, D. Barone, T. Nguyen, et al., "Variable Frequency Microwave and Convection Furnace Curing of Polybenzoxazole Buffer Layer for GaAs HBT Technology," Semiconductor Manufacturing, IEEE Transactions on, vol. 20, pp. 323-332, 2007.
[7] J. Yota, "Interlevel dielectric processes using PECVD silicon nitride, polyimide, and polybenzoxazole for GaAs HBT technology," Journal of The Electrochemical Society, vol. 156, pp. G173-G179, 2009.
[8] M. Topper, T. Fischer, T. Baumgartner, and H. Reichl, "A comparison of thin film polymers for Wafer Level Packaging," in Electronic Components and Technology Conference (ECTC), 2010 Proceedings 60th, 2010, pp. 769-776.
[9] B. Wunderle, E. Dermitzaki, O. Hölck, J. Bauer, H. Walter, Q. Shaik, et al., "Molecular dynamics approach to structure–property correlation in epoxy resins for thermo-mechanical lifetime modeling," Microelectronics Reliability, vol. 50, pp. 900-909, 2010.
[10] A. Tokoh, "Photosensitive polymers," Kansai Research Institute, pp. 89-90, 1999.
[11] M. Hasegawa, Y. Tsujimura, K. Koseki, and T. Miyazaki, "Poly(ester imide)s Possessing Low CTE and Low Water Absorption (II). Effect of Substituents," Polymer Journal, vol. 40, pp. 56-67, 2007.
[12] J. Ishii and T. Akamatsu, "Organo-Soluble Low CTE Polyimides and their Applications to Photosensitive Cover Layer Materials in Flexible Printed Circuit Boards," High Performance Polymers, vol. 21, pp. 123-138, 2009.
[13] N. Sensui, J. Ishii, A. Takata, Y. Oami, M. Hasegawa, and R. Yokota, "Ultra-Low CTE and Improved Toughness of PMDA/PDA Polyimide-based Molecular Composites Containing Asymmetric BPDA-type Polyimides," High Performance Polymers, vol. 21, pp. 709-728, 2008.
[14] M. Hasegawa, J. Kobayashi, and L. Vladimirov, "Solution-processable low-CTE polybenzoxazoles," Journal of Photopolymer Science and Technology, vol. 17, pp. 253-258, 2004.
[15] S. L.-C. Hsu and W.-C. Chen, "A novel positive photosensitive polybenzoxazole precursor for microelectronic applications," Polymer, vol. 43, pp. 6743-6750, 2002.
[16] Y. S. Kazuya Ebara, and Mitsuru Ueda, "Direct Synth esis of Photosensitive Poly(benzoxazole)," Journal of Photopolymer Science and Technology, vol. 14, pp. 55-60, 2001.
[17] Y. Maruyama, Y. Oishi, M. Kakimoto, and Y. Imai, "Synthesis and properties of fluorine-containing aromatic polybenzoxazoles from bis (o-aminophenols) and aromatic diacid chlorides by the silylation method," Macromolecules, vol. 21, pp. 2305-2309, 1988.
[18] J. McPherson and C. Dunn, "A model for stress‐induced metal notching and voiding in very large‐scale‐integrated Al–Si (1%) metallization," Journal of Vacuum Science & Technology B, vol. 5, pp. 1321-1325, 1987.
[19] F. Yost, "Voiding due to thermal stress in narrow conductor lines," Scripta metallurgica, vol. 23, pp. 1323-1328, 1989.
[20] A. E. Lozano, J. de Abajo, J. de la Campa, and J. Preston, "Aromatic polyamides with pendent heterocycles: 2. Benzoxazole groups," Polymer, vol. 35, pp. 1317-1321, 1994.
[21] 洪慶煌, "聚對二唑苯及其複合材料之特性研究," 長庚大學醫學暨工程學院學位論文, 1997.
[22] 日本東洋紡公司, ", www.toyobo.co.jp," 1999.
[23] E. W. Choe and S. N. Kim, "Synthesis, spinning, and fiber mechanical properties of poly (p-phenylenebenzobisoxazole)," Macromolecules, vol. 14, pp. 920-924, 1981.
[24] S. L.-C. Hsu, K.-S. Lin, and C. Wang, "Preparation of polybenzoxazole fibers via electrospinning and postspun thermal cyclization of polyhydroxyamide," Journal of Polymer Science Part A: Polymer Chemistry, vol. 46, pp. 8159-8169, 2008.
[25] H. H. Yang, "Aromatic high-strength fibers," 1989.
[26] J. Newell, D. Rogers, D. Edie, and C. Fain, "Direct carbonization of PBO fiber," Carbon, vol. 32, pp. 651-658, 1994.
[27] T. Kitagawa, H. Murase, and K. Yabuki, "Morphological study on poly‐p‐phenylenebenzobisoxazole (PBO) fiber," Journal of Polymer Science Part B: Polymer Physics, vol. 36, pp. 39-48, 1998.
[28] 陳琬琪, "正型鹼性水溶液顯影耐高溫感光性聚苯噁唑之研究," 成功大學材料科學及工程學系學位論文, pp. 1-107, 2002.
[29] 林佳儀, "正型水性顯影聚苯噁唑/黏土奈米感光 複合材料之研究," 成功大學材料科學及工程學系學位論文, pp. 1-107, 2004.
[30] J. H. Chang, D. K. Park, and K. J. Ihn, "Montmorillonite‐based nanocomposites of polybenzoxazole: Synthesis and characterization (I)," Journal of Polymer Science Part B: Polymer Physics, vol. 39, pp. 471-476, 2001.
[31] T. Fukumaru, T. Fujigaya, and N. Nakashima, "Mechanical Reinforcement of Polybenzoxazole by Carbon Nanotubes through Noncovalent Functionalization," Macromolecules, vol. 46, pp. 4034-4040, 2013.
[32] 王盟傑, "微電子用正型鹼性水溶液顯影聚苯噁唑共聚物合成與性質之研究," 成功大學材料科學及工程學系學位論文, pp. 1-135, 2006.
[33] 許瑋壬, "微電子用低溫環化正型感光性聚苯噁唑聚合物之研究," 成功大學材料科學及工程學系學位論文, pp. 1-126, 2011.
[34] J. H. Hodgkin, M. S. Liu, B. N. Dao, J. Mardel, and A. J. Hill, "Reaction mechanism and products of the thermal conversion of hydroxy-containing polyimides," European Polymer Journal, vol. 47, pp. 394-400, 2011.
[35] O. Y. Rusakova, Y. V. Kostina, A. S. Rodionov, G. N. Bondarenko, A. Y. Alent’ev, T. K. Meleshko, et al., "Study of the mechanism of the thermochemical reaction of polyimides with hydroxyl groups via vibrational-spectroscopy and quantum-chemistry methods," Polymer Science Series A, vol. 53, pp. 791-799, 2011.
[36] H. Wang, T.-S. Chung, and D. R. Paul, "Thickness dependent thermal rearrangement of an ortho-functional polyimide," Journal of Membrane Science, vol. 450, pp. 308-312, 2014.
[37] J. F. Wolfe, B. H. Loo, and F. Arnold, "Rigid-rod polymers. 2. Synthesis and thermal properties of para-aromatic polymers with 2, 6-benzobisthiazole units in the main chain," Macromolecules, vol. 14, pp. 915-920, 1981.
[38] G. Yang, Z. Xue, K. Zhang, X. Liu, X. Li, Q. Zhuang, et al., "Synthesis and Characterization of Polybenzobisoxazole Polymers Containing Trifluoromethyl or Sulfone Groups," Journal of Macromolecular Science, Part B, vol. 53, pp. 412-427, 2014.
[39] X.-H. Xu, X.-Y. Liu, Q.-X. Zhuang, and Z.-W. Han, "Rigid-rod polybenzoxazoles containing perylene bisimide: Synthesis, structures and photophysical properties," Journal of Applied Polymer Science, vol. 116, pp. 455-460, 2010.
[40] J. F. Wolfe and F. Arnold, "Rigid-rod polymers. 1. Synthesis and thermal properties of para-aromatic polymers with 2, 6-benzobisoxazole units in the main chain," Macromolecules, vol. 14, pp. 909-915, 1981.
[41] M. Ueda and H. Sugita, "Poly (Benzimidazole) synthesis by direct reaction of methoxyphthalic acids and tetramine," Journal of Polymer Science Part A: Polymer Chemistry, vol. 27, pp. 2815-2818, 1989.
[42] P. Morgan, "Low‐temperature solution polycondensation," in Journal of Polymer Science Part C: Polymer Symposia, 1963, pp. 1075-1096.
[43] T. Kubota and R. Nakanishi, "Preparation of fully aromatic polybenzoxazoles," Journal of Polymer Science Part B: Polymer Letters, vol. 2, pp. 655-659, 1964.
[44] S. H. Hsiao and L. R. Dai, "Synthesis and properties of novel aromatic poly (o‐hydroxy amide) s and polybenzoxazoles based on the bis (ether benzoyl chloride) s from hydroquinone and its methyl‐, tert‐butyl‐, and phenyl‐substituted derivatives," Journal of Polymer Science Part A: Polymer Chemistry, vol. 37, pp. 2129-2136, 1999.
[45] W. Joseph, J. Abed, R. Mercier, and J. E. Mcgrath, "Synthesis and characterization of fluorinated polybenzoxazoles via solution cyclization techniques," Polymer, vol. 35, pp. 5046-5050, 1994.
[46] T. Yamaoka, N. Nakajima, K. i. Koseki, and Y. Maruyama, "A study of novel heat‐resistant polymers: Preparation of photosensitive fluorinated polybenzoxazole precursors and physical properties of polybenzoxazoles derived from the precursors," Journal of Polymer Science Part A: Polymer Chemistry, vol. 28, pp. 2517-2532, 1990.
[47] M. Ghosh and K. Mittal, "Polyimides: fundamentals and applications, 1996," Marcel Dekker: New York, NY).(b) M. Tomikawa, S. Yoshida, N. Okamoto, Polym. J, vol. 41, p. 604, 2009.
[48] T. Dang, P. Mather, M. Alexander, C. Grayson, M. Houtz, R. Spry, et al., "Synthesis and characterization of fluorinated benzoxazole polymers with high Tg and low dielectric constant," Journal of Polymer Science Part A: Polymer Chemistry, vol. 38, pp. 1991-2003, 2000.
[49] L. Tao, H. Yang, J. Liu, L. Fan, and S. Yang, "Synthesis of fluorinated polybenzoxazoles with low dielectric constants," Journal of Polymer Science Part A: Polymer Chemistry, vol. 48, pp. 4668-4680, 2010.
[50] W. Huang, S. Li, C. Du, M. Xie, Y. Zhang, and J. Yin, "Synthesis and characterization of new cardo poly (bisbenzoxazole) s containing fluorenylidene unit," European Polymer Journal, vol. 45, pp. 3187-3195, 2009.