Polybenzoxazole/graphene nanocomposite for etching hardmask

Seung-Wook Shin; Jong Seon Kim; Seon Joon Kim; Dae Woo Kim; Hee-Tae Jung

Journal of Industrial and Engineering Chemistry, Vol.75, 296-303, July, 2019

DOI10.1016/j.jiec.2019.03.042 Export Citation

Polybenzoxazole/graphene nanocomposite for etching hardmask

Seung-Wook Shin, Jong Seon Kim, Seon Joon Kim¹, Dae Woo Kim^{2, †}, and Hee-Tae Jung^†

Department of Chemical and Biomolecular Engineering (BK-21 plus) & KAIST Institute for Nanocentury, Korea Advanced Institute of Science and Technology, Daejeon, 34141, Republic of Korea
¹Materials Architecturing Research Center, Korea Institute of Science and Technology (KIST), Seoul, 02792, Republic of Korea
²Department of Chemical and Biomolecular Engineering, Yonsei University, 50, Yonsei-ro, Seodaemun-gu, Seoul, 03722, Republic of Korea

E-mail:,

We demonstrate that graphene can enhance the etch resistance of polymeric hardmask significantly. Graphene oxide with a sub-micrometer diameter (nGO) was functionalized with fluorinated poly (hydroxyamide) (FPHA) via a chemical coupling reaction. The FPHA-functionalized-nGO can be dispersed in various organic solvents including methanol, cyclohexanone, dimethylformamide, and N-methyl pyrrolidone. In addition, the dispersions were spincoated to prepare hardmask films which were then thermally annealed to produce nRGO-fluorinated-polybenzoxazole (FPBO) film. Compared to pristine FPBO film, elastic modulus (122%), hardness (92%), and etch resistance (54%) were significantly enhanced at 17 wt.% graphene loading, surpassing the properties of commercial CHM009 film.

Keywords:Hardmask;Composite;Grapheme oxide;Patterning;Etch resistance

[References]

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Sakai I, Abe J, Hayashi H, Taniguchi Y, Kato H, et al., Jpn. J. Appl. Phys., 46, 4286 (2007)
Kofuji N, Negishi N, Ishimura H, Nishida T, Jpn. J. Appl. Phys., 53, 03DE01 (2014)
Zanchetta E, Della Giustina G, Grenci G, Pozzato A, Tormen M, Brusatin G, Adv. Mater., 25(43), 6261 (2013)
Oh C, Uh DS, Kim DH, Lee JK, Yun HC, et al., Proc. SPIE, 6519, 65192R (2007)
Oh C, Lee JK, Kim MS, Yoon KH, Cheon HS, et al., Proc. SPIE, 6923, 69232V (2008)
Cheon GS, Yoon KH, Kim MS, Oh SB, Song JY, et al., Proc. SPIE, 7140, 71402R (2008)
Cheon HS, Yoon KH, Kim MS, Oh SB, Song JY, et al., Proc. SPIE, 7273, 727310 (2009)
Gokan H, Esho S, Ohnish Y, J. Electrochem. Soc., 130, 143 (1983)
Kudo T, Rahman MD, McKenzie D, Anyadiegwu C, Doerrenbaecher S, et al., Proc. SPIE, 9051, 90511X (2014)
Haghi AK, Thomas S, Praveen KM, Pai AR, Apple Academic Press, Florida, 2018.
Haghi AK, Aguilar CN, Thomas S, Praveen KM, Physical Chemistry for Engineering and Applied Sciences, Apple Academic Press, Florida, 2018.
Lu X, Huang H, Nemchuk N, Ruoff RS, Appl. Phys. Lett., 75, 193 (1999)
Sakai I, Abe J, Hayashi H, Taniguchi Y, Kato H, et al., J. Appl. Phys., 46, 4286 (2007)
Glodde M, Engelmann S, Guillorn M, Kanakasabapathy S, Mclellan E, et al., Proc. SPIE, 7972, 797216 (2011)
Wakamatsu G, Goto K, Hishiro Y, Furukawa T, Murakami S, et al., Proc. SPIE, 8325, 83250T (2012)
Chang JH, Park KM, Lee SM, Oh JB, J. Polym. Sci. B: Polym. Phys., 38(19), 2537 (2000)
Frommhold A, Manyam J, Palmer RE, Robinson APG, Microelectron. Eng., 98, 552 (2012)
Kim DW, Choi J, Kim D, Jung HT, J. Mater. Chem. A, 4, 17773 (2016)
Kim D, Kim DW, Lim HK, Jeon J, Kim H, et al., Phys. Chem. Chem. Phys., 16, 22717 (2014)
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Baibarac M, Lapkowski M, Pron A, Lefrant S, Baltog I, J. Raman Spectrosc., 29, 825 (1998)
Lim J, Kim MC, Goh M, Yeo H, Shin DG, Ku BC, You NH, Carbon Lett., 14, 251 (2013)
Li Z, Young RJ, Wang RG, Yang F, Hao LF, Jiao WC, Liu WB, Polymer, 54(21), 5821 (2013)
Bortz DR, Heras EG, Martin-Gullon I, Macromolecules, 45(1), 238 (2012)
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Seino Y, Kobayashi K, Sho K, Kato H, Miyoshi S, et al., Proc. SPIE 6923, 6923O-6923O-8 (2008).

[1] Wu W, Chang EY, Cheon H, Kim SK, Cho HM, et al., Proc. SPIE, 7140, 71402Q (2008)

[2] Sakai I, Abe J, Hayashi H, Taniguchi Y, Kato H, et al., Jpn. J. Appl. Phys., 46, 4286 (2007)

[3] Kofuji N, Negishi N, Ishimura H, Nishida T, Jpn. J. Appl. Phys., 53, 03DE01 (2014)

[4] Zanchetta E, Della Giustina G, Grenci G, Pozzato A, Tormen M, Brusatin G, Adv. Mater., 25(43), 6261 (2013)

[5] Oh C, Uh DS, Kim DH, Lee JK, Yun HC, et al., Proc. SPIE, 6519, 65192R (2007)

[6] Oh C, Lee JK, Kim MS, Yoon KH, Cheon HS, et al., Proc. SPIE, 6923, 69232V (2008)

[7] Cheon GS, Yoon KH, Kim MS, Oh SB, Song JY, et al., Proc. SPIE, 7140, 71402R (2008)

[8] Cheon HS, Yoon KH, Kim MS, Oh SB, Song JY, et al., Proc. SPIE, 7273, 727310 (2009)

[9] Gokan H, Esho S, Ohnish Y, J. Electrochem. Soc., 130, 143 (1983)

[10] Kudo T, Rahman MD, McKenzie D, Anyadiegwu C, Doerrenbaecher S, et al., Proc. SPIE, 9051, 90511X (2014)

[11] Haghi AK, Thomas S, Praveen KM, Pai AR, Apple Academic Press, Florida, 2018.

[12] Haghi AK, Aguilar CN, Thomas S, Praveen KM, Physical Chemistry for Engineering and Applied Sciences, Apple Academic Press, Florida, 2018.

[13] Lu X, Huang H, Nemchuk N, Ruoff RS, Appl. Phys. Lett., 75, 193 (1999)

[14] Sakai I, Abe J, Hayashi H, Taniguchi Y, Kato H, et al., J. Appl. Phys., 46, 4286 (2007)

[15] Glodde M, Engelmann S, Guillorn M, Kanakasabapathy S, Mclellan E, et al., Proc. SPIE, 7972, 797216 (2011)

[16] Wakamatsu G, Goto K, Hishiro Y, Furukawa T, Murakami S, et al., Proc. SPIE, 8325, 83250T (2012)

[17] Chang JH, Park KM, Lee SM, Oh JB, J. Polym. Sci. B: Polym. Phys., 38(19), 2537 (2000)

[18] Frommhold A, Manyam J, Palmer RE, Robinson APG, Microelectron. Eng., 98, 552 (2012)

[19] Kim DW, Choi J, Kim D, Jung HT, J. Mater. Chem. A, 4, 17773 (2016)

[20] Kim D, Kim DW, Lim HK, Jeon J, Kim H, et al., Phys. Chem. Chem. Phys., 16, 22717 (2014)

[21] Kubota T, Nakanishi R, J. Polym. Sci. B: Polym. Phys., 2, 655 (1964)

[22] Kim SJ, Kim DW, Jung HT, RSC Adv., 3, 22909 (2013)

[23] Joen HJ, Kim KH, Baek Y, Kim DW, Jung HT, Nano Lett., 10, 3604 (2010)

[24] Chen D, Feng HB, Li JH, Chem. Rev., 112(11), 6027 (2012)

[25] Lee C, Wei X, Kysar JW, Hone J, Science, 321, 385 (2008)

[26] Mittal G, Dhand V, Rhee KY, Park SJ, Lee WR, J. Ind. Eng. Chem., 21, 11 (2015)

[27] Pei S, Cheng H, Carbon, 50, 3210 (2012)

[28] Mallamace F, Corsaro C, Mallamace D, Vasi S, Vasi C, Dugo G, Comput. Struct. Biotechnol. J., 13, 33 (2015)

[29] Nam YT, Choi J, Kang KM, Kim DW, Jung HT, ACS Appl. Mater. Interfaces, 8, 27376 (2016)

[30] Hung W, Tsou C, Guzman M, An Q, Liu Y, et al., Chem. Mater., 26, 2983 (2014)

[31] Kim H, Kim DW, Vasagar V, Ha H, Nazarenko S, Ellison CJ, Adv. Funct. Mater., 28, 180317 (2018)

[32] Chen Y, Zhuang Q, Liu X, Liu J, Lin S, Han Z, Nanotechnology, 24, 245702 (2013)

[33] Liu WW, Chai SP, Mohamedc AR, Hashim U, J. Ind. Eng. Chem., 20(4), 1171 (2014)

[34] Baibarac M, Lapkowski M, Pron A, Lefrant S, Baltog I, J. Raman Spectrosc., 29, 825 (1998)

[35] Lim J, Kim MC, Goh M, Yeo H, Shin DG, Ku BC, You NH, Carbon Lett., 14, 251 (2013)

[36] Li Z, Young RJ, Wang RG, Yang F, Hao LF, Jiao WC, Liu WB, Polymer, 54(21), 5821 (2013)

[37] Bortz DR, Heras EG, Martin-Gullon I, Macromolecules, 45(1), 238 (2012)

[38] Lim J, Yeo H, Goh M, Ku BC, Kim SG, et al., Chem. Mater., 27, 2040 (2015)

[39] Seino Y, Kobayashi K, Sho K, Kato H, Miyoshi S, et al., Proc. SPIE 6923, 6923O-6923O-8 (2008).