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Korean Chemical Engineering Research,
Vol.49, No.5, 669-675, 2011
Vol.49, No.5, 669-675, 2011
칼릭스아렌 포로젠을 이용한 다공성 박막의 초기 나노기공 형성과정에 관한 연구
A study on the Initial Nanopore Formation in the Calix Arene Based Porogen Templated Porous Thin Film
다공성 구조로 되어있는 차세대 저유전 박막(k<2.0)의 나노 기공의 초기 형성 과정을 이해하기 위하여 실세스퀴옥산(silsesquioxane; SSQ) 매트릭스에서 분산된 4-tert-butyl calix[4]arene-O,O',O",O"'-tetraacetic acid tetraethyl ester(CA[4]) 포로젠이 열분해에 의해서 나노 기공으로 전환되는 과정을 Fourier Transform Infrared Spectroscopy(FT-IR)와 in-situ Position Annihilation Lifetime Spectroscopy(PALS) 연구를 통해 분석하였다. SSQ/CA[4] 하이브리드 시스템은 열 경화에 따라 효과적인 기공 구조의 균일한 박막을 제공하였다. SSQ/CA[4] 10, 20% 두 종류의 하이브리드 박막을 in-situ PALS 분석을 시행한 결과, CA[4] 포로젠의 분해 거동이 달랐다. SSQ/CA[4] 10% 하이브리드 박막은 300 ℃ 이상부터 단분자 포로젠으로부터 기인한 메조포어(~1.5 nm)가 생성되기 시작하였으나, SSQ/CA[4] 20% 하이브리드 박막은 상대적으로 낮은 온도인 250 ℃부터 상태로 CA[4] 분자들이 자가 조립된 마이셀로부터 기인한 메조포어(2.5~3.0 nm)가 생성되었다. 이는 SSQ/CA[4] 20% 하이브리드 박막에서 생성된 기공의 구조가 매우 연결된 상태이기 때문에 초기에 포로젠이 분해되었을 때, 분해된 분자조각들이 쉽게 박막 외부로 빠져나올 수 있기 때문이라고 생각된다.
Fourier Transform Infrared Spectroscopy and in-situ Position Annihilation Lifetime Spectroscopy(PALS) analysis of hybrid film, which consist of silsesquioxane(SSQ) and 4-tert-butyl calix[4]arene-O,O',O",O'"-tetraacetic acid tetraethyl ester(CA[4]) have been investigated in order to understand initial formation of nanopore in the next generation porous low-k dielectrics(k < 2.0). SSQ/CA[4] can provide effective homogeneous thin film having porous structure. The porogen decomposition behavior were completely different in the two kinds of SSQ/CA[4] based hybrid film (i.e. SSQ/CA[4] 10 and SSQ/CA[4] 20%). Relatively small pores(1.5 nm) come from dispersion of uni-molecular CA[4] in the SSQ matrix have been generated at 300 ℃, while mesopores(2.5~3.0 nm) induced from self assembled CA[4] have been generated at 250 ℃. It might be due to highly interconnected structure of SSQ/CA[4] 20% hybrid thin film resulting in facile evacuating of decomposed fragment of CA[4] molecule.
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