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CLC number: TB381

On-line Access: 2013-07-01

Received: 2013-04-11

Revision Accepted: 2013-06-09

Crosschecked: 2013-06-21

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Citations:  Bibtex RefMan EndNote GB/T7714

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Journal of Zhejiang University SCIENCE A 2013 Vol.14 No.7 P.504-513


Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation*

Author(s):  Lei Zhang, Li Wang, Hao-jie Yu

Affiliation(s):  . State Key Laboratory of Chemical Engineering, Department of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China

Corresponding email(s):   opl_wl@zju.edu.cn

Key Words:  Dewetting behavior, Photoinduced morphology modulation, Atom transfer radical polymerization (ATRP), Block copolymer

Lei Zhang, Li Wang, Hao-jie Yu. Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation[J]. Journal of Zhejiang University Science A, 2013, 14(7): 504-513.

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author="Lei Zhang, Li Wang, Hao-jie Yu",
journal="Journal of Zhejiang University Science A",
publisher="Zhejiang University Press & Springer",

%0 Journal Article
%T Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation
%A Lei Zhang
%A Li Wang
%A Hao-jie Yu
%J Journal of Zhejiang University SCIENCE A
%V 14
%N 7
%P 504-513
%@ 1673-565X
%D 2013
%I Zhejiang University Press & Springer
%DOI 10.1631/jzus.A1300119

T1 - Surface pattern based on an azobenzene-containing copolymer thin film and its light-driven morphology modulation
A1 - Lei Zhang
A1 - Li Wang
A1 - Hao-jie Yu
J0 - Journal of Zhejiang University Science A
VL - 14
IS - 7
SP - 504
EP - 513
%@ 1673-565X
Y1 - 2013
PB - Zhejiang University Press & Springer
ER -
DOI - 10.1631/jzus.A1300119

A type of azobenzene-containing block copolymer polymethyl methacrylate-b-poly (n-butylmethacrylate-co-6-(4-(phenylazo) benzoate) hexyl methacrylate) (PMMA-b-(PnBMA-co-PAzoMA)) was synthesized by the atom transfer radical polymerization (ATRP). Macroinitiator polymethyl methacrylate (PMMA) was prepared by ATRP and used to initiate the copolymerization of monomer n-butyl methacrylate (nBMA) and azobenzene-based methacrylate monomer (AzoMA). Herein, three block copolymers with different molecular weights and block volume fractions were obtained and spin-coated on a silicon substrate or quartz plate before annealing at 180 °C for 14 h. The surface morphologies in these annealed copolymer films were observed by atomic force microscopy (AFM). Bicontinuous stripe or island patterns with different sizes were formed dependent on the film thickness. These ordered patterns are considered to be formed arising from the dewetting process of the surface layer in the copolymer film. Photoisomerization of azobenzene units in the copolymer films changed the dewetting behaviors of the surface layer of the thin film. Therefore, some copolymer annealed films showed a reversible morphology conversion between bicontinuous stripe and island structure when exposed to UV light and upon being stored in the dark. It was found that the composition of the block copolymer had obvious influences on the photoinduced morphology conversion behaviors in these copolymer thin films. When the volumes of PnBMA and PAzoMA phases in the block copolymer were large enough, the surface morphology could be modulated by UV light irradiation and storage in the dark. This work proposes a new possibility for photoinduced control and design of the dewetting processes of thin films using a linear block copolymer.

Darkslateblue:Affiliate; Royal Blue:Author; Turquoise:Article


[1] Aoki, K., Iwata, T., Nagano, S., Seki, T., 2010. Light-directed anisotropic reorientation of mesopatterns in block copolymer monolayers. Macromolecular Chemistry and Physics, 211(23):2484-2489. 

[2] Davis, K.A., Matyjaszewski, K., 2000. Atom transfer radical polymerization of tert-butyl acrylate and preparation of block copolymers. Macromolecules, 33(11):4039-4047. 

[3] Green, P.F., Limary, R., 2001. Block copolymer thin films: pattern formation and phase behavior. Advances in Colloid and Interface Science, 94(1-3):53-81. 

[4] Han, D., Tong, X., Zhao, Y., Zhao, Y., 2010. Block copolymers comprising π-conjugated and liquid crystalline subunits: induction of macroscopic nanodomain orientation. Angewandte Chemie International Edition, 49(48):9162-9165. 

[5] Jin, Q., Liu, G., Liu, X., Ji, J., 2010. Photo-responsive supramolecular self-assembly and disassembly of an azobenzene-containing block copolymer. Soft Matter, 6(21):5589-5595. 

[6] Kadota, S., Aoki, K., Nagano, S., Seki, T., 2005. Photocontrolled microphase separation of block copolymers in two dimensions. Journal of the American Chemical Society, 127(23):8266-8267. 

[7] Kadota, S., Aoki, K., Nagano, S., Seki, T., 2006. Morphological conversions of nanostructures in monolayers of an ABA triblock copolymer having azobenzene moiety. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 284-285(1):535-541. 

[8] Kim, J.K., Han, C.D., 2010. Phase behavior and phase transitions in AB- and ABA-type microphase-separated block copolymers. Advances in Polymer Science, 231(15):77-145. 

[9] Li, C., Lo, C., Zhu, D., Li, C., Liu, Y., Jiang, H., 2009. Synthesis of a photoresponsive liquid crystalline polymer containing azobenzene. Macromolecular Rapid Communications, 30(22):1928-1935. 

[10] Li, W., Dohi, T., Hara, M., Nagano, S., Haba, O., Yonetake, K., Seki, T., 2012. Phototriggered mass migration consorted with surface dewetting in thin films of a liquid crystalline azobenzene-containing dendrimer. Macromolecules, 45(16):6618-6627. 

[11] Limary, R., Green, P.F., 1999. Dewetting instabilities in thin block copolymer films: nucleation and growth. Langmuir, 15(17):5617-5622. 

[12] Lu, Z., Liu, Y., Hu, W., Lou, X., Li, C., 2011. Rewritable multicolor fluorescent patterns for multistate memory devices with high data storage capacity. Chemical Communications, 47(34):9609-9611. 

[13] Ma, M., He, Z., Yang, J., Wang, Q., Chen, F., Wang, K., Zhang, Q., Deng, H., Fu, Q., 2011. Vertical phase separation and liquid-liquid dewetting of thin PS/PCL blend films during spin coating. Langmuir, 27(3):1056-1063. 

[14] Morikawa, Y., Kondo, T., Nagano, S., Seki, T., 2007. Photoinduced 3D ordering and patterning of microphase-separated nanostructure in polystyrene-based block copolymer. Chemistry of Materials, 19(7):1540-1542. 

[15] Okano, K., Mikami, Y., Hidaka, M., Yamashita, T., 2011. Photoresponsive liquid-crystalline polymers containing a block mesogenic side chain: systematic studies on structural parameters for nanophase-separated structures. Macromolecules, 44(14):5605-5611. 

[16] Reiter, G., Auroy, P., Auvray, L., 1996. Instabilities of thin polymer films on layers of chemically identical grafted molecules. Macromolecules, 29(6):2150-2157. 

[17] Roos, S.G., Muller, A.H.E., 1999. Copolymerization of n-butyl acrylate with methyl methacrylate and PMMA macromonomers: comparison of reactivity ratios in conventional and atom transfer radical copolymerization. Macromolecules, 32(25):8331-8335. 

[18] Ruzette, A.V., Girault, S.T., Leibler, L., 2006. Molecular disorder and mesoscopic order in polydisperse acrylic block copolymers prepared by controlled radical polymerization. Macromolecules, 39(17):5804-5814. 

[19] Segalman, R.A., Green, P.F., 1999. Dynamics of rims and the onset of spinodal dewetting at liquid/liquid interfaces. Macromolecules, 32(3):801-807. 

[20] Sehgal, A., Ferreiro, V., Douglas, J.F., Amis, E.J., Karim, A., 2002. Pattern-directed dewetting of ultrathin polymer films. Langmuir, 18(18):7041-7048. 

[21] Seki, T., 2006. Photoresponsive self-assembly motions in polymer thin films. Current Opinion in Solid State and Materials Science, 10(5-6):241-248. 

[22] Seki, T., Kojima, J., Ichimura, K., 1999. Light-driven dot films consisting of single polymer chain. The Journal of Physical Chemistry B, 103(47):10338-10340. 

[23] Shipp, D.A., Wang, J.L., Matyjaszewski, K., 1998. Synthesis of acrylate and methacrylate block copolymers using atom transfer radical polymerization. Macromolecules, 31(23):8005-8008. 

[24] Sriprom, W., James, M., Perrier, S., Neto, C., 2009. Ordered microphase separation in thin films of PMMA-PBA synthesized by RAFT: effect of block polydispersity. Macromolecules, 42(8):3138-3146. 

[25] Sriprom, W., Neto, C., Perrier, S., 2010. Rapid photochromic nanopatterns from block copolymers. Soft Matter, 6(5):909-914. 

[26] Thompson, C.V., 2012. Solid state dewetting of thin films. Annual Review of Materials Research, 42:399-434. 

[27] Tokarczyk, K.K., Junginger, M., Belegrinou, S., Taubert, A., 2011. Amphiphilic polymers at interfaces. Advances in Polymer Science, 242(5):151-201. 

[28] Wang, X., Goswami, M., Kumar, R., Sumpter, B.G., Mays, J., 2012. Morphologies of block copolymers composed of charged and neutral blocks. Soft Matter, 8(11):3036-3052. 

[29] Xue, L., Agarwal, U., Lemstra, P., 2002. High molecular weight PMMA by ATRP. Macromolecules, 35(22):8650-8652. 

[30] Yan, D., Huang, H., Tian, H., Zhang, F., 2011. Coupling of microphase separation and dewetting in weakly segregated diblock co-polymer ultrathin films. Langmuir, 27(19):11973-11980. 

[31] You, J., Yoon, J.A., Kim, J., Huang, C., Matyjaszewski, K., Kim, E., 2010. Excimer emission from self-assembly of fluorescent diblock copolymer prepared by atom transfer radical polymerization. Chemistry of Materials, 22(15):4426-4434. 

[32] Yu, H., Iyoda, T., Ikeda, T., 2006. Photoinduced alignment of nanocylinders by supramolecular cooperative motions. Journal of the American Chemical Society, 128(34):11010-11011. 

[33] Yu, X., Luo, Y., Deng, Y., Yan, Q., Zou, G., Zhang, Q., 2008. Synthesis and properties of thermally cross-linkable main-chain azobenzene polymers containing diacetylene moieties. European Polymer Journal, 44(3):881-888. 

[34] Zhang, J., Yu, X., Yang, P., Peng, J., Luo, C., Huang, W., Han, Y., 2010. Microphase separation of block copolymer thin films. Macromolecular Rapid Communications, 31(7):591-608. 

[35] Zhao, Y., He, J., 2009. Azobenzene-containing block copolymers: the interplay of light and morphology enables new functions. Soft Matter, 5(14):2686-2693. 

[36] Zhao, Y., Tong, X., Zhao, Y., 2010. Photoinduced microphase separation in block copolymers: exploring shape incompatibility of mesogenic side groups. Macromolecular Rapid Communications, 31(11):986-990. 

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