高分子薄膜表征技术

曾娴; 杨朝晖; 张晓华

doi:10.7498/aps.65.176801

摘要

随着纳米技术在微电子、生物医药、能源等领域的快速发展，如何在纳米尺度构筑性能稳定、性质均一的多功能纳米器件已成为纳米科技领域最具有挑战性的前沿技术之一。具有广泛应用前景的高分子薄膜的制备、性质以及应用研究一直以来都受到学术界与工业界的高度关注对高分子薄膜的内部结构、表面形貌、机械性能、电化学性能等的检测一直是高分子领域的主要研究热点之一。本文综述了高分子薄膜的测试方法，包括原子力显微镜、电子显微镜、X 光散射、中子散射、椭圆偏振光等表征技术.

关键词:

高分子薄膜 /
纳米 /
表征技术

Abstract

The nanotechnology has emerged as an effective tool to fabricate next-generation microelectronics, biologically responsive materials, and structured membranes. The self-assembly of nanoscale phases has extensively been studied in thin films because of their potential applications in sub-100 nm structures. The control of the ordering of nanaoscale patterns is critical for various technological applications. A variety of approaches such as topographical and chemical patterning have resulted in an enhancement in long-range orders of nanoscale patterns. The macroscopically large areas of nanoscale domains with single-crystal order in polymer thin films can be utilized to fabricate portable ultra-high density data storages, advanced sensors and ultra-light electronic devices. However, as pattern size decreases below 100 nm, there appear many new challenges such as the cost of patterning and the precise control of the line edge roughness and line width roughness. Precisely controlling nanostructure shapes and placements in material is a continuing challenge. Measurement platform to provide accurate and detailed information about nanostructure orientations and placements is a key to this challenge. In this review, we examine the recent progress of characterization tools in polymer thin films. We highlight our efforts to control surface pattern formations of polymer thin films and our use of statistically-useful scattering techniques and real-space imaging tools to quantify the order of nanoscale patterns. In some technological applications of biological membranes, such as chemical separations, drug delivery and sensors, the orientation distribution of nanostructures is often more important. The real-space imaging methods of characterizing the orientation distribution of nanostructures, such as cross-sectional electron microscopy measurements and depth profiling by alternating etch and surface imaging steps are readily performed on thin polymer films over large areas. However, these real-space imaging techniques are destructive measures of nanostructures in polymer thin films. Also it is challenging to in-situ measure the evolution of orientation of nanoscale patterns during processing by using these destructive real-space imaging techniques. Rotational small-angle neutron scattering (RSANS) and grazing-incidence small-angle x-ray scattering (GISAXS) are effective and non-destructive measurement tools to measure the evolution of orientation distribution of nanoscale patterns during processing. In this rotational small angle neutron scattering method, the sample is rotated in the neuron beam. By accumulating the scattering density at each sample rotation angle, the three-dimensional Fourier space of the internal ordering in the nanostructured film can be mapped. By using this relatively new rotational small angle neutron scattering method and established models for nanoscale patterns, the full three-dimensional orientation distribution of nanoscale patterns can be obtained.

Keywords:

作者及机构信息

1.
苏州大学, 软凝聚态物理及交叉研究中心, 苏州 215006;

2.
苏州大学, 物理与光电·能源学部, 苏州 215006

通信作者: 杨朝晖, yangzhaohui@suda.edu.cn;zhangxiaohua@suda.edu.cn ; 张晓华, yangzhaohui@suda.edu.cn;zhangxiaohua@suda.edu.cn

基金项目: 国家自然科学基金（批准号：21274103，21204059）和2013年江苏省创新团队计划资助的课题.

Authors and contacts

1.
Center for Soft Condensed Matter Physics and Interdisciplinary Research, Suzhou University, Suzhou 215006, China;

2.
College of Physics, Optoelectronics and Energy, Soochow University, Suzhou 215006, China

Corresponding author: Yang Zhao-Hui, yangzhaohui@suda.edu.cn;zhangxiaohua@suda.edu.cn ; Zhang Xiao-Hua, yangzhaohui@suda.edu.cn;zhangxiaohua@suda.edu.cn

Funds: Project supported by the the National Natural Science Foundation of China (Grant Nos. 21274103, 21204059) and the Jiangsu Scientific and Technological Innovation Team (2013).

参考文献

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[49]	Anastasiadis S H, Karatasos K, Vlachos G, Manias E, Giannelis E P 2000 Phys. Rev. Lett. 84 915
[50]	Rajendran S, Sivakumar M, Subadevi R 2004 Mater. Lett. 58 641
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[52]	Flier B M, Baier M C, Huber J, Mullen K, Mecking S, Zumbusch A, Woll D 2012 J. Am. Chem. Soc. 134 480
[53]	Yung P K, Mckenna G B, Simon S L 2006 J. Polym. Sci., Part B: Polym. Phys. 44 3518
[54]	Efremov M Y, Olson E A, Zhang M, Zhang Z, Allen L H 2003 Phys. Rev. Lett. 91 085703
[55]	Madkour S, Yin H, Fullbrandt M, Schonhals A 2015 Soft Matter 11 7942
[56]	Glor E C, Composto R J, Fakhraai Z 2015 Macromolecules 48 6682
[57]	Zhang X, Lacerda S H, Yager K G, Berry B C, Douglas J F, Jones R L, Karim A 2009 ACS Nano 3 2115
[58]	Jinnai H, Kajihara T, Watashiba H, Nishikawa Y, Spontak R J 2001 Phys. Rev. E 64 010803
[59]	Park H W, Jung J, Chang T, Matsunaga K, Jinnai H 2009 J. Am. Chem. Soc. 131 46
[60]	Niihara K, Sugimori H, Matsuwaki U, Hirato F, Morita H, Doi M, Masunaga H, Sasaki S, Jinnai H 2008 Macromolecules 41 9318
[61]	Brinkmann M, Rannou P 2009 Macromolecules 42 1125
[62]	Salammal S T, Mikayelyan E, Grigorian S, Pietsch U, Koenen N, Scherf U 2012 Macromolecules 45 5575
[63]	Drummy L F, Yang J, Martin D C 2004 Ultramicroscopy 99 247
[64]	Donald A M, He C B, Royall C P, Sferrazza M, Stelmashenko N A, Thiel B L 2000 Colloids Surf. A 174 37
[65]	Marjanski M, Srinivasarao M, Mirau P A 1998 Solid State Nucl. Magn. Reson. 12 113
[66]	Fukushima T, Kimura H, Shimahara Y, Kaji H 2011 Appl. Phys.Lett. 99 223301

施引文献

[1]	Alcoutlabi M, McKennad G B 2005 J. Phys.: Condens. Matter. 17 461
[2]	Kanaya T 2013 Glass Transition, Dynamics and Heterogeneity of Polymer Thin Films Advances in Polymer Science (Berlin: Springer) pp29-63
[3]	Keddie J L, Jones R A L, Cory R A 1994 Euro. Phys. Lett. 27 59
[4]	Forrest J A, Dalnoki-Veress K, Stevens J R, Dutcher J R 1996 Phys. Rev. Lett. 77 2002
[5]	Fukao K, Miyamoto Y 2000 Phys. Rev. E 61 1743
[6]	Ellison C J, Torkelson J M 2003 Nat. Mater. 2 695
[7]	Inoue R, Kanaya T, Nishida K, Tsukushi I, Shibata K 2005 Phys. Rev. Lett. 95 056102
[8]	Koh Y P, Mckenna G B, Simon S L 2006 Polym. Phys. 44 3518
[9]	Yang Z H, Fujii Y, Lee F K, Lam C H, Tsui O K C 2010 Science 328 1676
[10]	Napolitano S 2015 Non-equilibrium Phenomena in Confined Soft Matter (Switzerland: Springer) pp25-46
[11]	Jiang H, Dou N N, Fan G Q, Yang Z H, Zhang X H 2013 J. Chem. Phys. 139 124903
[12]	Shi H F, Jiang H, Fan G Q, Yang Z H, Zhang X H 2015 RSC Adv. 5 60015
[13]	Zhang X H, Yager K G, Fredin N J, Ro H W, Jones R L, Karim A, Douglas J F 2010 ACS Nano 4 3653
[14]	Tang C, Tracz A, Kruk M, Zhang R, Smilgies D M, Matyjaszewski K, Kowalewski T 2005 J. Am. Chem. Soc. 127 6918
[15]	Mller-Buschbaum P, Bauer E, Maurer E, Schlogl K, Roth S V, Gehrke R 2006 Appl. Phys. Lett. 88 083114
[16]	Zhang X, Yager K G, Douglas J F, Karim A 2014 Soft Matter 10 3656
[17]	Park S, Kwon K, Cho D, Lee B, Ree M, Chang T 2003 Macromolecules 36 4662
[18]	Meier R, Schindler M, Mller-Buschbaum P, Watts B 2011 Phys. Rev. B 84 174205
[19]	DeLongchamp D M, Kline R J, Fischer D A, Richter L J, Toney M F 2011 Adv. Mater. 23 319
[20]	Rogers J T, Schmidt K, Toney M F, Bazan G C, Kramer E 2012 J. Am. Chem. Soc. 134 2884
[21]	Kim B J, Miyamoto Y, Ma B, Frechet J M J 2009 Adv. Func. Mater. 19 2273
[22]	Smith K A, Lin Y H, Mok J W, Yager K G, Strzalka J, Nie W, Mohite A D, Verduzco R 2015 Macromolecules 48 8346
[23]	Reiter G 1994 Macromolecules 27 3046
[24]	Reiter G 1993 Europhys. Lett. 26 579
[25]	Schmitt J, Decher G, Dressick W J, Brandow S L, Geer R E, Shashidhar R, Calver J M 1997 Adv. Mater. 9 61
[26]	Swaraj S, Wang C, Yan HP, Watts B, Jan L N, McNeill C R, Ade H 2010 Nano Lett. 10 2863
[27]	Ma W, Tumbleston J R, Wang M, Gann E, Huang F, Ade H 2013 Adv. Energy Mater. 3 864
[28]	Tong M H, Cho S, Rogers J T, Schmidt K, Hsu B B Y, Moses D, Coffin R C, Kramer E J, Bazan G C, Heeger A J 2010 Adv. Funct. Mater. 20 3959
[29]	Lai L F, Yang H P, Wang L, Teh B K, Zhong J Q, Chou H, Chen L W, Chen W, Shen Z X, Ruoff R S 2012 ACS Nano 6 5941
[30]	Gurau M C, Delongchamp D M, Vogel B M, Lin E K, Fischer D A, Sambasivan S, Richter L J 2007 Langmuir 2 834
[31]	Morin C, Ikeura-Sekiguchi H, Tyliszczak T, Cornelius R, Brash J L, Hitchcock A P, Scholl A, Nolting F, Appel G, Winesett 2001 J. Electron Spectrosc. Relat. Phenom. 121 203
[32]	Zhang X H, Berry B C, Yager K G, Kim S, Jones R L, Satija S, Pickel D L, Douglas J F, Karim A 2008 ACS Nano 2 2331
[33]	Zhang X H, Douglas J F, Satija S, Karim A 2015 RSC Adv. 5 32307
[34]	Schmidt-Rohr K, Chen Q 2008 Nat. Mater. 7 75
[35]	Jones R L, Kumar S K, Ho D L, Briber R M, Russell T P 1999 Nature 400 146
[36]	Muller-Buschbaum P, Gutmann J S, Cubitt R, Petry W 2004 Phys. B 350 207
[37]	Tanaka M, Sackmann E 2005 Nature 437 656
[38]	Parnell A J, Dunbar A D F, Pearson A J, Staniec P A, Dennison A J C, Hamamatsu H, Skoda M W A, Lidzey D G, Jones R A L 2010 Adv. Mater. 22 2444
[39]	Kajiyama T, Tanaka K, Satomi N, Takahara A 1998 Macromolecules 31 5150
[40]	Hammerschmidt J A, Gladfelter W L, Haugstad G 1999 Macromolecules 32 3360
[41]	Tsui O K C, Wang X P, Ho J Y L, Ng T K, Xiao X 2000 Macromolecules 33 4198
[42]	Fryer D S, Peters R D, Kim E J, Tomaszewski J E, de Pablo J J, Nealey P F, White C C, Wu W L 2001 Macromolecules 34 5627
[43]	Fryer D S, Nealey P F, de Pablo J J 2000 Macromolecules 33 6439
[44]	Kawana S, Jones R A L 2001 Phys. Rev. E 63 021501
[45]	Mattsson J, Forrest J A, Borjesson L 2000 Phys. Rev. E 62 5187
[46]	Cheng W, Sainidou R, Burgardt P, Stefanou N, Kiyanova A, Efremov M, Fytas G, Nealey P F 2007 Macromolecules 40 7283
[47]	Hartschuh R, Ding Y, Roh J H, Kisliuk A, Sokolov A P, Soles C L, Jones R L, Hu T J, Wu W L, Mahorowala A P 2004 J. Polym. Sci., Part B: Polym. Phys. 42 1106
[48]	Kwak G, Fukao S, Fujiki M, Sakaguchi T, Masuda T 2006 Chem. Mater. 18 2081
[49]	Anastasiadis S H, Karatasos K, Vlachos G, Manias E, Giannelis E P 2000 Phys. Rev. Lett. 84 915
[50]	Rajendran S, Sivakumar M, Subadevi R 2004 Mater. Lett. 58 641
[51]	Tress M, Erber M, Mapesa E U, Huth H, Muller J, Serghei A, Schick C, Eichhorn K J, Volt B, Kremer F 2010 Macromolecules 43 9937
[52]	Flier B M, Baier M C, Huber J, Mullen K, Mecking S, Zumbusch A, Woll D 2012 J. Am. Chem. Soc. 134 480
[53]	Yung P K, Mckenna G B, Simon S L 2006 J. Polym. Sci., Part B: Polym. Phys. 44 3518
[54]	Efremov M Y, Olson E A, Zhang M, Zhang Z, Allen L H 2003 Phys. Rev. Lett. 91 085703
[55]	Madkour S, Yin H, Fullbrandt M, Schonhals A 2015 Soft Matter 11 7942
[56]	Glor E C, Composto R J, Fakhraai Z 2015 Macromolecules 48 6682
[57]	Zhang X, Lacerda S H, Yager K G, Berry B C, Douglas J F, Jones R L, Karim A 2009 ACS Nano 3 2115
[58]	Jinnai H, Kajihara T, Watashiba H, Nishikawa Y, Spontak R J 2001 Phys. Rev. E 64 010803
[59]	Park H W, Jung J, Chang T, Matsunaga K, Jinnai H 2009 J. Am. Chem. Soc. 131 46
[60]	Niihara K, Sugimori H, Matsuwaki U, Hirato F, Morita H, Doi M, Masunaga H, Sasaki S, Jinnai H 2008 Macromolecules 41 9318
[61]	Brinkmann M, Rannou P 2009 Macromolecules 42 1125
[62]	Salammal S T, Mikayelyan E, Grigorian S, Pietsch U, Koenen N, Scherf U 2012 Macromolecules 45 5575
[63]	Drummy L F, Yang J, Martin D C 2004 Ultramicroscopy 99 247
[64]	Donald A M, He C B, Royall C P, Sferrazza M, Stelmashenko N A, Thiel B L 2000 Colloids Surf. A 174 37
[65]	Marjanski M, Srinivasarao M, Mirau P A 1998 Solid State Nucl. Magn. Reson. 12 113
[66]	Fukushima T, Kimura H, Shimahara Y, Kaji H 2011 Appl. Phys.Lett. 99 223301

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