Citation: Yuan-Yuan Pang, Sheng-Xiang Ji. Effect of Ink Molecular Weights and Annealing Conditions on Molecular Transfer Printing[J]. Chinese Journal of Polymer Science, ;2018, 36(6): 697-702. doi: 10.1007/s10118-018-2056-4 shu

Effect of Ink Molecular Weights and Annealing Conditions on Molecular Transfer Printing

Yuan-Yuan Pang ^a,b ,
Sheng-Xiang Ji ^a,,

a.
Key Laboratory of Polymer Ecomaterials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

Corresponding author: Sheng-Xiang Ji, sji@ciac.ac.cn
Received Date: 15 September 2017
Accepted Date: 7 October 2017
Available Online: 30 January 2018

The molecular transfer printing (MTP) technique has been invented to fabricate chemical patterns with high fidelity using homopolymer inks. In this work, we systematically studied the effects of the molecular weights of homopolymer inks and transfer conditions on the MTP process. We explored a large range of molecular weights (~3.5-56 kg·mol^-1) of hydroxyl-terminated polystyrene (PS-OH) and hydroxyl-terminated poly(methyl methacrylate) (PMMA-OH) in the MTP process, and found that the resulting chemical patterns on replicas from all five blends were functional and able to direct the assembly of films of the same blends. The transfer temperature and the film annealing sequences had an impact on the MTP process. MTP was sensitive to the transfer temperature and could only be performed within a certain temperature range, i.e. higher than the glass transition temperature (T_g) of copolymers and lower than the rearrangement temperature of the assembled domains. Pre-organization of the blend films was also necessary for MTP since the preferential wetting of PMMA domains at the replica surface might result in the formation of a PMMA wetting layer to prevent the presentation of underlying chemical patterns to the replica surface.
- Block copolymer,
- Molecular transfer printing,
- Thermal annealing,
- Chemical pattern,
- Directed self-assembly
1. [1]
  Ji S., Wan L., Liu C. C., Nealey P. F.. Directed self-assembly of block copolymers on chemical patterns:a platform for nanofabrication[J]. Prog. Polym. Sci., 2016,54-55:76-127. doi: 10.1016/j.progpolymsci.2015.10.006
2. [2]
  Li W., Mueller M.. Directed self-assembly of block copolymers by chemical or topographical guiding patterns:optimizing molecular architecture, thin-film properties, and kinetics[J]. Prog. Polym. Sci., 2016,54-55:47-75. doi: 10.1016/j.progpolymsci.2015.10.008
3. [3]
  Delgadillo P. A. R., Gronheid R., Thode C. J., Wu H., Cao Y., Neisser M., Somervell M., Nafus K., Nealey P. F.. Implementation of a chemo-epitaxy flow for directed self-assembly on 300-mm wafer processing equipment[J]. J. Micro-nanolitho. Mems. Moems., 2012,11(3)031302. doi: 10.1117/1.JMM.11.3.031302
4. [4]
  Mojarad N., Gobrecht J., Ekinci Y.. Interference lithography at euv and soft X-ray wavelengths:principles, methods, and applications[J]. Microelectron. Eng., 2015,143:55-63. doi: 10.1016/j.mee.2015.03.047
5. [5]
  Ji S., Liu C. C., Liu G., Nealey P. F.. Molecular transfer printing using block copolymers[J]. ACS Nano, 2010,4(2):599-609. doi: 10.1021/nn901342j
6. [6]
  Ji S., Liu C. C., Liao W., Fenske A. L., Craig G. S. W., Nealey P. F.. Domain orientation and grain coarsening in cylinder-forming poly(styrene-b-methyl methacrylate) films[J]. Macromolecules, 2011,44(11):4291-4300. doi: 10.1021/ma2005734
7. [7]
  Ji S., Nagpal U., Liao W., Liu C. C., de Pablo J. J., Nealey P. F.. Three-dimensional directed assembly of block copolymers together with two-dimensional square and rectangular nanolithography[J]. Adv. Mater., 2011,23(32):3692-3697. doi: 10.1002/adma.v23.32
8. [8]
  Jin X., Zhang X., Wan L., Nealey P. F., Ji S.. Fabrication of chemical patterns from graphoepitaxially assembled block copolymer films by molecular transfer printing[J]. Polymer, 2014,55(15):3278-3283. doi: 10.1016/j.polymer.2014.05.040
9. [9]
  Liu G., Nealey P. F.. Improved block copolymer domain dispersity on chemical patterns via homopolymer-blending and molecular transfer printing[J]. Polymer, 2017,116:99-104. doi: 10.1016/j.polymer.2017.03.049
10. [10]
  Onses M. S., Thode C. J., Liu C. C., Ji S., Cook P. L., Himpsel F. J., Nealey P. F.. Site-specific placement of au nanoparticles on chemical nanopatterns prepared by molecular transfer printing using block-copolymer films[J]. Adv. Funct. Mater., 2011,21(16):3074-3082. doi: 10.1002/adfm.201100300
11. [11]
  Thode C. J., Cook P. L., Jiang Y., Serdar Onses M., Ji S., Himpsel F. J., Nealey P. F.. In situ metallization of patterned polymer brushes created by molecular transfer print and fill[J]. Nanotechnology, 2013,24(15)155602. doi: 10.1088/0957-4484/24/15/155602
12. [12]
  Onses M. S.. Fabrication of nanopatterned poly(ethylene glycol) brushes by molecular transfer printing from poly(styreneblock-methyl methacrylate) films to generate arrays of Au nanoparticles[J]. Langmuir, 2015,31(3):1225-1230. doi: 10.1021/la504359f
13. [13]
  Inoue T., Janes D. W., Ren J., Suh H. S., Chen X., Ellison C. J., Nealey P. F.. Molecular transfer printing of block copolymer patterns over large areas with conformal layers[J]. Adv. Mater. Interfaces, 2015,2(10)1500133. doi: 10.1002/admi.201500133
14. [14]
  Solak H. H., David C., Gobrecht J., Golovkina V., Cerrina F., Kim S. O., Nealey P. F.. Sub-50 nm period patterns with EUV interference lithography[J]. Microelectron. Eng., 2003,67-68:56-62. doi: 10.1016/S0167-9317(03)00059-5
15. [15]
  Wang J., Song J. H., Lu Y. Y., Ruan Y. J., An L. J.. Phase behavior and interfacial properties of diblock copolymer-homopolymer ternary mixtures:influence of volume fraction of copolymers and interaction energy[J]. Chinese J. Polym. Sci., 2017,35(7):874-886. doi: 10.1007/s10118-017-1915-8
16. [16]
  Wei X. Y., Gu W. Y., Shen X. B., Strzalka J., Jiang Z., Russell T. P.. Deviations from bulk morphologies in thin films of block copolymer/additive binary blends[J]. Chinese J. Polym. Sci., 2013,31(9):1250-1259. doi: 10.1007/s10118-013-1320-x
17. [17]
  Jin X. S., Pang Y. Y., Ji S. X.. From self-assembled monolayers to chemically patterned brushes:controlling the orientation of block copolymer domains in films by substrate modification[J]. Chinese J. Polym. Sci., 2016,34(6):659-678. doi: 10.1007/s10118-016-1800-x
18. [18]
  Han E., In I., Park S. M., La Y. H., Wang Y., Nealey P. F., Gopalan P.. Photopatternable imaging layers for controlling block copolymer microdomain orientation[J]. Adv. Mater., 2007,19(24):4448-4452. doi: 10.1002/(ISSN)1521-4095
19. [19]
  In I., La Y. H., Park S. M., Nealey P. F., Gopalan P.. Side-chain-grafted random copolymer brushes as neutral surfaces for controlling the orientation of block copolymer microdomains in thin films[J]. Langmuir, 2006,22(18):7855-7860. doi: 10.1021/la060748g
20. [20]
  Ji S., Liao W., Nealey P. F.. Block cooligomers:a generalized approach to controlling the wetting behavior of block copolymer thin films[J]. Macromolecules, 2010,43(16):6919-6922. doi: 10.1021/ma1007946
21. [21]
  Ji S., Liu C. C., Son J. G., Gotrik K., Craig G. S. W., Gopalan P., Himpsel F. J., Char K., Nealey P. F.. Generalization of the use of random copolymers to control the wetting behavior of block copolymer films[J]. Macromolecules, 2008,41(23):9098-9103. doi: 10.1021/ma801861h
22. [22]
  Ji S., Liu G., Zheng F., Craig G. S. W., Himpsel F. J., Nealey P. F.. Preparation of neutral wetting brushes for block copolymer films from homopolymer blends[J]. Adv. Mater., 2008,20(16):3054-3060. doi: 10.1002/adma.v20:16
23. [23]
  Mansky P., Liu Y., Huang E., Russell T. P., Hawker C. J.. Controlling polymer-surface interactions with random copolymer brushes[J]. Science, 1997,275(5305):1458-1460. doi: 10.1126/science.275.5305.1458
24. [24]
  Pang Y., Wan L., Huang G., Zhang X., Jin X., Xu P., Liu Y., Han M., Wu G. P., Ji S.. Controlling block copolymersubstrate interactions by homopolymer brushes/mats[J]. Macromolecules, 2017,50(17):6733-6741. doi: 10.1021/acs.macromol.7b00743
25. [25]
  Ryu D. Y., Shin K., Drockenmuller E., Hawker C. J., Russell T. P.. A generalized approach to the modification of solid surfaces[J]. Science, 2005,308(5719):236-239. doi: 10.1126/science.1106604
26. [26]
  Liu G., Stoykovich M. P., Ji S., Stuen K. O., Craig G. S. W., Nealey P. F.. Phase behavior and dimensional scaling of symmetric block copolymer-homopolymer ternary blends in thin films[J]. Macromolecules, 2009,42(8):3063-3072. doi: 10.1021/ma802773h
27. [27]
  Kim S. O., Solak H. H., Stoykovich M. P., Ferrier N. J., de Pablo J. J., Nealey P. F.. Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates[J]. Nature, 2003,424(6947):411-414. doi: 10.1038/nature01775
28. [28]
  Stoykovich M. P., Muller M., Kim S. O., Solak H. H., Edwards E. W., de Pablo J. J., Nealey P. F.. Directed assembly of block copolymer blends into nonregular device-oriented structures[J]. Science, 2005,308(5727):1442-1446. doi: 10.1126/science.1111041
29. [29]
  Cheng J. Y., Rettner C. T., Sanders D. P., Kim H. C., Hinsberg W. D.. Dense self-assembly on sparse chemical patterns:rectifying and multiplying lithographic patterns using block copolymers[J]. Adv. Mater., 2008,20(16):3155-3158. doi: 10.1002/adma.v20:16
30. [30]
  Ruiz R., Kang H., Detcheverry F. A., Dobisz E., Kercher D. S., Albrecht T. R., de Pablo J. J., Nealey P. F.. Density multiplication and improved lithography by directed block copolymer assembly[J]. Science, 2008,321(5891):936-939. doi: 10.1126/science.1157626
31. [31]
  Liu G., Thomas C. S., Craig G. S. W., Nealey P. F.. Integration of density multiplication in the formation of device-oriented structures by directed assembly of block copolymer-homopolymer blends[J]. Adv. Funct. Mater., 2010,20(8):1251-1257. doi: 10.1002/adfm.v20:8
32. [32]
  Liu C. C., Ramirez-Hernandez A., Han E., Craig G. S. W., Tada Y., Yoshida H., Kang H., Ji S., Gopalan P., de Pablo J. J., Nealey P. F.. Chemical patterns for directed self-assembly of lamellae-forming block copolymers with density multiplication of features[J]. Macromolecules, 2013,46(4):1415-1424. doi: 10.1021/ma302464n
33. [33]
  Stoykovich M., Edwards E., Solak H., Nealey P.. Phase behavior of symmetric ternary block copolymer-homopolymer blends in thin films and on chemically patterned surfaces[J]. Phys. Rev. Lett., 2006,97(14)147802. doi: 10.1103/PhysRevLett.97.147802
34. [34]
  Edwards E. W., Montague M. F., Solak H. H., Hawker C. J., Nealey P. F.. Precise control over molecular dimensions of block-copolymer domains using the interfacial energy of chemically nanopatterned substrates[J]. Adv. Mater., 2004,16(15):1315-1319. doi: 10.1002/(ISSN)1521-4095
35. [35]
  Edwards E. W., Mueller M., Stoykovich M. P., Solak H. H., de Pablo J. J., Nealey P. F.. Dimensions and shapes of block copolymer domains assembled on lithographically defined chemically patterned substrates[J]. Macromolecules, 2007,40(1):90-96. doi: 10.1021/ma0607564
36. [36]
  Green P. F., Kramer E. J.. Temperature dependence of tracer diffusion coefficients in polystyrene[J]. J. Mater. Res., 1986,1(1):202-204. doi: 10.1557/JMR.1986.0202
37. [37]
  Welander A. M., Kang H., Stuen K. O., Solak H. H., Mueller M., de Pablo J. J., Nealey P. F.. Rapid directed assembly of block copolymer films at elevated temperatures[J]. Macromolecules, 2008,41(8):2759-2761. doi: 10.1021/ma800056s
1. [1]
  Changlin Su , Wensheng Cai , Xueguang Shao . Water as a probe for the temperature-induced self-assembly transition of an amphiphilic copolymer. Chinese Chemical Letters, 2025, 36(4): 110095-. doi: 10.1016/j.cclet.2024.110095
2. [2]
  Changhui Yu , Peng Shang , Huihui Hu , Yuening Zhang , Xujin Qin , Linyu Han , Caihe Liu , Xiaohan Liu , Minghua Liu , Yuan Guo , Zhen Zhang . Evolution of template-assisted two-dimensional porphyrin chiral grating structure by directed self-assembly using chiral second harmonic generation microscopy. Chinese Chemical Letters, 2024, 35(10): 109805-. doi: 10.1016/j.cclet.2024.109805
3. [3]
  Yiwen Lin , Yijie Chen , Chunhui Deng , Nianrong Sun . Integration of resol/block-copolymer carbonization and machine learning: A convenient approach for precise monitoring of glycan-associated disorders. Chinese Chemical Letters, 2024, 35(12): 109813-. doi: 10.1016/j.cclet.2024.109813
4. [4]
  Rui Wang , Yuan Tian , Xuefeng Gao , Lei Jiang . Design and fabrication of triangle-pattern superwettability hybrid surface with high-efficiency condensation heat transfer performance. Chinese Chemical Letters, 2025, 36(3): 110395-. doi: 10.1016/j.cclet.2024.110395
5. [5]
  Zhenzhu Wang , Chenglong Liu , Yunpeng Ge , Wencan Li , Chenyang Zhang , Bing Yang , Shizhong Mao , Zeyuan Dong . Differentiated self-assembly through orthogonal noncovalent interactions towards the synthesis of two-dimensional woven supramolecular polymers. Chinese Chemical Letters, 2024, 35(5): 109127-. doi: 10.1016/j.cclet.2023.109127
6. [6]
  Sifan Du , Yuan Wang , Fulin Wang , Tianyu Wang , Li Zhang , Minghua Liu . Evolution of hollow nanosphere to microtube in the self-assembly of chiral dansyl derivatives and inversed circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(7): 109256-. doi: 10.1016/j.cclet.2023.109256
7. [7]
  Cheng-Yan Wu , Yi-Nan Gao , Zi-Han Zhang , Rui Liu , Quan Tang , Zhong-Lin Lu . Enhancing self-assembly efficiency of macrocyclic compound into nanotubes by introducing double peptide linkages. Chinese Chemical Letters, 2024, 35(11): 109649-. doi: 10.1016/j.cclet.2024.109649
8. [8]
  Xiaofei NIU , Ke WANG , Fengyan SONG , Shuyan YU . Self-assembly of [Pd₆(L)₄]⁸⁺-type macrocyclic complexes for fluorescent sensing of HSO₃^-. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1233-1242. doi: 10.11862/CJIC.20240057
9. [9]
  Zengchao Guo , Weiwei Liu , Tengfei Liu , Jinpeng Wang , Hui Jiang , Xiaohui Liu , Yossi Weizmann , Xuemei Wang . Engineered exosome hybrid copper nanoscale antibiotics facilitate simultaneous self-assembly imaging and elimination of intracellular multidrug-resistant superbugs. Chinese Chemical Letters, 2024, 35(7): 109060-. doi: 10.1016/j.cclet.2023.109060
10. [10]
  Bing Niu , Honggao Huang , Liwei Luo , Li Zhang , Jianbo Tan . Coating colloidal particles with a well-defined polymer layer by surface-initiated photoinduced polymerization-induced self-assembly and the subsequent seeded polymerization. Chinese Chemical Letters, 2025, 36(2): 110431-. doi: 10.1016/j.cclet.2024.110431
11. [11]
  Yi Zhou , Wei Zhang , Rong Fu , Jiaxin Dong , Yuxuan Liu , Zihang Song , Han Han , Kang Cai . Self-assembly of two pairs of homochiral M₂L₄ coordination capsules with varied confined space using Tröger's base ligands. Chinese Chemical Letters, 2025, 36(2): 109865-. doi: 10.1016/j.cclet.2024.109865
12. [12]
  Minghao Hu , Tianci Xie , Yuqiang Hu , Longjie Li , Ting Wang , Tongbo Wu . Allosteric DNAzyme-based encoder for molecular information transfer. Chinese Chemical Letters, 2024, 35(7): 109232-. doi: 10.1016/j.cclet.2023.109232
13. [13]
  Yan Wang , Huixin Chen , Fuda Yu , Shanyue Wei , Jinhui Song , Qianfeng He , Yiming Xie , Miaoliang Huang , Canzhong Lu . Oxygen self-doping pyrolyzed polyacrylic acid as sulfur host with physical/chemical adsorption dual function for lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(7): 109001-. doi: 10.1016/j.cclet.2023.109001
14. [14]
  Yujuan Zhao , Zaiwang Zhao . Monolayer mesoporous nanosheets with surface asymmetry via a dual-emulsion-directed monomicelle assembly. Chinese Journal of Structural Chemistry, 2024, 43(2): 100238-100238. doi: 10.1016/j.cjsc.2024.100238
15. [15]
  Huanyu Liu , Gang Yu , Ruoyao Guo , Hao Qi , Jiayin Zheng , Tong Jin , Zifeng Zhao , Zuqiang Bian , Zhiwei Liu . Direct identification of energy transfer mechanism in Ce^Ⅲ-Mn^Ⅱ system by constructing molecular heteronuclear complexes. Chinese Chemical Letters, 2025, 36(2): 110296-. doi: 10.1016/j.cclet.2024.110296
16. [16]
  Qinghong Pan , Huafang Zhang , Qiaoling Liu , Donghong Huang , Da-Peng Yang , Tianjia Jiang , Shuyang Sun , Xiangrong Chen . A self-powered cathodic molecular imprinting ultrasensitive photoelectrochemical tetracycline sensor via ZnO/C photoanode signal amplification. Chinese Chemical Letters, 2025, 36(1): 110169-. doi: 10.1016/j.cclet.2024.110169
17. [17]
  Zixi Zou , Jingyuan Wang , Yian Sun , Qian Wang , Da-Hui Qu . Controlling molecular assembly on time scale: Time-dependent multicolor fluorescence for information encryption. Chinese Chemical Letters, 2024, 35(7): 108972-. doi: 10.1016/j.cclet.2023.108972
18. [18]
  Yutong Xiong , Ting Meng , Wendi Luo , Bin Tu , Shuai Wang , Qingdao Zeng . Molecular conformational effects on co-assembly systems of low-symmetric carboxylic acids investigated by scanning tunneling microscopy. Chinese Journal of Structural Chemistry, 2025, 44(2): 100511-100511. doi: 10.1016/j.cjsc.2025.100511
19. [19]
  Yu-Yu Tan , Lin-Heng He , Wei-Min He . Copper-mediated assembly of SO₂F group via radical fluorine-atom transfer strategy. Chinese Chemical Letters, 2024, 35(9): 109986-. doi: 10.1016/j.cclet.2024.109986
20. [20]
  Siwei Wang , Wei-Lei Zhou , Yong Chen . Cucurbituril and cyclodextrin co-confinement-based multilevel assembly for single-molecule phosphorescence resonance energy transfer behavior. Chinese Chemical Letters, 2024, 35(12): 110261-. doi: 10.1016/j.cclet.2024.110261

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(646)
HTML views(0)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142