基于表面起皱法的梯度图案的可控制备
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摘要
报道了基于非刻蚀法的表面起皱机制来实现高分子薄膜表面的周期性梯度图案的简单可控制备.即对于处于机械拉伸状态的聚二甲基硅氧烷(PDMS)弹性基底,在其底部垫入"积木",而后对其进行紫外-臭氧(UVO)和氧等离子体(OP)的联合表面处理."积木"的加入引起了表面处理后表面硅氧层(SiOx)梯度厚度的形成,进而当释放拉伸应变后,诱导产生了梯度皱纹图案.结果表明:当UVO与OP联用处理时,不仅实现了较小拉伸应变下梯度皱纹形貌的制备,而且扩大了UVO单独使用时梯度皱纹周期的变化范围.通过OP与UVO的处理顺序和处理时间等因素的简单调节,进一步实现了不同梯度皱纹微结构的精细构筑.
We reported a simple method to fabricate gradient patterns on polymer-based films, which was based on the non-lithographic surface wrinkling. Namely, a polydimethylsiloxane(PDMS) soft substrate was mechanically pre-strained with a "triangular block" beneath the strained PDMS sheet, followed by surface oxidation with ultraviolet ozone(UVO) and/or oxygen plasma(OP). A thin silica-like(SiO x) stiff layer was generated after the surface oxidization. Thus the surface wrinkling was induced on the as-formed film/substrate system of SiO x/PDMS bilayer when the pre-strain of the PDMS substrate was released slowly. It was found that aligned surface wrinkles with a uniform wavelength were yielded on the OP-exposed PDMS substrate. However,gradient patterns were obtained when the PDMS substrate was treated by UVO. The introduction of the"triangular block" beneath the strained PDMS sheet led to a change of the distance between the PDMS substrate and the UVO light, and thus an increased decay of UVO light intensity along with the exposed PDMS sheet happened. As a result, the gradient thickness of the SiO x layer was formed on the resulting Si Ox/PDMS bilayer and the corresponding gradient wrinkles were generated,since the wrinkle wavelength was closely related to the thickness of the stiff film. In contrast, the thickness of the as-formed SiO x layer was uniform during the OP exposure. It was noted that, for the single UVO exposure, a large pre-strain was required to induce the surface wrinkling on the UVO-exposed PDMS substrate. Interestingly, compared with the single UVO treatment, the combined UVO/OP surface oxidation treatment(e.g., UVO-OP and OP-UVO treatment) did not need the large pre-strain on the PDMS substrate. Furthermore, the wavelength range of the obtained gradient wrinkles was extended greatly. Consequently, different gradient patterns with well-defined microstructures were finely tuned by a simple manipulation of the exposure order and the exposure duration of the combined UVO/OP applied to the pre-strained PDMS substrate. Based on the systematical results, we revealed the underlying physics that was related to the formation of the current gradient wrinkle patterns.
We reported a simple method to fabricate gradient patterns on polymer-based films, which was based on the non-lithographic surface wrinkling. Namely, a polydimethylsiloxane(PDMS) soft substrate was mechanically pre-strained with a "triangular block" beneath the strained PDMS sheet, followed by surface oxidation with ultraviolet ozone(UVO) and/or oxygen plasma(OP). A thin silica-like(SiO x) stiff layer was generated after the surface oxidization. Thus the surface wrinkling was induced on the as-formed film/substrate system of SiO x/PDMS bilayer when the pre-strain of the PDMS substrate was released slowly. It was found that aligned surface wrinkles with a uniform wavelength were yielded on the OP-exposed PDMS substrate. However,gradient patterns were obtained when the PDMS substrate was treated by UVO. The introduction of the"triangular block" beneath the strained PDMS sheet led to a change of the distance between the PDMS substrate and the UVO light, and thus an increased decay of UVO light intensity along with the exposed PDMS sheet happened. As a result, the gradient thickness of the SiO x layer was formed on the resulting Si Ox/PDMS bilayer and the corresponding gradient wrinkles were generated,since the wrinkle wavelength was closely related to the thickness of the stiff film. In contrast, the thickness of the as-formed SiO x layer was uniform during the OP exposure. It was noted that, for the single UVO exposure, a large pre-strain was required to induce the surface wrinkling on the UVO-exposed PDMS substrate. Interestingly, compared with the single UVO treatment, the combined UVO/OP surface oxidation treatment(e.g., UVO-OP and OP-UVO treatment) did not need the large pre-strain on the PDMS substrate. Furthermore, the wavelength range of the obtained gradient wrinkles was extended greatly. Consequently, different gradient patterns with well-defined microstructures were finely tuned by a simple manipulation of the exposure order and the exposure duration of the combined UVO/OP applied to the pre-strained PDMS substrate. Based on the systematical results, we revealed the underlying physics that was related to the formation of the current gradient wrinkle patterns.
引文
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14 Liu Jianping(刘建平),Shi Jinxia(石锦霞),Yang Xiaomin(杨小敏),He Pingsheng(何平笙),Yang Haiyang(杨海洋).Acta Polymerica Sinica(高分子学报),2007,(2):42-46
15 Liu Bin(刘斌),Fu Ye(傅叶),Ruan Weiqing(阮维青),He Yaning(和亚宁),Wang Xiaogong(王晓工).Acta Polymerica Sinica(高分子学报),2008,(2):155-160
16 Yang Xiu(杨秀),Yin Jian(尹健),Han Xue(韩雪),Lu Conghua(鲁从华).Acta Polymerica Sinica(高分子学报),2016,(3):337-344
17 Genzer J,Groenewold J.Soft Matter,2006,2:310-323
18 Ohzono T,Shimomura M.Phys Rev B,2004,69(13):132202
19 Hou J,Li Q Y,Han X,Lu C H.J Phys Chem B,2014,118:14502-14509
20 Jiang H Q,Khang D Y,Song J Z,Sun Y G,Huang Y G,Rogers J A.Proc Natl Acad Sci,2007,104:15607-15612
21 Huang R,Stafford C M,Vogt B D.J Aerosol Sci,2007,20:38-44
22 Chen C M,Yang S.Polym Int,2012,61:1041-1047
23 Park J Y,Chae H Y,Chung,C H,Sim S J,Park J,Lee H H,Yoo P J.Soft Matter,2010,6:677-684
24 Genzer J,Fischer D A,Efimenko K.Adv Mater,2003,15:1545-1547
25 Stafford C M,Roskov K E,Epps T H,Fasolka M.Rev Sci Inst,2006,77(2):023908
26 Langley K R,Sharp J S.Langmuir,2010,26:18349-18356
27 Claussen K U,Tebbe M,Giesa R,Schweikart A,Fery A,Schmidt H W.RSC Adv,2012,2:10185-10188
28 Yin J,Chen X.Philos Mag Lett,2010,90:423-433
29 Sun Wei(孙巍),Zhou Yuchen(周雨辰),Chen Zhongren(陈忠仁).Acta Polymerica Sinica(高分子学报),2004,(12):1459-1464
30 Chen Anfu(陈安伏),Huang Hanxiong(黄汉雄),Guan Weisheng(关伟盛).Acta Polymerica Sinica(高分子学报),2015,(3):245-251
31 Lin P C,Yang S.Soft Matter,2009,5:1011-1018
32 Bowden N,Huck W T S,Paul K E,Whitesides G M.Appl Phys Lett,1999,75:2557-2559
33 Efimenko K,Wallace W E,Genzer J.J Colloid Interface Sci,2002,254:306-315
34 Bayley F A,Liao J L,Stavrinou P N,Chiched A,Cabral J T.Soft Matter,2014,10:1155-1166
35 Berdichevsky Y,Khandurina J,Guttman A,Lo Y H.Sens Actuators B,2004,97:402-408
36 Ye H,Gu Z Y,Gracias D H.Langmuir,2006,22:1863-1868
2 Chung J Y,Nolte A J,Stafford C M.Adv Mater,2011,23:349-368
3 Kim Y H,Lee Y M,Lee J Y,Ko M J,Yoo P J.ACS Nano,2012,6:1082-1093
4 Chan E P,Smith E J,Hayward R C,Crosby A J.Adv Mater,2008,20:711-716
5 Stroock A D,Whitesides G M.Acc Chem Res,2003,36:597-604
6 Khang D Y,Rogers J A,Lee H H.Adv Funct Mater,2008,19:1526-1536
7 Zhu W J,Low T,Perebeinos V,Bol A A,Zhu Y,Yan H,Tersoff J,Avouris P.Nano Lett,2012,12:3431-3436
8 Yu C,O’Brien K,Zhang Y H,Yu H B,Jiang H.Appl Phys Lett,2010,96(4):041111/1-041111/3
9 Gan Y C,Jiang X S,Yin J.Macromolecules,2012,45:7520-7536
10 Du Q,Guan Y,Zhu X X,Zhang Y J.Soft Matter,2015,11:1937-1944
11 Yang X,Zhao Y,Xie J X,Han X,Wang J J,Zong C Y,Ji H P,Zhao J X,Jiang S C,Cao Y P,Lu C H.ACS Nano,2016,10:3801-3808
12 Zong C Y,Zhao Y,Ji H P,Han X,Xie J X,Wang J J,Cao Y P,Jiang S C,Lu C H.Angew Chem Int Ed,2016,55:3931-3935
13 Zhao Nan(赵楠),Lu Conghua(鲁从华),Cao Weixiao(曹维孝).Acta Polymerica Sinica(高分子学报),2004,(3):458-461
14 Liu Jianping(刘建平),Shi Jinxia(石锦霞),Yang Xiaomin(杨小敏),He Pingsheng(何平笙),Yang Haiyang(杨海洋).Acta Polymerica Sinica(高分子学报),2007,(2):42-46
15 Liu Bin(刘斌),Fu Ye(傅叶),Ruan Weiqing(阮维青),He Yaning(和亚宁),Wang Xiaogong(王晓工).Acta Polymerica Sinica(高分子学报),2008,(2):155-160
16 Yang Xiu(杨秀),Yin Jian(尹健),Han Xue(韩雪),Lu Conghua(鲁从华).Acta Polymerica Sinica(高分子学报),2016,(3):337-344
17 Genzer J,Groenewold J.Soft Matter,2006,2:310-323
18 Ohzono T,Shimomura M.Phys Rev B,2004,69(13):132202
19 Hou J,Li Q Y,Han X,Lu C H.J Phys Chem B,2014,118:14502-14509
20 Jiang H Q,Khang D Y,Song J Z,Sun Y G,Huang Y G,Rogers J A.Proc Natl Acad Sci,2007,104:15607-15612
21 Huang R,Stafford C M,Vogt B D.J Aerosol Sci,2007,20:38-44
22 Chen C M,Yang S.Polym Int,2012,61:1041-1047
23 Park J Y,Chae H Y,Chung,C H,Sim S J,Park J,Lee H H,Yoo P J.Soft Matter,2010,6:677-684
24 Genzer J,Fischer D A,Efimenko K.Adv Mater,2003,15:1545-1547
25 Stafford C M,Roskov K E,Epps T H,Fasolka M.Rev Sci Inst,2006,77(2):023908
26 Langley K R,Sharp J S.Langmuir,2010,26:18349-18356
27 Claussen K U,Tebbe M,Giesa R,Schweikart A,Fery A,Schmidt H W.RSC Adv,2012,2:10185-10188
28 Yin J,Chen X.Philos Mag Lett,2010,90:423-433
29 Sun Wei(孙巍),Zhou Yuchen(周雨辰),Chen Zhongren(陈忠仁).Acta Polymerica Sinica(高分子学报),2004,(12):1459-1464
30 Chen Anfu(陈安伏),Huang Hanxiong(黄汉雄),Guan Weisheng(关伟盛).Acta Polymerica Sinica(高分子学报),2015,(3):245-251
31 Lin P C,Yang S.Soft Matter,2009,5:1011-1018
32 Bowden N,Huck W T S,Paul K E,Whitesides G M.Appl Phys Lett,1999,75:2557-2559
33 Efimenko K,Wallace W E,Genzer J.J Colloid Interface Sci,2002,254:306-315
34 Bayley F A,Liao J L,Stavrinou P N,Chiched A,Cabral J T.Soft Matter,2014,10:1155-1166
35 Berdichevsky Y,Khandurina J,Guttman A,Lo Y H.Sens Actuators B,2004,97:402-408
36 Ye H,Gu Z Y,Gracias D H.Langmuir,2006,22:1863-1868