Name: fabrication of large-area free-standing ultrathin polymer films
Uploaded: 2015-06-03T14:00:00.000+00:00
Duration: 10 min 8 s
Description: Watch this Scientific Journal Video about Fabrication of Large-area Free-standing Ultrathin Polymer Films at JoVE.com

根据合同DE-AC52-07NA27344美国能源署的主持下进行的由劳伦斯·利弗莫尔国家实验室的这项工作。

1.溶液的制备<ol><li>滤波器60乳酸乙酯的使用注射器和一个0.20微米的注射器过滤器。添加0.3克聚乙烯醇缩甲醛的乳酸乙酯。放置在50℃下将溶液放入烘箱4小时。摇动小瓶轻轻以查看是否在聚合物完全溶解。 <ol><li>如果溶液混浊或仍显示光的不均匀性，返回小瓶烘箱另外2小时。此配方是为0.5重量％的聚合物溶液，其典型地用于膜厚大约30毫微米。与较高的聚合物的重量含量的解决方案可以用于较厚的膜。 </li></ol></li><li>通过称量1.0克PDAC试剂在20ml的容量瓶中，并填充所述烧瓶用去离子（DI）水的测量线准备一个PDAC溶液。将其转移到贮藏容器之前轻轻摇动溶液中。 </li></ol> 2.基板制备<ol><li>小心。倒入60毫升浓硫酸的酸到一个干净的250毫升烧杯中。慢慢加入20毫升30％的过氧化氢。等到发烟补贴，然后摇动轻轻的解决方案。溶液中，将烧杯会变得非常热，该混合物是具有腐蚀性。 </li><li>将150毫米的培养皿上的热点板块，倒入酸入菜。设置加热板为100℃。 <ol><li>放置4&#39;的硅晶片与该抛光面朝上的酸。轻轻晶片向下推，中间有一对镊子的，以确保整个表面都被浸湿。留在酸晶片30分钟。 </li></ol></li><li>除去从酸晶片有一对镊子和冲洗的正面和背面的晶片的彻底用DI水从喷瓶。水应该片断以规则图案。干洁净工作台的晶片。 </li><li>冲洗一次性3毫升注射器和一个0.2微米的过滤器首先用DI水，然后用PDAC溶液由液体抽入注射器，在安装过滤器，并且Ñ​​推动液体通过过滤器。 </li><li>安装在旋涂机在清洁的晶片。制定1.0-1.2毫升PDAC溶液到注射器和分配它虽然过滤到晶片的中间。旋在4,000rpm下15秒，然后将晶片传送到一个​​热板（预热至50℃）并让它坐30秒。 </li><li>用去离子水冲洗干PDAC层关闭，让晶圆干燥洁净工作台。 </li></ol> 3.电影制作<ol><li>放置干燥PDAC处理晶片上旋涂机。 </li><li>冲洗一次性3毫升注射器和0.45微米的过滤器，使用下2.4的程序的乳酸乙酯溶液）。 </li><li>存款2.5毫升以200rpm通过过滤器的乳酸乙酯溶液用注射器在晶片和自旋的中间为10秒，然后，持续3秒在1700转（取决于所需的膜厚度）。应在晶片上均匀的液体膜。 </li><li>让该膜干燥，在旋涂机直到它明显地干燥（通常10-15分钟），然后将其放置在热板上（预热至50℃）10分钟。 </li><li>切块的薄膜成更小的最小二乘剥离，一般为2厘米×2厘米，但可以更大，这取决于所用片夹（3.5.1-3.5.2）的大小。另外，做两个文士的分层晶圆尺寸薄膜（3.5.3）。 注:标准片夹是19×19毫米，在中间的圆形开口的直径为13毫米。对于晶片尺寸薄膜，使用钢丝箍（形成为圆例如 ，不锈钢丝），其直径为1"比晶片小。圆形开口被选中，是因为离地升空和膨胀在影片通常会吸收水分。作为薄膜干燥支架上时，水被除去，薄膜将收缩。圆形开口允许均匀分布的压力。 <ol><li>放置在一切割模板的晶片。使用方形模板上的所有边缘比晶片更高防止直êDGE用于从接触晶圆刻划期间指导刀片。标记2厘米的间距的边缘，以引导放置在直刃的切割时。推动晶圆对两名边对齐。 </li><li>放置一个直边沿两个对准标记，并轻轻划刀片沿直刃刻划膜。施加足够的压力，以纪念这部电影，但不要太多，以纪念该晶片本身并产生颗粒。上较厚的膜，切割线将清晰可见。 </li><li>到剥离的膜在从晶片一片，隶用刀片晶片边缘。在晶片上的两个单位之间，隶带足够宽到晶片夹紧在齿条和小齿轮。 </li></ol></li><li>填写一个190×100毫米的培养皿用去离子水。晶片由大平板夹紧到齿条和小齿轮安装到倾斜阶段和缓慢向下放入DI水。这部电影应该分开晶圆在水位线。 <ol><li>继续降低WAF尔的速率，使该膜足够的时间来从晶片中分离出来，而不是推水线下的剥离界面。当方块的第一行已经与晶片分离并漂浮在表面上，暂停晶片的降低。对于一个晶片大小的膜，继续浸渍晶片直到薄膜分离完全。 </li><li>浸入片夹的头部入水和移动它的膜之下。排队的薄膜边缘之一箍的手柄的边缘，并与薄膜触摸箍。如果成功的话，这部电影会坚持到篮下。 <ol><li>对于一个晶片大小的膜，放置在刻划部下方的电线圈，只是一厘米远离边缘。确保箍是围绕膜之下开始捕捉，保持膜边缘与箍边缘之间有一定距离，使得薄膜缠绕箍和向后翻转折迭之前。 </li></ol></li><li>从水中拉回圈缓慢的的35°角。提起电影出来的水非常缓慢。 注意:对于薄膜小于20nm厚，增加角度后大约一半的膜一直拉到从水到几乎90°（ 即 ，垂直于水面），以避免通过支架拉膜。当改变电梯出角度，这样做的慢，以避免通过箍揪片子。 </li><li>当箍完全缩回，将其放置到一边干燥。确保箍的底部是免费滴把箍下来之前，并使用曲面（如晶圆托盘），以避免造成箍和表面之间的液体密封。 </li><li>如果更多的划线正方形留在晶片上，继续降低晶片放入水中，并重复步骤3.6.1-3.6.4上述剩余正方形。 </li><li>让薄膜干燥O / N。 </li></ol></li></ol>

<ol>
	<li>Cheng, W., Campolongo, M. J., Tan, S. J., Luo, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Freestanding+ultrathin+nano-membranes+via+self-assembly.">Freestanding ultrathin nano-membranes via self-assembly.</a> Nano Today. 4, 482-493 (2009).</li><li>Greco, F., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultra-thin+conductive+free-standing+PEDOT/PSS+nanofilms.">Ultra-thin conductive free-standing PEDOT/PSS nanofilms.</a> Soft Matter. 7, 10642-10650 (2011).</li><li>Matsui, J., Mitsuishi, M., Aoki, A., Miyashita, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Molecular+Optical+Gating+Devices+Based+on+Polymer+Nanosheets+Assemblies.">Molecular Optical Gating Devices Based on Polymer Nanosheets Assemblies.</a> J. Am. Chem. Soc. 126, 3708-3709 (2004).</li><li>Ulbricht, M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Advanced+functional+polymer+membranes.">Advanced functional polymer membranes.</a> Polymer. 47, 2217-2262 (2006).</li><li>Fujie, T., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Robust+Polysaccharide+Nanosheets+Integrated+for+Tissue-Defect+Repair.">Robust Polysaccharide Nanosheets Integrated for Tissue-Defect Repair.</a> Adv. Funct. Mater. 19, 2560-2568 (2009).</li><li>Okamura, Y., Kabata, K., Kinoshita, M., Saitoh, D., Takeoka, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Free-Standing+Biodegradable+Poly(lactic+acid)+Nanosheet+for+Sealing+Operations+in+Surgery.">Free-Standing Biodegradable Poly(lactic acid) Nanosheet for Sealing Operations in Surgery.</a> Adv. Mater. 21, 4388-4392 (2009).</li><li>Sreenivasan, R., Bassett, E. K., Hoganson, D. M., Vacanti, J. P., Gleason, K. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Ultra-thin+gas+permeable+free-standing+and+composite+membranes+for+microfluidic+lung+assist+devices.">Ultra-thin gas permeable free-standing and composite membranes for microfluidic lung assist devices.</a> Biomaterials. 32, 3883-3889 (2011).</li><li>Wan, L. -. S., Liu, Z. -. M., Xu, Z. -. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Surface+engineering+of+macroporous+polypropylene+membranes.">Surface engineering of macroporous polypropylene membranes.</a> Soft Matter. 5, 1775-1785 (2009).</li><li>Alcoutlabi, M., McKenna, G. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effects+of+confinement+on+material+behaviour+at+the+nanometre+size+scale.">Effects of confinement on material behaviour at the nanometre size scale.</a> Journal of Physics-Condensed Matter. 17, R461-R524 (2005).</li><li>Ellison, C. J., Torkelson, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+distribution+of+glass-transition+temperatures+in+nanoscopically+confined+glass+formers.">The distribution of glass-transition temperatures in nanoscopically confined glass formers.</a> Nature Materials. 2, 695-700 (2003).</li><li>Priestley, R. D., Ellison, C. J., Broadbelt, L. J., Torkelson, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Structural+relaxation+of+polymer+glasses+at+surfaces,+interfaces+and+in+between.">Structural relaxation of polymer glasses at surfaces, interfaces and in between.</a> Science. 309, 456-459 (2005).</li><li>Si, L., Massa, M. V., Dalnoki-Veress, K., Brown, H. R., Jones, R. A. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Chain+entanglement+in+thin+freestanding+polymer+films.">Chain entanglement in thin freestanding polymer films.</a> Phys. Rev. Lett. 94, (2005).</li><li>Torres, J. M., Stafford, C. M., Vogt, B. D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Elastic+Modulus+of+Amorphous+Polymer+Thin+Films:+Relationship+to+the+Glass+Transition+Temperature.">Elastic Modulus of Amorphous Polymer Thin Films: Relationship to the Glass Transition Temperature.</a> Acs Nano. 3, 2677-2685 (2009).</li><li>Baxamusa, S. H., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhanced+Delamination+of+Ultrathin+Free-Standing+Polymer+Films+via+Self-Limiting+Surface+Modification.">Enhanced Delamination of Ultrathin Free-Standing Polymer Films via Self-Limiting Surface Modification.</a> Langmuir. 30, 5126-5132 (2014).</li><li>Buck, M. E., Lynn, D. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Free-Standing+and+Reactive+Thin+Films+Fabricated+by+Covalent+Layer-by-Layer+Assembly+and+Subsequent+Lift-Off+of+Azlactone-Containing+Polymer+Multilayers.">Free-Standing and Reactive Thin Films Fabricated by Covalent Layer-by-Layer Assembly and Subsequent Lift-Off of Azlactone-Containing Polymer Multilayers.</a> Langmuir. 26, 16134-16140 (2010).</li><li>Freund, L. B., Suresh, S. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Thin Film Materials: Stress, Defect Formation and Surface Evolution. , (2003).</li><li>Dubas, S. T., Farhat, T. R., Schlenoff, J. B. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Multiple+Membranes+from+&#8220;True&#8221;+Polyelectrolyte+Multilayers.">Multiple Membranes from &#8220;True&#8221; Polyelectrolyte Multilayers.</a> J. Am. Chem. Soc. 123, 5368-5369 (2001).</li><li>Linder, V., Gates, B. D., Ryan, D., Parviz, B. A., Whitesides, G. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Water-soluble+sacrificial+layers+for+surface+micromachining.">Water-soluble sacrificial layers for surface micromachining.</a> Small. 1, 730-736 (2005).</li><li>Mamedov, A. A., Kotov, N. A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Free-Standing+Layer-by-Layer+Assembled+Films+of+Magnetite+Nanoparticles.">Free-Standing Layer-by-Layer Assembled Films of Magnetite Nanoparticles.</a> Langmuir. 16, 5530-5533 (2000).</li><li>Ono, S. S., Decher, G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+Ultrathin+Self-Standing+Polyelectrolyte+Multilayer+Membranes+at+Physiological+Conditions+Using+pH-Responsive+Film+Segments+as+Sacrificial+Layers.">Preparation of Ultrathin Self-Standing Polyelectrolyte Multilayer Membranes at Physiological Conditions Using pH-Responsive Film Segments as Sacrificial Layers.</a> Nano Lett. 6, 592-598 (2006).</li><li>Stroock, A. D., Kane, R. S., Weck, M., Metallo, S. J., Whitesides, G. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Synthesis of Free-Standing Quasi-Two-Dimensional Polymers. Langmuir. 19, 2466-2472 (2002).</li><li>Kriz, J., Dybal, J., Kurkova, D. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cooperativity+in+macromolecular+interactions+as+a+proximity+effect:+NMR+and+theoretical+study+of+electrostatic+coupling+of+weakly+charged+complementary+polyions.">Cooperativity in macromolecular interactions as a proximity effect: NMR and theoretical study of electrostatic coupling of weakly charged complementary polyions.</a> J. Phys. Chem. B. 107, 12165-12174 (2003).</li><li>Krogman, K. C., Zacharia, N. S., Schroeder, S., Hammond, P. T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Automated+Process+for+Improved+Uniformity+and+Versatility+of+Layer-by-Layer+Deposition.">Automated Process for Improved Uniformity and Versatility of Layer-by-Layer Deposition.</a> Langmuir. 23, 3137-3141 (2007).</li><li>Hall, D. B., Underhill, P., Torkelson, J. M. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spin+coating+of+thin+and+ultrathin+polymer+films.">Spin coating of thin and ultrathin polymer films.</a> Polymer Engineering &amp; Science. 38, 2039-2045 (1998).</li></ol>

作者什么都没有透露。

在PDAC基板处理是基于自限静电相互作用，这意味着任何尺寸的基板可以容易地处理过的，只要它们是带负电荷的（ 例如 ，硅或玻璃）。 图1-2显示了非常大的薄膜（13厘米在直径）制造使用此协议，唯一的变化是所用的试剂的体积。最终达到的尺寸出现仅由沉积和剥离设备或用于制造自支撑结构的聚合物的最终强度的限制。而前者显然是一个实际的问题，后者不是的聚合物的?...

自由站立薄聚合物膜被用在各种应用，包括传感器，1-3的MEMs，催化或过滤，4和组织工程。5-8它们还用于基础研究探索聚合物在封闭条件下的行为。9- 13所述的自立式膜是一个支撑在非连续基底例如环形环或环箍相对于在硅晶片或玻璃载玻片。这项工作描述了一个简单的，可重复的制造过程为超薄的自立聚合物膜，是适合于大面积膜或高通量的生产。它是一种具有多种不同的聚合物，包括聚（乙烯醇缩甲醛），聚苯乙烯，和聚（甲基丙烯酸甲酯）的兼容。它可被用于制造自支撑膜是一样大的13厘米直径或薄10纳米。 的自由站立的聚合物的制造包括三个基本步骤:1）D聚合物膜的eposition到传统衬底诸如晶片或幻灯片，2） 释放或从基材膜的剥离 ，和3） 捕获得到的膜的到载体上。本文详细介绍了我们在报道的各种版本方法的早期研究的过程。14 沉积可通过任何数目的基本聚合物薄膜的技术，如旋涂，蒸镀，或浸涂来实现。在这项工作中，我们采用标准的旋涂技术。 的"剥离浮于"技术是最常用的方法，用于从它的基底释放超薄膜15在这种技术中，薄膜和基板浸在适当的溶剂浴中。溶剂溶胀的膜和诱导自发分层，释放膜并使其漂浮到浴的顶部。最小膜厚度可使用提起被释放断开浮筒上通过与膨胀引起的应变能平衡界面剥离能量确定:16 <img alt="式（1）" src="/files/ftp_upload/52832/52832eq1.jpg" width="200" /> （1） 其中，L是膜厚度，νf是薄膜的泊松比，E是杨氏模量的膜，ξ为膜的溶胀比，和γ是剥离的界面能。的典型方式绕过由公式所施加的限制（1）是沉积膜和淀积衬底之间的牺牲层间17-20当此夹层溶解在溶剂浴，膜被释放，并且可以在支撑被捕获。一个相关的方法是牺牲覆盖层的方法，它利用膜的机械剥离到牺牲层PRIOR溶解。21 使用牺牲材料的有几个主要缺点。首先，增加了一个额外的处理材料和步骤，可能需要最佳膜制造条件和牺牲材料的加工条件之间的折衷。第二，牺牲材料可能难以存在不影响机械性能的最终自立式膜的或纯度。第三，该方法用于沉积牺牲材料必须优化并监测质量在整体自立式膜制造的操作。14 在这项工作中，我们描述了一种表面改性技术，降低了界面剥离能量，使剥离浮于技术用于超薄膜。淀积衬底通过组装一个自限，自优化近单层的聚阳离子polydiallyldiammonium氯（PDAC）改性。由于聚阳离子和基片之间的结合强度，该表面改性是稳健的后续工艺步骤。近单层形成的自我限制和自我优化性质要求几乎为零优化是容易扩展到大面积。 以下的去除，该膜浮到溶剂浴的顶部，其中它被捕获在环箍状支撑。尽管不十分重视在现存文献，在这项工作中，我们将描述用于捕获大面积薄膜在载体上，以减少撕裂或以其他方式损坏膜的概率技术。

<table><tbody><tr><td>Vinylec E</td><td>SPI</td><td></td><td></td></tr><tr><td>ethyl lactate, &gt;98%, FCC, FG</td><td>Sigma-Aldrich</td><td>W244007-1KG-K</td><td></td></tr><tr><td>4&quot; silicon wafers &amp;lt;100&gt;, Single side polished</td><td>International Wafer Service</td><td></td><td></td></tr><tr><td>sulfuric acid, 98%, ACS reagent grade</td><td>Sigma-Aldrich</td><td>320501-6X500ML</td><td></td></tr><tr><td>hydrogen peroxide, 30%, semiconductor grade</td><td>Sigma-Aldrich</td><td>316989-3.7L</td><td></td></tr><tr><td>isopropanol, ACS grade, 4 L</td><td>Fisher Scientific</td><td>A464-4</td><td></td></tr><tr><td>dichloromethane, ACS grade</td><td>Alfa-Aesar</td><td>22917</td><td></td></tr><tr><td>deionized water, distilled</td><td></td><td></td><td></td></tr><tr><td>PDAC reagent (Sigma-Aldrich 409014)</td><td>Sigma-Aldrich</td><td>409014</td><td></td></tr><tr><td>Spin Coater</td><td>Laurell Technologies&amp;nbsp;</td><td>WS-650-23</td><td></td></tr><tr><td>Barnstead/Thermolyne Super Nuova explosion-proof hot plate&amp;nbsp;</td><td></td><td></td><td></td></tr><tr><td>explosion-proof forced air oven</td><td>VWR&amp;nbsp;</td><td>1330 FMS&amp;nbsp;</td><td></td></tr><tr><td>balance with a range of 1&amp;nbsp;mg to 1,020&amp;nbsp;g</td><td>Mettler Toledo</td><td>MS1003S</td><td></td></tr><tr><td>reflectance spectrometer</td><td>Filmetrics</td><td>F20-UV</td><td></td></tr><tr><td>manipulator consisting of a Klinger tilt stage, a Brinkman rack-and-pinion and a lab jack&amp;nbsp;</td><td></td><td></td><td></td></tr><tr><td>Cutting tool/template, LLNL-built, no drawings</td><td></td><td></td><td></td></tr><tr><td>straight edge, LLNL, no drawings</td><td></td><td></td><td></td></tr><tr><td>Tent hoop, LLNL</td><td></td><td></td><td></td></tr><tr><td>culture dish 190 mm x 100 mm, Pyrex</td><td>VWR</td><td></td><td></td></tr><tr><td>20 ml beaker, Pyrex</td><td>VWR</td><td></td><td></td></tr><tr><td>250 ml beaker, Pyrex</td><td>VWR</td><td></td><td></td></tr><tr><td>1,000 ml beaker, Pyrex</td><td>VWR</td><td></td><td></td></tr><tr><td>60 ml glass vial with plastic stopper&amp;nbsp;</td><td>VWR</td><td></td><td></td></tr><tr><td>Petri dish, 150 mm diameter x2, Pyrex</td><td>VWR</td><td></td><td></td></tr><tr><td>600 ml beaker x2, Pyrex</td><td>VWR</td><td></td><td></td></tr><tr><td>tweezers, stainless steel</td><td></td><td></td><td></td></tr><tr><td>cutting blade</td><td>Exacto</td><td></td><td></td></tr><tr><td>clean room wipes</td><td>Contec&amp;nbsp;</td><td>PNHS-99</td><td></td></tr><tr><td>polyester knit 9/91 IPA/DI water wipes</td><td>Contec&amp;nbsp;</td><td>Prosat&amp;nbsp;</td><td></td></tr><tr><td>Fluoroware wafer trays</td><td>Ted Pella</td><td>1395-40</td><td></td></tr><tr><td>Nylon Micro fiber (camel hair)</td><td></td><td></td><td></td></tr><tr><td>Disposable BD 3-ml plastic syringe</td><td>VWR</td><td></td><td></td></tr><tr><td>0.2 &amp;#956;m Luer-lock PTFE filters</td><td>Acrodisc&amp;nbsp;</td><td></td><td></td></tr><tr><td>0.45 &amp;#956;m Luer-lock PTFE filters</td><td>Acrodisc&amp;nbsp;</td><td></td><td></td></tr></tbody></table>

fabrication of large-area free-standing ultrathin polymer films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films. Typically, ultrathin films are prepared using either sacrificial layers, which may damage the film or affect its mechanical properties, or they are made on freshly cleaved mica, a substrate that is difficult to scale. Further, the size of ultrathin film is typically limited to a few square millimeters. In this method, we modify a surface with a polyelectrolyte that alters the strength of adhesion between polymer and deposition substrate. The polyelectrolyte can be shown to remain on the wafer using spectroscopy, and a treated wafer can be used to produce multiple films, indicating that at best minimal amounts of the polyelectrolyte are added to the film. The process has thus far been shown to be limited in scalability only by the size of the coating equipment, and is expected to be readily scalable to industrial processes. In this study, the protocol for making the solutions, preparing the deposition surface, and producing the films is described.

图1示出了在大面积上一个独立的聚合物薄膜的一个例子。使用此处介绍的过程，并安装在一个13厘米直径的钢箍此为55nm厚的聚乙烯醇缩甲醛膜制成。发生脱层大面积不引入，导致撕开薄膜的缺陷。因此，聚乙烯醇缩甲醛的内在强度甚至可以为非常薄的膜利用。 图2示出了一个22纳米厚的自支撑膜是足够强以装载用表玻璃和铜珠称量的质量&gt; 3×10 5次电影本身。椭?...

Watch this Scientific Journal Video about Fabrication of Large-area Free-standing Ultrathin Polymer Films at JoVE.com

Fabrication of Large-area Free-standing Ultrathin Polymer Films

We describe a method for the fabrication of large-area (up to 13 cm diameter) and ultrathin (as thin as 8 nm) polymer films. Instead of using a sacrificial interlayer to delaminate the film from its substrate, we use a self-limiting surface treatment suitable for arbitrarily large areas.

大面积的制造自立性的超薄聚合物薄膜

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films.  Typically, ultrathin films are prepared ...

fabrication-of-large-area-free-standing-ultrathin-polymer-films

Research

JoVE Journal

Chemistry

15.2K 次观看.  Lawrence Livermore National Laboratory. We describe a method for the fabrication of large-area (up to 13 cm diameter) and ultrathin (as thin as 8 nm) polymer films. Instead of using a sacrificial interlayer to delaminate the film from its substrate, we use a self-limiting surface treatment suitable for arbitrarily large areas.

视频: Fabrication of Large-area Free-standing Ultrathin Polymer Films

Micropunching Lithography for Generating Micro- and Submicron-patterns on Polymer Substrates

Conducting polymers have attracted great attention since the discovery of high conductivity in doped polyacetylene in 19771. They offer the advantages of low weight, easy tailoring of properties and a wide spectrum of applications2,3. Due to sensitivity of conducting polymers to environmental conditions (e.g., air, oxygen, moisture, high temperature and chemical solutions), lithographic techniques present significant technical challenges when working with these materials4. For example, current photolithographic methods, such as ultra-violet (UV), are unsuitable for patterning the conducting polymers due to the involvement of wet and/or dry etching processes in these methods. In addition, current micro/nanosystems mainly have a planar form5,6. One layer of structures is built on the top surfaces of another layer of fabricated features. Multiple layers of these structures are stacked together to form numerous devices on a common substrate. The sidewall surfaces of the microstructures have not been used in constructing devices. On the other hand, sidewall patterns could be used, for example, to build 3-D circuits, modify fluidic channels and direct horizontal growth of nanowires and nanotubes.
A macropunching method has been applied in the manufacturing industry to create macropatterns in a sheet metal for over a hundred years. Motivated by this approach, we have developed a micropunching lithography method (MPL) to overcome the obstacles of patterning conducting polymers and generating sidewall patterns. Like the macropunching method, the MPL also includes two operations (Fig. 1): (i) cutting; and (ii) drawing. The "cutting" operation was applied to pattern three conducting polymers4, polypyrrole (PPy), Poly(3,4-ethylenedioxythiophen)-poly(4-styrenesulphonate) (PEDOT) and polyaniline (PANI). It was also employed to create Al microstructures7. The fabricated microstructures of conducting polymers have been used as humidity8, chemical8, and glucose sensors9. Combined microstructures of Al and conducting polymers have been employed to fabricate capacitors and various heterojunctions9,10,11. The "cutting" operation was also applied to generate submicron-patterns, such as 100- and 500-nm-wide PPy lines as well as 100-nm-wide Au wires. The "drawing" operation was employed for two applications: (i) produce Au sidewall patterns on high density polyethylene (HDPE) channels which could be used for building 3D microsystems12,13,14, and (ii) fabricate polydimethylsiloxane (PDMS) micropillars on HDPE substrates to increase the contact angle of the channel15.

A micropunching lithography approach is developed to generate micro- and submicron-patterns on top, sidewall and bottom surfaces of polymer substrates. It overcomes the obstacles of patterning conducting polymers and generating sidewall patterns. This method allows rapid fabrication of multiple features and is free of aggressive chemistry.

Micropunching为微型和亚微米模式聚合物基板上生成的光刻

Conducting polymers have attracted great attention since the discovery of high conductivity in doped polyacetylene in 19771. They offer the advantages of ...

科研

工程学

Towards Biomimicking Wood: Fabricated Free-standing Films of Nanocellulose, Lignin, and a Synthetic Polycation

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and lignin. Layer-by-layer (LbL) assembly process which relies on the assembly of oppositely charged molecules from aqueous solutions was used to build a freestanding composite film of isolated wood polymers of lignin and oxidized nanofibril cellulose (NFC). To facilitate the assembly of these negatively charged polymers, a positively charged polyelectrolyte, poly(diallyldimethylammomium chloride) (PDDA), was used as a linking layer to create this simplified model cell wall. The layered adsorption process was studied quantitatively using quartz crystal microbalance with dissipation monitoring (QCM-D) and ellipsometry. The results showed that layer mass/thickness per adsorbed layer increased as a function of total number of layers. The surface coverage of the adsorbed layers was studied with atomic force microscopy (AFM). Complete coverage of the surface with lignin in all the deposition cycles was found for the system, however, surface coverage by NFC increased with the number of layers. The adsorption process was carried out for 250 cycles (500 bilayers) on a cellulose acetate (CA) substrate. Transparent free-standing LBL assembled nanocomposite films were obtained when the CA substrate was later dissolved in acetone. Scanning electron microscopy (SEM) of the fractured cross-sections showed a lamellar structure, and the thickness per adsorption cycle (PDDA-Lignin-PDDA-NC) was estimated to be 17 nm for two different lignin types used in the study. The data indicates a film with highly controlled architecture where nanocellulose and lignin are spatially deposited on the nanoscale (a polymer-polymer nanocomposites), similar to what is observed in the native cell wall.

The objective of this research was to form synthetic plant cell wall tissue using layer-by-layer assembly of nanocellulose fibrils and isolated lignin assembled from dilute aqueous suspensions.&#160; Surface measurement techniques of quartz crystal microbalance and atomic force microscopy were used to monitor the formation of the polymer-polymer nanocomposite material.

朝仿生学木：纳米纤维素，木质素的装配式自由站立电影和合成聚阳离子

Woody materials are comprised of plant cell walls that contain a layered secondary cell wall composed of structural polymers of polysaccharides and ...

化学

Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in combination with their outstanding thermal and chemical stability, and low densities. However, their insoluble nature causes problems in their processing since usually applied techniques such as spin coating are not available. Especially for membrane applications, where the processing of CMP as thin films is desirable, the processing problems have hindered their commercial application.
Here we describe the interfacial synthesis of CMP thin films on functionalized substrates via molecular layer-by-layer (l-b-l) synthesis. This process allows the preparation of films with desired thickness and composition and even desired composition gradients.
The use of sacrificial supports allows the preparation of freestanding membranes by dissolution of the support after the synthesis. To handle such ultra-thin freestanding membranes the protection with sacrificial coatings showed great promise, to avoid rupture of the nanomembranes. To transfer the nanomembranes to the desired substrate, the coated membranes are upfloated at the air-liquid interface and then transferred via dip coating.

In this paper we describe the interfacial synthesis of conjugated microporous polymers (CMP) on sacrificial substrates, and the dissolution of the substrate for the preparation of freestanding CMP nanomembranes. In addition, we will describe how the fragile nanomembranes can be transferred to other substrates.

层 - 层的合成和独立式共轭微孔聚合物纳米薄膜的转移

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in ...

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. Conductive polymers, poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(3,4-propylenedioxythiophene) (PProDOT), and a semiconducting polymer, poly(thieno[3,2-b]thiophene) (PTT), were deposited on unconventional highly-disordered and textured substrates with high surface areas, such as paper, towels and fabrics. This reported deposition chamber is an improvement of previous vapor reactors because our system can accommodate both volatile and nonvolatile monomers, such as 3,4-propylenedioxythiophene and thieno[3,2-b]thiophene. Utilization of both solid and liquid oxidants are also demonstrated. One limitation of this method is that it lacks sophisticated in situ thickness monitors. Polymer coatings made by the commonly used solution-based coating methods, such as spin-coating and surface grafting, are often not uniform or susceptible to mechanical degradation. This reported vapor phase deposition method overcomes those drawbacks and is a strong alternative to common solution-based coating methods. Notably, polymer films coated by the reported method are uniform and conformal on rough surfaces, even at a micrometer scale. This feature allows for future application of vapor deposited polymers in electronics devices on flexible and highly textured substrates.

This paper presents a protocol for reactive vapor deposition of poly(3,4-ethylenedioxythiophene), poly(3,4-propylenedioxythiophene), and poly(thieno[3,2-b]thiophene) films on glass slides and rough substrates, such as textiles and paper.

任意基底上共轭聚合物薄膜的反应气相沉积

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. ...

Fabrication of Ultra-thin Color Films with Highly Absorbing Media Using Oblique Angle Deposition

Ultra-thin film structures have been studied extensively for use as optical coatings, but performance and fabrication challenges remain.&#160; We present an advanced method for fabricating ultra-thin color films with improved characteristics. The proposed process addresses several fabrication issues, including large area processing. Specifically, the protocol describes a process for fabricating ultra-thin color films using an electron beam evaporator for oblique angle deposition of germanium (Ge) and gold (Au) on silicon (Si) substrates.&#160; Film porosity produced by the oblique angle deposition induces color changes in the ultra-thin film. The degree of color change depends on factors such as deposition angle and film thickness. Fabricated samples of the ultra-thin color films showed improved color tunability and color purity. In addition, the measured reflectance of the fabricated samples was converted into chromatic values and analyzed in terms of color. Our ultra-thin film fabricating method is expected to be used for various ultra-thin film applications such as flexible color electrodes, thin film solar cells, and optical filters. Also, the process developed here for analyzing the color of the fabricated samples is broadly useful for studying various color structures.

We present a detailed method for fabricating ultra-thin color films with improved characteristics for optical coatings. The oblique angle deposition technique using an electron beam evaporator allows improved color tunability and purity. Fabricated films of Ge and Au on Si substrates were analyzed by reflectance measurements and color information conversion.

用斜角沉积法制备高吸收介质的超薄彩色薄膜

Ultra-thin film structures have been studied extensively for use as optical coatings, but performance and fabrication challenges remain.&#160; We present ...

Fabricating Reactive Surfaces with Brush-like and Crosslinked Films of Azlactone-Functionalized Block Co-Polymers

In this paper, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl dimethyl azlactone) (PGMA-b-PVDMA), are presented. Due to the high reactivity of azlactone groups towards amine, thiol, and hydroxyl groups, PGMA-b-PVDMA surfaces can be modified with secondary molecules to create chemically or biologically functionalized interfaces for a variety of applications. Previous reports of patterned PGMA-b-PVDMA interfaces have used traditional top-down patterning techniques that generate non-uniform films and poorly controlled background chemistries. Here, we describe customized patterning techniques that enable precise deposition of highly uniform PGMA-b-PVDMA films in backgrounds that are chemically inert or that have biomolecule-repellent properties. Importantly, these methods are designed to deposit PGMA-b-PVDMA films in a manner that completely preserves azlactone functionality through each processing step. Patterned films show well-controlled thicknesses that correspond to polymer brushes (~90 nm) or to highly crosslinked structures (~1-10 &#956;m). Brush patterns are generated using either the parylene lift-off or interface directed assembly methods described and are useful for precise modulation of overall chemical surface reactivity by adjusting either the PGMA-b-PVDMA pattern density or the length of the VDMA block. In contrast, the thick, crosslinked PGMA-b-PVDMA patterns are obtained using a customized micro-contact printing technique and offer the benefit of higher loading or capture of secondary material due to higher surface area to volume ratios. Detailed experimental steps, critical film characterizations, and trouble-shooting guides for each fabrication method are discussed.

Surface fabrication methods for patterned deposition of nanometer thick brushes or micron thick, crosslinked films of an azlactone block co-polymer are reported. Critical experimental steps, representative results, and limitations of each method are discussed. These methods are useful for creating functional interfaces with tailored physical features and tunable surface reactivity.

Azlactone 功能块共聚物的刷状和交联膜制备反应表面

In this paper, fabrication methods that generate novel surfaces using the azlactone-based block co-polymer, poly (glycidyl methacrylate)-block-poly (vinyl ...

Thin Film Composite Silicon Elastomers for Cell Culture and Skin Applications: Manufacturing and Characterization

In this protocol, we present methods to fabricate thin elastomer composite films for advanced cell culture applications and for the development of skin adhesives. Two different poly-(dimethyl siloxanes) (PDMS and soft skin adhesive (SSA)), have been used for in depth investigation of biological effects and adhesive characteristics. The composite films consist of a flexible backing layer and an adhesive top coating. Both layers have been manufactured by doctor blade application technique. In the present investigation, the adhesive behavior of the composite films has been investigated as a function of the layer thickness or a variation of the Young&#39;s modulus of the top layer. The Young&#39;s modulus of PDMS has been changed by varying the base to crosslinker mixing ratio. In addition, the thickness of SSA films has been varied from approx. 16 &#181;m to approx. 320 &#181;m. Scanning electron microscopy (SEM) and optical microscopy have been used for thickness measurements. The adhesive properties of elastomer films depend strongly on the film thickness, the Young&#39;s modulus of the polymers and surface characteristics. Therefore, normal adhesion of these films on glass substrates exhibiting smooth and rough surfaces has been investigated. Pull-off stress and work of separation are dependent on the mixing ratio of silicone elastomers.
Additionally, the thickness of the soft skin adhesive placed on top of a supportive backing layer has been varied in order to produce patches for skin applications. Cytotoxicity, proliferation and cellular adhesion of L929 murine fibroblasts on PDMS films (mixing ratio 10:1) and SSA films (mixing ratio 50:50) have been conducted. We have shown here, for the first time, the side by side comparison of thin composite films manufactured of both polymers and present the investigation of their biological- and adhesive properties.

A protocol for the manufacturing process of polymeric thin film composite structures possessing either different Young&#39;s moduli or thicknesses is presented. Films are produced for advanced cell culture studies or as skin adhesives.

用于细胞培养和皮肤应用的薄膜复合硅弹性体: 制造和表征

In this protocol, we present methods to fabricate thin elastomer composite films for advanced cell culture applications and for the development of skin ...

发育生物学

Procedure for the Transfer of Polymer Films Onto Porous Substrates with Minimized Defects

The fabrication of devices containing thin film composite membranes necessitates the transfer of these films onto the surfaces of arbitrary support substrates. Accomplishing this transfer in a highly controlled, mechanized, and reproducible manner can eliminate the creation of macroscale defect structures (e.g., tears, cracks, and wrinkles) within the thin film that compromise device performance and the usable area per sample. Here, we describe a general protocol for the highly controlled and mechanized transfer of a polymeric thin film onto an arbitrary porous support substrate for eventual use as a water filtration membrane device. Specifically, we fabricate a block copolymer (BCP) thin film on top of a sacrificial, water-soluble poly(acrylic acid) (PAA) layer and silicon wafer substrate. We then utilize a custom-designed, 3D-printed transfer tool and drain chamber system to deposit, lift-off, and transfer the BCP thin film onto the center of a porous anodized aluminum oxide (AAO) support disc. The transferred BCP thin film is shown to be consistently placed onto the center of the support surface due to the guidance of the meniscus formed between the water and the 3D-printed plastic drain chamber. We also compare our mechanized transfer-processed thin films to those that have been transferred by hand with the use of tweezers. Optical inspection and image analysis of the transferred thin films from the mechanized process confirm that little-to-no macroscale inhomogeneities or plastic deformations are produced, as compared to the multitude of tears and wrinkles produced from manual transfer by hand. Our results suggest that the proposed strategy for thin film transfer can reduce defects when compared to other methods across many systems and applications.

We present a procedure for highly controlled and wrinkle-free transfer of block copolymer thin films onto porous support substrates using a 3D-printed drain chamber. The drain chamber design is of general relevance to all procedures involving transfer of macromolecular films onto porous substrates, which is normally done by hand in an irreproducible fashion.

聚合物薄膜在多孔基板上的转移程序,具有最小化的缺陷

The fabrication of devices containing thin film composite membranes necessitates the transfer of these films onto the surfaces of arbitrary support ...

A Femtoliter Droplet Array for Massively Parallel Protein Synthesis from Single DNA Molecules

Advances in spatial resolution and detection sensitivity of scientific instrumentation make it possible to apply small reactors for biological and chemical research. To meet the demand for high-performance microreactors, we developed a femtoliter droplet array (FemDA) device and exemplified its application in massively parallel cell-free protein synthesis (CFPS) reactions. Over one million uniform droplets were readily generated within a finger-sized area using a two-step oil-sealing protocol. Every droplet was anchored in a femtoliter microchamber composed of a hydrophilic bottom and a hydrophobic sidewall. The hybrid hydrophilic-in-hydrophobic structure and the dedicated sealing oils and surfactants are crucial for stably retaining the femtoliter aqueous solution in the femtoliter space without evaporation loss. The femtoliter configuration and the simple structure of the FemDA device allowed minimal reagent consumption. The uniform dimension of the droplet reactors made large-scale quantitative and time-course measurements convincing and reliable. The FemDA technology correlated the protein yield of the CFPS reaction with the number of DNA molecules in each droplet. We streamlined the procedures about the microfabrication of the device, the formation of the femtoliter droplets, and the acquisition and analysis of the microscopic image data. The detailed protocol with the optimized low running cost makes the FemDA technology accessible to everyone who has standard cleanroom facilities and a conventional fluorescence microscope in their own place.

The overall goal of the protocol is to prepare over one million ordered, uniform, stable, and biocompatible femtoliter droplets on a 1 cm2 planar substrate that can be used for cell-free protein synthesis.

用于从单一DNA分子大规模平行蛋白质合成的Femtoliter滴体阵列

Advances in spatial resolution and detection sensitivity of scientific instrumentation make it possible to apply small reactors for biological and ...

A Simple and Scalable Fabrication Method for Organic Electronic Devices on Textiles

Today, wearable electronics devices combine a large variety of functional, stretchable, and flexible technologies. However, in many cases, these devices cannot be worn under everyday conditions. Therefore, textiles are commonly considered the best substrate to accommodate electronic devices in wearable use. In this paper, we describe how to selectively pattern organic electroactive materials on textiles from a solution in an easy and scalable manner. This versatile deposition technique enables the fabrication of wearable organic electronic devices on clothes.

In this paper, we present a protocol to selectively deposit organic materials on textiles, which allows for the direct integration of organic electronic devices with wearables. The fabricated devices can be fully integrated in textiles, respecting their mechanical appearance and enabling sensing capabilities.

关于纺织品有机电子设备的简单和可扩展的制作方法

Today, wearable electronics devices combine a large variety of functional, stretchable, and flexible technologies. However, in many cases, these devices ...