A Versatile Method for Tuning the Chemistry and Size of Nanoscopic Features by Living Free Radical Polymerization
A novel approach is presented for manipulating the size and chemistry of nanoscopic features using a combination of contact molding and living free radical polymerization. In this approach a highly cross-linked photopolymer, based on a methacrylate/acrylate mixture, was patterned into submicrometer-...
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| Veröffentlicht in: | Journal of the American Chemical Society 2003-04, Vol.125 (13), p.3831-3838 |
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| container_end_page | 3838 |
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| container_issue | 13 |
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| container_title | Journal of the American Chemical Society |
| container_volume | 125 |
| creator | von Werne, Timothy A Germack, David S Hagberg, Erik C Sheares, Valerie V Hawker, Craig J Carter, Kenneth R |
| description | A novel approach is presented for manipulating the size and chemistry of nanoscopic features using a combination of contact molding and living free radical polymerization. In this approach a highly cross-linked photopolymer, based on a methacrylate/acrylate mixture, was patterned into submicrometer-sized features on a silicon wafer using a contact-molding technique. A critical component of the monomer mixture was the incorporation of an initiator containing monomer into the network structure, which provides sites for functional group amplification. Features ranging in size from 5 μm to |
| doi_str_mv | 10.1021/ja028866n |
| format | Article |
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In this approach a highly cross-linked photopolymer, based on a methacrylate/acrylate mixture, was patterned into submicrometer-sized features on a silicon wafer using a contact-molding technique. A critical component of the monomer mixture was the incorporation of an initiator containing monomer into the network structure, which provides sites for functional group amplification. Features ranging in size from 5 μm to <60 nm were accurately replicated by this process and living free radical polymerizations, both atom transfer radical and nitroxide-mediated polymerization (NMP), could be conducted from these initiating sites to yield polymer brushes which represent a grafted layer of linear chains attached to the original network polymer. Grafts consisting of polystyrene, poly(methyl methacrylate), and poly(2-hydroxyethyl)methacrylate were grown with controlled thicknesses ranging from 10 to 143 nm and graft molecular weights of between 18 000 to 290 000 amu. As a result of this secondary graft process, feature sizes could be tuned from the original 100 nm down to 20 nm, and the surface chemistry varied from hydrophilic to hydrophobic starting from the same initial master pattern. The thin films and patterned features were characterized by contact angle, ellipsometry, optical, and atomic force microscopies.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/ja028866n</identifier><identifier>PMID: 12656616</identifier><identifier>CODEN: JACSAT</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Applied sciences ; Exact sciences and technology ; Organic polymers ; Physicochemistry of polymers ; Polymers with particular properties ; Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><ispartof>Journal of the American Chemical Society, 2003-04, Vol.125 (13), p.3831-3838</ispartof><rights>Copyright © 2003 American Chemical Society</rights><rights>2003 INIST-CNRS</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a482t-c5f297a2ddc2e2ed698637fa001216da0b123cf03da5c5eb6d12ca01adc7cb683</citedby><cites>FETCH-LOGICAL-a482t-c5f297a2ddc2e2ed698637fa001216da0b123cf03da5c5eb6d12ca01adc7cb683</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://pubs.acs.org/doi/pdf/10.1021/ja028866n$$EPDF$$P50$$Gacs$$H</linktopdf><linktohtml>$$Uhttps://pubs.acs.org/doi/10.1021/ja028866n$$EHTML$$P50$$Gacs$$H</linktohtml><link.rule.ids>315,781,785,2766,27081,27929,27930,56743,56793</link.rule.ids><backlink>$$Uhttp://pascal-francis.inist.fr/vibad/index.php?action=getRecordDetail&idt=14652395$$DView record in Pascal Francis$$Hfree_for_read</backlink><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/12656616$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>von Werne, Timothy A</creatorcontrib><creatorcontrib>Germack, David S</creatorcontrib><creatorcontrib>Hagberg, Erik C</creatorcontrib><creatorcontrib>Sheares, Valerie V</creatorcontrib><creatorcontrib>Hawker, Craig J</creatorcontrib><creatorcontrib>Carter, Kenneth R</creatorcontrib><title>A Versatile Method for Tuning the Chemistry and Size of Nanoscopic Features by Living Free Radical Polymerization</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>A novel approach is presented for manipulating the size and chemistry of nanoscopic features using a combination of contact molding and living free radical polymerization. In this approach a highly cross-linked photopolymer, based on a methacrylate/acrylate mixture, was patterned into submicrometer-sized features on a silicon wafer using a contact-molding technique. A critical component of the monomer mixture was the incorporation of an initiator containing monomer into the network structure, which provides sites for functional group amplification. Features ranging in size from 5 μm to <60 nm were accurately replicated by this process and living free radical polymerizations, both atom transfer radical and nitroxide-mediated polymerization (NMP), could be conducted from these initiating sites to yield polymer brushes which represent a grafted layer of linear chains attached to the original network polymer. Grafts consisting of polystyrene, poly(methyl methacrylate), and poly(2-hydroxyethyl)methacrylate were grown with controlled thicknesses ranging from 10 to 143 nm and graft molecular weights of between 18 000 to 290 000 amu. As a result of this secondary graft process, feature sizes could be tuned from the original 100 nm down to 20 nm, and the surface chemistry varied from hydrophilic to hydrophobic starting from the same initial master pattern. The thin films and patterned features were characterized by contact angle, ellipsometry, optical, and atomic force microscopies.</description><subject>Applied sciences</subject><subject>Exact sciences and technology</subject><subject>Organic polymers</subject><subject>Physicochemistry of polymers</subject><subject>Polymers with particular properties</subject><subject>Preparation, kinetics, thermodynamics, mechanism and catalysts</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2003</creationdate><recordtype>article</recordtype><recordid>eNptkMFuEzEURS0EoqGw4AeQNyCxmNb2xJ7JskSkqRRKRAMsrTf2G-IwsVN7BpF-Pa4SNRtWlvWOr989hLzl7IIzwS83wERdK-WfkRGXghWSC_WcjBhjoqhqVZ6RVylt8nUsav6SnOWxVIqrEbm_oj8wJuhdh_QL9utgaRsiXQ3e-V-0XyOdrnHrUh_3FLyld-4BaWjpLfiQTNg5Q2cI_RAx0WZPF-7P47tZRKTfwDoDHV2Gbr_F6B7yL8G_Ji9a6BK-OZ7n5Pvs82o6LxZfr2-mV4sCxrXoCyNbMalAWGsECrRqkntULTDGBVcWWMNFaVpWWpBGYqMsFwYYB2sq06i6PCcfDrm7GO4HTL3OLQx2HXgMQ9JVyUvO6jKDHw-giSGliK3eRbeFuNec6Ue_-slvZt8dQ4dmi_ZEHoVm4P0RgJS7txG8cenEjZUU5URmrjhw2Sz-fZpD_K1VVVZSr5Z3WnyaL3_O2bXmp1wwSW_CEH12958F_wEzOZ5x</recordid><startdate>20030402</startdate><enddate>20030402</enddate><creator>von Werne, Timothy A</creator><creator>Germack, David S</creator><creator>Hagberg, Erik C</creator><creator>Sheares, Valerie V</creator><creator>Hawker, Craig J</creator><creator>Carter, Kenneth R</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20030402</creationdate><title>A Versatile Method for Tuning the Chemistry and Size of Nanoscopic Features by Living Free Radical Polymerization</title><author>von Werne, Timothy A ; Germack, David S ; Hagberg, Erik C ; Sheares, Valerie V ; Hawker, Craig J ; Carter, Kenneth R</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a482t-c5f297a2ddc2e2ed698637fa001216da0b123cf03da5c5eb6d12ca01adc7cb683</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2003</creationdate><topic>Applied sciences</topic><topic>Exact sciences and technology</topic><topic>Organic polymers</topic><topic>Physicochemistry of polymers</topic><topic>Polymers with particular properties</topic><topic>Preparation, kinetics, thermodynamics, mechanism and catalysts</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>von Werne, Timothy A</creatorcontrib><creatorcontrib>Germack, David S</creatorcontrib><creatorcontrib>Hagberg, Erik C</creatorcontrib><creatorcontrib>Sheares, Valerie V</creatorcontrib><creatorcontrib>Hawker, Craig J</creatorcontrib><creatorcontrib>Carter, Kenneth R</creatorcontrib><collection>Istex</collection><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>von Werne, Timothy A</au><au>Germack, David S</au><au>Hagberg, Erik C</au><au>Sheares, Valerie V</au><au>Hawker, Craig J</au><au>Carter, Kenneth R</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>A Versatile Method for Tuning the Chemistry and Size of Nanoscopic Features by Living Free Radical Polymerization</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2003-04-02</date><risdate>2003</risdate><volume>125</volume><issue>13</issue><spage>3831</spage><epage>3838</epage><pages>3831-3838</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><coden>JACSAT</coden><abstract>A novel approach is presented for manipulating the size and chemistry of nanoscopic features using a combination of contact molding and living free radical polymerization. In this approach a highly cross-linked photopolymer, based on a methacrylate/acrylate mixture, was patterned into submicrometer-sized features on a silicon wafer using a contact-molding technique. A critical component of the monomer mixture was the incorporation of an initiator containing monomer into the network structure, which provides sites for functional group amplification. Features ranging in size from 5 μm to <60 nm were accurately replicated by this process and living free radical polymerizations, both atom transfer radical and nitroxide-mediated polymerization (NMP), could be conducted from these initiating sites to yield polymer brushes which represent a grafted layer of linear chains attached to the original network polymer. Grafts consisting of polystyrene, poly(methyl methacrylate), and poly(2-hydroxyethyl)methacrylate were grown with controlled thicknesses ranging from 10 to 143 nm and graft molecular weights of between 18 000 to 290 000 amu. As a result of this secondary graft process, feature sizes could be tuned from the original 100 nm down to 20 nm, and the surface chemistry varied from hydrophilic to hydrophobic starting from the same initial master pattern. The thin films and patterned features were characterized by contact angle, ellipsometry, optical, and atomic force microscopies.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>12656616</pmid><doi>10.1021/ja028866n</doi><tpages>8</tpages></addata></record> |
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| source | ACS Publications |
| subjects | Applied sciences Exact sciences and technology Organic polymers Physicochemistry of polymers Polymers with particular properties Preparation, kinetics, thermodynamics, mechanism and catalysts |
| title | A Versatile Method for Tuning the Chemistry and Size of Nanoscopic Features by Living Free Radical Polymerization |
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