Initiated and Oxidative Chemical Vapor Deposition of Polymeric Thin Films: iCVD and oCVD

The techniques of initiated chemical vapor deposition (iCVD) and oxidative chemical vapor deposition (oCVD) enable the fabrication of chemically well-defined thin polymeric films on complex objects with micro- and nano-scale features. By depositing polymers from the vapor phase, many wetting and solution effects are avoided, and conformal films can be created. In iCVD, a variant of hot filament CVD, the deposition rate is enhanced and chemical functionalities of the polymers' constituents are maintained by including a thermally labile initiator in the feed stream. Due to the low energy required when using an initiator, delicate substrates can be coated. In oCVD, infusible, electrically conductive films are formed directly on the substrate of interest as the oxidant and monomer are introduced into the reactor simultaneously. This Feature Article provides an overview of the work that has been done to develop iCVD and oCVD into platform technologies. Relevant background, fundamentals, and applications will be discussed.

[1]  J. Badyal,et al.  Epoxide-Functionalized Solid Surfaces , 2000 .

[2]  Haeseong Lee,et al.  The preparation and characteristics of conductive poly(3,4-ethylenedioxythiophene) thin film by vapor-phase polymerization , 2003 .

[3]  Lei Zhai,et al.  Decorated Electrospun Fibers Exhibiting Superhydrophobicity , 2007 .

[4]  K. Gleason,et al.  Vapor-Deposited Fluorinated Glycidyl Copolymer Thin Films with Low Surface Energy and Improved Mechanical Properties , 2006 .

[5]  K. Gleason,et al.  Initiated chemical vapor deposition of antimicrobial polymer coatings. , 2007, Biomaterials.

[6]  C. Frank,et al.  Surface-Initiated Vapor Polymerization of Various α-Amino Acids , 2003 .

[7]  Masatoshi Sato,et al.  Photoresist Characteristics of Polyurea Films Prepared by Vapor Deposition Polymerization , 1994 .

[8]  P. Sargeant.  Fluorocyclopropanes. I. Preparation and nuclear magnetic resonance spectra , 1970 .

[9]  H. Yasuda.  Luminous Chemical Vapor Deposition and Interface Engineering , 2004 .

[10]  K. Gleason,et al.  Initiated chemical vapor deposition of trivinyltrimethylcyclotrisiloxane for biomaterial coatings. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[11]  K. Gleason,et al.  Initiated CVD of Poly(methyl methacrylate) Thin Films , 2005 .

[12]  B. Olsen,et al.  Initiation of cyclic vinylmethylsiloxane polymerization in a hot-filament chemical vapor deposition process , 2002 .

[13]  K. Gleason,et al.  Particle Surface Design using an All‐Dry Encapsulation Method , 2006 .

[14]  K. Gleason,et al.  Positive-tone nanopatterning of chemical vapor deposited polyacrylic thin films. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[15]  K. Gleason,et al.  Initiated Chemical Vapor Deposition (iCVD) of Poly(alkyl acrylates): An Experimental Study , 2006 .

[16]  Mikko Ritala,et al.  Atomic layer deposition chemistry: recent developments and future challenges. , 2003, Angewandte Chemie.

[17]  K. Neoh,et al.  Plasma polymerization and deposition of glycidyl methacrylate on Si(100) surface for adhesion improvement with polyimide , 2001 .

[18]  Keld West,et al.  Base inhibited oxidative polymerization of 3,4-ethylenedioxythiophene with iron(III)tosylate , 2005 .

[19]  K. Gleason,et al.  Photoinitiated chemical vapor deposition of polymeric thin films using a volatile photoinitiator. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[20]  K. Gleason,et al.  Perfluorooctane Sulfonyl Fluoride as an Initiator in Hot-Filament Chemical Vapor Deposition of Fluorocarbon Thin Films , 2001 .

[21]  J. Feijen,et al.  Effect of dopants on the transparency and stability of the conductivity of plasma polymerised thiophene layers , 2002 .

[22]  Sung Gap Im,et al.  Systematic control of the electrical conductivity of poly(3,4-ethylenedioxythiophene) via oxidative chemical vapor deposition , 2007 .

[23]  Fred Wudl,et al.  Facile solid-state synthesis of highly conducting poly(ethylenedioxythiophene). , 2003, Angewandte Chemie.

[24]  K. Gleason,et al.  Initiated Chemical Vapor Deposition (iCVD) of Poly(alkyl acrylates): A Kinetic Model , 2006 .

[25]  B. Trout,et al.  Thermochemistry of gas phase CF2 reactions: A density functional theory study , 2000 .

[26]  R. Schropp,et al.  Initiated chemical vapour deposition (iCVD) of thermally stable poly-glycidyl methacrylate , 2007 .

[27]  Philippe Schottland,et al.  The mechanisms of pyrrole electropolymerization , 2000 .

[28]  F. Wudl,et al.  Solid-state synthesis of a conducting polythiophene via an unprecedented heterocyclic coupling reaction. , 2003, Journal of the American Chemical Society.

[29]  S. Baxamusa,et al.  Solventless Surface Photoinitiated Polymerization: Grafting Chemical Vapor Deposition (gCVD) , 2007 .

[30]  K. Gleason,et al.  All-dry synthesis and coating of methacrylic acid copolymers for controlled release. , 2007, Macromolecular bioscience.

[31]  K. Gleason,et al.  Initiated chemical vapor deposition of poly(1H,1H,2H,2H-perfluorodecyl acrylate) thin films. , 2006, Langmuir : the ACS journal of surfaces and colloids.

[32]  S. Ross,et al.  Linear method for determining monomer reactivity ratios in copolymerization , 1950 .

[33]  K. Neoh,et al.  Surface modification of poly(tetrafluoroethylene) films by plasma polymerization of glycidyl methacrylate and its relevance to the electroless deposition of copper , 2000 .

[34]  F. Jonas,et al.  Poly(3, 4-ethylenedioxythiophene): Conductive coatings, technical applications and properties , 1995 .

[35]  K. Gleason,et al.  Combinatorial initiated CVD for polymeric thin films , 2006 .

[36]  K. Gleason,et al.  Initiated chemical vapor deposition (iCVD) of polymeric nanocoatings , 2007 .

[37]  K. Gleason,et al.  Initiated chemical vapor deposition of alternating copolymers of styrene and maleic anhydride. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[38]  Wen‐Yaung Lee,et al.  Solventless polyimide films by vapor deposition , 1986 .

[39]  M. Szwarc.  Some remarks on the CH2[graphic omitted]CH2 molecule , 1947 .

[40]  Yoshikazu Takahashi,et al.  Synthesis of aromatic polyimide film by vacuum deposition polymerization , 1987 .

[41]  K. Gleason,et al.  Large-scale initiated chemical vapor deposition of poly(glycidyl methacrylate) thin films , 2006 .

[42]  K. Gleason,et al.  Air-Gap Fabrication Using a Sacrificial Polymeric Thin Film Synthesized via Initiated Chemical Vapor Deposition , 2006 .

[43]  D. Edell,et al.  Stable biopassive insulation synthesized by initiated chemical vapor deposition of poly(1,3,5-trivinyltrimethylcyclotrisiloxane). , 2007, Biomacromolecules.

[44]  Karen K. Gleason,et al.  Growth of fluorocarbon polymer thin films with high CF2 fractions and low dangling bond concentrations by thermal chemical vapor deposition , 1996 .

[45]  Keld West,et al.  Vapor-Phase Polymerization of 3,4-Ethylenedioxythiophene: A Route to Highly Conducting Polymer Surface Layers , 2004 .

[46]  Gary E. McGuire,et al.  Semiconductor materials and process technology handbook : for very large scale integration (VLSI) and ultra large scale integration (ULSI) , 1988 .

[47]  H. Sawin,et al.  Relationship of CF2 concentration to deposition rates in the pyrolytic chemical vapor deposition process , 2002 .

[48]  Jean-Luc Brédas,et al.  Conjugated polymers : the novel science and technology of highly conducting and nonlinear optically active materials , 1991 .

[49]  W. F. Gorham.  A New, General Synthetic Method for the Preparation of Linear Poly‐p‐xylylenes , 1966 .

[50]  K. Gleason,et al.  Initiated chemical vapor deposition of polyvinylpyrrolidone-based thin films , 2006 .

[51]  Robert Langer,et al.  From Advanced Biomedical Coatings to Multi‐Functionalized Biomaterials , 2006 .

[52]  C. Ober,et al.  Positive‐ and Negative‐Tone CVD Polyacrylic Electron‐Beam Resists Developable by Supercritical CO2 , 2006 .

[53]  D. Edell,et al.  Molecular Design of Fluorocarbon Film Architecture by Pulsed Plasma Enhanced and Pyrolytic Chemical Vapor Deposition , 1999 .

[54]  K. Gleason,et al.  Hot filament chemical vapor deposition of poly(glycidyl methacrylate) thin films using tert-butyl peroxide as an initiator. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[55]  P. Hammond,et al.  Grafted Conducting Polymer Films for Nano‐patterning onto Various Organic and Inorganic Substrates by Oxidative Chemical Vapor Deposition , 2007 .

[56]  K. Gleason,et al.  Initiated Chemical Vapor Deposition of a Surface-Modifiable Copolymer for Covalent Attachment and Patterning of Nucleophilic Ligands , 2007 .

[57]  C. Ober,et al.  Towards all-dry lithography: Electron-beam patternable poly(glycidyl methacrylate) thin films from hot filament chemical vapor deposition , 2004 .

[58]  K. Gleason,et al.  Oxidative Chemical Vapor Deposition of Electrically Conducting Poly(3,4-ethylenedioxythiophene) Films , 2006 .

[59]  Gareth H. McKinley,et al.  Superhydrophobic Carbon Nanotube Forests , 2003 .

[60]  H. Yasuda.  Plasma for Modification of Polymers , 1976 .

[61]  K. Gleason,et al.  Initiated chemical vapor deposition of linear and cross-linked poly(2-hydroxyethyl methacrylate) for use as thin-film hydrogels. , 2005, Langmuir : the ACS journal of surfaces and colloids.

[62]  D. Harding,et al.  Vapor deposition and curing of polybenzoxazole precursors , 2006 .