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CVD Polymers


CVD Polymers

Fabrication of Organic Surfaces and Devices
1. Aufl.

von: Karen K. Gleason

138,99 €

Verlag: Wiley-VCH
Format: PDF
Veröffentl.: 05.03.2015
ISBN/EAN: 9783527690268
Sprache: englisch
Anzahl Seiten: 488

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Beschreibungen

The method of CVD (chemical vapor deposition) is a versatile technique to fabricate high-quality thin films and structured surfaces in the nanometer regime from the vapor phase. Already widely used for the deposition of inorganic materials in the semiconductor industry, CVD has become the method of choice in many applications to process polymers as well. This highly scalable technique allows for synthesizing high-purity, defect-free films and for systematically tuning their chemical, mechanical and physical properties. In addition, vapor phase processing is critical for the deposition of insoluble materials including fluoropolymers, electrically conductive polymers, and highly crosslinked organic networks. Furthermore, CVD enables the coating of substrates which would otherwise dissolve or swell upon exposure to solvents. The scope of the book encompasses CVD polymerization processes which directly translate the chemical mechanisms of traditional polymer synthesis and organic synthesis in homogeneous liquids into heterogeneous processes for the modification of solid surfaces. The book is structured into four parts, complemented by an introductory overview of the diverse process strategies for CVD of polymeric materials. The first part on the fundamentals of CVD polymers is followed by a detailed coverage of the materials chemistry of CVD polymers, including the main synthesis mechanisms and the resultant classes of materials. The third part focuses on the applications of these materials such as membrane modification and device fabrication. The final part discusses the potential for scale-up and commercialization of CVD polymers.
List of Contributors XV 1 Overview of Chemically Vapor Deposited (CVD) Polymers 1Karen K. Gleason 1.1 Motivation and Characteristics 1 1.1.1 Quality 2 1.1.2 Conformality 2 1.1.3 Durability 3 1.1.4 Composition 3 1.2 Fundamentals and Mechanisms 4 1.2.1 Gas Phase and Surface Reactions 4 1.2.2 The Monomer Saturation Ratio 5 1.2.3 Process Simplification and Substrate Independence 6 1.3 Scale-Up and Commercialization 6 1.4 Process and Materials Chemistry 7 1.4.1 Initiated CVD (iCVD) and Its Variants 8 1.4.2 Plasma Enhanced CVD (PECVD) 8 1.4.3 Poly(p-xylylene) (PPX) and Its Derivatives (“Parylenes”) 9 1.4.4 Oxidative CVD (oCVD) 9 1.4.5 Vapor Deposition Polymerization (VDP) and Molecular Layer Deposition (MLD) 9 1.4.6 Additional Methods 10 1.5 Summary 10 Acknowledgments 11 References 11 Part I: Fundamentals 13 2 Growth Mechanism, Kinetics, and Molecular Weight 15Kenneth K. S. Lau 2.1 Introduction 15 2.2 iCVD Process 16 2.3 Kinetics and Growth Mechanism 18 2.3.1 Fluorocarbon Polymers 18 2.3.2 Organosilicon Polymers 25 2.3.3 Acrylate and Methacrylate Polymers 28 2.3.4 Styrene and Other Vinyl Polymers 37 2.3.5 Ring Opening Polymers 37 2.4 Summary 39 References 39 3 Copolymerization and Crosslinking 45Yu Mao 3.1 Introduction 45 3.2 Copolymer Composition and Structure 46 3.2.1 Confirmation of iCVD Copolymerization 46 3.2.2 Analysis of Copolymer Composition 47 3.2.3 Compositional Gradient 50 3.3 Copolymerization Kinetics 52 3.3.1 Copolymerization Equation and Reactivity Ratio 52 3.3.2 Types of iCVD Copolymerization 55 3.4 Tunable Properties of iCVD Copolymers 56 3.4.1 Mechanical Properties 56 3.4.2 Swelling 58 3.4.3 Thermal Properties 60 3.4.4 Surface Properties 61 3.5 Conclusions 62 References 62 4 Non-Thermal Initiation Strategies and Grafting 65Daniel D. Burkey 4.1 Introduction 65 4.2 Initiation Strategies 65 4.2.1 Plasma Initiation Strategies 65 4.2.2 Photoinitiation Strategies 71 4.3 Grafting 76 4.3.1 Surface Modification of Organic Substrates 77 4.3.2 Surface Modification of Inorganic Substrates 78 4.3.3 Grafting Summary 82 4.4 Summary 82 References 84 5 Conformal Polymer CVD 87Salmaan Baxamusa 5.1 Introduction 87 5.2 Vapor Phase Transport 87 5.3 Conformal Polymer Coating Applications 88 5.4 Conformal Polymer Coating Technologies 89 5.5 Gas and Surface Reactions 90 5.6 The Reaction-Diffusion Model 93 5.6.1 Reaction and Diffusion in a Pore 93 5.6.2 Initiator Controlled Consumption 96 5.6.3 Factors Affecting the Initiator Sticking Probability 99 5.6.4 Monomer Controlled Consumption 100 5.6.5 Other Polymer CVD Systems 101 5.7 Applications 102 5.8 Conclusion 106 Acknowledgment 107 References 107 6 Plasma Enhanced-Chemical Vapor Deposited Polymers: Plasma Phase Reactions, Plasma–Surface Interactions, and Film Properties 111Mariadriana Creatore and Alberto Perrotta 6.1 Introduction: Chemical Vapor Deposition Methods, Advantages, and Challenges 111 6.2 Plasma Parameters, Plasma Phase Reactions, and the Role of Diagnostics 114 6.3 Plasma Polymerization: Is It Just Chemistry? The Role of Ions in Film Growth 117 6.4 Considerations on the Macroscopic Kinetics Approach to Plasma Polymerization 118 6.5 Polymer Film Characteristics 120 6.5.1 Plasma Polymer Chemistry: From Precursor Fragmentation to Retention 120 6.5.2 Densification of the Film Micro-structure 124 6.5.3 Plasma Polymer Topography 127 Acknowledgments 129 References 130 7 Fabrication of Organic Interfacial Layers by Molecular Layer Deposition: Present Status and Future Opportunities 133Han Zhou and Stacey F. Bent 7.1 Introduction 133 7.2 MLD Coupling Chemistry 136 7.2.1 Pure Organic MLD 136 7.2.2 Organic–Inorganic Hybrid MLD 145 7.3 Applications of MLD Films 154 7.3.1 Applications of Pure Organic MLD Films 154 7.3.2 Applications of Organic–Inorganic Hybrid MLD Films 158 7.4 Study of MLD Film Structure 165 7.5 Challenges and Opportunities for MLD 166 7.6 Conclusions 167 Acknowledgments 167 References 168 Part II: Materials Chemistry 171 8 Reactive and Stimuli-Responsive Polymer Thin Films 173Wyatt E. Tenhaeff 8.1 Introduction 173 8.2 Reactive Polymer Thin Films 174 8.2.1 Motivation 174 8.2.2 Examples of Functionalization Reactions 175 8.2.3 Important CVD Capabilities 179 8.2.4 Applications of Reactive Films 181 8.3 Responsive Polymer Thin Films 186 8.3.1 Chemical-Responsive Polymers 187 8.3.2 pH Responsive Polymers 190 8.3.3 Temperature-Responsive Polymers 192 8.3.4 Piezoelectric Polymers 193 8.4 Conclusions 195 References 196 9 Multifunctional Reactive Polymer Coatings 199Xiaopei Deng, Kenneth C. K. Cheng and Joerg Lahann 9.1 Introduction 199 9.2 CVD Copolymer Coatings with Randomly Distributed Functional Groups 201 9.3 Multifunctional Gradient Coatings 203 9.3.1 Composition Gradient Preparation and Biomedical Applications 204 9.3.2 Formation of Steep Surface Gradient 207 9.4 Functional Coatings with Micro- and Nanopatterns 208 9.4.1 Microcontact Printing (?CP) 209 9.4.2 Photopatterning 211 9.4.3 Vapor-Assisted Patterning During CVD 211 9.4.4 Nanopatterning by Dip-Pen Lithography (DPN) 215 9.5 Summary and Future Outlook 216 Acknowledgments 216 References 216 10 CVD Fluoropolymers 219Jose L. Yagüe 10.1 Introduction 219 10.2 Polytetrafluoroethylene (PTFE) 220 10.3 Poly(vinylidene fluoride) (PVDF) 224 10.4 Poly(1H,1H,2H,2H-perfluorodecyl acrylate) [p(PFDA)] 226 10.5 Copolymerization of Fluorinated Monomers 228 10.5.1 Copolymers with 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) 228 10.5.2 Copolymers with Organosilicons 229 10.6 Summary 231 References 231 11 Conjugated CVD Polymers: Conductors and Semiconductors 233Rachel M. Howden 11.1 Overview 233 11.2 Reactors and Process 234 11.3 Chemistry and Mechanism 234 11.3.1 Monomers 236 11.3.2 Oxidants and Dopants 238 11.4 Grafting and Patterning 238 11.5 Conformality 241 11.6 Dopants, Rinsing, Stability 242 11.7 Semiconductors 243 11.8 Electrical Properties 246 11.9 Functional oCVD Copolymers 248 11.10 Concluding Remarks 251 References 251 Part III: Applications 255 12 Controlling Wetting with Oblique Angle Vapor-Deposited Parylene 257Melik C. Demirel and Matthew J. Hancock 12.1 Introduction 257 12.2 Definition of Anisotropy in Materials Science 258 12.3 OAP Surfaces: Fabrication 259 12.4 Directional OAP Surfaces: Form and Function 261 12.5 Modeling Adhesion, Wetting, and Transport on Directional Surfaces 266 12.5.1 Modeling Dry Adhesion 267 12.5.2 ModelingWetting, Adhesion, and Transport in Solid–Fluid Systems 267 12.6 Conclusions 274 Acknowledgments 275 References 275 13 Membrane Modification by CVD Polymers 279Rong Yang 13.1 Modification of Membrane Surface and Internal Pores 281 13.1.1 Conformal Coatings for Membrane Surface Modification 281 13.1.2 Nonconformal Coatings for Membrane Surface Modification 283 13.2 Membrane Surface Energy Control ViaThin-Film Coatings 285 13.2.1 Hydrophobic Thin-Film Coatings for Membranes 285 13.2.2 Hydrophilic Thin-Film Coatings for Membranes 286 13.3 Antifouling and Antimicrobial Coatings for Membranes 288 13.4 Membrane Modification for Sustainability 293 References 296 14 CVD Polymer Surfaces for Biotechnology and Biomedicine 301Anna Maria Coclite 14.1 Introduction 301 14.2 Biosensors 302 14.3 Controlled Drug Release 306 14.4 Tissue Engineering 308 14.5 Bio-MEMS 311 14.6 Biopassivating Coatings 311 14.7 Antimicrobial Coatings 313 14.8 Significance and Future Directions 317 References 318 15 Encapsulation, Templating, and Patterning with Functional Polymers 323Gozde Ozaydin Ince 15.1 Introduction 323 15.2 Encapsulation of 1D and 2D Structures with Functional Polymers 324 15.2.1 Encapsulation of Carbon Nanotubes (CNTs) 324 15.2.2 Encapsulation of Micro/Nanostructures 326 15.3 Patterning of Surfaces 329 15.3.1 Patterning of Multifunctional Surfaces 330 15.3.2 SurfaceWrinkling 335 15.4 Synthesis of Polymeric Micro/Nanostructures 337 15.4.1 Templating Using Porous Membranes 338 15.4.2 Micromolding 342 15.4.3 Surface-Imprinted Micro/Nanostructures 345 15.5 Summary 345 References 346 16 Deposition of Polymers onto New Substrates 349Malancha Gupta 16.1 Paper-Based Microfluidic Devices 350 16.2 Elastomeric Substrates 352 16.3 Liquids Substrates 356 16.4 Low-Temperature Substrates 360 Acknowledgments 362 References 363 17 Organic Device Fabrication and Integration with CVD Polymers 365Hyejeong Seong, Bong Jun Kim, Jae Bem You, Youngmin Yoo, and Sung Gap Im 17.1 Introduction 365 17.2 Energy Devices 366 17.2.1 Organic Photovoltaics (OPVs) 366 17.2.2 iCVD Polymer for Dye-Sensitized Solar Cell (DSSC) 374 17.2.3 oCVD PEDOT for Supercapacitor 374 17.3 Optical Devices 376 17.3.1 Bragg Mirror 376 17.3.2 Electrochromic Devices 377 17.4 Nano-Adhesives 378 17.4.1 iCVD Polymer as Nano-Adhesives 378 17.4.2 Application of iCVD Nano-Adhesives to Microfluidic Devices 382 17.5 Encapsulation of Electronic Devices 384 17.5.1 Thin-Film Barrier for Encapsulation of Electronic Devices 384 17.5.2 Fabrication of Multilayered Barrier Using iCVD Polymer and Inorganic Layers 385 17.6 Conclusion 386 Acknowledgments 387 References 387 18 CVD Polymers for the Semiconductor Industry 391Vijay Jain Bharamaiah Jeevendra Kumar, and Magnus Bergkvist 18.1 Introduction 391 18.2 Application Areas for iCVD 392 18.2.1 Lithography 392 18.2.2 Air Gap Dielectrics 394 18.3 Thin-Film Adhesives 398 18.3.1 iCVD forWafer Bonding Applications 399 18.4 Design Considerations for iCVD Tools in Semiconductor Manufacturing 400 18.4.1 iCVD for Semiconductor Manufacturing 401 18.4.2 iCVD Reactor Design 402 18.4.3 iCVD Subsystem Design 404 18.4.4 Economic Considerations 409 18.5 Summary 409 References 410 Part IV: Reactors and Commercialization 415 19 Commercialization of CVD Polymer Coatings 417W. Shannan O’Shaughnessy 19.1 Introduction 417 19.1.1 Precursor Considerations 418 19.1.2 Process Considerations 420 19.1.3 Application Considerations 422 19.1.4 Market Considerations 424 19.2 Case Study: CVD Deposited PTFE for Lubricity Applications 426 19.2.1 PTFE Precursor and Process Considerations 426 19.2.2 Lubricious CVD PTFE Application and Market Considerations 427 19.3 Commercial CVD Polymer Coating Systems 429 References 430 20 Carrier Gas-Enhanced Polymer Vapor-Phase Deposition (PVPD): Industrialized Solutions by Example of Deposition of Parylene Films for Large-Area Applications 431Peter Baumann, Markus Gersdorff, Juergen Kreis, Martin Kunat, and Markus Schwambera 20.1 Motivation and Targets (Customer Requirements) 431 20.2 Requirements for Industrial Solutions 432 20.2.1 State-of-the-Art Solutions for Parylene Deposition 434 20.2.2 Impacts of Process and Chemistry on the Design of an Implementation 437 20.2.3 From Process Engineering to System Engineering 438 20.2.4 Design Principles – Modularity as Enabling Criteria for Industrial Solutions 444 20.2.5 Building Blocks – A Closer Look 445 20.2.6 Results Example High-Throughput Deposition (e.g., Parylene) 448 20.3 Conclusion 449 20.3.1 Outlook – Building Blocks to Create Systems and Variants Addressing a Variety of Polymer CVD Applications, For Example, Initiated CVD, Oxidative CVD 450 20.3.2 Scaling Polymer Film Fabrication from R&D Toward Large-Area Production 451 References 453 Index 455
Karen K. Gleason is Associate Provost and the Alexander and I. Michael Kasser Professor of Chemical Engineering at MIT, USA.  Her BSc and MSc degrees are from MIT and her PhD is from the University of California at Berkeley.  Karen K. Gleason has authored more than 300 publications and holds 18 issued US patents for CVD polymers and their applications in optoelectronics, sensing, microfluidics, energy storage, and biomedical devices, and also for the surface modification of membranes. At MIT, she has served as Executive Officer of the Chemical Engineering Department; Associate Director for the Institute of Soldier Nanotechnologies; and as Associate Dean of Engineering for Research. She is a Member of the National Academy of Engineering, a Fellow of the American Institute of Chemical Engineering (AIChE) and has held the Donders Visiting Chair Professorship at Utrecht University in 2006.  Her awards include the ID TechEx Printed Electronics Europe Best Technical Development Materials Award, the AIChE Process Development Research Award, and Young Investigator Awards from both the National Science Foundation and the Office of Naval Research.
The method of CVD (chemical vapor deposition) is a versatile technique to fabricate high-quality thin films and structured surfaces in the nanometer regime from the vapor phase. Already widely used for the deposition of inorganic materials in the semiconductor industry, CVD has become the method of choice in many applications to process polymers as well. This highly scalable technique allows for synthesizing high-purity, defect-free films and for systematically tuning their chemical, mechanical and physical properties. In addition, vapor phase processing is critical for the deposition of insoluble materials including fluoropolymers, electrically conductive polymers, and highly crosslinked organic networks. Furthermore, CVD enables the coating of substrates which would otherwise dissolve or swell upon exposure to solvents. The scope of the book encompasses CVD polymerization processes which directly translate the chemical mechanisms of traditional polymer synthesis and organic synthesis in homogeneous liquids into heterogeneous processes for the modification of solid surfaces. The book is structured into four parts, complemented by an introductory overview of the diverse process strategies for CVD of polymeric materials. The first part on the fundamentals of CVD polymers is followed by a detailed coverage of the materials chemistry of CVD polymers, including the main synthesis mechanisms and the resultant classes of materials. The third part focuses on the applications of these materials such as membrane modification and device fabrication. The final part discusses the potential for scale-up and commercialization of CVD polymers.

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