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.

• List of Contributors XV1 Overview of Chemically Vapor Deposited (CVD) Polymers 1Karen K. Gleason1.1 Motivation and Characteristics 11.1.1 Quality 21.1.2 Conformality 21.1.3 Durability 31.1.4 Composition 31.2 Fundamentals and Mechanisms 41.2.1 Gas Phase and Surface Reactions 41.2.2 The Monomer Saturation Ratio 51.2.3 Process Simplification and Substrate Independence 61.3 Scale-Up and Commercialization 61.4 Process and Materials Chemistry 71.4.1 Initiated CVD (iCVD) and Its Variants 81.4.2 Plasma Enhanced CVD (PECVD) 81.4.3 Poly(p-xylylene) (PPX) and Its Derivatives (“Parylenes”) 91.4.4 Oxidative CVD (oCVD) 91.4.5 Vapor Deposition Polymerization (VDP) and Molecular Layer Deposition (MLD) 91.4.6 Additional Methods 101.5 Summary 10Acknowledgments 11References 11Part I: Fundamentals 132 Growth Mechanism, Kinetics, and Molecular Weight 15Kenneth K. S. Lau2.1 Introduction 152.2 iCVD Process 162.3 Kinetics and Growth Mechanism 182.3.1 Fluorocarbon Polymers 182.3.2 Organosilicon Polymers 252.3.3 Acrylate and Methacrylate Polymers 282.3.4 Styrene and Other Vinyl Polymers 372.3.5 Ring Opening Polymers 372.4 Summary 39References 393 Copolymerization and Crosslinking 45Yu Mao3.1 Introduction 453.2 Copolymer Composition and Structure 463.2.1 Confirmation of iCVD Copolymerization 463.2.2 Analysis of Copolymer Composition 473.2.3 Compositional Gradient 503.3 Copolymerization Kinetics 523.3.1 Copolymerization Equation and Reactivity Ratio 523.3.2 Types of iCVD Copolymerization 553.4 Tunable Properties of iCVD Copolymers 563.4.1 Mechanical Properties 563.4.2 Swelling 583.4.3 Thermal Properties 603.4.4 Surface Properties 613.5 Conclusions 62References 624 Non-Thermal Initiation Strategies and Grafting 65Daniel D. Burkey4.1 Introduction 654.2 Initiation Strategies 654.2.1 Plasma Initiation Strategies 654.2.2 Photoinitiation Strategies 714.3 Grafting 764.3.1 Surface Modification of Organic Substrates 774.3.2 Surface Modification of Inorganic Substrates 784.3.3 Grafting Summary 824.4 Summary 82References 845 Conformal Polymer CVD 87Salmaan Baxamusa5.1 Introduction 875.2 Vapor Phase Transport 875.3 Conformal Polymer Coating Applications 885.4 Conformal Polymer Coating Technologies 895.5 Gas and Surface Reactions 905.6 The Reaction-Diffusion Model 935.6.1 Reaction and Diffusion in a Pore 935.6.2 Initiator Controlled Consumption 965.6.3 Factors Affecting the Initiator Sticking Probability 995.6.4 Monomer Controlled Consumption 1005.6.5 Other Polymer CVD Systems 1015.7 Applications 1025.8 Conclusion 106Acknowledgment 107References 1076 Plasma Enhanced-Chemical Vapor Deposited Polymers: Plasma Phase Reactions, Plasma–Surface Interactions, and Film Properties 111Mariadriana Creatore and Alberto Perrotta6.1 Introduction: Chemical Vapor Deposition Methods, Advantages, and Challenges 1116.2 Plasma Parameters, Plasma Phase Reactions, and the Role of Diagnostics 1146.3 Plasma Polymerization: Is It Just Chemistry? The Role of Ions in Film Growth 1176.4 Considerations on the Macroscopic Kinetics Approach to Plasma Polymerization 1186.5 Polymer Film Characteristics 1206.5.1 Plasma Polymer Chemistry: From Precursor Fragmentation to Retention 1206.5.2 Densification of the Film Micro-structure 1246.5.3 Plasma Polymer Topography 127Acknowledgments 129References 1307 Fabrication of Organic Interfacial Layers by Molecular Layer Deposition: Present Status and Future Opportunities 133Han Zhou and Stacey F. Bent7.1 Introduction 1337.2 MLD Coupling Chemistry 1367.2.1 Pure Organic MLD 1367.2.2 Organic–Inorganic Hybrid MLD 1457.3 Applications of MLD Films 1547.3.1 Applications of Pure Organic MLD Films 1547.3.2 Applications of Organic–Inorganic Hybrid MLD Films 1587.4 Study of MLD Film Structure 1657.5 Challenges and Opportunities for MLD 1667.6 Conclusions 167Acknowledgments 167References 168Part II: Materials Chemistry 1718 Reactive and Stimuli-Responsive Polymer Thin Films 173Wyatt E. Tenhaeff8.1 Introduction 1738.2 Reactive Polymer Thin Films 1748.2.1 Motivation 1748.2.2 Examples of Functionalization Reactions 1758.2.3 Important CVD Capabilities 1798.2.4 Applications of Reactive Films 1818.3 Responsive Polymer Thin Films 1868.3.1 Chemical-Responsive Polymers 1878.3.2 pH Responsive Polymers 1908.3.3 Temperature-Responsive Polymers 1928.3.4 Piezoelectric Polymers 1938.4 Conclusions 195References 1969 Multifunctional Reactive Polymer Coatings 199Xiaopei Deng, Kenneth C. K. Cheng and Joerg Lahann9.1 Introduction 1999.2 CVD Copolymer Coatings with Randomly Distributed Functional Groups 2019.3 Multifunctional Gradient Coatings 2039.3.1 Composition Gradient Preparation and Biomedical Applications 2049.3.2 Formation of Steep Surface Gradient 2079.4 Functional Coatings with Micro- and Nanopatterns 2089.4.1 Microcontact Printing (μCP) 2099.4.2 Photopatterning 2119.4.3 Vapor-Assisted Patterning During CVD 2119.4.4 Nanopatterning by Dip-Pen Lithography (DPN) 2159.5 Summary and Future Outlook 216Acknowledgments 216References 21610 CVD Fluoropolymers 219Jose L. Yagüe10.1 Introduction 21910.2 Polytetrafluoroethylene (PTFE) 22010.3 Poly(vinylidene fluoride) (PVDF) 22410.4 Poly(1H,1H,2H,2H-perfluorodecyl acrylate) [p(PFDA)] 22610.5 Copolymerization of Fluorinated Monomers 22810.5.1 Copolymers with 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) 22810.5.2 Copolymers with Organosilicons 22910.6 Summary 231References 23111 Conjugated CVD Polymers: Conductors and Semiconductors 233Rachel M. Howden11.1 Overview 23311.2 Reactors and Process 23411.3 Chemistry and Mechanism 23411.3.1 Monomers 23611.3.2 Oxidants and Dopants 23811.4 Grafting and Patterning 23811.5 Conformality 24111.6 Dopants, Rinsing, Stability 24211.7 Semiconductors 24311.8 Electrical Properties 24611.9 Functional oCVD Copolymers 24811.10 Concluding Remarks 251References 251Part III: Applications 25512 Controlling Wetting with Oblique Angle Vapor-Deposited Parylene 257Melik C. Demirel and Matthew J. Hancock12.1 Introduction 25712.2 Definition of Anisotropy in Materials Science 25812.3 OAP Surfaces: Fabrication 25912.4 Directional OAP Surfaces: Form and Function 26112.5 Modeling Adhesion, Wetting, and Transport on Directional Surfaces 26612.5.1 Modeling Dry Adhesion 26712.5.2 ModelingWetting, Adhesion, and Transport in Solid–Fluid Systems 26712.6 Conclusions 274Acknowledgments 275References 27513 Membrane Modification by CVD Polymers 279Rong Yang13.1 Modification of Membrane Surface and Internal Pores 28113.1.1 Conformal Coatings for Membrane Surface Modification 28113.1.2 Nonconformal Coatings for Membrane Surface Modification 28313.2 Membrane Surface Energy Control ViaThin-Film Coatings 28513.2.1 Hydrophobic Thin-Film Coatings for Membranes 28513.2.2 Hydrophilic Thin-Film Coatings for Membranes 28613.3 Antifouling and Antimicrobial Coatings for Membranes 28813.4 Membrane Modification for Sustainability 293References 29614 CVD Polymer Surfaces for Biotechnology and Biomedicine 301Anna Maria Coclite14.1 Introduction 30114.2 Biosensors 30214.3 Controlled Drug Release 30614.4 Tissue Engineering 30814.5 Bio-MEMS 31114.6 Biopassivating Coatings 31114.7 Antimicrobial Coatings 31314.8 Significance and Future Directions 317References 31815 Encapsulation, Templating, and Patterning with Functional Polymers 323Gozde Ozaydin Ince15.1 Introduction 32315.2 Encapsulation of 1D and 2D Structures with Functional Polymers 32415.2.1 Encapsulation of Carbon Nanotubes (CNTs) 32415.2.2 Encapsulation of Micro/Nanostructures 32615.3 Patterning of Surfaces 32915.3.1 Patterning of Multifunctional Surfaces 33015.3.2 SurfaceWrinkling 33515.4 Synthesis of Polymeric Micro/Nanostructures 33715.4.1 Templating Using Porous Membranes 33815.4.2 Micromolding 34215.4.3 Surface-Imprinted Micro/Nanostructures 34515.5 Summary 345References 34616 Deposition of Polymers onto New Substrates 349Malancha Gupta16.1 Paper-Based Microfluidic Devices 35016.2 Elastomeric Substrates 35216.3 Liquids Substrates 35616.4 Low-Temperature Substrates 360Acknowledgments 362References 36317 Organic Device Fabrication and Integration with CVD Polymers 365Hyejeong Seong, Bong Jun Kim, Jae Bem You, Youngmin Yoo, and Sung Gap Im17.1 Introduction 36517.2 Energy Devices 36617.2.1 Organic Photovoltaics (OPVs) 36617.2.2 iCVD Polymer for Dye-Sensitized Solar Cell (DSSC) 37417.2.3 oCVD PEDOT for Supercapacitor 37417.3 Optical Devices 37617.3.1 Bragg Mirror 37617.3.2 Electrochromic Devices 37717.4 Nano-Adhesives 37817.4.1 iCVD Polymer as Nano-Adhesives 37817.4.2 Application of iCVD Nano-Adhesives to Microfluidic Devices 38217.5 Encapsulation of Electronic Devices 38417.5.1 Thin-Film Barrier for Encapsulation of Electronic Devices 38417.5.2 Fabrication of Multilayered Barrier Using iCVD Polymer and Inorganic Layers 38517.6 Conclusion 386Acknowledgments 387References 38718 CVD Polymers for the Semiconductor Industry 391Vijay Jain Bharamaiah Jeevendra Kumar, and Magnus Bergkvist18.1 Introduction 39118.2 Application Areas for iCVD 39218.2.1 Lithography 39218.2.2 Air Gap Dielectrics 39418.3 Thin-Film Adhesives 39818.3.1 iCVD forWafer Bonding Applications 39918.4 Design Considerations for iCVD Tools in Semiconductor Manufacturing 40018.4.1 iCVD for Semiconductor Manufacturing 40118.4.2 iCVD Reactor Design 40218.4.3 iCVD Subsystem Design 40418.4.4 Economic Considerations 40918.5 Summary 409References 410Part IV: Reactors and Commercialization 41519 Commercialization of CVD Polymer Coatings 417W. Shannan O’Shaughnessy19.1 Introduction 41719.1.1 Precursor Considerations 41819.1.2 Process Considerations 42019.1.3 Application Considerations 42219.1.4 Market Considerations 42419.2 Case Study: CVD Deposited PTFE for Lubricity Applications 42619.2.1 PTFE Precursor and Process Considerations 42619.2.2 Lubricious CVD PTFE Application and Market Considerations 42719.3 Commercial CVD Polymer Coating Systems 429References 43020 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 Schwambera20.1 Motivation and Targets (Customer Requirements) 43120.2 Requirements for Industrial Solutions 43220.2.1 State-of-the-Art Solutions for Parylene Deposition 43420.2.2 Impacts of Process and Chemistry on the Design of an Implementation 43720.2.3 From Process Engineering to System Engineering 43820.2.4 Design Principles – Modularity as Enabling Criteria for Industrial Solutions 44420.2.5 Building Blocks – A Closer Look 44520.2.6 Results Example High-Throughput Deposition (e.g., Parylene) 44820.3 Conclusion 44920.3.1 Outlook – Building Blocks to Create Systems and Variants Addressing a Variety of Polymer CVD Applications, For Example, Initiated CVD, Oxidative CVD 45020.3.2 Scaling Polymer Film Fabrication from R&D Toward Large-Area Production 451References 453Index 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.

• List of Contributors XV1 Overview of Chemically Vapor Deposited (CVD) Polymers 1Karen K. Gleason1.1 Motivation and Characteristics 11.1.1 Quality 21.1.2 Conformality 21.1.3 Durability 31.1.4 Composition 31.2 Fundamentals and Mechanisms 41.2.1 Gas Phase and Surface Reactions 41.2.2 The Monomer Saturation Ratio 51.2.3 Process Simplification and Substrate Independence 61.3 Scale-Up and Commercialization 61.4 Process and Materials Chemistry 71.4.1 Initiated CVD (iCVD) and Its Variants 81.4.2 Plasma Enhanced CVD (PECVD) 81.4.3 Poly(p-xylylene) (PPX) and Its Derivatives (“Parylenes”) 91.4.4 Oxidative CVD (oCVD) 91.4.5 Vapor Deposition Polymerization (VDP) and Molecular Layer Deposition (MLD) 91.4.6 Additional Methods 101.5 Summary 10Acknowledgments 11References 11Part I: Fundamentals 132 Growth Mechanism, Kinetics, and Molecular Weight 15Kenneth K. S. Lau2.1 Introduction 152.2 iCVD Process 162.3 Kinetics and Growth Mechanism 182.3.1 Fluorocarbon Polymers 182.3.2 Organosilicon Polymers 252.3.3 Acrylate and Methacrylate Polymers 282.3.4 Styrene and Other Vinyl Polymers 372.3.5 Ring Opening Polymers 372.4 Summary 39References 393 Copolymerization and Crosslinking 45Yu Mao3.1 Introduction 453.2 Copolymer Composition and Structure 463.2.1 Confirmation of iCVD Copolymerization 463.2.2 Analysis of Copolymer Composition 473.2.3 Compositional Gradient 503.3 Copolymerization Kinetics 523.3.1 Copolymerization Equation and Reactivity Ratio 523.3.2 Types of iCVD Copolymerization 553.4 Tunable Properties of iCVD Copolymers 563.4.1 Mechanical Properties 563.4.2 Swelling 583.4.3 Thermal Properties 603.4.4 Surface Properties 613.5 Conclusions 62References 624 Non-Thermal Initiation Strategies and Grafting 65Daniel D. Burkey4.1 Introduction 654.2 Initiation Strategies 654.2.1 Plasma Initiation Strategies 654.2.2 Photoinitiation Strategies 714.3 Grafting 764.3.1 Surface Modification of Organic Substrates 774.3.2 Surface Modification of Inorganic Substrates 784.3.3 Grafting Summary 824.4 Summary 82References 845 Conformal Polymer CVD 87Salmaan Baxamusa5.1 Introduction 875.2 Vapor Phase Transport 875.3 Conformal Polymer Coating Applications 885.4 Conformal Polymer Coating Technologies 895.5 Gas and Surface Reactions 905.6 The Reaction-Diffusion Model 935.6.1 Reaction and Diffusion in a Pore 935.6.2 Initiator Controlled Consumption 965.6.3 Factors Affecting the Initiator Sticking Probability 995.6.4 Monomer Controlled Consumption 1005.6.5 Other Polymer CVD Systems 1015.7 Applications 1025.8 Conclusion 106Acknowledgment 107References 1076 Plasma Enhanced-Chemical Vapor Deposited Polymers: Plasma Phase Reactions, Plasma–Surface Interactions, and Film Properties 111Mariadriana Creatore and Alberto Perrotta6.1 Introduction: Chemical Vapor Deposition Methods, Advantages, and Challenges 1116.2 Plasma Parameters, Plasma Phase Reactions, and the Role of Diagnostics 1146.3 Plasma Polymerization: Is It Just Chemistry? The Role of Ions in Film Growth 1176.4 Considerations on the Macroscopic Kinetics Approach to Plasma Polymerization 1186.5 Polymer Film Characteristics 1206.5.1 Plasma Polymer Chemistry: From Precursor Fragmentation to Retention 1206.5.2 Densification of the Film Micro-structure 1246.5.3 Plasma Polymer Topography 127Acknowledgments 129References 1307 Fabrication of Organic Interfacial Layers by Molecular Layer Deposition: Present Status and Future Opportunities 133Han Zhou and Stacey F. Bent7.1 Introduction 1337.2 MLD Coupling Chemistry 1367.2.1 Pure Organic MLD 1367.2.2 Organic–Inorganic Hybrid MLD 1457.3 Applications of MLD Films 1547.3.1 Applications of Pure Organic MLD Films 1547.3.2 Applications of Organic–Inorganic Hybrid MLD Films 1587.4 Study of MLD Film Structure 1657.5 Challenges and Opportunities for MLD 1667.6 Conclusions 167Acknowledgments 167References 168Part II: Materials Chemistry 1718 Reactive and Stimuli-Responsive Polymer Thin Films 173Wyatt E. Tenhaeff8.1 Introduction 1738.2 Reactive Polymer Thin Films 1748.2.1 Motivation 1748.2.2 Examples of Functionalization Reactions 1758.2.3 Important CVD Capabilities 1798.2.4 Applications of Reactive Films 1818.3 Responsive Polymer Thin Films 1868.3.1 Chemical-Responsive Polymers 1878.3.2 pH Responsive Polymers 1908.3.3 Temperature-Responsive Polymers 1928.3.4 Piezoelectric Polymers 1938.4 Conclusions 195References 1969 Multifunctional Reactive Polymer Coatings 199Xiaopei Deng, Kenneth C. K. Cheng and Joerg Lahann9.1 Introduction 1999.2 CVD Copolymer Coatings with Randomly Distributed Functional Groups 2019.3 Multifunctional Gradient Coatings 2039.3.1 Composition Gradient Preparation and Biomedical Applications 2049.3.2 Formation of Steep Surface Gradient 2079.4 Functional Coatings with Micro- and Nanopatterns 2089.4.1 Microcontact Printing (μCP) 2099.4.2 Photopatterning 2119.4.3 Vapor-Assisted Patterning During CVD 2119.4.4 Nanopatterning by Dip-Pen Lithography (DPN) 2159.5 Summary and Future Outlook 216Acknowledgments 216References 21610 CVD Fluoropolymers 219Jose L. Yagüe10.1 Introduction 21910.2 Polytetrafluoroethylene (PTFE) 22010.3 Poly(vinylidene fluoride) (PVDF) 22410.4 Poly(1H,1H,2H,2H-perfluorodecyl acrylate) [p(PFDA)] 22610.5 Copolymerization of Fluorinated Monomers 22810.5.1 Copolymers with 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) 22810.5.2 Copolymers with Organosilicons 22910.6 Summary 231References 23111 Conjugated CVD Polymers: Conductors and Semiconductors 233Rachel M. Howden11.1 Overview 23311.2 Reactors and Process 23411.3 Chemistry and Mechanism 23411.3.1 Monomers 23611.3.2 Oxidants and Dopants 23811.4 Grafting and Patterning 23811.5 Conformality 24111.6 Dopants, Rinsing, Stability 24211.7 Semiconductors 24311.8 Electrical Properties 24611.9 Functional oCVD Copolymers 24811.10 Concluding Remarks 251References 251Part III: Applications 25512 Controlling Wetting with Oblique Angle Vapor-Deposited Parylene 257Melik C. Demirel and Matthew J. Hancock12.1 Introduction 25712.2 Definition of Anisotropy in Materials Science 25812.3 OAP Surfaces: Fabrication 25912.4 Directional OAP Surfaces: Form and Function 26112.5 Modeling Adhesion, Wetting, and Transport on Directional Surfaces 26612.5.1 Modeling Dry Adhesion 26712.5.2 ModelingWetting, Adhesion, and Transport in Solid–Fluid Systems 26712.6 Conclusions 274Acknowledgments 275References 27513 Membrane Modification by CVD Polymers 279Rong Yang13.1 Modification of Membrane Surface and Internal Pores 28113.1.1 Conformal Coatings for Membrane Surface Modification 28113.1.2 Nonconformal Coatings for Membrane Surface Modification 28313.2 Membrane Surface Energy Control ViaThin-Film Coatings 28513.2.1 Hydrophobic Thin-Film Coatings for Membranes 28513.2.2 Hydrophilic Thin-Film Coatings for Membranes 28613.3 Antifouling and Antimicrobial Coatings for Membranes 28813.4 Membrane Modification for Sustainability 293References 29614 CVD Polymer Surfaces for Biotechnology and Biomedicine 301Anna Maria Coclite14.1 Introduction 30114.2 Biosensors 30214.3 Controlled Drug Release 30614.4 Tissue Engineering 30814.5 Bio-MEMS 31114.6 Biopassivating Coatings 31114.7 Antimicrobial Coatings 31314.8 Significance and Future Directions 317References 31815 Encapsulation, Templating, and Patterning with Functional Polymers 323Gozde Ozaydin Ince15.1 Introduction 32315.2 Encapsulation of 1D and 2D Structures with Functional Polymers 32415.2.1 Encapsulation of Carbon Nanotubes (CNTs) 32415.2.2 Encapsulation of Micro/Nanostructures 32615.3 Patterning of Surfaces 32915.3.1 Patterning of Multifunctional Surfaces 33015.3.2 SurfaceWrinkling 33515.4 Synthesis of Polymeric Micro/Nanostructures 33715.4.1 Templating Using Porous Membranes 33815.4.2 Micromolding 34215.4.3 Surface-Imprinted Micro/Nanostructures 34515.5 Summary 345References 34616 Deposition of Polymers onto New Substrates 349Malancha Gupta16.1 Paper-Based Microfluidic Devices 35016.2 Elastomeric Substrates 35216.3 Liquids Substrates 35616.4 Low-Temperature Substrates 360Acknowledgments 362References 36317 Organic Device Fabrication and Integration with CVD Polymers 365Hyejeong Seong, Bong Jun Kim, Jae Bem You, Youngmin Yoo, and Sung Gap Im17.1 Introduction 36517.2 Energy Devices 36617.2.1 Organic Photovoltaics (OPVs) 36617.2.2 iCVD Polymer for Dye-Sensitized Solar Cell (DSSC) 37417.2.3 oCVD PEDOT for Supercapacitor 37417.3 Optical Devices 37617.3.1 Bragg Mirror 37617.3.2 Electrochromic Devices 37717.4 Nano-Adhesives 37817.4.1 iCVD Polymer as Nano-Adhesives 37817.4.2 Application of iCVD Nano-Adhesives to Microfluidic Devices 38217.5 Encapsulation of Electronic Devices 38417.5.1 Thin-Film Barrier for Encapsulation of Electronic Devices 38417.5.2 Fabrication of Multilayered Barrier Using iCVD Polymer and Inorganic Layers 38517.6 Conclusion 386Acknowledgments 387References 38718 CVD Polymers for the Semiconductor Industry 391Vijay Jain Bharamaiah Jeevendra Kumar, and Magnus Bergkvist18.1 Introduction 39118.2 Application Areas for iCVD 39218.2.1 Lithography 39218.2.2 Air Gap Dielectrics 39418.3 Thin-Film Adhesives 39818.3.1 iCVD forWafer Bonding Applications 39918.4 Design Considerations for iCVD Tools in Semiconductor Manufacturing 40018.4.1 iCVD for Semiconductor Manufacturing 40118.4.2 iCVD Reactor Design 40218.4.3 iCVD Subsystem Design 40418.4.4 Economic Considerations 40918.5 Summary 409References 410Part IV: Reactors and Commercialization 41519 Commercialization of CVD Polymer Coatings 417W. Shannan O’Shaughnessy19.1 Introduction 41719.1.1 Precursor Considerations 41819.1.2 Process Considerations 42019.1.3 Application Considerations 42219.1.4 Market Considerations 42419.2 Case Study: CVD Deposited PTFE for Lubricity Applications 42619.2.1 PTFE Precursor and Process Considerations 42619.2.2 Lubricious CVD PTFE Application and Market Considerations 42719.3 Commercial CVD Polymer Coating Systems 429References 43020 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 Schwambera20.1 Motivation and Targets (Customer Requirements) 43120.2 Requirements for Industrial Solutions 43220.2.1 State-of-the-Art Solutions for Parylene Deposition 43420.2.2 Impacts of Process and Chemistry on the Design of an Implementation 43720.2.3 From Process Engineering to System Engineering 43820.2.4 Design Principles – Modularity as Enabling Criteria for Industrial Solutions 44420.2.5 Building Blocks – A Closer Look 44520.2.6 Results Example High-Throughput Deposition (e.g., Parylene) 44820.3 Conclusion 44920.3.1 Outlook – Building Blocks to Create Systems and Variants Addressing a Variety of Polymer CVD Applications, For Example, Initiated CVD, Oxidative CVD 45020.3.2 Scaling Polymer Film Fabrication from R&D Toward Large-Area Production 451References 453Index 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.

• List of Contributors XV1 Overview of Chemically Vapor Deposited (CVD) Polymers 1Karen K. Gleason1.1 Motivation and Characteristics 11.1.1 Quality 21.1.2 Conformality 21.1.3 Durability 31.1.4 Composition 31.2 Fundamentals and Mechanisms 41.2.1 Gas Phase and Surface Reactions 41.2.2 The Monomer Saturation Ratio 51.2.3 Process Simplification and Substrate Independence 61.3 Scale-Up and Commercialization 61.4 Process and Materials Chemistry 71.4.1 Initiated CVD (iCVD) and Its Variants 81.4.2 Plasma Enhanced CVD (PECVD) 81.4.3 Poly(p-xylylene) (PPX) and Its Derivatives (“Parylenes”) 91.4.4 Oxidative CVD (oCVD) 91.4.5 Vapor Deposition Polymerization (VDP) and Molecular Layer Deposition (MLD) 91.4.6 Additional Methods 101.5 Summary 10Acknowledgments 11References 11Part I: Fundamentals 132 Growth Mechanism, Kinetics, and Molecular Weight 15Kenneth K. S. Lau2.1 Introduction 152.2 iCVD Process 162.3 Kinetics and Growth Mechanism 182.3.1 Fluorocarbon Polymers 182.3.2 Organosilicon Polymers 252.3.3 Acrylate and Methacrylate Polymers 282.3.4 Styrene and Other Vinyl Polymers 372.3.5 Ring Opening Polymers 372.4 Summary 39References 393 Copolymerization and Crosslinking 45Yu Mao3.1 Introduction 453.2 Copolymer Composition and Structure 463.2.1 Confirmation of iCVD Copolymerization 463.2.2 Analysis of Copolymer Composition 473.2.3 Compositional Gradient 503.3 Copolymerization Kinetics 523.3.1 Copolymerization Equation and Reactivity Ratio 523.3.2 Types of iCVD Copolymerization 553.4 Tunable Properties of iCVD Copolymers 563.4.1 Mechanical Properties 563.4.2 Swelling 583.4.3 Thermal Properties 603.4.4 Surface Properties 613.5 Conclusions 62References 624 Non-Thermal Initiation Strategies and Grafting 65Daniel D. Burkey4.1 Introduction 654.2 Initiation Strategies 654.2.1 Plasma Initiation Strategies 654.2.2 Photoinitiation Strategies 714.3 Grafting 764.3.1 Surface Modification of Organic Substrates 774.3.2 Surface Modification of Inorganic Substrates 784.3.3 Grafting Summary 824.4 Summary 82References 845 Conformal Polymer CVD 87Salmaan Baxamusa5.1 Introduction 875.2 Vapor Phase Transport 875.3 Conformal Polymer Coating Applications 885.4 Conformal Polymer Coating Technologies 895.5 Gas and Surface Reactions 905.6 The Reaction-Diffusion Model 935.6.1 Reaction and Diffusion in a Pore 935.6.2 Initiator Controlled Consumption 965.6.3 Factors Affecting the Initiator Sticking Probability 995.6.4 Monomer Controlled Consumption 1005.6.5 Other Polymer CVD Systems 1015.7 Applications 1025.8 Conclusion 106Acknowledgment 107References 1076 Plasma Enhanced-Chemical Vapor Deposited Polymers: Plasma Phase Reactions, Plasma–Surface Interactions, and Film Properties 111Mariadriana Creatore and Alberto Perrotta6.1 Introduction: Chemical Vapor Deposition Methods, Advantages, and Challenges 1116.2 Plasma Parameters, Plasma Phase Reactions, and the Role of Diagnostics 1146.3 Plasma Polymerization: Is It Just Chemistry? The Role of Ions in Film Growth 1176.4 Considerations on the Macroscopic Kinetics Approach to Plasma Polymerization 1186.5 Polymer Film Characteristics 1206.5.1 Plasma Polymer Chemistry: From Precursor Fragmentation to Retention 1206.5.2 Densification of the Film Micro-structure 1246.5.3 Plasma Polymer Topography 127Acknowledgments 129References 1307 Fabrication of Organic Interfacial Layers by Molecular Layer Deposition: Present Status and Future Opportunities 133Han Zhou and Stacey F. Bent7.1 Introduction 1337.2 MLD Coupling Chemistry 1367.2.1 Pure Organic MLD 1367.2.2 Organic–Inorganic Hybrid MLD 1457.3 Applications of MLD Films 1547.3.1 Applications of Pure Organic MLD Films 1547.3.2 Applications of Organic–Inorganic Hybrid MLD Films 1587.4 Study of MLD Film Structure 1657.5 Challenges and Opportunities for MLD 1667.6 Conclusions 167Acknowledgments 167References 168Part II: Materials Chemistry 1718 Reactive and Stimuli-Responsive Polymer Thin Films 173Wyatt E. Tenhaeff8.1 Introduction 1738.2 Reactive Polymer Thin Films 1748.2.1 Motivation 1748.2.2 Examples of Functionalization Reactions 1758.2.3 Important CVD Capabilities 1798.2.4 Applications of Reactive Films 1818.3 Responsive Polymer Thin Films 1868.3.1 Chemical-Responsive Polymers 1878.3.2 pH Responsive Polymers 1908.3.3 Temperature-Responsive Polymers 1928.3.4 Piezoelectric Polymers 1938.4 Conclusions 195References 1969 Multifunctional Reactive Polymer Coatings 199Xiaopei Deng, Kenneth C. K. Cheng and Joerg Lahann9.1 Introduction 1999.2 CVD Copolymer Coatings with Randomly Distributed Functional Groups 2019.3 Multifunctional Gradient Coatings 2039.3.1 Composition Gradient Preparation and Biomedical Applications 2049.3.2 Formation of Steep Surface Gradient 2079.4 Functional Coatings with Micro- and Nanopatterns 2089.4.1 Microcontact Printing (μCP) 2099.4.2 Photopatterning 2119.4.3 Vapor-Assisted Patterning During CVD 2119.4.4 Nanopatterning by Dip-Pen Lithography (DPN) 2159.5 Summary and Future Outlook 216Acknowledgments 216References 21610 CVD Fluoropolymers 219Jose L. Yagüe10.1 Introduction 21910.2 Polytetrafluoroethylene (PTFE) 22010.3 Poly(vinylidene fluoride) (PVDF) 22410.4 Poly(1H,1H,2H,2H-perfluorodecyl acrylate) [p(PFDA)] 22610.5 Copolymerization of Fluorinated Monomers 22810.5.1 Copolymers with 1H,1H,2H,2H-perfluorodecyl acrylate (PFDA) 22810.5.2 Copolymers with Organosilicons 22910.6 Summary 231References 23111 Conjugated CVD Polymers: Conductors and Semiconductors 233Rachel M. Howden11.1 Overview 23311.2 Reactors and Process 23411.3 Chemistry and Mechanism 23411.3.1 Monomers 23611.3.2 Oxidants and Dopants 23811.4 Grafting and Patterning 23811.5 Conformality 24111.6 Dopants, Rinsing, Stability 24211.7 Semiconductors 24311.8 Electrical Properties 24611.9 Functional oCVD Copolymers 24811.10 Concluding Remarks 251References 251Part III: Applications 25512 Controlling Wetting with Oblique Angle Vapor-Deposited Parylene 257Melik C. Demirel and Matthew J. Hancock12.1 Introduction 25712.2 Definition of Anisotropy in Materials Science 25812.3 OAP Surfaces: Fabrication 25912.4 Directional OAP Surfaces: Form and Function 26112.5 Modeling Adhesion, Wetting, and Transport on Directional Surfaces 26612.5.1 Modeling Dry Adhesion 26712.5.2 ModelingWetting, Adhesion, and Transport in Solid–Fluid Systems 26712.6 Conclusions 274Acknowledgments 275References 27513 Membrane Modification by CVD Polymers 279Rong Yang13.1 Modification of Membrane Surface and Internal Pores 28113.1.1 Conformal Coatings for Membrane Surface Modification 28113.1.2 Nonconformal Coatings for Membrane Surface Modification 28313.2 Membrane Surface Energy Control ViaThin-Film Coatings 28513.2.1 Hydrophobic Thin-Film Coatings for Membranes 28513.2.2 Hydrophilic Thin-Film Coatings for Membranes 28613.3 Antifouling and Antimicrobial Coatings for Membranes 28813.4 Membrane Modification for Sustainability 293References 29614 CVD Polymer Surfaces for Biotechnology and Biomedicine 301Anna Maria Coclite14.1 Introduction 30114.2 Biosensors 30214.3 Controlled Drug Release 30614.4 Tissue Engineering 30814.5 Bio-MEMS 31114.6 Biopassivating Coatings 31114.7 Antimicrobial Coatings 31314.8 Significance and Future Directions 317References 31815 Encapsulation, Templating, and Patterning with Functional Polymers 323Gozde Ozaydin Ince15.1 Introduction 32315.2 Encapsulation of 1D and 2D Structures with Functional Polymers 32415.2.1 Encapsulation of Carbon Nanotubes (CNTs) 32415.2.2 Encapsulation of Micro/Nanostructures 32615.3 Patterning of Surfaces 32915.3.1 Patterning of Multifunctional Surfaces 33015.3.2 SurfaceWrinkling 33515.4 Synthesis of Polymeric Micro/Nanostructures 33715.4.1 Templating Using Porous Membranes 33815.4.2 Micromolding 34215.4.3 Surface-Imprinted Micro/Nanostructures 34515.5 Summary 345References 34616 Deposition of Polymers onto New Substrates 349Malancha Gupta16.1 Paper-Based Microfluidic Devices 35016.2 Elastomeric Substrates 35216.3 Liquids Substrates 35616.4 Low-Temperature Substrates 360Acknowledgments 362References 36317 Organic Device Fabrication and Integration with CVD Polymers 365Hyejeong Seong, Bong Jun Kim, Jae Bem You, Youngmin Yoo, and Sung Gap Im17.1 Introduction 36517.2 Energy Devices 36617.2.1 Organic Photovoltaics (OPVs) 36617.2.2 iCVD Polymer for Dye-Sensitized Solar Cell (DSSC) 37417.2.3 oCVD PEDOT for Supercapacitor 37417.3 Optical Devices 37617.3.1 Bragg Mirror 37617.3.2 Electrochromic Devices 37717.4 Nano-Adhesives 37817.4.1 iCVD Polymer as Nano-Adhesives 37817.4.2 Application of iCVD Nano-Adhesives to Microfluidic Devices 38217.5 Encapsulation of Electronic Devices 38417.5.1 Thin-Film Barrier for Encapsulation of Electronic Devices 38417.5.2 Fabrication of Multilayered Barrier Using iCVD Polymer and Inorganic Layers 38517.6 Conclusion 386Acknowledgments 387References 38718 CVD Polymers for the Semiconductor Industry 391Vijay Jain Bharamaiah Jeevendra Kumar, and Magnus Bergkvist18.1 Introduction 39118.2 Application Areas for iCVD 39218.2.1 Lithography 39218.2.2 Air Gap Dielectrics 39418.3 Thin-Film Adhesives 39818.3.1 iCVD forWafer Bonding Applications 39918.4 Design Considerations for iCVD Tools in Semiconductor Manufacturing 40018.4.1 iCVD for Semiconductor Manufacturing 40118.4.2 iCVD Reactor Design 40218.4.3 iCVD Subsystem Design 40418.4.4 Economic Considerations 40918.5 Summary 409References 410Part IV: Reactors and Commercialization 41519 Commercialization of CVD Polymer Coatings 417W. Shannan O’Shaughnessy19.1 Introduction 41719.1.1 Precursor Considerations 41819.1.2 Process Considerations 42019.1.3 Application Considerations 42219.1.4 Market Considerations 42419.2 Case Study: CVD Deposited PTFE for Lubricity Applications 42619.2.1 PTFE Precursor and Process Considerations 42619.2.2 Lubricious CVD PTFE Application and Market Considerations 42719.3 Commercial CVD Polymer Coating Systems 429References 43020 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 Schwambera20.1 Motivation and Targets (Customer Requirements) 43120.2 Requirements for Industrial Solutions 43220.2.1 State-of-the-Art Solutions for Parylene Deposition 43420.2.2 Impacts of Process and Chemistry on the Design of an Implementation 43720.2.3 From Process Engineering to System Engineering 43820.2.4 Design Principles – Modularity as Enabling Criteria for Industrial Solutions 44420.2.5 Building Blocks – A Closer Look 44520.2.6 Results Example High-Throughput Deposition (e.g., Parylene) 44820.3 Conclusion 44920.3.1 Outlook – Building Blocks to Create Systems and Variants Addressing a Variety of Polymer CVD Applications, For Example, Initiated CVD, Oxidative CVD 45020.3.2 Scaling Polymer Film Fabrication from R&D Toward Large-Area Production 451References 453Index 455