CVD polymers : fabrication of organic surfaces and devices
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CVD polymers : fabrication of organic surfaces and devices
Wiley-VCH, c2015
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Includes bibliographical references and index
Description and Table of Contents
Description
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.
Table of Contents
List of Contributors XV
1 Overview of Chemically Vapor Deposited (CVD) Polymers 1
Karen 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 15
Kenneth 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 45
Yu 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 65
Daniel 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 87
Salmaan 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 111
Mariadriana 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 133
Han 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 173
Wyatt 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 199
Xiaopei 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 219
Jose L. Yague
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 233
Rachel 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 257
Melik 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 279
Rong 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 301
Anna 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 323
Gozde 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 349
Malancha 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 365
Hyejeong 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 391
Vijay 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 417
W. 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 431
Peter 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
by "Nielsen BookData"
