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CVD Polymers: Fabrication of Organic Surfaces and Devices

ISBN: 978-3-527-33799-6
488 pages
June 2015
CVD Polymers: Fabrication of Organic Surfaces and Devices (3527337997) cover image

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.
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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 (μCP) 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. 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 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

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Author Information

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.

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