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Organized Organic Ultrathin Films: Fundamentals and Applications

Katsuhiko Ariga (Editor)
ISBN: 978-3-527-32733-1
226 pages
December 2012
Organized Organic Ultrathin Films: Fundamentals and Applications (3527327339) cover image

This handy reference is the first comprehensive book covering both fundamentals and recent developments in the field with an emphasis on nanotechnology.

Written by a highly regarded author in the field, the book details state-of-the-art preparation, characterization and applications of thin films of organic molecules and biomaterials fabricated by wet processes and also highlights applications in nanotechnology

The categories of films covered include monomolecular films (monolayers) both on a water surface and on a solid plate, Langmuir-Blodgett films (transferred multilayer films on a solid plate from a water surface), layer-by-layer films (adsorbed multilayer films on a solid support), and spontaneously assembled films in solution.

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Preface IX

List of Contributors XI

1 Introduction 1
Katsuhiko Ariga

2 Self-Assembled Monolayer (SAM) 7
Toshihiro Kondo, Ryo Yamada, and Kohei Uosaki

2.1 Introduction 7

2.2 Preparation and Characterization 8

2.2.1 Organothiols on Au 8

2.2.2 Organosilanes on SiOx Surfaces 15

2.2.3 SAMs on Si Surface via Si–C Bonding 17

2.3 Functions and Applications 20

2.3.1 Surface Coating and Patterning 21

2.3.2 Sensor Applications 23

2.3.3 Nanotribology 26

2.3.4 Advanced Applications 28

2.3.4.1 Electron Transfer 28

2.3.4.2 Photoinduced Electron Transfer 29

2.3.4.3 Luminescence 34

2.3.4.4 Catalytic Activity 34

2.4 Future Perspective 36

References 37

3 Langmuir–Blodgett (LB) Film 43
Ken-ichi Iimura and Teiji Kato

3.1 Concept and Mechanism 43

3.2 Preparation and Characterization 43

3.2.1 Gibbs Monolayers 43

3.2.2 Langmuir Monolayers 45

3.2.2.1 Basic Measurements of Properties of Langmuir Monolayers 45

3.2.2.2 A–T isobars 47

3.2.2.3 π–A isotherms 50

3.2.2.4 Stability of Langmuir Monolayers 52

3.2.3 In situ Characterization of Monolayers at the Subphase Surface 56

3.2.3.1 Brewster-Angle Microscopy (BAM) 56

3.2.3.2 Fourier Transform Infrared (FTIR) Spectroscopy 57

3.2.3.3 X-ray Refl ectometry and Grazing-Incidence X-ray Diffractometry 61

3.2.4 Transfer to Solid Supports 63

3.2.4.1 Instruments for LB Film Deposition 65

3.2.4.2 Turnover of Amphiphile Molecules during Deposition 67

3.2.4.3 Horizontal Lifting-Up Deposition 69

3.2.4.4 Horizontal Scooping-Up 71

3.3 Functions and Applications 73

3.3.1 Molecular Recognition 73

3.3.1.1 Molecular Recognition by Hydrogen Bonding and Electrostatic Interaction at the Air/Water Interface 73

3.3.1.2 Chiral Discrimination at the Air/Water Interface 77

3.3.1.3 Macrocyclic Hosts 79

3.3.1.4 Dynamic Host Cavity 80

3.3.2 Multilayer Films for Photoelectronic Functions 83

3.3.2.1 Molecular Photodiode 83

3.3.2.2 Fullerene C60 Containing LB Film 85

3.3.2.3 Optical Logic Gate/Photoswitch 87

3.3.3 Biomimetic Functions 88

3.3.3.1 Biomembrane Models – Langmuir Monolayers of Lipids 89

3.3.3.2 Lung Surfactants 93

3.3.3.3 Biomimetic Mineralization 94

3.3.4 Advanced Applications 95

3.3.4.1 Sensors 95

3.3.4.2 Photoresponsive Films 98

References 99

4 Layer-by-Layer (LbL) Assembly 107
Katsuhiko Ariga

4.1 Concept and Mechanism 107

4.2 Preparation and Characterization 109

4.2.1 Applicable Materials and Interactions 109

4.2.2 Thin-Film Preparation: Fundamental Procedure and Characterization 114

4.2.3 Various Driving Forces and Techniques 120

4.2.4 Three-Dimensional Assemblies 129

4.3 Functions and Applications 136

4.3.1 Physicochemical Applications of LbL Thin Films 137

4.3.2 Biomedical Applications of LbL Thin Films 143

4.4 Brief Summary and Perspectives 153

Further Reading 154

5 Other Thin Films 157
Mineo Hashizume, Takeshi Serizawa, and Norihiro Yamada

5.1 Bilayer Vesicle and Cast Film 157

5.1.1 Definition of a Bilayer Structure, a Bilayer Membrane, and a Bilayer Vesicle 157

5.1.2 Formation of a Bilayer Structure 159

5.1.2.1 Bilayer Forming Amphiphiles 159

5.1.2.2 Properties of Bilayer Membrane and Diagnostics of Bilayer Formation 162

5.1.2.3 Mechanism and Preparation of Bilayer Formation 164

5.1.2.4 Future of the Bilayer Vesicle 166

5.1.3 Cast Films Containing a Bilayer Structure 166

5.2 Self-Assembled Fibers, Tubes, and Ribbons 169

5.2.1 Introduction 169

5.2.2 Finding a Helical Superstructure 169

5.2.3 Organogel 172

5.2.4 Control of Aggregate Morphology 173

5.2.4.1 Composite Structure with Two or More Different Parts 175

5.2.4.2 Hydrogen Bonding to Immobilize Orderly Molecular Arrangement 175

5.2.4.3 Hierarchic Interaction and Further Interaction 177

5.3 Polymer Brush Layer 179

5.3.1 Definition of Polymer Brushes 179

5.3.2 Preparation of Polymer Brushes 180

5.3.3 Properties and Applications of Concentrated Polymer Brushes 182

5.4 Organic–Inorganic Hybrids 184

5.5 Colloidal Layers 191

5.6 Newly Appearing Techniques 195

5.6.1 Material-Binding Peptide 195

5.6.2 Block-Copolymer Films 197

5.6.3 Nanoimprint Lithography 200

References 200

Index 205

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Dr. Katsuhiko Ariga is the Director of Supermolecules Unit and Principal Investigator of World Premier International (WPI) Research Center for Materials Nanoarchitectonics (MANA), the National Institute for Materials Science (NIMS). He received his B.Eng., M.Eng., and Ph.D. degrees from the Tokyo Institute of Technology (TIT). He was Assistant Professor at TIT, worked as a postdoctoral fellow at the University of Texas at Austin, USA, and then served as a group leader in the Supermolecules Project at Japan Science and Technology Agency (JST). Thereafter, Dr. Ariga worked as Associate Professor at the Nara Institute of Science and Technology, and then became involved with the ERATO Nanospace
Project at JST. In January 2004, Dr. Ariga moved to NIMS. He was also appointed Professor at several Universities. His research field is based on supermolecular chemistry and surface science, including the boundary research areas of organic chemistry, physical chemistry,
biochemistry, and materials chemistry. His major interests are the fabrication of novel functional nanostructures based on molecular recognition and self-assembly, including Langmuir-Blodgett films, layer-by-layer films, and mesoporous materials.
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