organic electro-optics and photonics

Organic Electro-Optics and Photonics

This definitive guide to modern organic electro-optic and photonic technologies pro-vides critical insight into recent advances in organic electro-optic materials, from theunderlying quantum and statistical concepts through to the practical application ofmaterials in modern devices and systems.

� Introduces theoretical and experimental methods for improving organic electro-optic and photonic technologies

� Reviews the central concepts of nonlinear optics, focusing on multi-scale theor-etical methods

� Provides clear insight into the structure and function relationships critical tooptimizing the performance of devices based on organic electro-optic materials

Serving as a primer for the systematic nano-engineering of soft matter materials, this isan invaluable resource for those involved in the development of modern telecommuni-cation, computing, and sensing technologies depending on electro-optic technology.It is also an indispensable work of reference for academic researchers and graduatestudents in the fields of chemistry, physics, electrical engineering, materials science andengineering, and chemical engineering.

Larry R. Dalton is the Founding Director of the National Science Foundation Science &Technology Center on Materials and Devices for Information Technology Research,Director of the DARPA MORPH program, and Director of two Department of DefenseMURI Centers. He is a Fellow of the American Chemical Society, the MaterialsResearch Society, the Optical Society of America, the SPIE, and the American Associ-ation for the Advancement of Science.

Peter Günter is Emeritus Professor at the Swiss Federal Institute of Technology (ETH)and a member of the board of Rainbow Photonics Ltd in Zürich. He is a Fellow of theOptical Society of America.

Mojca Jazbinsek is a member of the ETH spin-out, Rainbow Photonics AG, where sheis currently working on applied research projects on organic nonlinear optical materialsfor high-speed electro-optics and THz-wave generation.

O-Pil Kwon is Associate Professor in the Departments of Molecular Science andTechnology and of Applied Chemistry and Biological Engineering at the Ajou Univer-sity in Korea.

Philip A. Sullivan is Assistant Research Professor in the Department of Chemistry andBiochemistry of Montana State University. He has worked in the area of organicmaterials for photonics applications for over ten years.

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Cambridge University Press9780521449656 - Organic Electro-Optics and Photonics: Molecules, Polymers, and CrystalsLarry R. Dalton, Peter Günter, Mojca Jazbinsek, O-pil Kwon and Philip A. SullivaNFrontmatterMore information

http://www.cambridge.org/9780521449656

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Organic Electro-Opticsand PhotonicsMolecules, Polymers, and Crystals

LARRY R. DALTONUniversity of Washington

PETER GÜNTERETH, Rainbow Photonics AG

MOJCA JAZBINSEKETH, Rainbow Photonics AG

O-P IL KWONAjou University

PH IL IP A. SULL IVANMontana State University

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© Larry R. Dalton, Peter Günter, Mojca Jazbinsek, O-Pil Kwon, and Philip A. Sullivan 2015

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First published 2015

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ISBN 978-0-521-44965-6 Hardback

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On September 30, 2008, Dr. Nicole Boand, wife of Larry Dalton, was struck by anout-of-control automobile, while sitting in a restaurant in Gig Harbor,Washington. She suffered, among other injuries, massive spinal column andspinal cord injuries, which required multiple operations and have led to alifelong struggle with mobility and pain. Fortunately, Nicole’s active lifestylebefore the accident, which involved horseback riding, helped to prevent totalmuscle atrophy and with great courage she has struggled on a daily basis tomaintain some level of use of her arms and legs. Despite the personaltribulations of her life, she has consistently encouraged completion of this book.It is in honor of her courage that the authors dedicate this book to her.






Contents

1 Introduction 11.1 Motivation 11.2 Overarching objective of this book 21.3 Overview of topics covered 31.4 A brief history 41.5 Units and conversion factors 7

2 Nonlinear optical effects 112.1 Nonlinear optical response and susceptibilities 112.2 Second-order nonlinear optical effects and applications 152.3 Third-order nonlinear optical effects and applications 23

3 Electro-optic effects 283.1 Fundamentals of the electro-optic effect 283.2 Frequency dependence 313.3 Wavelength dependence 343.4 Electro-optic modulation 353.5 High-frequency modulation 37

4 Molecular nonlinear optics 404.1 Microscopic and macroscopic nonlinearities of organic molecules 404.2 Organic molecules for second-order nonlinear optics 404.3 Numerical calculations 444.4 Characterization methods 624.5 Synthetic methods 64

5 Acentric self-assembled films 705.1 Polar Langmuir–Blodgett films 705.2 Acentric solution-deposited films 755.3 Acentric vapor-deposited films 78

6 Crystalline materials 886.1 Non-centrosymmetric organic crystalline packing: approaches 886.2 Examples of organic electro-optic crystals 91

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6.3 Ionic crystals: stilbazolium salts 916.4 Supramolecular hydrogen bonded crystals 1016.5 Molecular crystals: configurationally locked polyene crystals 1046.6 Crystal growth techniques 108

7 Electrically poled organic materials and thermo-optic materials 1187.1 Chromophore/polymer composites 1197.2 Covalently incorporated chromophore materials 1267.3 Matrix-assisted poling (MAP) materials 1287.4 Binary chromophore materials 1337.5 Complexity 1397.6 Thermal stability issues 1417.7 Optical loss issues 1467.8 Photochemical stability 1477.9 Experimental methods for evaluating r33 in poled EO materials 149

7.10 Optical measurement of poling-induced order: VAPRAS and VASE 1507.11 Processing options 1547.12 Fabrication of all-organic devices 1557.13 Fabrication of silicon photonic, plasmonic, and photonic crystal hybrid

devices 1607.14 Synthetic strategies for covalently incorporated chromophore

materials 1637.15 Summary of macromolecular electro-optic materials 1677.16 Thermo-optic materials 169

8 Overview of applications 1758.1 Device parameters and materials requirements 1758.2 Applications 182

9 Organic electro-optic waveguides, switches, and modulators 1889.1 Light propagation in optical waveguides 1889.2 Integrated phase and amplitude electro-optic modulators 1949.3 Optical coupling between waveguides 1959.4 Microring resonators 1989.5 Light propagation in periodic media: photonic crystals 2039.6 Single-crystalline organic waveguides and modulators 2079.7 Polymer waveguides and modulators 2169.8 Silicon–organic hybrid waveguides 221

10 Nonlinear optical infrared and terahertz frequency conversion 22810.1 Nonlinear optical frequency conversion 22810.2 Terahertz-wave generation with organic nonlinear optical materials 232

viii Contents






11 Photorefractive effect and materials 25011.1 Theoretical models of the photorefractive effect 25111.2 Steady-state space-charge field 25411.3 Space-charge field dynamics 25611.4 Model for photo-induced refractive index changes in

crystals and polymers 25711.5 Measurement of photo-induced refractive index changes 26411.6 Applications 26611.7 Materials requirements and figures-of-merit 26611.8 Photorefractive materials and their properties 268

12 Conclusions and future prospects 28212.1 General conclusions 28212.2 Future prospects: competing technologies for electrical-to-optical

signal transduction 28312.3 Future prospects: fundamental issues facing the development

and utilization of organic electro-optic materials 28412.4 Future prospects: optical sum and difference-frequency generation,

optical rectification, and THz generation 28612.5 Future prospects: final comments 286

Index 287

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organic electro-optics and photonics

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