Theory-inspired development of organic electro-optic materials.

Correlated time-dependent density functional theory (TDDFT) quantum mechanical and pseudo-atomistic Monte Carlo (PAMC) statistical mechanical methods have been used to assist in the understanding of and to guide the improvement of organic electro-optic (OEO) materials, prepared by electric field poling of pi-electron chromophore-containing materials near their glass transition temperature. Theoretical treatment of the effects of dielectric permittivity and optical frequency on molecular (chromophore) first hyperpolarizabilities has been carried out as well as the analysis of the influence of spatially anisotropic intermolecular electrostatic interactions on the poling-induced noncentrosymmetric order of chromophores. Three classes of OEO materials have been considered in correlated theoretical and experimental investigations: (1) traditional chromophore/polymer composite materials, (2) chromophores covalently incorporated into polymers, dendrimers, and dendronized polymers, and (3) recently discovered materials consisting of chromophores incorporated into chromophore-containing host materials. This latter class of materials is referred to as binary chromophore organic glasses (BCOGs). These BCOGs exhibit exceptional electro-optic activity because of a combination of high chromophore number density, the effect of high dielectric permittivity on molecular first hyperpolarizability, and improved acentric order arising from the intermolecular electrostatic interactions among the two types of chromophores. The electrical conductivity of materials can also influence achievable electro-optic activity, and thin metal oxide buffer layers, introduced to limit charge injection, can significantly improve poling efficiency. Chromophore order can also be influenced, in some cases, by novel processing techniques, such as laser-assisted electric field poling. Thermal and photostability are important parameters for practical application of materials and have been improved dramatically in recent times. Diels-Alder and fluorovinyl ether cycloaddition reactions have been used to elevate final material glass transition temperatures to above 200 degrees C. Photostability is dominated by the photoactivation of singlet oxygen and subsequent attack on electro-optic chromophores. Photostability can be improved by more than 4 orders of magnitude by chromophore modification and material packaging.

[1]  Larry R. Dalton,et al.  Recent progress in second-order nonlinear optical polymers and dendrimers , 2008 .

[2]  Jingdong Luo,et al.  Reinforced site isolation leading to remarkable thermal stability and high electrooptic activities in cross-linked nonlinear optical dendrimers , 2008 .

[3]  Bruce H Robinson,et al.  Rational enhancement of second-order nonlinearity: bis-(4-methoxyphenyl)hetero-aryl-amino donor-based chromophores: design, synthesis, and electrooptic activity. , 2008, Journal of the American Chemical Society.

[4]  Larry R. Dalton,et al.  Donor-Acceptor Thiolated Polyenic Chromophores Exhibiting Large Optical Nonlinearity and Excellent Photostability , 2008 .

[5]  A. Facchetti,et al.  High‐Performance Thin‐Film Transistors from Solution‐Processed Cadmium Selenide and a Self‐Assembled Multilayer Gate Dielectric , 2008 .

[6]  B. Eichinger,et al.  Frequency and Solvent Dependence of Nonlinear Optical Properties of Molecules , 2008 .

[7]  Bruce H. Robinson,et al.  Laser-Assisted Poling of Binary Chromophore Materials† , 2008 .

[8]  S. Suresh,et al.  High-Temperature Chromophores and Perfluorocyclobutyl Copolymers for Electro-optic Applications† , 2008 .

[9]  Larry R. Dalton,et al.  Binary Chromophore Systems in Nonlinear Optical Dendrimers and Polymers for Large Electrooptic Activities , 2008 .

[10]  Larry R. Dalton,et al.  Guest-Host Cooperativity in Organic Materials Greatly Enhances the Nonlinear Optical Response , 2008 .

[11]  Harrison L. Rommel,et al.  Orientation of Electro-optic Chromophores under Poling Conditions: A Spheroidal Model , 2007 .

[12]  Larry R. Dalton,et al.  Theory-inspired nano-engineering of photonic and electronic materials: Noncentrosymmetric charge-transfer electro-optic materials , 2007 .

[13]  Larry R. Dalton,et al.  Photostability studies of π-conjugated chromophores with resonant and nonresonant light excitation for long-life polymeric telecommunication devices , 2007 .

[14]  Robert A Norwood,et al.  Hybrid cross-linkable polymer/sol-gel waveguide modulators with 0.65 V half wave voltage at 1550 nm , 2007 .

[15]  A. A. Mistry,et al.  Tri-component Diels–Alder polymerized dendrimer glass exhibiting large, thermally stable, electro-optic activity , 2007 .

[16]  Antao Chen,et al.  Theory-guided design and synthesis of multichromophore dendrimers: an analysis of the electro-optic effect. , 2007, Journal of the American Chemical Society.

[17]  R. Norwood,et al.  Hybrid polymer/sol–gel waveguide modulators with exceptionally large electro–optic coefficients , 2007 .

[18]  B H Robinson,et al.  Comparison of static first hyperpolarizabilities calculated with various quantum mechanical methods. , 2007, The journal of physical chemistry. A.

[19]  Jingdong Luo,et al.  Ultralarge and thermally stable electro-optic activities from supramolecular self-assembled molecular glasses. , 2007, Journal of the American Chemical Society.

[20]  E. Davidson,et al.  Hyperpolarizability: Calibration of theoretical methods for chloroform, water, acetonitrile, and p-nitroaniline , 2006 .

[21]  Y. Tian,et al.  Ultralarge and Thermally Stable Electro‐optic Activities from Diels–Alder Crosslinkable Polymers Containing Binary Chromophore Systems , 2006 .

[22]  R. Hentschke,et al.  Dielectric properties and the ferroelectric transition of the Stockmayer-fluid via computer simulation , 2006 .

[23]  B H Robinson,et al.  Influence of isomerization on nonlinear optical properties of molecules. , 2006, The journal of physical chemistry. B.

[24]  Xiong Gong,et al.  New Architecture for High‐Efficiency Polymer Photovoltaic Cells Using Solution‐Based Titanium Oxide as an Optical Spacer , 2006 .

[25]  Jingdong Luo,et al.  Systematic study of the structure-property relationship of a series of ferrocenyl nonlinear optical chromophores. , 2005, Journal of the American Chemical Society.

[26]  Peiwang Zhu,et al.  Very large electro-optic responses in H-bonded heteroaromatic films grown by physical vapour deposition , 2004, Nature materials.

[27]  Kimberly A. Firestone,et al.  RETRACTED: Advances in organic electro-optic materials and processing , 2004 .

[28]  J. Grazul,et al.  Star-shaped azo-based dipolar chromophores: design, synthesis, matrix compatibility, and electro-optic activity. , 2004, Journal of the American Chemical Society.

[29]  I. Economou,et al.  Molecular Dynamics Simulations of Electric Field Poled Nonlinear Optical Chromophores Incorporated in a Polymer Matrix , 2004 .

[30]  A. Jen,et al.  A side-chain dendronized nonlinear optical polyimide with large and thermally stable electrooptic activity , 2004 .

[31]  A. Jen,et al.  Highly Efficient and Thermally Stable Electro‐optic Polymer from a Smartly Controlled Crosslinking Process , 2003 .

[32]  G. Stegeman,et al.  Photodegradation of selected π-conjugated electro-optic chromophores , 2003 .

[33]  Jingdong Luo,et al.  Design, Synthesis, and Properties of Highly Efficient Side‐Chain Dendronized Nonlinear Optical Polymers for Electro‐Optics , 2002 .

[34]  Larry R. Dalton,et al.  Highly Efficient and Thermally Stable Electro‐Optical Dendrimers for Photonics , 2002 .

[35]  S. Kawata,et al.  Photoinduced Reorientation of Azo Dyes Bonded to Polyurethane Studied by Polarized FT-IR Spectroscopy , 2001 .

[36]  A. Jen,et al.  Highly efficient and thermally stable nonlinear optical dendrimer for electrooptics. , 2001, Journal of the American Chemical Society.

[37]  Bruce H. Robinson,et al.  Rational Design of Organic Electro-Optic Materials , 2001 .

[38]  Tony C. Kowalczyk,et al.  Photodegradation of azobenzene nonlinear optical chromophores: the influence of structure and environment , 2000 .

[39]  P. Reid,et al.  The solvent-dependent isomerization dynamics of 4-(dimethylamino)azobenzene (DMAAB) studied by subpicosecond pump–probe spectroscopy , 1999 .

[40]  G I Stegeman,et al.  Effect of temperature and atmospheric environment on the photodegradation of some Disperse Red 1-type polymers. , 1999, Optics letters.

[41]  B H Robinson,et al.  The role of London forces in defining noncentrosymmetric order of high dipole moment-high hyperpolarizability chromophores in electrically poled polymeric thin films. , 1997, Proceedings of the National Academy of Sciences of the United States of America.

[42]  D. Haarer,et al.  The polarized absorption spectroscopy as a novel method for determining the orientational order of poled nonlinear optical polymer films , 1994 .

[43]  C. H. Wang.  Effects of the orientational pair correlation on second order nonlinear optical coefficients , 1992 .

[44]  Persoons,et al.  Hyper-Rayleigh scattering in solution. , 1991, Physical review letters.

[45]  Masud Mansuripur,et al.  Analysis of multilayer thin-film structures containing magneto-optic and anisotropic media at oblique incidence using 2×2 matrices , 1990 .

[46]  Mark G. Kuzyk,et al.  Second-order nonlinear-optical processes in orientationally ordered materials: relationship between molecular and macroscopic properties , 1987 .

[47]  J. Oudar,et al.  Hyperpolarizabilities of the nitroanilines and their relations to the excited state dipole moment , 1977 .

[48]  L. Onsager.  Electric Moments of Molecules in Liquids , 1936 .