Theory-inspired development of organic electro-optic materials

Abstract Real-time, time-dependent density functional theory (RTTDDFT) and pseudo-atomistic Monte Carlo–molecular dynamics (PAMCMD) calculations have been used in a correlated manner to achieve quantitative definition of structure/function relationships necessary for the optimization of electro-optic activity in organic materials. Utilizing theoretical guidance, electro-optic coefficients (at telecommunication wavelengths) have been increased to 500 pm/V while keeping optical loss to less than 2 dB/cm. RTTDDFT affords the advantage of permitting explicit treatment of time-dependent electric fields, both applied fields and internal fields. This modification has permitted the quantitative simulation of the variation of linear and nonlinear optical properties of chromophores and the electro-optic activity of materials with optical frequency and dielectric permittivity. PAMCMD statistical mechanical calculations have proven an effective means of treating the full range of spatially-anisotropic intermolecular electrostatic interactions that play critical roles in defining the degree of noncentrosymmetric order that is achieved by electric field poling of organic electro-optic materials near their glass transition temperatures. New techniques have been developed for the experimental characterization of poling-induced acentric order including a modification of variable angle polarization absorption spectroscopy (VAPAS) permitting a meaningful correlation of theoretical and experimental data related to poling-induced order for a variety of complex organic electro-optic materials.

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

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

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

[4]  Jingdong Luo,et al.  Terahertz all-optical modulation in a silicon–polymer hybrid system , 2006, Nature materials.

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

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

[7]  Chi H. Lee,et al.  Analysis of multiple reflection effects in reflective measurements of electro-optic coefficients of poled polymers in multilayer structures. , 2006, Optics express.

[8]  Bruce H. Robinson,et al.  Monte Carlo Statistical Mechanical Simulations of the Competition of Intermolecular Electrostatic and Poling-Field Interactions in Defining Macroscopic Electro-Optic Activity for Organic Chromophore/Polymer Materials† , 2000 .

[9]  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.

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

[11]  Bruce H. Robinson,et al.  Systematic development of high bandwidth, low drive voltage organic electro-optic devices and their applications , 2003 .

[12]  Zhang,et al.  Low (Sub-1-volt) halfwave voltage polymeric electro-optic modulators achieved by controlling chromophore shape , 2000, Science.

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

[14]  J J Rehr,et al.  Real-time time-dependent density functional theory approach for frequency-dependent nonlinear optical response in photonic molecules. , 2007, The Journal of chemical physics.

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

[16]  R Lawson,et al.  Optical modulation and detection in slotted Silicon waveguides. , 2005, Optics express.

[17]  Larry R. Dalton,et al.  Site-Isolated Electro-optic Chromophores Based on Substituted 2,2'-Bis(3,4-propylenedioxythiophene) π-Conjugated Bridges , 2008 .

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

[19]  P. Madden,et al.  Are dipolar liquids ferroelectric? Simulation studies. , 2007, The Journal of chemical physics.

[20]  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.

[21]  Larry R. Dalton,et al.  Nonlinear polymer-clad silicon slot waveguide modulator with a half wave voltage of 0.25 V , 2008 .

[22]  Larry R. Dalton.  New organic nonlinear optical materials and their integration into silicon nanophotonic circuits and devices , 2008, Security + Defence.