Nonlinear optical polymers with dipole moment aligned transverse to main chain

Tsutsumi, Naoto; Matsumoto, Osamu; Sakai, Wataru; Kiyotsukuri, Tsuyoshi

doi:10.1063/1.115123

Cited by 19 publications

(9 citation statements)

References 13 publications

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“…Recently, we have synthesized a new type of linear polyurethane (T-polymer) with NLO azobenzene chromophore whose dipole moment is aligned transverse to the main chain backbone and another linear urethane polymer (L-polymer) with NLO dipole chromophore incorporated in the main chain backbone. , The resultant poled T-polymer shows the large second-order nonlinearity of d 33 = 1.6 × 10 -7 esu (67 pm/V) with good thermal stability at the ambient conditions. , This polymer is amorphous with a high density of NLO chromophore moieties and can be fabricated to an optically transparent thin film by spin-casting or solvent casting. As pointed out by the previous work, the NLO chromophore in this arrangement can be easier to orient by an external electric field than in structures where the dipole moments are pointing along the polymer backbone.…”

Section: Introductionmentioning

confidence: 99%

Orientational Relaxation of Transversely Aligned Nonlinear Optical Dipole Moments to the Main Backbone in the Linear Polyurethane

1997

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This paper presents the orientational relaxation of nonlinear optical (NLO) chromophore in a linear polyurethane of T-polymer based on 4-[(2-hydroxyethyl)amino]-2-(hydroxymethyl)-4‘-nitroazobenzene (T-AZODIOL) and aromatic diisocyanate of tolylene 2,4-diisocyanate (TDI). T-polymer has the feature that NLO dipole moment is aligned transverse to the main chain. A remarkable difference of the orientational relaxation of NLO dipole moments was observed between the samples corona-poled at 80 and 94 °C. The time-dependent decay curve of second-order nonlinear susceptibility is fitted well by a Kohlrausch−Williams−Watts stretched exponential function. The relaxation time of T-polymer poled at 94 °C is 3 orders of magnitude larger than that poled at 80 °C, and the relaxation time for the sample poled at 94 °C is over 50 years at room temperature. The second-order nonlinear susceptibility of the sample poled at 94 °C is twice larger than that poled at 80 °C. Thermally stimulated discharge current measurement for the sample poled at 94 °C clearly indicates the broad current flow due to the segmental molecular motion and the sharp current flow due to the reorientation of NLO dipole moment at higher temperature which is significantly related to the effective transition temperature for SHG activity. The remarkable stability of second harmonic generation activity for the sample poled at 94 °C is ascribed to the smaller free volume for the sample poled at 94 °C and/or the orientational retaining of the aligned NLO chromophores by space charges formed in terms of the charges injected at 94 °C.

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Section: Introductionmentioning

confidence: 99%

Orientational Relaxation of Transversely Aligned Nonlinear Optical Dipole Moments to the Main Backbone in the Linear Polyurethane

1997

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“…In our study we used a side-chain 4-amino-4′-nitroazobenzene chromophore covalently attached to the polymer backbone of two epoxy-based oligomers containing hydroxyl groups (CFAO) ( T g = 130 °C, M w = 24 200) (Figure b) . In such a configuration, the dipole moment of the chromophore is aligned transverse to the main chain backbone (T-polymer) and provides a large quadratic nonlinearity with its good thermal stability . This is in contrast to azobenzene chromophores incorporated in the main chain backbone (L-polymer).…”

Section: Methodsmentioning

confidence: 99%

Experimental Evidence for Axial Anisotropy beyond the Diffraction Limit Induced with a Bias Voltage Plasmonic Nanoantenna and Longitudinal Optical Near-Fields in Photoreactive Polymer Thin Films

et al. 2014

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This work highlights a mechanism for inducing axial anisotropy in side-chain nitroazobenzene (NAB) polymer thin films based on the combined effect of both local dc electrical poling and the longitudinal optical near-field. We show that highly anisotropic NAB chromophores are effectively oriented in the glassy environment under optical pumping with 632.8 nm excitation wavelength, which is out of the absorption band of chromophores. Axial anisotropy across the polymer thin film and its non-centrosymmetric behavior beyond the diffraction limit are experimentally rendered with tip-enhanced Raman scattering microscopy and scanning Kelvin probe microscopy.

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“…Since polymers containing azobenzene groups have potentially photofunctional applications such as photon‐mode optical memories,19 transducing optical information and photoswitching of electron conductivity, they have received a lot of attention. The azobenzene linkages can be incorporated into the backbone of the polymer20, 21 or in the side‐chain 22, 23. Polymers containing azobenzene groups in the side‐chain are being studied as suitable materials for reversible optical storage 24–26…”

Section: Introductionmentioning

confidence: 99%

Synthesis, molecular and optical characterization of polycarbonates containing azobenzene side‐chains

Lee

Park

Lee

et al. 2006

Polymer International

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In this study, we report the synthesis and holographic characterization of polycarbonates containing an azobenzene group in their side‐chains. The polycarbonate (DR‐PC) was synthesized by the polyaddition reaction of Disperse Red 19 (DR 19) and carbon dioxide in N‐methyl‐2‐pyrrolidone for 24 h in air, and we investigated the mechanism in the presence of potassium carbonate. The film of polycarbonate was obtained by casting onto a slide glass in N,N‐dimethylformamide. The diffraction efficiency of the polycarbonate film was measured as a function of time and intensity of the induced laser. Independently of the intensity of the writing beam, the maximum diffraction efficiency in all DR‐PC films reached about 0.25%. Copyright © 2006 Society of Chemical Industry

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Nonlinear optical polymers with dipole moment aligned transverse to main chain

Abstract: Articles you may be interested inOptical properties and microring laser of conducting polymers with Sn atoms in main chains J. Appl. Phys. 95, 4193 (2004); 10.1063/1.1667272 Poling and orientational relaxation: Comparison of nonlinear optical mainchain and sidechain polymers

Cited by 19 publications

References 13 publications

Orientational Relaxation of Transversely Aligned Nonlinear Optical Dipole Moments to the Main Backbone in the Linear Polyurethane

Orientational Relaxation of Transversely Aligned Nonlinear Optical Dipole Moments to the Main Backbone in the Linear Polyurethane

Experimental Evidence for Axial Anisotropy beyond the Diffraction Limit Induced with a Bias Voltage Plasmonic Nanoantenna and Longitudinal Optical Near-Fields in Photoreactive Polymer Thin Films

Synthesis, molecular and optical characterization of polycarbonates containing azobenzene side‐chains

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