Conjugated polymers with degenerate ground state. The route to high performance third-order nonlinear optical response

Halvorson, C.; Hagler, T.W.; Moses, D.; Cao, Yong; Heeger, A.J.

doi:10.1016/0009-2614(92)87004-9

Cited by 52 publications

(9 citation statements)

References 22 publications

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“…Deviations from the power law ͑1͒ were also observed by others. 76,77 Furthermore, we see that the ͑3͒ data of several conjugated -electron systems which have max in the range between 450 and 500 nm can scatter over more than two orders of magnitude. This can lead to doubts as to whether a general scaling between linear and nonlinear optical properties exists at all.…”

Section: B Masterplot Of Third-order Nonlinearities For One-dimensiomentioning

confidence: 95%

“…Additionally some results of other groups are included for comparison, such as data of all-trans polyacetylene ͑t-PA͒, 56,57,76 cis polyacetylene ͑c-PA͒, 76 and all-trans ␤-carotene ͑␤-C͒, which was diluted in polystyrene. [53][54][55] Because ␤-C can be viewed as an oligomer of t-PA, the comparison of these materials is related to our study of OPV-n and PPV.…”

Section: B Masterplot Of Third-order Nonlinearities For One-dimensiomentioning

confidence: 99%

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Third-harmonic-generation spectroscopy of poly(p-phenylenevinylene): A comparison with oligomers and scaling laws for conjugated polymers

et al. 1996

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The third-order nonlinear optical susceptibility ͑3͒ ͑Ϫ3;,,͒ of thin films of poly͑p-phenylenevinylene͒ ͑PPV͒ and several corresponding oligomers ͑OPV-n͒ has been investigated by third-harmonic generation using variable laser wavelengths from 900 to 1520 nm. The oligomers show a single three-photon resonance of ͑3͒ ͑Ϫ3;,,͒ which is closely related to the linear absorption spectrum. We can identify, however, two maxima in the ͑3͒ spectrum of PPV. They are assigned to three-photon resonances with the maximum of the exciton absorption and with the threshold of the continuum of states, which can be located at 3.2Ϯ0.1 eV. This corresponds to an exciton binding energy of 0.7Ϯ0.1 eV. We observe a general scaling behavior for PPV, OPV-n, and other one-dimensional conjugated -electron systems in their neutral form. Their ͑3͒ values, evaluated at comparable resonant or low-resonant conditions, follow an empirical scaling relationship(3) /␣ max ϳ max x , where ␣ max and max denote the absorption coefficient and wavelength of the low-energy absorption maximum. We obtain an exponent xϭ10Ϯ1 which is much larger than expected from an earlier theory. Possible reasons for the difference between theory and experimental results are discussed.

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Section: B Masterplot Of Third-order Nonlinearities For One-dimensiomentioning

confidence: 95%

Section: B Masterplot Of Third-order Nonlinearities For One-dimensiomentioning

confidence: 99%

Third-harmonic-generation spectroscopy of poly(p-phenylenevinylene): A comparison with oligomers and scaling laws for conjugated polymers

et al. 1996

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“…For example, although films of unsubstituted polyacetylene have been found to possess large third-order susceptibilities, [7][8][9] they also exhibit extensive crystallinity, [10] resulting in poor optical quality and large scattering losses.…”

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confidence: 99%

Thick Optical‐Quality Films of Substituted Polyacetylenes with Large, Ultrafast Third‐Order Nonlinearities and Application to Image Correlation

et al. 2008

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Processable organic materials with large, ultrafast thirdorder susceptibilities, x (3) , could enable all-optical signal processing (AOSP) applications through either fabrication of large-area thick films or integration into hybrid organic/ silicon photonic devices. [1][2][3][4] Conjugated polymers, such as polyacetylene, have been shown to exhibit large optical nonlinearities upon application of intense electromagnetic fields.[3] Despite these nonlinearities, many conjugated polymers are inadequate for photonic applications because they lack sufficient processability, or form films with significant crystallinity [5] or inhomogeneous morphologies [6] resulting in poor optical quality. For example, although films of unsubstituted polyacetylene have been found to possess large third-order susceptibilities, [7][8][9] they also exhibit extensive crystallinity, [10] resulting in poor optical quality and large scattering losses.[11] A more processable soluble diester polyacetylene derivative has been reported; [2] however, only thin films have been produced from this material and the bulky side groups can be anticipated to lead to a reduced nonlinear response through a dilution effect. The diester polyacetylene was successfully used in an image-correlation application performed using degenerate four-wave mixing (DFWM) in the visible region with resonant excitation, although the diffraction efficiency was relatively low, due mainly to the limited interaction length. Ring-opening metathesis polymerization (ROMP) provides for the facile synthesis of a great variety of unsaturated polymers.[12] The ROMP method (Scheme 1) utilizes an organometallic alkylidene-based initiator (e.g., rutheniumbased Grubbs initiators [13][14][15] or four-coordinate tungsten-and molybdenum-based Schrock initiators [16][17][18] ) to polymerize strained-ring olefin monomers. [6,19] The ROMP process allows for in situ polymerization of liquid-phase monomers, which allows facile processing of neat films [11] as well as potential integration of the resulting polymers into micro-or nanostructured photonic devices. Moreover, this method is amenable to independent optimization of monomers and initiators to improve processing conditions, optical quality of films, and the third-order susceptibility of the resulting conjugated polymers.Here we report on the synthesis, processing, and linear and nonlinear optical characterization of substituted polyacetylenes obtained using ROMP of mono-substituted cyclooctatetraene (R-COT) monomers. Polymerization and processing conditions have been developed that have led to thick (2-200 mm), large-area (>1 cm Â 1 cm) films possessing large third-order nonlinearities in the near-infrared (NIR) region including the telecommunications bands. The good optical quality of a 200 mm thick poly(n-butyl-COT) film allowed for DFWM image correlation under off-resonant excitation to be performed with improved diffraction efficiency relative to that obtained using the diester polyacetylene derivative mentioned above; the resulting di...

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“…Numerous studies about the third-order nonlinear optical susceptibility x ͑3͒ have been devoted to conjugated polymers [3][4][5][6][7]. Recently, it has been reported that x ͑3͒ is anomalously enhanced in another type of 1D material, that is, 1D Mott insulators of copper oxide, Sr 2 CuO 3 [8,9], and halogenbridged Ni 31 -chain compounds [8].…”

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confidence: 99%

Large Third-Order Optical Nonlinearity of Cu-O Chains Investigated by Third-Harmonic Generation Spectroscopy

et al. 2001

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Spectra of the third-order nonlinear susceptibility chi((3)) have been investigated for one-dimensional Mott insulators, Sr(2)CuO(3) and Ca(2)CuO(3), by applying the third-harmonic generation (THG) spectroscopy on their single-crystalline thin films. The three-photon resonance to the lowest charge-transfer (CT) state with odd parity strongly enhances chi((3)), which is of the order of 10(-9) esu. The two-photon resonant structure unravels the even-CT state, located close to the odd-CT state. Two types of chi((3)) spectra obtained from THG and the electroreflectance measurements are explained based on the concept of spin-charge separation.

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Conjugated polymers with degenerate ground state. The route to high performance third-order nonlinear optical response

Cited by 52 publications

References 22 publications

Third-harmonic-generation spectroscopy of poly(p-phenylenevinylene): A comparison with oligomers and scaling laws for conjugated polymers

Third-harmonic-generation spectroscopy of poly(p-phenylenevinylene): A comparison with oligomers and scaling laws for conjugated polymers

Thick Optical‐Quality Films of Substituted Polyacetylenes with Large, Ultrafast Third‐Order Nonlinearities and Application to Image Correlation

Large Third-Order Optical Nonlinearity of Cu-O Chains Investigated by Third-Harmonic Generation Spectroscopy

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