Photoinduced motions in azo-containing polymers.

Linear and Nonlinear Optical Properties of Photochromic Molecules and Materials.

Department of Chemistry, William Mong Institute of Nano Science and Technology, Bioengineering Graduate Program, The Hong Kong University of Science & Technology (HKUST), Clear Water Bay, Kowloon, Hong Kong, China, and Department of Polymer Science and Engineering, Key Laboratory of Macromolecular Synthesis and Functionalization of the Ministry of Education, Institute of Biomedical Macromolecules, Zhejiang University, Hangzhou 310027, China

Acetylenic polymers: syntheses, structures, and functions.

The ability of nonlinear optical materials to transmit, process and store information forms the basis of emerging optoelectronic and photonic technologies. Organic chromophore-containing polymers, in which the refractive index can be controlled by light or an electric field, are expected to play an important role.

Design and synthesis of chromophores and polymers for electro-optic and photorefractive applications

The term nonlinear optics (NLO) was coined to describe the nonlinear relationship between dielectric polarization P and electric field E in optical media. NLO is a cornerstone of the emerging field of photonics, in which photons instead of electrons are used for signal transmission and processing. The vision of photonic signal transmission, processing, and storage has attracted a great deal of attention from both the engineering and the scientific communities because of its great impact in many of the existing and future information technologies. The first step toward realization of these revolutionary technologies is to develop tools to manipulate photons. For example, it is desirable to develop materials with the ability to alter the frequency of light, to amplify light signal, and to modulate light intensity or phase factors. NLO phenomena can be the key to achieving these important functions. One of the most common NLO behaviors is second-harmonic generation (SHG), in which a NLO material mediates the “adding-up” of two photons to form a new one with twice the frequency. The SHGphenomenonwas first demonstrated by Franken et al. in 1961. In their pioneering work, a laser beam with a wavelength of 694.2 nm was irradiated through a quartz crystal and an output ultraviolet radiation with a wavelength of 347.1 nm (double frequency) was detected. After this discovery, numerous nonlinear optical phenomena have been studied and a number of NLO-active materials have been developed. Second-harmonic generation can be quantitatively described by the second-order nonlinear optical susceptibility χ, a third-rank tensor with 27 components. The tensor elements are related to each other tomeet the requirements of both inherent and structural symmetries, which greatly reduces the number of independent components of the susceptibility tensor. Only crystals in noncentrosymmetric crystal classes can have nonvanishing χ. Moreover, for material crystallizing in the noncentrosymmetric 422, 622, and 432 crystal classes, the second-order NLO response might also vanish due to structural symmetry as well as Kleinman’s symmetry. Many inorganic compounds crystallize in noncentrosymmetric space groups and have been found to be SHG active. Some important examples are potassium dihydrogen phosphate (KDP = KH2PO4), lithium niobate (LiNbO3), and barium sodium niobate (Ba2NaNb5O15). 7 New inorganic compounds have been explored for NLO applications including but not limited to metal borates 12 and metal oxides. Recent structural studies on the inorganic systems have led to a better understanding of crystal growth/packing, paving the way for potentially manipulating their crystallization tendency to form noncentrosymmetric structures. Since the 1970s molecular NLO materials, including organic, organometallic, and inorganic complexes, have been of increasing interest to synthetic chemists. 19 The existing library of organic compounds was first screened, and the urea crystal has become a SHG standard because of its high SHG efficiency and usual availability. In a microscopic view, the second-order NLO susceptibility χ is related to the first hyperpolarizability β of a molecule. According to the classical two-level model, β is enhanced by a large transition moment and a large dipole moment difference between the ground and the charge transfer excited state. A donor acceptor type of molecule often possesses both a large transition moment and a large excited state dipole moment. As a result, most of the organic SHG chromophors belong to this category. However, most of the molecules with large β values also possess a large dipole moment, which induces formation of centrosymmetric assemblies of molecules due to dipole dipole interactions. One of the methods to avoid the centrosymmetric alignment of molecular dipoles is to trap them inside the channels of asymmetric porous host structures. 28 Other methods include formation of poled polymers in which the required asymmetry is imposed by the external electric field 35 and the Langmuir Blodgett (LB)

Rational synthesis of noncentrosymmetric metal-organic frameworks for second-order nonlinear optics.

Second-order nonlinearity in poled-polymer systems

The orientational decay of chemically and thermally stable high‐temperature chromophores doped into thin films made from polyimides and a variety of other polymeric hosts has been investigated. The chromophores are aligned using electric field poling and second‐harmonic generation (SHG) is used to probe the decay of the electric field poling induced alignment. The decay rate of the SHG signal from films poled using both a corona discharge and side‐by‐side in‐plane electrodes was measured. When electrodes are chosen so that the effects of charge injection are minimized, little difference has been observed between the orientational decays from films poled using the two methods for either an amorphous preimidized polyimide host or a highly anisotropic film poled during imidization. The films imidized during poling showed significant orientational stability at 250 °C for over 15 h after a fast initial partial decay. In addition, the decay of the SHG signal was measured as a function of temperature below the glass transition in a wide variety of different polymer host systems. The temperature dependence of the decay was found to be non‐Arrhenius, but could be strongly correlated with the glass transition temperature of the guest‐host system using an empirical relationship similar to the Williams–Landel–Ferry or Vogel–Tamann–Fulcher equation.

Orientational decay in poled second‐order nonlinear optical guest‐host polymers: Temperature dependence and effects of poling geometry

Two-beam-coupling gain coefficients exceeding the absorption coefficient are demonstrated for the first time to our knowledge in an organic photorefractive system. The material is based on the photoconducting polymer poly(N-vinylcarbazole), doped with the optically nonlinear chromophore 3-fluoro-4-N,N-diethylamino-β-nitrostyrene and sensitized for charge generation with 2,4,7-trinitro-9-fluorenone. The photorefractive performance is significantly better than that of any previously described organic. Diffraction efficiencies as large as 1% in a 125-μm sample, grating growth times of the order of 100 ms, and beam-coupling gain coefficients >10 cm−1 were observed at 647 nm (writing intensity of 1 W cm−2, applied field of 40 V μm−1).

Net two-beam-coupling gain in a polymeric photorefractive material.

The fullerene molecule C60 is shown to act as a useful sensitizer of a recently discovered photorefractive polymer. Measurements of the steady‐state diffraction efficiency, grating growth rate, and other photorefractive properties are presented as a function of C60 concentration, writing intensity, and applied electric field. The dc photoconductivity, grating growth rate, and steady‐state diffraction efficiency all increase by as much as a factor of 20 upon doping with up to 0.2 wt % C60. The sensitization appears to result from a small increase in the carrier generation efficiency and a larger increase in the useful optical absorption at the operating wavelength, 647 nm.

C60 sensitization of a photorefractive polymer

We investigate in detail the grating properties of a recently discovered organic photorefractive polymer as a function of electric field by using two-beam coupling. Using an oblique-incidence geometry, we present measurements of index and absorption grating phase relative to the intensity interference pattern as well as measurements of the amplitude of both the absorption and index gratings. We find that in low electric fields a weak in-phase grating (possibly photochromic) and the low electro-optic coefficient prevent observation of a phase-shifted photorefractive grating. However, in moderate-to-high electric fields a much stronger photorefractive index grating with a phase shift approaching 90° dominates. The presence of an index grating with a 90° phase shift at high fields provides strong evidence that these polymers are indeed photorefractive.

https://apps.dtic.mil/sti/pdfs/ADA243746.pdf

C. A. Walsh

Papers

Second-order nonlinearity in poled-polymer systems

Orientational decay in poled second‐order nonlinear optical guest‐host polymers: Temperature dependence and effects of poling geometry

Net two-beam-coupling gain in a polymeric photorefractive material.

C60 sensitization of a photorefractive polymer

Two-beam coupling measurements of grating phase in a photorefractive polymer