Nonlinear optical solids

Because of the generality of the symmetry principle that underlies the nonlinear optical spectroscopy of surfaces and interfaces, the approach has found application to a remarkably wide range of material systems. These include not only the conventional case of solid surfaces in ultrahigh vacuum, but also gas/solid, liquid/solid, gas/liquid and liquid/liquid interfaces. The infonnation attainable from the measurements ranges from adsorbate coverage and orientation to interface vibrational and electronic spectroscopy to surface dynamics on the femtosecond time scale. 

Brus L E 1993 NATO ASI School on Nanophase Materials ed G C Had]lpanayls (Dordrecht Kluwer) Allvisatos A P 1996 Semiconductor clusters, nanocrystals and quantum dots Science 271 933 Heath J R and Shlang J J 1998 Covalency In semiconductor quantum dots Chem. See. Rev. 27 65 Brus L 1998 Chemical approaches to semiconductor nanocrystals J. Phys. Chem. Solids 59 459 Brus L 1991 Quantum crystallites and nonlinear optics App/. Phys. A 53 465... 

Most of the envisioned practical applications for nonlinear optical materials would require solid materials. Unfortunately, only gas-phase calculations have been developed to a reliable level. Most often, the relationship between gas-phase and condensed-phase behavior for a particular class of compounds is determined experimentally. Theoretical calculations for the gas phase are then scaled accordingly. 

By the sol-gel-process, inorganic glassy and hybrid polymeric materials are accessible at comparatively low temperatures [1], Therefore, organic molecules or dyes can easily be incorporated into the oxide matrix. This combination is especially attractive for the development of the following devices optical filters, solid-state lasers, optical switches, nonlinear optical laser hosts, optical data storage media, and photoconductive devices and films [2]. 

The chapters cover the following areas (i) use of coordination complexes in all types of catalysis (Chapters 1-11) (ii) applications related to the optical properties of coordination complexes, which covers fields as diverse as solar cells, nonlinear optics, display devices, pigments and dyes, and optical data storage (Chapters 12-16) (iii) hydrometallurgical extraction (Chapter 17) (iv) medicinal and biomedical applications of coordination complexes, including both imaging and therapy (Chapters 18-22) and (v) use of coordination complexes as precursors to semiconductor films and nanoparticles (Chapter 23). As such, the material in this volume ranges from solid-state physics to biochemistry. 

We first discuss the materials research which includes monomer synthesis, growth of monomer crystalline structures and polymerization in the solid state, yielding the requisite polymer structures. Next, the nonlinear optical experimental research is discussed which includes a novel experimental technique to measure x (w). Linear and nonlinear optical data obtained for the polydiacetylene films is subsequently presented. Detailed theoretical analysis relating the data to x (< >) and subsequently to its molecular basis will be discussed in a later publication. 

Polydiacetylenes are obtained as single crystals by topochemical solid-state polymerization of the monomer single crystal. These compounds have received considerable attention because of their one-dimensionally -conjugated structure. Their unique --electron structures, and therefore superior third-order nonlinear optical properties, have been extensively investigated. 

Besides the spectroscopic investigations of solids by laser-excited spontaneous Raman or Brillouin scattering already discussed in Sections III.6 and 7, much new insight into the optical properties and the structure of solids has been gained by studying nonlinear optical effects. (Surveys and more detailed information about nonlinear optics can be found in refs. 306-308))... 

The interest in efficient optical frequency doubling has stimulated a search for new nonlinear materials. Kurtz 316) has reported a systematic approach for finding nonlinear crystalline solids, based on the use of the anharmonic oscillator model in conjunction with Miller s rule to estimate the SHG and electro optic coefficients of a material. This empirical rule states that the ratio of the nonlinear optical susceptibility to the product of the linear susceptibilities is a parameter which is nearly constant for a wide variety of inorganic solids. Using this empirical fact, one can arrive at an expression for the nonlinear coefficients that involves only the linear susceptibilities and known material constants. 

While the amount of electricity that can be conducted by polymer films and wires is limited, on a weight basis the conductivity is comparable with that of copper. These polymeric conductors are lighter, some are more flexible, and they can be laid down in wires that approach being one-atom thick. They are being used as cathodes and solid electrolytes in batteries, and potential uses include in fuel cells, smart windows, nonlinear optical materials, LEDs, conductive coatings, sensors, electronic displays, and in electromagnetic shielding. 

The first chemical transformations carried out with Cjq were reductions. After the pronounced electrophilicity of the fullerenes was recognized, electron transfer reactions with electropositive metals, organometallic compounds, strong organic donor molecules as well as electrochemical and photochemical reductions have been used to prepare fulleride salts respectively fulleride anions. Functionalized fulleride anions and salts have been mostly prepared by reactions with carbanions or by removing the proton from hydrofullerenes. Some of these systems, either functionalized or derived from pristine Cjq, exhibit extraordinary solid-state properties such as superconductivity and molecular ferromagnetism. Fullerides are promising candidates for nonlinear optical materials and may be used for enhanced photoluminescence material. 

Boling, N. L., Glass, A. 1., and Owyoung, A. 1978. Empirical relationships for predicting nonlinear refractive index changes in optical solids. IEEE J. Quant. Electron. 14 601-8. 

Second-Order Nonlinear Optical Processes in Molecules and Solids... 

Several isovalent ions form solid solutions with KTP (Table II), showing that this structure is relatively tolerant, with respect to isovalent impurities, as are the traditional nonlinear optical oxide crystal structures. But due to the relatively limited range of nonstoichiometry in KTP, aliovalent impurities, such as divalent Ba, Sr and Ca introduced through ion exchange in nitrate melts, which substitute on the K site, are incorporated at concentrations less than one mole percent.(36) Typical impurity concentrations present in flux and hydrothermally grown KTP are shown in Table ID. 

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