An experimental technique using powders is described which permits the rapid classification of materials according to(a) magnitude of nonlinear optical coefficients relative to a crystalline quartz standard and(b) existence or absence of phase matching direction(s) for second‐harmonic generation.Results are presented for a large number of inorganic and organic substances including single‐crystal data on phase‐matched second‐harmonic generation in HIO3, KNbO3, PbTiO3, LiClO4·3H2O, and CO(NH2)2. Iodic acid (HIO3) has a nonlinear coefficient d14∼1.5×d31 LiNbO3. Since it is readily grown from water solution and does not exhibit optical damage effects, this material should be useful for nonlinear device applications.

A Powder Technique for the Evaluation of Nonlinear Optical Materials

In 1978 it was discovered, largely through the work of Fleischmann, Van Duyne, Creighton, and their coworkers that molecules adsorbed on specially prepared silver surfaces produce a Raman spectrum that is at times a millionfold more intense than expected. This effect was dubbed surface-enhanced Raman scattering (SERS). Since then the effect has been demonstrated with many molecules and with a number of metals, including Cu, Ag, Au, Li, Na, K, In, Pt, and Rh. In addition, related phenomena such as surface-enhanced second-harmonic generation, four-wave mixing, absorption, and fluorescence have been observed. Although not all fine points of the enhancement mechanism have been clarified, the majority view is that the largest contributor to the intensity amplification results from the electric field enhancement that occurs in the vicinity of small, interacting metal particles that are illuminated with light resonant or near resonant with the localized surface-plasmon frequency of the metal structure. Small in this context is gauged in relation to the wavelength of light. The special preparations required to produce the effect, which include among other techniques electrochemical oxidation-reduction cycling, deposition of metal on very cold substrates, and the generation of metal-island films and colloids, is now understood to be necessary as a means of producing surfaces with appropriate electromagnetic resonances that may couple to electromagnetic fields either by generating rough films (as in the case of the former two examples) or by placing small metal particles in close proximity to one another (as in the case of the latter two). For molecules chemisorbed on SERS-active surface there exists a "chemical enhancement" in addition to the electromagnetic effect. Although difficult to measure accurately, the magnitude of this effect rarely exceeds a factor of 10 and is best thought to arise from the modification of the Raman polarizability tensor of the adsorbate resulting from the formation of a complex between the adsorbate and the metal. Rather than an enhancement mechanism, the chemical effect is more logically to be regarded as a change in the nature and identity of the adsorbate.

Surface-enhanced spectroscopy

Electric field poled organic electro-optic materials: state of the art and future prospects.

The development of nonlinear optical (NLO) materials has been driven by a multitude of important technological applications that can be realized if suitable materials are available 1–15. Future generations of optoelectronic devices for telecommunications, information storage, optical switching, and signal processing are predicted to a large degree on the development of materials with exceptional NLO responses 1–15. A large number of organic π-conjugated molecules have been investigated in the last thirty years for suitability to function as components in hypothetical NLO materials 1–19. Several books and reviews have appeared dealing with theory of nonlinear optics and the structural characteristics and applications of nonlinear optical molecules and materials 1–19. Truly, all-optical NLO effects were not discovered until the discovery of lasers. Second-harmonic generation (SHG) was first observed in a single crystal of quartz by Franken et.al. 20 in 1961. Parametric amplification was observed in lithium niobate (LiNbO3) by two-wave mixing in temperature-tuned single crystals 21. Rentzepis and Pao 22 made the first observation of SHG in an organic material, benzpyrene, in 1964. Heilmeir examined hexamethylenetetramine single crystal SHG in the same year 24. Two other organic materials followed rapidly: hippuric acid and benzil 25. Benzil was the first material that proved relatively easy to grow into large single crystals. Over the last two decades the study of nonlinear optical process in organic and polymer systems has enjoyed rapid and sustained growth 1–19, 25–39. One indication of the growth is the increase in the number of articles published in refereed society journals, as one can find from web of science 25, SCIFINDER 26 and Scopus 27 search. The four years period 1980–1983 saw the publication of 124 such articles. In the next four years period 1984–1987, the production of articles increased to 736 (nearly six times). From 1988–1992, the number of articles increased to more than 4000 25–27. In the last decade, academia, industry and government laboratories have been working in this field to replace electronics by photonics and as a result, the number of publications has reached more than 70,000 25–27.

The rapid growth of the field is mainly due to the technological promise of these materials 1–19, 28–37. Traditionally, the materials used to measure second-order NLO behavior were inorganic crystals, such as lithium niobate (LiNbO3) and potassium dihydrogen phosphate (KDP). The optical nonlinearity in these materials is to a large extent caused by the nuclear displacement in an applied electric field, and to a smaller extent by the movement of the electrons 1–10. This limits the bandwidth of the modulator. Organic materials have a number of advantages over inorganic materials for NLO applications 28–35. The ease of modification of organic molecular structures makes it possible to synthesize tailor-made molecules and to fine-tune the properties for the desired application 28–35. Unfortunately, not all organic materials display second-order NLO properties. At the molecular level, they need to be non-centrosymmetric. A large number of organic π-conjugated molecules have been investigated 1–9, 28–35 in the last twenty years. The outcome of the results has helped to establish certain guidelines for molecular design to get good second order NLO materials. However, roughly more than 80% of all π-conjugated organic molecules crystallize in centro-symmetric space groups 1–19, therefore producing materials with no second order bulk susceptibility. To overcome this limitation, organic NLO material doped or covalently attached in polymers, have been introduced by Dalton et. al 5,6,16,38–39. A few of these chromophores have served as components of functioning polymer-based optoelectronic devices; the physical properties of all these prototype materials possess one or more critical deficiencies that render commercialization of these systems impractical 28–39. These facts suggest that new types of molecular design are necessary if significant advances are to be realized.

From 1998 onwards, researchers started effort on developing various nanomaterials, with high second order NLO properties and seeking for their applications in photonics as well as chemical and biological detection 40–106. The surface-enhanced phenomenon is predicted to have a particularly important impact in nonlinear optical NLO applications, since the generally weak nonlinear effects can be significantly increased via strong electromagnetic fields at the surfaces of metallic nanostructures 60–129. NLO based sensing have provided great potentials and opportunities for detecting different environmental toxins that exhibit some specific advantages, compared to other conventional and nanomaterial based techniques. Aim of this review is mainly to summarize and evaluate the achievements in development of nanoparticle based second order NLO materials with different sizes and shapes and it will focus on the following three major issues: (i) design of novel NLO active materials using nanoparticles (ii) nonlinear optical properties of single nanoparticle, nanoparticle aggregates and self assembly, and (iii) applications in chemical and biological sensing.

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Size and shape dependent second order nonlinear optical properties of nanomaterials and their application in biological and chemical sensing.

The modification of the absorption, emission, and Raman scattering intensities of molecules near metal surfaces is discussed with emphasis on the last. These modifications are usually referred to as surface selection rules. We show that in Raman scattering, the ‘‘rule,’’ which states that only those modes will be active which belong to the irreducible representation to which α′zz also belongs, is only approximately obeyed. The circumstances under which modes which are represented by nondiagonal derived polarizibility tensors are ‘‘surface‐active’’ are considered, as well as the geometrical strategies which should be followed in studying the Raman spectra of molecules adsorbed on flat, metal surfaces.

Surface selection rules

The symmetry properties of the third‐rank tensor β which comprises the set of coefficients of quadratic terms in the expansion of the induced‐dipole moment in the electric field are investigated, and the various linear combinations belonging to the irreducible representations are tabulated for the important molecular symmetry groups. Depolarization ratios are calculated for a sample composed of randomly oriented molecules (liquid phase). Examples of the selection rules in both liquid and crystalline phases are discussed, and these selection rules are contrasted with the ones appropriate for infrared absorption and the ordinary Raman effect.Molecular modes allowed in the infrared are always allowed in the hyper‐Raman effect and have a depolarization ratio (for linearly polarized incident radiation) ≤⅔, while allowed hyper‐Raman transitions forbidden in the infrared have a depolarization ratio of ⅔.

J. C. Decius

Papers

Theory of Hyper-Raman Effects (Nonlinear Inelastic Light Scattering): Selection Rules and Depolarization Ratios for the Second-Order Polarizability