Structural, vibrational and thermal studies of a new nonlinear optical material: L-Asparagine-L-tartaric acid

Crystals of a new nonlinear optical (NLO) material, viz., L-asparagine-L-tartaric acid (LALT)(1) were grown by slow evaporation of an aqueous solution containing equimolar concentrations of L-asparagine and t-tartaric acid. The structure of the title compound which crystallizes in the non-centrosymmetric monoclinic space group P2(1) consists of a molecule of L-asparagine and a molecule of free L-tartaric acid both of which are interlinked by three varieties of H-bonding interactions namely O-H center dot center dot center dot O, N-H center dot center dot center dot O and C-H center dot center dot center dot O. The UV-Vis-NIR spectrum of 1 reveals its transparent nature while the vibrational spectra confirm the presence of the functional groups in 1. The thermal stability and second harmonic generation (SHG) conversion efficiency of 1 were investigated. (C) 2012 Elsevier B.V. All rights reserved.

Lithium D-Isoascorbate Monohydrate, a New Nonlinear Optical Material

Single crystals of lithium D-isoascorbate monohydrate (LDAM), (C6H7O6Li center dot H2O), are grown by a solution growth method. The crystal structure of LDAM is solved using single crystal X-ray diffraction. The space group is orthorhombic P2(1)2(1)2(1) with four formula units per unit cell and lattice parameters a = 7.7836(3) angstrom, b = 8.7456(3) angstrom, and c = 11.0368(4) angstrom. Solubility of the material in water is determined thermogravimetrically and found to have a positive temperature coefficient of solubility. Large optical quality single crystals are subsequently grown from aqueous solution by a slow cooling method. The crystal has a bulky prismatic habit and among the prominent faces the c face appears as the only principal morphological face. The crystal exhibits a (010) cleavage. Dielectric spectroscopy reveals a nearly Debye type Cole-Cole behavior with anisotropy in relaxation. Optical transmission range is found to be from 300 to 1400 nm. The principal refractive indices of this biaxial crystal, measured using Brewster's angle method, at wavelengths 405, 543, and 632.8 nm, show high dispersion. The crystal is negative biaxial with 2V(z) = 107.8 degrees (405 nm) and belongs to the Hobden class 3. Theoretically generated type 1 and type 2 second order phase matching curves match very well with the experimental results. The second-order nonlinear coefficient d(14) was determined to be 7 x 10(-13) m/V. For the optimum phase matching direction (type 2), the second-order effective nonlinear coefficient and the walk off angle are determined to be 0.84 times d(14) and 3.5 degrees respectively. The crystal possesses high multiple surface damage thresholds of 18 GW/cm(2) and 8 GW/cm(2) at laser wavelengths 1064 and 532 nm, respectively.

Crystal growth and defects characterization of zinc tris (thiourea) sulfate: a novel metalorganic nonlinear optical crystal

Single crystals of the metalorganic nonlinear optical material zinc tris (thiourea) sulfate (ZTS) were grown from aqueous solution. The morphology of the crystals was indexed. The grown crystals were characterized by recording the powder X-ray diffraction pattern and by identifying the diffracting planes. Spectrophotometric studies on ZTS reveal that it has good transparency for the Nd: YAG laser fundamental wavelength. Differential thermal analysis of ZTS indicates that the material does not sublime before melting but decomposes immediately after melting. The defect content of the crystals was estimated using etching and X-ray topography. The mechanical hardness anisotropy was evaluated in the (100) plane, which indicates the presence of soft directions.

Nonlinear Optical Properties and Temperature-Dependent UV-Vis Absorption and Photoluminescence Emission in 2D Hexagonal Boron Nitride Nanosheets

Recently, a lot of interest has been centred on the optical properties of hexagonal boron nitride (h-BN), which has a similar lattice structure to graphene. Interestingly, h-BN has a wide bandgap and is biocompatible, so it has potential applications in multiphoton bioimaging, if it can exhibit large nonlinear optical (NLO) properties. However, extensive investigation into the NLO properties of h-BN have not been done so far. Here, NLO properties of 2D h-BN nanosheets (BNNS) are reported for the first time, using 1064-nm NIR laser radiation with a pulse duration of 10 ns using the Z-scan technique. The reverse saturable absorption occurs in aqueous colloidal solutions of BNNS with a very large two-photon absorption cross section (sigma(2PA)) of approximate to 57 x 10(-46) cm(4) s(-1) photon(-1). Also, by using UV-Vis absorption spectroscopy, the temperature coefficient of the bandgap (dE(g)/dT) of BNNS is determined to be 5.9 meV K-1. Further defect-induced photoluminescence emission in the UV region is obtained in the 283-303 K temperature range, under excitations of different wavelengths. The present report of large sigma(2PA) combined with stability and biocompatibility could open up new possibilities for the application of BNNS as a potential optical material for multiphoton bioimaging and advanced photonic devices.

Growth and defect characterization of L-arginine phosphate monohydrate

L-arginine phosphate monohydrate (LAP) is a relatively new organic nonlinear optical material. In this paper, the results of our recent investigations on the growth of this crystal are presented. The growth of the undesirable micro-organisms was prevented by protecting the solution surface by placing a thick layer of n-hexane over it. Colouration of the solution could be avoided by keeping the growth temperature low and by protecting it from light. The effect of pH value of the solution on the solubility and habit was analysed. The grown crystals were characterized by means of X-ray topography.

Defect characterization of KTP single crystals

Potassium titanyl phosphate (KTP) is a relatively new nonlinear optical material with excellent combination of physical properties. This paper presents the combined etching and X-ray topographic studies carried out on KTP crystals with a view to characterizing their defects. KTP crystals employed in this investigation were grown from flux. Optical microscopic study of habit faces revealed growth layers and growth hillocks on (100) and (011) faces respectively. Etching of (011) habit faces proved that growth hillocks corresponded to the emergence point of dislocation out crops on these faces. The suitability of the new etchant to reveal dislocation was confirmed by etching the matched pairs obtained by cleaving. The defects present in the crystal were also studied by X-ray topography. The defect configuration in these crystals is characteristic of crystals grown from solution. The dislocations arc predominantly linear with their origin either at the nucleation centre or inclusions. In general, grown crystals were found to have low dislocation density and often large volumes of crystals free from dislocation could be obtained.

3-nitroacetanilide

The title compound, also known as N-(3-nitrophenyl)acetamide, C8H8N2O3, is an organic non-linear optical material. It crystallizes in the monoclinic system in the chiral space group P2(1), and there are four independent molecules in the asymmetric unit.

Polymer microfabrication by scanning based microstereolithography: Optical design and material functionality

Several research groups have attempted to optimize photopolymerization parameters to increase the throughput of scanning based microstereolithography (MSL) systems through modified beam scanning techniques. Efforts in reducing the curing line width have been implemented through high numerical aperture (NA) optical setups. However, the intensity contour symmetry and the depth of field of focus have led to grossly non-vertical and non-uniform curing profiles. This work tries to review the photopolymerization process in a scanning based MSL system from the aspect of material functionality and optical design. The focus has been to exploit the rich potential of photoreactor scanning system in achieving desired fabrication modalities (minimum curing width, uniform depth profile, and vertical curing profile) even with a reduced NA optical setup and a single movable stage. The present study tries to manipulate to its advantage the effect of optimized lower c] (photoinitiator (PI) concentration) in reducing the minimum curing width to similar to 10-20 mu m even with a higher spot size (similar to 21.36 mu m) through a judiciously chosen ``monomer-PI'' system. Optimization on grounds of increasing E-max (maximum laser exposure energy at surface) by optimizing the scan rate provides enough time for the monomer or resin to get cured across the entire resist thickness (surface to substrate similar to 10-100 mu m), leading to uniform depth profiles along the entire scan lengths. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4750975]

Optical detection of submicromolar levels of nitro explosives by a submicron sized metal-organic phosphor material

Two isomorphous submicron sized metal-organic network compounds, Y-2(PDA)(3)(H2O)1]center dot 2H(2)O (PDA = 1,4-phenylenediacetate), 1 and Y1.8Tb0.2(PDA)(3)(H2O)1]center dot 2H(2)O, Tb@1 have been synthesized by employing solvent assisted liquid grinding followed by heating at 180 degrees C for 1' min and washing with water. Single crystal X-ray data of bulk 1 confirmed a three dimensional porous structure. The structure and morphology of 1 and Tb@1 were systematically characterized by PXRD, TGA, DSC, IR, SEM and EDX analysis. Dehydrated Tb@1 Tb@1'] shows a high intense visible green emission upon exposure to UV light. The green emission of Tb@1' was used for the detection of nitro explosives, such as 2,4,6-trinitrophenol (TNP), 1,3-dinitro benzene (DNB), 2,4-dinitro toluene (DNT), nitro benzene (NB), and 4-nitro toluene (NT) in acetonitrile. The results show that the emission intensity of dehydrated Tb@1' can be quenched by all the nitro analytes used in the present work. Remarkably, Tb@1' exhibited a high efficiency for TNP, DNB and DNT detection with K-SV K-SV = quenching constant based on linear Stern-Volmer plot] values of 70 920, 44 000 and 35 430 M-1, respectively, which are the highest values amongst known metal-organic materials. Using this material submicromolar level (equivalent to 0.18 ppm), a detection of nitro explosives has been achieved.

Interferometry with a novel composite material

An interesting application of optical phase conjugation is phase conjugate interferometry. We report here a new approach to real-time interferometry which combines the high phase conjugate efficiency of photorefractive crystals and the fast response times offered by dye-doped polymer films by using a composite structure. The ability of this material to generate two independent but overlapping phase conjugate waves. which can interfere to reveal the phase changes in a test object, is discussed and demonstrated with a specific example.

Optical and electrical properties of SnS semiconductor crystals grown by physical vapor deposition technique

Tin sulfide (SnS) is a material of interest for use as an absorber in low cost solar cells. Single crystals of SnS were grown by the physical vapor deposition technique. The grown crystals were characterized to evaluate the composition, structure, morphology, electrical and optical properties using appropriate techniques. The composition analysis indicated that the crystals were nearly stoichiometric with Sn-to-S atomic percent ratio of 1.02. Study of their morphology revealed the layered type growth mechanism with low surface roughness. The grown crystals had orthorhombic structure with (0 4 0) orientation. They exhibited an indirect optical band gap of 1.06 eV and direct band gap of 1.21 eV with high absorption coefficient (up to 10(3) cm(-1)) above the fundamental absorption edge. The grown crystals were of p-type with an electrical resistivity of 120 Omega cm and carrier concentration 1.52 x 10(15) cm(-3). Analysis of optical absorption and diffuse reflectance spectra showed the presence of a wide absorption band in the wavelength range 300-1200 nm, which closely matches with a significant part of solar radiation spectrum. The obtained results were discussed to assess the suitability of the SnS crystal for the fabrication of optoelectronic devices. (C) 2011 Elsevier B.V. All rights reserved.

Structural and optical properties of RF sputtered Bi2VO5.5 thin films

Thin films of Bismuth Vanadate Bi2VO5.5 (BiV) have been deposited on amorphous quartz and polycrystalline silicon substrates by r.f. sputtering technique and characterised for their structural and optical properties. The os-deposited films at room temperature are found to be amorphous and transparent over the spectral range of 0.55 mu m to 12 mu m. Post-deposition annealing at 400 degrees C in air shows the formation of the BiV crystalline phase. The optical constants namely refractive index. extinction coefficient and optical bandgap of both amorphous and crystalline films have been determined. The refractive index of the as-deposited film is around 2.4 at 0.7 mu m and drops to 2.26 at 1.56 mu m. The optical bandgap of the material has been determined from the computed values of the absorption coefficients.

Highly Efficient and Thermally Stable Second-Order Nonlinear Optical Chromophores and Electrooptic Polymers

Organic polymeric electro-optic (E-O) materials have attracted significant attention because of their potential use as fast and efficient components of integrated photonic devices (1,2). However, the practical application of these materials in optical devices is somewhat limited by the stringent material requirements imposed by the device design, fabrication processes and operating environments. Among the various material requirements, the most notable ones are large electro-optic coefficients (r(33)) and high thermal stability (3). The design of poled polymeric materials with high electro-optic activity (r(33)) involves the optimization of the percent incorporation of efficient (large beta mu) second order nonlinear optical (NLO) chromophores into the polymer matrices and the effective creation of poling-induced non-centrosymmetric structures. The factors that affect the material stability are a) the inherent thermal stability of the NLO chromophores, b) the chemical stability of the NLO chromophores during the polymer processing conditions, and c) the long-term dipolar alignment stability at high temperatures. Although considerable progress has been made in achieving these properties (4), organic polymeric materials suitable for practical E-O device applications are yet to be developed. This chapter highlights some of our approaches in the optimization of molecular and material nonlinear optical and thermal properties.

The physics and technology of gallium antimonide: An emerging optoelectronic material

Recent advances in nonsilica fiber technology have prompted the development of suitable materials for devices operating beyond 1.55 mu m. The III-V ternaries and quaternaries (AlGaIn)(AsSb) lattice matched to GaSb seem to be the obvious choice and have turned out to be promising candidates for high speed electronic and long wavelength photonic devices. Consequently, there has been tremendous upthrust in research activities of GaSb-based systems. As a matter of fact, this compound has proved to be an interesting material for both basic and applied research. At present, GaSb technology is in its infancy and considerable research has to be carried out before it can be employed for large scale device fabrication. This article presents an up to date comprehensive account of research carried out hitherto. It explores in detail the material aspects of GaSb starting from crystal growth in bulk and epitaxial form, post growth material processing to device feasibility. An overview of the lattice, electronic, transport, optical and device related properties is presented. Some of the current areas of research and development have been critically reviewed and their significance for both understanding the basic physics as well as for device applications are addressed. These include the role of defects and impurities on the structural, optical and electrical properties of the material, various techniques employed for surface and bulk defect passivation and their effect on the device characteristics, development of novel device structures, etc. Several avenues where further work is required in order to upgrade this III-V compound for optoelectronic devices are listed. It is concluded that the present day knowledge in this material system is sufficient to understand the basic properties and what should be more vigorously pursued is their implementation for device fabrication. (C) 1997 American Institute of Physics.

Lithium borate-strontium bismuth tantalate glass nanocomposite: a novel material for nonlinear optic and ferroelectric applications

Glass nanocomposites in the system (100 - x)Li2B4O7-xSrBi(2)Ta(2)O(9) (0 less than or equal to x less than or equal to 22.5, in molar ratio) were fabricated via a melt quenching technique followed by controlled heat-treatment. The as-quenched samples were confirmed to be glassy and amorphous by differential thermal analysis (DTA) and X-ray powder diffraction (XRD) techniques, respectively. The phase formation and crystallite size of the heat-treated samples (glass nanocomposites) were monitored by XRD and transmission electron microscopy (TEM). The relative permittivities (epsilon(tau)') of the glass nanocomposites for different compositions were found to lie in between that of the parent host glass (Li2B4O7) and strontium bismuth tantalate (SBT) ceramic in the frequency range 100 Hz-40 MHz at 300 K, whereas the dielectric loss (D) of the glass nanocomposite was less than that of both the parent phases. Among the various dielectric models employed to predict the effective relative permittivity of the glass nanocomposite, the one obtained using the Maxwell's model was in good agreement with the experimentally observed value. Impedance analysis was employed to rationalize the electrical behavior of the glasses and glass nanocomposites. The pyroelectric response of the glasses and glass nanocomposites was monitored as a function of temperature and the pyroelectric coefficient for glass and glass nanocomposite (x = 20) at 300 K were 27 muC m(-2) K-1 and 53 muC m(-2) K-1, respectively. The ferroelectric behavior of these glass nanocomposites was established by P vs. E hysteresis loop studies. The remnant polarization (P-r) of the glass nanocomposite increases with increase in SBT content. The coercive field (E-c) and P-r for the glass nanocomposite (x = 20) were 727 V cm(-1) and 0.527 muC cm(-2), respectively. The optical transmission properties of these glass nanocomposites were found to be composition dependent. The refractive index (n = 1.722), optical polarizability (am = 1.266 6 10 23 cm 3) and third-order nonlinear optical susceptibility (x(3) = 3.046 6 10(-21) cm(3)) of the glass nanocomposite (x = 15) were larger than those of the as-quenched glass. Second harmonic generation (SHG) was observed in transparent glass nanocomposites and the d(eff) for the glass nanocomposite (x = 20) was found to be 0.373 pm V-1.