Growth and characterization of two new NLO materials from the amino acid family: l-Histidine nitrate and l-Cysteine tartrate monohydrate

Single crystals of organic nonlinear optical (NLO) materials l-Histidine nitrate (C₆H₁₀N₃O₂)⁺ · (NO₃)⁻ and l-Cysteine tartrate monohydrate (C₃H₈NO₂S)⁺ · (C₄H₅O₆)⁻ · H₂O were grown by submerged seed solution method. Characterization of the crystals was made using single crystal X-ray diffraction. Fourier transform infrared (FTIR) spectroscopic studies, optical behaviour such as UV-visible-NIR absorption spectra and second harmonic generation (SHG) conversion efficiency were investigated to explore the NLO characteristics of the above materials. Microhardness measurements and dielectric studies of the compounds were also carried out.     

Generation of tunable infrared radiation in rubidium titanyl phosphate crystal for the optical measurement of number density, absorption cross-section of methane gas

Tunable near-infrared radiation has been generated in a rubidium titany1 phosphate (RTP) crystal by employing non-collinear difference-frequency mixing (DFM) technique. The input radiation sources are Nd:YAG laser radiation and its second harmonic pumped dye laser radiation. For the generation of 2.0 radiation, the maximum value of the conversion efficiency (quantum) obtained in the process is 49% from the dye (0.6945 μm) to the infrared (2.0 μm) radiation in the 7.9-mm-long crystal. The generated tunable mid-infrared radiation has been used to measure the number density, absorption cross-section and minimum detectable concentration of methane gas in its 2ν₃ band in a multi-pass cell at 30.075 Torr pressure. The number density and column density of the methane molecules are found to be 1.068×10¹⁸ cm⁻³ and 3.02×10²¹ cm⁻², respectively, whereas the minimum still-detectable concentration at 1.658 μm wavelength is estimated to be 4.523×10¹⁷/cm³.     

Effect of organic dyes on the dielectric properties of KH<Subscript>2</Subscript>PO<Subscript>4</Subscript> crystals

The effect of organic dyes on the dielectric properties of KH₂PO₄ (KDP) crystals is studied over a wide range of temperatures. The dielectric properties of KDP crystals doped with molecules of the Chicago Sky Blue and Amaranth organic dyes are investigated for the first time. The dye molecules can be incorporated into the crystal lattice of KDP and selectively paint the pyramidal growth sectors of the crystal. The influence of dye organic impurities on the domain contribution to the permittivity is analyzed with due regard for the sectoral crystal structure. It is demonstrated that, upon doping of KDP crystals with organic dyes, the blocking effect of background impurities on domain walls is substantially weakened in the prismatic growth sector of the crystal in the polar phase. This leads to a noticeable change in the dielectric properties, specifically to an increase in the domain contribution to the permittivity of the crystal.     

Characterization of biaxial crystals for tangentially phase-matched frequency conversion

Ultraviolet radiation has been generated by tangentially phase-matched sum-frequency mixing in biaxial L-arginine phosphate (LAP) crystal for the first time using Nd:YAG output at 1064 nm and Rh 6G dye laser output at 560 nm as the two input sources. Characterization has also been made of such a cheap, biaxial crystal for its possible use in devices for tangentially phase-matched short wavelength generation. If the crystal is of proper cut, thickness and quality so that its maximum capability can be exploited it can replace the potassium dihydrogen phosphate (KDP) group of crystals for various applications.     

Growth and characterization of a new organic NLO material: Glycine nitrate

Single crystals of glycine nitrate [(C₂H₆NO₂)⁺ · (NO₃)⁻] were grown using submerged seed solution method. The crystals were characterized by using single crystal X-ray diffraction and density measurements. Spectroscopic, thermal and optical studies were carried out for analyzing the presence of the functional groups, thermal stability, decomposition and transparency of the sample. These studies showed that the crystals are thermally stable upto 145 °C and transparent for the fundamental and second harmonic generation of Nd:YAG (λ = 1064 nm) laser. Second harmonic generation (SHG) conversion efficiency was investigated to explore the NLO characteristics of this material. Microhardness and dielectric studies were also carried out.     

Mechanism of phase conjugation via stimulated Brillouin scattering in narrow band gap semiconductors

We develop a theoretical model to study optical phase conjugation via stimulated Brillouin scattering (OPC-SBS) in narrow band gap transversely magnetized semiconductors. Threshold value of pump electric field and reflectivity of the image radiation for the onset of OPC-SBS are estimated. The analysis is applied to both cases viz. centrosymmetric (CS) and non-centrosymmetric (NCS) crystals. Numerical estimates made for n-type InSb crystal at liquid nitrogen temperature duly irradiated by nanosecond pulsed 10.6 μm CO₂ laser shows that high OPC-SBS reflectivity (90%) can be achieved in NCS crystals at moderate pump electric fields if the crystal is used as an optical waveguide with relatively large interaction length (L = 5 mm) which proves its potential in practical applications such as fabrication of phase conjugate mirrors.     

l-Cystine hydrochloride: A novel semi-organic nonlinear optical material for optical devices

A new semi-organic nonlinear optical (NLO) material l-cystine hydrochloride (LCHCl) was grown in large size measuring 19 × 5 × 3 mm³ by slow solvent evaporation technique for the first time in literature. The cell parameter values were determined by single crystal X-ray diffraction studies. Fourier Transform Infrared spectroscopic analysis was carried out on the grown sample to ascertain the fundamental functional groups. Thermal behavior of the grown LCHCl sample was analyzed by TG & DTA analysis. The mechanical properties of the grown crystals have been studied using Vickers microhardness tester. The optical transmission studies and second harmonic generation (SHG) efficiency studies justified the device quality of the grown crystal and the SHG study reveals that the grown sample has nearly 1.2 times higher efficiency than that of potassium dihydrogen phosphate (KDP), a well known NLO material.     

Optimization of optical parametric chirped pulse amplification with different pump wavelengths

Optical parametric chirped pulse amplification with different pump wavelengths was investigated using LBO crystal, at signal central wavelength of 800 nm. According to our theoretical simulation, when pump wavelength is 492.5 nm, there is a maximal gain bandwidth of 190 nm centered at 805 nm in optimal noncollinear angle using LBO. Presently, pump wavelength of 492.5 nm can be obtained from second harmonic generation of a Yb:Sr₅(PO₄)₃F laser. The broad gain bandwidth can completely support ∼6 fs with a spectral centre of seed pulse at 800 nm. The deviation from optimal noncollinear angle can be compensated by accurately tuning crystal angle for phase matching. The gain spectrum with pump wavelength of 492.5 nm is much better than those with pump wavelengths of 400, 526.5 and 532 nm, at signal centre of 800 nm.     

Synthesis, growth and characterization of novel second harmonic nonlinear chalcone crystal

Nonlinear optical (NLO) materials are useful in many of the industrial applications. New NLO chalcone derivative (2E)-3-[4-(methylsulfanyl)phenyl]-1-(4-nitrophenyl)prop-2-en-1-one (4N4MSP) crystals have been grown by slow evaporation technique at ambient temperature. The grown crystals were subjected to single crystal X-ray diffraction study. The crystal has noncentrosymmetric structure in the orthorhombic system with space group Aba2 and unit cell parameters a=14.0647(15) Å, b=33.738(4) Å and c=6.0039(6) Å. To confirm the presence of various functional groups in the compound, FT-IR spectrum was recorded. The crystal was subjected to TGA/DTA analysis to find its thermal stability. The grown crystals were characterized for their optical transmission and mechanical hardness. The second harmonic generation (SHG) efficiency of the crystal is obtained by classical powdered technique using Nd:YAG laser and its value is 28.57 times that of urea. The laser damage threshold for 4N4MSP crystal was determined using Q-switched Nd:YAG laser. The refractive index values for green and red wavelengths were measured by Brewster angle technique. The dielectric and electrical measurements were carried out to study the different polarization mechanism and conductivity of the crystal. Good thermal, mechanical, transmission and SHG response make it desirable for the NLO applications.     

Effect of xylenol orange on the crystalline perfection,optical, piezoelectric and NLO behavior of unidirectionally grown imidazolium L-Tartrate single crystal

Pure and 0.1 mol% Xylenol orange (XO) doped Imidazolium L-tartrate (IMLT) nonlinear optical (NLO) single crystals were grown using Sankaranarayanan–Ramasamy (SR) method of uniaxial solution crystallization technique. The pure IMLT crystal is 100 mm in length and 15 mm in diameter. The doped IMLT crystal is 25 mm in length and 10 mm in diameter. UV–Vis-NIR spectrum shows that the pure and XO doped IMLT crystals' cut off wavelength is 235 nm. High-resolution X-ray diffraction (HRXRD) measurement and birefringence interferometry confirm that the SR method grown crystal has good crystalline perfection and optical homogeneity. The wavelength dependent refractive index and piezoelectric d₃₃ coefficient were measured. The difference refractive index (Δn) of (100) plane in parallel and perpendicular directions shows a strong dependence on wavelength. The dielectric constant, hardness and SHG conversion efficiency were also increased as a result of XO dye doping in IMLT crystal.     

Growth and design of novel nonlinear optical material (NLO) ⿿ Glycine barium nitrate potassium nitrate (GBNPN) crystal

A potentially useful semi organic nonlinear optical (NLO) material ? glycine with barium nitrate and potassium nitrate (GBNPN) has been synthesized by slow evaporation technique. Good transparent GBNPN crystals were obtained in a time span of 3 weeks. The grown crystals were characterized by single crystal/powder XRD, UV?vis?IR absorption, FTIR, thermal analysis and powder SHG measurements have been studied. The grown crystals were thermally stable up to 137.53 °C. The GBNPN crystal exhibits second harmonic generation efficiency of about 1.35 times than that of potassium di hydrogen phosphate (KDP). Mechanical properties such as micro hardness (H_v) and Mayer's index, n, have been carried out by indentation method. The refractive index (μ) has been measured by the Brewster's angle method.     

Intra-cavity second harmonic generation with Nd:YVO4/BIBO laser at 542 nm

We report, for the first time, an efficient intra-cavity second-harmonic generation (SHG) at 1084 nm in a nonlinear optical crystal, BiB₃O₆(BIBO) at the direction of (θ, ?) = (170.1°, 90°), performed with a LD end-pumped cw Nd:YVO₄ laser. With 590 mW diode pump power, a continuous-wave (cw) SHG output power of 19 mW at 542 nm yellow-green color has been obtained using a 1.5 mm-thick BIBO crystal. The optical conversion efficiency was 3.22%. It was found that the output wavelength could be 532 nm, 537 nm or 542 nm according to regulating the angle of BIBO.     

Theoretical estimation of optical hyperpolarizability appearance in fullerene molecule and carbon nanotubes interacting with ionic crystal surface

The first hyperpolarizability (HP) of fullerene and finite length carbon nanotubes (FCN), attached to the neutral surfaces of SiO₂ (1 1 0), CdS(1 1 2 0), and CdTe(1 1 0) crystals, is calculated in the framework of the semi-empirical version of the time-dependent Hartree-Fock theory (TDHF). The norm of β-vector invariant, induced by the substrate, is of the same order as in some organic molecules with the observed nonlinear optical properties. The orthogonal to the substrate β-component is responsible for generation of the second harmonic by fullerene according to Hoshi and co-authors [H. Hoshi, N. Nakamura, Y. Maruyama, T. Nakagawa, S. Suzuki, H. Shiromaru, Y. Achiba, Jpn. J. Appl. Phys. 30 (1991) L1397]. The calculated value of this component is shown sufficient for the weak generation. It is found that zig-zag FCN, in contrast to armchair FCN, are characterized by the resonant behaviour of HP for second harmonic generation (SHG) at low frequencies due to the existence of quasi-degenerate (hyperbolic) levels in the close vicinity of the Fermi level. This ability is created by the external ionic crystal potential and affected by mutual electron interaction of molecules in the layer.     

Characterization of optical waveguide in Nd: LuVO4 crystals by triple-energy oxygen ion implantation

We report on the optical planar waveguide formation and modal characterization in Nd:LuVO₄ crystals by triple-energy O³⁺-ion implantation at energies of 2.4, 3.0, and 3.6 MeV and doses of 1.4, 1.4, and 3.1×10¹⁴ ions/cm², respectively. The prism-coupling method is used to investigate the dark-mode property at a wavelength of 633 nm. The refractive index profiles of the waveguide are reconstructed by the reflectivity calculation method (RCM). The modal analysis shows that the fields of TE modes are well restricted in the guiding region, which indicates the formation of non-leaky waveguide in the crystal.     

Retardation calculation for achromatic and apochromatic quarter and half wave plates of gypsum based birefringent crystal

This paper presents retardation calculations for achromatic and apochromatic half and quarter wave retarders of gypsum based birefringent crystal. The calculations indicate that an achromatic wave plates can be obtained by combining gypsum crystal with KDP, ADP, MgF₂, sapphire and calcite birefringent crystals. The residual variation percentages of retardations as a function of wavelength for gypsum/KDP, gypsum/ADP, gypsum/MgF₂, gypsum/sapphire and gypsum/calcite were found to be ± 1.7%, ± 3%, ± 12.2%, ± 12.0% and ± 7.2%, respectively. To reduce the spectral variation of retardations, a third layer (apochromatic) of birefringet material is added to the aforementioned achromatic wave plates. The proposed apochromatic wave plates are gypsum/KDP/quartz, gypsum/ADP/quartz, MgF₂/ADP/gypsum, MgF₂/KDP/gypsum and gypsum/sapphire/MgF₂. The addition of a third layer has reduced spectral residual variation percentages of retardations of the aforementioned apochromatic designs to ± 0.27, ± 0.33, ± 0.3, ± 0.17 and ± 0.45, respectively.     

Structural analysis of nonlinearities of Ca4ReO(BO3)3 (Re = La, Nd, Sm, Gd, Er, Y)

4 ReO(BO₃)₃ (CReOB, Re=La, Nd, Sm, Gd, Er, and Y) have been theoretically predicted. The d₁₁ tensor coefficient of CReOB is predicted to be -11 d₃₆(KDP), which is the largest d_ij tensor that has been found in borate crystals. From the structural characteristic of CReOB, we find the isolated BO₃ ^3- clusters play a dominant role in contributions to the total nonlinearity, and the largest d₁₁ tensor of CReOB-type crystals is also ascribed to these BO₃ ^3- clusters. We also find the NLO property of this family does not change dramatically for different rare-earth elements. The details of the calculation of CGdOB only are presented. Received: 3 March 1998/Accepted: 22 June 1998     

Nonlinear optical properties of orthorhombic barium formate and magnesium barium fluoride

The nonlinear optical susceptibility tensors of barium formate (point group 222) and magnesium barium fluoride (point group mm 2) have been determined by the method of Maker fringes on the basis of a more rigorous theoretical treatment of second-harmonic generation of electromagnetic waves in plane-parallel plates of optically biaxial crystals. The measurements have been carried out in comparison with the KDP standard at awavelength of 1.064 μm (Nd: YAG). Both crystals possess nonlinear coefficients smaller than KDP (d ₃₆); they are phase matchable; magnesium barium fluoride exhibits a noncritical phase matching at a fundamental wavelenght of 1.04 μm.     

Z-Scan studies of KYW, KYbW, KGW, and Ba(NO3)2 crystals

We present the studies of nonlinear refraction and nonlinear absorption in promising crystals which are extensively used in Raman lasers or as solid-state laser host materials: Ba(NO₃)₂, KGW, KYW, and KYbW. The single-beam z-scan technique with 1 ps laser pulses at 790 and 395 nm has been applied for the study. Nonlinear refraction-index intensity-coefficients and two-photon absorption coefficients have been determined for the crystals. The considerable enhancement of nonlinear refraction is observed in the crystals at 395 nm.     

Sum and difference frequency generation of white light continuum with the ps pulses of Nd:YAG laser in a thick BBO crystal

The white light continuum (WLC) generated in water/D₂O mixture by pumping with the fundamental of ps Nd⁺³:YAG laser has been used as a variable frequency source for the sum frequency generation as well as for its amplification. 35 ps long pulses with 8 mJ energy at 1064 nm were mixed collinearly with the WLC generated by the same laser beam in a 20 mm thick BBO crystal. The obtained tunable output has been identified as the sum frequency between the fundamental and a portion of the WLC with the required phase matching. Theoretical simulations are also given along with a few initial experiments to use this combination for the difference frequency generation (optical parametric amplification) under non-collinear geometry.     

Nonlinear optical properties of (B3O7)5- and (B3O6)3- groups

3 O₅ (LBO) crystal has been studied by using the bond valence theory of complex crystals. Chemical bond parameters and linear and nonlinear optical (NLO) properties of each type of constituent chemical bonds are quantitatively determined. Because of the different crystal structure characteristics of LBO from those of β-BaB₂O₄ (BBO), the two anionic groups, (B₃O₇)^5- in LBO and (B₃O₆)^3- in BBO, play different roles in contributions to their own total NLO tensor coefficients of LBO and BBO, respectively. By comparison, we find that planar (B₃O₆)^3- groups are the ideal structure model, leading to little cancellation of contributions of each kind of bond in these groups, and this gives us a useful guide to design new NLO materials in the future. Received: 24 January 1997/Accepted: 27 March 1997