Semiorganic NLO Material Research Articles

Development and Evaluation of an Efficient Second Order Non-Linear Optical Single Crystal – 2-(3-Aminopyridinium-1-yl)-3-Carboxy-Proponate Monohydrate

A slow evaporation solution approach was used to create high-quality single crystals of 2-(3-aminopyridinium-1-yl)-3-carboxyproponate monohydrate (3ACPM). The single crystal X-ray diffraction was used to determine the crystal system and lattice characteristics. Software called Krystal Shaper was used to mimic the morphology of the 3ACPM. To evaluate the optical transmittance, UV-vis spectral analysis was used. The Nd:YAG laser was used to assess the laser-induced surface damage threshold (LISDT) of 3ACPM single crystal. The presence of second harmonic generation (SHG) was evaluated using the Kurtz-Perry powder method. Full Text: PDF References Y. Zhang, H. Li, B. Xi, Y. Che,vJ. Zheng, "Growth and characterization of l-histidine nitrate single crystal, a promising semiorganic NLO material", Mater. Chem. Phys. 108, 192 (2008), CrossRef S. Draguta, M.S. Fonari, A.E. Masunov, J. Zazueta, S. Sullivan, M.Y. Antipin, T.V. Timofeeva, "New acentric materials constructed from aminopyridines and 4-nitrophenol", Cryst. Eng. Comm. 15, 4700 (2013) CrossRef G. Peramaiyan, R. Mohan Kumar, "Nonlinear optical and laser damage threshold studies of an ammonium p-toluenesulfonate crystal", Appl. Phys. A 119, 707 (2015), CrossRef G.M. Corrales, D. Morales-Morales,S. Hernandez-Ortega, J.J. Campos-Gaxiolaa, A. Cruz Enrıquez, "2-(3-Aminopyridinium-1-yl)-3-carboxypropanoate monohydrate", Acta Cryst. E68, o853 (2012), CrossRef S.K. Kurtz, T.T. Perry, "A Powder Technique for the Evaluation of Nonlinear Optical Materials", J. Appl. Phys. 39, 3798 (1968), CrossRef S. Panchapakesan, K. Subramani, B.Srinivasan, "Growth, characterization and quantum chemical studies of an organic single crystal: 3-Aminopyridine 4-Nitrophenol for opto-electronic applications", J. Mater. Sci: Mater. Electron. 28, 5754 (2017), CrossRef

Sankaranarayanan-Ramasamy (SR) technique L- threonine lithium chloride single crystal: Unidirectional growth, optical and mechanical studies

L-Threonine Lithium Chloride (LTLC), an effective semi-organic NLO material, was successfully produced as a bulk single crystal using the Sankaranarayanan Ramasamy (SR) process. According to a study of a single crystal's X-ray diffraction, LTLC crystallises in an orthorhombic system with space group P212121. From the powder XRD method, unidirectional development along the plane (110) was established. The optical absorption spectra reveals that LTLC has a broad bandgap of 3.75 eV and is very transparent over the whole visible region. On the magnified crystal, photoconductivity measurements show positive photoconductivity. According to the photoluminescence investigation, LTLC emits green light with a wavelength of 535 nm. Vickers microhardness testing was done to determine the crystal's mechanical strength. At different temperatures and frequencies, the dielectric constant and dielectric loss were calculated. In addition to the density functional theory (DFT) calculations such as frontier molecular orbital’s (FMOs), analysis was carried out. Utilizing Kurtz's Nd:YAG Laser, powder testing is another method used to assess the produced crystal's SHG activity.

Discovery of NLO Semiorganic (C5H6ON)+(H2PO4)-: Dipole Moment Modulation and Superior Synergy in Solar-Blind UV Region.

We herein report a novel semiorganic NLO material, (C5H6ON)+(H2PO4)-, 4HPP, showing promising excellent properties in the important solar-blind UV region where LAP and its deuterated form DLAP are the only commercialized semiorganic materials. For the first time, the 4-hydroxypyridine (4HP+, (C5H6ON)+) cation is identified as NLO active and how to eliminate the dipole-dipole interaction to avoid the unwanted center-symmetry-trap caused by the polar-induced susceptibility is well demonstrated. Remarkably, 4HPP exhibits competitive and even better properties compared with LAP that include better thermal stability (decomposition at 166 vs 112 °C of LAP); wider transparency range (0.26-1.50 μm); very strong SHG response (3 × KDP); a suitable large birefringence (Δncal = 0.25 vs 0.075 of LAP); and a high laser-induced damage threshold (2.2 × KDP). First-principles calculations show that the π-conjugated organic (4HP)+ cation governs the optical anisotropy, whereas the synergy of the organic and inorganic moieties dominates the SHG process. Our discovery points out a new path for the rational design of high performance semiorganic materials that require an acentric structure.

Investigation on key properties of solution grown l-Leucine hydrobromide single crystal: A semi-organic NLO material

Good quality single crystals of l-Leucine hydrobromide, a prominent NLO material, have been grown successfully by conventional slow evaporation solution technique to meet the requirement of photonics industry. To confirm the identity of the synthesized material and the % composition of constituent element CHN analysis was carried out. HRXRD rocking curve confirms the better crystalline perfection as it has single sharp peak with FWHM 17.59 arc sec and almost uniform on both sides. Thermal properties were investigated by DSC and photo-acoustic anlaysis. Thermal diffusivity, conductivity and effusivity have been calculated from photo-acoustic analysis. Some electronic parameters of technical importance were also calculated by Clausius- Mossotti relation. Mechanical behavior has been examined by employing nano-indentation technique. Several useful mechanical properties like hardness, stiffness, Young's modulus were studied and found that both hardness and Young's modulus depends upon the peak load.

Investigation on structural, optical and thermal properties of L-asparagine monohydrate potassium iodide (LAMPI) NLO crystals

A semi-organic NLO material of L-Asparagine monohydrate and potassium iodide had been grown efficaciously as L-Asparagine Monohydrate Potassium Iodide (LAMPI) via solution increase strategies and slow evaporation technique at room temperature. The single crystal X-Ray diffraction was used to calculate the lattice parameters and space group P212121 for LAMPI crystal. Powder XRD data analyses were confirmed the crystalline nature of LAMPI crystal. The grown crystal LAMPI had been confirmed from the presence of FTIR practical functional groups. The UV–vis-NIR study identified in spectral range 200–1100 nm. The optical studies have measured transmittance cut-off wavelength of the crystal by 254 nm and Tauc’s plot in band gap energy 4.8 eV. 1H NMR of the grown LAMPI crystal was analyzed molecular shape. The TG and DTG as used to confine the thermal stability. From thermal studies, confirmed that LAMPI crystal can be used up to 234 °C for NLO utilities. The dielectric studies recognized the variant of dielectric loss and its constant. The mechanical stability of the LAMPI crystal belongs to the hard material. For the LAMPI crystal powder pattern Kurtz Perry becomes tested and hence LAMPI crystal shows 3.6 times better SHG efficiency than KDP.

Molecular structure, NLO properties and vibrational analysis of l-Histidine tetra fluro borate by experimental and computational spectroscopic techniques.

l-histidine tetra fluroborate (L-HTFB) is a semi-organic NLO material. Ab-initio computations were performed at CAM-B3LYP/ 6-311++g(d,p) level of theory to arrive at the structures, energies, and vibrational wave numbers. The experimental FT-IR and FT-Raman spectra of L-HTFB have been recorded and analyzed. It is compared with the simulated spectra. The scaled wave numbers obtained are in good agreement with the experimental values. Hirshfeld surface analysis represented in the 2D fingerprint plot reveals the interaction within the compound. Optimized geometry reveals that the complexes l -histidine (L-H) and tetrafluoroborate (TFB) are linked by H-F bond which provides inter and intra molecular hydrogen bonded interactions such as N10-H16⋯F25, N11-H17⋯F22, N11-H14⋯F24, N11-H14⋯N10 and N11-H15⋯O12. The inter-molecular distances H17⋯F22, H14⋯F24 and H16⋯F25 are in between 1.82 Å and 2.53 Å. The intra molecular distances H14⋯N10 and H15⋯O12 are found to be at 2.17 Å and 1.71 Å which stabilizes lone pair electron of N10 and O12 with energies 11.89 and 59.91 KJ/mol respectively. The intra and inter molecular hyperconjugations responsible for the stability of the molecule are well identified theoretically using the NBO analysis. Third order optical nonlinearity is measured by means of the open aperture Z-scan technique which reveals that the crystal has optical limiting property. Photoluminescence results clearly indicate the use of L-HTFB as a new violet-light emitting material.

Second and third-order NLO response of 2-amino-5-nitropyridinium tetrafluoroborate

Based on host-guest chemistry, a semiorganic NLO material 2-amino-5-nitropyridinium tetrafluoroborate [2A5NPFB] was synthesized and grown as single crystals. SXRD of 2A5NPFB reveals its crystal structural details as orthorhombic crystal system, Fdd2 space group, a = 22.474 (1) Å, b = 30.127 (9) Ǻ, c = 4.9584 (1) Ǻ and α = β = γ = 90°. Protonation site, charge transfer interaction and molecular structure were studied by FTIR analysis. Thermal studies predicts the melting point of 2A5NPFB as 145 °C. 2A5NPFB possess strong absorption (λmax = 350 nm) in ultraviolet region and has a broad transparency window (420–1100 nm). Kurtz and Z-scan technique explores the second and third-order NLO response of 2A5NPFB single crystal. Compared to KDP crystal, 2A5NPFB single crystal possesses 35 times higher Second Harmonic Generation efficiency. 2A5NPFB crystal exhibit saturable absorption, self defocusing and optical limiting action under continuous wave Nd:YAG green laser.

An investigation of optical constants, solid state parameters and NLO properties of glycine sodium iodide (GSI): a new auspicious semi organic NLO crystal for optoelectronics applications

Optically very nice quality single crystals of a new semi organic NLO material, glycine sodium iodide (abbreviated as GSI) C2H5NO2·NaI had been grown by exploiting slow evaporation technique. The yielded crystals had been of average dimensions 22 × 4 × 5 mm3. FTIR spectroscopy showed the vibration frequencies of numerous functional groups in the cultivated crystal. Single and powder X-ray diffraction studies were executed to determine the crystal structure and lattice parameters of the synthesized compound. Optical constants such as band gap, refractive index, reflectance, extinction coefficient and electric susceptibility have been deliberated for the cultivated material from the UV–Vis–NIR spectrum. The optical band gap of the harvested crystal is perceived to be 5.09 eV. The chemical composition of GSI is analyzed by employing EDX analysis. The dielectric constant and dielectric loss of the synthesized material have been measured in different frequency range from 100 Hz to 5 MHz at three different temperatures (40, 50 and 60 °C). Moreover, solid state electronic properties, such as plasma energy, Penn gap energy, Fermi energy and electronic polarizability of the cultivated crystal have been calculated. Surface morphology of the harvested material is studied with the aid of scanning electron microscope. From the second harmonic generation analysis, it is evident that GSI has the efficiency 1.53 times that of potassium dihydrogen phosphate and hence it is an exemplary material for optoelectronics applications.

Synthesis, Crystal Growth and Characterization of Semi Organic NLO Materials: L-Valine Zinc Chloride as Optic Sensor

Synthesis, Crystal Growth and Characterization of Semi Organic NLO Materials: L-Valine Zinc Chloride as Optic Sensor

Influence of original and simulated microscopic units on SHG response in semiorganic NLO materials

The SHG effect increase was explored by combining the electronic structure, SHG density, molecular orbital analysis and hyperpolarizability density.

Effects of semi-organic additives on the solubility, growth, optical, thermal, mechanical, dielectric and NLO behaviors of ADP crystals for optoelectronic applications

Effects of the addition of semi-organic NLO materials potassium hydrogen malate monohydrate (PHMM) and sodium acid phthalate (NaAP) on the growth and various properties of ammonium dihydrogen phosphate (ADP) single crystal grown by the slow cooling method have been studied. The metastable zonewidth of pure and doped ADP were determined and compared. Nucleation studies show that metastable zonewidth and growth rate of ADP are enhanced by the dopants PHMM and NaAP. The grown crystals were subjected to Powder XRD, FT-IR, UV–vis, TG/DSC, microhardness and dielectric studies. The grown crystal has good optical transparency in the entire visible region, which is an essential requirement for a nonlinear crystal. Dielectric measurements reveal that doped ADP crystals have low dielectric loss and higher dielectric constant than pure ADP. The relative SHG efficiency measurements revealed that the dopant has enhanced the efficiency. Presence of dopant was confirmed by energy-dispersive spectrometry.

Growth and characterization studies of l-threonine phosphate (LTP) a new semiorganic NLO crystal

A semiorganic NLO material l-threonine phosphate (LTP) has been synthesized. Good quality single crystal of LTP of dimension 17×4×3mm3 was successfully grown by slow evaporation method. The unit cell dimensions were determined from single crystal X-ray diffraction analysis confirming that LTP crystal belongs to the orthorhombic system with noncentrosymmetric space group Pna21. Orientation of hkl planes were identified by Powder XRD technique. The presence of functional groups was estimated qualitatively by FTIR analysis. 1H1 NMR spectral analysis confirmed the presence of hydrogen bonded network in the grown crystal. The optical cut-off wavelength of LTP was found to be 230nm. The variations of dielectric constant (ɛr) and dielectric loss (D) with frequency at different temperatures were studied. Thermal stability was studied through TG/DSC measurements. SHG efficiency of the LTP crystal is 1.6 times that of KDP determined by Kurtz–Perry powder test.

Growth and characterization studies of a new NLO single crystal potassium l-asparaginate

Potassium l-asparaginate (PLA) is a new semiorganic NLO material of amino acid family. In this work, we have grown PLA single crystal by slow evaporation method. The lattice parameters were calculated from single crystal XRD data. XRD analysis yielded a space group of P21 with lattice parameters a=10.470Å, b=8.839Å, c=12.808Å, α=β=90°≠γ, volume=1185.30Å3. Solubility studies were made at different temperatures with various solvents. The solubility was found to be 17g in 100ml of water at room temperature. The functional groups present in the grown sample were identified from the vibrational frequencies of the recorded FTIR spectrum. UV–vis-NIR spectrum of PLA crystal shows the cut off wavelength of the crystal to be at 230nm. The second harmonic generation efficiency of PLA single crystal estimated using Kurtz and Perry method. The nature of variation of dielectric constant (ɛr) and dielectric loss (D) with frequency at different temperatures were investigated. The AC conductivity measurements done on PLA reveal that PLA crystal has a sharp electrical conductivity with an increase of temperature.

Effect of phosphorous on the growth, optical, mechanical and thermal properties of L-alanine crystals

Single crystals of L-alanine were grown from aqueous solution with a small amount of orthophosphoric acid (H 3 PO 4 ). The single crystal X-ray diffraction (XRD) analysis was employed to identify the cell parameters. The grown crystal was characterized by Energy Dispersive X-ray (EDX) spectrum. The UV-visible transmittance was recorded. The presence of a functional group was confirmed by FTIR analysis. The TGA/DTA studies showed the thermal properties of the crystals. The mechanical strength was analyzed by measuring microhardness of the grown compounds. The second harmonic generation of grown crystals was confirmed by the Kurtz-Perry method using an Nd:YAG laser. Full Text: PDF References D.S. Chemla, J. Zyss, (Eds.), Nonlinear Optical Properties of Organic Molecules and Crystals (Academic Press, Orlando, New York, 1987). C. Razzetti, M. Ardoino, L. Zanotti, M. Zha, C. Paorici, "Solution Growth and Characterisation of L-alanine Single Crystals", Cryst. Res. Technol. 37, 456 (2002). CrossRef E. Ramachandran, S. Natarajan, "Synthesis of L-valine crystals", Cryst. Res. Technol. 44, 641 (2009). CrossRef K. Srinivasan, "Growth of non-linear optical ?-glycine single crystals and their characterization", J. Arumugam, Optic. Mater. 30, 40 (2007). CrossRef Sd. Z. Ali Ahamed, G.R. Dillip, L. Manoj, P. Raghavaiah, B. Deva Prasad Raju, "Growth and characterization of new NLO material: L-serine sodium nitrate", Phot. Letters Poland 2(4), 183 (2010). CrossRef S. Dhanuskodi, J. Ramajothi, "Crystal growth, thermal and optical studies of L-histidine tetrafluoroborate: A semiorganic NLO material", Cryst. Res. Tech. 39, 592 (2004). CrossRef R. Ittyachan, P. Sagayaraj, "Growth and characterization of a new promising NLO L-histidine bromide crystal", J. Cryst. Growth 249, 557 (2003). CrossRef M. Lydia Caroline, R. Sankar, R.M. Indirani, S. Vasudevan, "Growth, optical, thermal and dielectric studies of an amino acid organic nonlinear optical material: l-Alanine", Mater. Chem. Phys. 114, 490 (2009). CrossRef G. Ravi, S. Anbukumar, P. Ramasamy, "On the growth and characterization of mixed crystals of the triglycine sulphate family", J. Cryst. Growth 133, 212 (1993). CrossRef N. Nakatani, M. Yoshio, "Crystal Form of Phosphoric-Acid-Doped Triglycine Sulfate", Jpn. J. Appl. Phys. 35, L 508 (1996). CrossRef N. Nakatani, M. Yoshio, "Doping of Phosphoric Acid into Ferroelectric Triglycine Sulfate Crystal", Jpn. J. Appl. Phys. 35, 5752 (1996). CrossRef A. Saxena, V. Gupta, K. Sreenivas, "Characterization of phosphoric acid doped TGS single crystals", J. Cryst. Growth 263, 192 (2004). CrossRef M. Anbuchezhiyan, S. Ponnusamy, C. Muthamizhchelvan, C.C. Kanakam, S.P. Singh, P.K. Pal, P.K. Datta, "Etching, micro hardness and laser damage threshold studies of a nonlinear optical material L-valine", Eur. Phys. J. Appl. Phys. 58, 10201 (2012). CrossRef K. Seethalakshmi, S. Perumal, "Studies on growth, structure and optical studies of undoped and KBr doped Lalanine single crystals", Recent Research Sc. Techn. 4(6), 13 (2012). DirectLink Ferdousi Akhtar, Jiban Podder, "A Study on Growth, Structural, Optical and Electrical Characterization of L-alanine Single Crystal for Optoelectronic Devices", Research J. Physics 6(2), 31 (2012). CrossRef K. Sangwal, B. Surowska, "Study of indentation size effect and microhardness of SrLaAlO 4 and SrLaGaO 4 single crystals", Mater. Res. Innovat. 7, 91 (2003). DirectLink S.K. Kurtz, T.T. Perry, "A Powder Technique for the Evaluation of Nonlinear Optical Materials", J. Appl. Phys. 39, 3798 (1968). CrossRef

Semiorganic nonlinear optical material: Crystal growth, structure and optical properties of NaB(L-C4H4O5)2

Single crystal of the semiorganic NLO material NaB(L-C4H4O5)2 has been grown with sizes up to 8×5×2mm3 by the slow evaporation method. The crystal structure of this compound was determined by single crystal X-ray diffraction. It crystallizes in the Monoclinic space group P2 with lattice parameters a=5.4045(11)Å, b=11.692(2)Å, c=9.4773(19)Å and Z=2. Thermal analysis demonstrated NaB(L-C4H4O5)2 are thermally stable up to 280°C. NaB(L-C4H4O5)2 exhibits an absorption edge about 220nm in the UV region. The powder second-harmonic generation (SHG) measurement performed on the ground crystal indicates that it has a NLO efficiency of about 2 times that of KDP (KH2PO4) standard. In addition, the origin of stronger SHG effect was discussed.

Growth and spectral characterization of ethylene diamine tetra acetic acid (EDTA) doped zinc sulphate hepta hydrate – A semi organic NLO material

Semi-organic non-linear optical single crystals of ethylene diamine tetra acetic acid (EDTA) doped zinc sulphate hepta hydrate crystals were grown by slow evaporation solution growth technique, at room temperature, using de-ionized water as solvent. The modes of vibrations of different molecular groups present in the grown crystal were identified by FT-IR technique. The optical absorbance/transmittance was recorded in the wavelength range of 190–1100nm. Thermal properties of the grown crystal were studied by thermo gravimetric analysis and differential thermal analysis. The melting point of the grown crystal was estimated by differential scanning calorimetric analysis. The inclusion of the dopant (EDTA) was confirmed by colorimetric estimation method. The second harmonic generation efficiency is about 30% of potassium dihydrogen orthophosphate.

Synthesis, growth and characterization of bisthiourea zinc bromide for optical limiting applications

Bisthiourea zinc bromide (BTZB), a novel semi-organic NLO material, has been synthesized and characterized by X-ray diffraction, FT-IR absorption and electron diffraction techniques. Single crystals of BTZB with size in the range 5 × 4 × 3 mm 3 have been grown from aqueous solution by slow evaporation method. Thermal analysis has been performed on the material to study its thermal stability in the temperature range 303 K–1073 K. BTZB belongs to the category soft materials as evidenced by Vicker’s microhardness tests. The material has lower dielectric constant (14.1) than its parent molecule thiourea (15.6). From optical absorption and photoluminescence spectra, the band gap has been determined to be 3.5 eV. The nonlinear optical properties have been investigated by Z-scan method and the material is found to be self-defocusing in nature. In this paper we report the optical limiting behavior in the low-power regime for the first time in literature using a 532 nm second harmonic of a diode pumped Nd: YAG laser.

Growth and characterization of a new semi organic NLO material: L‐tyrosine hydrochloride

AbstractSingle crystals of L‐Tyrosine hydrochloride were grown by using the submerged seed solution method. The grown crystals were characterized by using single crystal X‐ray diffraction. Functional groups and the modes of vibrations were identified by FTIR spectroscopy. The TGA/DTA studies showed that the crystal is stable up to 232°C. Microhardness study revealed that the crystal is a hard material. It is transparent in the entire visible region. The SHG efficiency was determined by the Kurtz and Perry method. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)

Growth and characterization of Lithium hydrogen oxalate monohydrate, a new semiorganic NLO material

Single crystals of the semiorganic NLO material, lithium hydrogen oxalate monohydrate was grown and characterized by using single crystal X-ray diffraction. Spectroscopic, thermal and optical studies were carried out. These studies show that the crystals are thermally stable up to 100 °C, 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 and it was found that the efficiency is about 91% of that of the standard KDP crystals. Laser damage threshold study was also carried out.

Growth and characterization of L‐histidine hydrochloride monohydrate single crystals

AbstractGood optical quality single crystal of L‐histidine hydrochloride monohydrate (LHC) a novel semi organic NLO material was grown by slow solvent evaporation technique. The crystal was characterized by X‐ray diffractometry (XRD), Fourier Transform Infra‐red (FTIR), UV‐Vis‐NIR, TGA, DTA, microhardness and solubility studies. The SHG efficiency is found to be higher than that of KDP crystal. The dielectric constant and dielectric loss of the crystal was studied as function of frequency and the results are discussed. Photoconductivity studies were also carried out which reveals the positive photoconducting properties of the sample. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)