(pei 125 (2014) 164-169 Contents ist avaliable at ScienceDirect Optik Journal homepage: www.elsevier.de/iieo Generation of 532 nm laser radiation and phase matching properties of organic nonlinear optical material S.Tamilselvan®, M. Vimalan’*, I. Vetha Potheher'**, R. Jeyasekaran®, F. Yogam‘, J. Madhavan’ * Departmen Phys, vga ame Government es College, Cheyyor 604407 no ® Depariment of Ps, Thro Engineering Col, ilar, Kancheepuram 621 SSL no « Deprtent of Ps Anna Univers BI Campus Trachrappll 20 024 nda Deparment of Pass VNSN,Cllge Viudhunager 6260, nda “Deparment of Phys Anand fst of Higher Technolgy Chena 603103. dla * Deparment of ysis, aye College henna 620034, ada ARTICLE INFO ABSTRACT Il wiry Received 29 january 2013, ‘Accepted June 2013 Organic nonlinear optical single crystal oft-asparagine-t-tartaric aid (LAST) was grown by slow evapora ‘ion technique at room temperature, The grown etystal was confirmed by single erystal Xray difraction and FT-IRstudes. The direct band gap energy was found to be 5.4. TheSHC efficiency of the samples {imes higher than that of KDP crystal. The laser damage threshold of the grown erstal was 5.7 Wem Rewer: Organic mares Nonlinear optics Laser damage tieshola (pial band gapenezay ‘sation era ‘The grown crystal was thermally sable up to 141°C. Low dielectric constant at higher frequency was found by dielectric measurements. The activation energy Was calculated from Atthenivs relation and it was found to be 0.088 eV. Negative photoconducting nature was obtained by photoconductivty mea- (© 2013 Elsevier GmbH, Al rghts reserved. 1. Introduction Organic NLO materials have subsequently produced very good materials with highly desirable characteristics. However most of the organic NLO materials are susceptible to damage because of theirpoor mechanical and thermal properties | In the recent past, ‘amino-acid family single crystals are gaining importance as highly Feasible second order NLO materials. Considerable effortshave been ‘made to combine amino-acids with interesting organic and inor- ‘ganic matrices to produce outstanding materials to challenge the ‘established inorganic materials like niobates and the borates. This is due to the fact tha all the amino acids contain chiral carbon and ‘crystallize in noncentrosymmetric space groups. Hence, they are regarded as potential candidates for second harmonic generation (SHG), optical parametric amplification (OPA) and optical para metric oscillation (OPO). The absence of strong conjugated bonds and the presence of chromophores such as amino groups and car- boxy! group lead to exhibit wide transparency in the entire UV-vis * Corresponding author. Mobi: +91 80031 93588, + Conesponding author Mobile: +9 9942094274. E-mail eddreses: martvimalanégralom (M. Vinal) pothehert1Ogmaiicom(L VethaPtheher (0020-40268 - see fon natter©:2012 Elsevier Gan. Al ight eserve, tp/dxdo or/ 1016) en 201206024 region, thus meeting out one of the essential requirements of non-linear optical activity [2], The presence of 2witter ions influ- fences the physical and chemical properties of amino acids. The proton donor carboxyl acid (~COO) group donates its proton to acceptor amino (—NH2) group. Thus, an amino acid exists as a dipolar ion in which carboxy! group is present as carboxylate jon and amino group is present as ammonium ion. Due to this dipolar nature, they possess good mechanical and physical prop- erties, viz. erystal hardness and high melting point, which make ‘them ideal candidates for NLO applications. Among the synthetic materials that have been suggested as sources of piezoelectric ele- ments, some tartrates, eg Rochelle sat (sodium potassium tartrate tetrahydrate) and ethylene diamine tartrate (EDT) are strongly Piezoelectric, It therefore seemed likely that the examination of other organic tartrates might be fruitful [3]-Crystal and molecular structure of Urea-(+) tartaric acid was reported by Wentao etal Growth and characterization of organic nonlinear optical crystals of ‘tartaric acid-nicotinamide and p-tartaricacid-nicotinamide were ‘done by Jun Shen ef al, [5], The crystal structure of L-asparagine- Letartaric acid (LAST) was solved by Natarajan et al. 6]. In the compound LAST, the amino acid molecule exists as a zwittetion, an uncommon ionization state in the crystal structures of amino carboxylic acid complexes. Usually. a proton transfer is favored from the carboxylic acid to the amino acid in these complexes, the5: Taian cl. / Opt 1252014) 164-169 165 Fig: Photograph ofa grown LAS single crystals, former exists in the anionic state and the latter in the cationic state, ‘Similar awiterionic state for the amino acid molecule is observed in L-phenylalanine fumaric acid and t-phenylalanine benzoic acid [7.8], The aggregation pattern observed inthe structure has striking similarities to those observed in other related amino acld-tartaric acid complexes, eg. sarcosinium tartrate (9| and L-prolinium tar~ trate [10], In this view the present investigation focused on the growth of single crystals of t-asparagine-L-tartaric acid (LAST). eis ‘potential semi-organic NLO material. The slow evaporation tech- hnique was employed for the growth process. The grown crystals, ‘were characterized by single crystal X-ray diffraction, FIR, optical transmission, optical absorption spectroscopy and TC & DTA anal- ysis. Mechanical and electrical properties of the grown crystal was also studied and reported for the fist time. 2. Experimental procedure 2.1. Synthesis of AST LAsparagine-L-tartaric acid (LAST) was synthesized by dissolv- ing one mole of -asparagine (Merck 99%) n double distilled water containing one mole of t-tartaric acid. The reaction is as follows CaHsN205 + CcHo0s-> CaHsN20s.CaHo0s The synthesized salt was further purified by repeating the crys- tallization process at least thrice. 22. Growth of LAST single crystals The synthesized salt of LAsT was purified by repeated crystal- lization and saturated solution was prepared in accordance with, the solubility data. In arder to achieve single crystals of good opti- cal quality, needle shaped and relatively large size, many growth, attempts have been made. The easiest method was to form tiny ‘aystalsby spontaneous nucleation: among them seed crystals with perfect shape and free from defects were chosen for growth exper iments. The seeds were suspended in the mother solution with rnylon thread. Crystals of dimension up to 10mm x 2mm x 2mm, ‘were harvested after a period of 25-30 days. Fig. 1 shows the ‘able Single crystal XRD data of LAST single rst piel forma Ea N05 CEOs Crystal sytem Monoclinic Space group Pa » Dera < 189A Volume 58226718) photograph of as grown crystal of LAST. The grown crystals are sta~ bile, do not decompose in air and non-hygroscopic in nature, AN {important observation during the growth of LAST is the absence of, any kind of microbial contamination during the growth period, 23, Characterization The grown crystal of LAST was confirmed by single crystal X- ray difftaction analysis. Single crystal XRD data were collected by ENRAF NONIUS CAD4-F single crystal X-ray diffractometer with (Mo Ke (2.=0.71073A) radiation, The FT-IR spectrum was recorded using BRUKER IFS-G6V FT-IR Spectrometer with KBr pellet tech- nique for the range 4000-450cm~". The optical absorption and study was carried out using a Shimadzu UV-2400 PC Spectropho- tometer in the range of 200-11001nm. The band gap energy was calculated using the relation E= vy, where itis Planck's constant, v is frequency. The NLO efficiency of LAST ctystal was evaluated by Kurtz and Perry powder technique [11] using a Q-switched, mode Jocked Nd:YAG laser emitting 1.06 um, 8ns laser pulses. The ther= ‘mal behavior of LAST crystal was investigated using NETSZCH STA -409C and PERKIN ELMER thermal analyzer. Microhardness studies have Deen carried outon LAST crystalusing a Vickersmierohatdness tester fitted witha Vickers diamond pyramidal indenter attached to an incident light microscope. The frequeney dependent dielectric constant and dielectric loss of LAST were measured using Agi- lent 4284A LCR METER for various temperatures (313-363 K). The capacitance of the sample was noted by varying the frequency from, 1001Hz to 1 Miz The dc conductivity measurements were carried cout by conventional two probe technique for temperatures ra ging from 313 0 423K, Photoconducting nacure of the sample was studied by Keithley 485 picoammeter. 3. Results and discussion 3.1, Single crystal XRD study The lattice parameters of LAST are determined using 25 reflec- tions collected through random search routine with graphite ‘monachromated Mo Ka (4=0.71073A) radiation and indexed by the method of short vectors followed by the least squares refine- ment, The XRD data reveals that LAST crystal belongs to monoclinic structure with a noncentrosymmettc space group of P2y. The unit cell parameters of LAST are given in Table 1. The single crystal X- ray diffraction data of the crystal is in good agreement with the reported Values and thus confirming the grown crystal (6. 3.2, FIR analysis Fig, 2 shows the FT-IR transmission spectrum of LAST in the region 4000-400cm-~1.Irisevident from the spectrum that, there is, broad band between 3800 and 2700 em" Itincludes OH stretch166, ‘Tomtom eal Opi 25 (204) 164-169, Fig. 2. FL spectrum of LAST. ‘of water at 3450cm~t and N-H vibration at 3320 and 3280cm~1 ‘The characteristic CH vibrations of tartaric acid produce peaks at 297 and 2960em-", In the overtone region, there is a promi- hnent band near 2002150 um. The levelof SHG response of agiven material isinherently dependent upon its structural attributes. Ona molecular scale, the extent of charge transfer across the NLO chro- mophore determines the level of SHG output, greater the charge transfer larger is the SHG output. The presence of strong inter- molecular interactions, such as hydrogen bonds can extend this level of charge transfer into the supramolecular realm, owing to their electrostatic and directed nature, thereby enhancing the SHG response [16]. High optical quality single erystals cut in phase-matching direc~ tions are very essential for NLO applications. The phase matching property was confirmed in LAsT using the same Kurtz powder SHG Setup. n such organic crystals, asthe thickness of crystal inereases, instead of increasing SH intensity, a decrease of SH intensity was ‘observed due to phase mismatch between the fundamental and the SH waves as they propagate inside the crystal, One easy way of confirming the existence of phasematching property in new NLO crystals is by studying the grain size dependence of SH intensity in powder form, The particle size dependency of SHG intensity in5. Tain Ope 1252014) 164-169 67 ew 6 ouput a 150 wm and above this, range; it deviates from the linearity and starts to attain saturation, This type of grain size dependence of SH intensity was observed only with phasematchable crystals. This phase-matching property ‘may open up opportunities for LAST crystal inefficient frequency conversion applications. Most important considerations in the choice of a material for 'NLO applications re ts optical damage tolerance and inNLO mate- tial it may severely affect the performance of high power laser systems. High damage threshold isa significant parameter for NLO ‘material, LAST crystal was prepared for laser damage threshold (LOT measurements. Experimentally. a Q-switched diode array side ‘pumped Nd:YAG laser operating at332:nm radiation was used with, ns pulse width. During laser irradiation, the power meter records, the energy density of the input laser beam for which the crystal gets damaged. In the present study. laser damage was found to be 5.7 GWjem?. The high damage threshold contributes to attractive ness ofthe present compound in practical applications. 45. Thermal analysis TG-DTA was catried out on the grown LAST sample for qualita- tive analysis and the respective curves are shown in Fig. 5. From the DTA curve it has been observed that endothermic peakat about 141 Corresponds to the melting point of the compound which is coinciding with the stability of the material shown by TGA trace. This is attributed to utilization of the thermal energy to overcome the valence bonding between the L-asparagine cation and tartrate anion, which happens in the initial stage of decomposition. The enperae(°o) ig 5. TCA and DTA curves of Ast 400. i 2 oh & & & toed am Flig.6. Vickers hardnes pro of LAsT as function of applied los, two broad endothermic peaks at 141 and 275°C represent the decomposition of molecular fragments in two stages, This weight loss is followed by a major weight loss pattern between 172 and 267 °C occurring in two stages, the total weightloss ofthese stages correspond to 20% of the substance due to release of CO, and CO ‘molecules in tartaric acid. The reactions of simplest amino acids induced by heating include the condensation reactions of carboxyl and amino groups leading to the formation of peptide bonds. The total weight loss nearly equals to 90% and the resulting residue (105) is stable up to 800°C. Iris concluded from the thermal analy sis, the material can be useful up to 141 °Cfor the NLO applications. 36. Microhardness study Microhardness plays a Key role in device fabrication. Vickers hardness measurements were made on the prominent(1 00) plane using Leitz-Wetzler hardness tester fitted with a diamond pyrami- dal indenter. The static indentations were made for different loads of 10-50g with a constant indentation time of 10s forall the tials. Diagonal lengths of the indented impressions obtained at various Toads were measured using a calibrated micrometer attached t0 the eve piece of the microscope. Several indentation were made on LAST. The average value of the diagonal lengths of the indentation ‘mark for each load was used to calculate the hardness. The varia- tions of Hy for various applied loads are plotted and shown in Fig. The graph indicates that the microharcness number decreases with the increasing load. The decrease in microhardness number with the increasing load satisfes normal indentation size effect (ISE). The work hardening coefficient (n) was calculated by plotting log Vs. loga and it was found to be 1.66. According to Onitsch, if n> 2, the microhardness number H, increases with increasing load and ifn<2, Hy decreases with increasing load [17] 3.7, Electrical studies ‘The dielectric study on grown LAST crystals were carried out using Agilent 42844 LCR meter and was used to measure the capacitance and dielectric loss of the grown crystal as a func~ tion of frequency. The observations are made in the frequency ange100 Hz~1 MHz in the temperature range 313-363 K. Fig. 7a and b shows the plot of dielectric constant and dielectric lass of LAST as a function of log frequency for different temperatures 613-363). The dielectric constant has a higher value (15.7) at 313K in the lower-frequeney region (100H2) and it then decreases (13.47) at 313K with the applied high frequency (1 MHz). In Miller tule and the Phillips-Van Vechten-Levine-Xue bond theory [18], the lower value of dielectric constant at higher frequencies is a16s ‘Tomtom eal Opi 25 (204) 164-169, arto ws] $ + mak) Sk . «33K WS = ‘20 a a a logt boas dass g loot Fig 7 a] Variation of dct constant with og frequency at itferet temper ares for LAS single cyst (b)Valton of deer ss with og equency 3 “ierent temperatures for LAST sine cst suitable parameter for the enhancement of SHG coefficient [19] ‘The higher value of dielectrieconstantis due to higher space-charge polarization at lower frequency region. This may be explained on the basis of the mechanism of polarization similar to the conduc- tion process. The electronic exchange of the number of ions in the crystal gives local displacement of the applied field, which gives the polarization, As the frequency increases, at which the space ‘charge cannot sustain and comply the external field, Therefore the Polarization decreases and exhibiting the reduction in the value of dielectric constant with increasing frequency. The dielectric con- stant of materials is due to the contribution of electronic. ionic, «dipolar and space charge polarizations, which depend on frequen- ies [20], AClow frequencies, all these polarizations are active, The space charge polarization is generally active at lower frequencies and high temperatures [21 From Fig. 7b, it can be noticed that as the frequency increases the dielectric loss decreases. This behav- ior is similar to that of the dielectric constant. At low frequencies the dipotes can easily switch alignment with the changing fled. As the frequency increases the dipoles are less capable of rotating and maintaining phase with the feld; thus they reduce their contri- bution to the polarization field, and hence the observed reduction in dielectric constant and dielectric loss, The characteristic of low dielectric loss with high frequency for a given sample suggests that the sample possesses enhanced optical quality with lesser defects ‘and this parameter isof vital importance for nonlinear optical mate tials in their application (22), ‘Well sized crystal of LAST was used for de conductivity study. ‘The conductivity ofLASTis shown in Fig. Saandb. Fig. 8a represents the temperature dependence of conductivity of the sample is found a = a-drecion LAs oainhoem") g “300” S10” 20” S80” S40” 360” 360” 370 ‘Temperature (K) bas 0007 (6) Fig.8 2)DCelecrcaleanductvy for LAsTexystal (0) PletofIn (eu) versus 1000/7 for LAs single crys to increase with increase in temperature. The de activation energy (Fig. 8b) of the LAST crystal is found to be 0.088 ev. 38, Photoconductivity study ‘The applied field was varied from 150 to 3820Vjem. For mea- suring the dark current, the sample Was kept unexposed from any radiation, After measuring the dark current the photocurrent was measured by illuminating the sample with a halogen lamp of 100W Power. A spot of light on the sample was focused withthe help of convex lens. The resulting photocurrent was measured by varying ‘current (a4) ose eeegges ‘> sb 10001500" 2000 2500 3000 3500 4000 ‘opi Field (Vem) Fig 9. Feld dependent photoconductivityofLAS single crystal‘5 Tamiselan ea Op 125 (204) 164-169, 169, the applied field for the same range. The variation of dark cur- rent and photocurrent with applied fleld are shown in Fig. 8. Ie is observed from the plots that the dark current is always higher than the photo current. Thus, LAST single crystal is Four to exhibit negative photoconductivty. 4. Conclusion Single crystals of t-asparagine-t-tartaric acid (LAST) of dimen- sion Tommx2mmx2mm is conveniently grown by slow evaporation technique at room temperature. A solvent of deionized ‘water is used for the growth process. The single crystal XRD data proves that LAST crystal belongs fo monoclinic in structure with a nnoncentrosymmetric space group P2}. Optical absorption studies, confirm the UV cut-off wavelength of LAsT at 230 nm and the opti- calband gap energy is found to be 5.4eV. Thermal analysis revealed ‘thatthe sample i thermally stable up to 141°C and various stages (of weight losses also discussed. The frequency dependence of the dielectric constant/dielectric loss of LAsT are investigated. The acti vation energy of the sample is calculated by dc conductivity studies. The negative photoconducting nature of LAsT is studied by photo- conductivity investigations. INT K Selvaraj &Vallvan K.Kirubavathi S.Kumararaman, vestigation on the higestion Kets of eargiine acetate single cyt, Mat. et 61 (2007) Sonne DB], Kishnakumar, R Nagaaksha, Polarised Raman and ifated spectral analysis of alanine raat (GH)NO,)~a nonKnear optical single stl Spectre, Acta 6 (2006) 736-743, DB] NC Viton Rajesh Kumar, 5. Tarliclan,P.Sagayar, CK. Mahadevan, [Growth and properties of novel organi onlnear otal cyst: lannium, tatate (UAT, Physica a (2010) 3907-3913 tte cg Maing sal anole safe) 15] shen. zheng ¥-Che BX Growth nd properties of organi nonlnestop- {Gl enstaltaarteac-neonnamie nd >-tarare sex ncoinam ‘ys Grow 2572003) 136-1a. [61's Nataaan, Vv Hema, J Kalyana Sundar, J. Suresh, PL Aantha tae Suman UASpuagineiafare acid (1/1) Aa Cystallge. E68 (2010) 2230, UM. Algae, RY. Krishnakumar, K Raagopal M. Subba Nandhin s Natorjinchenyllanine fmare ag. Acta Crystal 5" (2003) 22-054. [s] | Sores. Rv. Keishnakuma, 5. Natarajan. Phenylalanine benzoic ac), ‘eta crystllogr E61 (2005) 3625-3627 [9] RV Krishnakumar Subha NandhinS Natarajan, sarosinium arate, Acta Crystal C'37 (2001) 165-155. [10] M?Subha Nandini RV eshoakumar, Natarajan. Prliniam arate, Acta iystallopr C57 (2001) 425-424. (011 SK kurta ery. A pow etnigue forthe evaluation of ontnear opal atria Apo Phys 391968) 3798-3813. [02] Fram’ VethaPotheer.M Vimalan. R Jeyasclaran,T.Resh Kuma, . Saayara Growth and physiochemical properties of {petunia ‘maleate; + novel nonlinear optical crystal Spectrochim, Acta A 95 (2012) 369373, 103] K Vasana,S.Dhanoskod, Single crystal growth and characterization of Dhase-matchable varunine maleate: «potential nolines? opti tater ‘ays crown 2652004) 385-341 [144 Pil jeyakuman, Danas, 5, Manivannan, Phase matchablesemioe- amie NLD material for frequency” doubling’ arginine tetaluoroborte, Spectrochim. Acta 63 (2000) 91-95, [15] Tave,in:] Tave (2), Amorphous an Liquid Semiconductors, Plenum, New Von ist (15) Hang, ¥, Sun, X chen, Xan, 8, Sun, Crystal grt and characterization af organi single erst 2: Aydouybenaylidene) seeiahyarande, | Ct Growth 324 2011) 196-200. 7] EM Onich. Tae present status of testing che hardness of materia, Mkostope 5 (1059) 12-14 [1] Due, "zhang. Chemical bond analysis of the creation bene erysat ‘Seat and nonlinear opts! properties a eomplek crystals, Pai B 262 (1909) 7°85, {19} CJusin Ras Dinakaran,.KeshnanB Milton Boaz. R Rober SJerome Ds Studies omoptical mechanical and transpr: properties NLO active laine formate single eystal grown by modi Sanlaranarayann- Ramsay (SE) ‘method pt, Commun 281 (2008) 285-2290 [20] D: Xue. K. Kitamura, Deere characterization ofthe defect coneenta- ‘oni htm niobate single cyst, Sod Slate Commun. 122 (2002) 337-54, [2] AW. Betienman.H, Cole, Dynamical dactin of X rays by perfect esta Bey. Mod. Phys 361964) 81-717, {22] CBalarew.R Duhlew, Applicaton of the hard and sof acids and bases concept ‘explain Land coordination in double sa structures Sob state Chem. 35 (rasa.