World Journal of Science and Technology 2011, 1(3): 01-06 ISSN: 2231 2587

GROWTH, STRUCTURAL AND OPTICAL STUDIES OF PURE AND BISTHIOUREA ZINC CHLORIDE DOPED POTASSIUM DIHYDROGEN PHOSPHATE SINGLE CRYSTALS
Fernando Loretta1*, T. Josephine Rani2, P. Selvarajan3, S. Perumal4 and S. Ramalingom5 Department of Physics, Holy Cross College, Nagercoil 629 004, Tamil Nadu, India Department of Physics, Aditanar College of Arts and Science, Tiruchendur-628 216, 4 Physics Research Centre, S.T. Hindu College, Nagercoil 629 002, Tamil Nadu, India. 5 Department of Physics, Vivekananda College, Agasteeswaram 629 701, Tamil Nadu, India.
3 1*,2

Corresponding author e-mail: pselvarajanphy@yahoo.co.in

Abstract
Optically good quality single crystals of pure and Bisthiourea zinc chloride (BTZC) doped potassium dihydrogen phosphate (KDP) were grown from aqueous solution employing slow evaporation technique. Structural characterization of the grown pure and BTZC doped KDP crystals was carried out by single crystal and powder Xray diffraction analysis. The functional groups present in the grown crystals were ascertained using FTIR spectroscopic analysis. The second harmonic generation efficiency (SHG) and the UV-Vis spectral studies justified that the doping has enhanced the nonlinear optical property and the optical transparency of the grown KDP crystals. The various investigations indicate the changes in structural, optical and NLO properties of the KDP crystal due to the incorporation of the semi-organic dopant into the KDP crystal lattice. Keywords: nonlinear optical materials, crystal growth, doping, impurity, characterization.

Introduction
Potassium dihydrogen phosphate (KDP) and its isomorphs are representatives of hydrogen bonded materials that posses important piezoelectric, ferroelectric, electro-optic and nonlinear properties. They have attracted the interest of many theoretical and experimental researchers probably because of their comparatively simple structure and very fascinating properties associated with a hydrogen bond system involving a large isotopic effect, broad transparency range, a high laser damage threshold and relatively low production cost [1,2]. This classical material which belongs to the scalenohedral class of tetragonal crystal system having tetramolecular unit cell with lattice parameters a=b=7.448 and c=6.977 has a wide range of applications such as frequency conversion, laser fusion and electro-optical

modulation [3,4]. The rapid growth of good quality crystals and various studies of organic and inorganic impurities doped KDP crystals have been reported by various investigators [5-16]. Improvement in the quality of KDP crystal and the performance of KDP based devices can be realized with suitable dopants such as transition metals, organic and inorganic dopants added in appropriate mol%. During the recent years the scope for the creation of new nonlinear optical media based on complex combinations of water soluble inorganic matrixes with organic and inorganic impurity is actively discussed in the scientific literature. Therefore, special consideration is given not only to the possibility of changing significant functional characteristics of the crystal, but also to the creation of new properties which are not new to the pure crystal [17,18]. Current interest is focused on the development of new non-

World Journal of Science and Technology | www.worldjournalofscience.com | 2011 | 1(3): 01-06

linear optical (NLO) semi-organic materials which organic posses the advantage of both organic and inorganic materials. Thiourea molecule is an interesting matrix modifier due to its large dipole moment and ability to form extensive network hydrogen bonds. Thiourea in combination with metal complexes forms semi semiorganic compounds having a low cut-off wavelength off and hence appreciable for high power frequency conversion, and Bisthiourea zinc chloride is one such potential semi-organic nonlinear optical material organic which has been reported[19]. The effect of the metal ions and organic material present in the semi semi-organic impurity copper thiourea complex [20] and L L-arginine hydrochloride [21] on the NLO property of KDP crystals has been so far analyzed. Mot Motivated by this, in the present investigation pure and Bisthiourea zinc chloride doped KDP crystals have been grown and characterized by single crystal XRD, powder XRD, FTIR , UV-Vis transmission and second harmonic Vis generation (SHG) studies to identify the changes in the structural, spectral, optical and NLO properties of KDP due to this semiorganic dopant.

2CS[NH2]2 + ZnCl2 Zn[CS(NH2)2]2 Cl2. . From the saturated aqueous solution rom prepared using the synthesized salt of BTZC and deionised water, small transparent colourless single ransparent crystals of BTZC were grown within 15-20 days employing slow evaporation technique at constant room temperature. The identity of the grown BTZC crystals were confirmed by FTIR analysis[19]. These analysis[1 crystals were further purified by re-crystallization and urified re powdered. KDP salt was added to the powdered crystalline sample of BTZC in the molar ratio 1:0.01 to form a saturated solution. The solution was thoroughly stirred for homogenization and then filtered into a borosill beaker using Whatmann filter paper. The pH of the solution was noted as 3.8 The beaker containing the saturated solution (200ml) was closed with perforated cover and kept in a dust free atmosphere to allow slow evaporation of the solvent. Single colourless, transparent crystals of BTZC doped KDP were harvested within 20-30 days.The 20 photograph of pure and 1 mol% BTZC doped KDP % crystals are shown in Fig.1(a) and 1(b) respectively.

Experimental Procedure
Crystal Growth Single crystals of pure and 1 mol% BTZC doped KDP were grown by solution growth employing slow evaporation technique at room temperature. Using pure KDP salt (G.R.,Merk) and deionised water, the saturated solution of KDP was prepared in accordance with the solubility data. The e solution was thoroughly stirred for homogenization and then filtered into a borosil beaker using Whatmann filter paper.The pH of the solution was noted as 3.8. The beaker containing the saturated solution (200 ml) was closed with pe perforated cover and kept in a dust free atmosphere to allow slow evaporation of the solvent. Transparent, good quality KDP crystals were harvested within 20 20-30 days. For the growth of BTZC doped KDP crystals initially the semiorganic dopant Bisthiourea zinc chloride was c synthesized using AR grade thiourea and zinc chloride in the molar ratio 2:1. The component salts were very well dissolved in deionised water and thoroughly mixed using a magnetic stirrer and the mixture was heated at 500 C till the white c crystalline salt of BTZC was obtained. The mechanism of the reaction is as follows

Figure 1. Photograph of grown (a) pure KDP . and (b) 1 mol% BTZC doped KDP crystals Characterization Single Crystal X-ray Diffraction Analysis ray Single crystal X-ray diffraction analysis has ray been carried out to confirm the crystallinity and to find the lattice parameters of the grown crystals .Single crystals of pure and BTZC doped KDP crystals were subjected to single crystal X-ray diffraction X studies using BRUKER NONIUS CAD4 single crystal x-ray diffractometer to obtain the unit cell parameters. ray

World Journal of Science and Technology | www.worldjournalofscience.com | 2011 | 1(3): 01-06 ournalofscience.com

The obtained results show that the lattice parameters for pure KDP crystals are a=b=7.441, c=6.987, ===90and volume=386.859()3, and are in line with literature values[3,4], and for BTZC doped KDP crystals a=b=7.445, c=6.991, ===90, and volume=387.497()3.The results confirm that the BTZC doped KDP crystals are crystalline and crystallize in the same tetragonal structure as that of pure KDP .The incorporation of BTZC into the lattice of KDP crystal has resulted in changes in the lattice parameters of doped KDP without changing its basic structure. Powder X-ray Diffraction Analysis Pure and BTZC doped KDP crystals were subjected to powder X-ray diffraction studies. The Xray powder diffraction pattern of the grown crystals was obtained using XPERT-PRO X-ray diffractometer with Copper (K alpha1) radiation of wavelength 1.54056 . The scanning rate was maintained at 1.6/min over a 2 range of 100 to 700 employing the reflection mode for scanning. All the observed reflections were indexed using the software package TREOR. The indexed powder x-ray diffraction pattern of pure and BTZC doped KDP crystals are shown in Fig 2. and Fig 3. respectively. The calculated unit cell parameters for pure KDP crystals are a=b=7.450, c=6.985, ===90and volume=387.684()3 , for BTZC doped KDP crystals a=b=7.456, c=6.982, ===90, and volume=388.142()3. The well defined, sharp peaks in the XRD patterns signify the good crystalline and single phase nature of the pure and BTZC doped KDP crystals. There is change in intensity with slight shift and in the reflection peaks of the doped crystal compared to the pure crystal, which results in small variations in the cell parameters with slight distortion in structure, this may be attributed to the strains due to the substitution of the semiorganic impurity into the KDP crystal lattice.

5000
(200)

PURE KDP

4000
(112)

Intensity (counts)

3000
(312)

(420)

(202)

0 10 20 30 40 50 60 70

Figure 2. Powder XRD pattern of pure KDP

5000

BTZC DOPED KDP

4000
(200)

Intensity (counts)

2000

(112)

(312)

3000

(411) (303)

(103)

(213) (400)

(101)

(211)

(420)

(3-30)

0 10 20 30 40 50 60 70

Figure 3. Powder XRD pattern of BTZC doped KDP

Fourier Transform Infrared Analysis The influence of the semiorganic dopant BTZC on the vibration frequencies of the functional groups of KDP has been identified by FTIR spectroscopy. The FTIR spectra were recorded in the region 400- 4000 cm-1 by using a Perkin-Elmer RXI spectrometer by KBr pellet technique. Figure 4 and 5 show the FTIR spectra for pure and BTZC doped KDP crystals respectively, and Table 2 presents the frequency assignment. The interaction and entry of the dopant into the lattice sites of KDP is clearly indicated by the absent and additional peaks and also by the broadening and shift in the vibrational absorption frequencies of the FTIR spectra.

World Journal of Science and Technology | www.worldjournalofscience.com | 2011 | 1(3): 01-06

(332)

(224)

(512)

1000

(321) (213) (400)

(220) (202) (301) (103)

(204)

(224)

1000

(204) (332) (323)

(101)

(211)

(301)

(321)

(512)

2000

(220)

Table 2. FTIR assignments for pure and BTZC doped KDP crystals

Pure KDP Wavenumber (cm-1) 3941 3428 2782 2464 2354 1642 1300 1095 904 542 458

BTZC doped KDP Wavenumber (cm-1) 3924 3814 3385 3179 2836 2476 1616 1466 1407 1361 1084 927 778 727 629 535 474

Assignment O H stretching due to water of crystallization Free O H stretching O H stretching hydrogen bonded N H symmetric stretching in NH2 group P O H asymmetric stretching O=P OH asymmetric stretching P O H bending O=P OH symmetric stretching N C N stretching C = S asymmetric stretching C N H stretching P = O stretching P O H stretching N H wagging C N stretching Zn O P = O stretching HO P OH bending N H torsional oscillation

World Journal of Science and Technology | www.worldjournalofscience.com | 2011 | 1(3): 01-06

Optical Transmission Spectral Studies The UV-Visible optical transmission spectra of the pure and BTZC doped KDP crystals were recorded in the wavelength range 190 -1100 nm using Perkin Elmer UV-Vis-NIR spectrometer (Model:Lambda 35). Optically polished single crystals of 2 mm thickness were used for the study. It is inferred from the spectra(fig.6) that both pure and doped crystals have large transmission window in the entire visible region, and the BTZC doped KDP crystal has higher transmittance compared to pure KDP crystal this is because in the case of metal-organic coordination complexes the organic ligand is more dominant in the NLO and dielectric effects. As for the metallic part, focus is on the group (11B) metals (Zn, Cd, Hg), these compounds usually have high transparency in the UV region, because of their closed d10 shells [22].Hence the incorporation of Zn present in the semiorganic dopant BTZC into the KDP crystal lattice has progressively improved the quality of KDP crystals with higher transparency.
100 90 80 70 60 50 40 30 20 10 200 300 400 500 600 700 800 900 1000 1100

causes more delocalization of electrons in the case of thiourea doped KDP crystals which increases the non centro symmetric structure of KDP and hence enhances its nonlinearity [24,25]. Hence it is inferred that the BTZC dopant has increased the SHG efficiency of KDP crystal.

Conclusion
Good quality single crystals of pure and Bisthiourea zinc chloride doped Potassium Dihydrogen Phosphate were grown by solution growth technique for the first time. Structural characterization of the grown pure and BTZC doped KDP crystals was carried out by single crystal and powder X-ray diffraction studies, and the lattice parameters have been evaluated.The functional groups present in the grown crystals were ascertained using FTIR spectral analysis. The UV-Vis spectrum shows good optical transmittance in the entire visible region for both the pure and doped KDP crystals and BTZC doping has enhanced the optical transparency of the KDP crystal. Second harmonic generation measurements show increase in (SHG) efficiency of KDP crystal due to the incorporation of the semiorganic dopant Bisthiourea zinc chloride into the KDP crystal lattice.

PURE KDP BTZC DOPED KDP

Transmission (%)

Acknowledgement
Two of the authors ( Fernando Loretta and T. Josephine Rani ) are thankful to the University Grants Commission, New Delhi for the award of teacher fellowship under the FDP during XI plan period. The support extended in their research by RRL(Trivandrum), Cresent Engineering College(Chennai), St.Josephs College(Trichy) and M.K.University (Madurai) are also gratefully acknowledged.

Wavelength (nm)

Figure 6. Transmission spectra of pure and 1 mol% BTZC doped KDP NLO Studies The NLO property of the grown pure and BTZC doped KDP crystals was confirmed by KurtzPerry Powder technique[23]. The output of Nd:YAG with 1064 nm laser radiation, with width of 6ns and repetition rate of 10Hz was used. It was observed that the crystalline powder sample converts the 1064nm radiation into green light (=532nm) while passing the Nd:YAG laser output into the powdered sample. The SHG relative efficiency was found to be 7.9 mJ/pulse for pure KDP and 10.02 mJ/pulse for BTZC doped KDP samples .Hence the measured SHG efficiency of BTZC doped KDP is 1.268 times higher than that of the pure KDP . This is due to the fact that the sulfur present in thiourea is more electronegative. This

References
1. M.D. Shirsat, S.S Hussaini, N.R. Dhumane, and V.G.Dongre.(2008). Cryst .Res.Technol. 43 :756-761. 2. V.Kannan,R. Bairava Ganesh, Sathyalakshmi, N.P.Rajesh and Ramasamy. (2002). Mat. Lett. 56:578. R. P.

World Journal of Science and Technology | www.worldjournalofscience.com | 2011 | 1(3): 01-06

3. C.Justin Raj,S. Krishnan,S. Dinakaran,R.Uthrakumar,and S.JeromeDas. (2008). Cryst.Res. Technol. 43 :245-247. 4. T.H Freeda andC.K Mahadevan. (2000). Bull. Mater. Sci. 23:335-340. 5. N.P Zaitseva, L.N Rashkovich and S.V Bogatyreva .(1995). J.Cryst Growth 48:276282. 6. Mark A.Rhodes,B.Woods,J.J,De Yoreo, D.Roberts , L.J Atherton.(1995). J.Appl. Opt.34:5312-5325. 7. S.Balamurugan,P.Ramasamy, Yutthapong Inkong, Prapun Manyum. (2009).Mater. Chem. Phys.113 :622-625. 8. N.P Zaitseva , J.J Devoreo, M.R Dhehaven, R.L Vital , K.E Montgomery,M. Richardson.et al, (1977). J. Cryst Growth 180 :255-62. 9. V.K Dixit , B.V Rodrigues and H.L Bhat ,Bull.(2001). Mater.Sci. 24 :455-59. 10. R.Ananda Kumari and R.Chandramani. (2003). Bull. Mater. Sci. 26:255-259. 11. M.Priya, C.MPadma, T.HFreeda, C.K Mahadevan and C.Balasingh.(2001). Bull. Mater. Sci, 24 :511-514. 12. K.D Parikh , D.J Dave ,B.B Parekh , M.J Joshi.(2007). Bull. Mater. Sci, 30 :105-112. 13. P.V Dhanaraj , C.K Mahadevan , G Bhagavannarayanan, , P.Ramasamy, N.P Rajesh. (2008). J. Cryst. Growth 310:53415346.

14. P.Kumeresan, S.Moorthy Babu , P.M Anbarasan.(2008). J. Cryst. Growth 310:1999- 2004 15. P.VDhanaraj,N.PRajesh,C.KMahadevan and G.Bhagavannarayana. (2009).Physica B 404: 2503-2508 16. K.D Parikh , D.J Dave ,B.B Parekh , M.J Joshi.(2010). Cryst. Res. Technol.45: 603610. 17. I.Pritula, A. Kosinova, M.Kolybayeva,V. Tsurikov, S. Bondarenko et al . (2008). Mater. Res. Bull.43 :2778-2789. 18. B. Karh, and R.W. Gurney. (2001). Chem Rev. 101:893. 19. P.A.Angeli Mary, and S.Dhanuskodi. (2001). Cryst. Res. Technol.36:1231-1237. 20. P. Kumeresan, S.Moorthy Babu ,P.M Anbarasan,J. Optoelectron. (2008). Advan. Mater.l9:2787-2791. 21. P.VDhanaraj, K.Santheep.Mathew and N.P Rajesh. (2008). J.Cryst. Growth 310:25322536. 22. M. H. Jiang and Q. Fang. (1999). Adv. Mater. 11:1147-1151. 23. S.K. Kurtz and T.T. Perry,.(1968). J. Appl. Phys. 39 :3798-3813. 24. S.S Hussaini, N.R. Dhumane, G. Rabbani, P. Karmuse, V.R. Dongre and M. D Shirsat . (2007). Cryst. Res.Technol. 42:1110-1116. 25. C.K. Lakshmanha Perumal, A. Aruchakkaravarthi and S.Santharaghavan. (2002). J. Cryst. Growth 241: 200.

World Journal of Science and Technology | www.worldjournalofscience.com | 2011 | 1(3): 01-06