Abstract
Zinc(tris) thiourea sulphate (ZTS) is as one of the potential candidates for nonlinear optical applications due to its high nonlinearity and excellent optical properties. The synthesis of pure and titan yellow dye doped ZTS has been done and good quality rod-like single crystals of size ∼60 mm long and 2 mm diameter were grown through simplest and low cost route. The structural and vibrational analysis rules out any extra phase or change in structure of ZTS due to dye doping. Scanning electron microscope study reveals that the grown crystals are of good quality with rod-like morphology. Diffuse reflectance spectrum show a new absorption band at ∼460 nm, which may be predicted as a signature of dye. The optical band gap was calculated to be 4.6 eV for pure and 4.5 eV for doped ZTS crystals. The violet-blue emission centered at 412 nm in pure and at 414 nm in doped crystals with an additional green emission bands at 528 nm with high intensity in the photoluminescence spectra were observed. The value of ε1 is found to be enhanced from 10 (in pure) to 14 (in doped) crystals. The properties are enhanced due to dye doping and may be more useful than pure crystals in optoelectronic devices.
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B. Saleh: MC Teich Fundamentals of Photonics (John Wiley & Sons: New York, 1991).
B.G. Penn, B.H. Cardelino, C.E. Moore, A.W. Shields, and D. Frazier: Growth of bulk single crystals of organic materials for nonlinear optical devices: An overview. Prog. Cryst. Growth Charact. Mater. 22 (1), 19 (1991).
M. Shakir, B. Singh, B. Kumar, and G. Bhagavannarayana: Ferroelectricity in glycine picrate: An astonishing observation in a centrosymmetric crystal. Appl. Phys. Lett. 95 (25), 252902 (2009).
M. Shakir, S. Kushwaha, K. Maurya, and R. Bhatt: Unidirectional growth of l-proline cadmium chloride monohydrate single crystal and its characterization for structural, vibrational, LDT, optical and dielectric properties. Mater. Chem. Phys. 120, 566 (2010).
M. Shkir, H. Abbas, S. Kumar, G. Bhagavannarayana, and S. AlFaify: Experimental and theoretical studies on bis (glycine) lithium nitrate (BGLiN): A physico-chemical approach. J. Phys. Chem. Solids 75 (8), 959 (2014).
M. Shkir, S. AlFaify, H. Abbas, and G. Bhagavannarayana: A physico-chemical approach to study the experimental and theoretical properties of l-ornithine monohydrochloride: An organic nonlinear optical material. Mater. Chem. Phys. 155, 36–46 (2015).
J. Badan, R. Hierle, A. Perigaud, J. Zyss, and D. Williams: NLO properties of organic molecules and polymeric materials, in American Chemical Society Symposium Series, Vol. 233 (American Chemical Society, Washington, DC, 1993).
N. Zaitseva and L. Carman: Rapid growth of KDP-type crystals. Prog. Cryst. Growth Charact. Mater. 43 (1), 1 (2001).
M. Shkir, S. Muhammad, S. AlFaify, A. Irfan, and I. Yahia: A dual approach to study the electro-optical properties of a noncentrosymmetric l-asparagine monohydrate. Spectrochim. Acta, Part A 137, 432 (2015).
M. Shkir, S. Muhammad, and S. AlFaify: Experimental and density functional theory (DFT): A dual approach to study the various important properties of monohydrated L-proline cadmium chloride for nonlinear optical applications. Spectrochim. Acta, Part A 143, 128–135 (2015).
P. Newman, L. Warren, P. Cunningham, T. Chang, D. Cooper, G. Burdge, P. Polak-Dingels, and C. Lowe-Ma: Semiorganics: A new class of NLO materials. In MRS Proceedings, Vol. 173 (Cambridge University Press, Cambridge, 1989); p. 557.
P.H. Cunningham, L.F. Warren, Jr., O. Marcy, and M.J. Rosker: Semi-organic crystals for nonlinear optical devices. Google Patents, 1996.
N.R. Dhumane, S.S. Hussaini, V.G. Dongre, and M.D. Shirsat: Influence of glycine on the nonlinear optical (NLO) properties of zinc(tris) thiourea sulfate (ZTS) single crystal. Opt. Mater. 31 (2), 328 (2008).
D.J. Williams: Organic polymeric and non-polymeric materials with large optical nonlinearities. Angew. Chem., Int. Ed. Engl. 23 (9), 690 (1984).
M. Shkir, B. Riscob, M. Ajmal Khan, S. AlFaify, E. Dieguez, and G. Bhagavannarayana: Effect of organic ligands (l-proline and l-methionine) on growth, structural, vibrational, crystalline perfection, SHG efficiency, microscopic and optical properties of KDP single crystals. Spectrochim. Acta, Part A 124, 571 (2014).
M. Shkir, V. Ganesh, N. Vijayan, B. Riscob, A. Kumar, D.K. Rana, M. Shoeb Khan, M. Hasmuddin, M. Wahab, and R. Ramesh Babu: Analysis on structural, SHG efficiency, optical and mechanical properties of KDP single crystals influenced by glycine doping. Spectrochim. Acta, Part A 103, 199 (2013).
G. Bhagavannarayana, S. Parthiban, and S. Meenakshisundaram: An interesting correlation between crystalline perfection and second harmonic generation efficiency on KCl-and oxalic acid-doped ADP crystals. Cryst. Growth Des. 8 (2), 446 (2007).
S. Meenakshisundaram, S. Parthiban, N. Sarathi, R. Kalavathy, and G. Bhagavannarayana: Effect of organic dopants on ZTS single crystals. J. Cryst. Growth 293 (2), 376 (2006).
S. Bhandari, N. Sinha, G. Ray, and B. Kumar: Enhanced optical, dielectric and piezoelectric behavior in dye doped zinc tris-thiourea sulphate (ZTS) single crystals. Chem. Phys. Lett. 591, 10 (2014).
N. Sinha, N. Goel, B.K. Singh, M.K. Gupta, and B. Kumar: Enhancement in ferroelectric, pyroelectric and photoluminescence properties in dye doped TGS crystals. J. Solid State Chem. 190, 180 (2012).
Y. Li, E.G. Johnson, C.D. Nie, J.A. Harrington, and R. Shori: Ho:YAG single crystal fiber: Fabrication and optical characterization. Opt. Express 22 (12), 14896 (2014).
J. Didierjean, M. Castaing, F. Balembois, P. Georges, D. Perrodin, J.M. Fourmigué, K. Lebbou, A. Brenier, and O. Tillement: High-power laser with Nd:YAG single-crystal fiber grown by the micro-pulling-down technique. Opt. Lett. 31 (23), 3468 (2006).
M. Enculescu: Morphological and optical properties of doped potassium hydrogen phthalate crystals. Phys. B 405 (17), 3722 (2010).
B. Raju, A. Saritha, G. Bhagavannarayana, and K.A. Hussain: A comparative study on growth, structural, optical, thermal and mechanical properties of undoped and dye doped bis glycine cadmium chloride single crystals. J. Cryst. Growth 324 (1), 184 (2011).
S. Chandran, R. Paulraj, and P. Ramasamy: Influence of amaranth dye on the growth and properties of KDP single crystal. Mater. Res. Bull. 68, 210 (2015).
N. Zaitseva, L. Carman, I. Smolsky, R. Torres, and M. Yan: The effect of impurities and supersaturation on the rapid growth of KDP crystals. J. Cryst. Growth 204 (4), 512 (1999).
S. Hirota, H. Miki, K. Fukui, and K. Maeda: Coloring and habit modification of dyed KDP crystals as functions of supersaturation and dye concentration. J. Cryst. Growth 235 (1–4), 541 (2002).
A. Barbon, M. Bellinazzi, J.B. Benedict, M. Brustolon, S.D. Fleming, S-H. Jang, B. Kahr, and A.L. Rohl: Luminescent probes of crystal growth: Surface charge and polar axis sense in dye-doped potassium hydrogen phthalate. Angew. Chem., Int. Ed. 43 (40), 5328 (2004).
K.L. Wustholz, B. Kahr, and P.J. Reid: Single-molecule orientations in dyed salt crystals. J. Phys. Chem. B 109 (34), 16357 (2005).
J.B. Benedict, P.M. Wallace, P.J. Reid, S.H. Jang, and B. Kahr: Up-conversion luminescence in dye-doped crystals of potassium hydrogen phthalate. Adv. Mater. 15 (13), 1068 (2003).
V.V. Poborchii, T. Tada, and T. Kanayama: A visible-near infrared range photonic crystal made up of Si nanopillars. Appl. Phys. Lett. 75 (21), 3276 (1999).
S.M. Yang and G.A. Ozin: Opal chips: Vectorial growth of colloidal crystal patterns inside silicon wafers. Chem. Commun. 24, 2507–2508, 2507 (2000).
M.C. Wanke, O. Lehmann, K. Müller, Q. Wen, and M. Stuke: Laser rapid prototyping of photonic band-gap microstructures. Science 275 (5304), 1284 (1997).
P.M. Ushasree, R. Jayavel, C. Subramanian, and P. Ramasamy: Growth of zinc thiourea sulfate (ZTS) single crystals: A potential semiorganic NLO material. J. Cryst. Growth 197 (1–2), 216 (1999).
G.D. Andreetti, L. Cavalca, and A. Musatti: The crystal and molecular structure of tris (thiourea) zinc (II) sulphate. Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. 24 (5), 683 (1968).
V. Venkataramanan, M. Srinivasan, and H. Bhat: Vibrational spectroscopic study of zinc tris (thiourea) sulphate, a new organometallic non-linear optical crystal. J. Raman Spectrosc. 25 (10), 805 (1994).
M. Oussaid, P. Becker, M. Kemiche, and C. Carabatos-Nédelec: Low temperature phase transitions in zinc tris (thiourea) sulfate (ZTS) determined by Raman scattering. Phys. Status Solidi B 207 (1), 103 (1998).
B.S. Samuel, R. Krishnamurthy, and R. Rajasekaran: Effect of l-aspartic acid on the growth, structure and spectral studies of zinc (tris) thiourea sulphate (ZTS) single crystals. Spectrochim. Acta, Part A 132 (0), 526 (2014).
A.E. Morales, E.S. Mora, and U. Pal: Use of diffuse reflectance spectroscopy for optical characterization of un-supported nanostructures. Rev. Mex. Fis. S 53 (5), 18 (2007).
D.G. Barton, M. Shtein, R.D. Wilson, S.L. Soled, and E. Iglesia: Structure and electronic properties of solid acids based on tungsten oxide nanostructures. J. Phys. Chem. B 103 (4), 630 (1999).
P. Kubelka and F. Munk: A contribution to the optics of pigments. Z. Tech. Phys. 12, 593 (1931).
B.M. Weckhuysen and R.A. Schoonheydt: Recent progress in diffuse reflectance spectroscopy of supported metal oxide catalysts. Catal. Today 49 (4), 441 (1999).
F. Urbach: The long-wavelength edge of photographic sensitivity and of the electronic absorption of solids. Phys. Rev. 92 (5), 1324 (1953).
M. Shkir, B. Riscob, V. Ganesh, N. Vijayan, R. Gupta, J. Plaza, E. Dieguez, and G. Bhagavannarayana: Crystal growth, structural, crystalline perfection, optical and mechanical properties of Nd3+ doped sulfamic acid (SA) single crystals. J. Cryst. Growth 380, 228 (2013).
M. Shakir, S. Kushwaha, K. Maurya, G. Bhagavannarayana, and M. Wahab: Characterization of ZnSe nanoparticles synthesized by microwave heating process. Solid State Commun. 149 (45), 2047 (2009).
M. Shkir, H. Abbas, and Z.R. Khan: Effect of thickness on the structural, optical and electrical properties of thermally evaporated PbI2 thin films. J. Phys. Chem. Solids 73 (11), 1309 (2012).
M. Shkir, S. Alfaify, M. Ajmal Khan, E. Dieguez, and J. Perles: Synthesis, growth, crystal structure, EDX, UV-vis-NIR and DSC studies of l-proline lithium bromide monohydrate—A new semiorganic compound. J. Cryst. Growth 391, 104 (2014).
M. Shkir, B. Riscob, M. Hasmuddin, P. Singh, V. Ganesh, M. Wahab, E. Dieguez, and G. Bhagavannarayana: Optical spectroscopy, crystalline perfection, etching and mechanical studies on P-nitroaniline (PNA) single crystals. Opt. Mater. 36 (3), 675 (2014).
S. Xu, G. Li, S. Chua, X. Wang, and W. Wang: Observation of optically-active metastable defects in undoped GaN epilayers. Appl. Phys. Lett. 72 (19), 2451 (1998).
S. Kushwaha, K. Maurya, N. Vijayan, A. Gupta, D. Haranath, B. Kumar, D. Kanjilal, and G. Bhagavannarayana: Au9+ swift heavy ion irradiation of Zn [CS(NH2)2]3·SO4 crystal: Crystalline perfection and optical properties. Nucl. Instrum. Methods Phys. Res., Sect. B 338, 1 (2014).
A.A. Bol, J. Ferwerda, J.A. Bergwerff, and A. Meijerink: Luminescence of nanocrystalline ZnS:Cu2+. J. Lumin. 99 (4), 325 (2002).
M. Pal, S. Bera, S. Sarkar, and S. Jana: Influence of Al doping on microstructural, optical and photocatalytic properties of sol–gel based nanostructured zinc oxide films on glass. RSC Adv. 4 (23), 11552 (2014).
S. Kushwaha, K. Maurya, D. Haranath, and G. Bhagavannarayana: The effect of Cr3+ doping on the crystalline perfection and optical properties of zinc tris (thiourea) sulfate, a nonlinear optical material. J. Appl. Crystallogr. 44 (5), 1054 (2011).
D. Xue and K. Kitamura: Dielectric characterization of the defect concentration in lithium niobate single crystals. Solid State Commun. 122 (10), 537 (2002).
N.E. Hill: Dielectric properties and molecular behaviour (Van Nostrand Reinhold, 1969).
J. Przeslawski, T. Iglesias, and J. Gonzalo: Dielectric losses behaviour under frequency and ac field amplitude variation in TGSe crystals. Solid State Commun. 96 (4), 195 (1995).
M. Shakir, S. Kushawaha, K. Maurya, S. Kumar, M. Wahab, and G. Bhagavannarayana: Enhancement of second harmonic generation, optical and dielectric properties in L-asparagine monohydrate single crystals due to an improvement in crystalline perfection by annealing. J. Appl. Crystallogr. 43 (3), 491 (2010).
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The author is highly thankful to King Khalid University, Abha, Saudi Arabia for providing all necessary facilities for current research.
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Shkir, M. Effect of titan yellow dye on morphological, structural, optical, and dielectric properties of zinc(tris) thiourea sulphate single crystals. Journal of Materials Research 31, 1046–1055 (2016). https://doi.org/10.1557/jmr.2016.116
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DOI: https://doi.org/10.1557/jmr.2016.116