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Structural phase transition in Zn1.98Mn0.02P2O7: EPR evidence for enhanced line broadening and large zero-field splitting parameter in high temperature phase

Published online by Cambridge University Press:  11 November 2013

Santosh K. Gupta*
Affiliation:
Radiochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai-400085, India
Ramakant Mahadeo Kadam
Affiliation:
Radiochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai-400085, India
Pradeep Samui
Affiliation:
Product Development Division, Bhabha Atomic Research Center, Trombay, Mumbai-400085, India
Krishnan Kesavaiyer
Affiliation:
Fuel Chemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai-400085, India
Venkataraman Natarajan
Affiliation:
Radiochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai-400085, India
Shrikant Vasant Godbole
Affiliation:
Radiochemistry Division, Bhabha Atomic Research Center, Trombay, Mumbai-400085, India
*
a)Address all correspondence to this author. e-mail: [email protected]
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Abstract

Zn1.98Mn0.02P2O7 was synthesized by the wet chemical route. The purity of the phase and the oxidation state of manganese ion were investigated by x-ray diffraction (XRD) and electron paramagnetic resonance (EPR). Structural phase transition in α-Zn2P2O7 was investigated by high-temperature XRD (HTXRD), differential scanning calorimetry (DSC), and EPR studies. There is a distinct signature of phase transitions between 390 and 400 K in our powder sample by EPR and HTXRD. There was a sharp reduction in the volume of unit cell, while going from alpha to beta phase; with discontinuity in 405 K, which confirmed the transition to be of first order. Similarly, the effect of temperature on zero-field splitting parameter (D) also showed that there is a sudden jump (discontinuity) in the value at around 400 K (phase transition temperature) confirming the transition to be of first order. DSC studies corroborated these findings.

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Articles
Copyright
Copyright © Materials Research Society 2013 

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References

REFERENCES

Brixner, L.H.: New x-ray phosphor. Mater. Chem. Phys. 16, 253 (1987).CrossRefGoogle Scholar
Zhao, M., Li, L., Zheng, J., Yang, L., and Li, G.: Is BiPO4 a better luminescent host? Case study on doping and annealing effects. Inorg. Chem. 52, 807 (2013).CrossRefGoogle ScholarPubMed
Naidu, B.S., Vishwanadh, B., Sudarsan, V., and Vatsa, R.: BiPO4: A better host for doping lanthanide ions. Dalton Trans. 41, 3194 (2012).CrossRefGoogle ScholarPubMed
Song, E., Zhao, W., Zhou, G., Dou, X., Ming, H., and Yi, C.: White light emitting from single phased K2Ca1−x−yP2O7: xEu2+, yMn2+ phosphors under UV excitation. Curr. Appl. Phys. 11, 13741378 (2012).CrossRefGoogle Scholar
Day, D.E., Wu, Z., Ray, C.S., and Hrma, P.: Chemically durable iron phosphate glass waste forms. J. Non-Cryst. Solids 241 1 (1998).CrossRefGoogle Scholar
Marasinghe, G.K., Karabulut, M., Ray, C.S., Day, D.E., Shuh, D.K., Allen, P.G., Saboungi, M.L., Grimsditch, M., and Haefner, D.: Properties and structure of vitrified iron phosphate nuclear waste forms. J. Non-Cryst. Solids 263264, 146 (2000).CrossRefGoogle Scholar
Karabulut, M., Marasinghe, G.K., Ray, C.S., Day, D.E., Waddill, G.D., Booth, C.H., Allen, P.G., Bucher, J.J., Caulder, D.L., and Shuh, D.K.: An investigation of the local iron environment in iron phosphate glasses having different Fe (II) concentrations. J. Non-Cryst. Solids 306, 182 (2002).CrossRefGoogle Scholar
Boukhari, A.: Diphosphate structures related to the dichromate or thortveitite type. J. Alloys Compd. 188, 14 (1992).CrossRefGoogle Scholar
Brown, I.D. and Calvo, C.: The crystal chemistry of large cation dichromates, pyrophosphates, and related compounds with stoichiometry X2Y2O7. J. Solid State Chem. 1, 173 (1970).CrossRefGoogle Scholar
Lefkowitz, I., Lukaszewez, K., and Megaw, H.D.: The high-temperature phases of sodium niobate and the nature of transitions in pseudosymmetric structures. Acta Cryst. 20, 670 (1966).CrossRefGoogle Scholar
Robertson, B.E. and Calvo, C.: Crystal structure of α-Zn2P2O7. J. Solid State Chem. 1, 120 (1970).CrossRefGoogle Scholar
Katnack, F.L. and Hummel, F.A.: Phase equilibria in the system ZnO-P2O5. J. Electrochem. Soc. 105, 125 (1958).CrossRefGoogle Scholar
Roy, R., Middleswarth, E.T., and Hummel, F.A.: Mineralogy and thermal behavior of phosphates I. Magnesium pyrophosphate. Am. Mineral. 33, 458 (1948).Google Scholar
Chambers, J.G., Datars, W.R., and Calvo, C.: ESR study of the crystallographic phases in Zn2P2O7:Mn and Zn2P2O7:Cu. J. Chem. Phys. 41, 806 (1964).CrossRefGoogle Scholar
Labrinia, M., Saadounea, I., Almaggoussib, A., Elhaskouric, J., and Amoros, P.: The LiyNi0.2Mn0.2Co0.6O2 electrode materials: A structural and magnetic study. Mater. Res. Bull. 47, 1004 (2012).CrossRefGoogle Scholar
Orive, J., Balda, R., Fernandez, J., Lezama, L., and Arriortua, M.I.: Low temperature red luminescence of a fluorinated Mn-doped zinc selenite. Dalton Trans. 42, 12481 (2013).CrossRefGoogle ScholarPubMed
Voronov, V.N. and Petrakovskaya, E.A.: EPR investigation of local paramagnetic centers in perovskite-like crystals. Phys. Solid State 55, 730 (2013).CrossRefGoogle Scholar
Falin, M.L., Gerasimov, K.I., Latypov, V.A., Leushin, A.M., and Khaidukov, N.M.: EPR and optical spectroscopy of structural phase transition in an Rb2NaYF6 crystal. Phys. Rev. B 87, 115145 (2013).CrossRefGoogle Scholar
Zhang, J., Yan, S., Zhao, S., Xu, Q., and Li, C.: Photocatalytic activity for H2 evolution of TiO2 with tuned surface crystalline phase. Appl. Surf. Sci. 280, 304 (2013).CrossRefGoogle Scholar
Hubaud, A.A., Schroeder, D.J., Key, B., Ingram, B.J., Dogan, F., and Vaughey, J.T.: Low temperature stabilization of cubic (Li7-xAl x/3) La3Zr2O12: Role of aluminum during formation. J. Mater. Chem. A 31, 8813 (2013).CrossRefGoogle Scholar
Rani, G. and Sahare, P.D.: Effect of phase transitions on thermoluminescence characteristics of nanocrystalline alumina. Nucl. Instrum. Methods Phys. Res., Sect. B 311, 71 (2013).CrossRefGoogle Scholar
Bottcher, R., Langhammer, H.T., Muller, T., and Abicht, H.P.: Evaluation of lattice site and valence of manganese in hexagonal BaTiO3 by electron paramagnetic resonance. J Phys. Condens. Matter 17, 4925 (2005).CrossRefGoogle Scholar
Sengupta, A., Kadam, R.M., Rajeswari, B., Dhobale, A.R., Babu, Y., and Godbole, S.V.: Characterization of Indian serpentine by X-ray diffraction, photoacoustic spectroscopy and electron paramagnetic resonance spectroscopy. Appl. Clay Sci. 50, 305 (2010).CrossRefGoogle Scholar
Singh, V., Chakradhar, R.P.S., Rao, J.L., and Kim, D-K.: Synthesis, characterization, photoluminescence and EPR investigations of Mn doped MgAl2O4 phosphors. J. Solid State Chem. 180, 2067 (2007).CrossRefGoogle Scholar
Momma, K. and Izumi, F.: VESTA: A three-dimensional visualization system for electronic and structural analysis. J. Appl. Cryst. 41, 653 (2008).CrossRefGoogle Scholar
Calvo, C.: Crystal structure of β-Zn2P2O7. Can. J. Chem. 43, 1147 (1965).CrossRefGoogle Scholar
Calvo, C., Nest, J.P.V., and Datars, W.R.: Luminescence and the cation coordination number in the phosphate system. Mater. Res. Bull. 2, 283 (1967).CrossRefGoogle Scholar