Research Article
BibTex RIS Cite

Ferroelectricity of Ca9Fe(PO4)7 and Ca9Mn(PO4)7 ceramics with polar whitlockite-type crystal structure

Year 2020, , 559 - 564, 25.06.2020

Umut Adem

https://doi.org/10.17776/csj.723752
Cited By: 1

Abstract

Ca9Fe(PO4)7 is a member of the double phosphate family having polar whitlockite-type crystal structure. The phase transition from the room temperature polar R3c to the high temperature non-polar R c phase has been called a ferroelectric phase transition using complementary experiments such as temperature dependent second harmonic generation and dielectric constant measurements however no ferroelectric hysteresis measurement has been reported. In order to be able to call these polar materials ferroelectric, measurement of a saturated ferroelectric hysteresis loop is necessary to demonstrate that the electrical polarization of these materials is switchable. In order to realize this goal, we have synthesized Ca9Fe(PO4)7 as well as structurally identical Ca9Mn(PO4)7 using solid state synthesis. Crystal structure of the ceramics were confirmed using Rietveld refinement of the x-ray diffraction (XRD) patterns. Differential scanning calorimetry (DSC) measurements revealed phase transition temperatures of 848 and 860 K for Ca9Fe(PO4)7 and Ca9Mn(PO4)7, respectively. Our ferroelectric hysteresis measurements and current electric field loops (I-E) derived from the hysteresis loops showed that the loops cannot be saturated and the direction of the electrical polarization of both materials cannot be switched up to the largest applied electric field of 100 kV/cm. Possible origins of this behaviour are discussed.

Keywords

Ferroelectricity Phosphates Rietveld Refinement Phase transitions

Supporting Institution

Izmir Institute of Technology

Project Number

BAP2015İYTE29

Thanks

This work is supported by İzmir Institute of Technology via BAP Project with the project number 2015İYTE29. We thank IZTECH Department of Chemical Engineering for the DSC experiments and Celal Bayar University’s DEFAM for the use of XRD.

References

  • [1] Dorozhkin S.V., Calcium orthophosphates in nature, biology and medicine, Materials (Basel), 2 (2009) 399-498.
  • [2] Engin N.Ö. and Taş A.C., Preparation of Porous Ca10(PO4)6(OH)2 and β-Ca3(PO4)2 Bioceramics, J. Am. Ceram. Soc., 83 (2000) 1581-1584.
  • [3] Zhu G., Li Z., Wang C. et al., Highly Eu3+ ions doped novel red emission solid solution phosphors, Ca18Li3(Bi,Eu)(PO4)14 : Structure design, characteristic luminescence and abnormal thermal quenching behavior investigation, Dalt. Trans., 48 (2019) 1624-1632.
  • [4] Huang C.H., Chen T.M., Liu W.R., Chiu Y.C., Yeh Y.T. and Jang S.M., A single-phased emission-tunable phosphor Ca9Y(PO4)7:Eu2+,Mn2+ with efficient energy transfer for white-light-emitting diodes, ACS Appl. Mater. Interfaces, 2 (2010) 259-264.
  • [5] Liang S., Dang P., Li G. et al. Controllable two-dimensional luminescence tuning in Eu2+, Mn2+ doped (Ca,Sr)9Sc(PO4)7 based on crystal field regulation and energy transfer, J. Mater. Chem. C, 6 (2018) 6714-6725.
  • [6] Chen M., Xia Z., Molokeev M.S., Wang T. and Liu Q., Tuning of Photoluminescence and Local Structures of Substituted Cations in xSr2Ca(PO4)2–(1–x)Ca10Li(PO4)7:Eu2+Phosphors, Chem. Mater. 29 (2017) 1430-1438.
  • [7] Morozov V.A., Belik A.A., Stefanovich S.Y. et al., High-temperature phase transition in the whitlockite-type phosphate Ca9In(PO4)7, J. Solid State Chem., 165 (2002) 278-288.
  • [8] Lazoryak B.I., Morozov V.A., Belik A.A. et al., Ferroelectric phase transition in the whitlockite-type Ca9Fe(PO4)7; crystal structure of the paraelectric phase at 923 K, Solid State Sci., 6 (2004) 185-195.
  • [9] Deineko D.V., Stefanovich S.Y., Mosunov A.V., Baryshnikova O.V. and Lazoryak B.I., Structure and properties of Ca9-xPbx R(PO4)7 (R = Sc, Cr, Fe, Ga, In) whitlockite-like solid solutions, Inorg. Mater. 49 (2013) 507-512.
  • [10] Belik A.A., Deyneko D.V., Baryshnikova O.V., Stefanovich S.Y. and Lazoryak B.I., Sr9In(VO4)7 as a model ferroelectric in the structural family of β-Ca3(PO4)2-type phosphates and vanadates, RSC Adv., 10 (2020) 10867-10872.
  • [11] Larson A.C. and Von Dreele R.B., General Structure Analysis System (GSAS), Los Alamos National Laboratory Report LAUR, (2004) 86-748.
  • [12] Jain A., Ong S.P., Hautier G. et al., Commentary: The Materials Project: A materials genome approach to accelerating materials innovation, APL Mater., 1 (2013) 011002.
  • [13] Shannon R.D., Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr. Sect. A., 32 (1976) 751-767.
  • [14] Jin L., Li F. and Zhang S.J., Decoding the Fingerprint of Ferroelectric Loops: Comprehension of the Material Properties and Structures, J. Am. Ceram. Soc., 97 (2014) 1-27.
  • [15] Yan H., Inam F., Viola G. et al., the Contribution of Electrical Conductivity, Dielectric Permittivity and Domain Switching in Ferroelectric Hysteresis Loops, J. Adv. Dielectr., 01 (2011) 107-118.
  • [16] Song S., Jang H.M., Lee N.S. et al., Ferroelectric polarization switching with a remarkably high activation energy in orthorhombic GaFeO3 thin films, NPG Asia Mater., 8 (2016) e242.
  • [17] De C. and Sundaresan A., Nonswitchable polarization and magnetoelectric coupling in the high-pressure synthesized doubly ordered perovskites NaYMnWO6 and NaHoCoWO6, Phys. Rev. B., 97 (2018) 214418.
  • [18] Garrity K.F., High-throughput first-principles search for new ferroelectrics, Phys. Rev. B., 97 (2018) 024115.
  • [19] Buurma A.J.C., Blake G.R., Palstra T.T.M. and Adem U., Multiferroic Materials: Physics and Properties, Reference Module in Materials Science and Materials Engineering: https://www.sciencedirect.com/science/article/pii/B9780128035818092456, Elsevier Ltd., (2016).
  • [20] Li M-R., Adem U., McMitchell S.R.C. et al., A polar corundum oxide displaying weak ferromagnetism at room temperature, J. Am. Chem. Soc., 134 (2012) 3737-3747.
  • [21] Catalan G. and Scott J.F., Physics and applications of bismuth ferrite, Adv. Mater., 21 (2009) 2463-2485.
  • [22] Ning H.P., Yan H.X. and Reece M.J., A High Curie Point Ferroelectric Ceramic Ca3(VO4)2, Ferroelectrics, 487 (2015) 94-100.
  • [23] Teterskii A.V., Morozov V.A., Stefanovich S.Y. and Lazoryak B.I., Dielectric and nonlinear optical properties of the Ca9R(PO4)4 (R=Ln) phosphates, Russ. J. Inorg. Chem. 50 (2005) 986-989.

Year 2020, , 559 - 564, 25.06.2020

Umut Adem

https://doi.org/10.17776/csj.723752
Cited By: 1

Abstract

Project Number

BAP2015İYTE29

References

  • [1] Dorozhkin S.V., Calcium orthophosphates in nature, biology and medicine, Materials (Basel), 2 (2009) 399-498.
  • [2] Engin N.Ö. and Taş A.C., Preparation of Porous Ca10(PO4)6(OH)2 and β-Ca3(PO4)2 Bioceramics, J. Am. Ceram. Soc., 83 (2000) 1581-1584.
  • [3] Zhu G., Li Z., Wang C. et al., Highly Eu3+ ions doped novel red emission solid solution phosphors, Ca18Li3(Bi,Eu)(PO4)14 : Structure design, characteristic luminescence and abnormal thermal quenching behavior investigation, Dalt. Trans., 48 (2019) 1624-1632.
  • [4] Huang C.H., Chen T.M., Liu W.R., Chiu Y.C., Yeh Y.T. and Jang S.M., A single-phased emission-tunable phosphor Ca9Y(PO4)7:Eu2+,Mn2+ with efficient energy transfer for white-light-emitting diodes, ACS Appl. Mater. Interfaces, 2 (2010) 259-264.
  • [5] Liang S., Dang P., Li G. et al. Controllable two-dimensional luminescence tuning in Eu2+, Mn2+ doped (Ca,Sr)9Sc(PO4)7 based on crystal field regulation and energy transfer, J. Mater. Chem. C, 6 (2018) 6714-6725.
  • [6] Chen M., Xia Z., Molokeev M.S., Wang T. and Liu Q., Tuning of Photoluminescence and Local Structures of Substituted Cations in xSr2Ca(PO4)2–(1–x)Ca10Li(PO4)7:Eu2+Phosphors, Chem. Mater. 29 (2017) 1430-1438.
  • [7] Morozov V.A., Belik A.A., Stefanovich S.Y. et al., High-temperature phase transition in the whitlockite-type phosphate Ca9In(PO4)7, J. Solid State Chem., 165 (2002) 278-288.
  • [8] Lazoryak B.I., Morozov V.A., Belik A.A. et al., Ferroelectric phase transition in the whitlockite-type Ca9Fe(PO4)7; crystal structure of the paraelectric phase at 923 K, Solid State Sci., 6 (2004) 185-195.
  • [9] Deineko D.V., Stefanovich S.Y., Mosunov A.V., Baryshnikova O.V. and Lazoryak B.I., Structure and properties of Ca9-xPbx R(PO4)7 (R = Sc, Cr, Fe, Ga, In) whitlockite-like solid solutions, Inorg. Mater. 49 (2013) 507-512.
  • [10] Belik A.A., Deyneko D.V., Baryshnikova O.V., Stefanovich S.Y. and Lazoryak B.I., Sr9In(VO4)7 as a model ferroelectric in the structural family of β-Ca3(PO4)2-type phosphates and vanadates, RSC Adv., 10 (2020) 10867-10872.
  • [11] Larson A.C. and Von Dreele R.B., General Structure Analysis System (GSAS), Los Alamos National Laboratory Report LAUR, (2004) 86-748.
  • [12] Jain A., Ong S.P., Hautier G. et al., Commentary: The Materials Project: A materials genome approach to accelerating materials innovation, APL Mater., 1 (2013) 011002.
  • [13] Shannon R.D., Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides, Acta Crystallogr. Sect. A., 32 (1976) 751-767.
  • [14] Jin L., Li F. and Zhang S.J., Decoding the Fingerprint of Ferroelectric Loops: Comprehension of the Material Properties and Structures, J. Am. Ceram. Soc., 97 (2014) 1-27.
  • [15] Yan H., Inam F., Viola G. et al., the Contribution of Electrical Conductivity, Dielectric Permittivity and Domain Switching in Ferroelectric Hysteresis Loops, J. Adv. Dielectr., 01 (2011) 107-118.
  • [16] Song S., Jang H.M., Lee N.S. et al., Ferroelectric polarization switching with a remarkably high activation energy in orthorhombic GaFeO3 thin films, NPG Asia Mater., 8 (2016) e242.
  • [17] De C. and Sundaresan A., Nonswitchable polarization and magnetoelectric coupling in the high-pressure synthesized doubly ordered perovskites NaYMnWO6 and NaHoCoWO6, Phys. Rev. B., 97 (2018) 214418.
  • [18] Garrity K.F., High-throughput first-principles search for new ferroelectrics, Phys. Rev. B., 97 (2018) 024115.
  • [19] Buurma A.J.C., Blake G.R., Palstra T.T.M. and Adem U., Multiferroic Materials: Physics and Properties, Reference Module in Materials Science and Materials Engineering: https://www.sciencedirect.com/science/article/pii/B9780128035818092456, Elsevier Ltd., (2016).
  • [20] Li M-R., Adem U., McMitchell S.R.C. et al., A polar corundum oxide displaying weak ferromagnetism at room temperature, J. Am. Chem. Soc., 134 (2012) 3737-3747.
  • [21] Catalan G. and Scott J.F., Physics and applications of bismuth ferrite, Adv. Mater., 21 (2009) 2463-2485.
  • [22] Ning H.P., Yan H.X. and Reece M.J., A High Curie Point Ferroelectric Ceramic Ca3(VO4)2, Ferroelectrics, 487 (2015) 94-100.
  • [23] Teterskii A.V., Morozov V.A., Stefanovich S.Y. and Lazoryak B.I., Dielectric and nonlinear optical properties of the Ca9R(PO4)4 (R=Ln) phosphates, Russ. J. Inorg. Chem. 50 (2005) 986-989.
There are 23 citations in total.

Details

Primary Language English
Subjects Classical Physics (Other), Engineering
Journal Section Engineering Sciences
Authors

Umut Adem 0000-0002-2930-5567

Project Number BAP2015İYTE29
Publication Date June 25, 2020
Submission Date April 20, 2020
Acceptance Date May 31, 2020
Published in Issue Year 2020

Cite

APA Adem, U. (2020). Ferroelectricity of Ca9Fe(PO4)7 and Ca9Mn(PO4)7 ceramics with polar whitlockite-type crystal structure. Cumhuriyet Science Journal, 41(2), 559-564. https://doi.org/10.17776/csj.723752

Cited By

Structure evolution and tunable magneto‐optical multifunctional property study of novel Ca 18 K 3 Sc 1‐x Sm x (PO 4 ) 14 phosphors
Journal of the American Ceramic Society
Zhuowei Li
https://doi.org/10.1111/jace.17620