Facile Synthesis of CaCo₃ and CaCo₃:Eu³⁺ Phosphors by Solid State Reaction at Room Temperature and the Luminescence Properties

Abstract:

The CaCO₃ and CaCO₃:Eu³⁺ phosphors have been synthesized by solid state reaction at room temperature without further sintering treatment. The morphology, crystalline structure, and fluorescent properties of the samples were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), spectrofluorometer, respectively. Also, the influences of Eu³⁺-doping concentration on the photoluminescence (PL) properties were investigated in detail. The results indicate that the morphology of as-prepared CaCO₃ particles are irregular cubic in shape and about 200-400nm in size, while the CaCO₃:Eu³⁺ particles are the aggregates of many small nanoparticles with nearly 30nm in size, indicating that Eu³⁺ ions have a great influence on the CaCO₃ particle morphology and size. The lines around 392nm in luminescence excitation spectrum is the most noticeable. Upon excitation at 392nm, the PL emission spectrum is composed of two band and strong peaks at 589nm and at 613nm. The peaks at 589nm is attributed to magnetic dipole transition ⁵D₀–⁷F₁ and with the increase of the Eu³⁺-doped concentration, the intensity decreases gradually; but it shows the opposite trend for the peak at 613nm which is attributed to the hyper sensitively forced electric dipole transition⁵D₀–⁷F₂.

• Periodical: Materials Science Forum (Volumes 809-810)
• Pages: 711-718
• DOI: https://doi.org/10.4028/www.scientific.net/MSF.809-810.711
• Online since: December 2014
• Authors: Hua Yue Wang, Fu Zhong Gong*, Li Ya Zhou, Lu Sun
• Keywords: Calcium Carbonate, Doping, Europium, Phosphors, Solid State Reaction, Synthesis

References

[1] C. Feldmann, T. Jüstel, C.R. Ronda, P.J. Schmidt, Inorganic luminescent materials: 100 years of research and application , Adv. Funct. Mater., Vol. 13 (2003) No. 7, p.511.

DOI: 10.1002/adfm.200301005

[2] Y. Kojima, S. Kamei, N. Nishimiya. Preparation and fluorescence property of red-emitting Eu3+-activated amorphous calcium silicate phosphor, Materials Research Bulletin, Vol. 45 (2010) No. 2, p.121.

DOI: 10.1016/j.materresbull.2009.09.032

[3] M. Mikami, N. Kijima,B. Bertrand, M. Stankovski,X. Gonze, Theoretical approach for white-LED phosphors: from crystal structures to optical properties, Materials Science and Engineering, Vol. 18(2011) No. 10, p.1.

DOI: 10.1088/1757-899x/18/10/102001

[4] S. Nishiura, S. Tunabe, K. Fujioka, Y. Fujimoto, Properties of transparent Ce: YAG ceramic phosphors for white LED, Optical Materials, Vol. 33 (2011) No. 5, p.688.

DOI: 10.1016/j.optmat.2010.06.005

[5] Q.L. Dai, M.E. Foley, C.J. Breshike, A. Lita and G.F. Strouse, Ligand-passivated Eu: Y2O3 nanocrystals as a phosphor for white light emitting diodes, Journal of the American Chemical Society, Vol. 133 (2011) No. 39, p.15475.

DOI: 10.1021/ja2039419

[6] C.C. Lin R.S. Liu, Advances in phosphors for light-emitting diodes, The Journal of Physical Chemistry Letters, Vol. 2 (2011) No. 3, p.1268.

[7] Y. Yan F.B. Cao Y.W. Tian and L.S. Li. Improved luminescent properties of red-emitting Ca0. 54Sr0. 16Gd0. 12(MoO4)0. 2(WO4)0. 80 phosphor for LED application by charge compensation, J ournal of Luminescence, Vol. 131 (2011) No. 6, p.1140.

DOI: 10.1016/j.jlumin.2011.02.022

[8] G.R. Dillip S.J. Dhoble,L. Manoj,C. MadhukarReddy, B. DevaPrasadRaju. A potential red emitting K4Ca(PO4)2: Eu3+ phosphor for white light emitting diodes. Journal of Luminescence, Vol. 387 (2004) No. 1, p.2.

DOI: 10.1016/j.jlumin.2012.06.029

[9] S. Neeraj, N. Kijima, A.K. Cheetham. Novel red phosphors for solid-state lighting: the system NaM(WO4)2−x(MoO4)x: Eu3+ (M= Gd, Y, Bi), Chemical Physics Letters, Vol. 182 (2009) No. 14, p.203.

DOI: 10.1016/j.cplett.2003.12.130

[10] M. Thomas, P. PrabhakarRao, M. Deepa, M.R. Chandran, P. Koshy. Novel powellite-based red-emitting phosphors: CaLa1-xNbMoO8: xEu3+ for white lightemitting diodes, Journal of Solid State Chemistry, Vol. 182 (2009) No. 14, p.203.

DOI: 10.1016/j.jssc.2008.10.015

[11] J. Sytsma, A. Meijer, G. Blasse, Spectroscopy of Gd3+ and Eu3+ in the calcite structure, J. Solid State Chem., Vol. 99 (1992) No. 1, p.78.

DOI: 10.1016/0022-4596(92)90291-3

[12] Y. Kojima, S. Doi, T. Yasue, Synthesis of europium (II) doped calcium carbonate phosphor under coexisting ammonium chloride and its fluorescence property, J. Ceram. Soc. Jpn., Vol. 111(2003) No. 1293, p.343.

DOI: 10.2109/jcersj.111.343

[13] B. Zhou, B. S Liu, H.F. Zou, et al. Facile synthesis of cubic and spindle-shaped CaCO3 particles and their applications as red phosphor doped with Eu3+, Colloids Surf., Vol. 447 (2014) No. 1, p.166.

DOI: 10.1016/j.colsurfa.2013.12.078

[14] Y. Kojima, K. Machi, T. Yasue, Y. Arai, Synthesis of Ce3+ and Mn2+ codoped calcium carbonate phosphor emitting by black light irradiation and its fluorescence property, J. Ceram. Soc. Jpn., Vol. 108 (2000) No. 9, p.836.

DOI: 10.2109/jcersj.108.1261_836

[15] L. Hu, Z. Mao, C. Gao, Fabrication of fluorescent microparticles by doping water-soluble CdTe nanocrystals into calcium carbonate for monitoring intracellular uptake, Colloids Surf., Vol. 336(2009) No. 1, p.115.

DOI: 10.1016/j.colsurfa.2008.11.031

[16] Z. Lu, L. Chen, Y. Tang, Y. Li, Preparation and luminescence properties of Eu3+-doped MSnO3(M=Ca, Sr and Ba) perovskite materials, J. Alloys Compd., Vol. 387 (2005) No. 1, p. L1.

DOI: 10.1016/j.jallcom.2004.06.036

[17] T. Katsumata, K. Sasajima, T. Nabae, Characteristics of strontium aluminate crystals used for long-duration phosphors , J. Am. Ceram. Soc., Vol. 81 (2005) No. 2, p.413.

DOI: 10.1111/j.1151-2916.1998.tb02349.x

[18] M. Yang, Q. Huang, X.Q. Jin. Facile synthesis of the assembled hexagonal vaterite plates and the application as red phosphor doped with Eu3+ ions, Colloids and Surfaces A: Physicochem. Eng. Aspects, Vol. 386 (2011) No. 1, p.87.

DOI: 10.1016/j.colsurfa.2011.06.028

[19] S.P. Bao, X.Y. Chen, Z. Li, B.J. Yang, Y.C. Wu, Effects of solvent and additive on controllable mineralization of MCO3 (M = Ca, Ba Sr) crystals and their applications as red phosphors doped with Eu3+ ions, CrystEngComm., Vol. 13 (2011).

DOI: 10.1039/c0ce00794c

[20] Y.X. Pan, M.M. Wu, Q. Su. Synthesis of Eu3+ doped calcium and strontium carbonate phosphors at room temperature, Mater Res Bull, Vol. 38 (2003) No. 9, p.1537.

DOI: 10.1016/s0025-5408(03)00174-0

[21] M. Kang, J. Liu, G. Yin, S. Rong, Preparation and characterization of Eu3+-doped CaCO3 phosphor by microwave synthesis, Rare Met., Vol. 28 (2009) No. 5, p.439.

DOI: 10.1007/s12598-009-0085-4

[22] A. Birkel, N. A. DeCino, N.C. George, K.A. Hazelton, B.C. Hong, R. Seshadri. Eu2+-doped M2SiO4 (M =Ca, Ba) phosphors prepared by a rapid microwave-assisted sole-gel method: Phase formation and optical Properties, Solid State Sciences, Vol. 19 (2013).

DOI: 10.1016/j.solidstatesciences.2013.02.003

[23] R. Sun, W.Q. Yan, J. Liu, et al. Hydrothermal synthesis of red phosphors CaCO3: Eu3+, Joural of the chinese ceramic society, Vol. 38(2010) No. 2, p.332.

[24] T.R.N. Kutty, M. Nayak, Photoluminescence of Eu2+-doped mullite(xAl2O3·ySiO2; x/y = 3/2 and 2/1) prepared by a hydrothermal method, Mater. Chem. Phys., Vol. 65 (2000) No. 2, p.158.

DOI: 10.1016/s0254-0584(00)00232-7

[25] F.Q. Ren, D.H. Chen. A promising red-emitting phosphor for white-light-emitting diodes prepared by a modified solid-state reaction, Optics & Laser Technology, Vol. 42 (2010) No. 1, p.110.

DOI: 10.1016/j.optlastec.2009.05.005

[26] F.W. Mo, L.Y. Zhou, Q. Pang, F.Z. Gong, Z.J. Liang. Potential red-emitting NaGd(MO4)2: R(M= W, Mo, R=Eu3+, Sm3+, Bi3+) phosphors for white light emitting diodes applications, Ceramics International, Vol. 38 (2012) No. 8, p.6289.

DOI: 10.1016/j.ceramint.2012.04.084

[27] W.J. Park, M.K. Jung, S.M. Kang, T. Masaki, D.H. Yoon, Synthesis and photoluminescence characterization of Ca3Si2O7: Eu2+ as a potential green-emitting white LED phosphor,J. Phys. Chem. Solids, Vol. 69 (2008) No. 5, p.1505.

DOI: 10.1016/j.jpcs.2007.10.093

[28] I.M. Nagpure,S. Saha S.J. Dhoble. Photoluminescence and thermoluminescence characterization of Eu3+- and Dy3+ -activated Ca3(PO4)2 phosphor, Journal of Luminescence, Vol. 129 (2009) No. 9, p.898.

DOI: 10.1016/j.jlumin.2009.03.034