Abstract
1 mol% Re2O3–99 mol% Ca3(PO4)2 (Re = Sm, Dy and Er) powder samples were prepared by solid-state sintering method. The structural, thermal, vibrational and optical properties were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), differential scanning calorimetry (DSC), Raman and photoluminescence techniques. XRD studies confirm the formation of β-Ca3(PO4)2 with the rhombohedral crystal structure. FESEM images reveal the formation of flake-like agglomerated particles of size in the range of 100–700 nm. DSC analysis shows that β-TCP → α-TCP structural phase transition occurs at 1286 ºC, followed by α-TCP → α'-TCP transformation at 1469 ºC. Raman spectra of the samples show antisymmetric and symmetric stretching and bending vibration bands of P-O linkages. Photoluminescence studies found intense reddish-orange emission in Sm-doped samples, white light emission in Dy-doped samples and yellow emission in Er-doped samples. The luminescence intensity of Sm and Dy-doped β-TCP samples is found to be significantly higher than that of Er-doped samples.
Similar content being viewed by others
References
Adler HH (1964) Infrared spectra of phosphate minerals: symmetry and substitutional effects in the pyromorphite series. Am Mineral J Earth Planet Mater 49(7–8):1002–1015
Adler HH, Kerr PF (1965) Variations in infrared spectra, molecular symmetry and site symmetry of sulfate minerals. Am Mineral J Earth Planet Mater 50(1–2):132–147
Akkarachaneeyakorn K, Li M, Harris J, Davis SA, Mann S (2014) Bioactive hybrid organogels based on miniemulsion synthesis of morphologically complex polymer/surfactant/calcium phosphate nanostructures. Chem Mater 26(20):5965–5972
Barbosa HP, Silva IG, Felinto MCF, Teotonio EE, Malta OL, Brito HF (2017) Photoluminescence of single-phased white light emission materials based on simultaneous Tb3+, Eu3+ and Dy3+ doping in CaWO4 matrix. J Alloy Compd 696:820–827
Ben Y, Zhang L, Wei S, Zhou T, Li Z, Yang H, Wong C, Chen H (2017) Improved forming performance of β-TCP powders by doping silica for 3D ceramic printing. J Mater Sci: Mater Electron 28(7):5391–5397
Brazete D, Torres P, Abrantes J, Ferreira J (2018) Influence of the Ca/P ratio and cooling rate on the allotropic α ↔ β-tricalcium phosphate phase transformations. Ceram Int 44(7):8249–8256
Cai Y, Tang R (2008) Calcium phosphate nanoparticles in biomineralization and biomaterials. J Mater Chem 18(32):3775–3787
Carrodeguas RG, De Aza AH, Turrillas X, Pena P, De Aza S (2008) New approach to the β → α polymorphic transformation in magnesium-substituted tricalcium phosphate and its practical implications. J Am Ceram Soc 91(4):1281–1286
Cho S (2018) Synthesis and Photoluminescence Properties of BaWO4: RE3+ (RE= Eu or Sm) Phosphors. J Korean Phys Soc 72(8):959–965
Dasgupta S, Bose S (2009) Reverse Micelle-Mediated Synthesis and Characterization of Tricalcium Phosphate Nanopowder for Bone Graft Applications. J Am Ceram Soc 92(11):2528–2536
El Khouri A, Elaatmani M, Della Ventura G, Sodo A, Rizzi R, Rossi M, Capitelli F (2017) Synthesis, structure refinement and vibrational spectroscopy of new rare-earth tricalcium phosphates Ca9RE(PO4)7 (RE= La, Pr, Nd, Eu, Gd, Dy, Tm, Yb). Ceram Int 43(17):15645–15653
Frost RL, Čejka J, Weier M, Martens WN (2006) A Raman spectroscopic study of the uranyl phosphate mineral parsonsite. J Raman Spectrosc 37(9):879–891
Ghosh R, Sarkar R (2016) Synthesis and characterization of sintered beta-tricalcium phosphate: A comparative study on the effect of preparation route. Mater Sci Eng C 67:345–352
Höppe HA (2009) Recent developments in the field of inorganic phosphors. Angew Chem Int Ed 48(20):3572–3582
Jia Y, Pang R, Li H, Sun W, Fu J, Jiang L, Zhang S, Su Q, Li C, Liu R-S (2015) Single-phased white-light-emitting Ca4(PO4)2O: Ce3+, Eu2+ phosphors based on energy transfer. Dalton Trans 44(25):11399–11407
Jillavenkatesa A, Condrate R Sr (1998) The infrared and Raman spectra of β- and α-tricalcium phosphate (Ca3(PO4)2). Spectrosc Lett 31(8):1619–1634
Kannan S, Goetz-Neunhoeffer F, Neubauer J, Pina S, Torres P, Ferreira J (2010) Synthesis and structural characterization of strontium-and magnesium-co-substituted β-tricalcium phosphate. Acta Biomater 6(2):571–576
Kaur P, Khanna A (2021) Structural, thermal and light emission properties of Eu, Sm, Dy, Er and Mn doped CaAl2O4 and SrAl2O4. Ceram Int 47(10):14655–14664
Kaur P, Khanna A, Fábián M (2020a) Effects of annealing temperature on structural and photoluminescence properties of Eu, Dy and Sm doped CaWO4 nanoparticles. Ceram Int 46(17):27262–27274
Kaur P, Kumar R, Davessar S, Khanna A (2020b) Structural and optical characterization of Er-doped CaMoO4 down-converting phosphors. Acta Crystallograph Sect B Struct Sci Crystal Eng Mater 76(5):926–938
Khan SA, Hao Z, Wei-Wei H, Hao L-Y, Xu X, Khan NZ, Agathopoulos S (2017) Novel single-phase full-color emitting Ba9Lu2Si6O24: Ce3+/Mn2+/Tb3+ phosphors for white LED applications. J Mater Sci 52(18):10927–10937
Kumar JS, Pavani K, Babu AM, Giri NK, Rai S, Moorthy LR (2010) Fluorescence characteristics of Dy3+ ions in calcium fluoroborate glasses. J Lumin 130(10):1916–1923
Lecointre A, Bessière A, Viana B, Benhamou RA, Gourier D (2010) Thermally stimulated luminescence of Ca3(PO4)2 and Ca9Ln(PO4)7 (Ln= Pr, Eu, Tb, Dy, Ho, Er, Lu). Radiat Meas 45(3–6):273–276
Lian H, Hou Z, Shang M, Geng D, Zhang Y, Lin J (2013) Rare-earth ions doped phosphors for improving efficiencies of solar cells. Energy 57:270–283
Liu Y, Liu Y, Liu G, Dong X, Wang J (2015) Up/down conversion, tunable photoluminescence and energy transfer properties of NaLa(WO4)2: Er3+, Eu3+ phosphors. RSC Adv 5(119):97995–98003
Maheshwary, Singh B, Singh R (2015) Color tuning in thermally stable Sm3+-activated CaWO4 nanophosphors. New J Chem 39(6):4494–4507
Malik C, Kaur N, Singh B, Pandey A (2020) Luminescence properties of tricalcium phosphate doped with dysprosium. Appl Radiat Isot 158:109062
Meenambal R, Poojar P, Geethanath S, Sanjeevi K (2017) Structural insights in Dy3+-doped β-Tricalcium phosphate and its multimodal imaging characteristics. J Am Ceram Soc 100(5):1831–1841
Pawade V, Zanwar A, Birmod R, Dhoble S, Koao L (2017) Optical and bandgap study of rare-earth doped phosphate phosphor. J Mater Sci Mater Electron 28(21):16306–16313
Prasad M, Mondal M, Mukhopadhyay L, Pattnaik S, Rai VK (2021) Photoluminescence investigation in tungstate based materials. Mater Today Proc 46:6388–6391
Pushpendra, Kunchala RK, Kalia R, Naidu BS (2020) Excitation dependent visible and NIR photoluminescence properties of Er3+, Yb3+ co-doped NaBi(MoO4)2 nanomaterials. RSC Adv 10(25):14525–14530
Shang H-B, Chen F, Wu J, Qi C, Lu B-Q, Chen X, Zhu Y-J (2014) Multifunctional biodegradable terbium-doped calcium phosphate nanoparticles: facile preparation, pH-sensitive drug release and in vitro bioimaging. RSC Adv 4(95):53122–53129
Torres P, Abrantes J, Kaushal A, Pina S, Döbelin N, Bohner M, Ferreira J (2016) Influence of Mg-doping, calcium pyrophosphate impurities and cooling rate on the allotropic α↔β-tricalcium phosphate phase transformations. J Eur Ceram Soc 36(3):817–827
Wang F, Chen J-j, Mao Z-y, Wang D-J (2015) Phase evolution induced color-tunable emission for Calcium-phosphate based phosphors. Mater Lett 152:98–101
Wang Y, Liu X, Jing L, Niu P (2016) Tunable white light and energy transfer of Dy3+ and Eu3+ doped Y2Mo4O15 phosphors. Ceram Int 42(11):13004–13010
Yashima M, Sakai A (2003) High-temperature neutron powder diffraction study of the structural phase transition between α and α′ phases in tricalcium phosphate Ca3(PO4)2. Chem Phys Lett 372(5–6):779–783
Yashima M, Sakai A, Kamiyama T, Hoshikawa A (2003) Crystal structure analysis of β-tricalcium phosphate Ca3(PO4)2 by neutron powder diffraction. J Solid State Chem 175(2):272–277
Zhang Y, Gong W, Yu J, Pang H, Song Q, Ning G (2015) A new single-phase white-light-emitting CaWO4: Dy3+ phosphor: synthesis, luminescence and energy transfer. RSC Adv 5(77):62527–62533
Zhou W, Han J, Pan F, Zhang J, Xie Q, Lian S, Yu L, Wang J (2014) Preparation and luminescence properties of Eu2+ and Mn2+ coactivated tricalcium phosphate phosphors. J Am Ceram Soc 97(11):3631–3635
Acknowledgements
Atul Khanna acknowledges Department of Science and Technology and Council of Scientific and Industrial Research, India, for research grants.
Author information
Authors and Affiliations
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Author’s conribution
AK conceptualized the research problem and planned the experiments. S prepared and characterized the samples. PK and SS carried out DSC measurements on the samples. The data analysis was done by S and AK. The manuscript writing and editing was done by S and AK.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Saloni, Kaur, P., Sharma, S. et al. Synthesis and characterization of Sm, Dy and Er-doped β-Ca3(PO4)2 phosphors. Chem. Pap. 77, 795–803 (2023). https://doi.org/10.1007/s11696-022-02497-2
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11696-022-02497-2