Abstract
UV-to-red downshifting phosphors such as BaAl2O4:Eu3+ find broad range of application in sensors, displays, and in solid-state lighting, yet new synthetic routes to improve their luminescence are envisaged. In this regard, herein, it is introduced two new methods to synthesize this environmentally friendly BaAl2O4:Eu3+, by an adapted sol–gel route and a modified Pechini synthesis. Additionally, a systematic study was carried out about the Eu3+ doping concentration and charge compensation effects on the structural, morphological and spectroscopic features. Both routes enabled high-crystalline and nanostructured phosphors displaying optic bandgap near to 4.4 eV, although the sol–gel route also led to low amounts of BaCO3 spurious phase. Upon UV (250 nm) excitation, all Eu3+-doped samples emit red light displaying high emission color purity, characteristic of the 5D0 → 7F0-4 electronic transitions of Eu3+. The Pechini method led to the highest intrinsic emission quantum yield (85% for the 3%-doped sample). Eu3+ replaces Ba2+ within the BaAl2O4 lattice, but in the sol–gel-derived samples, the dopant may also replace Ba2+ into the BaCO3 spurious phase, confirming that the Pechini route is the best one to optimize the luminescence and structure of the phosphor.
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Moscardini SB, Sverzut L, Massarotto WL, Nassar EJ, Rocha LA (2020) Multi-color emission from lanthanide ions doped into niobium oxide. J Mater Sci Mater Electron 31:5241–5252. https://doi.org/10.1007/s10854-020-03084-5
Kim CH, Kwon IE, Park CH, Hwang YJ, Bae HS, Yu BY, Pyun CH, Hong GY (2000) Phosphors for plasma display panels. J Alloys Compd 311:33–39. https://doi.org/10.1016/S0925-8388(00)00856-2
Edgar A (2004–2021) Luminescent Materials. In: Kasap S, Capper P (eds) Springer Handbook of Electronic and Photonic Materials. Springer, Cham., pp. 1–1.
Bispo-Jr AG, Lima SAM, Pires AM (2018) Energy transfer between terbium and europium ions in barium orthosilicate phosphors obtained from sol-gel route. J Lumin 199:372–378. https://doi.org/10.1016/j.jlumin.2018.03.057
Wang L, Xie RJ, Suehiro T, Takeda T, Hirosaki N (2018) Down-Conversion nitride materials for solid state lighting: recent advances and perspectives. Chem Rev 118:1951–2009. https://doi.org/10.1021/acs.chemrev.7b00284
Bispo-Jr AG, Lima SAM, Carlos LD, Ferreira RAS, Pires AM (2020) Red-emitting coatings for multifunctional UV/Red emitting LEDs applied in plant circadian rhythm control. ECS J Solid State Sci Technol 9:016008. https://doi.org/10.1149/2.0122001JSS
Bispo-Jr AG, Saraiva LF, Lima SAM, Pires AM, Davolos MR (2021) Recent prospects on phosphor-converted LEDs for lighting, displays, phototherapy, and indoor farming. J Lumin 237:118167. https://doi.org/10.1016/j.jlumin.2021.118167
Carlos LD, Ferreira RAS, Bermudez VZ, Julian-Lopez B, Escribano P (2011) Progress on lanthanide-based organic–inorganic hybrid phosphors. Chem Soc Rev 40:536–549. https://doi.org/10.1039/c0cs00069h
Kaur J, Jaykumar B, Dubey V, Shrivastava R, Suryanarayana NS (2015) Optical properties of rare earth-doped barium aluminate synthesized by different methods-A Review. Res Chem Intermed 41:2317–2343. https://doi.org/10.1007/s11164-013-1349-z
Shimokawa Y, Sakaida S, Iwata S, Inoue K, Honda S, Iwamoto Y (2015) Synthesis and characterization of Eu3+ doped CaZrO3-based perovskite type phosphors part II: PL properties related to the two different dominant Eu3+ substitution sites. J Lumin 157:113–118. https://doi.org/10.1016/j.jlumin.2014.08.042
Wiglusz RJ, Grzyb T (2013) Sol–gel synthesis of micro and nanocrystalline BaAl2O4:Eu3+ powders and their luminescence properties. Opt Mater 36:539–545. https://doi.org/10.1016/j.optmat.2013.10.029
Binnemans K (2015) Interpretation of europium(III) spectra. Coord Chem Rev 295:1–45. https://doi.org/10.1016/j.ccr.2015.02.015
Nakauchi D, Okada G, Kato T, Kawaguchi N, Yanagida T (2020) Crystal growth and scintillation properties of Eu:BaAl2O4 crystals. Radiat Meas 135:106365. https://doi.org/10.1016/j.radmeas.2020.106365
Raia RK, Upadhyay AK, Kher RS, Dhoble SJ, Mehta M (2011) BaAl2O4: Eu - Phosphor for mechanoluminescence dosimetry. Radiat Meas 46:1393–1396. https://doi.org/10.1016/j.radmeas.2011.08.016
Chatterjee R, Saha S, Sen D, Panigrahi K, Ghorai UK, Das GC, Chattopadhyay KK (2018) Neutralizing the Charge Imbalance Problem in Eu3+-Activated BaAl2O4 Nanophosphors: Theoretical Insights and Experimental Validation Considering K+ Codoping. ACS Omega 3:788–800. https://doi.org/10.1021/acsomega.7b01525
Marí B, Singh KC, Verma N, Mollar M, Jindal J (2015) Luminescence Properties of the Eu2+/Eu3+ activated barium aluminate phosphors with Gd3+ concentration variation. Trans Ind Ceram Soc 74:1–5. https://doi.org/10.1080/0371750X.2015.1082932
Grzeta B, Lutzenkirchen-Hecht D, Vrankic M, Bosnar S, Saric A, Takahashi M, Petrov D, Biscan M (2018) Environment of the Eu3+ ion within nanocrystalline Eu-Doped BaAl2O4: correlation of X-ray diffraction, mossbauer spectroscopy, X-ray absorption spectroscopy, and photoluminescence investigations. Inorg Chem 57:1744–1756. https://doi.org/10.1021/acs.inorgchem.7b02322
Rezende MVS, Montes PJR, Andrade AB, Macedo ZS, Valerio MEG (2016) Mechanism of X-ray excited optical luminescence (XEOL) in europium doped BaAl2O4 phosphor. Phys Chem Chem Phys 18:17646. https://doi.org/10.1039/C6CP01183G
Rezende MVS, Montes PJ, Valerio MEG, Jackson RA (2012) The optical properties of Eu3+ doped BaAl2O4: a computational and spectroscopic study. Opt Mater 34:1434–1439. https://doi.org/10.1016/j.optmat.2012.02.050
Rezende MVS, Andrade AB, William C, Paschoal A (2018) Co-doping effect of Ca2+ on luminescent properties of BaAl2O4:Eu3+ phosphors. J Electron Spectros Relat Phenomena 225:62–65. https://doi.org/10.1016/j.elspec.2018.04.002
Araujo RM, Mattos EFS, Júnior BFS, Rezende MVS, Valerio MEG, Jackson RA (2021) Optical spectroscopy study of Eu-doped ions in BaAl2O4 phosphors. J Lumin 236:118011. https://doi.org/10.1016/j.jlumin.2021.118011
Gomes MA, Andrade AB, Rezende MVS, Valerio MEG (2017) Production of Eu-doped BaAl2O4 at low temperature via an alternative solgel method using PVA as complexing agent. J Phys Chem Solids 102:74–78. https://doi.org/10.1016/j.jpcs.2016.11.010
Verma N, Marí B, Singh KC, Jindal J, Yadav S, Mittal A (2019) Enhanced luminescence by tunable coupling of Eu3+ and Tb3+ in ZnAl2O4:Eu3+:Tb3+ phosphor synthesized by solution combustion method. J Aust Ceram Soc 55:179–185. https://doi.org/10.1007/s41779-018-0223-2
Kumar N, Marí B, Jindal J, Mittal KK, Maken S (2019) Near ultraviolet excited down conversion Eu and Er co-doped CaAl2O4 color tunable nano-phosphors: Structural, morphological and photolumniscent characteristics. Mater Today Proc 19:646–649. https://doi.org/10.1016/j.matpr.2019.07.747
Bispo-Jr AG, Ceccato DA, Lima SAM, Pires AM (2017) Red phosphor based on Eu3+-isoelectronically doped Ba2SiO4 obtained via sol–gel route for solid state lightning. RSC Adv 7:53752. https://doi.org/10.1039/C7RA10494D
Oliveira NA, Bispo-Jr AG, Shinohara GMM, Lima SAM, Pires AM (2021) The influence of the complexing agent on the luminescence of multicolor-emitting Y2O3:Eu3+, Er3+, Yb3+ phosphors obtained by the Pechini’s method. Mater Chem Phys 257:123840. https://doi.org/10.1016/j.matchemphys.2020.123840
Aflaki M, Davar F (2016) Synthesis, luminescence and photocatalyst properties of zirconita nanosheets by modified Pechini method. J Mol Liq 221:1071–1079. https://doi.org/10.1016/j.molliq.2016.06.067
Loghman-Estarki MR, Razavi RS, Edris H, Pourbafrany M, Jamali H, Ghasemi R, Lifetime of new SYSZ thermal barrier coatings produced by plasma spraying method under thermal shock test and high temperature treatment. Ceram Int 40:1405–1414. https://doi.org/10.1016/j.ceramint.2013.07.023
Patterson AL (1939) The Scherrer formula for X-ray particle size determination. Phys Rev 56:978. https://doi.org/10.1103/PhysRev.56.978
Murphy AB (2007) Band-gap determination from diffuse reflectance measurements of semiconductor films, and application to photoelectrochemicalwater-splitting. Sol Energy Mater Sol Cells 91:1326–1337. https://doi.org/10.1016/j.solmat.2007.05.005
Kubelka P, Munk F (1931) EinBeitragzurOptik der Farbanstriche. Z Tech Phys 15:593–601
Duarte AP, Gressier M, Menu M, Dexpert-Ghys J, Caiut JMA, Ribeiro SJL (2012) Structural and luminescence properties of silica-based hybrids containing new Silylated-Diketonato Europium(III) Complex. J Phys Chem C 116:505–515. https://doi.org/10.1021/jp210338t
Weber MJ, (2002) Handbook of Optical Materials, first ed., CRC Press.
Kodaira C, Brito HF, Malta OL, Serra OA (2003) Luminescence and energy transfer of the europium (III) tungstate obtained via the Pechini method. J Lumin 101:11–21. https://doi.org/10.1016/S0022-2313(02)00384-8
Bispo-Jr AG, Lima SAM, Lanfredi S, Praxedes FR, Pires AM (2019) Tunable blue-green emission and energy transfer properties in Ba2SiO4:Tb3+ obtained from sol-gel method. J Lumin 214:116604. https://doi.org/10.1016/j.jlumin.2019.116604
Phule PP, Risbud SH (1980) Low-temperature synthesis and processing of electronic materials in the BaO-TiO2 system. J Mater Sci 25:1169–2118. https://doi.org/10.1007/BF00585422
López MDCB, Fourlaris G, Rand B, Riley FL (1999) Characterization of barium titanate powders: Barium carbonate identification. J Am Ceram Soc 82:1777–1786. https://doi.org/10.1111/j.1151-2916.1999.tb01999.x
Andrade-Espinosa G, Escobar-Barrios V, Rangel-Mendez R (2010) Synthesis and characterization of silica xerogels obtained via fast sol–gel process. Colloid Polym Sci 288:1697–1704. https://doi.org/10.1007/s00396-010-2311-x
Brinker CJ, Scherrer GW (1990) Sol-gel science, the physics and chemistry of sol-gel processing. Academic, San Diego
Perullini M, Jobbagy M, Bilmes SA, Torriani IL, Candal R (2011) Effect of synthesis conditions on the microstructure of TEOS derived silica hydrogels synthesized by the alcohol-free sol–gel route. J Sol-Gel Sci Technol 59:174–180. https://doi.org/10.1007/s10971-011-2478-8
Amaral FA, Santana LK, Campos IO, Fagundes WS, Xavier FFS, Canobre SC, Pechini Synthesis of Nanostructured Li1.05M0.02Mn1.98O4 (M = Al3+ or Ga3+). Mater Res 18:250–259. doi: https://doi.org/10.1590/1516-1439.361514
Loghman-Estarki MR, Hajizadeh-Oghaz M, Edris H, RS, (2013) Comparative studies on synthesis of nanocrystalline Sc2O3–Y2O3 doped zirconia (SYDZ) and YSZ solid solution via modified and classic Pechini method. Cryst Eng Comm 15:5898–5909. https://doi.org/10.1039/C3CE40288F
Macedo WC, Bispo-Jr AG, Rocha KO, Albas AES, Pires AM, Teixeira SR, Longo E (2020) Photoluminescence of Eu3+-doped CaZrO3 red-emitting phosphors synthesized via microwave-assisted hydrothermal method. Mater Today Commun 24:100966. https://doi.org/10.1016/j.mtcomm.2020.100966
Hiratsuka RS, Santili CV, Pulcinelli SH, (1995) O processo sol-gel:uma visão físico-química. Quim. Nova 18:171–180. https://doi.org/10.21577/0100-4042.20170623
Oliveira HFN, Trinca RB, Gushikem Y (2009) Síntese e estudo de ortossilicatos de zinco luminescentes com aplicação da técnica sol-gel. Quim Nova 32:1346. https://doi.org/10.1590/S0100-40422009000500045
Zhang LW, Wang L, Zhu YF, Synthesis and performance of BaAl2O4 with a wide spectral range of optical absorption. Adv Funct Mater 17:3781–3790. doi: https://doi.org/10.1002/adfm.200700506
Carnall, WT, Crosswhite, H, Crosswhite, HM (1978) Energy level structure and transition probabilities in the spectra of the trivalent lanthanides in LaF2. USDOE Office of Science, United States.
Tanner PA (2013) Some misconceptions concerning the electronic spectra of tri-positive europium and cerium. Chem Soc Rev 42:5090–5101. https://doi.org/10.1039/C3CS60033E
Tanner PA, Yeung YY, Ning L (2013) What Factors Affect the 5D0 Energy of Eu3+? An investigation of nephelauxetic effects. J Phys Chem A 117:2771–2781. https://doi.org/10.1021/jp400247r
Moura RT, Neto ANC, Longo RL, Malta OL (2016) On the calculation and interpretation of covalency in the intensity parameters of 4f–4f transitions in Eu3+ complexes based on the chemical bond overlap polarizability. J Lumin 170:420. https://doi.org/10.1016/j.jlumin.2015.08.016
Uitert LG (1967) Characterization of energy transfer interactions between rare earth ions. J Electrochem Soc 14:1048–1053. https://doi.org/10.1149/1.2424184
Ting L, Qingyu M, Wenjun S (2015) Luminescent properties of Eu3+ doped NaY(WO4)2 nanophosphors prepared by molten salt method. J Rare Earths 33:915–921. https://doi.org/10.1016/S1002-0721(14)60505-6
Grzyb T, Wecławiak M, Rozowska J, Lis S (2013) Structural and spectroscopic properties of YOF:Eu3+ nanocrystals. J Alloy Compd 576:345–349. https://doi.org/10.1016/j.jallcom.2013.05.207
Som S, Das S, Dutta S, Visser HG, Pandey MK, Kumar P, Dubey RK, Sharma SK (2015) Synthesis of strong red emitting Y2O3:Eu3+ phosphor by potential chemical routes: comparative investigations on the structural evolutions, photometric properties and Judd-Ofelt analysis. RSC Adv 5:70887–70898. https://doi.org/10.1039/C5RA13247A
Bispo-Jr AG, Shinohara GMM, Pires AM, Cardoso CX (2018) Red phosphor based on Eu3+-doped Y2(MoO4)3 incorporated with Au NPs synthesized via Pechini’s method. Opt Mater 84:137–145. https://doi.org/10.1016/j.optmat.2018.06.023
Acknowledgements
Authors are thankful to the Brazilian agencies CNPq (Grant No. 304003/2018-2) and FAPESP for the financial research support. Laboratório de Microscopia Eletrônica de Varredura (FCT-UNESP, Prof. Dr. N. Alves), Laboratório de Materiais Cerâmicos (LaMaC, FCT-UNESP), and Laboratório Multiusuário de Análises Químicas (IQ/UNESP – Araraquara).
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Oliveira, N.A., Bispo-Jr, A.G., Lima, S.A.M. et al. Red-emitting BaAl2O4:Eu3+ synthesized via Pechini and sol–gel routes: a comparison of luminescence and structure. J Mater Sci 57, 170–184 (2022). https://doi.org/10.1007/s10853-021-06633-3
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DOI: https://doi.org/10.1007/s10853-021-06633-3