Switching Red to Green Upconversion Emission in Y₂O₃:Yb,Er Phosphor With La³⁺ Doping and Exploring Optical Thermometric Applications

Abstract

The upconversion (UC) phosphors in the series (100-x-y-z)Y₂O₃+xLa₂O₃+yYb₂O₃+zEr₂O₃ with x=0, 2, 4, 6, 8, and 10; y=3; z=0.1 were prepared by a combustion method to know the effect of La³⁺ doping on UC emission wavelengths and their intensities. The UC emission has been studied under the 980 nm (power 166 mW) and 932 nm (variable power) diode laser excitation. The phosphors show the green and red band emission pertaining to Er³⁺ ions. It has been observed that with a lower concentration of La³⁺ ions (up to 6 mol%), the emission intensity of both bands decreased, with the red band emission remaining dominant. However, as the doping concentration exceeded 6 mol%, the emission intensity of the green band increased significantly, leading to a switch from the red to green band emission at 10 mol% La³⁺ doping. The variation in the UC emission intensity with the pump power and temperature has been measured. The Er³⁺ and Yb³⁺ co-doped UC phosphor with 10 mol% La³⁺ doping can be used in optical thermometry with the maximum absolute sensitivity of 0.054 3 K⁻¹ at 303.15 K. The cubic crystal structure of prepared samples has been confirmed by a powder X-ray diffraction study. Doping of La³⁺ did not change the crystal structure, but the variation in lattice parameters was witnessed due to the modification of the crystal field by the La³⁺ ion. The absorbance of samples over the spectral range of 200 nm–1 100 nm has been measured by the diffuse reflectance spectroscopy. All samples exhibited large band gaps. The morphology of particles has been studied by the scanning electron microscopy. Commission International de I’Eclairage (CIE) color coordinates have been determined.

Keywords

Upconversion / optical thermometry / powder X-ray diffraction / combustion synthesis / yttrium oxide

References

[1] ShangY, HaoS, YangC, ChenG. Enhancing solar cell efficiency using photon upconversion materials. Nanomaterials, 2015, 5: 1782-1809.

[2] LiangG, WangH, ShiH, WangH, ZhuM, JingA, et al. . Recent progress in the development of upconversion nanomaterials in bioimaging and disease treatment. Journal of Nanobiotechnology, 2020, 18: 154.

[3] GhazyA, SafdarM, LastusaariM, SavinH, KarppinenM. Advances in upconversion enhanced solar cell performance. Solar Energy Materials and Solar Cells, 2021, 230: 111234.

[4] ZhangN, ZhangW, WuY, XieX, JiangR, LuoF, et al. . Upconversion nanoparticles anchored MnO₂ nanosheets for luminescence ‘turn on’ detecting hydrogen peroxide. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2023, 299: 122819.

[5] SarkW, WildJ, RathJ, MeijerinkA, SchroppR. Upconversion in solar cells. Nanoscale Research Letters, 2013, 8: 81.

[6] ZhouB, ShiB, JinD, LiuX. Controlling upconversion nanocrystals for emerging applications. Nature Nanotechnology, 2015, 10: 924-936.

[7] WilhelmS, HirschT, PattersonW, ScheucherE, MayrT, WolfbeisO. Multicolor upconversion nanoparticles for protein conjugation. Theranostics, 2013, 34239-248.

[8] MahataM, BaeH, LeeK. Upconversion luminescence sensitized pH-nanoprobes. Molecules, 2017, 22122064.

[9] RaiV, AraújoC, LedemiY, BureauB, PoulainM, MessaddeqY. Optical spectroscopy and upconversion luminescence in Nd³⁺ doped Ga₁₀Ge₂₅S₆₅ glass. Journal of Applied Physics, 2009, 10610103512.

[10] GuptaG, BalajiS, BiswasK, AnnapurnaK. Frequency upconversion mechanism in Ho³⁺/Yb³⁺-codoped TeO₂–TiO₂–La₂O₃ glasses. Applied Physics B, 2019, 125: 28.

[11] KrishnaiahK, HuesoJ, SureshK, VenkataiahG, RichardsB, JayasankarC. Spectroscopy and near infrared upconversion of Er³⁺-doped TZNT glasses. Journal of Luminescence, 2016, 169: 270-276.

[12] DeyR, KumariA, SoniA, RaiV. CaMoO₄:Ho³⁺–Yb³⁺–Mg²⁺ upconverting phosphor for application in lighting devices and optical temperature sensing. Sensors and Actuators B: Chemical, 2015, 210: 581-588.

[13] TyagiN, ReddyA, NagarajanR. KLaF₄:Er an efficient upconversion phosphor. Optical Materials, 2010, 33142-47.

[14] SunL, DongH, ZhangP, YanC. Upconversion of rare earth nanomaterials. Annual Review of Physical Chemistry, 2015, 66: 619-642.

[15] LiA, LuR, ZhaoY, YangJ, WangJ, ZhaoG. Electronic transition pathways in energy transfer processes for upconversion photoluminescence of Yb³⁺/Ho³⁺ co-doped NaLa(MoO₄)₂ microcrystals. Journal of Luminescence, 2022, 248: 118962.

[16] WangX, ZhuQ, LiJ, HuZ, ZhuG, WangC. La₂O₂S:Tm/Yb as a novel phosphor for highly pure near-infrared upconversion luminescence. Scripta Materialia, 2018, 149: 121-124.

[17] PassuelloT, PiccinelliF, PedroniM, BettinelliM, MangiariniF, NaccacheR, et al. . White light upconversion of nanocrystalline Er/Tm/Yb doped tetragonal Gd₄O₃F₆. Optical Materials, 2011, 334643-646.

[18] WangG, QinW, ZhangJ, ZhangJ, WangY, CaoC, et al. . Enhancement of violet and ultraviolet upconversion emissions in Yb³⁺/Er³⁺-codoped YF₃ nanocrystals. Optical Materials, 2008, 312296-299.

[19] QinF, ZhengY, YuY, ZhengC, LiangH, ZhangZ, et al. . Ultraviolet upconversion luminescence in Er³⁺-doped Y₂O₃ excited by 532 nm CW compact solid-state laser. Journal of Luminescence, 2009, 129101137-1139.

[20] DeyR, RaiV, PandeyA. Green upconversion emission in Nd³⁺–Yb³⁺–Zn²⁺:Y₂O₃ phosphor. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2012, 99: 288-291.

[21] DevarajuluG, KumarB, BabuP, DhananjayaM, BakN, PasupuletiK, et al. . Sensitization effect of Nd³⁺ ions on Yb³⁺/Nd³⁺ co-doped oxyfluoride glasses and study of their optical, fluorescence, and upconversion abilities for visible laser and NIR amplifier applications. Ceramics International, 2022, 481724550-24559.

[22] LiangH, ZhengY, ChenG, WuL, ZhangZ, CaoW. Enhancement of upconversion luminescence of Y₂O₃:Er³⁺ nanocrystals by codoping Li⁺–Zn²⁺. Journal of Alloys and Compounds, 2011, 5092409-413.

[23] BaiY, YangK, WangY, ZhangX, SongY. Enhancement of the upconversion photoluminescence intensity in Li⁺ and Er³⁺ codoped Y₂O₃ nanocrystals. Optics Communications, 2008, 281102930-2932.

[24] FanT, LüJ. Enhanced 1.5 µm and green upconversion emissions in Y₂O₃:Er³⁺ nanoparticles codoped with Li⁺ ions. Optics Communications, 2013, 300: 5-7.

[25] DeG, QinW, ZhangJ, ZhangJ, WangY, CaoC, et al. . Effect of OH⁻ on the upconversion luminescent efficiency of Y₂O₃:Yb³⁺, Er³⁺ nanostructures. Solid State Communications, 2006, 1379483-487.

[26] DeG, QinW, ZhangJ, ZhangJ, WangY, CaoC, et al. . Upconversion luminescence properties of Y₂O₃:Yb³⁺,Er³⁺ nanostructures. Journal of Luminescence, 2006, 119–120: 258-263.

[27] PerrellaR, SantosD, PoirierG, GóesM, RibeiroS, SchiavonM, et al. . Er³⁺-doped Y₂O₃ obtained by polymeric precursor: synthesis, structure and upconversion emission properties. Journal of Luminescence, 2014, 149: 333-340.

[28] QinX, ZhouG, YangH, YangY, ZhangJ, WangS. Synthesis and upconversion luminescence of monodispersed, submicron-sized Er³⁺:Y₂O₃ spherical phosphors. Journal of Alloys and Compounds, 2010, 4931–2672-677.

[29] XieN, PeiM, MingC. Strong upconversion emissions in Er³⁺ doped Y₂O₃ nanocrystals prepared using a ‘PMMA-polymerization’ route. Optik, 2018, 174: 125-128.

[30] SantosL, MartinsJ, LimaK, GomesL, MeloM, TedescoA, et al. . In vitro assays and nanothermometry studies of infrared-to-visible upconversion of nanocrystalline Er³⁺, Yb³⁺ co-doped Y₂O₃ nanoparticles for theranostic applications. Physica B: Condensed Matter, 2022, 624: 413447.

[31] SunM, LiuJ, NieL. Effect of Zn²⁺ and Li⁺ ions doped on microstructure and upconversion luminescence of Y₂O₃:Er³⁺–Yb³⁺ thin films. Journal of Alloys and Compounds, 2020, 816: 152575.

[32] XuB, SongC, SongJ, HuangR, LinS, LinZ, et al. . Effect of Y:Zn ratio on microstructure and emission of Er³⁺/Yb³⁺ codoped Y₂O₃–ZnO ceramic phosphors. Journal of Rare Earths, 2023, 41121883-1894.

[33] DwivediA, SrivastavaM, DwivediA, SrivastavaA, MishraA, SrivastavaS K. Synthesis and enhanced photoluminescence properties of red emitting divalent ion (Ca²⁺) doped Eu:Y₂O₃ nanophosphors for optoelectronic applications. Journal of Rare Earths, 2022, 4081187-1198.

[34] YangM, SuiY, WangS, WangX, WangY, LüS, et al. . Effects of Bi³⁺ doping on the optical properties of Er³⁺:Y₂O₃. Journal of Alloys and Compounds, 2011, 5093827-830.

[35] LiuH, LiuY, ZuoC, GaoG, LiuD, WangT, et al. . Spectroscopic characterization and temperature-dependent upconversion behavior of Er³⁺/Gd³⁺ co-doped Y₂O₃. Journal of Luminescence, 2019, 207: 177-181.

[36] UpadhyayM, KumarK. Gd³⁺ ion induced UV upconversion emission and temperature sensing in Tm³⁺/Yb³⁺:Y₂O₃ phosphor. Journal of Rare Earths, 2023, 4191295-1301.

[37] HuS, YuanM, HuangH, SongC, HanK, CuiW, et al. . Effect of Ce dopant on upconversion and temperature sensing performances in homogeneous ultra small Y₂O₃:Yb³⁺/Ho³⁺ nanoparticles through flame aerosol synthesis. Ceramic International, 2023, 49710953-10960.

[38] SarkarM I, KumarK. Combustion synthesized La₂O₃:Er³⁺/Yb³⁺ phosphor for simultaneous upconversion emission and photo-thermal signal generation. Surfaces and Interfaces, 2024, 44: 103776.

[39] ChenG, LeiR, XuS, WangH, ZhaoS, HuangF, et al. . Effect of Li⁺ ion concentration on upconversion emission and temperature sensing behavior of La₂O₃:Er³⁺ phosphors. Journal of Rare Earths, 2018, 362119-124.

[40] MizunoM, RouanetA, YamadaT, NoguchiT. Phase diagram of the system La₂O₃–Y₂O₃ at high temperatures. Journal of the Ceramic Association, Japan, 1976, 84971342-348.

[41] DouC, YangQ, HuX, XuJ. Cooperative up-conversion luminescence of ytterbium doped yttrium lanthanum oxide transparent ceramic. Optical Communications, 2008, 2814692-695.

[42] LeiR, WangH, XuS, TianY, YangQ. Combustion synthesis and enhanced 1.5 µm emission in Y₂O₃:Er³⁺ powders codoped with La³⁺ ions. Journal of Rare Earths, 2016, 342125-129.

[43] WangN, ZhangX, BaiZ. Fabrication of highly transparent Er³⁺, Yb³⁺:Y₂O₃ ceramics with La₂O₃/ZrO₂ as sintering additives and the near-infrared and upconversion luminescence properties. Journal of Alloys and Compounds, 2020, 842: 155932.

[44] PandeyA, RaiV K, DeyR, KumarK. Enriched green upconversion emission in combustion synthesized Y₂O₃:Ho³⁺–Yb³⁺ phosphor. Materials Chemistry and Physics, 2013, 1392–3483-488.

[45] RaiV, DeyR, KumarK. White upconversion emission in Y₂O₃:Er^3+–Tm^3+–Yb³⁺ phosphor. Materials Research Bulletin, 2013, 4862232-2236.

[46] ChudinovychO, AndrievskayaO, BogatyryovaJ, KovylyaevV, BykovO. Phase equilibria in the La₂O₃–Y₂O₃–Nd₂O₃ system at 150 0 °C. Journal of the European Ceramic Society, 2021, 41136606-6616.

[47] KumarL, KumarP, NarayanA, KarM. Rietveld analysis of XRD patterns of different sizes of nanocrystalline cobalt ferrite. International Nano Letters, 2013, 381-12

[48] CullityBElements of X-ray Diffraction, 1978Reading, USAAddison-Wesley102-110

[49] MuleyG. Growth and characterization of pure and Cd-doped zinc tris-thiourea sulphate (ZTS) single crystals. Journal of Electronic Materials, 2014, 43: 439-446.

[50] SinghV, RaiV K, ShameryK, NordmannJ, HaaseM. NIR to visible upconversion in Er³⁺/Yb³⁺ co-doped CaYAl3O7 phosphor obtained by solution combustion process. Journal of Luminescence, 2011, 131122679-2682.

[51] JakutisJ, GomesL, AmancioC, KassabL, MartinelliJ, WetterN. Increased Er³⁺ upconversion in tellurite fibers and glasses by co-doping with Yb³⁺. Optical Materials, 2010, 331107-111.

[52] ZhouY, XiaoY, TangF, ZhaoB, LvS. Large negative thermal quenching of upconversion luminescence through selective excitation in a YAG:Yb/Er transparent ceramics. Journal of Luminescence, 2023, 263: 120075.

[53] XuL, ZhengH, PangT, MaoJ. Multicolor luminescence of hexagonal NaYF₄:Yb³⁺/Ho³⁺/Ce³⁺ microcrystals with tunable morphology under 940 nm excitation for temperature-responsive anti-counterfeiting. Journal of Rare Earths, 2022, 403406-414.

[54] YadavR, VermaR, KaurG, RaiS. Change in structural morphology on addition of ZnO and its effect on fluorescence of Yb³⁺/Er³⁺ doped Y₂O₃. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013, 103: 216-221.

[55] DuP, LuoL, YueQ, LiW. The simultaneous realization of high- and low-temperature thermometry in Er³⁺/Yb³⁺-codoped Y₂O₃ nanoparticles. Materials Letters, 2015, 143: 209-211.

[56] WangX, WangY, Marques-HuesoJ, YanX. Improving optical temperature sensing performance of Er³⁺ doped Y₂O₃ microtubes via co-doping and controlling excitation power. Scientific Reports, 2017, 7: 758.

[57] RaiV, PandeyA, DeyR. Photoluminescence study of Y₂O₃:Er³⁺–Eu³⁺–Yb³⁺ phosphor for lighting and sensing applications. Journal of Applied Physics, 2013, 1138083104.

[58] YangX, WuZ, YangZ, ZhaoX, SongC, YuanM, et al. . Flame-made Y₂O₃:Yb³⁺/Er³⁺ upconversion nanoparticles: mass production synthesis, multicolor tuning and thermal sensing studies. Journal of Alloys and Compounds, 2021, 854: 157078.

RIGHTS & PERMISSIONS

The Author(s)