Novel Cr³⁺-activated far-red emitting phosphors with β-Ca₃(PO₄)₂-type structure for indoor plant cultivation

Abstract

Cr³⁺-activated far-red and near-infrared phosphors have drawn considerable attention owing to their adjustable emission wavelengths and wide applications. Herein, we reported a series of Cr³⁺-doped phosphors with β-Ca₃(PO₄)₂-type structure, of which Ca₉Ga(PO₄)₇:Cr³⁺ possessed the highest far-red emission intensity. At an excitation of 440 nm, the Ca₉Ga(PO₄)₇:Cr³⁺ phosphors exhibited a broad emission band ranging from 650 to 850 nm and peaking at 735 nm, and the broadband superimposed two sharp lines centering at 690 and 698 nm. The optimal sample Ca₉Ga_0.97(PO₄)₇:0.03Cr³⁺ had an internal quantum efficiency of 55.7%. The luminescence intensity of the Ca₉Ga_0.97(PO₄)₇:0.03Cr³⁺ phosphor obtained at 423 K could maintain 68.5% of that at room temperature, demonstrating its outstanding luminescence thermal stability. A phosphor-conversion light-emitting diode was fabricated, indicating that the Ca₉Ga(PO₄)₇:Cr³⁺ phosphor has potential applications in indoor plant cultivation.

Keywords

far-red / near-infrared / luminescence / trivalent chromium ion / plant cultivation

References

[1] Wang SY, Sun Q, Devakumar B, Sun LL, Liang J, Huang XY. Novel SrMg₂La₂W₂O₁₂:Mn⁴⁺ far-red phosphors with high quantum efficiency and thermal stability towards applications in indoor plant cultivation LEDs. RSC Adv., 2018, 8(53): 30191.

[2] Huang XY, Guo H. Finding a novel highly efficient Mn⁴⁺-activated Ca₃La₂W₂O₁₂ far-red emitting phosphor with excellent responsiveness to phytochrome P_FR: Towards indoor plant cultivation application. Dyes Pigm., 2018, 152, 36.

[3] Cao RP, Shi ZH, Quan GJ, Chen T, Guo SL, Hu ZF, Liu P. Preparation and luminescence properties of Li₂MgZrO₄: Mn⁴⁺ red phosphor for plant growth. J. Lumin., 2017, 188, 577.

[4] Liang J, Sun LL, Devakumar B, Wang SY, Sun Q, Guo H, Li B, Huang XY. Far-red-emitting double-perovskite CaLaMgSbO₆:Mn⁴⁺ phosphors with high photoluminescence efficiency and thermal stability for indoor plant cultivation LEDs. RSC Adv., 2018, 8(55): 31666.

[5] D. von Wettstein, S. Gough, and C.G. Kannangara, Chlorophyll biosynthesis, Plant Cell, 7(1995), No. 7, art. No. 1039.

[6] Tamulaitis G, Duchovskis P, Bliznikas Z, Breive K, Ulinskaite R, Brazaityte A, Novickovas A, Žukauskas A. High-power light-emitting diode based facility for plant cultivation. J. Phys. D: Appl. Phys., 2005, 38(17): 3182.

[7] Sharrock RA. The phytochrome red/far-red photoreceptor superfamily. Genome Biol., 2008, 9(8): 230.

[8] Li L, Pan YX, Huang Y, Huang SM, Wu MM. Dualemissions with energy transfer from the phosphor Ca₁₄Al₁₀ Zn₆O₃₅:Bi³⁺,Eu³⁺ for application in agricultural lighting. J. Alloys Compd., 2017, 724, 735.

[9] Chen JY, Guo CF, Yang Z, Li T, Zhao J. Li₂SrSiO₄: Ce³⁺, Pr³⁺ phosphor with blue, red, and near-infrared emissions used for plant growth LED. J. Am. Ceram. Soc., 2016, 99(1): 218.

[10] Chen ZL, Liu K, Yuan XY, Chen KX. Luminescence properties of nitrogen-rich Ca-SiAlON:Eu²⁺ phosphors prepared by freeze-drying assisted combustion synthesis. Int. J. Miner. Metall. Mater., 2020, 27(5): 687.

[11] Unal F, Kaya F, Kazmanli K. Synthesis, characterization and radioluminescence properties of erbium-doped yttria phosphors. Int. J. Miner. Metall. Mater., 2021, 28, 1.

[12] Liang J, Sun LL, Devakumar B, Wang SY, Sun Q, Guo H, Li B, Huang XY. Novel Mn⁴⁺-activated LiLaMgWO₆ far-red emitting phosphors: High photoluminescence efficiency, good thermal stability, and potential applications in plant cultivation LEDs. RSC Adv., 2018, 8(48): 27144.

[13] Franklin KA, Quail PH. Phytochrome functions in Arabidopsis development. J. Exp. Bot., 2010, 61(1): 11.

[14] L. Shi, S. Wang, Y.J. Han, Z.X. Ji, D. Ma, Z.F. Mu, Z.Y. Mao, D.J. Wang, Z.W. Zhang, and L. Liu, Sr₂LaSbO₆:Mn⁴⁺ far-red phosphor for plant cultivation: Synthesis, luminescence properties and emission enhancement by Al³⁺ inns, J. Lumin., 221(2020), art. No. 117091.

[15] Zhou ZW, Zheng JM, Shi R, Zhang NM, Chen JY, Zhang RY, Suo H, Goldys EM, Guo CF. Ab initio site occupancy and far-red emission of Mn⁴⁺ in cubic-phase La(MgTi)_1/2O₃ for plant cultivation. ACS Appl. Mater. Interfaces, 2017, 9(7): 6177.

[16] Li K, Lian HZ, van Deun R, Brik MG. A far-red-emitting NaMgLaTeO⁶:Mn⁴⁺ phosphor with perovskite structure for indoor plant growth. Dyes Pigm., 2019, 162, 214.

[17] Li K, van Deun R. Novel intense emission-tunable Li_1.5La_1.5WO₆:Mn⁴⁺,Nd³⁺,Yb³⁺ material with good luminescence thermal stability for potential applications in c-Si solar cells and plant-cultivation far-red-NIR LEDs. ACS Sustainable Chem. Eng., 2019, 7(19): 16284.

[18] Shi L, Han YJ, Wang HX, Shi DC, Geng XY, Zhang ZW. High-efficiency and thermally stable far-red emission of Mn⁴+ in double cubic perovskite Sr₉Y₂W₄O₂₄ for plant cultivation. J. Lumin., 2019, 208, 307.

[19] Zheng YJ, Zhang HM, Zhang HR, Xia ZG, Liu YL, Molokeev MS, Lei BF. Co-substitution in Ca_1−xY_xAl_12−x Mg_xO₁₉ phosphors: Local structure evolution, photoluminescence tuning and application for plant growth LEDs. J. Mater. Chem. C, 2018, 6(15): 4217.

[20] B.B. Su, M.Z. Li, E.H. Song, and Z.G. Xia, Sb³⁺-doping in cesium zinc halides single crystals enabling high-efficiency near-infrared emission, Adv. Funct. Mater., 31(2021), No. 40, art. No. 2105316.

[21] J.W. Qiao, G.J. Zhou, Y.Y. Zhou, Q.Y. Zhang, and Z.G. Xia, Divalent europium-doped near-infrared-emitting phosphor for light-emitting diodes, Nat. Commun., 10(2019), art. No. 5267.

[22] Fang MH, de Guzman GNA, Bao Z, Majewska N, Mahlik S, Grimberg M, Leniec G, Kaczmarek SM, Yang CW, Lu KM, Sheu HS, Hu SF, Liu RS. Ultra-high-efficiency near-infrared Ga₂O₃:Cr³⁺ phosphor and controlling of phytochrome. J. Mater. Chem. C, 2020, 8(32): 11013.

[23] Liu SQ, Wang ZZ, Cai H, Song Z, Liu QL. Highly efficient near-infrared phosphor LaMgGa₁₁O₁₉:Cr³⁺. Inorg. Chem. Front., 2020, 7(6): 1467.

[24] Huang DC, Zhu HM, Deng ZH, Yang HY, Hu J, Liang SS, Chen DJ, Ma E, Guo W. A highly efficient and thermally stable broadband Cr³⁺-activated double borate phosphor for near-infrared light-emitting diodes. J. Mater. Chem. C, 2021, 9(1): 164.

[25] Yao LQ, Shao QY, Han SY, Liang C, He JH, Jiang JQ. Enhancing near-infrared photoluminescence intensity and spectral properties in Yb³⁺ codoped LiScP₂O₇:Cr³⁺. Chem. Mater., 2020, 32(6): 2430. LinkOut]

[26] Zhou J, Xia ZG, Li X, Yun XY, Sun JY, Xu DH. A novel near-infrared LiGaW₂O₈:Yb³⁺,Cr³⁺ up-conversion phosphor with enhanced luminescence intensity based on Ho³⁺/Er³⁺ bridges. J. Mater. Chem. C, 2020, 8(35): 12189.

[27] Zeng HT, Zhou TL, Wang L, Xie RJ. Two-site occupation for exploring ultra-broadband near-infrared phosphor—double-perovskite La₂MgZrO₆:Cr³⁺. Chem. Mater., 2019, 31(14): 5245.

[28] X.F. Zhou, W.Y. Geng, J.Y. Li, Y.C. Wang, J.Y. Ding, and Y.H. Wang, An ultraviolet-visible and near-infrared-responded broadband NIR phosphor and its NIR spectroscopy application, Adv. Opt. Mater., 8(2020), No. 8, art. No. 1902003.

[29] X.X. Xu, Q.Y. Shao, L.Q. Yao, Y. Dong, and J.Q. Jiang, Highly efficient and thermally stable Cr³⁺-activated silicate phosphors for broadband near-infrared LED applications, Chem. Eng. J., 383(2020), art. No. 123108.

[30] Liu TY, Cai H, Mao N, Song Z, Liu QL. Efficient near-infrared pyroxene phosphor LiInGe₂O₆:Cr³⁺ for NIR spectroscopy application. J. Am. Ceram. Soc., 2021, 104(9): 4577.

[31] Zhang LL, Zhang S, Hao ZD, Zhang X, Pan GH, Luo YS, Wu HJ, Zhang JH. A high efficiency broad-band near-infrared Ca₂LuZr₂Al₃O₁₂:Cr³⁺ garnet phosphor for blue LED chips. J. Mater. Chem. C, 2018, 6(18): 4967.

[32] Cai H, Liu SQ, Song Z, Liu QL. Tuning luminescence from NIR-I to NIR-II in Cr³+-doped olivine phosphors for nondestructive analysis. J. Mater. Chem. C, 2021, 9(16): 5469.

[33] Zhao FY, Song Z, Zhao J, Liu QL. Double perovskite Cs₂AgInCl₆:Cr³⁺: Broadband and near-infrared luminescent materials. Inorg. Chem. Front., 2019, 6(12): 3621.

[34] Zhao FY, Cai H, Song Z, Liu QL. Structural confinement for Cr³⁺ activators toward efficient near-infrared phosphors with suppressed concentration quenching. Chem. Mater., 2021, 33(10): 3621.

[35] Zhou XQ, Qiao JW, Xia ZG. Learning from mineral structures toward new luminescence materials for light-emitting diode applications. Chem. Mater., 2021, 33(4): 1083.

[36] Roisnel T, Rodríquez-Carvajal J. WinPLOTR: A windows tool for powder diffraction pattern analysis. Mater. Sci. Forum, 2001, 378–381, 118.

[37] Chen MY, Xia ZG, Molokeev MS, Wang T, Liu QL. Tuning of photoluminescence and local structures of substituted cations in xSr₂Ca(PO₄)₂-(1−x))Ca₁₀Li(PO₄)₇:Eu²⁺ phosphors. Chem. Mater., 2017, 29(3): 1430.

[38] Yashima M, Sakai A, Kamiyama T, Hoshikawa A. Crystal structure analysis of β-tricalcium phosphate Ca₃(PO₄)₂ by neutron powder diffraction. J. Solid State Chem., 2003, 175(2): 272.

[39] Shannon RD. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. Sect. A, 1976, 32(5): 751.

[40] X.J. Kang, C.Y. Jia, H.C. Wang, Y.S. Xiao, and W. Lü, Structural, tunable emission and energy transfer of Ca₉In(PO₄)₇:Ce³⁺, Tb³⁺/Dy³⁺ phosphors, Mater. Chem. Phys., 240(2020), art. No. 122239.

[41] J. Zhou, X.M. Rong, P. Zhang, M.S. Molokeev, P.J. Wei, Q.L. Liu, X.W. Zhang, and Z.G. Xia, Manipulation of Bi³⁺/In³⁺ transmutation and Mn²⁺-doping effect on the structure and optical properties of double perovskite Cs₂NaBi_1−xIn_xCl₆, Adv. Opt. Mater., 7(2019), No. 8, art. No. 1801435.

[42] Malysa B, Meijerink A, Jüstel T. Temperature dependent Cr³+ photoluminescence in garnets of the type X₃Sc₂Ga₃O₁₂ (X = Lu, Y, Gd, La). J. Lumin., 2018, 202, 523.

[43] de Guzman GNA, Rajendran V, Bao Z, et al. Multi-site cation control of ultra-broadband near-infrared phosphors for application in light-emitting diodes. Inorg. Chem., 2020, 59(20): 15101.

[44] E.T. Basore, W.G. Xiao, X.F. Liu, J.H. Wu, and J.R. Qiu, Broadband near-infrared garnet phosphors with near-unity internal quantum efficiency, Adv. Opt. Mater., 8(2020), No. 12, art. No. 2000296.

[45] A. Zabiliūtė, S. Butkutė, A. Žukauskas, P. Vitta, and A. Kareiva, Sol-gel synthesized far-red chromium-doped garnet phosphors for phosphor-conversion light-emitting diodes that meet the photomorphogenetic needs of plants, Appl. Opt., 53(2014), No. 5, art. No. 907.

[46] Liu SQ, Cai H, Zhang SY, Song Z, Xia ZG, Liu QL. Site engineering strategy toward enhanced luminescence thermostability of a Cr³⁺-doped broadband NIR phosphor and its application. Mater. Chem. Front., 2021, 5(10): 3841.

[47] N. Mao, S.Q. Liu, Z. Song, Y. Yu, and Q.L. Liu, A broadband near-infrared phosphor Ca₃Y₂Ge₃O₁₂:Cr³⁺ with garnet structure, J. Alloys Compd., 863(2021), art. No. 158699.

[48] Henderson B, Imbusch GF. Optical Spectroscopy of Inorganic Solids, 1989, New York, Oxford University Press, 410

[49] M. Zhao, S.Q. Liu, H. Cai, F.Y. Zhao, Z. Song, and Q.L. Liu, Efficient broadband near-infrared phosphor Sr₂ScSbO₆:Cr³⁺ for solar-like lighting, China Mater, (2021). DOI: https://doi.org/10.1007/s40843-021-1785-6

[50] Trueba A, García-Lastra JM, Garcia-Fernandez P, Aramburu JA, Barriuso MT, Moreno M. Cr³⁺-doped fluorides and oxides: Role of internal fields and limitations of the Tanabe-Sugano approach. J. Phys. Chem. A, 2011, 115(46): 13399.

[51] Malysa B, Meijerink A, Jüstel T. Temperature dependent photoluminescence of Cr³+ doped Sr₈MgLa(PO₄)₇. Opt. Mater., 2018, 85, 341.