Eliminating disorderly A sites: Significantly enhanced external quantum efficiency of Bi³⁺ luminescence in double perovskite phosphor

Abstract

Highly efficient inorganic phosphors activated with Bi³⁺ are increasingly needed due to their fascinating multicolor luminescence and versatile applications. Nevertheless, achieving high external quantum efficiency (EQE) is challenging. Here, ordering A sites in double perovskite structure develops a highly efficient Bi³⁺-activated A₂BB'O₆ phosphor, in which the EQE is boosted by 3.9 times. The transformation from the disordered A sites in Ca₂LaNbO₆ (CLNO) to the ordered A sites in Ca₂YNbO₆ (CYNO) occurs via the full substitution of Y³⁺ for La³⁺. Bi³⁺ activators occupy the A and B sites, which is confirmed by direct aberration-corrected transmission electron microscopy (AC-TEM) proof, as well as the theoretical and spectral proofs. Subsequently, a representative CYNO:1%Bi³⁺ product is practically applied, exhibiting superior fluorescence thermometer (S_r-max = 3.12% K⁻¹ at 473 K), high color rendering index lighting (R_a = 91), and accurate latent fingerprint detecting performances. This work invigorates the progress of Bi³⁺-activated phosphors with high EQE for versatile utilizations.

Keywords

bismuth / double perovskite / luminescence efficiency / multifunctional applications / occupancy modulation

References

[1] Xiang YF, Yang L, Liao CY, et al. Thermometric properties of Na₂Y₂TeB₂O₁₀:Tb³⁺ green phosphor based on fluorescence/excitation intensity ratio. J Adv Ceram. 2023; 12(4): 848-860.

[2] Hua YB, Yu JS, Li L, Hua Y. Rare-earth and transition metal ion single-/co-doped double-perovskite tantalate phosphors: validation of suitability for versatile applications. J Adv Ceram. 2023; 12(5): 954-971.

[3] Liang P, Zhang HS, Wang JF, et al. A novel yellow phosphor(Ba₃Sc₂(BO₃)₄:Eu²⁺) suitable for full-spectrum lighting, featuring tunable photoluminescence and enhanced luminous thermal stability. Laser Photonics Rev. 2025; 19:2402304.

[4] Zhang Q, Yang ZT, Zhou XQ, et al. Achieving high quantum efficiency in Mn⁵⁺ activated phosphors for NIR-II deep bioimaging application. Laser Photonics Rev. 2024; 18:2400781.

[5] Hariyani S, Sójka M, Setlur A, et al. A guide to comprehensive phosphor discovery for solid-state lighting. Nat Rev Mater. 2023; 8(11): 759−775.

[6] Gao ZH, Fu FY, Niu LL, et al. Emission-tunable Ba₂Y_1−xSc_xNbO₆:Bi³⁺ (0 ≤ x ≤ 1.0) phosphors for white LEDs. J Rare Earths. 2022; 40(12): 1819-1826.

[7] Xia WQ, Du F, Zhao QQ, et al. Realization of narrow-band blue emission based on structurally engineering-designed Bi³⁺-doped phosphors. JOL. 2025; 277:120896.

[8] Wu S, Liu Q, Xiong PX, et al. Single Bi³⁺ ultrabroadband white luminescence in double perovskite via crystal lattice engineering toward light-emitting diode applications. Adv Opt Mater. 2022; 10(11):2102842.

[9] Xia WQ, Zhao QQ, Du LS, et al. Realization and optimization of bismuth-activated Ba₃Ga₂O₅Cl₂ yellow phosphor for high-quality white LEDs. Chem Eng J. 2024; 484:149723.

[10] Liu DJ, Yun XH, Li GG, et al. Enhanced cyan emission and optical tuning of Ca₃Ga₄O₉:Bi³⁺ for high-quality full-spectrum white light-emitting diodes. Adv Opt Mater. 2020; 8:2001037.

[11] Liu RZ, Wu HY, Wang SW, et al. Ba₃LuGa₂O_7.5:Bi³⁺ phosphors with potential application in full-spectrum WLEDs and temperature sensing. J Mater Chem C. 2023; 11(7): 2653-2663.

[12] Wu QS, Li YY, Wang YJ, et al. A novel narrow-band blue-emitting phosphor of Bi³⁺-activated Sr₃Lu₂Ge₃O₁₂ based on a highly symmetrical crystal structure used for WLEDs and FEDs. Chem Eng J. 2020; 401:126130.

[13] Ye SS, Liu H, Wang YJ, et al. Design of a bismuth-activated narrow-band cyan phosphor for use in white light emitting diodes and field emission displays. ACS Sustain Chem Eng. 2020; 8(49): 18187-18195.

[14] Fei HH, Jing BL, Han J, et al. Bi³⁺ yellow luminescence, and high quantum efficiency of Ba₃SbAl₃Ge₂O₁₄:Bi³⁺ phosphor for white light-emitting diodes. Inorg Chem Front. 2024; 11:2616.

[15] Zhang HZ, Li H, Li JP, et al. Absolutely structural disorder boosting bandwidth toward full-spectrum white light from single occupancy of activator. Adv Mater. 2024; 36(48):2412099.

[16] Li XH, Zhou L, Tang Q, et al. Broad-band emission of A₃B′B′′₂O₉ complex perovskites (A = Ba, Sr; B′ = Zn; B′′ = Ta, Nb) realized by structural variations of the B site order–disorder. J Mater Chem C. 2018; 6(46):12566.

[17] Wen DW, Liu HM, Gao Y, et al. Disorder–order conversion-induced enhancement of thermal stability of pyroxene near-infrared phosphors for light-emitting diodes. Angew Chem Int Ed. 2022; 61:e202204411.

[18] Solana-Madruga E, Arévalo-López Á, Dos Santos-García A, et al. Double cation order in the high-pressure perovskites MnRMnSbO₆. Angew Chem Int Ed. 2016; 55(32): 9340-9344.

[19] Chen SG, Du YF, Zhao HT, et al. Disorder–order transition and metal-to-metal charge transfer induced rare orangish-red emission in Bi³⁺-activated double perovskite phosphors. Chem Eng J. 2024; 502:157928.

[20] Liu Q, Li XB, Zhan B, et al. Structure evolution and delayed quenching of the double perovskite NaLaMgWO₆:Eu³⁺ phosphor for white LEDs. Ceram Int. 2016; 42(14): 15294-15300.

[21] Lin B, Yang C, Ma RB, et al. Double perovskite CaSrMSbO₆ (M = La, Gd, Y): Bi³⁺ phosphors for multifunctional application. Ceram Int. 2024; 50(23): 51139-51151.

[22] Niu SJ, Wang P, Zhang D, et al. Unlocking the multifunctional applications of a novel bismuth-activated high-brightness orange-emitting phosphor through lattice engineering. Chem Eng J. 2025; 505:159228.

[23] Gao PX, Li Q, Zhou C, et al. High-efficiency continuous-luminescence-controllable performance and antithermal quenching in Bi³⁺-activated phosphors. Inorg Chem. 2022; 61(33): 13104-13114.

[24] Peng S, Deng LW, Ma JY, et al. Crystal structures, bond characteristics, and microwave dielectric properties of Ca₂LaNbO₆ ceramics. J Eur Ceram Soc. 2024; 889:161671.

[25] Shi YZ, Cui RR, Gong XY, et al. A novel red phosphor Ca₂YNbO₆:Eu³⁺ for WLEDs. Luminescence. 2022; 37(8): 1343-1351.

[26] Li H, Niu YF, Liu CL, et al. Remarkable role of B site regulation on a highly heat-resistant double-perovskite phosphor with versatile NIR utilizations. Chem Eng J. 2025; 510:161635.

[27] Lyu TS, Dorenbos P. Charge carrier trapping management in Bi³⁺ and lanthanides doped Li(Sc,Lu)GeO₄ for x-ray imaging, anti-counterfeiting, and force recording. Appl Phys Rev. 2024; 11(1):11415.

[28] Zhang ZH, Jin Y, Xie HY, et al. Bi³⁺/K⁺-activated calcium lutetium gallate and the devices under UV chip for warm WLED and plant lighting. ACS Appl Mater Interfaces. 2025; 17(15): 22882-22891.

[29] Shang RP, Lyu ZY, Liu KJ, et al. Novel GdAlGe₂O₇:Bi³⁺,Eu³⁺ phosphors with anti-thermal quenching properties for high sensitivity optical temperature measurement. Mater Today Phys. 2024; 43:101391.

[30] Jiao MM, He ZF, Chen JY, et al. Theoretically guided development of excitation-wavelength-dependent multifunctional phosphor based on gallium vacancy perturbation. ACS Appl Mater Interfaces. 2025; 17(4): 6577-6587.

[31] Su K, Mei LF, Liu ZQ, et al. Customized Cr³⁺-doped disordered structures enhance optical manometry. Adv Funct Mater. 2025; 35(48):2507563.

[32] Zhao D, Li YN, Zhang RJ, et al. Tuning emission from greenish to blue via chemical composition modulation in solid solutions (Sr_1−yCa_y)₂Sb₂O₇:Bi³⁺ under near-UV light excitation. ACS Sustain Chem Eng. 2021; 9(22): 7569-7577.

[33] Zhang JN, Zhang LL, Liu F, et al. Smaller stokes shift induced highly efficient broadband near infrared garnet phosphor. Laser Photonics Rev. 2023; 17:2200586.

[34] Wang YI, Shang MM, Sun YX, et al. Small stokes shift and two-site occupation in the ANb₂O₆:Cr³⁺ (A = Zn/Mg) phosphors toward highly efficient ultra-broadband near-infrared emission for multifunctional applications. Adv Opt Mater. 2024; 12:2302611.

[35] Xia WX, Ye YL, Mao QA, et al. Engineering efficient blue and far-red dual-emitting phosphor for plant growth. Mater Today Chem. 2024; 36:10958.

[36] Yang H, Li P, Fu X, et al. A novel blue emitting phosphor LaScO₃:Bi³⁺ for white LEDs: high quantum efficiency, high color purity and excellent thermal stability. Mater Today Chem. 2022; 26:101050.

[37] Piao SQ, Wang YC, Zhou G, et al. Structural design and evolution of a novel Bi³⁺-doped narrow-band emission blue phosphor with excellent photoluminescence performance for wide color gamut Wled. J Mater Chem C. 2021; 9:14777.

[38] Chen XX, Pang R, Wang SW, et al. Design and synthesis of a novel blue-emitting CaNaSb₂O₆F:Bi³⁺ phosphor for optical temperature sensing. Dalton Trans. 2022; 51(17): 6908-6917.

[39] Lin HY, Jin Y, Fang F, Lin H, Chen H, Li Y. Superior temperature sensitive luminescent properties of BaY₂Al₂Ga₂GeO₁₂:Bi³⁺. Mater Today Commun. 2023; 37:107226.

[40] Dang PP, Liu D, Yun X, et al. Ultra-broadband cyan-to-orange emitting Ba_1+xSr_1−xGa₄O₈:Bi³⁺ phosphors: luminescence control and optical temperature sensing. J Mater Chem C. 2020; 8(5): 1598-1607.

[41] Xie HY, Jin Y, Zhang ZH, et al. Bi³⁺ ion enhanced self-activated blue phosphor Ba₃Ga₂O₆ for temperature sensing. Mater Today Commun. 2025; 42:111374.

[42] Ding JY, Li YW, Zhou XF, et al. A novel Bi³⁺-activated garnet phosphor with site-selected excitations and high temperature sensitivity. Ceram Int. 2022; 48(16): 23784-23792.

[43] Xue Y, Chen Y, Li G, et al. Bi³⁺-activated dual-wavelength emitting phosphors toward effective optical thermometry. Chin Chem Lett. 2024; 35(3):108447.

[44] Li GH, Yang QH, Wang RR, et al. Cation defects succeed in triggering super stability of narrow-band blue-emitting phosphors Ca₃Sc₂Si₃O₁₂:Bi³⁺ for backlighting display application. Ceram Int. 2023; 49(17): 28159-28166.

[45] Zuo CY, Chen RJ, Jiang XL, et al. Effect of ion occupancy and Li⁺ ion doping on luminescence characteristics of CaLaGaO₄:Bi³⁺ blue phosphor. Ceram Int. 2024; 50(17): 29580-29589.

[46] Yang YQ, He MX, Yao JJ, et al. Bi³⁺-activated high-efficiency full-spectrum WLEDs with broadband yellow-green emission Ba₂Gd₅B₅O₁₇:Bi³⁺ phosphor. Ceram Int. 2025; 51(18): 27023-27031.

[47] Ruan NN, Qiu QF, Wei XQ, et al. De novo green fluorescent protein chromophore-based probes for capturing latent fingerprints using a portable system. J Am Chem Soc. 2024; 146(3): 2072-2079.

[48] Girisha H, Manjunatha K, Wu SY, et al. Stimuli-responsive color-tunable BaLa₂ZnO₅:Bi³⁺ phosphor for the encryption and authentication of security patterns and latent fingerprint detection. Colloids Surf A Physicochem Eng Asp. 2023; 666:131219.

[49] Haider AA, Huang XT, Xie JT, et al. Dopant and excitation wavelength-sensitive emitting-color variation in thermostable Na₂Y₂TeO₄(BO₃)₂:Dy³⁺,Eu³⁺ phosphors for multifunctional security detections. Mater Today Chem. 2025; 45:102684.

[50] Huo XX, Zhang XS, Yu XY, et al. A novel cyan-emitting phosphor K₃Ca_0.3Y_0.7Si₂O₇:Ce³⁺ enables full-spectrum lighting and fingerprint detection via phase-structure alteration. Laser Photonics Rev. 2025;e01663.

[51] Liu GL, Qin R, Zhai DB, et al. Mn²⁺-activated NaYF₄:Yb, Er red-emitting nanophosphors for accurate latent fingerprint identification by an artificial intelligence program. J Alloys Compd. 2024; 1002:175269.

[52] Tian R, Wang YL, Li C, Zhu M-Q. Turn-on green fluorescence imaging for latent fingerprint applications. Mater Chem Front. 2022; 6(9): 1188.

[53] Dong XY, Niu XQ, Zhang ZY, Wei JS, Xiong HM. Red fluorescent carbon dot powder for accurate latent fingerprint identification using an artificial intelligence program. ACS Appl Mater Interfaces. 2020; 12(26): 29549-29555.

[54] Gao JB, Chen R, Wang LF, et al. Meticulously designed red emission carbon dots as efficient and stable luminescent species for rapid latent fingerprint recognition and light emitting diodes. Chem Eng J. 2024; 491:152121.

RIGHTS & PERMISSIONS

2026 The Author(s). InfoMat published by UESTC and John Wiley & Sons Australia, Ltd.