Efficient near-infrared emission in lanthanum ion doped double perovskite Cs₂NaScCl₆ via Cr³⁺ sensitization under visible light excitation

Abstract

Herein, we synthesized Cr³⁺/Ln³⁺ (Er³⁺, Tm³⁺)-codoped rare earth-based Cs₂NaScCl₆ double perovskite, and the near-infrared emission of Ln³⁺ can be excited by visible light through the energy transfer (ET) from Cr³⁺ to Ln³⁺. Moreover, there are two independent emission bands, which stems from ⁴T₂ → ⁴A₂ transition of Cr³⁺ (970 nm) and f-f transition of Ln³⁺ (1542 nm for Er³⁺ and 1220 nm for Tm³⁺), respectively. Particularly, both compounds have ultra-high photoluminescence quantum yield (PLQY) of 60% for 10%Cr³⁺/6%Er³⁺-codoped Cs₂NaScCl₆ (Er³⁺ emission: ~26%) and 68% for 10%Cr³⁺/4.5%Tm³⁺-codoped Cs₂NaScCl₆ (Tm³⁺ emission: ~56%), which can be attributed to the ultra-high ET efficiency from Cr³⁺ to Ln³⁺ and the similar ionic activity of Sc³⁺ and Ln³⁺ allowing more dopants enter the host lattice. Considering the excellent stability of the samples, we demonstrated Cr³⁺/Tm³⁺-codoped Cs₂NaScCl₆ in the applications of near-infrared imaging and night vision. Finally, we reported 10%Cr³⁺/4.5%Tm³⁺/9%Er³⁺-tridoped Cs₂NaScCl₆ and further applied it for optical thermometry.

Keywords

Cr ³⁺ sensitization / energy transfer / green light excitation / lead-free double perovskite / near-infrared emission

References

[1] Cao L, Jia X, Gan W, et al. Strong self-trapped exciton emission and highly efficient near-infrared luminescence in Sb³⁺-Yb^3+-Co-doped Cs₂AgInCl₆ double perovskite. Adv Funt Mater. 2023;33(13):2212135.

[2] Su B, Li M, Song E, Xia Z. Sb³⁺-doping in cesium zinc halides single crystals enabling high-efficiency near-infrared emission. Adv Funt Mater. 2021;31(40):2105316.

[3] Liu BM, Guo XX, Huang L, et al. A super-broadband NIR dual-emitting Mg₂SnO₄:Cr³⁺Ni²⁺ phosphor for ratiometric phosphor-converted NIR light source applications. Adv Mater Technol. 2022;8(4):2201181.

[4] Arfin H, Kaur J, Sheikh T, Chakraborty S, Nag A. Bi³⁺-Er³⁺ and Bi³⁺-Yb³⁺ codoped Cs₂AgInCl₆ double perovskite near-infrared emitters. Angew Chem Int Edit. 2020;59(28):11307-11311.

[5] Li X, Shen X, Lu M, et al. Wide-coverage and efficient NIR emission from single-component nanophosphors through shaping multiple metal-halide packages. Angew Chem Int Edit. 2023;62(14):e202217832.

[6] Pei Y, Tu D, Li C, et al. Boosting near-infrared luminescence of lanthanide in Cs₂AgBiCl₆ double perovskites via breakdown of the local site symmetry. Angew Chem Int Edit. 2022;61(30):e202205276.

[7] Peng H, Wang X, Huang W, et al. Efficient tunable visible and near-infrared emission in Sb³⁺/Sm³⁺-codoped Cs₂NaLuCl₆ for near-infrared light-emitting diode, triple-mode fluorescence anti-counterfeiting and information encryption. Chinese Chem Lett. 2024;109462.

[8] Matulionyte M, Skripka A, Ramos-Guerra A, Benayas A, Vetrone F. The coming of age of neodymium: redefining its role in rare earth doped nanoparticles. Chem Rev. 2022;123(1):515-554.

[9] Zeng H, Zhou T, Wang L, Xie R-J. Two-site occupation for exploring ultra-broadband near-infrared phosphor-double-perovskite La₂MgZrO₆:Cr³⁺. Chem Mater. 2019;31(14):5245-5253.

[10] Zhang W, Zheng W, Li L, et al. Dual-band-tunable white-light emission from Bi³⁺/Te⁴⁺ emitters in perovskite-derivative Cs₂SnCl₆ microcrystals. Angew Chem Int Edit. 2022;61(9):e202116085.

[11] Liu Y, Wu Y, Juan Z, et al. Efficient stable and tunable cold/warm white light from lead-free halide double perovskites Cs₂Zr_1-xTe_xCl₆. Adv Opt Mater. 2021;9(24):2100815.

[12] Shen X, Wang Z, Tang C, et al. Near-infrared LEDs based on quantum cutting-activated electroluminescence of ytterbium ions. Nano Lett. 2023;23(1):82-90.

[13] Liu S, Lin Y, Yan D. Hydrogen-bond organized 2D metal-organic microsheets: direct ultralong phosphorescence and color-tunable optical waveguides. Sci Bull. 2022;67(20):2076-2084.

[14] Tian Y, Peng H, Wei Q, et al. Moisture-induced reversible structure conversion of zero-dimensional organic cuprous bromide hybrids for multiple photoluminescent anti-counterfeiting information encryption and rewritable luminescent paper. Chem Eng J. 2023;458:141436.

[15] Zhou B, Qi Z, Dai M, Xing C, Yan D. Ultralow-loss optical waveguides through balancing deep-blue TADF and orange room temperature phosphorescence in hybrid antimony halide microstructures. Angew Chem Int Edit. 2023;62(39):e202309913.

[16] Cong M, Zhang Q, Yang B, et al. Bright triplet self-trapped excitons to dopant energy transfer in halide double-perovskite nanocrystals. Nano Lett. 2021;21(20):8671-8678.

[17] Zeng Z, Sun M, Zhang S, et al. Rare-earth-based perovskite Cs₂AgScCl₆:Bi for strong full visible spectrum emission. Adv Funt Mater. 2022;32(32):2204780.

[18] Chen B, Guo Y, Wang Y, et al. Multiexcitonic emission in zero-dimensional Cs₂ZrCl₆:Sb³⁺ perovskite crystals. J Am Chem Soc. 2021;143(42):17599-17606.

[19] Dang P, Zhang G, Yang W, Lian H, Li G, Lin J. Red-NIR luminescence in rare-earth and manganese ions codoped Cs₄CdBi₂Cl₁₂ vacancy-ordered quadruple perovskites. Chem Mater. 2023;35(4):1640-1650.

[20] Saikia S, Joshi A, Arfin H, Badola S, Saha S, Nag A. Sb³⁺-Er³⁺-codoped Cs₂NaInCl₆ for emitting blue and short-wave infrared radiation. Angew Chem Int Edit. 2022;61(32):e202201628.

[21] Sun J, Zheng W, Huang P, et al. Efficient near-infrared luminescence in lanthanide-doped vacancy-ordered double perovskite Cs₂ZrCl₆ phosphors via Te⁴⁺ sensitization. Angew Chem Int Edit. 2022;61(26):e202201993.

[22] Wang Y, Bai S, Liang H, et al. Lanthanide ions doped rare earth-based double perovskite single crystals for light-emitting diodes. J Alloy Compd. 2023;934:167952.

[23] Wang Y, Bai S, Sun J, et al. Highly efficient visible and near-infrared luminescence of Sb³⁺ Tm³⁺ co-doped Cs₂NaYCl₆ lead-free double perovskite and light emitting diodes. J Alloy Compd. 2023;947:169602.

[24] Chen D, Zhang X, Wei J, et al. Simultaneous enhancement of near infrared luminescence and stability of Cs₂AgInCl₆:Cr³⁺ double perovskite single crystals enabled by a Yb³⁺ dopant. Inorg Chem Front. 2022;9(18):4695-4704.

[25] Zhao F, Song Z, Zhao J, Liu Q. Double perovskite Cs₂AgInCl₆:Cr³⁺: broadband and near-infrared luminescent materials. Inorg Chem Front. 2019;6(12):3621-3628.

[26] Lin Q, Wang Q, Liao M, et al. Trivalent chromium ions doped fluorides with both broad emission bandwidth and excellent luminescence thermal stability. ACS Appl Mater Interfaces. 2021;13(15):18274-18282.

[27] Gan W, Cao L, Gu S, Lian H, Xia Z, Wang J. Broad-band sensitization in Cr³⁺-Er³⁺ co-doped Cs₂AgInCl₆ double perovskites with 1.5 μm near-infrared emission. Chem Mater. 2023;35(14):5291-5299.

[28] Luo J, Wang X, Li S, et al. Efficient and stable emission of warm-white light from lead-free halide double perovskites. Nature. 2018;563(7732):541-545.

[29] Huang W, Peng H, Wei Q, et al. Tunable efficient white emission in holmium doped double perovskites Cs₂KInCl₆ via antimony sensitization. Adv Opt Mater. 2023;11(10):2203103.

[30] Zhu F, Gao Y, Zhao C, Pi J, Qiu J. Achieving broadband NIR-I to NIR-II emission in an all-inorganic halide double-perovskite Cs₂NaYCl₆:Cr³⁺ phosphor for night vision imaging. ACS Appl Mater Interfaces. 2023;15(33):39550-39558.

[31] Suo H, Wang Y, Zhao X. Rapid nondestructive detection enabled by an ultra-broadband NIR pc-LED. Laser Photonics Rev. 2022;16(7):2200012.

[32] Zhang R, Wang Z, Xu X, et al. All-inorganic rare-earth halide double perovskite single crystals with highly efficient photoluminescence. Adv Opt Mater. 2021;9(19):2100689.

[33] Zhang A, Liu Y, Liu G, Xia Z. Dopant and compositional modulation triggered broadband and tunable near-infrared emission in Cs₂Ag_1-xNaxInCl₆:Cr³⁺ nanocrystals. Chem Mater. 2022;34(7):3006-3012.

[34] Wang J, Han X, Zhou Y, et al. Ion substitution dtrategy toward high-efficiency near-infrared photoluminescence of Cs₂KIn_1-yAl_yF₆:Cr³⁺ solid solutions. J Phys Chem Lett. 2023;14(6):1371-1378.

[35] Song E, Ming H, Zhou Y, et al. Cr³⁺-doped Sc-based fluoride enabling highly efficient near infrared luminescence: a case study of K₂NaScF₆:Cr³⁺. Laser Photonics Rev. 2020;15(2):2000410.

[36] Wu Z, Han X, Zhou Y, et al. Efficient broadband near-infrared luminescence of Cr³⁺ doped fluoride K₂NaInF₆ and its NIR-LED application toward veins imaging. Chem Eng J. 2022;427:131740.

[37] Wu Z, Han X, Wang J, et al. Highly efficient and thermally stable broadband near-infrared emitting fluoride Cs₂KGaF₆:Cr³⁺ for multiple LED applications. J Mater Chem C. 2022;10(28):10292-10301.

[38] Gan W, Liu BM, Huang L, et al. Manganese ion-sensitized near-infrared light in Cs₂NaBi_1-xEr_xCl₆ lead-free double perovskite. Adv Opt Mater. 2022;60(2):540-542.

[39] Wang Y, Dang P, Qiu L, et al. Multimode luminescence tailoring and improvement of Cs₂NaHoCl₆ cryolite crystals via Sb³⁺/Yb³⁺ alloying for versatile photoelectric applications. Angew Chem Int Edit. 2023;62(45):e202311699.

[40] Nie J, Li H, Fang S, et al. Efficient red photoluminescence in holmium-doped Cs₂NaInCl₆ double perovskite. Cell Reports Rys Sci. 2022;3(4):100820.

[41] Li X, Wang D, Zhong Y, et al. Halide double perovskite nanocrystals doped with rare-earth ions for multifunctional applications. Adv Sci. 2023;10(20):e2207571.

RIGHTS & PERMISSIONS

2024 The Authors. EcoMat published by The Hong Kong Polytechnic University and John Wiley & Sons Australia, Ltd.