Efficient Multicolor and White Photoluminescence in Erbium- and Holmium-Incorporated Cs₂NaInCl₆:Sb³⁺ Double Perovskites

Abstract

Inorganic lead-free halide perovskites with a broadband emission of self-trapped excitons (STEs) have attracted great attention in lighting applications. However, it remains a fundamental challenge to expand the display color gamut because it is difficult to individually tune the emitting proportion at different wavelengths. Herein, we employ a doping route to incorporate Sb 3+ , Er 3+ , and Ho 3+ ions into the Cs 2 NaInCl 6 , which enables multicolor emissions with narrow full width at half-maxima and high photoluminescence quantum yields (PLQYs). The blue emission (445 nm) originates from STEs in the [SbCl 6 ] 3− octahedrons, while the narrowband green (550 nm) and red (655 nm) emissions are mainly derived from the Er 3+ and Ho 3+ ions, respectively. An efficient energy transfer between multiple luminescent centers is the key point to achieve such an efficient and tunable emission. By controlling the lanthanide doping level, the emission color can be systematically modulated, and cold 10401 K (0.278, 0.286) to warm 4608 K (0.347, 0.298) adjustable white-light emission (PLQY of ∼70%) can be achieved successfully. The results provide inspiration for the material design of lead-free perovskites with efficient and tunable light-emitting properties for optoelectronic applications.

Emission Mechanism of Self-Trapped Excitons in Sb3+-Doped All-Inorganic Metal-Halide Perovskites

“…24,26 However, the identical PLE with Sb 3+doped samples and the non-feed ones cannot originate from bare In 3+ ions, which have no s-electrons. 24,26,33 It is worth noting that Sb 3+ and In 3+ ions have remarkable similarities of chemical characteristics, valence states, and ionic radii, which may make it challenging to adequately separate them. ICP tests were performed on InCl 3 reagents purchased from four different sources (Sigma-Aldrich, 3A Materials, Alfa, and Aladdin).…”

“…Doping or alloying an s -electron dopant in bare B-cation sites is one of the most effective strategies for achieving efficient broadband emission. , Among the diverse s -electron dopants, the Sb 3+ ion has attracted increasing research interest. − Light emission with high PL quantum yield (PLQY) and color diversity has been achieved in various Sb 3+ -doped inorganic metal-halide hosts, such as blue-emitting Cs 2 NaInCl 6 : Sb 3+ (PLQY ∼84%), green-emitting Cs 2 KInCl 6 : Sb 3+ (PLQY ∼80%), Rb 3 InCl 6 : Sb 3+ (PLQY ∼90%), and Rb 4 CdCl 6 : Sb 3+ (PLQY ∼70%), yellow-emitting Cs 2 InCl 5 ·H 2 O: Sb 3+ (PLQY ∼96%), and red-emitting Cs 2 ZnCl 4 : Sb 3+ (PLQY ∼80%) and Cs 2 SnCl 6 : Sb 3+ (PLQY ∼37%) . Furthermore, by co-doping Sb 3+ with other dopants, such as Bi 3+ , Mn 2+ , or Ln 3+ , white light composed of blue and yellow dual emissions can be generated, which exhibits a high color render index and adjustable correlated color temperature. ,− However, a consensus on the underlying mechanism of the broadband emission in Sb 3+ -doped full-inorganic perovskites has not been reached.…”

“…The shapes of the PL spectra were not obviously different, indicating that the light emission could be from the same radiative transition process, irrespective of C or A band excitation. It is still under debate whether the STE states originage from Sb 3+ doping centers or perovskite hosts. − The debate is aroused by the bewildering low-intensity fluorescence seen in samples without Sb 3+ feeding that exhibit profiles similar to those of samples that have been doped with Sb 3+ . , However, the identical PLE with Sb 3+ -doped samples and the non-feed ones cannot originate from bare In 3+ ions, which have no s -electrons. ,, It is worth noting that Sb 3+ and In 3+ ions have remarkable similarities of chemical characteristics, valence states, and ionic radii, which may make it challenging to adequately separate them. ICP tests were performed on InCl 3 reagents purchased from four different sources (Sigma-Aldrich, 3A Materials, Alfa, and Aladdin).…”

Lead-free broadband orange-emitting zero-dimensional Sb3+-doped indium-based organic–inorganic metal halides

“…Lead-free indium-based metal halide materials have attracted extensive attention in recent years due to their good stability under environmental conditions and excellent photoelectric properties. [26][27][28][29][30][31][32][33][34][35][36][37][38][39][40][41][42]56,59 Moreover, the diversity of organic cations provides favourable conditions for the construction of organic-inorganic hybrid metal halide materials. In existing reports, zero-dimensional (0D) InCl 6 (C 4 H 10 SN) 4 ÁCl:Sb 3+ was produced by doping Sb 3+ into InCl 6 (C 4 H 10 SN) 4 ÁCl, which undergoes a significant enhancement of the emission peak at 550 nm (PLQY 90%).…”

Multicolor emission based on a N, N′—Disubstituted dihydrodibenzo [a, c] phenazine crown ether macrocycle

“…Supramolecular chemistry ( Lehn, 2005 ; Stoddart, 2012 ; Yan et al, 2012 ; Yeung and Yam, 2015 ; Kolesnichenko and Anslyn, 2017 ; Liu et al, 2017 ; Zhou et al, 2017 ; Gu et al, 2018 ; Jana et al, 2018 ; Xia et al, 2020 ; Gu and Lehn, 2021 ; Shen et al, 2021 ; Zhang et al, 2021 ; Zhang et al, 2022a ; Zhang et al, 2022b ; Huang et al, 2022 ) is undergoing tremendous speed of development, being important tools to modulate optical properties of chemical systems. Multicolor emission has been extensively investigated over the past decade due to its considerable application prospects in displays ( Nie et al, 2022 ; Zou et al, 2022 ), illumination ( Lee et al, 2016 ; Zhang et al, 2019a ; Gong et al, 2019 ), molecular/ion recognition ( Wang et al, 2012 ; Li et al, 2017 ; Li et al, 2018a ; Zhang et al, 2019b ; Chen et al, 2019 ; Sun et al, 2020 ), and biosensing ( Zhou et al, 2019 ; Dong et al, 2020 ; Yan et al, 2021 ; Du and Wei, 2022 ). Doping ( Nie et al, 2022 ) or hybridizing ( Cui et al, 2017 ) of different fluorophores are effective methods to generate multicolor emission, these systems usually requires more than a single excitation wavelength or stimulation methods to achieve multicolor emissions.…”