Multifunctional Phosphor with High-Efficient Near-Infrared Emission Based on Antimony-Zinc Halides.

Metal halide-based broadband near-infrared (NIR) luminescent materials face problems such as complicated preparation, high cost, low photoluminescence quantum yield, and high excitation energy. Here, incorporating Sb3+ and Br- into (C20H20P)2ZnCl4 crystals allowed for the achievement of efficient broadband near-infrared emission under 400 nm excitation while maintaining satisfactory environmental and thermal stability. The compounds exhibit a broad range of emission bands from 550 to 1050 nm, with a photoluminescence quantum yield of 93.57%. This is a groundbreaking achievement for organic-inorganic hybrid metal halide NIR luminescent materials. The near-infrared emission is suggested to originate from [SbX5]2-, as supported by the femtosecond transient absorption spectra and density-functional theory calculations. This phosphor-based NIR LEDs successfully demonstrate potential applications in night vision, medical imaging, information encryption, and anticounterfeiting.

Sb3+-Doped Indium-Based Metal Halide (Gua)3InCl6 with Efficient Yellow Emission.

In recent years, low-dimensional organic-inorganic hybrid metal halides (OIHMHs) have shown excellent photophysical properties due to their quantum structure, adjustable energy levels, and energy transfer between inorganic and organic components, which have attracted extensive attention from researchers. Herein, we synthesize a zero-dimensional (0D) OIHMH, Sb3+:(Gua)3InCl6, by introducing Sb3+ into (Gua)3InCl6, which undergoes a significant enhancement of the emission peak at 580 nm with the photoluminescence quantum yield (PLQY) boosted from 17.86 to 95.72% when excited at 340 nm. This boost in photoluminescence of the doped sample was studied by combining ultrafast femtosecond transient absorption, temperature-dependent photoluminescence (PL) spectra, and density functional theory (DFT) calculation, revealing the process of self-trapped exciton (STE) recombination to emit light at both Sb and In sites in this 0D structure simultaneously. This material with the lowest dark STE level at the In site for emission in the undoped sample can amazingly yield very strong emission in the doped sample, which has never been observed before. Finally, we tested its application in a photoelectric device. This work not only helps to gain a deeper understanding of the formation of STEs in In-based halides but also plays a certain guiding role in the design of new luminescent materials.

Tunable dual-emission of Sb3+, Ho3+Co-doped Cs2NaScCl6single crystals for light-emitting diodes.

Lead-free halide double perovskites are considered as one of the most promising materials in optoelectronic devices, such as solar cells, photodetectors, and light-emitting diodes (LEDs), due to their environmental friendliness and chemical stability. However, the extremely low photoluminescence quantum yield (PLQY) of self-trapped excitons (STEs) emission from lead-free halide double perovskites impedes their applications. Herein, Sb3+ions were doped into rare-earth-based double perovskite Cs2NaScCl6single crystals (SCs), resulting in a large enhancement of PLQY from 12.57% to 87.37%. Moreover, by co-doping Sb3+and Ho3+into Cs2NaScCl6SCs, the emission color can be tuned from blue to red, due to an efficient energy transfer from STEs to Ho3+ions. Finally, the synthesized sample was used in multicolor LED, which exhibited excellent stability and optical properties. This work not only provides a new strategy for improving the optical properties of Cs2NaScCl6SCs, but also suggests its potential application in multicolor LEDs.

Nickel(II)-Doped Lead-Free Halide Crystals Exhibiting Highly Efficient Tunable Blue-Emitting out of Antiferromagnetic Ni-Ni Coupling.

Metal halide crystals are widely used in optoelectronic fields due to their excellent optical properties. The hunt for a lead-free halide semiconductor with superior optical performance is a particularly fascinating topic in order to avoid the toxicity of lead. Here, we incorporate Ni2+ into a series of halide nanocrystals (NCs) through solution-phase synthesis. By modifying the A-site and varying the halide compositions, we successfully achieved significant tunability of the blue emission of the Ni2+-doped AX (A = K+, Rb+, NH2CH = NH2+ (FA), CH3NH3+ (MA); X = Br, I) NCs, ranging from 375 to 490 nm, due to the antiferromagnetic polaron (AMP), which is in contrast with the excitonic magnetic polarons (EMP) from those with ferromagnetic (FM) coupling between transition metal ions in similar compounds. This work shows that Ni2+-doped halide crystals could become a typical example providing AMP excitation as the optional emission centers for use in light emitting devices.

Luminescence and Mechanism of Mn2+ Substitution in Cs7Cd3Br13 with Two Types of Coordination Number.

Cadmium-based perovskite materials as promising optoelectronic materials have been widely explored, but there are still some special microscopic interaction-dependent properties not fully understood. Here, we successfully synthesized Cs7(Cd1-XMnX)3Br13 crystal by a simple hydrothermal method. In Cs7Cd3Br13 crystals with their intrinsic self-trapped exciton (STE) emission, Cd2+ ions stay in both different coordination sites, and partial replacement of Cd2+ with Mn2+ can modify their luminescence properties significantly. The luminescence peak position of the doped sample was adjusted from 610 nm in the undoped sample to 577 nm in the doped one by the combination of STE and Mn d-d transition, with enhanced photoluminescence quantum yield (PLQY) of ∼50% at a Mn precursor ratio of 40%. Their magnetic responses occur from the coexisting ferromagnetic (FM) and antiferromagnetic (AFM) coupling of Mn pairs in four and six coordination sites, modifying its whole emission profile. This material is valuable for studying the structure-optical properties and finding applications in optoelectronic devices.

H2O-NH4+-Induced Emission Modulation in Sb3+-Doped (NH4)2InCl5·H2O.

Lead-based metal halide perovskites have received widespread attention for their promising application prospects in the field of lighting and display due to their excellent optical properties. However, the toxicity of lead may hinder their further commercial application. Herein, a zero-dimensional (0D) metal halide (NH4)2InCl5·H2O with an orthorhombic structure and the Pnma space group was produced. With doping with Sb3+, these products exhibit one highly efficient and wide yellow emission band (∼450-850 nm) in their photoluminescence (PL) spectra, which covers almost the entire visible spectral range at room temperature; however, they give two emission bands with long decay lifetimes (microseconds) at low temperature. Temperature-dependent steady-state PL, transient PL spectroscopy, temperature-dependent Raman spectra characterization, and theoretical band structure calculations confirm that the dual-band emission at low temperature originates from the dual vibronic levels of the self-trapped exciton (STE) in the hole-vibration state, whose vibration energy is related to the H2O-NH4+ connection in the valence band. This result proves that the vibronic state in STE formation involves both electrons and holes in the excited states, the opposite of this happens in the electron-vibration band in most perovskite halides. These results provide new insight into the luminescent mechanism of Sb3+ in halide perovskites, especially used for emission color modulation by the temperature-dependent electron- or hole-vibration processes.

Experimental Investigations on Subsequent Yield Surface of Pure Copper by Single-Sample and Multi-Sample Methods under Various Pre-Deformation.

Using copper thin-walled tubular specimens, the subsequent yield surfaces under pre-tension, pre-torsion and pre-combined tension-torsion are measured, where the single-sample and multi-sample methods are applied respectively to determine the yield stresses at specified offset strain. The rule and characteristics of the evolution of the subsequent yield surface are investigated. Under the conditions of different pre-strains, the influence of test point number, test sequence and specified offset strain on the measurement of subsequent yield surface and the concave phenomenon for measured yield surface are studied. Moreover, the feasibility and validity of the two methods are compared. The main conclusions are drawn as follows: (1) For the single or multi-sample method, the measured subsequent yield surfaces are remarkably different from cylindrical yield surfaces proposed by the classical plasticity theory; (2) there are apparent differences between the test results from the two kinds of methods: the multi-sample method is not influenced by the number of test points, test order and the cumulative effect of residual plastic strain resulting from the other test point, while those are very influential in the single-sample method; and (3) the measured subsequent yield surface may appear concave, which can be transformed to convex for single-sample method by changing the test sequence. However, for the multiple-sample method, the concave phenomenon will disappear when a larger offset strain is specified.