High-Performance Tunable Near-Infrared Emitters of Cr3+-Activated Garnet Phosphor Enabled by Chemical Unit Co-Substitution.

The escalating demand for portable near-infrared (NIR) light sources has posed a formidable challenge to the development of NIR phosphors characterized by high efficiency and exceptional thermal stability. Taking inspiration from the chemical unit co-substitution strategy, high-performance tunable (Lu3- xCax)(Ga5- xGex)O12:6%Cr3+ (x = 0-3) phosphors are designed with an emission center from 704 to 780 nm and a broadest full width at half maximum (FWHM) of up to 172 nm by introducing Ca2+ and Ge4+ ions into the garnet structure. In particular, Lu3Ga5O12:6%Cr3+ demonstrates an anti-thermal quenching phenomenon (I423K = 113.1%). Compared to Lu3Ga5O12:6%Cr3+, Lu2CaGa4GeO12:6%Cr3+ exhibits significantly improved FWHM and IQE by 108 nm and 25.5%, respectively, while maintaining good thermal stability (I423K = 80.4%). Finally, Lu2CaGa4GeO12:6%Cr3+ phosphor is combined with a 465 nm blue LED chip to fabricate NIR LED devices, exhibiting a NIR electroluminescence efficiency of 13.31%@100 mA and demonstrating successful applications in nocturnal illumination and biomedical imaging technology. This work offers a fresh perspective on the design of highly efficient NIR garnet phosphors.

Eu-Based Porphyrin MOF Enables High-Performance Carbon-Based Perovskite Solar Cells.

The low power conversion efficiency (PCE) of hole transport materials (HTM) - free carbon-based perovskite solar cells (C-PSCs) poses a challenge. Here, a novel 2D Eu-TCPP MOF (TCPP; [tetrakis (4-carboxyphenyl) porphyrin]) sandwiched between the perovskite layer and the carbon electrode is used to realize an effective and stable HTM-free C-PSCs. Relying on the synergistic effect of both the metal-free TCPP ligand with a unique absorption spectrum and hydrophobicity and the EuO4(OH)2 chain in the Eu-TCPP MOF, defects are remarkably suppressed and light-harvesting capability is significantly boosted. Energy band alignment is achieved after Eu-TCPP MOF treatment, promoting hole collection. Förster resonance energy transfer results in improved light utilization and protects the perovskite from decomposition. As a result, the HTM-free C-PSCs with Eu-TCPP MOF reach a champion PCE of 18.13%. In addition, the unencapsulated device demonstrates outstanding thermal stability and UV resistance and keeps 80.6% of its initial PCE after 5500 h in a high-humidity environment (65%-85% RH).

From Ancient Blue Pigment to Unconventional NIR Phosphor: A Thermal-Stable Near-Infrared I/II Broadband Emission from Ca1-xSrxCuSi4O10 Solid Solution.

Phosphors used in NIR spectroscopy require broadband emission, high external quantum yield, good ability, as well as a tunable spectral range to meet the detection criteria. Two-dimensional copper silicates MCuSi4O10 (M = Ca, Sr, Ba) play an important part in ancient art and technology as synthetic blue pigments. In the recent years, these compounds were reported to show a broad near-infrared emission when excited in the visible region. Inspired by the tunable structure of MCuSi4O10, a series of broadband phosphors Ca1-xSrxCuSi4O10 were designed for realizing continuously tunable NIR emission by a modulated Cu2+ crystal field environment. The emission maximum exhibits a red shift from 915 to 950 nm and the integral intensity enhances as the Sr2+ content varies in the range of 0-0.50, which is led by the lattice expansion and the following weakened crystal field splitting on tetrahedral-coordinated Cu2+. Compared to CaCuSi4O10, the optimized sample Ca0.5Sr0.5CuSi4O10 shows enhanced NIR emission by about 2.0-fold. It exhibits quite a high external quantum efficiency covering the NIR-I and -II regions (λmax = 950 nm, fwhm = 135 nm, EQE = 26.3%) with a strong absorption efficiency (74.7%) and a long excited-state lifetime (134 µs). These solid-solution phosphors (x = 0.0-0.5) show excellent thermal stability and maintain over 50% of the RT intensity at 200 °C. The optimized phosphor was encapsulated with red-light chips to fabricate NIR pc-LED and put into night-vision application. These good properties make these Cu2+-activated NIR phosphors appealing for multiple applications such as nondestructive testing, night version, lasers, and luminescent solar concentrators.

Circularly Polarized Luminescence Induced by Hydrogen-Bonding Networks in a One-Dimensional Hybrid Manganese(II) Chloride.

Chiral hybrid metal halides hold great potential as circularly polarized luminescence light sources. Herein, we have obtained two enantiomeric pairs of one-dimensional hybrid chiral manganese(II) chloride single crystals, R/S-(3-methyl piperidine)MnCl3 (R/S-1) and R/S-(3-hydroxy piperidine)MnCl3 (R/S-2), crystallizing in the non-centrosymmetric space group P212121. In comparison to R/S-1, R/S-2 single crystals not only show red emission with near-unity photoluminescence quantum yield (PLQY) and high resistance to thermal quenching but also exhibit circularly polarized luminescence with an asymmetry factor (glum) of 2.5×10-3, which can be attributed to the enhanced crystal rigidity resulting from the hydrogen bonding networks between R/S-(3-hydroxy piperidine) cations and [MnCl6]4- chains. The circularly polarized luminescence activities originate from the asymmetric [MnCl6]4- luminophores induced by N-H⋅⋅⋅Cl hydrogen bonding with R/S-(3-hydroxy piperidine). Moreover, these samples demonstrate great application potential in circularly polarized light-emitting diodes and X-ray scintillators. This work shows a highly efficient photoluminescent Mn-based halide and offers a strategy for designing multifunctional chiral metal halides.

Tetracoordinate Fe3+ Activated Li2ZnAO4 (A = Si, Ge) Near-Infrared Luminescent Phosphors.

Fe3+-doped near-infrared (NIR) phosphors have received a lot of interest because they are nontoxic, inexpensive, and ecologically benign. In this work, Fe3+-activated Li2ZnAO4 (A = Si, Ge) phosphors were synthesized by solid-phase reactions, in which Fe3+ entered the Zn2+ tetrahedral site. When excited by 300 nm UV light, broad NIR emission bands at 750 nm (Li2ZnSiO4: Fe3+) and 777 nm (Li2ZnGeO4: Fe3+) were observed, with internal quantum efficiencies (IQE) of 62.70% (Li2ZnSiO4: Fe3+) and 30.57% (Li2ZnGeO4: Fe3+). The thermal stability was increased from 35.43 to 49.79% at 373 K via cationic regulation. The combination of activation energy, electron-phonon coupling, and Debye temperature explained the improved thermal stability of Li2ZnGeO4: Fe3+ phosphor. Besides, the as-synthesized phosphor demonstrated sensitive and selective Cu2+ ion detection.

Ultra-Broadband Near-Infrared Phosphors Realized by the Heterovalent Substitution Strategy.

Near-infrared (NIR) phosphor-converted light-emitting diodes with broadband emission have received considerable interest. However, there remains a challenge in the construction of ultra-broadband NIR phosphors, hindering their further application. In this work, a heterovalent substitution strategy is proposed to construct a novel ultra-broadband NIR-emitting LaTiTaO6:Cr3+ phosphor with a full width at half maximum of ∼300 nm. Crystal structure, time-resolved emission spectroscopy, and electron paramagnetic resonance analyses confirm that only one crystallographic site of Cr3+ with separated ions exists. Electron and phonon coupling (EPC) evaluated by the Huang-Rhys factor (S) reveals that the heterovalent substitution strategy contributes to strong EPC with S = 9.185, resulting in ultra-broadband emission. Interestingly, a remarkable blue shift of emission from 1050 to 922 nm with increasing temperature is observed. Moreover, the application of LaTiTaO6:Cr3+ phosphor is demonstrated in the qualitative analysis of ethanol/water mixtures. The work will enrich the toolbox for designing broadband NIR-emitting materials.

Sharp-Line Near-Infrared Emission from Tetrahedron-Occupied Ni2+ in Ca2GeO4.

As far as we are concerned, the phenomenon of Ni2+ luminescence in tetrahedral coordination has not been reported. For the first time, a new NIR phosphor Ca2GeO4:Ni2+ is developed in this work. It is found that the NIR emission from this phosphor is a sharp peak attributed to the unusual Ni2+-occupied GeO4 site in the lattice, instead of the conventional broadband luminescence of Ni2+ in the octahedrally coordinated site. Crystal-field analysis has been applied, and the parameters Dq, B, and Δ are calculated to reveal the relationship between the emission profile and the crystal field strength. The optimal Ni2+ doping concentration is found to be 1%. Ca2GeO4:Ni2+ provides an efficient sharp-line (fwhm = 16 nm) emission centered at 1164 nm which originates from the 1T2 → 3T1 transition with an internal quantum efficiency of 23.1% and a decay lifetime of about 300 µs. This work could provide some new insights to explore novel NIR luminescent materials based on transition-metal elements.

Preparation of hollow metal-organic frameworks via epitaxial protection and selective etching.

Hollow metal-organic frameworks (MOFs) with only a shell may be used for efficient catalysis. In this work, a general sequential synthesis was employed to successfully create Hf-based hollow MOFs, such as UiO-66, MOF-808, and PCN-223. Etchants including monocarboxylic acids and H2O are required to remove the interior of the MOFs to form hollow structures, while the different stability of the interior and surface of the MOFs partly resulting from surface epitaxy protection was responsible for the selective etching. With these insights, scale-up of hollow octahedral UiO-66 was realized. This work paves a way to rationally design hollow MOFs.

Nanoscale Metal-Organic Frameworks and Metal-Organic Layers with Two-Photon-Excited Fluorescence.

Metal-organic frameworks (MOFs) based on 9,10-diphenylanthracene-derived ligands had been reported to exhibit upconverted fluorescence through triplet-triplet annihilation. We found that zirconium MOFs based on 9,10-diphenylanthracene can also give upconverted fluorescence via two-photon absorption without adding a triplet photosensitizer when a femtosecond pulsed laser is used as the excitation source. By tuning the synthetic condition, we obtained nanoscale MOFs of UiO structure in both octahedral and hexagonal nanoplate shapes, as well as a hexagonal nanoplate of MOFs of hcp-UiO structure and two-dimensional metal-organic layers. All of them, as well as a homogeneous solution of the 9,10-diphenylanthracene ligand, exhibit upconverted fluorescence upon excitation using a laser pulse of 60 fs with a pulse energy of ∼1.1 × 106 nJ/cm2 (unfocused). Moreover, we observed different emission spectra by two-photon excitation compared to those by one-photon excitation, which indicates access to a unique initial excited state via two-photon excitation. This phenomenon is not observed for a homogeneous solution of the ligand. These nanoscale MOFs may find application in two-photon fluorescence imaging.

A simple photoelectrochemical aptasensor based on MoS2/rGO for aflatoxin B1 detection in grain crops.

Designing a simple and sensitive photoelectrochemical (PEC) sensor is crucial to addressing the limitations of routine analytical methods. The sensitivity of the PEC sensor, however, relies on the photoelectric material used. In this manuscript, composites of MoS2/rGO (MG) with a large area and layered structure are prepared by simple steps. This material exhibits sensitivity to visible light and demonstrates outstanding photoelectric conversion performance. The constructed PEC aptasensor using this material to detect aflatoxin B1 (AFB1) shows significantly higher sensitivity and stability compared to similar sensors. This may be attributed to the presence of surface defects in MoS2, which provide more active sites for photocatalysis. Additionally, graphene oxide (GO) is reduced to rGO by thiourea and forms a heterojunction with MoS2, enhancing charge carrier separation and interfacial electron transfer. Our research has revealed that the photocurrent intensity of the aptamer electrode decreases with an increase in AFB1 concentration, resulting in a "signal-off" PEC aptasensor. The detection limit of this aptasensor is 2.18 pg mL-1, with a linear range of 0.001 to 100 ng mL-1. This result will also provide a reference for the study of other mycotoxins in food.

Ligand-Induced In Situ Epitaxial Growth of PbI2 Nanosheets/MAPbI3 Heterojunction Realizes High-Performance HTM-Free Carbon-Based MAPbI3 Solar Cells.

Hole-transporting layer-free carbon-based perovskite solar cells (HTL-free C-PSCs) hold great promise for photovoltaic applications due to their low cost and outstanding stability. However, the low power conversion efficiency (PCE) of HTL-free C-PSCs mainly results from grain boundaries (GBs). Here, epitaxial growth is proposed to rationally design a hybrid nanostructure of PbI2 nanosheets/perovskite with the desired photovoltaic properties. A post-treatment technique using tri(2,2,2-trifluoromethyl) phosphate (TFEP) to induce in situ epitaxial growth of PbI2 nanosheets at the GBs of perovskite films realizes high-performance HTL-free C-PSCs. The structure model and high-resolution transmission electron microscope unravel the epitaxial growth mechanism. The epitaxial growth of oriented PbI2 nanosheets generates the PbI2/perovskite heterojunction, which not only passivates defects but forms type-I band alignment, avoiding carrier loss. Additionally, Fourier-transform infrared spectroscopy, 31P NMR, and 1H NMR spectra reveal the passivation effect and hydrogen bonding interaction between TFEP and perovskite. As a result, the VOC is remarkably boosted from 1.04 to 1.10 V, leading to a substantial gain in PCE from 14.97% to 17.78%. In addition, the unencapsulated PSC maintains the initial PCE of 80.1% for 1440 h under air ambient of 40% RH. The work offers a fresh perspective on the rational design of high-performance HTL-free C-PSCs.

Metal Halide Perovskite Nanocrystals for Near-Infrared Circularly Polarized Luminescence with High Photoluminescence Quantum Yield via Chiral Ligand Exchange.

Using ligand exchange on FAPbI3 perovskite nanocrystals (PNCs) surface with chiral tridentate l-cysteine (l-cys) ligand, we successfully prepared chiral FAPbI3 PNCs that show circularly polarized luminescence (CPL) (dissymmetry factor; glum = 2.1 × 10-3) in the near-infrared (NIR) region from 700 to 850 nm and a photoluminescence quantum yield (PLQY) of 81%. The chiral characteristics of FAPbI3 PNCs are ascribed to induction by chiral l/d-cys, and the high PLQY is attributed to the passivation of the PNCs defects with l-cys. Also, effective passivation of defects on the surface of FAPbI3 PNCs by l-cys results in excellent stability toward atmospheric water and oxygen. The conductivity of the l-cys treated FAPbI3 NC films is improved, which is attributed to the partial substitution of l-cys for the insulating long oleyl ligand. The CPL of the l-cys ligand treated FAPbI3 PNCs film retains a glum of -2.7 × 10-4. This study demonstrates a facile yet effective approach to generating chiral PNCs with CPL for NIR photonics applications.

Photoelectrochemical detection for 3,3',4,4'-tetrachlorobiphenyl in fish based on synergistic effects by Schottky junction and sensitization.

In this study, a novel signal amplification strategy on photoelectrochemical (PEC) aptasensor was designed for high-sensitivity and -selectivity detection of 3,3',4,4'-tetrachlorobiphenyl (PCB77) on the basis of Schottky junction and sensitization. First, the Schottky barrier not only provided an electron-transfer irreversible passage from CuO to Au Nanoparticles (NPs) but also generated excellent local surface plasmon resonance between CuO and Au NPs, thus improving the efficiency of charge separation and light absorption. Second, to further improve the response of the PEC aptasensor under the action of the sensitization, the complementary-DNA-functionalized CdS quantum dots were introduced onto the surface of CuO/Au NPs via hybridization of the target aptamer. The PEC aptasensor exhibited a low detection limit of 17.3 pg L-1, and a wide linear response was shown at a range of 0.2-220 ng L-1 depending on the variation of photocurrent before and after incubation.

Improved Energy Transfer in Mn-Doped Cs3Cu2I5 Microcrystals Induced by Localized Lattice Distortion.

With nontoxicity and high emission efficiency, luminescent copper(I)-based halides have attracted much attention as alternatives for lead-based perovskites in photoelectric domains. However, extending the emission wavelength by doping with Mn2+ in a facile way is still a challenge. In this work, Mn2+-doped Cs3Cu2I5 microcrystals were synthesized by a mild solution method, and double emission bands from self-trapped excitons (STEs) and Mn2+ peaking at 445 and 560 nm, respectively, were observed. More importantly, further introduction of alkali metal ions (Rb+, K+, Na+) considerably promoted the luminescence performance of the Cs3Cu2I5-Mn microcrystals. The STE → Mn2+ energy transfer efficiency of the typical sample doped with Na+ increased from ∼0 to 21.30%, and the photoluminescence quantum yield (PLQY) increased from 47.32% to 62.06%. The detailed structural and optical characterizations combined with DFT calculations proved that the doping with alkali metal ions causes lattice distortion and enhances the coupling between [MnI4] and [CuI4] tetrahedra, thus promoting the energy transfer efficiency and the PLQY.

Two-dimensional metal-organic layers constructed from Hf6/Hf12-oxo clusters and a trigonal pyramidal phosphine oxide ligand.

Metal-organic layers (MOLs), a category of two-dimensional materials, have attracted wide interest due to their molecular tunability and the ease of surface modification. Herein, we reported the synthesis and structural determination of a free-standing MOL, {[Hf6O8H4(HCOO)2(H2O·OH)4]3[Hf12O16H8(HCOO)6.8(H2O·OH)11.2](TPO)8}n, constructed from Hf6-oxo and Hf12-oxo clusters as secondary building units (SBUs) and the tris(4-carboxylphenyl)phosphine oxide (TPO) ligand. We establish a structure model of this new MOL based on the combined information from different characterization methods.

Observation of formation and local structures of metal-organic layers via complementary electron microscopy techniques.

Metal-organic layers (MOLs) are highly attractive for application in catalysis, separation, sensing and biomedicine, owing to their tunable framework structure. However, it is challenging to obtain comprehensive information about the formation and local structures of MOLs using standard electron microscopy methods due to serious damage under electron beam irradiation. Here, we investigate the growth processes and local structures of MOLs utilizing a combination of liquid-phase transmission electron microscopy, cryogenic electron microscopy and electron ptychography. Our results show a multistep formation process, where precursor clusters first form in solution, then they are complexed with ligands to form non-crystalline solids, followed by the arrangement of the cluster-ligand complex into crystalline sheets, with additional possible growth by the addition of clusters to surface edges. Moreover, high-resolution imaging allows us to identify missing clusters, dislocations, loop and flat surface terminations and ligand connectors in the MOLs. Our observations provide insights into controllable MOL crystal morphology, defect engineering, and surface modification, thus assisting novel MOL design and synthesis.

Energy transfer on a two-dimensional antenna enhances the photocatalytic activity of CO2 reduction by metal-organic layers.

Excited state energies on a two-dimensional light-harvesting metal-organic layer (MOL) are efficiently transported to Re- and Ir-based reaction centers for converting CO2 to CO or HCOOH. Such energy transfer enhances the photocatalytic CO2 reduction activity because it enables multiple photo-electron injections in a short time period in the photocatalysis.

Color-tunable emission and energy transfer investigation in Sr3Y(PO4)3:Ce3+,Tb3+ phosphors for white LEDs.

A novel color-tunable phosphor Sr3Y(PO4)3:Ce3+,Tb3+ was synthesized through solid-state reaction method. Several techniques, such as X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and energy dispersive X-ray spectroscopy, were used to investigate the obtained phosphors. Results of luminescence spectra and decay time measurements revealed that an efficient energy transfer occurred from Ce3+ to Tb3+ via a dipole-dipole mechanism, where Ce3+ exhibited a strong excitation band in the near-ultraviolet region. CIE chromaticity coordinates were tuned from deep blue (0.162, 0.090) to green (0.230, 0.411) by adjusting the relative concentrations between Ce3+ and Tb3+ ions. Results revealed that the as-synthesized phosphors had color-tunable characteristics and can be used as promising materials in the field of phosphor-converted white light-emitting diodes.

Luminescence and energy transfer of the color-tunable phosphor Li6Gd(BO3)3:Tb³âº/Bi³âº, Eu³âº.

Bi(3+)/Tb(3+), Eu(3+) co-doped Li6Gd(BO3)3 (LGBO) phosphors were synthesized via a traditional solid-state method. Phase purity was investigated using X-ray diffraction, absorption strength of the phosphors were investigated by UV-vis absorption spectra, and the photoluminescence properties of the phosphors were studied systematically. Results showed that the emission intensity of Bi(3+), Eu(3+) co-doped LBOG was 2.76 times higher than that of Eu(3+)-doped LGBO irradiated at 275 nm, thereby implying the possibility of energy transfer from Bi(3+) to Eu(3+). The excitation spectra of Tb(3+), Eu(3+) co-doped LGBO phosphors are broader in comparison with single-doped phosphors and show tunable colors from green to yellow to orange-red when the ratio of Tb(3+) to Eu(3+) is adjusted These results demonstrate that LGBO:Tb(3+), Eu(3+) phosphors have potential use in light-emitting diodes.

Luminescence and energy transfer of color-tunable Li6Gd(BO3)3:Ce(3+), Tb(3+) phosphor.

A series of novel color-tunable phosphors of Ce(3+), Tb(3+)-codoped Li6Gd(BO3)3 was synthesized through a classic solid-state reaction. The color of these phosphors changes from blue to green by adjusting the ratio of Ce(3+) to Tb(3+). The photoluminescence properties of the synthesized phosphors were investigated, and several major emission bands that belong to Ce(3+) and Tb(3+) ions were irradiated with near ultraviolet light. Moreover, the energy transfer mechanism between Ce(3+) and Tb(3+) in Li6Gd(BO3)3 was explored. The photoluminescence decay curves were performed to validate the energy transfer. The analysis demonstrated that the energy transfer from Ce(3+) to Tb(3+) arose from dipole-dipole interaction with a critical distance of approximately 17.6 Å.