Self-Trapped Exciton Emission in Highly Polar 0D Hybrid Ammonium/Hydronium-Based Perovskites Triggered by Antimony Doping.

Various monovalent cations are employed to construct metal halide perovskites with various structures and functionalities. However, perovskites based on highly polar A-site cations have seldom been reported. Here, a novel hybrid 0D (NH4)x(OH3)3-xInCl6 perovskite with highly polar hydronium OH3+ cations is introduced in this study. Upon doping with Sb3+, hybrid 0D (NH4)x(OH3)3-xInCl6 single crystals exhibited highly efficient broadband yellowish-green (550 nm) and red (630 nm) dual emissions with a PLQY of 86%. The dual emission arises due to Sb3+ occupying two sites within the crystal lattice that possess different polarization environments, leading to distinct Stokes shift energies. The study revealed that lattice polarity plays a significant role in the self-trapped exciton emission of Sb3+-doped perovskites, contributing up to 25% of the Stokes shift energy for hybrid 0D (NH4)x(OH3)3-xInCl6:Sb3+ as a secondary source, in addition to the Jahn-Teller deformation. These findings highlight the potential of Sb3+-doped perovskites for achieving tunable broadband emission and underscore the importance of lattice polarity in determining the emission properties of perovskite materials.

An Active Bio-Based Food Packaging Material of ZnO@Plant Polyphenols/Cellulose/Polyvinyl Alcohol: DESIGN, Characterization and Application.

Active packaging materials protect food from deterioration and extend its shelf life. In the quest to design intriguing packaging materials, biocomposite ZnO/plant polyphenols/cellulose/polyvinyl alcohol (ZnPCP) was prepared via simple hydrothermal and casting methods. The structure and morphology of the composite were fully analyzed using XRD, FTIR, SEM and XPS. The ZnO particles, plant polyphenols (PPL) and cellulose were found to be dispersed in PVA. All of these components share their unique functions with the composite's properties. This study shows that PPL in the composite not only improves the ZnO dispersivity in PVA as a crosslinker, but also enhances the water barrier of PVA. The ZnO, PPL and cellulose work together, enabling the biocomposite to perform as a good food packaging material with only a 1% dosage of the three components in PVA. The light shielding investigation showed that ZnPCP-10 can block almost 100% of both UV and visible light. The antibacterial activities were evaluated by Gram-negative Escherichia coli (E. coli) and Gram-positive staphylococcus aureus (S. aureus), with 4.4 and 6.3 mm inhibition zones, respectively, being achieved by ZnPCP-10. The enhanced performance and easy degradation enables the biocomposite ZnPCP to be a prospect material in the packaging industry.

Fabrication of ZnO@Plant Polyphenols/Cellulose as Active Food Packaging and Its Enhanced Antibacterial Activity.

To investigate the efficient use of bioresources and bioproducts, plant polyphenol (PPL) was extracted from larch bark and further applied to prepare ZnO@PPL/Cel with cellulose to examine its potential as an active package material. The structure and morphology were fully characterized by XRD, SEM, FTIR, XPS and Raman spectra. It was found that PPL is able to cover ZnO and form a coating layer. In addition, PPL cross-links with cellulose and makes ZnO distribute evenly on the cellulose fibers. Coating with PPL creates a pinecone-like morphology in ZnO, which is constructed by subunits of 50 nm ZnO slices. The interactions among ZnO, PPL and cellulose have been attributed to hydrogen bonding, which plays an important role in guiding the formation of composites. The antibacterial properties against Gram-negative Escherichia coli (E. coli) and Gram-positive Staphylococcus aureus (S. aureus) were tested by the inhibition zone method. Our composite ZnO@PPL/Cel has superior antibacterial activity compared to ZnO/Cel. The antibacterial mechanism has also been elaborated on. The low cost, simple preparation method and good performance of ZnO@PPL/Cel suggest the potential for it to be applied as active food packaging.

Modulation of the Excitation States in All-Inorganic Halide Perovskites via Sb3+ and Bi3+ Codoping.

Sb3+-doped halide perovskites are promising candidates for solid-state lighting due to their diverse fluorescent colors and high efficiency. However, the mismatched high excitation energy with commercial UV chips is one of the critical issues to be addressed. Herein, a Bi3+ codoping strategy was established as a general and efficient approach to modulate the excitation spectrum from the Sb3+-doping center in all-inorganic perovskites of Cs2InCl5·H2O, Cs2NaInCl6, and Rb3InCl6. The incorporated Bi3+ greatly enhanced the splitting of the A band (1S0-3P1 transition) and boosts the enormous redshift of the low-energy branch in all these systems. The interactions persist strongly even at extremely low doping concentrations, suggesting a dipole-based long-range interaction. The results provide an in-depth insight into the contribution mechanism of Bi3+ to Sb3+ in all-inorganic perovskites, which throws light upon tuning the excitation spectrum of broadband emission from the extrinsic self-trapped exciton (STE).

Zero-Dimensional Tellurium-Based Organic-Inorganic Hybrid Halide Single Crystal with Yellow-Orange Emission from Self-Trapped Excitons.

Organic-inorganic hybrid halides and their analogs that exhibit efficient broadband emission from self-trapped excitons (STEs) offers an unique pathway towards realization of highly efficient white light sources for lighting applications. An appropriate dilution of ns2 ions into a halide host is essential to produce auxiliary emissions. However, the realization of ns2 cation-based halides phosphor that can be excited by blue light-emitting diode (LED) is still rarely reported. In this study, a zero-dimensional Te-based single crystal (C8H20N)2TeCl6 was synthesized, which exhibits a yellow-orange emission centered at 600 nm with a full width at half maximum of 130 nm upon excitation under 437 nm. Intense electron-phonon coupling was confirmed in the (C8H20N)2TeCl6 single crystal and the light emitting mechanism is comprehensively discussed. The results of this study are pertinent to the emissive mechanism of Te-based hybrid halides and can facilitate discovery of unidentified metal halides with broadband excitation features.

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

Sb3+ doping confers highly efficient and color-diverse broadband light emission to all-inorganic metal-halide perovskites. However, the emission mechanism is still under debate. Herein, a trace amount of Sb3+ ions (<0.1% atomic percentage) doping in the typical all-inorganic perovskites Cs2NaInCl6, Rb3InCl6, and Cs2InCl5·H2O allows universal observation of the fine structure in the photoluminescence excitation spectrum of the ns2 electron. A lifetime mapping method was utilized to reveal the origin of broadband emission triggered by Sb3+ doping, by which various fluorescence components can be differentiated. In particular, free-exciton emission was identified at the high-energy end of the broadband emission for all three doped systems. The excitation-energy- and temperature-dependent fluorescence decay further indicates the existence and origin of self-trapped states. The observed structural and vibrational symmetry-dependent emission behaviors suggest dipole interactions can dramatically alter Stokes-shift energy and modulate the light-emitting wavelength.

Cryogenic enabled multicolor upconversion luminescence of KLa(MoO4)2:Yb3+/Ho3+ for dual-mode anti-counterfeiting.

The rational development of multicolor upconversion (UC) luminescent materials is particularly promising for achieving high-tech anti-counterfeiting and security applications. Here, an Ho3+ and Yb3+ ion co-doped KLa(MoO4)2 material can achieve multicolored UC luminescence by thermally manipulating the electron transition process, which could be developed to execute advanced optical anti-counterfeiting applications. The emission color of this material turns from bright green to deep orange with the temperature controlled from 85 K to 240 K in a cryogenic environment. The maximum absolute sensitivity and relative sensitivity of this temperature-sensing material based on non-thermally coupled levels of Ho3+ ions reached 0.049 K-1 and 4.6% K-1. And utilizing the thermochromic luminescence properties and high sensitivity for low temperature of the KLa(MoO4)2:Yb3+/Ho3+ UC material, we created KLa(MoO4)2:Yb3+/Ho3+ fluorescent security inks and UC photonic barcodes to realize novel visual reading and digital recognition dual-mode anti-counterfeiting in a secure manner. These results may provide useful enlightenment for the design and modulation of high-sensitivity temperature-sensing materials for high-level anti-counterfeiting applications.

Experimental and first-principle computational exploration on biomass cellulose/magnesium hydroxide composite: Local structure, interfacial interaction and antibacterial property.

The specification of the local structure and clarification of interfacial interactions of biomass composites is of tremendous significance in synthesizing novel materials and advancing their performance in various demanding applications. However, it remains challenging due to the limitations of experimental techniques, particularly for the manner that biomass composites commonly have hydrogen bonds involved in the vicinity of active sites and interfaces. Herein, the cellulose/Mg(OH)2 nanocomposite has been synthesized via a simple hydrothermal approach and examined by density functional theory (DFT) calculations. The composite exhibits a layered morphology; Mg(OH)2 flakes are around 50 nm in size and well-dispersed. They either anchor onto the cellulose surface or intercalate between layers. The specific composite structure was confirmed theoretically, in line with XRD, SEM and TEM observations. The interfacial interactions were found to be hydrogen bonding. The average adsorption energy per hydroxyl group was computed to be within -0.47 and -0.26 eV for a composite model comprising three cellulose chains and a two-layered Mg(OH)2 cluster. The combined computational/experimental results allow to postulate the antibacterial mechanism of the nanocomposite.