Modulating the thermal emission of a material in the infrared (IR) range can be essential for various practical applications such as smart textiles, camouflage, and anti-counterfeiting. Although many different materials or structures have been proposed, the complex manufacturing processes are still hindering their widespread use. Herein, a facile femtosecond laser processing technology and a drop-coating method are introduced to form a patternable low emissivity film. Laser-treated polyimide films resulted in superhydrophilic structured surfaces that are uniformly coated with silver-nanowires (AgNWs) in aqueous solutions for low emissivity surfaces. Furthermore, the emissivity of the samples is as low as ∼0.2 without deterioration over 800 bending-releasing cycles. The as-prepared films also display good thermal camouflage properties, namely, the films reduced the thermal radiation temperature of an object by 35.8 °C when the object temperature was ∼69.1 °C. Additionally, this IR camouflage effect of the AgNWs coated samples shows excellent stability even in harsh environments such as immersion in water, acid, alkali, and salt solution and applied voltage. We also show that information encryption was possible by adjusting the amount of AgNWs. The design of this programmable patterned low emissivity film indicates an idea for the thermal camouflage and anti-counterfeiting technology, which can carry more abundant application scenario and disguise them more complex and sophisticated.

Femtosecond laser-textured superhydrophilic coral-like structures spread AgNWs enable strong thermal camouflage and anti-counterfeiting

Low dimensional lead‐free metal halides have become the spotlight of the research on developing multifunctional optoelectronic materials as their properties show a wide range of tunability. However, most reported low dimensional metal halides only function in the ultra‐violet to visible range due to their large bandgap. Moreover, the organic cation based low dimensional metal halides show limited thermal stability; on the other hand, their inorganic cation based counterparts suffer from limited solution processability. A hybrid cation approach is proposed, where a zero dimensional (0D) metal halide ((DFPD)2CsBiI6) is developed by using mixed organic–inorganic cations: 4, 4‐difluoropiperidine (DFPD) and cesium (Cs+). This ensures both thermal stability and solution processability. Furthermore, [BiI6]3− octahedra are serving as active light absorption units, which ensures the bandgap to be located at the visible region. Its photoluminescence (PL) is further shifted to the near infrared (NIR) region by doping (DFPD)2CsBiI6 with antimony (Sb3+). The developed materials show multifunctional properties: thermochromic behavior, light detection, and NIR light emitting. This study expands the scope of developing multifunctional 0D metal halides.

Turning Self‐Trapped Exciton Emission to Near‐Infrared Region in Thermochromism Zero‐Dimensional Hybrid Metal Halides

Abstract Recently, many lead‐free metal halides with diverse structures and highly efficient emission have been reported. However, their poor stability and single‐mode emission color severely limit their applications. Herein, three homologous Sb 3+ ‐doped zero‐dimensional (0D) air‐stable Sn(IV)‐based metal halides with different crystal structures were developed by inserting a single organic ligand into SnCl 4 lattice, which brings different optical properties. Under photoexcitation, (C 25 H 22 P)SnCl 5 @Sb·CH 4 O ( Sb 3+ −1 ) does not emit light, (C 25 H 22 P) 2 SnCl 6 @Sb‐α ( Sb 3+ −2α ) shines bright yellow emission with a photoluminescence quantum yield (PLQY) of 92%, and (C 25 H 22 P) 2 SnCl 6 @Sb‐β ( Sb 3+ −2β ) exhibits intense red emission with a PLQY of 78%. The above three compounds show quite different optical properties should be due to their different crystal structures and the lattice distortions. Particularly, Sb 3+ −1 can be successfully converted into Sb 3+ −2α under the treatment of C 25 H 22 PCl solution, accompanied by a transition from nonemission to efficient yellow emission, serving as a “turn‐on” photoluminescence (PL) switching. Parallelly, a reversible structure conversion between Sb 3+ −2α and Sb 3+ −2β was witnessed after dichloromethane or volatilization treatment, accompanied by yellow and red emission switching. Thereby, a triple‐mode tunable PL switching of off–on I –on II can be constructed in Sb 3+ ‐doped Sn(IV)‐based compounds. Finally, we demonstrated the as‐synthesized compounds in fluorescent anticounterfeiting, information encryption, and optical logic gates. 

Realizing efficient emission and triple‐mode photoluminescence switching in air‐stable tin(IV)‐based metal halides via antimony doping and rational structural modulation

Recently, 0D metal halides have attracted widespread interest because of their diverse structures and rich luminescence properties. Nevertheless, the controllable synthesis of metal halide clusters with the ideal configuration using chemical methods remains a great challenge. In addition, the relationship between the coordination configuration and the optical properties of 0D metal halides is not well understood. In this study, two homologous Sb3+‐doped 0D Sn (IV)‐based metal halides with different coordination configurations are developed by inserting a single organic ligand, tetrabutylphosphonium chloride (TBPCl), into a SnCl4 lattice, resulting in different optical properties. Under photoexcitation, Sb3+‐doped (TBP)SnCl5·DMF shows a negligible luminescence from the organic cation of TBP+, while Sb3+‐doped (TBP)2SnCl6 shows a bright orange emission band at 650 nm with a photoluminescence quantum yield (PLQY) of 99%. The above two compounds show quite different optical properties, which should be due to the too‐large lattice distortion of Sb3+‐doped (TBP)SnCl5·DMF, and the DMF will cause the efficient non‐radiation relaxation. In particular, Sb3+‐doped (TBP)2SnCl6 exhibits remarkable anti‐water stability, which shows stability in water for 48 h without structural degradation, and the luminous intensity remains at a high level. Combined with its excellent optical properties and impressive stability, Sb3+‐doped (TBP)2SnCl6 is used in white‐light‐emitting diodes (WLED).

Achieving Highly Efficient Orange Emission in Tin (IV)‐Based Metal Halides with Outstanding Anti‐Water Stability Through Antimony Doping and Reasonable Structural Modulation

A novel dual emission ratiometric fluorescence sensor Eu3+/CDs@UiO-66 to achieve Cu2+ detection in water environment

Single-matrix white light-emitting diodes are still a challenge. Achieving tunable white light emission from lead-free perovskites attracts much attention. Herein, nanoscale Rb2SnCl6 (RSC) vacancy ordered double perovskite were synthesized by an optimized precipitation method. Further, using ns2 ions (Bi3+, Te4+, and Sb3+) doped RSC vacancy ordered double perovskite to obtain broadband blue, yellow-green, and orange-red emission. The color temperature adjustable high-quality white light emission based on the codoping strategy is obtained by controlling the doping ratio of Bi3+ and Te4+. Additionally, the white light-emitting diodes encapsulated by this single matrix white luminescent material exhibit excellent stability. Combined with theoretical calculations, it is elucidated that these high-efficiency emissions are not only derived from the unique electronic transition of ns2 ions but also related to the energy band properties and the crystal field. This work shows that ns2 ions doped RSC vacancy ordered double perovskite can meet the needs of different luminous colors and color temperature tunable white light emission. Meanwhile, it is a strong competitor to replace the lead-based perovskite.

Excitation-Dependent Tunable White Light of ns2 Ions Doped Rb2SnCl6 Vacancy Ordered Double Perovskite.

Excitation wavelength-dependent continuous color-tunable luminescence of fluorescent dyes encapsulated into lanthanide metal-organic framework for anti-counterfeiting

Synthesis and characterization of a far-red-emitting Sr2ScNbO6: Mn4+ phosphor for short-day plant cultivation

Realize Intelligent Anti-Counterfeiting and Efficient Near-Infrared Emission of Indium-Based Perovskite Through Crystal Phase and Energy Band Engineering

Metal-organic frameworks (MOFs) are a unique class of multifunctional hybrid crystals that have been successfully utilized in diverse ranges of applications. However, since MOFs are prone to aqueous degradation, the development of stable luminescent MOF platforms in aqueous media is still a huge challenge. Here, a novel dual-ligand Eu3+/DUT-52-COOH composite is prepared based on the luminescent DUT-52 prototype structure via a dual-ligand strategy and a post-synthetic modification (PSM) method. The functionalized Eu3+/DUT-52-COOH material exhibits dual emission and good photothermal stability in aqueous media. Thus, Eu3+/DUT-52-COOH is developed as a ratiometric luminescent sensor to achieve highly selective and sensitive detection of Cu2+ and Cr2O72- in aqueous solutions and has a low detection limit of 3.43 μM and 25.7 nM, respectively. This work is one of the few cases of detecting Cu2+ and Cr2O72- in aqueous media based on a DUT-52, and the detection signals can be observed by the bare eye without using sophisticated analytical instruments. The possible sensing mechanism is discussed in detail. The results obtained in this project may provide broad prospects for developing smart sensing systems to accomplish highly efficient, easily operable and quantitative intelligent recognition of Cu2+ and Cr2O72-.

A new dual-ligand DUT-52-type metal-organic framework for ratiometric luminescence detection of aqueous-phase Cu2+ and Cr2O72.

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