A novel organic–inorganic hybrid perovskite crystal, [ClC6H4(CH2)2NH3]2CuBr4 (1), having experienced an invertible high-temperature phase transition near Tc (the Curie temperature Tc = 355 K), has been successfully synthesized. The phase-transition characteristics for compound 1 are thoroughly revealed by specific heat capacity (Cp), differential thermal analysis, and differential scanning calorimetry tests, possessing 16 K broad thermal hysteresis. Multiple-temperature powder X-ray diffraction analysis further proves the phase-transition behavior of compound 1. Moreover, compound 1 exhibits a significant steplike dielectric response near Tc, revealing that it can be deemed to be a promising dielectric switching material. The variable-temperature fluorescence experiments show distinct photoluminescence (PL) changes of compound 1. Further investigation and calculation disclose that the fluorescence lifetime of compound 1 can reach as long as 55.46 μs, indicating that it can be a potential PL material. All of these researches contribute a substitutable avenue in the design and construction of neoteric phase-transition compounds combining high Curie temperature and PL properties.
The ability to reversibly manipulate the surface nature of luminescent nanoparticles upon external stimulation enables the development of advanced optical probes for biological sensing and data encoding. Herein, we report the synthesis of a new class of smart carbon dots (CDs) via surface modification of amine-enriched CDs with CO2-responsive groups of amidine. We present that alternative CO2 and N2 bubbling can not only lead to a reversible phase transfer of the CDs between an organic phase and an aqueous phase but also give rise to a corresponding reversible luminescence change between blue and cyan-green. We attribute these observations to changes in both the surface chemistry and the emission states of the CDs triggered by the alternative CO2/N2 introduction. We also find a similar luminescence change of the CDs upon alternative exposure to a humid vapor of CO2 and a mixture of NH3 and N2 at room temperature, allowing them to be used as a new class of optical materials for optical encoding.
Man Li,Yifei Zhao,Shuai Zhang,Ruirui Yang,Weidong Qiu,Pin Wang,Maxim S. Molokeev,Shi Ye
The photoinduced reversible ion exchanges in mixed halide perovskites and the resulting luminescent variations make them promising for constructing anti-counterfeiting patterns; however, its understanding in an interfacial view is lacking. In this work, nominal CsPbBr1.5Cl1.5 (CPBC) nanocrystals (NCs) were introduced into macroporous Y2O3:Eu3+ (MYE) to realize emission color variations from red emission of MYE to green emission of halide NCs. The large surface area of MYE helps the formation of Y–Cl/Br bonds which induces fluctuation in the halide composition, while water and intrinsic halogen defects have also been proved to be essential in the reversible ion segregation process. The PL variations of several samples with different pore sizes were investigated upon irradiation of light with different photon energies and excitation power at certain temperatures. According to combined results of density functional theory calculation, the research reveals the presence of two energy barriers that would be overcome correspondingly by the excitation photon and the concentration difference in the ion exchange and recovery process. A photochromic anti-counterfeiting quick response (QR) code was constructed facilely with the perovskite composites. This work provides a deeper understanding from the interfacial aspect and also proposes a feasible strategy to realize reversible PL variation for anti-counterfeiting applications.
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