Posokhova Svetlana M, Morozov Vladimir A, Deyneko Dina V, Nikiforov Ivan V, Redkin Boris S, Spassky Dmitry A, Belik Alexei A, Pavlova Erzhena T, Lazoryak Bogdan I
Chemistry Department, Moscow State University, 119991 Moscow, Russia.
Institute of Solid State Physics of Russian Academy of Sciences (ISSP RAS), 142432 Chernogolovka, Russia.
Inorg Chem. 2022 May 23;61(20):7910-7921. doi: 10.1021/acs.inorgchem.2c00548. Epub 2022 May 6.
This paper describes the influence of sintering conditions and Eu/Tb content on the structure and luminescent properties of KEuTb(MoO) (KETMO). KETMO samples were synthesized under two different heating and cooling conditions. A KTb(MoO) (KTMO) colorless transparent single crystal was grown by the Czochralski technique. A continuous range of solid solutions with a trigonal palmierite-type structure (α-phase, space group 3̅) were presented only for the high-temperature (HT or α-) KETMO (0 ≤ ≤ 1) prepared at 1123 K followed by quenching to liquid nitrogen temperature. The reversibility of the β ↔ α phase transition for KTMO was revealed by a differential scanning calorimetry (DSC) study. The low-temperature (LT)LT-KEuTb(MoO) structure was refined in the space group. Additional extra reflections besides the reflections of the basic palmierite-type R-subcell were present in synchrotron X-ray diffraction (XRD) patterns of LT-KTMO. LT-KTMO was refined as an incommensurately modulated structure with (3 + 1)D superspace group (0β0)00 and the modulation vector = 0.684*. The luminescent properties of KETMO prepared at different conditions were studied and related to their structures. The luminescence spectra of KTMO samples were represented by a group of narrow lines ascribed to D → F ( = 3-6) Tb transitions with the most intense emission line at 547 nm. The KTMO single crystal demonstrated the highest luminescence intensity, which was ∼20 times higher than that of LT-KTMO. The quantum yield λ = 481 nm for the KTMO single crystal was measured as 50%. The intensity of the D → F Tb transition increased with the increase of from 0.2 to 1 for LT and HT-KETMO. Emission spectra of KETMO samples with = 0.2-0.9 at λ = 377 nm exhibited an intense red emission at ∼615 nm due to the D → F Eu transition, thus indicating an efficient energy transfer from Tb to Eu.
本文描述了烧结条件和铕/铽含量对KEuTb(MoO)(KETMO)结构和发光性能的影响。KETMO样品在两种不同的加热和冷却条件下合成。采用提拉法生长了无色透明的KTb(MoO)(KTMO)单晶。仅对于在1123 K制备并淬火至液氮温度的高温(HT或α-)KETMO(0≤≤1),呈现出具有三方磷镁矿型结构(α相,空间群3̅)的连续固溶体范围。通过差示扫描量热法(DSC)研究揭示了KTMO的β↔α相变的可逆性。低温(LT)LT-KEuTb(MoO)结构在空间群中进行了精修。在LT-KTMO的同步辐射X射线衍射(XRD)图谱中,除了基本磷镁矿型R子晶的反射外,还存在额外的附加反射。LT-KTMO被精修为具有(3 + 1)D超空间群(0β0)00和调制矢量= 0.684*的非公度调制结构。研究了在不同条件下制备的KETMO的发光性能,并将其与结构相关联。KTMO样品的发光光谱由一组归因于D→F(= 3 - 6)Tb跃迁的窄线表示,最强发射线位于547 nm处。KTMO单晶表现出最高的发光强度,比LT-KTMO高约20倍。KTMO单晶在λ = 481 nm处的量子产率测得为50%。对于LT和HT-KETMO,D→F Tb跃迁的强度随着从0.2增加到1而增加。在λ = 377 nm处,= 0.2 - 0.9的KETMO样品的发射光谱在约615 nm处表现出强烈的红色发射,这是由于D→F Eu跃迁,从而表明从Tb到Eu的有效能量转移。