This paper describes the influence
of sintering conditions and
Eu3+/Tb3+ content on the structure and luminescent
properties of K5Eu1–
x
Tb
x
(MoO4)4 (KETMO). KETMO samples were synthesized under two different heating
and cooling conditions. A K5Tb(MoO4)4 (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 R3̅m) were presented only for the high-temperature (HT or α-)
KETMO (0 ≤ x ≤ 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-K5Eu0.6Tb0.4(MoO4)4 structure was refined in the C2/m 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 C2/m(0β0)00 and the modulation vector q = 0.684b*. 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 5D4 → 7F
J
(J = 3–6) Tb3+ 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
λex = 481 nm for the KTMO single crystal was measured
as 50%. The intensity of the 5D4 → 7F5 Tb3+ transition increased with the
increase of x from 0.2 to 1 for LT and HT-KETMO.
Emission spectra of KETMO samples with x = 0.2–0.9
at λex = 377 nm exhibited an intense red emission
at ∼615 nm due to the 5D0 → 7F2 Eu3+ transition, thus indicating
an efficient energy transfer from Tb3+ to Eu3+.
The influence of preparation techniques on the structure and luminescent properties of K5Eu(MoO4)4 (KEMO) was investigated. KEMO phosphors were synthesized by three different techniques: solid state and sol-gel (sg) methods...
The influence of different synthesis routes on the structure and luminescent properties of KTb(MoO 4 ) 2 (KTMO) was studied. KTMO samples were prepared by solid-state, hydrothermal, and Czochralski techniques. These methods lead to the following different crystal structures: a triclinic scheelite-type α-phase is the result for the solid-state method, and an orthorhombic KY(MoO 4 ) 2 -type γ-phase is the result for the hydrothermal and Czochralski techniques. The triclinic α-KTMO phase transforms into the orthorhombic γ-phase when heated at 1273 K above the melting point, while KTMO prepared by the hydrothermal method does not show phase transitions. The influence of treatment conditions on the average crystallite size of orthorhombic KTMO was revealed by X-ray diffraction line broadening measurements. The electrical conductivity was measured on KTMO single crystals. The orthorhombic structure of KTMO that was prepared by the hydrothermal method was refined using synchrotron powder X-ray diffraction data. K + cations are located in extensive two-dimensional channels along the c-axis and the a-axis. The possibility of K + migration inside these channels was confirmed by electrical conductivity measurements, where strong anisotropy was observed in different crystallographic directions. The evolution of luminescent properties as a result of synthesis routes and heating and cooling conditions was studied and compared with data for the average crystallite size calculation and the grain size determination. All samples' emission spectra exhibit a strong green emission at 545 nm due to the 5 D 4 → 7 F 5 Tb 3+ transition. The maximum of the integral intensity emission for the 5 D 4 → 7 F 5 emission under λ ex = 380 nm excitation was found for the KTMO crashed single crystal.
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