KMgF3及KMgF3：Eu^2＋晶体的射线辐照效应

KMgF3F Eu晶体中Eu^3＋→Eu^2＋的转换率在低浓度掺杂时接近100％，完全转换的饱和掺杂摩尔分数为0．29％．实验条件下，KMgF，晶体的X射线1h辐照损伤可在约100h后恢复；KMgF3：Eu^2＋晶体经X射线辐照后，360nm锐峰发射强度略有降低．不同剂量的γ射线辐照，KMgF3晶体热释光曲线的各个温度峰强度变化明显不同，即使小剂量辐照，造成的损伤也较难恢复，如γ射线辐照剂量为10^3Gy时，辐照损伤的恢复时间约需30d．KMgF3：Eu^2＋晶体360nm锐峰发射强度随γ射线辐照剂量增大

Shape and Phase-Controlled Synthesis of KMgF3 Colloidal Nanocrystals via Microwave Irradiation

In this paper, we present a facile one-step route to controlled synthesis of colloidal KMgF3 nanocrystals via the thermolysis of metal trifluoroacetate precursors in combined solvents (OA/OM) using microwave irradiation. X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric and differential thermal analysis (TG-DTA), Fourier transform infrared (FT-IR) spectra, and photoluminescence (PL) spectra were employed to characterize the samples. Only through the variation of the OA/OM ratio, can the phase and shape of nanocrystals be readily controlled, resulting in the formation of well-defined near-spherical nanoparticles, and nanoplates of cubic-phased KMgF3, as well as nanorods of tetragonal-phased MgF2, and a possible mechanism has been proposed to elucidate this effect. Furthermore, all these samples in this system can be well dispersed in nonpolar solvents such as cyclohexane to form stable and clear colloidal solutions, due to the successful coating of organic surfactants (OA/OM) on the nanocrystal surface.

Preparation of KMgF3 and Eu-doped KMgF3 nanocrystals in water-in-oil microemulsions

In this study, KMgF3:Eu2+ luminescent nanocrystals (NCs) were prepared in water/cetyltrimethylammonium bromide (CTAB)/2-octanol microemulsions. The KMgF3:Eu2+ NCs were characterized by transmission electron microscopy (TEM), X-ray diffractometer (XRD), fluorescence spectrum, infrared spectroscopy (IR) and elementary analysis. The results showed that the size of the KMgF3:Eu2+ NCs was hardly affected by water content and surfactant (CTAB) concentration. The emission spectrum showed that the position of the 362 nm peak is due to the K+ sites substituted Eu2+. Two emission peaks located at 589 and 612 nm can be attributed to Eu3+, which exist at two different types of Eu3+ centers: one is Eu3+ at a K+ site, the other is clustering of Eu3+ ions in the interstices of KMgF3 host lattice.

Study on stimulated emission of Eu2+ in crystal KMgF3 : Eu2+

The line emission peak of Eu2+ ion in crystal KMgF3 is at 360 nm. The probability of stimulated emission on 4f(7) (P-6(7/2))-> 4f(7)(S-8(7/2)) transition was predicted with a four-level decay model of Eu2+6P7/2 excited states proposed by the authors. Optic gain and net gain coefficient (g = 11.4 +/- 3.2)cm(-1) of 360 nm emission in crystal KMgF3 : Eu2+ were measured by ASE method, and the predication was proved by experiment. The net gain coefficient can be increased by annealing or doping crystal KMgF3 : Eu2+ with Gd3+ or Ce3+.

Spectroscopic studies on charge transfer from Ce3+, to Yb3+ in KMgF3 : Ce, Yb nanocrystals

Nanocrystals of KMgF3 single-doped and codoped with Ce3+ or/and Yb3+ were synthesized separately by the microemulsion method. The X-ray diffraction(XRD) patterns were indexed to show that the KMgF, crystal system was unchanged. The fluorescent spectra of KMgF3:Ce, Yb polycrystal powders were studied and compared with those of the Ce, Yb doped KMgF3 crystals produced using the high-temperature solid phase method. The diffuse reflection spectra and infrared. emission of KMgF3:Ce, Yb were investigated. From the results, the authors could confirm that there were charge transfer processes from Ce3+ to Yb3+ in both KMgF3: Ce,Yb nanocrystals and polycrystal powders.

Synthesis and fluorescence properties of Eu2+-doped KMgF3 nanoparticles

The phase diagram of a cetyltrimethyl ammonium bromide( CTAB)/n-butanol/n-octane/KNO3-Mg( NO3)(2) system was drawn. Nanoparticles of Eu2+-doped KMgF3 were prepared from the quaternary microemulsions of cetyltrimethyl ammonium bromide(CTAB), n-butanol, n-octane and water. The X-ray diffraction(XRD) patterns were indexed to a pure KMgF3 cubic phase. The environmental scanning electron microscopic (ESEM) images show the presence of spherical Eu2+-doped KMgF3 nanoparticles with a diameter of ca. 20 nm. The emission of KMgF3: Eu2+ nanoparticles peaks at 360 mn. The excitation band was observed at 250 nm with a blue shift of ca. 70 nm compared with that of KMgF3: Eu2+ single crystal. The preparation method of nano-KMgF3: Eu2+/PMMA composite films was inquired into.

Optical spectroscopy properties of KMgF3 : Eu2+ nanocrystals and powder synthesized by microemulsion and solvothermal process

Nanocrystals and powders of KMgF3 doped with Eu2+ were synthesized by the microemulsion method and the solvothermal process, respectively. The emission and excitation spectra of KMgF3:Eu2+ phosphors were measured and compared with those of the samples synthesized through a solid. state reaction, Bridgman-Stockbarger method, and mild hydrothermal technique. The KMgF3: Eu2+ samples synthesized by means of the microemulsion method and the solvothermal process show only a sharp emission peak located at 360 nm, in the emission spectra, which arises from the f -> f(P-6(1/2)-> S-8(1/2)) transition of Eu2+. The broad emission bands appear at 420 nm,,which arises from Eu2+ <- O2- cannot be observed(in the mild hydrothermal and single crystal samples, the emission peak at 420 nm besides the emission of Eu2+ at 360 nm is observed). In the excitation spectrum of the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process, the excitation peaks show an intensive blue shift. The blue shift can he attributed to the lower oxygenic content in the KMgF3: Eu2+ samples synthesized by the microemulsion method and the solvothermal process.

Growth and vibrational spectra of doped KMgF3 single crystal

The different ions doped KMgF3 single crystals are prepared by the vertical Bridgman method. The near-infrared absorption spectra for different parts of all as-growth crystals indicate that there is the best transparency in middle part. The correlation between the vibronic frequencies of Eu2+ and the site displacement of Cu+ co-doped ions is firstly studied, which indicates that Cu+ ions replace the site of the Mg2+ ions. The co-doped Eu2+ counteracts the charge misfit causing by the replacement of Mg2+ with Cu+. The overlapping of the emission spectra of the Eu2+ and the excitation spectra of the Cu+ results in the energy transfer from Eu2+ to Cu+.

Solvothermal synthesis of the complex fluorides KMgF3 and KZnF3 with the Perovskite structures

The complex fluorides KMgF3 and KZnF3 with Perovskite structures were solvothermally synthesised at 150-180degreesC and characterised by means of X-ray powder diffraction, scanning electron microscopy, thermogravimetric analysis and infrared spectroscopy.

Study of color centers and trace oxygen in KMgF3 : Eu single crystal

Using the Bridgeman-Stockbarger method, the KMgF3:EU2+ single crystal was grown. The color centers in unirradiated KMgF3:Eu crystal were studied. By thermal annealing, we confirmed the 422-nm emission resulted from color centers and oxygen centers, and we proved the energy transfer from EU2+ to color centers. From spectra, the relative oxygen content in crystal was calculated, and the relationships of oxygen displacing fluorine were studied.

P-6(7/2)-excited-state decay mechanism and energy-transfer processes in KMgF3 : Eu2+ and KMgF3 : EuX (X = Gd, Ce, Cr)

A four-level decay model in KMgF3:Eu2+ is proposed. The decay profiles of the P-6(7/2) excited state of Eu2+ are biexponential, and the physical implication of each term in the fit equation responsible for the model is interpreted. The evidence obtained spectroscopically for supporting the model is presented. A new method to study energy transfer between Eu2+ and X3+ in KMgF3:Eu-X (X = Gd, Ce, Cr) is established on the basis of the proposed model.

Mild hydrothermal synthesis and optical properties of the complex fluoride KMgF3 doped with Eu

KMgF3 doped with Eu was synthesized by mild hydrothermal method at 240 degreesC for the first time. The excitation and emission spectra of the KMgF3 : Eu2+ phosphor were measured. Comparing with the sample synthesized through solid state reaction, the variation in the excitation spectra at 360 nm resulted from the existences of V-K color centers; the low emission intensity was due to Eu2+ having transferred part energy to V-K color centers.

Vibronic transitions and site substitution of Eu2+ and codoped ions in KMgF3 : Eu-X (X=Ce, Cr, Gd, Cu) system

The high-resolution emission spectra of KMgF3 : Eu and KMgF3 : Eu-X(X = Ce, Cr, Gd, Cu) single crystals were measured at 300 and 77 K. The vibronic side bands of Eu2+ were characterized and an assignment of the normal mode frequencies to particular vibrations has been made. The correlation between the vibronic frequencies of Eu2+ and the site substitution of other co-dopcd ions was first found. The relationship between vibronic intensity of Eu2+ and other doped ions concentration showed that Cr3+, Gd3+ ions competed K+ sites with Eu2+ ions. Ce3+ and Eu3+ occurred the electron transference. The introduction of Cu+ made for Eu2+ substuting for K+ sites.

Site substitution and energy transfer of Eu2+ and Ce3+ in KMgF3 : Eu and KMgF3 : Eu-Ce single crystals

The high-resolution emission spectra of KMgF3 : Eu and KMgF3 : Eu-Ce single crystals were measured at 77 K. The site substitution of Eu2+ and Eu2+-Ce3+ co-doped system in KMgF3 was discussed. Eu2+ substituted for K+ sites on three different site-symmetry: cubic, trigonal and tetragonal. The attribution of all lines occurring in the emission spectra were ascertained. The indirect energy transfer from P-6(5/2) states of Eu2+ to 4f5d states of Ce3+ in KMgF3 : Eu-Ce was observed and the energy transfer mechanism was studied. The d-d interaction among levels was proposed.

Four-level decay model of P-6(7/2) excited state of Eu2+ ion in KMgF3

A four-level model of P-6(7/2) excited state of Eu2+ ion in KMgF3: Eu2+ has been proposed. The decay profiles of the P-6(7/2) excited sstate of Eu2+ are two exponential and the physical implication of each term in the fit equation responsible for the model is interpreted. The data obtained spectroscopically are in good agreement with the fit results.