NaBa12(BO3)7F4 (NBBF) dichroic crystals: optical properties and dielectric permittivity.

Three NaBa12(BO3)7F4 crystals were grown in the BaO-BaF2-B2O3-Na2O system from three different compositions of high-temperature solution. With the use of optical spectroscopy, energy-dispersive X-ray spectroscopy, and the Schering bridge method it was found that the crystals revealed sharp differences in their optical and dielectric properties. The relative permittivity of the crystals in direction perpendicular to the optical axis reached 319(5). The minimum deviation technique was used for refractive index measurements.

A Photoluminescence Study of Eu3+, Tb3+, Ce3+ Emission in Doped Crystals of Strontium-Barium Fluoride Borate Solid Solution Ba4-xSr3+x(BO3)4-yF2+3y (BSBF).

The present study is aimed at unveiling the luminescence potential of Ba4-xSr3+x(BO3)4-yF2+3y (BSBF) crystals doped with Eu3+, Tb3+, and Ce3+. Owing to the incongruent melting character of the phase, the NaF compound was used as a solvent for BSBF crystal growth. The structure of BSBF: Eu3+ with Eu2O3 concentration of about 0.7(3) wt% was solved in the non-centrosymmetric point group P63mc. The presence of Eu2O3 in BSBF: Eu3+ leads to a shift of the absorption edge from 225 nm to 320 nm. The photoluminescence properties of the BSBF: Ce3+, BSBF: Tb3+, BSBF: Eu3+, and BSBF: Eu3+, Tb3+, Ce3+ crystals have been studied. The unusual feature of europium emission in BSBF is the intensively manifested 5D0→7F0 transition at about 574 nm, which is the strongest for BSBF: Eu3+ at 370 nm excitation and for BSBF: Eu3+, Tb3+, Ce3+ at 300 nm and 370 nm excitations. No evidence of Tb3+→Eu3+ energy transfer was found for BSBF: Eu3+, Tb3+, Ce3+. The PL spectra of BSBF: Eu3+ at 77 and 300 K are similar with CIE chromaticity coordinates of (0.617; 0.378) at 300 nm excitation and (0.634; 0.359) at 395 nm excitation and low correlated color temperature which implies application prospects in the field of lightning. Due to the high intensity of 5D0→7F0 Eu3+ transition at 370 nm excitation, the BSBF: Eu3+ emission is yellow-shifted.

LiBa12(BO3)7F4 (LBBF) crystals doped with Eu3+, Tb3+, Ce3+: structure and luminescence properties.

The luminescent properties of single crystals and polycrystalline samples of LiBa12(BO3)7F4 (LBBF) doped and co-doped with Eu3+, Tb3+, and Ce3+ have been studied in order to disclose their potential for application in white light-emitting diodes. Deciphering of LBBF:Eu3+ crystal structure (P42/mbc) makes it possible to determine the scheme of heterovalent isomorphic substitution 3Ba2+ ← 2Eu3+ + □, □ - vacancy in barium sites. Luminescent properties of LBBF crystals co-doped with Eu3+, Tb3+, Ce3+ and Eu3+, Tb3+ are compared. Both crystals demonstrate the luminescence close to day light with CIE coordinates and correlated color temperature (0.280; 0.305), 9232 K for LBBF:Eu3+,Tb3+,Ce3+ and (0.353; 0.390), 4849 K for LBBF:Eu3+,Tb3+ at 300 K at 370 nm excitation. The study of polycrystalline samples LBBF:Ce3+, LBBF:Tb3+, and LBBF:Eu3+, using X-ray diffraction, shows that the homogeneity regions of solid solutions differ significantly. In solid solutions LBBF:Tb3+ and LBBF:Eu3+, a gradual change in symmetry in the "tetragonal → orthorhombic → tetragonal" series takes place as the concentration of the dopant increases. When excited at a wavelength 395 nm, LBBF:Eu3+ samples with the content of Eu3+ 0.5 wt% and 2 wt% demonstrate intense red light with a high quantum yield of 63 and 60%, respectively, which allows them to be used as red components of composite phosphors for white LEDs.

Experimental and Ab Initio Studies of Intrinsic Defects in "Antizeolite" Borates with a Ba12(BO3)66+ Framework and Their Influence on Properties.

The porous Ba12(BO3)66+ framework of the so-called "antizeolite" borates with channels along the c axis is capable of accommodating various guest anionic groups, e.g. [BO3]3-, [F2]2-, [F4]4-, and [(Li,Na)F4]3-. Taking as an example the Ba12(BO3)6[BO3][LiF4] crystal, we put forward the argument that the optical properties of "antizeolite" borates are strongly influenced by the degree of channel packing with anionic groups and, correspondingly, by the conjugated intrinsic defects. With the use of optical, electron-spin resonance, Raman spectroscopy, and ab initio calculations, it was shown that intrinsic defects largely impact the absorption of light in the visible and UV regions (the color of the bulk crystals can change from colorless to dark brown), absorption-edge position, dichroism, and other optical properties. The change in the optical absorption in the visible range is caused by the appearance of new states in the electronic structure inside the band gap, which are associated mainly with the presence of single and double F centers-fluorine vacancies that capture electrons-in [□F4]4-, [F2]2-, and [LiF4]3- groups. The formation of F centers in the [F2]2- group is the most energetically favorable. It has been found that Ba12(BO3)6[BO3][LiF4] crystals are optically active gyrotropic with an isotropic point at 499 nm at 300 K and are of interest for practical application as narrow-band light filters.

Nature of the Color of Borates with "Anti-Zeolite" Structure.

Crystals of the Mn xBa12(BO3)8-2 xF8 x phase were grown from a high-temperature solution. This new fluoride borate is built of positively charged [Ba12(BO3)6]6+ blocks, the so-called "anti-zeolite" pattern. Using X-ray single-crystal diffraction, the bulk atomic arrangement in the centrosymmetric tetragonal unit cell in I4/ mcm could be elucidated. Crystals of the (MnF6)4- group-containing solid solution Mn xBa12(BO3)8-2 xF8 x are dark brown in color in contrast to the differently colored crystals of (LiF4)3- group-containing "anti-zeolite" LiBa12(BO3)7F4 ( P42 bc). According to the electron spin resonance and optical spectroscopic investigation, the absorption spectrum of LiBa12(BO3)7F4 crystals results from the absorption of light by both exciton and free charge carriers and can be tuned by varying the initial composition of the high-temperature solution.