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In this review we discuss general trends in the use of alkali bromide and iodide (ABI) fluxes for exploratory crystal growth. The ABI fluxes are ionic solution fluxes at moderate to high temperatures, 207 to ~1,300°C, which offer a good degree of flexibility in the selection of the temperature profile and solubility. Although their main use is to dissolve and recrystallize “soft” species such as chalcogenides, many compositions with “hard” anions, including oxides and nitrides, have been obtained from the ABI fluxes, highlighting their unique versatility. ABI fluxes can serve to provide a reaction and crystallization medium for different types of starting materials, mostly the elemental and binary compounds. As the use of alkali halide fluxes creates an excess of the alkali cations, these fluxes are often reactive, incorporating one of its components to the final compositions, although some examples of non-reactive ABI fluxes are known.

A new germanate garnet compound, Ce2CaMg2Ge3O12, was synthesized via flux crystal growth. Truncated spherical, reddish-orange single crystals with a typical size of 0.1–0.3 mm were grown out of a BaCl2-CaCl2 melt. The single crystals were characterized by single-crystal X-ray diffraction analysis, which revealed that it adopted a cubic garnet-type structure with a = 12.5487(3) Å in the space group Ia−3d. Its composition is best described as A3B2C3O12, where Ce/Ca, Mg, and Ge occupied the A, B, and C sites, respectively. A UV–vis absorption spectroscopy measurement on the germanate garnet revealed a clear absorption edge corresponding to a band gap of 2.21 eV (λ = 561 nm). First-principle calculations indicated that the valence band maximum was composed of Ce 4f bands, whereas the conduction band minimum mainly consisted of Ce 5d bands. These findings explain the observed absorption edge through the Ce 4f → 5d absorption. Photoluminescence emission spectra exhibited a very broad peak centered at 600 nm, corresponding to transition from the lowest energy d level to the 4f levels.

Single crystals of four new layered uranyl phosphates, including three oxyfluoride-phosphates, were synthesized by molten flux methods using alkali chloride melts, and their structures were determined by single-crystal X-ray diffraction. Cs11[(UO2)12(PO4)3O13] (1) and Rb11[UO2)12(PO4)3O12F2] (2) contain uranyl phosphate layers exhibiting a new sheet topology that can be related to that of β-U3O8, while Cs4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (3) and Rb4.4K0.6[(UO2)6O4F(PO4)4(UO2)] (4) contain layers of a known isomer of the prominent phosphuranylite topology. The location of the fluorine in structures 2-4 is discussed using bond valence sums. First principles calculations were used to explore why a pure oxide structure is obtained for the Cs containing phase (1) and in contrast an oxyfluoride phase for the Rb containing phase (2). Ion exchange experiments were performed on 1 and 2 and demonstrate the ability of these structures to exchange approximately half of the parent alkali cation with a target alkali cation in an aqueous concentrated salt solution. Optical measurements were performed on 1 and 2 and the UV-vis and fluorescence spectra show features characteristic of the UO22+ uranyl group.

In this review we discuss general trends in the use of alkali bromide and iodide (ABI) fluxes for exploratory crystal growth. The ABI fluxes are ionic solution fluxes at moderate to high temperatures, 207 to ~1,300°C, which offer a good degree of flexibility in the selection of the temperature profile and solubility. Although their main use is to dissolve and recrystallize "soft" species such as chalcogenides, many compositions with "hard" anions, including oxides and nitrides, have been obtained from the ABI fluxes, highlighting their unique versatility. ABI fluxes can serve to provide a reaction and crystallization medium for different types of starting materials, mostly the elemental and binary compounds. As the use of alkali halide fluxes creates an excess of the alkali cations, these fluxes are often reactive, incorporating one of its components to the final compositions, although some examples of non-reactive ABI fluxes are known., (Copyright © 2020 Klepov, Juillerat, Pace, Morrison and zur Loye.)

A new germanate garnet compound, Ce 2 CaMg 2 Ge 3 O 12 , was synthesized via flux crystal growth. Truncated spherical, reddish-orange single crystals with a typical size of 0.1-0.3 mm were grown out of a BaCl 2 -CaCl 2 melt. The single crystals were characterized by single-crystal X-ray diffraction analysis, which revealed that it adopted a cubic garnet-type structure with a = 12.5487(3) Å in the space group Ia -3 d . Its composition is best described as A 3 B 2 C 3 O 12 , where Ce/Ca, Mg, and Ge occupied the A, B , and C sites, respectively. A UV-vis absorption spectroscopy measurement on the germanate garnet revealed a clear absorption edge corresponding to a band gap of 2.21 eV (λ = 561 nm). First-principle calculations indicated that the valence band maximum was composed of Ce 4 f bands, whereas the conduction band minimum mainly consisted of Ce 5 d bands. These findings explain the observed absorption edge through the Ce 4 f → 5 d absorption. Photoluminescence emission spectra exhibited a very broad peak centered at 600 nm, corresponding to transition from the lowest energy d level to the 4 f levels., (Copyright © 2020 Chen, Yan, Kuwabara, Smith, Iwasa, Ogino, Matsushita, Tsujimoto, Yamaura and zur Loye.)

Single crystals of four new layered uranyl phosphates, including three oxyfluoride-phosphates, were synthesized by molten flux methods using alkali chloride melts, and their structures were determined by single-crystal X-ray diffraction. Cs 11 [(UO 2 ) 12 (PO 4 ) 3 O 13 ] ( 1 ) and Rb 11 [UO 2 ) 12 (PO 4 ) 3 O 12 F 2 ] ( 2 ) contain uranyl phosphate layers exhibiting a new sheet topology that can be related to that of β-U 3 O 8 , while Cs 4.4 K 0.6 [(UO 2 ) 6 O 4 F(PO 4 ) 4 (UO 2 )] ( 3 ) and Rb 4.4 K 0.6 [(UO 2 ) 6 O 4 F(PO 4 ) 4 (UO 2 )] ( 4 ) contain layers of a known isomer of the prominent phosphuranylite topology. The location of the fluorine in structures 2 - 4 is discussed using bond valence sums. First principles calculations were used to explore why a pure oxide structure is obtained for the Cs containing phase ( 1 ) and in contrast an oxyfluoride phase for the Rb containing phase ( 2 ). Ion exchange experiments were performed on 1 and 2 and demonstrate the ability of these structures to exchange approximately half of the parent alkali cation with a target alkali cation in an aqueous concentrated salt solution. Optical measurements were performed on 1 and 2 and the UV-vis and fluorescence spectra show features characteristic of the UO 2 2 + uranyl group.