High-temperature Solution Method Research Articles

Polarized spectroscopic properties of Tm3+/Ho3+:YPO4 single crystal: A potential gain medium for tunable and ultrafast pulse laser at 2.0 μm

YPO4 crystals co-doped with Tm3+ and Ho3+ ions (Tm3+/Ho3+:YPO4) have been prepared using the high temperature solution method. The crystal structure, electronic band and polarized spectroscopy were characterized. It has intense and broad absorption bands around 800 nm with a full width at half maximum of 14.31 nm and 22.95 nm for π- and σ-polarizations, respectively. Based on Judd-Ofelt theory, relevant parameters about the radiative properties were systematically analyzed. The broad emission bands of Tm3+ and Ho3+ from 1600 to 2300 nm allow wide tunability of laser oscillation. The energy transfer efficiency from Tm3+: 3F4 to Ho3+: 5I7 level in YPO4 crystal was calculated to be 54.59 %. The results show that Tm3+/Ho3+:YPO4 is expected to be applied in tunable and ultrafast pulse laser at 2.0 μm.

Crystal growth and spectroscopic performances of Dy3+:YPO4 and Dy3+/Tb3+:YPO4 crystal as potential yellow laser gain mediums

Exploring new Dy3+-doped laser gain medium is still a challenge for constructing efficient yellow solid-state laser at current stage. In this paper, high quality Dy3+:YPO4 and Dy3+/Tb3+:YPO4 crystals were grown by the high temperature solution method. The crystal structure, chemical composition, phonon energy, polarized absorption and emission spectra, fluorescence lifetime were investigated. The obtained large FWHMs (6 nm) and absorption cross-sections (3.87×10−21 cm2) of Dy3+:YPO4 and Dy3+/Tb3+:YPO4 crystals at 454 nm indicate that they can be efficiently pumped by the commercial blue laser diodes. J-O intensity (Ω2, Ω4, Ω6), fluorescence branching rate and radiative lifetime of Dy3+ ions were calculated by J-O theory. Benefiting from the appropriate phonon energy, the emission cross-section of Dy3+: YPO4 crystal at 575 nm can reach 5.04×10−21 cm2. Moreover, after co-doping Tb3+ as deactivating ion, the emission cross-section of Dy3+/Tb3+: YPO4 crystal at 575 nm was promoted to 5.98×10−21 cm2 by a resonance energy transfer process between the Dy3+-6H13/2 and Tb3+-7F4. Therefore, both Dy3+:YPO4 and Dy3+/Tb3+:YPO4 crystals are potential candidates for yellow laser gain mediums.

NaRbB10O14(OH)4 and Na3CsB10O16(OH)2: Two Cases of Hydroxyborates with [B5Om(OH)n] Units and Deep Ultraviolet Cutoff Edges.

Two deep ultraviolet (DUV) hydroxylated-alkali-metal borates, NaRbB10O14(OH)4 (I) and Na3CsB10O16(OH)2 (II), have been successfully synthesized by a high-temperature solution and solvothermal method. Both of them feature [B5Om(OH)n] units, which form chains for (I) and bilayers with nine-membered boron rings for (II). It is worth noting that both compounds exhibit very wide theoretical band gaps of 7.33 and 6.55 eV for (I) and (II), respectively, which denotes that they should have desirable DUV transmittance ability. Moreover, the title compounds have moderate birefringence owing to the π-conjugated [BO3], [BO2(OH)] groups, corresponding to 0.070 for (I) and 0.054 for (II) at 1064 nm. The structure characteristics and optical properties were also investigated and discussed. The results make it beneficial for exploring novel DUV hydroxylated borate optical crystals.

Ba5Gd3(BO3)6F: A new alkaline earth-rare earth fluoroborate with magnetocaloric effect

A new alkaline-earth and Gd3+ borate, Ba5Gd3(BO3)6F, has been successfully grown through a high-temperature solution method employing a BaF2-NaF-B2O3 flux. This compound crystallizes in the monoclinic space group P21/c with lattice parameters of a = 13.679(4) Å, b = 8.694(3) Å, c = 7.664(2) Å, β = 99.116(7)°, V = 899.9(5) Å3, and Z = 1. Its three-dimensional structure consists of the [Ba/GdO] polyhedra and [FBa4Gd2] octahedra layers. Magnetic analysis reveals that Ba5Gd3(BO3)6F exhibits a magnetocaloric effect with a maximum −ΔSm of 29.86 J kg–1 K–1 at 3 K and 9 T. Additionally, the thermal stability, along with infrared (IR) and ultraviolet–visible–near-infrared (UV–Vis–NIR) diffuse reflectance spectra, were thoroughly examined. First-principles calculations further explored the electronic band structure and densities of states.

Pb3[O10Pb20](SiO4)4X10 (X = Cl, Br): The First Pb-Containing Halogen Silicates with Mirror-Symmetric Pseudo-Aurivillius Bilayers.

Two new congruently melting Pb-containing halogen silicates, Pb3[O10Pb20](SiO4)4X10 (X = Cl, Br), have been synthesized using a high-temperature solution method. Their crystal structures were determined by single-crystal X-ray diffraction, and both compounds crystallize in the orthorhombic space group Cmca. In both structures, the mirror-symmetric bilayer composed of Pb-O polyhedra is observed for the first time in Pb-containing silicates and belongs to α-PbO derivatives and is related to the Aurivillius phase. Thermal behavior analysis, UV-vis diffuse-reflectance spectroscopy, and IR spectroscopy were also performed. The Pb3[O10Pb20](SiO4)4Cl10 matrix was doped with Eu3+ ions as a dopant, and its potential application in fluorescence was confirmed from the resulting orange-red emission.

Crystal Structure and Optical Characteristics of K2Nd2O(BO3)2

A rare earth oxyborate crystal K2Nd2O(BO3)2 has been grown by means of high temperature solution method for the first time. It crystallizes in monoclinic P21/c (No. 14) space group, and the lattice parameters are a=11.318(6) Å, b=6.575(4) Å, c=10.689(6) Å, β=117.062(12)°, and Z=4. The absorption spectrum, emission spectrum, and fluorescence lifetime of K2Nd2O(BO3)2 have been evaluated, and the foundational spectral parameters have been analysed according to the Judd‐Ofelt theory. The high concentration of activated ions (1.13×1022 ions/cm3), large absorption coefficient (87.63 cm‐1), long fluorescence lifetime (91.2 μs), and large emission cross section (2.03×10‐20 cm2) of K2Nd2O(BO3)2 suggest its potential applications of microchip lasers.

Rb3MgB5O10 and LiBaAl(BO3)2: covalent tetrahedra MO4-containing borates with deep-ultraviolet cutoff edges.

Borates are favored by materials scientists and chemists because of the significant electronegativity difference between B and O atoms and their flexible assembly modes resulting in abundant structures and excellent properties. For the design of deep-ultraviolet (DUV) optical crystals with excellent macroscopic performance, it is crucial to choose appropriate cations and anionic groups and microscopically reasonable assembly patterns. Herein, by introducing covalent tetrahedra ([MO4], M = Mg, Al), two new mixed alkali metal and alkaline earth metal borates, Rb3MgB5O10 and LiBaAl(BO3)2, were synthesized using the melt method and high-temperature solution method. They contain M-B-O two-dimensional (2D) layers (2∞[MgB5O10] and 2∞[Al(BO3)2], respectively) composed of isolated B-O groups ([B5O10]5- and [BO3]3-, respectively) and metal-centered tetrahedral connectors ([MgO4]6- and [AlO4]5-, respectively). Combining experiments and theoretical calculations shows that the two compounds have short cutoff edges (<200 nm) and moderate birefringences. Further analysis manifests that the isolated [MO4] covalent tetrahedra can optimize the arrangement of anion groups, guarantee the balanced optical properties of materials, and point out the direction for further exploration of novel borate structures.

Two new rare-earth oxyborates Ba4BiTbO(BO3)4 and Ba1.54Sr2.46BiTbO(BO3)4 and luminescence properties of the Ba4BiTb1-xEuxO(BO3)4 phosphors.

Single crystals of two new terbium oxyborates Ba4BiTbO(BO3)4 and Ba1.54Sr2.46BiTbO(BO3)4 were obtained by the high-temperature solution method. They crystallize in the hexagonal P63/mmc group (Z = 2) with lattice parameters of a = 5.41865(9) Å, c = 26.3535(5) Å, V = 670.12(3) Å3 and a = 5.36534(19) Å, c = 26.0661(10) Å, V = 649.83(5) Å3, respectively. Their crystal structures feature two kinds of layers: [Tb(BO3)2]n3n- formed by corner-sharing TbO6 octahedra and BO3 triangles, as well as [Bi(BO3)2O]n5n- consisting of Bi2O13 dimers and BO3 groups, with alkali-earth cations sitting inside and between the layers. In addition, solid solutions of Ba4BiTb1-xEuxO(BO3)4 (0 ≤ x ≤ 0.2) were prepared via the solid-state reaction method. The obtained products were characterized by powder XRD, SEM, IR/Raman, XPS, DRS, and luminescence spectroscopy. It was found that as the Eu3+ doped content varies from x = 0 to 0.2, the emission color of the Ba4BiTb1-xEuxO(BO3)4 phosphors can be adjusted from cyan to near-white and then to orange-red or from green to orange and then to red under the excitation of 349 and 377 nm, respectively. Furthermore, the emission intensities and chromaticity coordinates were found to be sensitive to the temperature for the phosphor Ba4BiTb0.999Eu0.001O(BO3)4 upon 377 nm excitation. The above results demonstrate that Ba4BiTb1-xEuxO(BO3)4 phosphors have potential as multifunctional materials for solid-state lighting and temperature sensing applications.

Ba5Y12Zn[O(SiO4)]8: a novel non-centrosymmetric silicate with a short ultraviolet cut-off edge featuring [ZnSi4O16] and [SiO4] units

A new silicate Ba5Y12Zn[O(SiO4)]8 was synthesized by a high-temperature solution method and experimental results show a short cut-off edge of 204 nm, an SHG response (0.3 × KDP), and thermal stability. Meanwhile, the effect of the nM : nSi ratio on the Si–O framework was studied.

Structural characterisation and optical properties of new alkaline earth phosphate CaMg(P4O12) and alkaline alumophosphate Cs3Al4(PO4)5

Two new family members of mixed alkali-earth metal phosphate and aluminophosphate CaMg(P4O12) and Cs3Al4(PO4)5 were prepared from phosphates system using a high-temperature solution method. The structural analysis results show that...

Cd8(BO3)4SiO4: Metal Cation Inducing the Formation of Isolated [BO3] and [SiO4] Units in Borate Silicate.

The first compound of cadmium-borate silicate Cd8(BO3)4SiO4, crystallizing in space group P42/n (no. 86), has been successfully synthesized by the conventional high-temperature solution method and melts congruently. The zero-dimensional anionic groups of Cd8(BO3)4SiO4 are isolated [BO3] triangles and isolated [SiO4] tetrahedra which are filled in the framework formed by [CdO6] polyhedra. It has a moderate birefringence (Δn = 0.053 at 546 nm), which is measured by experiment and evaluated by first-principles calculations; meanwhile, the source of birefringence is revealed through the response electronic distribution anisotropy method. The UV-vis-NIR diffuse reflectance spectrum indicates that Cd8(BO3)4SiO4 possesses a wide optical transparency range, with a UV cutoff edge at about 254 nm. This work enriches the structure chemistry of borate silicates, and we discussed the possible methods for the exploration and synthesis of novel optical crystals possessing zero-dimensional anionic groups in the borate silicate system.

Crystal growth and spectral properties of a mixed crystal Nd3+:LuYPO4

A new mixed orthophosphate crystal of Nd3+:LuYPO4 was grown by high temperature solution method successfully. The optical properties including polarized absorption and emission spectra as well as the fluorescence decay curve have been investigated in detail. The calculated absorption cross-sections were 18.6 × 10−20 cm2 at 803 nm with a FWHM of 6.10 nm for π-polarization and 8.96 × 10−20 cm2 at 804 nm with a FWHM of 6.07 nm for σ-polarization, respectively. The broad absorption bands wider than those of Nd:YPO4 and Nd:LuPO4 crystals confirm that the incorporation of Lu3+ ions results in a effectively inhomogeneous broadening of the spectra. Based on J-O theory, some typical parameters such as J-O intensity, fluorescence branching rate and radiation lifetime of Nd3+ ions in Nd:LuYPO4 crystal were systematically calculated. Besides, five strong emission peaks located at 1054, 1061, 1066, 1076 and 1081 nm can be observed obviously from fluorescence spectra. All the results show that Nd:LuYPO4 crystal is a promising laser material applied to 1.0 μm with multi-wavelength emission characteristics.

K2Sr4(PO3)10: A Polyphosphate with Deep-UV Cutoff Edge and Enlarged Birefringence.

A new polyphosphate K2Sr4(PO3)10 is synthesized by a high-temperature solution method. This compound crystallizes in the triclinic space group of P1̅, consisting of the 1D infinite [PO3]∞ chains and K and Sr ions between the chains. Compared with AM2(PO3)5 (A = K, Rb, Cs; M = Ba, Pb), K2Sr4(PO3)10 exhibits a more complex [PO3]∞ chain structure and more diverse metal cationic coordination environment. More importantly, K2Sr4(PO3)10 has both a deep-UV cutoff edge (<200 nm) and a significantly enlarged birefringence. First-principles calculations indicate that the birefringence of K2Sr4(PO3)10 is 0.017 at 1064 nm, about 2 times that of RbBa2(PO3)5 (0.008 at 1064 nm), which reaches a new height among the reported mixed alkali metal and alkaline earth metal phosphate. Theoretical calculations and structural analyses show that the enlarged birefringence of K2Sr4(PO3)10 mainly originates from the [PO3]∞ chains arranged in an inverted zigzag. This discovery introduces a new strategy for devising novel phosphate deep-UV optical crystals with a large birefringence.

Improvement on Magnetocaloric Effect through Structural Evolution in Gadolinium Borate Halides Ba2Gd(BO3)2X (X = F, Cl).

A new Gd3+-containing borate Ba2Gd(BO3)2F has been successfully grown via the high-temperature solution method using BaF2-NaF-B2O3 flux. Ba2Gd(BO3)2F crystallizing in the orthorhombic space group Pnma is with lattice parameters a = 7.571(4) Å, b = 10.424(5) Å, c = 8.581(4) Å, α = β = γ = 90°, and Z = 2. Its three-dimensional framework was constructed from interesting pinwheel-like [Gd(BO3)F]∞ layers bridged by sharing [BO3]3-, which is different from the [Gd(BO3)]∞ layer in the model structure Ba2Gd(BO3)2Cl. The magnetic measurements indicated that Ba2Gd(BO3)2F has a larger magnetocaloric effect with -ΔSm,max = 27.82 J·kg-1·K-1at 2 K and 9 T than that of Ba2Gd(BO3)2Cl under the same conditions. Moreover, thermal stability, infrared spectrum (IR), and ultraviolet-visible-near-infrared diffuse reflectance spectrum were carried out to characterize the title compounds. The first-principles computations also looked into the electronic band structures, densities of states, and refractive indices.

Ba3.75MgB7O14F2.5: A Mixed Alkaline-Earth Metal Borate Fluoride with Short Ultraviolet Cutoff Edge and Large Birefringence.

Fluorine-containing borate crystal materials are particularly attractive due to their rich structural chemistry and excellent properties for optical applications. In this work, a new compound Ba3.75MgB7O14F2.5 has been synthesized through the high-temperature solution method. In the crystal structure of Ba3.75MgB7O14F2.5, the [B7O14] basic building unit and the [MgO3F3] octahedra are interconnected to create a complex three-dimensional network. The structural feature of the less commonly observed [B7O14] units is discussed, and it has been found that such units in Ba3.75MgB7O14F2.5 are most conducive to achieving large birefringence. In addition, Ba3.75MgB7O14F2.5 exhibits good thermal stability, a short ultraviolet cutoff of 203 nm, and large birefringence (0.081@546 nm), indicating its potential as a new UV birefringent crystal.

Rare-Earth Scandium Borate Fluoride with a Deep-Ultraviolet Cutoff Edge.

Through reasonable selections of raw materials and experimental methods, a new rare-earth borate fluoride K11Sc5(B5O10)4F6 is synthesized successfully by the high-temperature solution method in a closed system, which is the first noncentrosymmetric scandium borate fluoride. It crystallizes in the Fdd2 space group of the orthorhombic crystal system and features an extremely complicated structure constructed by the fundamental building blocks [B5O10] units, Sc-based, and K-based polyhedra. To our knowledge, K11Sc5(B5O10)4F6 is the only rare-earth borate that contains two kinds of [B5O10] groups and crystallizes in the Fdd2 space group, enriching the structural chemistry of rare-earth borates and rare-earth borate fluorides. Additionally, it is discussed in detail how F can significantly improve performance by modifying the modules in a comparison of structures. Discussion on rational synthetic conditions is instructive for obtaining rare-earth borate fluorides. Furthermore, a short cutoff edge (<190 nm) is experimentally confirmed, indicating the potential application of K11Sc5(B5O10)4F6 in ultraviolet/deep-ultraviolet regions.

Preparation, spectral properties and Judd-Ofelt analysis of Ho3+:YPO4 crystal

The Ho3+:YPO4 crystal was grown by the high-temperature solution method successfully. The preparation process, crystal structures and spectroscopic properties, including polarized absorption spectra, FT-IR and Raman spectra, polarized fluorescence spectra and lifetime were characterized and analyzed in detail. The absorption cross-sections at around 643 nm were calculated to be 6.93 × 10−20 cm2 for π-polarization and 2.30 × 10−20 cm2 for σ-polarization, respectively. And the spectroscopic quality factor (Ω4/Ω6) was determined to be 1.18. The full width at half the maximum (FWHM) of emission bands at the peak of 2070 nm can reach 102.43 nm for π-polarization and 83.83 nm for σ-polarization, respectively. The results show that Ho3+:YPO4 crystal is a promising laser medium which is expected to be used in around 2.0 μm.

Stereochemically Active Tin(II)-Induced Enhancement of Birefringence in SnII SnIV (PO4 )2 and SrSn(PO4 )PO2 (OH)2.

Two new tin(II) phosphates, SnII SnIV (PO4 )2 and SrSn(PO4 )PO2 (OH)2 , were synthesized by the high-temperature solution method and hydrothermal method, respectively. Theoretical study indicates that by introducing tin(II) with stereochemical activity lone pairs (SCALP) in metal phosphates, the birefringence was enhanced, 0.048@1064 nm for SnII SnIV (PO4 )2 and 0.080@1064 nm for SrSn(PO4 )PO2 (OH)2 .

Three Polyborates with High-Symmetry [B12O24] Units Featuring Different Dimensions of Anion Groups.

Three polyborates, namely, LiNa11B28O48, Li1.45Na7.55B21O36, and Li2Na4Ca7Sr2B13O27F9, were synthesized via the high-temperature solution method. All of them feature high-symmetry [B12O24] units, yet their anion groups exhibit distinct dimensions. LiNa11B28O48 features a three-dimensional anionic structure of 3[B28O48]∞ framework, which is composed of three units: [B12O24], [B15O30], and [BO3]. Li1.45Na7.55B21O36 possesses a one-dimensional anionic structure of 1[B21O36]∞ chain consisting of [B12O24] and [B9O18] units. The anionic structure of Li2Na4Ca7Sr2B13O27F9 is composed of two zero-dimensional isolated units, namely, [B12O24] and [BO3]. The novel FBBs [B15O30] and [B21O39] are present in LiNa11B28O48 and Li1.45Na7.55B21O36, respectively. The anionic groups in these compounds exhibit a high degree of polymerization, thereby augmenting the structural diversity of borates. And the crystal structure, synthesis, thermal stability, and optical properties were meticulously discussed to guide the synthesis and characterization of novel polyborates.

Structural Motif Cosubstitution Strategy for Designing Fluoroaluminoborate with the Sr2Be2B2O7-Type Double-Layered Structure.

The cosubstitution strategy often was applied to design borate optical crystal materials. Revealingly, a fluoroaluminoborate Sr2Al2.18B5.82O13F2 with Sr2Be2B2O7 (SBBO) double-layered like configuration has been rationally designed and successfully synthesized based on structural motif cosubstitution strategy via the high-temperature solution method. In Sr2Al2.18B5.82O13F2, a structural motif, the [Al2B6O14F4] unit, with edge-sharing [AlO4F2] octahedra was filled in interlamination of double-layer structure. The research indicates that Sr2Al2.18B5.82O13F2 features a short ultraviolet cutoff edge (<200 nm) and moderate birefringence (∼0.058 @ 1064 nm). As the first reported linker in the interlamination of double-layer structures, the [Al2B6O14F4] unit enlightens the synthesis and discovery of new layered structures in borates.