Synthesis and optical properties of Cr-doped Ba2In2O5 orange-brown oxides

Cr-doped Ba₂In_2-xCr_xO_5+y (0?≤?x?≤?0.5) orange-brown inorganic oxides have been successfully synthesized by solid-state reaction. X-ray diffraction (XRD) patterns show that their crystal structures transform from orthorhombic to cubic by increasing the Cr doping amount. Field emission scanning electron microscopy (FESEM) measurements show powder particles of irregular shape with average particle size of about 10?µm. The colors of the compounds are tuned from light yellow (x?=?0) to orange (x?=?0.1) and then to dark brown (x?=?0.5). X-ray photoelectron spectroscopy and UV–Vis absorption spectroscopy demonstrate the oxidation state of Cr to be +?6 and the change in color to be due to the metal-ligand charge transfer of Cr⁶⁺-O^2-.     

Preparation and conductive properties of double perovskite oxides Ba3Ba1+xTa2-xO9-δ

In this work, Ba₃Ba_1+xTa_2-xO_9-δ (x = 0, 0.1, 0.3, and 0.5) double perovskite proton conductors were prepared by solid-state reaction process. Phase compositions and microstructures were characterized by X-ray diffraction and field emission scanning electron microscope techniques. valence and semi-quantitative composition of components were identified by X-ray photoelectron spectroscopy. Conductivities of Ba₃Ba_1+xTa_2-xO_9-δ were then measured under various vapor and oxygen pressures by AC impedance spectroscopy technique. Results revealed linear increase in total conductivities of Ba₃Ba_1+xTa_2-xO_9-δ oxides as a function of temperature. Ba₃Ba_1.3Ta_1.7O_8.55 exhibited the highest total conductivity of 8.41 × 10^?4 S cm^?1 under humidity and 800 °C. The transport numbers calculated by defect equilibria model revealed. Ba₃Ba_1+xTa_2-xO_9-δ oxides as pure proton conductors at 400–800 °C. Also, transport numbers of oxide ions and holes both increased with temperature. Ba₃Ba_1.3Ta_1.7O_8.55 illustrated the highest protonic transport number of 0.60 at 800 °C. In sum, these results suggest that Ba₃Ba_1+xTa_2-xO_9-δ oxides display excellent proton conductivity.     

The effect of co-substitution on the microwave dielectric properties of Ba6-3xNd8+2xTi18O54(x=2/3) ceramics

In this work, the microwave dielectric properties of Ba₄(Nd_1-yBi_y)_28/3Ti_18-x(Al_1/2Ta_1/2)_xO₅₄(0≤x≤2, 0.05≤y≤0.2) ceramics co-substituted by A/B-site were studied. Firstly, (Al_1/2Ta_1/2)⁴⁺ was used for substitution at B-site. At 0≤x≤1.5, the above mentioned ceramic was found to exist in single-phase tungsten bronze structure, but at x = 2.0, the secondary phase appeared. Although the dielectric constant decreased by doping the (Al_1/2Ta_1/2)⁴⁺, but the quality factor was observed to improve by 40% and the temperature coefficient of resonant frequency decreased by 75%. Based on the above results, Bi³⁺ was introduced to Ba₄Nd_28/3Ti₁₇(Al_1/2Ta_1/2)O₅₄. The introduction of Bi³⁺ reduced the sintering temperature, greatly improved the dielectric constant, and ultimately decreased the temperature coefficient of resonant frequency, but it led to deterioration of quality factor. At last, with appropriate site-substitution content control (x = 1.0,y = 0.15), excellent comprehensive properties (ε_r = 89.0, Q × f = 5844 GHz @ 5.89 GHz，TCF = +8.7 ppm/°C) were obtained for the samples sintered at 1325 °C for 4 h.     

Rapid fabrication and phase transition of Nd and Ce co-doped Gd2Zr2O7 ceramics by SPS

A series of Nd and Ce co-doped Gd_2-xNd_xZr_2-yCe_yO₇ (0.0 ≤ x, y ≤ 2.0) ceramics were rapidly fabricated through spark plasma sintering (SPS) within 3?min. The effects of Nd and Ce contents on the phase composition, lattice parameter, active modes, microtopography and microstructure have been investigated in detail. XRD studies reveal that the compositions corresponding to 0.0 ≤ y ≤ 1.0 show a single phase and beyond 1.0 exhibit multiphase. The lattice parameters increase with elevated Nd and Ce content. The grains are densely packed on each other with cube-like shape, and the elements are almost homogeneously distributed in the compound. This synthetic method provides a simple pathway for the preparation of highly densified single phase ceramic at 1600–1700 ℃ for 3?min under pressure of 80?MPa.     

Simultaneously enhanced piezoelectricity and curie temperature in BiFeO3-based high temperature piezoelectrics

We report the structure, dielectric, ferroelectric and piezoelectric properties of Cr-Mn co-doped (1-y)BiFe_1-xCr_xO₃-yBaTi_1-xMn_xO₃ (0≤x≤0.04, 0.2≤y≤0.27) ceramics. By varying both x and y, a series of samples near morphotropic phase boundaries exhibiting both high ferroelectric Curie temperature T_C (∼580−643 °C) and relatively large piezoelectric constant d₃₃ are constructed. Especially, the sample with y = 0.24 and x = 0.02 is found to show coexistence of high depolarization temperature T_d (∼551 °C) and relatively large d₃₃∼116 pC/N, superior to most of those of BiFeO₃ based high-temperature piezoceramics reported previously. The enhanced ferroelectric T_C in the Cr-Mn modified samples can be ascribed to the combined effects of large lattice distortion and high tetragonal phase content. These results demonstrate that constructing morphotropic phase boundaries via considering simultaneously the role of lattice distortion might be effective route to realize high-temperature and high piezoelectricity in BiFeO₃-based systems.     

Oxide/oxide composites in the system Cr2O3-Y2O3-Al2O3

Ceramic compacts in the systems Al₂O₃–Y₂O₃, Cr₂O₃–Y₂O₃ and Y₃(Cr_yAl_1-y)₅O₁₂ (Cr-doped YAG) were prepared by solid state reaction in calcined co-precipitated powder mixtures of appropriate compositions. Various solid-solution phases were formed, e.g. Y₃(Al_1-xCr_x)₅O₁₂, YAl_yCr_1-yO₃ and Al_2-xCr_xO₃. Composite materials in the pseudo-binary or ternary systems Al₂O₃–Y₃Al₅O₁₂, Cr₂O₃–Y₂O₃ and Y₃(Al_1–xCr_x)₅O₁₂–YAl_yCr_1–yO₃–(Al_zCr_1−z)₂O₃ were obtained by hot-pressing appropriate powder precursors at 1600–1650°C for 1 h. The microstructure of the prepared materials was studied in a scanning electron microscope with element analysis facilities. X-ray diffraction was used to reveal the phases present and their lattice parameters. The chemical compatibility of these phases was investigated. The results are discussed with a special emphasis on the solubility of Cr in the YAG structure, and on the compatibility relationship between Cr-doped YAG and its neighbouring phases. A gel-coating process for preparing Al₂O₃–YAG composites with tailored microstructures is also described.     

Synthesis and optical properties of Ni/Co/Cr doped BaMg6Ti6O19

Novel green and blue chromophores based on Ni/Co/Cr doped BaMg₆Ti₆O₁₉ solid solutions are successfully synthesized through a solid-state reaction. The crystal structure of all the samples belongs to the magnetoplumbite structure with the space group of P6₃/mmc. The BaMg_6-x/2Ti_6-x/2Ni_xO₁₉ (0 ≤ x ≤ 0.3) compounds exhibit a light green (x = 0.1) to yellow-green (x = 0.3) color. The oxidation state of Ni is confirmed to be +2 valence and the d-d transition of Ni²⁺ in octahedral sites is responsible for color. BaMg_6-x/2Ti_6-x/2Co_xO₁₉ (0 ≤ x ≤ 0.3) series show a blue color and the intensity of blueness is increasing with the increase of Co content. The blue color is due to d-d transitions within Co²⁺ present in the tetrahedral sites. For BaMg_6-x/2Ti_6-x/2Cr_xO₁₉ (0 ≤ x ≤ 2) phases the color varies from light green (x = 0.2) to green (x = 2). Chromium exists in +3 and + 6 oxidation states and the observed color is due to charge transfer transition between Cr³⁺–Ti⁴⁺ and d-d transitions within octahedral Cr³⁺ sites resulting in strong absorption in the visible region. The synthesized colored oxides are mixed with PMMA to prepare novel green and blue PMMA polymer composites to evaluate their compatibility in plastics.     

High-entropy oxide phases with magnetoplumbite structure

Sintering of oxides and carbonates at 1400 °C gives crystalline high-entropy single phase products with a BaFe₁₂O₁₉ (magnetoplumbite) structure containing 5 doping elements at high concentration level: Ba(Fe₆Ti_1·2Co_1·2In_1.2Ga_1.2Cr_1.2)O₁₉. The complete list of explored substitutions includes K, Ca, Sr, Pb, La, Bi, Al, Ga, In, Ti, V, Cr, Mn, Co, and Ni. Loading to the batch more than 5 dopants or introduction of NiO, or V₂O₅ initiates formation of second phases like spinels or vanadates. Bi₂O₃ and K₂O are too volatile at sintering temperature and were evaporated from the samples.Due to large ionic radius, the In³⁺ cation is likely to be incorporated not only on Fe³⁺ sites, but also on Ba²⁺ sites, that follow from resulting crystal composition. The smallest di-valent and tri-valent cations, Sr²⁺ and Al³⁺, are found to preferably concentrate together in the same magnetoplumbite phase crystals within one sample.According to elemental analysis of selected hexagonal crystals in the investigated 8 doped samples the most prospective compositions for obtaining high-entropy single phase with magnetoplumbite structure can be formulated as (Ca,Sr,Ba,Pb,La)Fe_x(Al,Ga,In,Ti,Cr,Mn,Co)_12-xO₁₉ where x = 1.5–6.     

Effects of Sr2+ substitution on the crystal structure,Raman spectra,bond valence and microwave dielectric properties of Ba3-xSrx(VO4)2 solid solutions

The effects of Sr²⁺ substitution for Ba²⁺ on microwave dielectric properties and crystal structure of Ba_3-xSr_x(VO₄)₂ (0 ≤ x ≤ 3, BSVO) solid solution were investigated. Such Sr²⁺ substitution contributes to significant reduction in sintering temperature from 1400 °C to 1150 °C. Both permittivity (∑_r) and quality factor (Q × f) values decreased with increasing x value, which was determined to be related with the descending values of average polarizability and packing fraction, whereas the increase in τ_f value was explained by the decreased average VO bond length, A-site bond valence. BSVO ceramics possessed encouraging dielectric performances with ∑_r = 12.2–15.6 ± 0.1, Q × f = 44,340 - 62,000 ± 800 GHz, and τ_f = 24.5–64.5 ± 0.2 ppm/°C. Low-temperature sintering was manipulated by adding B₂O₃ as sintering additive for the representative Sr₃V₂O₈ (SVO) ceramic and only 1 wt.% B₂O₃ addition successfully contributed to a 21.7% decrease in sintering temperature to 900 °C, showing good chemical compatibility with silver electrodes, which render BSVO series and SVO ceramics potential candidates in multilayer electronic devices fabrication.     

Enhanced magnetodielectric properties of Co2Z ferrite ceramics for ultrahigh frequency applications achieved via Cr3+ ion doping

Phase formation, microstructure, magnetic properties, and dielectric properties of Ba_1.5Sr_1.5Co₂Fe₍₂₃−_x)Cr_xO₄₁ (0.0 ≤ x ≤ 1.0) ceramics, in which Fe³⁺ ions were substituted by Cr³⁺ ions, were systematically investigated. X-ray diffraction results reveal that Z-type hexagonal ferrite was formed by sintering at 1250 °C, and Cr³⁺ ions successfully enter lattice without destroying crystal structure. Analysis of the microstructure reveals that Cr³⁺ ion doping has significant effect on crystal micromorphology. Samples with x = 0.4 have the most homogeneous micromorphology and the highest sintering density of 5.12 g/cm³. In addition, under the influence of external magnetic field, all samples exhibit typical soft magnetic character and hysteresis characteristics, with saturation magnetization up to 63.86 emu/g (x = 0.6). Particularly, compared with undoped sample, Cr-doped samples have outstanding magnetic–dielectric properties. Firstly, with increasing Cr³⁺ amount, real part of the permeability (μ′) reaches the maximum value of 10.70 at x = 0.4, while cutoff frequency exceeds 2 GHz, and Snoek constant reaches ∼19.50 GHz. Furthermore, due to more homogeneous microstructure, samples with x = 0.4 have low magnetic loss and can maintain high quality factor (Q) over a broad frequency range. Moreover, real part of the permittivity (ε′) reaches the maximum value of 16.90 at x = 0.6, and dielectric loss remains lower than 0.013 for frequencies below 0.7 GHz. Consequently, magnetic–dielectric materials prepared in this work are expected to have extensive application prospects for ultrahigh-frequency devices.     

Synthesis,structure and luminescence properties of a novel red fluorescent material Ba2MgB2O6:Eu3+

The crystal structure of Ba_2-xMgB₂O₆:xEu³⁺ phosphors, synthesized using a solid-state reaction, have been confirmed by X-ray diffraction analysis. This study focuses on the site occupancy preference of Eu³⁺ ions within the matrix, which was determined using bond energy theory, fluorescent spectra, and a consideration of energy transport and decay curves. The impact of Eu³⁺ ion concentration on luminescence has been assessed, and an optimal concentration (x = 0.22) identified. The critical distance, R_c was 9.6 Å, with a calculated θ value of 19.67, indicating that quadrupole-quadrupole interaction plays a critical role in the quenching Ba_2-xMgB₂O₆:xEu³⁺ phosphors. The Ba_2-xMgB₂O₆:xEu³⁺ phosphors exhibited a color purity of 99.26%, and a quantum efficiency of 49.68%. The activation energy Ea was determined to equal 0.2987 eV. The results have established Ba_1.78MgB₂O₆:0.22Eu³⁺ as a red fluorescent powder with high quantum efficiency and a millisecond fluorescence lifetime.     

Tunable luminescence properties and efficient energy transfer in Eu,Mn co-doped Ba2MgP4O13

A series of Ba₂Mg_1−xMn_xP₄O₁₃ (x = 0-1.0) and Ba_1.94Eu_0.06Mg_1−xMn_xP₄O₁₃ (x = 0-0.15) phosphors were prepared by conventional solid-state reaction. X-ray powder diffraction (XRD), the photoluminescence spectra, and the decay curves are investigated. XRD analysis shows that the maximum tolerable substitution of Mn²⁺ for Mg is about 50 mol% in Ba₂MgP₄O₁₃. Mn²⁺-singly doped Ba₂MgP₄O₁₃ shows weak red-luminescence peaked at about 615 nm. The Eu²⁺/Mn²⁺ co-doped phosphor emits two distinctive luminescence bands: a blue one centered at 430 nm originating from Eu²⁺ and a broad red-emitting one peaked at 615 nm from Mn²⁺ ions. The luminescence of Mn²⁺ ions can be greatly enhanced with the co-doping of Eu²⁺ in Ba₂MgP₄O₁₃. The efficient energy transfer from Eu²⁺ to Mn²⁺ is verified by the excitation and emission spectra together with the luminescence decay curves. The emission colors could be tuned from the blue to the red-purple and eventually to the deep red. The resonance-type energy transfer via a dipole-quadrupole interaction mechanism is supported by the decay lifetime data. The energy transfer efficiency and the critical distance are calculated and discussed. The temperature dependent luminescence spectra of the Eu²⁺/Mn²⁺ co-doped phosphor show a good thermal stability on quenching effect.     

Structural,magnetic properties,and electronic structure of Cr1−xMnxO2 solid solution

Bulk Cr_1-xMn_xO₂ samples are prepared by high pressure synthesis technology. The crystal structure, magnetic properties and electronic structure of the samples are investigated by experiments and theoretical calculation. The crystal structure of the samples are indexed to a rutile structure with space group P4₂/mnm. The lattice parameter a of the samples remains basically unchanged in accordance with Vegard's law, but the lattice parameter c decreases due to increasing Mn dopant content (x) as well as strong Metal–Metal bonding along the c-axis. The saturation magnetization of the Cr_1-xMn_xO₂ samples decreases with an increase in x. According to XPS analysis, there is electron transfer between Mn and Cr in Cr_1-xMn_xO₂. Mn exists as Mn²⁺ and Mn³⁺ions, and part of Cr is oxidized to Cr⁶⁺. Based on the XPS analysis, the magnetic moment of Cr_1-xMn_xO₂ is calculated and its value is in accordance with the experimental data.     

Effect of isovalent substitution on phase transition and negative thermal expansion of In2−xScxW3O12 ceramics

Solid solutions of In_2−xSc_xW₃O₁₂ (0≤x≤2) were successfully synthesized using the solid state reaction method. Effects of substituted scandium content on the phase composition, microstructure, phase transition temperatures and thermal expansion behaviors of the resulting In_2−xSc_xW₃O₁₂ (0≤x≤2) samples were investigated using X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and thermal mechanical analyzer (TMA). Results indicate that the obtained In₂W₃O₁₂ ceramic undergoes a structure phase transition from monoclinic to orthorhombic at 248 °C. This phase transition temperature of In₂W₃O₁₂ can be easily shifted to a lower temperature by partly substituting the In³⁺ with Sc³⁺. When the x value increased from 0 to 1, the phase transition temperatures of In_2−xSc_xW₃O₁₂ (0≤x≤2) samples decreased from 248 to 47 °C. All the In_2−xSc_xW₃O₁₂ (0≤x≤2) ceramics show fine negative thermal expansion below their corresponding phase transition temperatures. The negative thermal expansion coefficients of the In_2−xSc_xW₃O₁₂ (0≤x≤2) ceramics change in the range from −1.08×10⁻⁶ °C⁻¹ to −7.13×10⁻⁶ °C⁻¹.     

Layered perovskite-like compounds Y1 − x CaxBa2Cu3 − y ZnyO7 − δ: Physicochemical and electrical properties

Two series of yttrium cuprates Y_0.8Ca_0.2Ba₂Cu_{3 ? y} Zn_yO_{7 ? δ} (0 ≤ y ≤ 0.25) with isovalent substitutions and Y_{1 ? x} Ca_xBa₂Cu_2.8Zn_0.2O_{7 ? δ} (0 ≤ x ≤ 0.25) with heterovalent substitutions are investigated. It is demonstrated that these compounds have an YBa₂Cu₃O_{7 ? δ}-type structure in the orthorhombic crystal system. The isomorphous miscibility ranges and the concentration dependences of the unit cell parameters are determined for the solid solutions based on yttrium cuprates. The temperature dependences of the resistivity and the dependences of the critical temperature on the dopant concentration are analyzed.     

The relationship between the micro-mechanism and macroscopic dielectric properties in Ba1−xBixTi1−x−yZn0.75xW0.25x+yO3+y systems

A novel lead-free, high dielectric constant, ultra-wide temperature stable dielectric ceramic Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y (0.22≤x≤0.30, y=0.015) was synthesized by the traditional solid-state reaction method. The phase composition, electric and dielectric properties of the Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO₃ ceramics were investigated. The P-V-L dielectric theory was introduced. And, the chemical bond energy was calculated to track the changes in micro-structure. The relationships between chemical bond energy and the macroscopic dielectric properties(ε_r, dielectric stability and dielectric loss) in Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramics were discussed systematically. Owing to the inhomogeneous micro-structure and the diffusion in phase transition, Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramics showed a stable permittivity (~800±15%) over a ultra-wide temperature range (−30 to 375 °C). Moreover, dielectric loss was less than 0.02 and the insulation resistance was over 10¹² Ω cm. These features suggested that the Ba_1−xBi_xTi_1−x−yZn_0.75xW_0.25x+yO_3+y ceramic could be considered as a promising candidate material for energy storage applications in harsh environment.     

Effect of Sr and Ca substitution of Ba on the photoluminescence properties of the Eu2+ activated Ba2MgSi2O7 phosphor

The effects of Sr and Ca substitution of Ba on the Ba_1.98-xSr_x(Ca_x)MgSi₂O₇:Eu²⁺ photoluminescence properties have been investigated. The physical mechanisms for the photoluminescence variations are discussed. With Rietveld refinement method, the crystal structure of Ba_1.98MgSi₂O₇:0.02Eu²⁺ and the lattice parameters of Sr and Ca substituted phosphors were refined. The emission band shift, the photoluminescence intensity variation, the phosphor chromaticity evolution, the Eu²⁺ lifetime distribution and the thermal stability elevation were investigated. With Sr and Ca substitution, the cell is shrinks. The cell shrinkage is resulting in the increase of the Eu²⁺ 5d electron crystal field splitting intensity, which is the reason for the emission band shift towards the long wavelength band. The photoluminescence intensity is increased firstly and then decreased. The intensity variation is the competitive result between the increase of the crystal structure rigidity and the rise of the lattice defect. The correlated color temperature can be cut down and the color purity can be adjusted. The photoluminescence life time of Eu²⁺ is raised firstly and then decreased. For Sr and Ca substitution, the thermal stability can be elevated. With the forbidden band gap calculation, the reason for the thermal stability elevation was investigated that for the substituted phosphors the forbidden band gap is enlarged and then limits the Eu²⁺ 5d self-ionization from the splitting levels to the conduction band. This work reveals that the Sr and Ca substitution of Ba can elevate the Ba_1.98-xSr_x(Ca_x)MgSi₂O₇:Eu²⁺ photoluminescence properties and improve the applications for the White Light Emitting Diode.     

Synthesis and optical properties of intense blue colors oxides based on Mn5+ in tetrahedral sites in Ba7Al2-xMnxO10+y

Mn-doped Ba₇Al_2-xMn_xO_10+y (0 ≤ x ≤ 0.7) samples with intense blue colors are successfully prepared by solid state reactions. With the increase of Mn content, the colors of compounds are tuned from cyan to ocean blue. FT-IR absorption spectrum and ²⁷Al NMR spectrum indicate that the structure contains a dominating portion of Al–O tetrahedral sites while a small number of Al–O octahedral sites may also exist. The oxidation state of Mn is proved to be +5. Based on all the analysis, the intense blue shades of the samples are proposed as the d-d transition of Mn⁵⁺ ions in [AlO₄] tetrahedral sites.     

CdO-CuO-TiO2 ternary dielectric systems: Subsolidus phase diagram and the effects of Cu segregation

Valence of Cu cations and Cu segregation of CdCu₃Ti₄O₁₂ ceramics are initially examined by establishing the subsolidus phase diagram of Cd_1-xCu_3+x+2yTi_4-yO₁₂ (?7 ≤ x ≤ 0.07, ?1.333 ≤ y ≤ 2.91) systematically. Different from CaO-CuO-TiO₂ system, the co-existence of hexagonal and orthorhombic CdTiO₃ phases is observed in the line between CdTiO₃ and CuO. Basing on the obtained phase diagram, three typical ceramics with Cu-equal (CdCu₃Ti₄O₁₂), Cu-rich (Cd_0.930Cu_3.070Ti₄O₁₂), and Cu-poor (Cd_1.137Cu_2.863Ti₄O₁₂), showing high dielectric constant, are chosen as target samples to investigate the role of Cu valence and segregation in dielectric behaviors. Cu³⁺ ions, rather than Cu⁺ ones as reported previously, forms in the grain to act as the hopping charge carriers as demonstrated by X-ray photoelectron spectroscopy and High-energy X-ray absorption Near Edge Structure. This work would give a hint in tuning the stoichiometry for achieving more fascinating structures and properties in new ceramic material design.     

The relationship between crystal structure and modified microwave dielectric properties of Ca3SnSi2-xGexO9 ceramics

Ca₃SnSi_2-xGe_xO₉ (0 ≤ x ≤ 0.8) and (1–y) Ca₃SnSi_1.6Ge_0.4O₉ – y CaSnSiO₅ – 2 wt% LiF (y = 0.4 and 0.5) microwave dielectric ceramics were prepared by traditional solid-state reaction through sintering at 1250°C–1425°C for 5 h and at 875°C for 2 h, respectively. Ge⁴⁺ replaced Si⁴⁺, and Ca₃SnSi_2-xGe_xO₉ (0 ≤ x ≤ 0.4) solid solutions were obtained. At 0.1 ≤ x ≤ 0.4, the Ge⁴⁺ substitution for Si⁴⁺ decreased the sintering temperature of Ca₃SnSi_2-xGe_xO₉ from 1425 to 1300°C, the SnO₆ octahedral distortions, and the average CaO₇ decahedral distortions, which affected the τ_f value. The large average decahedral distortions corresponded with nearer-zero τ_f values at Ca₃SnSi_2-xGe_xO₉ (0.1 ≤ x ≤ 0.4) ceramics. The τ_f value and sintering temperature of Ca₃SnSi_2-xGe_xO₉ (x = 0.4) ceramic were adjusted to near-zero by CaSnSiO₅ and decreased to 875°C upon the addition of 2 wt% LiF. The (1 – y) Ca₃SnSi_1.6Ge_0.4O₉ – y CaSnSiO₅ – 2 wt% LiF (y = 0.5) ceramic sintered at 875°C for 2 h exhibited good microwave dielectric properties: ε_r = 10.3, Q × f = 14 300 GHz (at 12.2 GHz), and τ_f = ‒5.8 ppm/°C.