Effect of Mn2+ doping on the lattice and the microwave dielectric properties of MgTa2O6 ceramics

A series of Mn²⁺-doped Mg_1-xMn_xTa₂O₆ (x = 0.02, 0.04, 0.06, 0.08, 0.10, 0.12) ceramics were synthesized by solid-state reaction method. The influence of introducing Mn–O bonds as a partial replacement for Mg–O bonds on the lattice and microwave dielectric properties was systematically investigated. XRD and Rietveld refinement confirm that Mn²⁺ occupies the 2a Wyckoff position and forms a pure trirutile phase. Moreover, based on the chemical bond theory, the dielectric constant is mainly affected by the ionicity of the Ta–O bond. The lattice and dielectric properties remain relatively stable with Mn²⁺ doping below 0.1, but excessive Mn²⁺ doping leads to pronounced distortion of the lattice, which is not beneficial for lattice stability and microwave dielectric properties. Introducing an appropriate amount of Mn–O bonds with high bond dissociation energy facilitates MgO6 octahedron stability, which improves the thermal stability of the lattice. Accordingly, the microwave dielectric properties for 0.06 Mn²⁺-doped MgTa₂O₆ ceramics were determined: ε_r = 28, Q × f = 105,000 GHz (at 7.5 GHz), τ_f = 19.5 ppm/^°C.     

Low-temperature synthesis and microwave dielectric properties of trirutile-structure MgTa2O6 ceramics by aqueous sol–gel process

Trirutile-structure MgTa₂O₆ ceramics were prepared by aqueous sol–gel method and microwave dielectric properties were investigated. Highly reactive nanosized MgTa₂O₆ powders were successfully synthesized at 500 °C in oxygen atmosphere with particle sizes of 20–40 nm. The evolution of phase formation was detected by DTA–TG and XRD. Sintering characteristic and microwave dielectric properties of MgTa₂O₆ ceramics were studied at different temperatures ranging from 1100 to 1300 °C. With the increase of sintering temperature, density, ?_r and Q · f values increased and saturated at 1200 °C with excellent microwave properties of ?_r ～ 30.1, Q · f ～ 57,300 GHz and τ_f ～ 29 ppm/°C. The sintering temperature of MgTa₂O₆ ceramics was significantly reduced by aqueous sol–gel process compared to conventional solid-state method.     

Effects of Magnesium–Tungsten co-substitution on crystal structure and microwave dielectric properties of CaTi1-x(Mg1/2W1/2)xO3 ceramics

CaTi_1-x (Mg_1/2W_1/2)_xO₃ (x = 0, 0.02, 0.04, 0.06, 0.08) dielectric ceramics were synthesized via the traditional solid-state reaction method. Crystal structure and microwave dielectric properties of CaTi_1-x (Mg_1/2W_1/2)_xO₃ system were systematically investigated based on chemistry bond theory (P–V-L theory) for the first time. The pure perovskite phase was obtained for all doped samples, as confirmed through the XRD and Rietveld refinement results. The lattice characteristics were closely related to the microwave dielectric properties. The bond ionicity, lattice energy, and bond energy affected the dielectric constant, quality factor, and temperature stability of the ceramic material. Through the use of (Mg_1/2W_1/2)⁴⁺ doped on B-site, the CaTi_1-x (Mg_1/2W_1/2)_xO₃ system can maintain a high dielectric constant (ε_r > 100) while effectively reducing the τ_f value from 800 ppm/^°C to less than 300 ppm/^°C and improving the Q × f value to 9650 GHz (at 3.76 GHz).     

Crystal structure,infrared-reflectivity spectra,and microwave dielectric properties of novel Ce2(MoO4)2(Mo2O7) ceramics

Novel Ce₂(MoO₄)₂(Mo₂O₇) (CMO) ceramics were prepared by a conventional solid-state method, and the microwave dielectric properties were investigated. X-ray diffraction results illustrated that pure Ce₂(MoO₄)₂(Mo₂O₇) structure formed upon sintering at 600 °C-725 °C. [CeO₇], [CeO₈], [MoO₄], and [MoO₆] polyhedra were connected to form a three-dimensional structure of CMO ceramics. Analysis based on chemical bond theory indicated that the Mo–O bond critically affected the ceramics’ performance. Furthermore, infrared-reflectivity spectra analysis revealed that the primary polarisation contribution was from ionic polarisation. Notably, the optimum microwave dielectric properties of ε_r = 10.69, Q·f = 49,440 GHz (@ 9.29 GHz), and τ_f = −30.4 ppm/°C were obtained in CMO ceramics sintered at 700 °C.     

Ilmenite-type MgTiO3 ceramics by complex (Mn1/2W1/2)4+ cation co-substitution producing improved microwave characteristics

In this article, the (Mn_1/2W_1/2)⁴⁺ complex cation co-doped ilmenite MgTiO₃ ceramics with improved microwave characteristics were synthesized. The correlations between the crystal structural evolution induced by ionic substitution and the microwave characteristics were investigated using the structural analysis and the P–V–L bond theory. Theoretically, the Mg–O bond should have a larger value of covalency than Ti–O bond, attributing to the distribution of densities of states, where the s and p states of the Mg atom overlap with those of the O atom. This conclusion fits well the bond theory estimation. The dielectric constant is dominated predominantly by the average bond covalency, which is intrinsically caused by the increase of doping contents. Moreover, the structural stability declines slightly with the increase of (Mn_1/2W_1/2) contents. From the perspective of structural evolution, this dielectric performance is also reflected by the variations of the Raman shift and the FWHM value of A_g⁵ mode. The actual Q × f value, however, experiences a great enhancement at x = 0.010, which benefits generally from the uniformity of the grain size and the inhibition of reduction of Ti⁴⁺ valence. The excellent microwave characteristics of MgTi_0.99(Mn_1/2W_1/2)_0.01O₃ ceramics were achieved: a ε_r of 18.74, a Q × f value of 160992 GHz and a τ_f of ?58.2 ppm/°C, when sintered at 1325 °C.     

Bond characteristics and microwave dielectric properties of high-Q materials in li-doped Zn3B2O6 systems

The bond characteristics, Raman spectroscopy, and microwave dielectric properties of Zn_3-xLi_2x(BO₃)₂ ceramics prepared by solid-state reaction method were investigated. According to the complex chemical bond theory, the bond ionicity and lattice energy of the B–O bond were proved to contributed more to the electric polarization and phase structure stability than that of A-site bond. Thus, the B–O bond had a dominant effect on the dielectric constant and Q × f values. The optimization of the τ_f value can be attributed to the bond valence. Moreover, the shift and full width at half maximum of the Raman peak were closely related to the dielectric constant and Q × f values, respectively. On the whole, Li⁺ substitution contributed greatly to improve the temperature stability and reducing the dielectric loss of Zn_3-xLi_2x(BO₃)₂ ceramics. Additionally, Zn_2.99Li_0.02(BO₃)₂ ceramics sintered at 850 °C exhibited satisfactory microwave dielectric properties of ε_r=6.59, Q × f=122,030 GHz, τ_f=−76.9 ppm/°C, and had good chemical compatibility with silver.     

Microwave dielectric properties,microstructure, and bond energy of Zn3-xCoxB2O6 low temperature fired ceramics

Low temperature co-fired ceramics (LTCCs) technology plays an important role in modern wireless communication. Zn_3-xCo_xB₂O₆ (x = 0–0.25) low temperature fired ceramics were synthesized via traditional solid-state reaction method. Influences of Co²⁺ substitution on crystal phase composition, grain size, grain morphology, microwave dielectric properties, bond energy, and bond valence were investigated in detail. X-ray diffraction analysis indicated that the major phase of the ceramics was monoclinic Zn₃(BO₃)₂. Solid solution was formed with Co²⁺ substituted for Zn²⁺ because no individual phase that contained Co was observed. An increase in the amount of Co²⁺ substitution changed average grain sizes, and regrowth of grains were observed with Co²⁺ substitution. Appropriate amount of Co²⁺ substitution improved densification. With changes in Co²⁺ substitution, bond energy of major phase and average bond valence of B–O were positively correlated to temperature coefficient of resonant frequency. The Zn_2.927Co_0.075B₂O₆ ceramic sintered at 875 °C for 4 h exhibited excellent microwave properties with ε_r = 6.79, Q × f = 140,402 GHz, and τ_f = −87.42 ppm/°C. This ceramic is regarded as candidate for LTCC applications.     

Structure‐Dependent Microwave Dielectric Properties and Middle‐Temperature Sintering of Forsterite (Mg1–xNix)2SiO4 Ceramics

The crystal structure, microstructure, and microwave dielectric properties of forsterite‐based (Mg_1–xNi_x)₂SiO₄ (x = 0.02–0.20) ceramics were systematically investigated. All samples present a single forsterite phase of an orthorhombic structure with a space group Pbnm except for a little MgSiO₃ secondary phase as x > 0.08. Lattice parameters in all axes decrease linearly with increasing Ni content due to the smaller ionic radius of Ni²⁺ compared to Mg²⁺. The substitution of an appropriate amount of Ni²⁺ could greatly improve the sintering behavior and produce a uniform and closely packed microstructure of the Mg₂SiO₄ ceramics such that a superior Q × f value (152 300 GHz) can be achieved as x = 0.05. The τ_f value was found to increase with increasing A‐site ionic bond valences. In addition, various additives were used as sintering aids to lower the sintering temperature from 1500°C to the middle sintering temperature range. Excellent microwave dielectric properties of ε_r~6.9, Q × f~99800 GHz and τ_f~?50 ppm/°C can be obtained for 12 wt% Li₂CO₃‐V₂O₅‐doped (Mg_0.95Ni_0.05)₂SiO₄ ceramics sintered at 1150°C for 4 h.     

Effects of W6+ substitution on crystal structure and microwave dielectric properties of Li3Mg2NbO6 ceramics

Li₃Mg₂(Nb_1-xW_x)O_6+x/2 (0 ≤ x ≤ 0.08) ceramics were synthesized by the solid-state reaction route. The effects of W⁶⁺ substitution on the phase composition, microstructure and microwave dielectric properties of Li₃Mg₂NbO₆ ceramics were investigated systematically. The XRD results showed that all the samples formed a pure solid solution in the whole doping range. The SEM iamges and relative density revealed the dense structure of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The relationship between the crystal structure and dielectric properties of Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics was researched through polarizability, average bond valence, and bond energy. The substitution of W⁶⁺ for Nb⁵⁺ in Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics significantly promoted the Q × f values. In addition, the increase of W⁶⁺ content improved the thermal stability of the Li₃Mg₂(Nb_1-xW_x)O_6+x/2 ceramics. The Li₃Mg₂(Nb_0.94W_0.06)O_6.03 ceramics sintered at 1175 °C for 6h possessed excellent properties: ε_r ~ 15.82, Q × f ~ 124,187 GHz, τ_f ~ −18.28 ppm/°C.     

Crystal structure and enhanced microwave dielectric properties of Ta5+ substituted Li3Mg2NbO6 ceramics

Composition and structure play dominant roles in realizing the microwave dielectric properties that are necessary for the ever-increasing demands of the Internet of Things and related communication technologies. In the present study, the substitution of Ta⁵⁺ in Li₃Mg₂Nb_1−xTa_xO₆ ceramics and its effect on the structural characteristics and microwave dielectric performances is systematically studied. All the substituted compositions were determined to be pure phase orthorhombic Li3Mg2NbO6 structure of space group Fddd. Furthermore, a NbO₆ octahedral distortion, Nb-O bond valence, packing fraction and polarizability were calculated to explore the structure-property-performance paradigm in the context of microwave dielectric performance. Scanning electron microscopy revealed homogeneous microstructures, with the introduction of Ta⁵⁺ promoting grain growth. Raman spectra indicated that the variation of the band (blue shift and red shift) at 771 cm⁻¹ was highly correlated with the variation in unit cell volume. The polarizability significantly impacted ɛ_r values. The Q × f values were strongly influenced by the packing fraction and grain size. The changes in the NbO₆ octahedral distortion and Nb–O bond valence impacted the τ_f values. The Li₃Mg₂Nb_0.98Ta_0.02O₆ composition displayed the most dramatic improvements in microwave dielectric properties: ε_r = 15.58, Q × f = 113 000 GHz and τ_f  = −4.5 ppm/°C, providing a potential candidate for next generation microwave and millimeter-wave applications.     

Bond characteristics and microwave dielectric properties on Zn3-xCux(BO3)2 ceramics with ultralow dielectric loss

The crystal structure and microwave dielectric properties of Zn_3-xCu_x(BO₃)₂ (x = 0–0.12) ceramics prepared via a traditional solid-state reaction method were investigated by means of X-ray diffraction (XRD) utilizing the Rietveld refinement, complex chemical bond theory, and Raman spectroscopy. XRD showed that all samples were single phase. The samples maintained a low permittivity, even at higher Cu²⁺ contents, which is conducive to the shortening of signal delay time, and intimately related to the average bond ionicity and Raman shift. Moreover, proper Cu²⁺ substitution greatly reduced the dielectric loss associated with the lattice energy. Cu²⁺ entering the lattice optimized the temperature coefficient of resonance frequency (τ_f) values and improved the temperature stability of samples by affecting the bond energy. Optimal microwave dielectric properties were: ε_r = 6.64, Q × f = 160,887 GHz, τ_f = ?42.76 ppm/°C for Zn_2.96Cu_0.04(BO₃)₂ ceramics sintered at 850 °C for 3 h, which exhibited good chemical compatibility with silver and are therefore good candidate materials for Low temperature co-fired ceramic applications.     

Influences of B2O3/CuO additions on the sintering behavior,microstructure and microwave dielectric properties of 6Nd[(Zn0.7Co0.3)0.5Ti0.5]O3–4(Na0.5Nd0.5)TiO3 ceramics

B₂O₃ and CuO were codoped into 6Nd[(Zn_0.7Co_0.3)_0.5Ti_0.5]O₃–4(Na_0.5Nd_0.5)TiO₃ (abbreviated as 6NZCT–4NNT) ceramics as sintering aids. The influences of the sintering aids on the sintering characteristics, microstructure and microwave dielectric properties of the 6NZCT–4NNT ceramics were systematically investigated as a function of the proportion of B₂O₃ and CuO. Codoping could greatly reduce the sintering temperature from 1410 °C to 1150 °C, indicating that B₂O₃/CuO are good sintering aids for 6NZCT–4NNT ceramics. The B₂O₃/CuO sintering aids had no significant impact on the phase purity of the investigated ceramics, even though a solid solution was formed due to Cu²⁺ ion substitution. However, they had evident influences on the surface morphology and grain size. The average grain size was enlarged with increasing amounts of CuO in the B₂O₃/CuO sintering aids. Remarkable deterioration of the microwave dielectric properties for 6NZCT-4NNT ceramics was not observed when codoping an appropriate amount of B₂O₃ and CuO. The 6NZCT–4NNT ceramics codoped with 2.0 mol% B₂O₃ and 2.0 mol% CuO sintered at 1150 °C for 3 h exhibited a homogeneous microstructure and promising microwave dielectric properties: an appropriate dielectric constant (ε_r = 49.37), a high quality factor (QF = 47,295 GHz), and a near-zero temperature coefficient of resonant frequency (TCF = +0.9 ppm/^°C).     

Novel temperature stable NiSnTa2O8 microwave dielectric ceramics with trirutile structure

A novel low-loss and temperature stable NiSnTa₂O₈ ceramic with trirutile structure was prepared using traditional solid-state method. The structure-performance relationships were investigated by Rietveld refinement, chemical bond theory and far-infrared spectrum. The results show that the relative densities play a dominant role in the change of dielectric constant. Theoretical dielectric constant calculated via bond theory, Clausius-Mossotti equation and fitted result of far-infrared spectrum are close to experimental value. Ta–O bonds with greatest bond ionicity and bond energy have the primary contributions to dielectric polarizabilities and dielectric loss. The optimal microwave dielectric performances of NiSnTa₂O₈ ceramics were obtained: ε_r ∼21.04, Q×f ∼31328 GHz and τ_f = −2.63 ppm/^°C at 1425 °C.     

Microwave dielectric properties of Mg1.8R0.2Al4Si5O18 (R = Mg,Ca, Sr,Ba, Mn,Co, Ni,Cu, Zn) cordierite ceramics and their application for 5G microstrip patch antenna

In this work, the effects of divalent ions on the phase structure, microstructure, and microwave dielectric properties of Mg_1.8R_0.2Al₄Si₅O₁₈ (R = Mg, Ca, Sr, Ba, Mn, Co, Ni, Cu, Zn) cordierite ceramics were investigated. Complex chemical bond theory, Raman spectrum and infrared reflectance spectrum were employed to understand the relationship among structural characteristics, vibration modes and microwave dielectric properties for alkaline earth and transitional metal divalent elements doped cordierite ceramics. The optimal microwave dielectric properties were obtained for Mg_1.8Ni_0.2Al₄Si₅O₁₈ with ε_r of 4.53, Q×f of 61,880 GHz and τ_f of -32 ppm/℃. Finally, a 5G-Sub 6GHz patch antennas with a central frequency of 4.91 GHz was successfully designed and fabricated using a Mg_1.8Ni_0.2Al₄Si₅O₁₈ substrate. The antenna exhibited excellent performance with a gain of 5.83 dBi and an efficiency of 76 %, showing promise to be employed in 5 G/6G millimeter-wave communication technology.     

Effects of Ni2+ substitution on the crystal structure,bond valence,and microwave dielectric properties of BaAl2–2xNi2xSi2O8–x ceramics

BaAl_2?2xNi_2xSi₂O_8?x (x = 0, 0.005, 0.01, 0.02, 0.03) ceramics were prepared using traditional solid phase reaction method. The microwave dielectric properties, including permittivity (ε_r), quality factor (Q × f), and temperature coefficient of resonant frequency (τ_f), were discussed based on the bond valence theory. The first-principle calculation was adopted to determine the site (Ba, Al, and Si) where doping element (Ni²⁺) would be inclined to occupy. The substitution of Ni²⁺ for Al³⁺ contributed to the breaking of Al-O and Si-O bonds and then facilitated the BaAl₂Si₂O₈ (BAS) hexacelsian-celsian transformation. Moreover, this substitution could change the bond strength between cation and oxygen anion due to the variation of the bond valence, which reasonably explained the variation of ε_r, Q × f, and τ_f values. Well-sintered and completely transformed celsian ceramics can be obtained after doping with Ni²⁺. When x = 0.01, compact BaAl_1.98Ni_0.02Si₂O_7.99 ceramic exhibited highly promising microwave dielectric properties: ε_r = 6.89, Q × f = 53, 287 GHz and τ_f = -25.31 × 10^?6 /°C.     

Crystal Structure and Microwave Dielectric Properties of LiRE9(SiO4)6O2 Ceramics (RE = La,Pr, Nd,Sm, Eu,Gd, and Er)

The crystal structure and microwave dielectric properties of apatite‐type LiRE₉(SiO₄)₆O₂ ceramics (RE = La, Pr, Nd, Sm, Eu, Gd, and Er) have been investigated. The densification of lithium apatites has been greatly improved with the addition of 1 wt% LiF. Selected area electron diffraction and X‐ray diffraction (XRD) Rietveld analysis confirm that these compounds belong to the P6₃/m (No. 176) space group with hexagonal crystal symmetry. The porosity‐corrected relative permittivity was found to decrease with decreasing ionic polarizability of RE³⁺ ions. Relationships between the structural parameters and microwave dielectric properties have been examined. The observed variation in the quality factor of LiRE₉(SiO₄)₆O₂ + 1 wt% LiF ceramics (RE = La, Pr, and Nd) was correlated with average cation covalency (%). The temperature coefficient of resonant frequency was found to depend on the bond valence sum of cations. LiEr₉(SiO₄)₆O₂ + 1 wt% LiF ceramics showed good microwave dielectric properties with ε_r = 12.8, Q_u × f = 13000 GHz and τ_f = +17 ppm/°C. All the compositions showed low coefficient of thermal expansion with thermal conductivity in the range 1.3–2.8 W (m K)^?1.     

Crystal structure and microwave dielectric properties of (Mg0.2Ni0.2Zn0.2Co0.2Mn0.2)2SiO4 - A novel high-entropy ceramic

Novel (Mg_0.2Ni_0.2Zn_0.2Co_0.2Mn_0.2)₂SiO₄ (A5SO) high-entropy microwave dielectric ceramics with olivine structure were prepared in the sintering temperature range of 1100 °C–1300 °C via the solid-phase reaction route. The crystal structure was confirmed by XRD, Raman, and Rietveld refinement. Optimal microwave dielectric properties (ε_r = 8.02, tanδ = 0.00051 at 14.5 GHz, and τ_f = ?38.2 ppm/°C) were obtained at the sintering temperature of 1250 °C, where a relative density of 95.1% was detected. The complex chemical bonding theory manifests that the ε_r value of A5SO is mainly affected by the ionicity of A-O (A = Mg, Ni, Zn, Co, Mn) bond, while the dielectric loss is affected by both A-O and Si–O lattice energy. The τ_f value is mainly influenced by the [A(2)O₆] oxygen octahedral distortion (1.8 × 10^?3). The experimental results of this study provide both theoretical and practical guidance for high-entropy microwave dielectric ceramic applications.     

Effects of ionic polarizability and crystal structure on microwave dielectric properties of RE2O3 (RE = La,Eu) ceramics with opposite τf and high Q

Hexagonal La₂O₃ and monoclinic Eu₂O₃ ceramics were prepared, and their microwave dielectric properties were investigated. La₂O₃ sintered at 1400 °C exhibited promising microwave dielectric properties of ε_r = 18.6, Q×f = 71,400 GHz, and a negative τ_f of − 35.1 ppm/°C, while Eu₂O₃ sintered at 1500 °C possessed relative lower ε_r and Q×f values of 17.9 and 35,000 GHz, respectively, with an abnormally positive τ_f of + 19.6 ppm/°C. The difference in their microwave dielectric properties is mainly due to lattice-induced strain, which can be characterized by bond valence. To investigate the degradation of RE₂O₃ (RE = La, Eu) ceramics in air, a series of La_2−xEu_xO₃ (x = 0.5, 1, and 1.5) ceramics were prepared. The results of the present study suggest that the introduction of Eu³⁺ effectively prevents the decomposition of La₂O₃.     

Li+ enrichment to improve the microwave dielectric properties of Li2ZnTi3O8 ceramics and the relationship between structure and properties

Herein, Li⁺-enriched Li_(1+x)2ZnTi₃O₈ ceramics are prepared via the solid-phase methods. As x increases, the unit cell volume gradually increases, while the grain size initially increases and then decreases gradually. The Li_(1+0.06)2ZnTi₃O₈ ceramics exhibit the best dielectric properties: ε_r = 25.92, Q × f = 109534 GHz (@7.37 GHz, which is a 48 % increase compared with the stoichiometric counterpart.), and τ_f = ?8.21 ppm/°C. The complex chemical bond theory and Raman spectroscopy reveal that Ti-O bonds have a significant effect on the dielectric properties. An optimal Li⁺ enrichment leads to an overall reduction in the distortion of the Li/ZnO₄ tetrahedra, resulting in a reduction in τ_f. First-principles calculations demonstrate that a suitable excess of Li⁺ leads to an increase in the band-gap as well as an enhanced electron cloud density in the internal space of the Li1/ZnO₄ tetrahedra, thereby increasing the Q × f. In summary, Li⁺-enriched Li_(1+0.06)2ZnTi₃O₈ ceramics are promising for a wide array of applications in microwave communications.     

A low-permittivity microwave dielectric ceramic BaZnP2O7 and its performance modification

Complex pyrophosphates compounds have attracted much attention as promising candidates for substrate applications. In the work, a low-permittivity BaZnP₂O₇ ceramic was synthesized through solid-state reaction. The pure phase BaZnP₂O₇ was crystallized in the triclinic P−1 space group. Excellent microwave dielectric properties of the BaZnP₂O₇ ceramic with ε_r = 8.23, Qf = 56170 GHz, and τ_f = −28.7 ppm/°C were obtained at 870°C for 4 h. The substitution of Mg²⁺ for Zn²⁺ was found to have positive effects on grain morphology and dielectric properties. Optimized performance of ε_r = 8.21, Qf = 84760 GHz, and τ_f = −21.9 ppm/°C was yielded at 900°C for the BaZn₀.₉₈Mg_0.02P₂O₇ ceramic. Intrinsic dielectric properties of BaZn_1-xMg_xP₂O₇ ceramics were studied via Clausius–Mossotti equation and complex chemical bond theory.