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Design and Fabrication of a Satellite Communication Dielectric

Resonator Antenna with Novel Low Loss and Temperature-
Stabilized (Sm1−xCax) (Nb1−xMox)O4 (x = 0.15−0.7) Microwave
Ceramics
Fangfang Wu, Di Zhou,* Chao Du, Di-Ming Xu, Rui-Tao Li, Zhong-Qi Shi, Moustafa A. Darwish,
Tao Zhou, and Heli Jantunen*
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Downloaded via Moustafa Adel Darwish on January 26, 2023 at 15:21:17 (UTC).

ABSTRACT: Phase transition−structure−dielectric properties in microwave band correla-

tions were determined for the (Sm1−xCax) (Nb1−xMox)O4 (SNCMo@x) system. X-ray and
Raman analyses along with selected-area electron diffraction indicated that SNCMo@x (0.15
≤ x < 0.375) ceramics crystallize in the I2/a space group (monoclinic fergusonite), whereas
the I41/a space group (tetragonal scheelite) best describes SNCMo@x (0.375 ≤ x ≤ 0.7),
suggesting that the increased ionic radius of the A-site effectively contributed to the
ferroelastic phase transition and ensures the stability of the scheelite phase. The SNCMo@x
ceramic materials exhibit composition-dependent permittivity (εr) with a distribution
between 12.0 and 17.7. The distortion and deformation of the [BO] polyhedra should be
responsible for the shift from negative to positive temperature coefficient of resonant
frequency (TCF) and the irregular behavior of the quality factor (Q × f). An optimum
microwave dielectric performance was achieved for SNCMo@0.18 (εr ∼ 17.1, Q × f ∼ 52,
800 GHz at ∼8.80 GHz, and TCF ∼ −1.4 ppm/°C). This work demonstrates the important role of simultaneous substitution of A/
B cations on [BO] polyhedral distortion and deformation in RENbO4 materials and its significant effect on the microwave dielectric
properties. Also, the SNCMo@0.18 ceramic has been designed as a cylindrical dielectric resonator antenna with a high simulated
radiation efficiency (97.1%) and gain (5.96 dBi) at the center frequency (7.75 GHz), indicating its promising application in X-band
satellite communication (7.62−7.89 GHz) because of its adjustable permittivity, low loss, and good temperature stability.

■ INTRODUCTION
Ever-growing data requirements, such as high throughput,
The permittivity (ε r), quality factor (Q × f), and
temperature coefficient at resonant frequency (TCF) are the
three important parameters to assess the properties of
global and seamless connectivity, excellent reliability, low
microwave dielectric ceramics and which also affect the
latency, and massive connectivity,1 set challenging standards qualities of communication devices. Proper εr, high Q × f,
for the wireless networks of the future. Satellite communica- and near-zero TCF values are the objectives for microwave
tion, one of the most intriguing technologies of modern dielectric ceramics. For example, low-εr ceramics are used for
communication systems, is an extremely promising solution to millimeter-wave communication as well as substrates for
overcome these obstacles.2 Communication satellites consist of microwave-integrated circuits; medium-εr ceramics are used
a receiver and a transmitter, both of which are linked to an for satellite communications and in mobile phone base
antenna, which makes the exploitation of the antenna an stations; and high-εr materials are used for mobile phone
essential part of this project. Meanwhile, microwave dielectric handsets where miniaturization is essential. Unfortunately, the
materials are relied upon by many modern electronic devices, TCFs of numerous microwave dielectric ceramics possess large
such as global positioning systems, satellite navigations, mobile negative values within K10−K20, as is evident from the review
base stations, military radar, and other engineering fields3−6 articles by Sebastian and Ubic et al.,10,11 which is also
owing to their miniaturization, low loss, and high stability.
Nowadays, the dielectric resonator antennas (DRAs) attract Received: August 30, 2022
growing interest by virtue of their high radiation efficiency Revised: December 13, 2022
(lack of conductive loss), high gain, high design flexibility Published: December 23, 2022
(various material options and 3D geometries), and easy
integration with planar circuits.7−9 Hence, the design of DRAs
for communication satellites is imminent.

© 2022 American Chemical Society https://doi.org/10.1021/acs.chemmater.2c02663

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evidenced in the RENbO4-based (RE = La, Nd, Sm, Dy, Er, with proper permittivity, high-quality factor, and near-zero
and Lu) system (Table S1, Supporting Information). Given the TCF (|TCF| < 10.0 ppm/°C) in the RN family.
intrinsic association between these three vital dielectric Here, the simultaneous substitution of Ca/Mo for SmNbO4
parameters, only a minority of materials exhibit the overall (SN) ceramic has been investigated via the solid-phase
desirable microwave dielectric properties. Consequently, it is a reaction method, and excellent microwave dielectric perform-
priority to research novel materials with low εr, high Q × f , ance was achieved with (Sm0.82Ca0.18) (Nb0.82Mo0.18)O4
and near-zero TCF to reduce signal delay12 and improve (SNCMo@0.18, red star solid in Figure 1). To clarify the
frequency selectivity and thermal stability, respectively, correlation between the structural variations and microwave
matching the satellite communication standard. dielectric properties of the (Sm 1−x Cax ) (Nb 1−x Mox )O 4
The excellent microwave dielectric properties (εr ∼ 16.6− (SNCMo@x) ceramics, room-temperature X-ray diffraction
19.6, Q × f ∼ 33,000−56,600 GHz, and TCF ∼ −24.0 to (XRD), Raman, transmission electron microscopy (TEM), and
−66.0 except La ∼ +9.0 ppm/°C) of the rare-earth niobate thermal expansion measurements were used to demonstrate
family RENbO4 have attracted widespread attention, following the correlation of A/B-site substitution with TF−S. Microwave
the first report by Kim.13 Rare earth niobates (RENbO4: RN) dielectric measurements demonstrated the dependence of
exhibits a monoclinic structure at room temperature and dielectric properties on ceramic components and TF−S. Far-
undergoes a second-order reversible ferroelastic phase infrared/THz experiments explored the availability of the high-
transition (monoclinic fergusonite → tetragonal scheelite, frequency band. Significantly, a cylindrical DRA (CDRA) was
TF-S) which is influenced in temperature by the radius of the designed and prototyped to develop practical applications in X-
A- or B-site cation. Lower ionic radius at the A-site or higher band satellite communication.
ionic radius at the B-site drives up TF-S, whereas a lower B-site
ionic radius reduces it, even down to room temper-
ature.5,9,13−21 The modification of the microwave dielectric
properties by the substitution of A-, B-, and A/B-sites (both
■ METHODS
Materials Synthesis. The SNCMo@x (x = 0.15−0.7) ceramics
were synthesized by the conventional solid-state reaction method, and
aliovalent and isovalent) proved to be remarkably effective the raw materials were the high-purity powders of Sm2O3 (99.9%),
(Table S1, Supporting Information). A-site substitutions have Nb2O5 (99.99%), CaCO3 (99%), and MoO3 (99.95%). All of the
been summarized in our previous work,5 and the B-site is materials were weighed according to the stoichiometric formulation of
illustrated in Figure 1. Based on the reports, εr is ∼18.0 ± 6, SNCMo@x (x = 0.15−0.7), and Sm2O3 powder was calcined at 1200
°C for 4 h before weighting. Then, these powders were mixed with
zirconia balls and ethanol in a certain proportion and milled in a
nylon jar together for 4 h to achieve uniform mixing. The powder
mixtures were rapidly dried and calcined at 1100 °C for 4 h to allow
the primary reaction of the original oxide and obtain the presintered
powders. The calcined powders were ball-milled in ethanol for 5 h to
improve the reactivity and obtain better homogeneity. Finally, the
dried powders were granulated with 5 wt % polyvinyl alcohol adhesive
and pressed into a cylindrical mold to obtain several samples (10 mm
in diameter and 4−5 mm in height). The samples were sintered in the
temperature range from 1460 to 1540 °C for 3 h.
Materials Characterization. The phase purity of the samples was
investigated using room-temperature XRD with Cu Kα radiation
(Rigaku D/MAX-2400 X-ray diffractometry, Tokyo, Japan). The
Rietveld profile refinement method was employed to analyze the
crystal structure of ceramics using Fullprof program, and the
diffraction pattern was obtained with 2θ in the range of 10−120°.
Figure 1. Dielectric properties (εr, Q × f, and TCF) of RENbO4 (RE The room-temperature Raman spectra were analyzed with a laser
= lanthanides) compounds as a function of B-site ionic Raman spectrometer of the natural surface of samples and acquired
radius9,22,25,28−36 [red star solid denotes the microwave dielectric with a 532 nm laser excitation source. The HRTEM images and
properties of (Sm0.82Ca0.18) (Nb0.82Mo0.18)O4]. SAED patterns were measured on JEM-2100 with an accelerating
voltage of 200 kV. The microstructures of the sintered specimens
were observed by a SEM system (Quanta 250, FEI). The mean grain
size was calculated from each SEM image of the SNCMo@x (x =
indicating that εr of RN is not highly sensitive to crystal 0.15−0.7) ceramics using image analysis software (Nano Measurer
distortion/phase transition, preferring to be correlated with the 1.2). The room-temperature infrared reflectivity spectra were
polarizabilities. This has been confirmed in the RN (R = Sm measured using a Bruker IFS 66v Fourier transform infrared
and La) system.9,22 The Q × f values (∼39.0k−100.0k GHz), spectrometer in the infrared beamline station (U4) at the National
however, are strongly dependent on the crystal structure and Synchrotron Radiation Lab (NSRL), China. The shrinkage value of
especially on the distortion and transformation of the [BO] the sample was measured with a horizontal-loading dilatometer with
polyhedra,9,22 which are determined by the level of lattice alumina rams and boats (DIL 402C, Netzsch Instruments, Germany)
energy. Normally, a higher lattice energy corresponds to lower with different heating rates of 5, 10, and 15 K/min from ambient
lattice vibration and, therefore, lower dielectric loss. Addition- temperature to 800 °C, respectively. The bulk density of these
sintered cylinders was measured by the Archimedes method and
ally, grain size has an effect on Q × f values.5,23−25 TCFs have
compared with the theoretical density obtained by the Rietveld
large negative values which coincide with those expected refinement. The microwave dielectric properties were measured with
because low permittivity (<20.0) is accompanied by a positive a TE01δ dielectric resonator with a network analyzer (8720ES, Agilent,
temperature coefficient of permittivity (τε).26,27 Moreover, the Palo Alto, CA) and a temperature chamber (Delta 9023, Delta
TCF of RN is associated with monoclinic distortion and the Design, Poway, CA). The TCF was measured in the temperature
proximity of TF-S. In summary, it is urgent to obtain ceramics range from 25 to 85 °C and calculated by the following formula

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Figure 2. (a) XRD patterns of (Sm1−xCax) (Nb1−xMox)NbO4 (x = 0.15−0.7) ceramics. (b) Lattice constants as a function of x values (M�
monoclinic fergusonite; T�tetragonal scheelite). (c,d) Rietveld refinement plot of (Sm1−xCax) (Nb1−xMox)NbO4 (x = 0.3, 0.375) ceramics. (e,f)
Schematic of the crystal structure for (Sm1−xCax) (Nb1−xMox)NbO4 (x = 0.15, 0.375) ceramics.

f85 f25 technology. The CDRA is obtained by machining the prepared

TCF = × 106 SNCMo@x ceramics based on simulation-optimized dimensions by
f25 (85 25) (1) means of a ceramic wire-cutting technique, and finally the CDRA is
where f 85 and f 25 are the TE01δ resonant frequencies at temperatures glued to the center of the metal ground plate by means of a
85 and 25 °C, respectively. conductive adhesive.
Antenna Design and Fabrication. The CDRA antenna of the
SNCMo@0.18 ceramic is designed and simulated by CST software,
and the return loss |S11| of CDRA antenna was measured by a
■ RESULTS AND DISCUSSION
It can be confirmed that only peaks associated with the
microwave network analyzer. The experimental procedures are as
follows: the ground plate material is the Rogers RT5880 substrate monoclinic fergusonite-type (I2/a, JCPDS # 22-1104) were
(εr,sub = 2.20; tan δ = 0.0009), which was purchased and processed in present for 0.15 ≤ x < 0.375, tetragonal scheelite-type (I41/a,
Taizhou Aoling Electronic Technology Co., Ltd. Meanwhile, the JCPDS # 29-0351) at 0.375 ≤ x ≤ 0.7, and no two-phase
electrode material on the substrate is metallic copper, where the coexistence region for 0.15 ≤ x ≤ 0.7, as shown in Figures
electrode structures were prepared by means of printed circuit board 2a,c,d and S1 (Supporting Information). According to our
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Figure 3. HRTEM images of the (Sm0.82Ca0.18) (Nb0.82Mo0.18)O4 ceramic: (a) section showing the parallel domains and SAED patterns. (b)
Magnified HRTEM image of the domain section. The HRTEM images of the (Sm0.6Ca0.4) (Nb0.6Mo0.4)O4 ceramic: (c) section showing the
parallel domains and SAED patterns. (d) Magnified HRTEM image of the domain section.

Figure 4. Raman spectra (a) of (Sm1−xCax) (Nb1−xMox)NbO4 (x = 0−0.7) and thermal properties (b) of (Sm1−xCax) (Nb1−xMox)NbO4 (x =
0.15−0.35) ceramics.

previous studies, the substitution of V5+ for Nb5+ in the SN the slope varies from the monoclinic to tetragonal structure.
system induced no TF−S; instead, a tetragonal zircon structure Meanwhile, the monoclinic β decreases from 93.71 to 90.00°,
was formed. Similarly, the A-site substitution by Bi3+ did not and finally the tetragonal structure is stable at room
undergo the phase transition.5,9 It is revealed that the temperature (x ≥ 0.375). The increased long-axis dimensions
simultaneous substitution of Ca/Mo in the SN system due to the weakening of the interlayer force constant between
effectively promotes the ferroelastic phase transition and the near-neighboring [Nb/MoO4] tetrahedra and the enlarged
ensures the stability of the high-temperature scheelite phase.
equivalent ionic radius at the A-site are responsible for
Combined with the RN (R = La, Ce, and Nd) systems
increasing the cell volume.38−40 The fergusonite lattice,
reported by Aldred et al.,37,38 it is inferred that the increased
radius of the A-site ions (R Sm3+/Ca 2+ = 1.094 Å > R Sm3+ = 1.079 SNCMo@0.15, exhibits layers of edge-sharing octahedra
[NbO6], and Sm/Ca atoms are dodecahedral in the eight-
Å, x = 0.375)39 should be responsible for promoting TF−S
(Table S2, Supporting Information). The crystallographic coordinate environment (Figure 2e).
structural parameters of SNCMo@x (x = 0.15−0.7) provided SNCMo@0.375, the scheelite lattice, consists of an isolated
by Rietveld refinements are displayed in Tables S3 and S4 [NbO4] tetrahedron, with the [SmO8] units housed in the
(Supporting Information). As x increases, in Figure 2b, the spreading chains of [NbO4]-sharing oxygen (Figure 2f).
base dimensions of the monoclinic unit cell (aM and cM) merge Overall, the simultaneous substitution of A/B-site is an
smoothly and become the edge of the tetragonal unit cell (aM efficient method for inducing TF−S in the RN system at
= bM). The long-axis dimension (bM//cT) also increases, and room temperature.
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The TEM images and diffraction patterns show that clear

parallel domains (Figure 3a,c) and lattice fringes (Figure 3b,d)
are observed in both SNCMo@0.18 and SNCMo@0.4. There
are two crystallographic domain structures with different
orientations (I and II) in fergusonite-type, associated with the
decrease in symmetry of the point group (4/m to 2/m) from
the second-order ferroelastic phase transition,5,9,41−45 in Figure
3a, and the SAED pattern describes the double-domain
patterns along the [010]m direction, suggesting that the
crystal grows along the b-axis. Only a mono-oriented domain
structure is present in the scheelite-type, in Figure 3c, and the
domain structure becomes smaller with respect to the
monoclinic phase. In the HRTEM images of the domains, in
Figure 3b,d, the distance between the lattice fringes was
established to be 2.67 Å of the (200) plane and 1.91 Å of the
(2̅02) plane for fergusonite, and 2.38 Å of the (022) plane for
scheelite, respectively, in agreement with the XRD analysis
(Figure 2a).
Figure 5. Diagram of the main ABO4 structure types and some related
Group theory calculations reveal 18 Raman modes (8Ag +
compounds based on Manjón ’s 21,37,38,57−63 [★ (Sm 1−x Ca x )
10Bg) for the fergusonite-type (I2/a) and 13 Raman modes (Nb1−xMox)O4 (x ≥ 0.375) in this paper].
(3Ag + 5Bg + 5Eg) for the scheelite-type (I41/a) of the RN
system.46−49 The Raman spectra of the fergusonite structure
are convergent with earlier reports, as demonstrated in our that the preservation of the high-temperature scheelite
previous work.5,9,50 The undetectable modes occur because of structure at ambient temperature is probably driven by a
deviation from the symmetry of the space group.51 With reduction in the B-site cation size, as La(Nb0.75V0.25)O4,22,37
increasing x, a new Raman mode appears near 878 cm−1 and Ce(Nb0.7V0.3)O4,38 Nd(Nb0.65V0.35)O4,38 and (Sm0.625Ca0.375)
becomes stronger, in Figure 4a, which is not evident in XRD (x (Nb0.625Mo0.375)O4 (★ in Figure 5).
= 0.15−0.3, no phase transition or second-phase formation), The surface morphology and particle size distribution of
probably because Nb has not been completely substituted by SNCMo@x ceramics are shown in Figure S2 (Supporting
Mo, some Mo−O vibrational modes belonging to the [MoO4] Information). Relatively dense microstructures with mean
residue, as well as Raman being more sensitive to variations in grain sizes ranging from 2.11 to 8.81 μm were present in all
the crystal structure than XRD, and further research is needed. samples. Energy-dispersive system (EDS) analysis results of the
For completeness, we note that in the scheelite structure, the SNCMo@0.18 ceramic in the dashed area are exhibited in
external vibrational modes [105 cm−1�Bg, and 213 cm−1�νf.t. Figure 6a−e, which confirm the presence and uniform
(Ag)] are connected to the lattice phonons and correspond to distribution of Sm, Ca, Nb, Mo, and O elements in the
the motion of Sm/Ca cations relative to the rigid [Nb/MoO4] SNCMo@0.18 ceramic, revealing the homogeneity of Ca and
tetrahedron units. The intrinsic vibrational modes (300−900 Mo elements in the SN matrix. The respective content of
cm−1) of the [Nb/MoO4] cluster unit are evidenced by ν1 elements is illustrated in Figure 6f.
(Ag), v3 (Bg), and ν3 (Eg), assigned as the Nb/Mo−O Figure 7 illustrates the microwave dielectric properties of
stretching vibrations, and ν2 (Ag), ν2 (Bg), and ν4 (Bg) for the SNCMo@x (x = 0.15−0.7) ceramics and the governing
Nb/Mo−O bending modes.52−54 The Raman band at 879 factors. εr, in Figure 7a, which is determined by internal
cm−1 is attributed to the Nb/Mo−O symmetric stretching parameters including structural features and polarizability,
vibration mode. Meanwhile, two bending Nb/Mo−O together with external parameters such as secondary phase,
vibrations ν2 (Ag) and ν2 (Bg) appear at nearly 333 cm−1, grain size, and porosity,23,64 reduces progressively from 17.7 to
where the ν2 (Ag) mode coincides with the Nb−O symmetric 12.0 with increasing x. Here, the secondary phase could be
vibration (333 cm−1). The Raman pattern of SNCMo@x (x ≥ neglected as no second phase is generated (Figure 2a). Despite
0.375) ceramics corresponds well with previous reports,55,56 the similar tendency of εp (modified by the Bosman and
revealing that it is a tetragonal scheelite structure, which is Havinga correction65) and εr, its high density (Figure S3,
identical to the XRD and TEM analyses. It is noticed that TF−S Supporting Information) and similar values (εr ∼ 12.0−17.7,
generates a drastic decrease from 800 °C (SN)9,13 to room εp ∼ 13.1−18.2) indicate that porosity is not the dominant
temperature (SNCMo@0.35) with increasing x, in the inset of factor. Given the low polarizability of Ca2+ (3.16 Å3 < 4.74 Å3
Figure 4b, which is attributed to the reduction in [NbO4] = Sm3+) and Mo6+ (3.28 Å3 < 3.97 Å3 = Nb5+),66,67 Shannon’s
tetrahedra distortion caused by the ferroelastic phase additive rule (eq 2) and the Clausius−Mossotti relation (eq 3)
transition, reducing the driving force for the fergusonite-to- are applied.
scheelite transition.9,21
The normal stability region was discussed based on Bastide’s ax = (1 x)aSm3+ + xaCa 2+ + (1 x)aNb5+ + xa Mo6+
diagram by Manjón et al. of monoclinic fergusonite (0.7 < rA/ + 4a o 2 (2)
rO < 1.0, and rB/rO ∼ 0.4), tetragonal scheelite (0.6 < rA/rO <
1.1, and rB/rO ∼ 0.3), and tetragonal zircon structures (0.54 < 3Vm + 8 ax
rA/rO < 0.72, and rB/rO ∼ 0.2).62,63 Considering the ionic s =
3Vm 4 ax (3)
radius of all RE in the zircon region, the value of rA/rO in
Figure 5 is expanded to 0.82. Indeed, the smaller B-site cation where aSm3 +, aCa 2+, aNb5+ , a Mo6+ , and ao2 are the polarizabilities
radius corresponds to a lower coordination number, indicating of Sm3+, Ca2+, Nb5+, Mo6+, and O2−, respectively, and Vm is the
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Figure 6. EDS mapping images of the (Sm0.82Ca0.18) (Nb0.82Mo0.18)NbO4 ceramic. (a−e) Elements marked as their abbreviations and (f) spectra of
EDS.

Figure 7. (a) Permittivity (εr: measured; εs: calculated by Shannon’s additive rule and the Clausius−Mossotti relation; and εp: modified by the
Bosman and Havinga correction). (b) Q × f, packing fraction, and mean grain size. (c) TCF values of (Sm1−xCax) (Nb1−xMox)NbO4 (x = 0.15−
0.7) ceramics as the functions of x. (d) Variation of TCF for the (Sm1−xCax) (Nb1−xMox)NbO4 (x = 0.15, 0.18, and 0.4) ceramics as a function of
temperature (from −40 to +120 °C).

molecular molar volume. The measured (εr) and calculated indicating a non-negligible influence of the structural features.
(εs) values display the similar trend and εr (12.0−17.7) are Hence, the errors in the polarizabilities of lanthanides and
smaller than the εs values (14.0−24.4), which could be caused structural features combine to cause variations in the
by errors in the polarizabilities of lanthanides, as evidenced by permittivity. The structural characteristics displayed in Figure
the calculated permittivity (εs and εf) based on the dielectric 2e,f mainly exhibit a shift from [NbO6] to [NbO4]; hence, the
polarizabilities of Sm3+ provided by Shannon (4.74 Å3) and distortion and deformation of the [BO] polyhedra might be
Feteira et al. (3.89 Å3), respectively, illustrated in Figure S4 responsible for the irregular behavior of the Q × f double
(Supporting Information).66,68 Furthermore, the difference hump (Figure 7b), as in the RE(Nb, V)O4 (RE = La, Ce, and
between εr and εs is more pronounced in the monoclinic phase, Sm) systems.9,22 Structural distortion has been reported to be
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Figure 8. (a) Experimental and fitted infrared reflection spectra of (Sm1−xCax) (Nb1−xMox)NbO4 (x = 0.15−0.7) ceramics. (b−d) Complex
dielectric spectrum of (Sm0.82Ca0.18) (Nb0.82Mo0.18)NbO4, (Sm0.625Ca0.375) (Nb0.625Mo0.375)NbO4, and (Sm0.3Ca0.7) (Nb0.3Mo0.7)NbO4 ceramics
(solid line -, circle ○, and square □ denote fitted, experimental, and measured values in the microwave band. Square ■ denotes measured values in
the THz band; υ1, υ2, υ3, and υ4 correspond to the symmetric stretch, symmetric bending, antisymmetric stretch, and antisymmetric bending,
respectively).

evaluated in terms of packing fraction in the SNCMo@x Based on Figure 4b, the aL values for fergusonite and
system, as defined by eq 4 scheelite are approximately (12 ∼ 18) and (9 ∼ 15) ppm/°C,
3 3
respectively, confirming that the effect of aL is minimal and
3 /4 × (r(Sm/Ca) + r(Nb/Mo) + 4rO3) negligible. The sign shift of TCF is attributed to τε, as shown in
packing fraction =
Vcell eq 6 reported by Bosman and Havinga65
ÄÅ
( r 1)( r + 2) ÅÅÅÅ 1 ij V yz
×4 (4)
1 ij r yz V
= jj zz = ÅÅ jj zz +
where r(Sm/Ca), r(Nb/Mo), rO, and Vcell are the effective ionic r k T {P 3 r Å
ÅÅÇ V k T { P m
radius at each coordination number and the unit cell volume, ÑÉÑ
respectively. The correlation between Q × f values, mean grain ij m yz 1 ij V yz I ij m yz ÑÑÑ ( r 1)( r + 2)
jj zz · jj zz + jj zz ÑÑ =
size, and packing fraction is evident in Figure 7b. All show the k V {T k { P
V T m k T {V Ñ
ÑÑ 3 r
same tendency in fergusonite-type (omit x = 0.3) and Ö
scheelite-type (omit x = 0.7) ceramics, respectively. A high (A + B + C ) (6)
packing fraction means low lattice vibrations and thereby low
inherent loss. Besides, the mean grain size has a certain impact where (A + B) is the parameter associated with the volume
on Q × f. For x = 0.7, both the packing fraction and mean grain expansion and normally has a positive value (<10.0 ppm/°C)
size increase, and Q × f values decrease, probably in view of the and is therefore generally ignored. C represents the direct
lower density compared to others (<95.0%, Figure S3), dependence of the polarizability on temperature, which is
whereas the opposite happens for x = 0.3, which requires correlated with the structure and lattice parameter as it denotes
further investigation. TCF values, with increasing substitution, the restoring force (depending on the shape of the potential
increased markedly from negative (−12.4 ppm/°C, x = 0.15) well) acting on the ions.69 Unit cell volume is highly correlated
to positive and reached a maximum value of +38.3 ppm/°C (x with lattice energy, resulting in τε proportional to the relative
= 0.3) before dropping to −42.8 ppm/°C (x = 0.7), as shown magnitude of the unit cell volume in AMoO 4 /AWO 4
in Figure 7c. Commonly, TCF is associated with the systems.67,70 It is evident from Figure 2b that the volume of
temperature coefficient of permittivity (τε) and the linear the unit cell (monoclinic phase) increased with increasing x,
coefficient of thermal expansion (aL), as shown by eq 5 and the average bond length of the Nb/Mo−O bond
decreased (Table S4), implying a reduced volume of the
TCF = jij + a zyz [BO] polyhedra and increased lattice energy. Consequently,
j Lz
k2 { (5) the restoring force which resulted in the tilting on the oxygen
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Figure 9. Geometries (unit: millimeter) (a), front (b), and rear (c) views for the fabricated CDRA. The simulated and measured return loss |S11| of
the proposed antenna (d). 3D simulated radiation patterns of co-polarized and cross-polarized (e,f) CDRA at the resonant frequency (7.75 GHz).
The simulation results of electric field (g) and magnetic field (h) at 7.75 GHz. Simulated antenna radiation efficiency and realized gain (i) of the
CDRA.

octahedron increased, and the TCF trended toward positive The relevant parameters in eqs 7 and 8 are provided as
values.71 The subsequent variation is caused by the phase depicted in an earlier work.5 The monoclinic fergusonite phase
transition and the negative TCF (−57 ppm/°C) of tetragonal has been described in detail in previous studies; consequently,
scheelite CaMoO4.56 To evaluate the stability in various the emphasis here is on the analysis of the tetragonal scheelite
temperature environments, the thermal stability of SNCMo@x structure. Five internal modes including 802 (υ3−Eu), 775
(x = 0.15, 0.18, and 0.4) ceramics was measured over an (υ3−Au), 425 (υ4−Au), 318 (υ4−Eu), and 245 (υ4−Au) cm−1
ultrawide temperature range (−40 to +120 °C), as illustrated and three external modes at 208 (Eu), 196 (Au), and 150 (Eu)
in Figure 7d. With the increase of temperature, the resonant cm−1 were reported.55 All five internal vibrational modes and
frequencies of SNCMo@0.15 and SNCMo@0.4 decrease two external modes were observed owing to the substitution of
linearly, whereas that of SNCMo@0.18 decreases first and Sm3+/Nb5+ by Ca2+/Mo6+, influencing the motion of the [Sm/
then increases (∼60 °C), giving a near-zero TCF over an CaO8] clusters and rigid [Nb/MoO4] tetrahedron units
ultrawide range (table inset of Figure 7d). Notably, excellent coupled with the distortion of the [Nb/MoO4] tetrahedra,
microwave dielectric properties (εr ∼ 17.1, Q × f ∼ 52, 800 which probably affected the position and intensity as well as
GHz at ∼8.80 GHz, and TCF ∼ −1.4 ppm/°C) and the “survival” of peaks in the vibrational modes (Figure 8a).
temperature stability over the ultrawide temperature range With increasing x, the υ1 vibration (∼900 cm−1) is activated,
are obtained with the SNCMo@0.18 ceramic, which has which was considered as the IR-active Au mode.72 Also, the
promising applications in microwave devices. original υ3 vibrational mode at 830 cm−1 becomes stronger,
Infrared reflection spectra (IR) are often considered very and a new υ3 vibrational peak appears at 755 cm−1. The
useful tools for investigating the intrinsic permittivity and loss. merging of the υ4 vibrational modes should be contributed to
Figure 8a reveals that the IR-active vibration modes of both the phase transition. Compared with the vibrational modes υ3
monoclinic fergusonite and tetragonal scheelite phase and υ4, only slight variations in the vibrational peaks of υ2 and
SNCMo@x ceramics are fitted well by the Lorentzian formula external mode are observed. Figure 8b−d depicts the curves of
(eq 7) and the Fresnel formula (eq 8). the real and imaginary parts extended to the microwave region
of SNCMo@0.18, SNCMo@0.375, and SNCMo@0.7, and the
n 2
pj parameters are obtained and listed in Table S5 (Supporting
*( ) ( )= Information). The optical frequency permittivity of 3.6, 3.8,
2 2
oj j (7)
j =1 j and 3.4 for SNCMo@0.18, SNCMo@0.375, and SNCMo@0.7
and the intrinsic permittivity of 11.4, 9.5, and 11.0,
2 respectively, deviate slightly from the measured values of
1 *( ) 17.1 at 8.80 GHz, 15.3 at 9.0 GHz, and 12.0 at 10.1 GHz,
R( ) = which could be attributed to the preparation of the specimen,
1+ *( ) (8) indicating that the principal polarization originates mostly from
111 https://doi.org/10.1021/acs.chemmater.2c02663
Chem. Mater. 2023, 35, 104−115
Chemistry of Materials pubs.acs.org/cm Article

ionic polarization. Moreover, the external modes of Ca/Sm− high radiation efficiency (>90.0%) and gain (5.51−5.95 dBi)
O, especially Eu modes, dominate the dielectric polarization within the range of 7.64−7.86 GHz, which satisfies the working
despite the overlap of the Nb/Mo−O vibrational modes requirements of X-band satellite communication.
corresponding to the ferroelastic transition. Furthermore, the
real part (ε′) of the permittivity obtained from the THz
(0.20−2.00 THz) measurement (13.1 for SNCMo@0.18, 12.9
■
*
ASSOCIATED CONTENT
sı Supporting Information
for SNCMo@0.375, and 11.1 for SNCMo@0.7) is near to the
experimental value as well as to the IR, while the imaginary The Supporting Information is available free of charge at
part (ε″) is still acceptable in the millimeter waves despite https://pubs.acs.org/doi/10.1021/acs.chemmater.2c02663.
slight fluctuations. This means that the SNCMo@x ceramic Microwave dielectric properties of A-, B-, and A/B-site
system is an excellent candidate for high-frequency applica- substituted RENbO4-based compounds; Rietveld refine-
tions. ment plot of SNCMo@x (x = 0.15, 0.18, 0.4, and 0.7)
Figure 9a−c shows the dimensions and the prototype of the ceramics; room-temperature crystal structure of RE-
CDRA designed with the SNCMo@0.18 ceramic. The (Nb1−xVx)O4 (Re = La, Ce, Nd, and Sm) compounds;
measured and simulated |S11| values (Figure 9d) are −21.34 crystallographic structural parameters of SNCMo@x (x
dB at 7.76 GHz with a return loss bandwidth of 260 MHz = 0.15−0.7) ceramics; SEM images and mean size of the
(7.64−7.90 GHz) and −32.18 dB at 7.75 GHz with a return CNVx (x = 0−0.4) specimens; permittivity (εr, εs, and
loss bandwidth of 270 MHz (7.62−7.89 GHz), respectively. εf) and relative density as a function of x; phonon
The measured central frequency is displaced slightly with parameters obtained by fitting the infrared reflection
respect to the simulated value, potentially owing to the spectrum of SNCMo@x (x = 0.18, 0.375, and 0.7)
consequence of tolerance in the fabrication and loss tangent of ceramics; and comparison of the proposed antenna with
the Rogers RT5880 substrate,73−75 indicating that SNCMo@x other DRA systems (PDF)
ceramics are good candidates for X-band satellite communi-
cation (7.10−7.90 GHz),76,77 point-to-point wireless applica-
tions (5.93−8.50 GHz),78 and ITU-R (7.73−8.50 GHz).79Fig-
Figure 9e,f presents the 3D simulated radiation pattern of the
■ AUTHOR INFORMATION
Corresponding Authors
CDRA at 7.75 GHz. As displayed in Figure 9g,h, the E-field is Di Zhou − Key Laboratory of Multifunctional Materials and
along the y-axis direction, and the H-field is semicircular in the Structures, Ministry of Education, School of Electronic Science
CDRA (xoy-plane), indicating that the HE11δ mode of the and Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi
cylindrical SNCMo@0.18 ceramic (DR) is activated. Figure 9i 710049, China; orcid.org/0000-0001-7411-4658;
shows the simulated gain curve and the radiation efficiency at Email: zhoudi1220@gmail.com
7.75 GHz. With reference to the figure, the designed antenna Heli Jantunen − Microelectronics Research Unit, University of
has a radiation efficiency above 90% in the frequency range of Oulu, Oulu FI-90014, Finland; Email: heli.jantunen@
7.64−7.86 GHz because of the presence of the ceramic oulu.fi
dielectric, with the corresponding gain range of 5.51−5.65 and
5.96 dBi at the central resonant frequency (7.75 GHz). The Authors
comparison of the proposed antenna with other DRA system is Fangfang Wu − Key Laboratory of Multifunctional Materials
displayed in Table S6 (Supporting Information), demonstrat- and Structures, Ministry of Education, School of Electronic
ing that the CDRA is a promising candidate for applications Science and Engineering, Xi’an Jiaotong University, Xi’an,
with X-band communication antenna. Shaanxi 710049, China; Microelectronics Research Unit,
University of Oulu, Oulu FI-90014, Finland
■ CONCLUSIONS
In this paper, we have presented novel SNCMo@x ceramics
Chao Du − Key Laboratory of Multifunctional Materials and
Structures, Ministry of Education, School of Electronic Science
with excellent microwave dielectric properties. The crystal and Engineering, Xi’an Jiaotong University, Xi’an, Shaanxi
structures of the ceramics were proved to be fergusonite-type 710049, China
in the range of x < 0.375 and scheelite-type for x ≥ 0.375. Di-Ming Xu − Key Laboratory of Multifunctional Materials
There were two different orientational domain structures in the and Structures, Ministry of Education, School of Electronic
fergusonite-type, as revealed by TEM. The primary contributor Science and Engineering, Xi’an Jiaotong University, Xi’an,
to εr comes from the phonon absorption of Ca/Sm−O bonds Shaanxi 710049, China
(Eu modes) within the microwave frequency band. The Rui-Tao Li − Key Laboratory of Multifunctional Materials
distortion and deformation of the [BO] polyhedral may be and Structures, Ministry of Education, School of Electronic
responsible for the irregular behavior of the Q × f double Science and Engineering, Xi’an Jiaotong University, Xi’an,
hump and TCF. Both εr and Q × f measured in THz (0.20− Shaanxi 710049, China
2.00 THz) are consistent with the experimental values as well Zhong-Qi Shi − State Key Laboratory for Mechanical
as the infrared values, indicating that the ceramic could Behaviour of Materials, Xi’an Jiaotong University, Xi’an
probably be effective in satellite communication. Importantly, 710049, P. R. China
the optimal microwave dielectric properties (εr ∼ 17.1, Q × f ∼ Moustafa A. Darwish − Physics Department, Faculty of
52, 800 GHz at ∼8.80 GHz, and TCF ∼ −1.4 ppm/°C) of the Science, Tanta University, Tanta 31527, Egypt;
SNCMo@0.18 ceramic were obtained. Accordingly, a orcid.org/0000-0001-6315-8209
cylindrical prototype DRA with resonance at 7.76 GHz (|S11| Tao Zhou − School of Electronic and Information Engineering,
= −21.34 dB) was designed and fabricated using the Hangzhou Dianzi University, Hangzhou 310018, China
SNCMo@0.18 sample. Good agreement was observed Complete contact information is available at:
between the simulated and measured results, together with a https://pubs.acs.org/10.1021/acs.chemmater.2c02663
112 https://doi.org/10.1021/acs.chemmater.2c02663
Chem. Mater. 2023, 35, 104−115
Chemistry of Materials pubs.acs.org/cm Article

Author Contributions Ultra-Low Dielectric Loss for Dielectric Resonator Antenna

D.Z. and F.F.W. carried out the laboratory research and wrote Applications. J. Mater. Chem. C 2021, 9, 9962−9971.
the draft of the manuscript; C.C. carried out the design and (10) Sebastian, M. T.; Ubic, R.; Jantunen, H. Low-Loss Dielectric
performance measurement of antenna; D.M.X. carried out the Ceramic Materials and Their Properties. Int. Mater. Rev. 2015, 60,
characterization of TEM; R.T.L. carried out the character- 392−412.
(11) Sebastian, M. T.; Ubic, R.; Jantunen, H.Microwave Materials
ization of dielectric performance; Z.Q.S., M.A.D., and T.Z.
and Applications; John Wiley & Sons, 2017; pp 714−927.
carried out the characterization of the microstructures; and (12) Jean, J. H.; Gupta, T. K. Design of Low Dielectric Glass
H.J. reviewed the manuscript, improved the quality of English, +Ceramics for Multilayer Ceramic Substrate. IEEE Trans. Compon.,
and corrected the scientific inaccuracies and explanations. Packag., Manuf. Technol., Part B 1994, 17, 228−233.
Notes (13) Kim, D. W.; Kwon, D. K.; Yoon, S. H.; Hong, K. S. Microwave
The authors declare no competing financial interest. Dielectric Properties of Rare-Earth Ortho-Niobates with Ferroelas-
ticity. J. Am. Ceram. Soc. 2006, 89, 3861−3864.
■ ACKNOWLEDGMENTS
This work was supported by the National Natural Science
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Transformation in a Ceramic Rare-Earth Orthoniobate, LaNbO4. J.
Am. Ceram. Soc. 1997, 80, 803−806.
Foundation of China (52072295 and 62175056), the Interna- (15) Vullum, F.; Nitsche, F.; Selbach, S. M.; Grande, T. Solid
tional Cooperation Project of Shaanxi Province (2021KWZ- Solubility and Phase Transitions in the System LaNb1−xTaxO4. J. Solid
10), the Zhejiang Provincial Science and Technology Program State Chem. 2008, 181, 2580−2585.
under grant LGG20F010007, the Fundamental Research (16) Brandão, A. D.; Antunes, I.; Frade, J. R.; Torre, J.; Kharton, V.
Funds for the Central University, and the 111 Project of V.; Fagg, D. P. Enhanced Low-Temperature Proton Conduction in
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