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Doping-dependent negative dielectric permittivity

realized in mono-phase antimony tin oxide
Cite this: J. Mater. Chem. C, 2020,
8, 11610 ceramics†
a
Guohua Fan, Zhongyang Wang,a Kai Sun, b
Yao Liu *a and Runhua Fanb
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Materials with negative permittivity have recently become a research hotspot due to their potential
applications in electromagnetic shielding, novel capacitance, inductor design, etc. Negative permittivity
realized in metamaterials and multicomponent composites are determined by the critical building blocks
within them. Herein, from the perspective of intrinsic properties of mono-phase materials, Sb-doped SnO2
(ATO) was synthesized by a hydrothermal method and sintered into mono-phase ceramics to be negative
permittivity materials. The influences of Sb-doping on the electric and dielectric properties of the ceramics
were studied. It was found that the electron concentration was increased as Sb-doping amount increases in
a certain range, leading to the decrease in resistivity. Negative permittivity was observed owing to the
Received 10th May 2020, plasma oscillations of free carriers derived from donor Sb-dopants. Moreover, the evident dielectric loss
Accepted 12th July 2020 accompanied with plasma-like negative permittivity was completely caused by loss of conduction. In
DOI: 10.1039/d0tc02266g addition, reactance analysis revealed that epsilon-negative ceramics were electrically inductive. This
work explored the unusual dielectric properties of ATO ceramics and elucidated the mechanism and
rsc.li/materials-c physical significance of negative permittivity in doped mono-phase ceramics.

1 Introduction NiO,12,13 SrTiO3,14 TiO2,15–17 etc. Meanwhile, other materials of

positive-k, such as ferroelectrics, antiferroelectrics, and micro-
For most dielectric materials, the permittivity that reflects wave dielectrics, can also be modified through element doping
responding modes and abilities of the material in an electric to meet the application requirements of energy-storage or
field is usually positive.1–3 Positive permittivity (positive-k) electrically tunable microwave devices.18–21 Thus, chemical
dielectrics have been widely used in various electric devices doping as a facile and effective method is widely used in
or platforms for their easily tailored properties.4,5 One of the tailoring dielectrics’ properties. Interestingly, Yan’s work
top research interests for materials with positive-k is colossal reported that Sr-doped LaMnO3 exhibited completely different
permittivity and low dielectric loss for novel capacitances to dielectric phenomena, where common positive permittivity
achieve miniaturization of components and high-density turned into negative due to the double-exchange effect of doped
energy storage.6,7 In addition to the multicomponent compo- Sr atoms increasing the carrier concentration, which induced a
sites based on percolation theory, element doping for pure plasmonic state within the ceramics.22,23 It is of research
phase materials (especially for ceramics), is also an effective significance that the fancy dielectric behavior of negative
way to enhance the dielectric permittivity.8,9 In the past several permittivity (negative-k) can make the positive indices of more
years, internal barrier layer capacitance mechanism and conventional materials single or double negative in nature, like
electron-pinned defect dipoles effect have been successively metamaterials.24,25
proposed and verified to elucidate the ultimate reasons of giant In fact, investigations of negative-k in conventional materials
positive permittivity in doped ceramics like CaCu3Ti4O12,10,11 were initially carried out in composites comprising homoge-
neously dispersed conductor fillers.26,27 Negative dielectric per-
a
Key Laboratory for Liquid-Solid Structural Evolution and Processing of Materials mittivity of composites is mainly caused by the critical structures
(Ministry of Education), Shandong University, Jinan 250061, China. of conductor fillers, in which collective oscillations of the deloca-
E-mail: [email protected] lized carriers take place with the fluctuation of electric field.28,29 In
b
College of Ocean Science and Engineering, Shanghai Maritime University,
recent years, the realization and regulation of negative permittivity
Shanghai 201306, China
† Electronic supplementary information (ESI) available: XRD patterns of the
in composites has increasingly become a research hotspot. Var-
calcined ATO powders (S1), SEM images of the calcined ATO powders (S2), and ious ceramic matrix composites (CMCs) including TiN/Al2O3,30
EDS analysis for the powders of SnO2:8Sb (S3). See DOI: 10.1039/d0tc02266g graphene/CaCu3Ti4O12,31 and Cu/Y3Fe5O12,32 as well as polymer

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matrix composites (PMCs) like graphene/PDMS,33 Al/APU,34 and to obtain a solution with a concentration of 0.5 mol L1. Then,
CNTs/POE35 have been designed and fabricated to obtain tailor- the right amount of SbCl3 was added into the solution to ensure
able negative dielectric properties in specified frequency regions. the mole ratio of Sb is 0, 1, 2, 4, 6, 8, and 10 mol%, respectively.
Meanwhile, CMCs and PMCs with negative-k have shown great Next, plenty of (NH4)2CO3 was dissolved into the mixture
potential in various applications such as electromagnetic shield- solution and fully stirred. Finally, the obtained solution was
ing and multi-layer capacitances due to the abnormal negative poured into a Teflon-sealed autoclave and reacted at 180 1C for
permittivity response providing new ideas for performance 10 hours. Afterwards, the resultant solution was centrifuged
design.36–38 Compared with metamaterials, composites avoid and the collected powders were washed with water and alcohol
the sophisticated periodical artificial structures and simplify the successively, then dried in an oven at 80 1C for 24 hours.
processes to realize negative permittivity in natural ‘‘real’’ Finally, the powders were calcined at 800 1C for 2 hours to
materials.39 However, negative permittivity of composites in most promote further doping of Sb atoms into SnO2 lattices and
reports is roughly attributed to the critical percolating structures stabilize the crystal structure.
of building blocks, and there still exist inevitable difficulties for ATO ceramics were sintered by a pressureless sintering
composites to achieve molecular and even atomic level homo- method. Green bodies were dry pressed with a pressure of
geneous metamaterials that are more conducive to be used as 20 MPa for 5 min. The pressureless sintering conditions were
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coatings, films, or even other lower-dimensional materials or 1100 1C and 4 h under an air atmosphere. The final samples
devices. Furthermore, epsilon-negative responses of materials were round ceramic plates with a diameter of about 15 mm and
are determined by the plasmonic oscillations of electrons and a thickness of about 2 mm. The overall preparation process of
the magnitude of negative permittivity is closely associated to ATO ceramics is schematically illustrated in Fig. 1.
electron concentration.40 However, to our best knowledge,
although the study of negative permittivity based on carrier
2.3 Characterization
characteristics is more in-depth, there are few reports that have
investigated it on this aspect. Therefore, it is of interest and Phase composition and microstructure of the synthesized
significance to properties tailorable negative permittivity prop- powders and the sintered polycrystalline ceramics were char-
erties in mono-phase materials and elaborate the mechanism acterized by X-ray diffraction (XRD, DMAX-2500PC, Rigaku) and
of it from a more microscopic perspective. scanning electron microscopy (SEM, JSM-7800F, JEOL) equipped
In addition to the doped LaMnO3 ceramics and some polymers with energy dispersive X-ray spectroscope (EDS, XMax-80, Oxford
like PANI, doped oxide ceramics are highly possible candidates to Instruments), respectively. Element composition and chemical
be negative permittivity materials.23,24 It is noteworthy that anti- valence states were characterized by X-ray photoelectron spectro-
mony tin oxide (SnO2:Sb, ATO) has been widely studied for scopy (XPS, Axis Supra, Shimadzu). Carrier concentration and
transparent infrared blocking and photovoltaic applications due mobility were measured using the Van der Pauw method with a
to the easily tailored optical dielectric functions and electric hall effect test system (Model HALL series, Semishare) at room
properties by antimony-doping.41,42 According to the free electron temperature.44 The samples were processed into square slices
theory, negative permittivity in radio-frequency and even kHz with a side length of 10 mm and a thickness of 0.5 mm for hall
regions that are far below the optical band can also be achieved measurements. The applied magnetic field strength was 0.3 T and
with a suitable carrier concentration.30,43 Therefore, in this work, the excitation current was 5 mA. Radio-frequency dielectric prop-
tin oxide (SnO2) was doped with antimony (Sb) to improve the erties and ac conductivity were measured from 10 MHz to 1 GHz,
carrier concentration in order to realize negative permittivity with
the doped ceramics. Furthermore, relationships among the com-
position, microstructure, carrier concentration and mobility, as
well as dielectric properties with varied amounts of Sb-dopants
were discussed.

2 Experimental
2.1 Materials
Tin chloride pentahydrate (SnCl45H2O, 99.9%), antimony chlor-
ide (SbCl3, 99.9%), and ammonium carbonate ((NH4)2CO3, 99.9%)
were all purchased from Shanghai Aladdin Bio-Chem Technology
Co., Ltd and were used as received without any further purification.

2.2 Sample preparation

Antimony-doped tin oxide (ATO) powders were synthesized
with a simple hydrothermal reaction and calcination process. Fig. 1 Schematic diagram of the synthesis process of ATO powders (a and
SnCl45H2O was dissolved into deionized water at room temperature b) and the sintered polycrystalline ceramics (c).

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using a precise impedance analyzer (E4991A, Agilent) fitted with a inside the polycrystalline ceramics and all samples maintained
16453A dielectric test fixture.45 a compact structure.
XRD patterns of the sintered ceramics are shown in Fig. 3.
All sintered samples retain the crystal structure of tetragonal
3 Results and discussion SnO2 (PDF#41-1445) and no diffraction peaks of other phases
appear, which is consistent with that of the calcined ATO
3.1 Microstructure and composition powders. In addition, pattern details near 2y = 271 indicate
XRD patterns and SEM images of the calcined ATO powders are that the diffraction peaks shift to a lower angle as the amount
shown in Fig. S1–S3 (ESI†). It’s suggested that ATO powders of Sb-dopants increases, as shown in Fig. 3(b). Sb-Doping
with the main phase of tetragonal SnO2 (PDF#41-1445) were affects the original crystal plane spacing of SnO2 and causes
successfully synthesized. No diffraction peaks of Sb-oxides are lattice distortion, which leads to the displacement of diffraction
observed on the XRD patterns as Sb-doping amount varied from peaks on XRD patterns. A similar phenomenom of shifting of
2 to 10 mol%. SEM images show the calcined ATO powders diffraction peaks caused by doping is also observed in ATO thin
are irregular spherical particles and loosely agglomerated. The films.48 There are no observed second phases formed by Sb-
particle size tends to increase with the increasing amount of dopants. This indicates that Sb atoms have doped into SnO2
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Sb-dopants. Further EDS analysis demonstrates the existence of lattices. Thus, mono-phase ceramics of ATO were successfully
Sn, Sb, and O elements in the prepared powders. Therefore, it is sintered with the synthesized powders.
confirmed that Sb-doped SnO2 powders were successfully synthe- XPS spectra are analyzed to further investigate the composi-
sized via the facile hydrothermal method and calcination process. tion of the sintered ATO ceramics. As shown in Fig. 4(a),
Fig. 2 shows the microstructure of sintered SnO2 and all doped samples show photoelectron peaks of Sn, Sb, and
ATO ceramics. Grains of all samples are in close contact and O elements, revealing the existence of Sb atoms in ATO cera-
grain boundaries are clear. The grain size of the undoped SnO2 mics. The content ratio of [Sb]/[Sn] of the sintered ceramics was
ceramic is mainly distributed in the range from 80 to 120 nm, obtained by calculating the area ratio of the peaks on the XPS
while that of the doped samples is mainly distributed between spectra, suggesting that the content of Sb-dopants in the final
40 and 60 nm and there is little difference among samples with samples is nearly consistent with the set doping ratio, as shown
different dopant amounts. It is suggested that the grain size of by the black plots in Fig. 4(c). The electric properties of ATO
ATO ceramics is smaller than that of the undoped SnO2, which ceramics are determined by Sb-dopants, while Sb atoms usually
is attributed to the fact that the Sb-contained compounds exist with both 3+ (Sb3+) and 5+ (Sb5+) oxidation states in doped
at grain boundaries inhibited the growth of grains during SnO2 crystal lattices.47 Sb-Dopants produce n-type carriers (i.e.,
sintering.46,47 In addition, all doped samples are dense cera- electrons) as donor dopants only in the Sb5+ state, while Sb3+
mics with nanoscale grains and there is no evident difference has nearly no positive effect on increasing electron concen-
for the microstructures as the amount of Sb-dopants varies tration. Due to the fact that the Sb 3d5/2 peak overlaps with the
from 2 to 10 mol%. No distinctly different substances appear O 1s peak at around 531 eV, Sb 3d3/2 spectra were selected for

Fig. 2 SEM images of the sintered ATO ceramics and the inserted graph shows the distribution of grain size. The amount of Sb-dopants for (a–f) is 0, 2,
4, 6, 8, and 10 mol%, respectively.

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electric performance of doped SnO2 ceramics. Meanwhile, the

resultant Sb5+ content calculated from the Sb5+/Sb3+ ratio is
related to the nominal doping amount. As the amount of Sb-
dopants increases from 2 to 10 mol%, the content of Sb5+ in
sintered ATO ceramics increases almost linearly.

3.2 Carriers and Sb-doping

Carriers in ATO ceramics were determined to be n-type carriers
(i.e., electrons) with the Van der Pauw method. Fig. 5 shows the
measured carrier concentration, mobility, and resistivity of ATO
ceramics with different amounts of Sb-dopants. Carrier concen-
Fig. 3 XRD patterns of ATO ceramics with different amounts of Sb-dopants.
tration increases with increasing Sb-dopants and reaches the
maximum near 3.0  1019 cm3, which is consistent with the
variation tendency of Sb5+ content, suggesting Sb atoms with 5+
further analysis to determine the Sb5+/Sb3+ ratio and Sb5+ oxidation state are effective donor dopants to provide n-type
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content in ATO ceramics. The deconvoluted results of Sb 3d3/2 carriers.44,50 The other intrinsic parameter of carriers is mobi-
spectra of different samples are given in Fig. 4(b). The Sb 3d3/2 lity, which is usually influenced by impurity scattering, grain
spectra were split into two peaks, in which the peak with a boundary scattering, and lattice vibration scattering.42 All sam-
higher binding energy corresponds to Sb5+ and the peak with a ples were measured at the same room temperature, thus the
lower binding energy corresponds to Sb3+.49 The Sb5+/Sb3+ ratio effect of lattice vibration scattering on the mobility of different
was determined by calculating the area ratio of the two fitted samples is not taken into consideration in this discussion.
peaks. As shown in Fig. 4(c), the content of Sb5+ is more than Microstructure analysis suggested samples with an Sb-dopant
that of Sb3+ and the ratio of Sb5+/Sb3+ in all samples fluctuates amount higher than 2 mol% have more uniform grain and
around 1.4 as the amount of Sb-dopants increases. It is con- boundary distributions, thus the mobility increases as Sb-
firmed that Sb5+ plays the dominating role in improving the dopants increase from 2 to 6 mol%. However, when the amount

Fig. 4 XPS spectra of ATO ceramics with different amounts of Sb-dopants. (a) Survey spectra, (b) fine spectra of Sb 3d3/2, and (c) [Sb]/[Sn] ratio, Sb5+/
Sb3+ ratio, and Sb5+ content of the sintered ceramics calculated from the XPS results.

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real part permittivity (e 0 ) of the pure SnO2 ceramic is almost

frequency independent and maintains a value near 10. With the
incorporation of Sb-dopants, e 0 of the doped ceramics rises
rapidly with the increasing amount of dopant. Meanwhile, the
imaginary part of permittivity (e00 ), which indicates energy loss
of dielectrics, also increases as the amount of dopant increases,
suggesting the incremental loss properties of the doped cera-
mics. Strikingly, the frequency dispersions of e 0 for doped
ceramics with an Sb-dopant amount no less than 6 mol%
exhibit completely different features, as shown in Fig. 6(b).
Negative permittivity (e 0 o 0) is observed and frequency depen-
dences vary with the increasing amount of Sb-dopants. For ATO
ceramics with Sb-dopant amounts of 8 and 10 mol%, e 0 is
negative in the whole test band and the absolute value of
Fig. 5 Resistivity, carrier concentration and mobility of ATO ceramics
negative permittivity decreases as frequency increases, which
determined via Hall effect measurements.
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is similar to the plasma behavior of metals.51 Solid lines in

Fig. 6(b) were fitted by the Drude model of the classical free
of Sb-dopants is further increased, mobility decreases, which is electron theory, as described below.52
attributed to the effect of impurity scattering. Resistivity is
op2
closely related to carrier concentration and mobility. With the e¼1 (1)
o2  joot
increasing amount of Sb-dopants, the general trend of resistiv-
ity is decreasing owing to the increased carrier concentration. sffiffiffiffiffiffiffiffiffiffi
For the sample with 10 mol% dopants, the resistivity is slightly 0 op2 ne2
e ¼1 2 ; op ¼ (2)
increased due to the decreased mobility. o þ ot2 m  e0

where o is the angular frequency of the exerted electric field, op

3.3 Radio-frequency dielectric properties is the angular plasma frequency which is determined by
Frequency dependences of permittivity for SnO2 and the doped electron concentration (n) and effective mass (m*), ot is the
ceramics are shown in Fig. 6. In the current testing band, the damping factor which depicts electrons collision frequency.

Fig. 6 Frequency dependences of the real part permittivity (a and b), the imaginary part permittivity (c), and ac conductivity (d) for ATO ceramics.

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When the sample is put into an electric field, free electrons in these two samples are dominated by the extensive free electrons.
ATO ceramics will oscillate with the fluctuation of external Therefore, the gigantic e00 values of the epsilon-negative ceramics
electric field and induce a plasmonic state, which is similar are mainly caused by obvious conduction loss. In fact, conduction
to the plasma oscillations of metals. As a result, negative loss (ec00 ) is closely related to the electric conductivity of the
permittivity is observed in doped ATO ceramics with proper material,30 as described below.
carrier concentration. In addition, as shown in Fig. 6(c), the 00 s
epsilon-negative ceramics possess huge values of e00 , larger by ec ¼ (4)
oe0
nearly one magnitude order than that of ceramics with positive
permittivity, which is discussed in following content. Solid lines in Fig. 6(c) are the calculated results of this equation
Fig. 6(d) shows the frequency dependences of ac conductiv- with the measured data of sac. Calculated ec00 of samples with 8
ity (sac) for SnO2 and the doped ceramics. It can be seen that sac and 10 mol% Sb-dopants coincides well with measured e00 ,
is obviously influenced by the amount of Sb-dopant. On the one suggesting the dielectric loss mainly originates from electric
hand, carrier concentration increases as Sb atoms are doped conduction. Meanwhile, the imaginary part of permittivity derived
and sac increases with increasing amount of Sb-dopant, which from the Drude model of eqn (1) is given below.
is consistent with the electric properties determined by the 00 op2 ot
eDrude ¼ (5)
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abovementioned Hall effect measurements. On the other hand, oðo2 þ ot2 Þ

sac of ATO ceramics with varied dopant amounts exhibits
different dispersion features. For samples with low doping Taking eqn (3) into (4), the conduction loss ec00 is deduced as
amounts, sac increases with increasing frequency, which is in follows.
line with the typical conductivity characteristics in insulator 00 ne2 ot 00
ec ¼  ¼ eDrude (6)
dielectrics.53 As the amount of Sb-dopants continues to increase, m e0 oðo2 þ ot2 Þ
sac shows decreasing trends with increasing frequency and can be
fitted by the Drude model for conductivity,22 as in the following. It is confirmed that ec00 equals the imaginary permittivity of the
Drude model in this case. That is to say, the dielectric loss of
sdc ot2 ne2 plasma-like negative permittivity is caused entirely by conduction
sac ¼ ; sdc ¼ (3) loss. Therefore, loss properties of the ceramics with 8 and 10 mol%
o2 þ ot2 m o t
Sb-dopants are evidently caused by their conduction. In addition,
The fitting results agree well with experimental data for samples for negative permittivity that does not conform to perfect plasma-
with 8 and 10 mol% Sb-dopants, indicating that sac values of like behaviors, there exist multiple mechanisms for the causes of

Fig. 7 Frequency dependences of reactance (a and b) and impedance phase angle (c) for ATO ceramics. (d) Schematic showing the phase angle at
100 MHz shifting from negative to positive with increasing amount of Sb-dopant.

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dielectric loss. Apart from the conduction loss, usually polarization amount of Sb-dopant increases in a certain range, resulting in
loss also contributes to the total dielectric loss.54,55 Therefore, there the decreased resistivity. Radio-frequency dielectric properties
exists deviation between the measured and calculated data in the of ATO ceramics were drastically affected by Sb-doping. Negative
high frequency region for the sample with 6 mol% Sb-dopants, as permittivity appeared due to the induced plasmonic state of free
shown in the inset of Fig. 6(c). electrons. Furthermore, the magnitudes and dispersions of nega-
tive permittivity were determined by electron concentration.
3.4 Reactance analysis of ATO ceramics Meanwhile, the dielectric loss of plasma-like negative permittivity
Reactance of a material is the parameter that reflects phase was completely caused by conduction loss. Reactance analysis
relationships between current and voltage within the matter in revealed that epsilon-negative ceramics are electrically inductive.
an alternating electric field, and a particular aspect that differ- This work explored the anomalous dielectric properties of ATO
entiates inductive from capacitive is that the reactance is and the obtained negative permittivity ceramics are illuminating
positive.28,30 When the voltage phase lags behind that of the for metamaterials and novel inductance design.
current, the reactance is negative, indicating the material is
electric capacitive. In contrast, the positive reactance of induc- Conflicts of interest
tive character means that the current phase falls behind the
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voltage phase. Fig. 7(a) and (b) show the frequency depen- There are no conflicts to declare.
dences of reactance for samples with different amounts of Sb-
dopant. Reactance for samples with a low doping amount is
negative, while positive reactance begins to appear as the Acknowledgements
amount of Sb-dopants reaches up to 6 mol%. Moreover, it is This work was supported by the National Natural Science
noteworthy that the transition for reactance changing from Foundation of China [grant numbers 51771104, 51871146,
negative to positive corresponds exactly to permittivity switch- and 51971119], the Future Plan for Young Talent of Shandong
ing from positive to negative. Meanwhile, Fig. 7(c) gives the University [grant number 2016WLJH40], and the Innovation
frequency dependences of impedance phase angle for samples Program of Shanghai Municipal Education Commission [grant
with different Sb-dopants and (d) schematically shows the number 2019-01-07-00-10-E00053].
phase angle at 100 MHz shifting from negative to positive with
the increasing amount of Sb-dopants. It is suggested that the
phase relationship between voltage and current in epsilon- Notes and references
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