High permittivity Li and Al doped NiO ceramics

Yuanhua Lin, Jianfei Wang, Lei Jiang, Yu Chen, and Ce-Wen Nan

Citation: Applied Physics Letters 85, 5664 (2004); doi: 10.1063/1.1827937

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 APPLIED PHYSICS LETTERS VOLUME 85, NUMBER 23 6 DECEMBER 2004

High permittivity Li and Al doped NiO ceramics

Yuanhua Lin,a) Jianfei Wang, Lei Jiang, Yu Chen, and Ce-Wen Nan
State Key Laboratory of New Ceramics and Fine Processing, Department of Materials Science and
Engineering, Tsinghua University, Beijing, 100084, People’s Republic of China
(Received 6 April 2004; accepted 12 October 2004)
High-permittivity dielectric NiO-based ceramics co-doped with Li and Al (LANO) have been
prepared by a traditional solid-state synthesis. Analyses of the ceramic microstructure and
composition indicate that Al ions are distributed in grain boundaries, and that uniform boundaries
indexed as NiAl2O4 surround the grains. The concentration of Al has a remarkable effect on the
dielectric properties of the LANO ceramics. The dielectric constant remains almost constant
共⬃104 – 105兲 at low frequency and has a steplike decrease toward higher frequencies. The
high-dielectric-constant response of the LANO ceramics is mainly enhanced by Maxwell–Wagner
polarization. © 2004 American Institute of Physics. [DOI: 10.1063/1.1827937]

Recently, high-permittivity dielectric materials have at-
tracted ever-increasing attention for their uses in microelec-
tronics as important devices such as capacitors and memory
devices.1,2 The high dielectric constant was found in ferro-
electric perovskite oxides near the Curie temperature 共TC兲
such as lead ziaconia-titanate (PZT), and ferroelectric-based
relaxor oxides PbMg1/3Nb2/3O3.3,4 Recently, another
perovskite-related material CaCu3Ti4O12 (CCTO)5 and non-
perovskite materials Li0.05Ti0.02Ni0.93O (LTNO)6 have been
reported for its unusual high dielectric constant of ⬃104 – 105
at room temperature, and ascribed to the origin of the high
permittivity to extrinsic mechanisms such as the formation of
boundary-layer capacitors. Raevski and co-workers also re-
ported the high dielectric permittivity 共⬃104兲 in
AFe1/2B1/2O3 nonferroelectric perovskite ceramics 共A
= Ba, Sr, Ca; B = Nb, Ta, Sb兲 in a wide temperature range,7
and proposed that such a high dielectric permittivity is due to
the Maxwell–Wagner relaxation. Generally, the Maxwell–
Wagner polarization, also known as the interfacial polariza-
tion, is widely adopted to explain the high permittivity ob-
served in the materials, including single-phase ceramics,
single crystals, and multiphase composites.8,9 This often
arises in a material consisting of grains separated by more
insulating intergrain barriers.
In this letter, we investigated the dielectric permittivity
of Li and Al doped NiO (LANO) ceramics. We found out
that all of the LANO ceramics studied exhibit high dielectric
permittivity 共⬃104 – 105兲 by the impedance spectroscopy in a
wide temperature and frequency range, and showed that such
a high dielectric permittivity is associated with the Maxwell–
Wagner polarization mechanism.
Ni共NO3兲2 · 6H2O (A.R.), LiNO3 (A.R.), Al共NO3兲3
(A.R.), and citric acid were employed as raw materials. Four
different LANO ceramic samples, i.e., Li0.04Al0.02Ni0.94O
(LANO-1), Li0.04Al0.04Ni0.92O (LANO-2), Li0.04Al0.06Ni0.90O
(LANO-3), and Li0.04Al0.10Ni0.86O (LANO-4) were designed
and prepared by the following procedure. Stoichiometric
amounts of Ni共NO3兲2 · 6H2O, LiNO3, and citric acid were
mixed and dissolved into distilled water. Afterwards
Al共NO3兲3 solution was added slowly into the above mixed
solution, followed by heating and stirring to form the semi-
transparent gel. Dried gel was then calcined at 800 °C for 1 h
in air to obtain the precursor powders. The resultant powders
were pressed into green pellets of 10 mm in diameter and
about 1.2– 1.8 mm in thickness at 10 MPa by using polyvi-
nyl alcohol as a binder. Finally, these pellets were sintered at
1250 °C for 2 h in air.
X-ray diffraction (XRD) and scanning electron micros-
copy (SEM) equipped with energy dispersive x-ray spec-
trometer (EDX) were employed to reveal the microstructure
and phase composition of the LANO ceramics. The ceramic
samples were polished, and electroded by silver paint on
both sides of the disk-shape samples fired at 800 °C for
30 min. The dielectric behavior was measured by using a
HP4194A impedance analyzer in the frequency range from
100 Hz to 1 MHz and at a bias voltage of 1.0 V and at
different temperatures from −50 to 100 °C.
Figure 1 shows the XRD patterns of the LANO ceramic
samples with various Al-doped contents. Because the radius
of Ni2+ ion 共0.69 Å兲 is almost the same as that of Li+ ion
共0.68 Å兲, Ni2+ ion in lattice structure can be replaced by Li+
ions and Al3+ ions. Additionally, it can be seen that a second
phase NiAl2O4 can be observed from the XRD patterns as
the Al dopant content increases up to 6 mol %, which might
be attributed to that the Al dopant content is over the solid
solution limitation of Al– Ni– O system.

a)
Electronic mail: linyh@tsinghua.edu.cn FIG. 1. XRD patterns of various LANO ceramic samples.

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 Appl. Phys. Lett., Vol. 85, No. 23, 6 December 2004 Lin et al. 5665

FIG. 2. Frequency dependence of the dielectric constant of various LANO

ceramic samples.

Figure 2 illustrates an almost constant low-frequency di-

electric constant and a steplike decrease in the dielectric con-
stant toward higher frequencies observed in these LANO
samples. Of interest to note, the dielectric constant is about
three to four orders of magnitude higher than that in pure
NiO ceramics 共⑀ ⬃ 30兲. As shown in Fig. 3, the temperature
dependence of the real part of the complex permittivity,
␧⬘共T兲, in the measuring temperature range from −50 to
100 °C for the as-sintered samples implies that ␧⬘共T兲 has a
step, and above the temperature of this step, ␧⬘共T兲 are nearly
independent of T. Moreover, the characteristic temperature
of this step shifts to higher temperature as the Al dopant
content increases. Such a behavior is typical for the
Maxwell–Wagner relaxation, and has been observed in the
other high dielectric ceramics, e.g., CCTO,5 BaFe1/2Nb1/2O3
(BFN) samples.10,11 Normally, high dielectric constants are
expected for ferroelectrics in a narrow temperature range
close to TC. However, the high dielectric constant in the
LANO ceramics persists over a broad temperature range.
Obviously, such a temperature dependence of the dielectric
permittivity does not obey the Curie–Weiss law, and there- FIG. 4. SEM graphs (a) and EDX spectra (b) of the fractured surface of the
LANO-3 sample.
fore, the samples do not exhibit the ferroelectric-related
properties.
The Maxwell–Wagner polarization, or interfacial polar- relaxation with extremely high permittivity.12 The common
ization model was usually employed to explain the dielectric interpretation assumes a whole series of boundary barriers
and grains, or even a series-parallel array of boundary barri-
ers, which arises if the material consists of grains separated
by more insulating intergrain barriers as in boundary layer
capacitors.
Figure 4 gives the typical SEM and EDX images of the
LANO-3 sample. The SEM micrograph indicates that the
grain size of the bulk is several microns, and there obviously
exists a boundary between adjacent grains. According to the
results of EDX spectra and XRD shown in Fig. 1, Al dopant
exists as an insulative boundary-NiAl2O4 phase. This fact
implies that the samples studied contain a large number of
highly insulating grain boundaries NiAl2O4, while the NiO
grain core is semiconductive.
A typical frequency and temperature spectra of LANO-4
ceramic sample are presented in Figs. 5 and 6 at several
temperatures and frequencies. As shown in Fig. 5, ␧⬘共T兲 ex-
hibits a steplike dispersion at intermediate frequencies and a
monotonous increase at low frequency 共100 Hz– 100 kHz兲.
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FIG. 3. Temperature dependence of ␧⬘ measured at 10 kHz. As the temperature increases, the steplike dispersion shifts to
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 5666 Appl. Phys. Lett., Vol. 85, No. 23, 6 December 2004
FIG. 5. Temperature dependence of the real part of the dielectric constant
for the LANO-4 sample.
higher frequencies. As shown in Fig. 6, a maximum in ␧⬙共T兲
(the imaginary part of the complex permittivity) can be ob-
served. With the temperature increasing, this maximum shifts
to high frequencies. Such behavior can also be observed in
the other LANO ceramic samples. The observations suggest
also that the Maxwell–Wagner relaxation mechanism might
play an important role in the dielectric response of the core-
shell NiO-based ceramics.
NiO is a Mott–Hubbard insulator at room temperature.13
However, introduction of Ni2+ vacancies 共VNi ⬙ 兲 and/or doping
with monovalent cations like Li can increase the conductiv-
⬙ can produce some defect dipoles14,15 in
ity. Normally, the VNi
the LANO ceramics. In the Li– Al– Ni– O system, Ni vacan-
⬙ 兲 and O vacancies 共VO••兲 are responsible for maintain-
cies 共VNi
ing the charge balance. Because the doping concentration of
Li keeps constant, the effect of doped Al on the dielectric
properties is the main factor. VNi ⬙ vacancies have weakly
bound holes, which contributes to polarization and results in
FIG. 6. Frequency dependence of the imaginary part of the dielectric con-
stant for the LANO-4 sample at various temperatures.
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Lin et al.
the appearance of the step in ␧⬘共T兲 and the maximum in
␧⬙共T兲 as shown in Figs. 5 and 6. We assume that the interfa-
cial layers at the grain boundaries are nonconducting or less
conducting, while the bulk of the grains is semiconducting or
conducting. Under the applied electric field, the carrier-
conducting access is blocked by the insulating grain bound-
ary layers, and thus the opposite charges would accumulate
at the two edges of the insulator layer, which can be consid-
ered as a micro-parallel capacitor. This effect is well known
in a number of dielectric materials.6–9 The application of an
electric field breaks the symmetry of these charges and a
macroscopic dipole is thus created. Consequentially, the po-
larization formation primarily depends on the accumulation
of the charge via conducting in the grain interior, which re-
sults in the large values of dielectric permittivity in the
LANO ceramics studied. Therefore, with increasing content
of Al doped, the resultant various amounts of VNi ⬙ and differ-
ent thickness of the boundary layer for these LANO samples
lead to their different dielectric properties.
In conclusion, the LANO ceramic samples sintered ex-
hibit high dielectric constants, and the dielectric constant
reaches about 5.0⫻ 104 for the LANO-1 sample at 1 kHz
and room temperature. EDX and XRD results show that the
main component in the boundary layer is NiAl2O4 phase.
The origin of the high dielectric permittivity observed in
these LANO ceramics is attributed to the Maxwell–Wagner
polarization.
This work was financially supported by National High
Technology Research and Development Program of China
(No. 2003AA302120) and the Ministry of S & T of China
through a 973-Project (No. 2002CB613303).
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