Shivakumar Hunagund

Base metal electrode-MLCCs Electro materials assignment – I, BSc

Nanotechnology

Introduction

As the electronic equipment such as computers and phones were driven towards
miniaturisation, higher performance and lower electric power consumption, it speeded up
passive component integration into the chips in order to achieve those factors. Multi-layer
ceramic capacitors (MLCCs) have been used primarily due to their properties of high
capacitance with their high reliability, high frequency characteristics and their small size.
The structure of MLCC has many dielectric layers and internal electrodes are
alternatively stacked and the internal electrodes are parallelly connected. MLCC’s
capacitance C is represented as C = εr.εo.( n – 1 ). s/t where s is the internal electrodes
overlap area, n is the no. of internal electrode layers, εr is the relative dielectric constant
(k) of the dielectric ceramic, t is the thickness of the dielectric layer, and εo is the
dielectric constant of free space. Therefore for achieving MLCCs of high capacitance
with small size requires higher dielectric k value, thinning of dielectric layers, increasing
no. of stacked layers increasing overlap area of internal electrodes, and improving
stacking precision. For forming dielectric layers, sheeting and printing methods are used
in practice for MLCCs fabrication. MLCCs based on BaTiO 3 (ABO3) have been
fabricated using conventional methods with noble metals as internal electrodes. For cost
reduction of internal electrodes two methods are employed – 1: For achieving low
temperature sintering of the dielectrics, Ag-Pd alloys electrodes are used with high Ag
content and 2: Use of base metals such as nickel and copper as internal electrodes with
nonreducible dielectric which can be fired in a reducing atmosphere.

BaTiO3 based dielectrics which are low temperature fired have lower k values due to their
addition of low melting point additives which have low k. Dielectrics like Y5V and X7R
have higher k values which can be fired below 1100° C by the addition of a glass
component and are compatible with Ag-Pd electrode. There are other dielectrics which
are ferroelectric materials called Pb based complex perovskite having higher k than

1
BaTiO3 which can be sintered at low temperatures and are represented by a general
formula Pb(B’, B”)O3 where Pb occupies the A-site and multiple cations having different
valences occupy the B-site. Another cost effective method is replacing Pb with base
metals like Ni or Cu which can easily oxidise in air at high temperature and therefore the
dielectric materials must be fired in a reducing atmosphere. The conventional dielectrics
are reduced to semiconductive material when fired under reducing atmosphere therefore
nonreducible dielectrics should be developed which can maintain high insulation
resistance after that process.

In the early process of development of nonreducible dielectrics, MnO and Cr 2O3

(acceptors) were added in order to trap conduction electrons so as to enhance insulating
resistance. Also increasing A-site excess in the BaO/TiO2 ratio and addition of CaO
(acceptor) is found to obtain nonreducible BaTiO3 based dielectrics and formation of
Ba2TiO4 grain boundary phases were found to enhance nonreducibility of BaTiO3, but
BaTiO3 based dielectrics with excess A-site show poor sinterability and the resulting chip
components offer poor humidity resistance. This problem was overcome by adding a
glass component which has high insulation resistance under a reducing atmosphere, but
this kind of material losses insulation resistance property at high temperature and electric
field. Therefore various models were proposed to address the mechanism of insulation
resistance degradation : 1) grain boundary model - A high electric field generated by
Maxwell-Wagner polarisation across the grain boundary leads to a local dielectric
breakdown process, 2) reduction model – electro migrated oxygen vacancy conc. at the
cathode leads to ceramic reduction to the anode, and 3) de-mixing model - oxygen
vacancy enrichment near to the cathode and depletion near the anode leads to the
enhancement of the electronic charge carrier conc. between the electrodes resulting in the
formation of pn junction. The important assumption about these models is that oxygen
vacancies generated by acceptor dopant plays an essential part in degradation process of
insulation resistance and also it is well know that insulation resistance degradation of
dielectrics in a high electric field is influenced by donor-to-acceptor ratio of added
components. Doping of nonreducible BaTiO3 based dielectrics with rare earth elements
were carried out in order to investigate the effects and study the changes in dielectrics

2
properties. Rare earth elements having ionic radii between those of Ba and Ti ions were
dissolved in both Ba and Ti sites (Both A and B sites depending on A/B ratio) containing
MgO and a glass component. The rare earth elements are believed to act as a donor when
dissolved at A-site or acceptor when dissolved at B-site. The addition of rare earth ions
significantly improved the dielectrics lifetime since they balanced oxygen vacancies
caused by acceptors which were introduced to enhance nonreducibility. The site
occupancy of rare earth elements in the ABO3 lattice might depend on their ionic radius
and any change in the dissolution ratio of A/B affects the donor/acceptor ratio therefore
influences the electrical characteristics and microstructure.

Doping effect on Dielectrics properties and microstructure

Good electrical conductivity is dependent on intermediate ionic radius rare earth elements
doped samples which facilitates oxygen diffusion process in the cooling stage. Larger
ionic radius rare earth elements cause lower conductivity and smaller lifetime. Hysteresis
loops (Ni-MLCC sample) confirmed increased change in capacitance overtime is due to
an increased remanant polarization of the dielectrics due to space charge in the dielectrics
such as oxygen vacancy which causes a change in remanant polarization. Two samples
analysed in TEM (Sm2O3 doped and Ho2O3 doped) exhibited core shell structure. The
sample with Sm2O3 doped showed many dislocation loops in the shell region with slight
grain growth and the other with Ho2O3 had no dislocation loop, which suggests these
dislocation loops to be a set type location of oxygen vacancies. Observed load life test of
capacitance change with time concludes long time period change in capacitance is caused
by oxygen vacancies in the grains and the short time change is due to cation vacancies at
grain boundaries. Hence the solubility states of rare earth elements in the BiTiO 3 lattice
depending on their ionic radii are closely related to the oxygen vacancy concentration in
the samples and strongly influence the dielectric properties and reliability of Ni-MLCCs.

When BiTiO3 MgO Ho2O3 based system was investigated for formation behaviour of the
core-shell structure influenced by MgO and Ho2O3 it was found that MgO reacts with
BiTiO3 at low temperature to form a shell phase which reacts with Ho2O3 at high

3
temperatures but its diffusion into the core and grain growth was suppressed by MgO.
Large amount of MgO can suppress grain growth and form the core shell structure for the
larger ionic radius rare earth doped samples than for the intermediate ionic rare earth
doped samples. Therefore higher diffusivity into the core phase rare earth ions was
related to their ionic radii. Increasing MgO content decreased the aging rate in all the
samples but observed change is modest for intermediate ionic radius rare earth doped
samples than for larger ionic radius rare earth doped samples which was relatively high.
When investigated the influence of rare earth ionic radius doped samples and the
microstructure growth under increasing firing temperature using Dy2O3 and Ho2O3 doped
samples for which ionic radius for Dy is slightly higher than that of Ho, Dy2O3 showed
increasing average grain size and Ho2O3 showed no grain growth but showed higher
stability. Therefore ionic radius of the rare earth element strongly determines the grain
size and a change in microstructure alters the dielectric properties. The solubility state of
rare earth elements and MgO in the BiTiO3 lattice depends on ionic radius of the rare
earth elements. Larger ions (act as donor dopants) predominantly occupy the A-state and
the smaller ions (act as acceptor dopants) predominantly occupy B-site and the
intermediate ions (act as both donor and acceptor dopants) occupy both A and B sites.
Diffusion of the rare earth element into the core phase depends on its ionic radius, which
determines the stability of the core shell structure against variation in the rare earth
content and firing temperature depending on the tendency for B-site occupation of the
rare earth elements. Further investigation on nonreducible BiTiO3 based dielectrics
containing rare earth elements and acceptor components showed that the site occupancy
of the rare earth elements strongly influenced the donor/acceptor ratio and the valence of
the acceptor component, and significantly affected the re-oxidation behaviour and the
resultant dielectric properties of Ni MLCCs.

Influence of dielectric layer thickness on electrical properties of BME MLCCs

On decreasing dielectric layer thickness improves capacitance and increases the intensity
of the applied electric field significantly. Investigation was carried out using Y5V
dielectrics based on Ba (Ti, Zr) O3 to observe effect of AC electric field on Ni MLCCs

4
 having various thickness. Dielectric layer thickness determines the peak of k value and is
temperature dependant; decreasing layer thickness broadens the peak of k value and
shifted toward a lower temperature. The temperature dependence of the k at various
thickness of the dielectric layer can be elucidated by the intensity dependence of the AC
electric field. In reoxidation treatment of the two samples at different thickness suggested
that oxygen vacancy generated during firing in a reducing atmosphere increased as the
dielectric layer thickness decreased. When both temperature and dc electric field is
simultaneously applied to the dielectrics, insulation resistance degrades due to electro
migration of positively charged oxygen vacancies toward the cathode. Grain boundaries
are found to act as barriers against elecromigration of oxygen vacancies but are not
sufficiently large when the dielectric layer is thin having few grains. Oxygen vacancies
pileup near the cathode decreases the resistivity at the ceramic/electrode interface by
either the physical change of the crystal lattice or change in the interface thickness. This
results in insulation resistance degradation of Ni MLCCs which is strongly affected by
both state of the grain boundaries and state of the ceramic/electrode interface.
Microstructure determines the electrical properties of the dielectrics and therefore it is
necessary to analyse the compositional distribution, dopants conc., and the site occupancy
of the rare earth elements in the shell phase which all influence the microstructure in
dielectrics.

Conclusion

The effect of rare earth dopants on the electrical properties and microstructureBiTiO 3
MgO R2O3 based system are strongly dependant on the change of site occupancy of rare
earth oxides in the BiTiO3 lattice. Investigations revealed that large ions occupy A-sites,
small ions occupy B-sites and intermediate ions occupy both A and B sites. The site
occupancy of intermediate ionic size rare earths in BiTiO3 lattice is effective for
controlling the donor/acceptor dopant ratio and the microstructure, also affected the
changes in Tc and dielectric properties for Ni MLCCs by reoxidation treatment. The
temperature dependant k value on the layer thickness can be explained by magnitude of
AC electric field applied to the dielectrics.

Reference: H Kishi, Y Mizuno and H Chazono BME MLCCs: Past present and future perspectives Appl.
Phys J Jpn. 5