Metal Oxides Semiconductor Ceramics

Most of the ceramics oxides offer high resistance to charge transfer and are therefore more
beneficial as electric insulators while some electro-ceramics are very useful for the electronic
conduction. A wide material variety is a unique feature of oxide semiconductors. Semi-
conductive oxides are, however, restricted to transition metal or heavy metal cation-bearing
materials. Representative light metal oxides, e.g group silicon and group -! materials, can
either be p-type or n-type depending upon the access of number of holes or negative charges.
"hey often undergo electron transfer reactions, i.e., oxidation-reduction reactions with the
surrounding environment# these materials are highly useful as chemo-resistive gas sensors and
electronic conductor utili$ing nano-structures built-in crystal structure.
onic conduction is achieved by the movement of ions %atoms carrying either positive or negative
charge& through the solid. "his charge transfer is usually done via point defects called vacancies
in the crystal lattice. Such movement can require high energy, ma'ing ionic conduction very
strongly dependent on temperature. onic conductors are useful in gas sensors, fuel cells and
batteries. Materials that can accommodate electron conductivity as well as ionic conductivity are
'nown as mixed conductors and are particularly useful as solid oxide fuel cell %S()*&
electrodes.
Properties of Metal Oxides Materials
Metal oxides ceramics have traditionally been admired for their mechanical and thermal stability.
"heir unique electrical, optical and magnetic properties have become of increasing importance in
academic research as well as advanced technologies including communications, energy
conversion and storage, electronics and automation. Such materials are now classified under
electro ceramics as distinguished from other functional ceramics such as advanced structural
ceramics. +erovs'ite-phase metal oxides have a variety of interesting physical properties
including ferroelectric, dielectric, pyro-electric, and pie$oelectric etc.
,-
Electrical Conductivities
"he electrical properties of solid-state materials depend on their band structure. "he highest
filled electronic state at ./ is called the )ermi energy 0f. )igure -.1 demonstrates the four
different band structures of solids at ./.
(a) A conductor typical of many metals e.g., copper which has a partially filled outermost band.
0ach copper atom has one 2s electron to ma'e 2s band half filled. 0lectrons in this band are free
to move whenever an electric field is applied.
(b) A conductor e.g., magnesium in which filled and empty bands overlap each other. n case of
magnesium, there is an overlap between the 3s and 3p band.
(c) An insulator in which all the electrons are restricted within the valence band with the
conduction band empty completely. "he band gap, that is several electron volts, means it is
energetically unli'ely for an electron in the valence band to be promoted to the empty conduction
band.
(d) A semiconductor, where a small gap separates the completely filled valence band from an
empty conduction band, because of which electrons can gain sufficient energy to promote into
the empty conduction band.
"he various band structures in solids at ./ representing %a& and %b& conductors, %c&
semiconductors and %d& insulators.
,1,,3
Shows electrical conductivity values of conductors, semiconductors and insulators.
CONDUCTOS SEM!CONDUCTOS !NSU"#TOS
*opper, Silver, "ungsten
0lectrons free to move
Resistivity %(hm-cm&-.
-4
to -.
-,
Silicon dioxide, -! and -
!
0lectrons partially move
-.
-1
to -.
5
Rubber, Sulpher
0lectrons do not move
-.
-1
to -.
11
Most of the structural ceramics are electric insulators, while some electro-ceramics are very
useful for the electronic conduction. Semiconducting ceramics can be either p-type or n-type
depending upon the access of number of holes or negative charges. "hey mostly undergo redox
reactions with surroundings and they are highly useful as chemoresitive gas sensors.
Dielectric Materials
6ielectric materials are electrical insulators, used principally in capacitors and electrical
insulators. )or practical applications, they should be able to withstand high voltages without
undergoing degradation and becoming electrically conducting as well as possess low dielectric
loss i.e., in an alternating electric field, the electrical energy loss in the form of heat should be
minimi$ed. 7hen a potential difference is applied across a dielectric, polari$ation of charge
within the material will ta'e place, although long range motion of ions or electrons cannot occur.
"he polari$ation disappears as the voltage is removed. f a material is placed between two plates
of the capacitor, the total charge already stored in it will change which depends upon the
polari$ability of the material under an electric field. "he change in charge storage is determined
by the dielectric constant or permittivity of the material. 8igh dielectric constants are necessary
for high capacity applications.
$erroelectricit%
"hese are the special type of dielectrics materials which have extremely large permittivities and
retain some residual electrical polari$ation in the absence of an electric field. 7ith the increase in
applied potential difference across a dielectric substance, the induced polari$ation, + or stored
charge, 9, increases proportionally, represented by following equation.
9o : *o!
7here ! and *o are potential difference and capacitance, respectively. "he ferroelectrics do not
follow this simple linear relation between + and !, as shown.
8ysteresis loop of a ferroelectric. "he dashed line passing through the origin represents the
behavior of normal dielectric materials.
"he ferroelectric state is mostly a low temperature state because the effect of increasing thermal
motions at high temperatures is adequate to brea' down the common displacement in ad;acent
octahedra and destroy the domain structure. "he temperature at which brea'down occurs is the
ferroelectric *urie temperature, "c. Above "c, the material is para-electric %i.e. non-ferroelectric&.
Some common ferroelectric materials are listed in table -.1. )erroelectric materials are a sub-
class of pyro-electric materials in which the direction of the electric dipole can be reversed by
applying an electric field.
6ipole orientation in a ferroelectric ceramic material.
A basic condition for a crystal to have spontaneous polari$ation and be ferroelectric is that its
space group should be non-centrosymmetric. (n the other hand, mostly the symmetry of the
para-electric phase, stable above "c is centrosymmetric and the ordering transition that occurs on
cooling simply involves a lowering of symmetry to that of a non-centric space group.
)erroelectric ceramic oxide materials with curie temperature
Ceramic Oxide Material Tc(&C)
<arium titanate, <a"i(3 -1. -1.
<ismuth titanate, <i2"i3(-1 ,=4
>ithium niobate, >i?b(3 -1-.
>ead titanate, +b"i(3 25.
>ead @irconate titanate, +@", +b%@rx"i--x&(3 6epends on x
+otassium dihydrogen phosphate, /+6, /81+(2 --4.
+otassium niobate, /?b(3 232
Rochelle salt, /?a*282(,.281( <etween A-B and C12
#ntiferroelectricit%
Antiferroelectric *eramic Materials is a type of spontaneously polari$ed materials in which
individual dipoles occurs but these are generally arrange themselves in anti-parallel to ad;acent
dipoles, is 'nown as antiferroelectric material. *onsequently, the net spontaneous polari$ation
becomes $ero. A dipole orientation in an antiferroelectric ceramic material is given in figure -.4.
Above the antiferroelectric *urie temperature, the materials revert to normal paraelectric
behavior. "he examples of antiferroelectric, with their *urie temperatures are given in table -.3.
6ipole orientation in an antiferroelectric material.
Antiferroelectric ceramic material with curie temperature.
#ntiferroelectric
Curie temperatures
(TC)
$irconate, +b@r(
3
sodium niobate, ?a?b(
3
ammonium dihydrogen phosphate %?8
2
8
1
+(
2
&
133 D*
,3BD*
E-14 D*
$errielectricit%
A type of polari$ation phenomenon in which the structure is antiferroelectric in certain
direction%s& only %in the x direction&. n this direction, the net polari$ation is $ero and structure is
called antiferroelectric. <ut in other direction %$ direction&, a net spontaneous polari$ation
occurs. "his type of structure is 'nown as ferrielectric. 6ipole orientation in a ferrielectric
ceramic material is given in figure -.,. )or example, <i
2
"i
3
(
-1
and lithium ammonium tartrate
monohydrate etc.
$i'ure ()*+ 6ipole orientation in a ferrielectric material
Pie,oelectricit%
+ie$oelectric crystals polari$e and develop electrical charges on opposite crystal faces when
applying mechanical stress is applied. Fust li'e +yroelectric and ferroelectric materials. "he
crystal must belong to one of the non-centrosymmetric point groups. "he occurrence of
pie$oelectricity depends on the crystal structure of the material as well as the direction of applied
stress, e.g. quart$ develops a polari$ation when sub;ected to a compressive stress along G-..H but
not when stressed along G..-H. "he polari$ation, + and stress I are related to the pie$oelectric
coefficient, d, is given as,
+ : d I
8owever, when an external stress is applied, the charges are displaced and the charge distribution
is no longer symmetric and a net polari$ation is created. A material can only be pie$oelectric if
the crystallographic unit cell has no center of inversion. 7ell-'nown materials used in practical
applications are lead $irconate titanate %+@"&, quart$, Rochelle salt or >i
1
S.
2
.8
1
..
8istorical application of pie$oelectric materials is in transducer for converting mechanical
energy to electrical energy. As time passes, many diverse applications come in every field of
electronics. Such as laud spea'ers, stereo pic'-ups, bimorphs in microphone, and earphones, as
fuses, cigarette lighters, solenoid ignition systems, sonar generators and ultrasound cleaners etc.
More complicated systems with better performance are used in transformers, filters and
oscillators. Many crystals containing tetrahedral groups are pie$oelectric, e.g., @n( and @nS. "he
most important pie$oelectric is lead $irconate titanate, +@", which is a series of solid solutions
between +b@r(
3
and +b"i(
3
.

d-based pie$oelectric ceramics such as +@" and +M?-+" are often
used as the compositions of other pie$oelectric materials. "he lead-based ceramics caused
serious lead pollution in environment and instability of the compositions because of the high
toxicity of lead oxide and its high volatility during sintering. 6ue to their inherent defects, lead-
based ceramics are not suitable for use in applications that require good mechanical and
electrical reliability. "herefore, it is necessary to produce lead-free pie$oelectric ceramics with
desired properties.
P%roelectricit%
+yroelectric crystals possess a unique polar axis even in the unstrained condition. "hey are non-
centrosymmetric and have a net spontaneous polari$ation, +s. "his is called the +yroelectric
effect. 8owever, the direction of +s cannot be reversed by an applied electric field. +s is usually
temperature dependent.
J +s : K J "
7here K is the pyroelectric coefficient. "his is mainly because the thermal expansion that occurs
on heating changes the si$e of %length& dipoles. "he best example is the wurt$ite crystal of @n(.
Since high dielectric constant ferroelectric materials are not suitable for applications in detectors.
+yroelectric crystals have wide applications in R detectors. "hey can be made spectrally
sensitive by coating the crystal surface by appropriate absorbing material.
Several systems of lead-free materials, such as potassium sodium niobate %/??&-based and
strontium barium niobate %S<?&-based have been reported for pyroelectric applications. Among
them S<? crystals and textured ceramics have been reported to have excellent pyroelectric
propertied comparable to +@" ceramics.
Ma'netism and Ma'netic Materials
7hen a magnetic field is applied to the material, lines of force penetrate the material. "he no. of
lines per unit area passing through the material is called magnetic flux density, <. "he magnetic
field, 8, applied on free space and magnetic flux density, <, are related by the permeability of
free space, L
o
by the relationM
< : L
o
8
f a magnetic material is placed in field, flux density reduces for diamagnetic materials while
increases for paramagnetic materials.
"he field strength observed by the sample is called magnetisation M. n S units it is expressed in
A m
--
.
< : L
o
%8 CM&
"here is L
o
8, which is the externally imposed field and the component -
o
M originating as a
result of something that has happened within the material.
"he ratio of the magneti$ation M %Nthe resultO& to 8 %Nthe causeO&, which is obviously a measure
of how susceptible the material is to becoming magneti$ed, is called the magnetic susceptibility,
P
m
of the materialM
M : P
m
8
"herefore magnetic susceptibility %which is dimensionless& is related to the relative permeability,
L
r
: LQL
o
by
L
r
: -C P
m
Diama'netic Materials
6iamagnetic materials have a very wea' negative susceptibility typically of the order of --.
-4
and
the relative permeability is slightly less than one. Some materials may also be paramagnetic or
ferromagnetic and their positive paramagnetic or ferromagnetic susceptibilities may be larger
than their negative diamagnetic susceptibility. So that their overall susceptibility is positive. "he
explanation of causes of diamagnetic mechanism at the atomic level requires a quantum
mechanical treatment, but we can understand the phenomenon qualitatively classically.
>etRs consider an atomic nucleus surrounded by electrons moving in orbits around the nucleus.
7hen an atom %or a large collection of atoms in a macroscopic sample of matter& is placed in a
magnetic field, a current is induced within the atom by electromagnetic induction. "hat is, the
individual magnetic moments no longer cancel completely and the molecule then acquires an
induced magnetic moment, in such a direction as to oppose the increase in external magnetic
field that causes it. Such type of materials is called diamagnetic. <ecause of this happening to all
of the atoms in a macroscopic sample is that < within the diamagnetic material will now be less
than that in vacuum and the susceptibility will be negative. n fact, it persists as long as the
magneti$ing field persists. "his type of magnetism is of no practical importance. <arium titanate
%<a"i(
3
& is the most common ferroelectric oxide with the perovs'ite A<(
3
structure is used as a
capacitor because of its high dielectric constant.
Parama'netic Materials
"he atoms or molecules may have a permanent dipole moment by virtue of incomplete
cancellation of electron spin andQor orbital magnetic moments and such materials are
paramagnetic. "he magnetic moment of an atom of a molecule is typically of the order of a <ohr
magneton %a <ohr magneton is about 5.3 S -.
-12
? m "T-&. "he presence of a permanent
magnetic moment is often the result of unpaired electron spins. "he liquid oxygen indeed is
paramagnetic. 7hen a paramagnetic material is placed in a magnetic field, the magnetic
moments experience a torque and they tend to orient themselves in the direction of the magnetic
field, thus augmenting, rather than diminishing <. Unsurprisingly, the effect is greatest at low
temperatures, where the random motion of atoms and molecules is low. At liquid helium
temperatures %of order - /&, susceptibilities can be of order -F--.V3 or C-.V1, thus greatly
exceeding the small negative susceptibility. "he magnetic susceptibility graph for a paramagnetic
material is shown in )igure -.= in which W decrease with rise in temperature because rise in
temperature causes disturbance in order in which electrons are oriented.

$i'ure ().+ "emperature dependence of magnetic susceptibility.
$erroma'netic Materials
n ferromagnetic materials the alignment of all the electrons is parallel with the external
magnetic field. "his leads to the magnetic susceptibility as shown in graph in )igure -.B. A sharp
rise occurs in the magneti$ation when the electrons align with the field. "he temperature at
which sharp rise occurs is called the *urie temperature %TC&. )ace centred cubic nic'el nano
si$es have a ferromagnetic spin structure. "he magnetic properties of the material changes with
change in particle si$e. "he magnetic susceptibility is temperature dependent. t could be
reasonably considered as a result of increase in thermal energy.
Magnetic susceptibility curve for a ferromagnetic material.
=4
Optical Properties
Metal oxides exhibit optical properties and their studies have directly revealed the ground state
electronic structures as well as several excitations of charge, spin, orbital, and lattice degrees of
freedom. n recent years, the progress of the experimental techniques developed the optical
experiments as direct probes for the electronic structure in metal oxides, e.g., the angular
resolved photoemission spectroscopy, the P-ray diffraction and absorption spectroscopy by
utili$ing the high brilliant synchrotron P-ray and so on. "he optical properties of oxides have
broaden their area of technological applications such as the optical and optoelectric devices by
utili$ing the large nonlinear optical responses, magneto-optical effect, photo-refractive effect,
elasto-optic effect and so on. >ong time ago, a wide variety of well 'nown applications of
several metal oxides have been explored, e.g., the famous ruby %*rM Al
1
(
3
& and ?d M X
3
Al
4
(
-1
&
lasers, the well developed nonlinear optical crystals >i?b(
3
and <a
1
?a?b
4
(
-4
and the
photocatalytic materials "i(
1
. "he optical and dielectric properties in conventional dielectric and
ferroelectric metal oxides have been reviewed in several boo's and articles. Some prominent
optical properties exhibited by metal oxides are optical conductivity and Raman scattering.
#ntiferroma'netic Material
t involves materials in which the magnetic spins on the neighboring atoms align antiparallel, the
material is 'nown as antiferromagnetic in which there is an overall drop in the magneti$ation. A
sudden drop in magnetic susceptibility occurs at a particular temperature, called the ?eel
temperature %TN&, shown in )igure -.5.
Magnetic susceptibility curve for an antiferromagnetic material.
$errima'netic Material
Spinels such as *o)e
1
(
2
have two magnetic ions on two different sites, one octahedral and one
tetrahedral in the ratio 1M-. "he structure of a spinel and the magnetic moments of its electrons
are shown in figure -.-.. 7hen the materials li'e these order antiferro magnetically, there is an
overall positive magnetic moment because there are more unpaired electrons on one site than the
other. Such materials are called the )errimagnetic materials.
Structure of a spinel and ordering of its magnetic moments. >arger arrows represent more
electrons than do smaller ones, giving an overall moment despite the antiferromagnetic ordering.