_______________________________________________9

PTC MATERIALS

9.1 MECHANISM OF PTC PHENOMENON

(1) PTC Phenomenon

When barium titanate (BaTiO3) is doped with lanthanum at levels less than 0.3
atm%, the ceramic becomes semiconducting with a resistivity in the range of 10 -
103 Ω .cm. Moreover, the resistivity is drastically increased, by 3 - 5 orders of
magnitude, with increasing temperature around the Curie point. This phenomenon
was discovered in 1954, and is referred to as the PTC or PTCR (positive
temperature coefficient of resistivity) effect. Since then it has been investigated
intensively by many researchers.1,2) Figure 9.1 shows the impact of various
dopants on the resistivity of the BaTiO 3 PTC ceramic as a function of temperature.

Fig. 9.1 Resistivity as a function of temperature for several doped BaTiO 3 PTCR
ceramics. Dopant concentrations are indicated near each curve.

243
244 Chapter 9

Fig. 9.2 Resistivity vs. temperature curves for BaTiO3 PTCR thermistors
containing isovalent substitution of Sr or Pb for Ba.

The PTC dopants typically have a higher ionic valence than either the Ba (replaced
by ions such as La, Sm, Ce or Gd) or the Ti (replaced by ions such as Nb, Ta, Bi) of
the host structure. Since the temperature at which the resistivity anomaly occurs is
closely related with the Curie point, the temperature coefficient can be easily
modified by forming an appropriate solid solution with BaTiO3. Figure 9.2 shows
various PTCR curves for two such solid solution series. The solid line represents
BaTiO 3 and the dashed lines show the effect of Sr (resistivity curve shifted to left)
and Pb (resistivity curve shifted to right) substitution in the proportions indicated.

(2) Mechanism of the PTC Phenomenon

The theory for the PTC effect has not been established completely. Let us consider
the effect in terms of two mechanisms: the semiconducting properties of the doped
barium titanate and the grain boundary barrier effect.

When sintered at high temperature, lanthanum-doped BaTiO 3 is expected to

become an n-type semiconductor through the following reaction:3)

Ba1-xLa xTiO3 ---> Ba 2+ 1-x La 3+ xTi4+ 1-xTi3+ xO 2- 3.

PTC Materials 245

The conduction takes place via transfer of electrons between titanium ions
according to

Ti4+ + e - ↔ Ti3+

Thus, the BaTiO 3 grains in the ceramic are semiconducting and remain
semiconducting even on cooling down to room temperature.

However, the grain boundary region changes during cooling. Oxygen is absorbed
on the surface of the ceramic and diffuses to grain boundary sites, altering the defect
structure along the grain boundaries. The added oxygen ions attract electrons from
nearby Ti3+ ions, thereby creating an insulating barrier between grains. If excess
oxygen ions are added per formula unit, the composition of the grain boundary
region can be described as follows:

(Ba 2+ 1-xLa 3+ x)(Ti4+ 1-x+2y Ti3+ x-2y )O 2- 3+y .

This situation is illustrated in Fig. 9.3.

Fig. 9.3 Schematic illustration of the Ba 1-xLa xTiO 3 structure near the surface of a
grain boundary. Atmospheric oxygen dissociates and diffuses along a grain
boundary where the atoms attract electrons and form insulating layers.3)
246 Chapter 9

-eφ
+ + Conduction band
- - - + + - - -
+ +
L
Fermi level
Ns
Grain boundary

Fig. 9.4 Energy-level diagram near a grain boundary of the PTCR BaTiO 3.

In order to explain the PTC or PTCR phenomenon, the most acceptable model is
illustrated in Fig. 9.4, which was initially proposed by Heywang at al.1) When the
two semiconductive (n-type) ceramic particles are in contact at a grain boundary,
an electron energy barrier (Schottky barrier) is generated and the barrier height is
given by the following equation:

φ = eNs 2/2ε0 εNd , (9.1)

where Nd is the concentration of donor atoms and Ns is the surface density of

negatively charged acceptors (here assumed to be confined to the surface due to Ba
vacancies). Note that the permittivity ε obeys the Curie-Weiss law

ε = C / (T – T0 ) , (9.2)

above TC, and that the low resistance at TC is thus accounted for by the lowering of
the potential barrier due to the increase in permittivity as the temperature falls to
TC. Below TC the permittivity falls, but the spontaneous polarization appears and
controls the electron concentration to reduce the barrier height. This keeps the
resistivity in a rather low range.

Example Problem 9.1_________________________________________________

Electronic properties in ceramics are strongly affected by the surface layer or by the
grain boundary. Suppose that a grain boundary between n-type semiconductive
grains possesses acceptor impurities, and that electrons flow into the acceptor levels
and an energy barrier is generated as shown in Fig. 9.4. Using the simple charge
distribution model represented in Fig. 9.5:

ρ(x) = eND (0 < |x| < L) ; ρ(x) = 0 (|x| > L) , (P9.1.1)

answer the following questions:

PTC Materials 247

Charge density ρ(x) eNd

+ + + + + +

+ + + + + +
-L - L x
-
-
- Ns
-

Fig. 9.5 Charge density distribution near the grain boundary between n-type
semiconductive grains.

(a) Describe the potential φ(x) by using the donor density ND, the barrier thickness
L, the permittivity ε0 ε and electronic charge e. Suppose that the change in φ
occurs within a region 0 < |x| < L.

(b) Describe the barrier thickness L generated by the donor density ND and the
surface acceptor density Ns .

(c) In semiconductive BaTiO3, the permittivity is decreased significantly above the

Curie temperature (= 130o C). Explain the resistivity change by considering the
barrier height - e φ0 .

Solution

(a) Poisson's equation is given by

∂2 φ/ ∂x2 = - eN D/ ε0ε . (0 < |x| < L) (P9.1.2)

Taking into account the boundary conditions:

φ(L) = φ(- L) = φ(∞) , - φ'(L) = E = 0 (P9.1.3)

with a general solution φ(x) = - (eND/ 2ε0ε) x2 + A x + B, we obtain the particular

solution:

φ(x) = φ(∞) - (eND/ 2ε0 ε) (|x| - L)2 . (P9.1.4)

The potential depth at x = 0 is thus obtained as

φ0 = - (eND/ 2ε0 ε) L2 . (P9.1.5)

248 Chapter 9

(b) Considering charge neutralization, we obtain

2 eND L = eNs . (P9.1.6)

Then,
L = Ns / 2ND . (P9.1.7)

(c) The energy barrier height - e φ0 is represented as

- e φ0 = e2 N D L2/ 2ε0 ε
= e2 Ns 2/ 8ε0 ε N D . (P9.1.8)

Considering the Curie-Wess law;

ε = C/ (T - T 0), (P9.1.9)

we obtain

- e φ0 = (e 2 Ns 2/ 8ε0 C ND )(T - T0 ). (P9.1.10)

The barrier height increases in proportion to temperature. Since the resistivity is

proportional to exp(- e φ0 / kT), it increases drastically with temperature (∝ exp(1 -
T0 / T)) for T > T C.

When we consider the situation below TC, the permittivity falls, but the
spontaneous polarization appears and controls the electron concentration to reduce
the barrier height. This keeps the res istivity in a rather low range. For a
temperature region much higher than TC, the resistivity falls because of the very
high thermal energy (kT) of electrons which tunnel through the energy barrier.
___________________________________________________________________

9.2 PTC THERMISTORS

PTC thermistors are applicable not only for temperature-change detection but also
for active current controllers. The thermistor, when self-heated, exhibits a decrease
in the current owing to a large increase in resistivity. Practical applications for
these devices are found in over-current/voltage protectors, starting switches for
motors, and automatic demagnetization circuits for color TVs.4)

"Ceramic heaters" have also been widely commercialized in panel heaters,

electronic thermos bottles and hair dryers. Figure 9.6 shows a PTC honeycomb air
heater for hair dryers and automotive chokes manufactured by NGK.
PTC Materials 249

Fig. 9.6 PTC honeycomb air heater for a hair dryer (photo courtesy of NGK).

Example Problem 9.2_________________________________________________

The resistivity vs. temperature characteristic of a barium titanate PTC ceramic is

shown in Fig. 9.7. Taking into account heat generation through Joule heating,
discuss the current vs. voltage relationship under a room-temperature ambient
condition qualitatively.

Fig. 9.7 Resistivity vs. temperature characteristic of a barium titanate PTC

ceramic.
250 Chapter 9

Fig. 9.8 Current vs. voltage relationship for a barium titanate PTC ceramic.

Solution

At the initial stage, the current-voltage relation obeys Ohm's law (that is, ρ is almost
constant), and power is dissipated via the Joule heating (V2/R). Around the point A
(where a dramatic ni crease in ρ is observed), the current becomes maximized,
beyond which it decreases with increasing applied voltage (see Fig. 9.8). Between
the points B and C, the temperature of the device is almost stabilized, leading to the
relation V x I = constant. Much above the point C, a dramatic increase in current is
anticipated, because the saturation of the resistivity and the subsequent NTC
(negative temperature coefficient) effect occur in this temperature range. Thus, to
realize a stable temperature in the PTC thermistor, the applied voltage must be
adjusted between B and C.
___________________________________________________________________

9.3 GRAIN BOUNDARY LAYER CAPACITORS

When a semiconductive BaTiO3 ceramic is oxidized to make a resistive surface
layer, it can be used as a high capacitance condenser. The capacitance is adjustable
in the range of 0.4 - 0.5 µF/cm2 . A new type of grain boundary layer (GBL)
capacitor has been developed using electrically resistive grain boundaries. The
model for this structure is illustrated in Fig. 9.9. In practice, CeO2 or Bi2 O3 is
coated on a semiconductive ceramic and diffused into the grain boundaries by
thermal treatment so as to make the boundary layer highly resistive. The resistive
grain boundary layers of 1 µm thickness are fully connected in the ceramic with
grain size of 10 µm. This type of capacitor exhibits excellent frequency
characteristics and can be used as a wide bandpass capacitor up to several GHz.
PTC Materials 251

Fig. 9.9 Model of the grain boundary layer capacitor.

Example Problem 9.3_________________________________________________

When a GBL capacitor is composed of many cubic core -shell units of a grain size D
with a resistive skin of dielectric constant εs (δ: skin thickness, half of the grain
boundary thickness), calculate the apparent dielectric constant εapp of this
composite material. Assume the sample has an electrode area S and an electrode
gap d, and zero resistivity inside the grains.

Solution

As shown in Fig. 9.10, let us divide the sample into two regions: C 1 and C2.

(a) C1:
Since the area and the thickness are provided by [S - (D - 2δ) 2 (S/D2)] and d,
respectively,

C1 = ε0 εs (S/d) [1 - (1 - 2δ/D) 2]
= ε0 εs (S/d) (4δ/D) . (δ /D << 1) (P9.3.1)

(b) C2 :
Since this is a series connection (number d/D) of a capacitor with an area (D -
2δ)2 (S/D2 ) and thickness 2δ,

C2 = (D/d) ε0εs [S(1 - 2δ/D) 2]/2δ

= ε0 εs (S/d) (D /2δ) . (δ /D << 1) (P9.3.2)
252 Chapter 9

Area S

d
D

C1 C2
(Conductor included) (εs )

Fig. 9.10 Core-shell model of a GBL capacitor.

Ctotal = C1 + C 2
= ε0 εs (S/d) (D /2δ) . (P9.3.3)

Thus the apparent dielectric constant is provided by εs (D /2δ).

___________________________________________________________________

CHAPTER ESSENTIALS_________________________________
1. When barium titanate (BaTiO3 ) is doped with lanthanum at levels less than 0.3
atm%, the ceramic becomes semiconducting with a resistivity in the range of 10
- 10 3 Ω .cm.

2. PTC effect: the resistivity is drastically increased, by 3 - 5 orders of magnitude,

with increasing temperature around the Curie point.

3. Applications of PTC ceramics:

(1) thermistors: over-current/voltage protectors, starting switches for motors,

automatic demagnetization circuits for color TVs
(2) "Ceramic heaters": panel heaters, electronic thermos bottles, hair dryers,
automotive chokes

4. GBL capacitors: capacitors made of semiconductive BaTiO3 ceramics with

highly resistive grain boundaries.
___________________________________________________________________
PTC Materials 253

CHAPTER PROBLEMS

9.1 Explain the current vs. voltage relationship for ZnO varistors, and describe
their applications in comparison with the PTC material.

9.2 Electric properties in ceramics are strongly dependent on the characteristics

of surfaces and/or grain boundaries. Let us consider here an n-type
semiconductor. When acceptor dopants are localized on a semiconductor
surface, and their surface levels exist lower than the Fermi level of the
semiconductor, the electrons in the semiconductor flow into the acceptor
levels, making a potential barrier. The barrier height Vd (potential) can be
expressed as

Vd = eND L2/ 2ε0 ε,

using the ionized donor density ND in the semiconductor, barrier thickness

L, semiconductor permittivity ε0ε, and the electron unit charge e. Since
the electron density is very small in this barrier, and the electron needs to
be highly excited to overcome this barrier height, the crystal surface can be
considered to be highly resistive. Answer the following questions:

(a) The density of the surface acceptor levels NS is related with the donor
density ND as

2eND L = eNS .

Derive an expression of Vd in terms of ND and NS .

(b) On the surface of an n-type semiconductor such as SnO2 and ZnO,

negative oxygen charges (O- or O 2- ) are adsorbed, generating a
potential barrier. When this surface is contacted with flammable gas,
the amount of the adsorbed oxygen is decreased through oxidation
reaction, leading to an decrease in electrical resistance. This
phenomenon is an operating principle of a gas sensor. Supposing that
the adsorbed oxygen is decreased by half due to a flammable gas,
calculate the change in the potential barrier height. Also discuss the
change in resistance due to the flammable gas with the donor density
of the semiconductor, in consideration of the change in the electron
density.

(c) The energy band structure at the grain boundary can be considered in a
similar fashion to the above; that is, an interface with surface levels
caused by impurities. In a semiconductive barium titanate ceramic,
254 Chapter 9

the permittivity is decreased dramatically above the Curie temperature

(around 120o C). Discuss the resistance change (i.e., PTCR effect)
with temperature.

REFERENCES
1) W. Heywang: J. Amer. Ceram. Soc. 47, 484 (1964).
2) E. Andrich: Electr. Appl. 26, 123 (1965-66).
3) R. E. Newnham: "Structure-Property Relations in Electronic Ceramics," J.
Materials Education, Vol.6-5.
4) Murata Mfg. Comp. Catalog, "Misterious Stones."