Nonlinear Resistors

Nonlinear Resistors Introduction (1)
type varistor physical effect grain boundary phenomena in semiconducting ceramicsy grain boundary phenomena in semiconducting ferroelectric ceramics self heating effects hopping condution in metal oxides self heating effects material n-doped ZnO n-doped BaTiO3 102...103 S/m spinells e.g. (Ni,Mn)3O4 10-2 S/m
PTC
NTC
glossary Thermistor: NTC: PTC: Varistor: thermally sensitive resistor negative temperature coefficient positive temperature coefficient variable resistor
[Schaumburg 1990]
Materials and Devices in Electrical Engineering
Institut fr Werkstoffe der Elektrotechnik
Nonlinear Resistors.ppt, slide: 1, 11.02.2006
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Nonlinear Resistors Introduction (2)
NTC
PTC
Varistor
PTC-heater with metalized surface
arrangement of PTCs and radiators
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Varistor Variable Resistor (Voltage dependent Resistor)
symbol varistor
U
[www.staratech.com]
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Varistor Nonlinear I/V-Characteristic
I IK UK UK U
varistor: variable resistor voltage dependent resistor with symmetrical I/V-chracteristic
IK
I = K U
geometry parameter K
nonlinearity coefficient
materials: SiC, ZnO typical -values: SiC: 5...7 ZnO: 30...70
[Heywang 1984]
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Varistor Equivalent Circuit

microstructure path I path II path I equivalent circuit path II
equivalent circuity grain
RD CD
RP CP 2 RK
secondary phase
grain boundary
CD 240 nF/cm K 1 cm P 80 kcm CP 90 nF/cm

[Ein 1982]
RD CD varistor
RP CP leakage current
leakage current RP, CP in parallel
grain- (RK) and grain boundary (varistor) (RD) resistance RD and CD in parallel RD and CD are voltage dependent
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Varistor Defects and Band-Structure in ZnO-Varistoren

point defects in ZnO (2-dimensional view) VZn EA2 = 2,8 eV EA1 = 0,7 eV electroneutrality n + [VZn] + 2[VZn] = p + [VO] + 2[VO] VO, VO: VZn, VZn: e, (n): h, (p): O-vacancies Zn-vacancies electron (-concentration) hole (-concentration) (ED1, ED2) (EA1, EA2) y D: donor A: acceptor band structure with energy levels of schottky-defects (EA, ED) EC ED1 = 0,05 eV ED2 = 2,0 eV EV
e VO
Eg = 3,2 eV

[Heywang 1984 ]
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Varistor Grain Boundary Properties

processing (sintering temperature 1300 C) high temperature equilibrium: oxygen vacancy excess charge carrier: n = [VO] + 2[VO] operation (operating temperature < 100 C) low temperature equilibrium: [ VZn ] + 2[ VZn ] [ VO ] + 2[ VO ] n << low temperature equilibrium only at the grain boundaries
ZnO-grain
controlled cooling process (+ additional doping of grain boundaries) x
ZnO-grain frozen high temperature equilibrium n - type x

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Varistor Band Structure of the Grain Boundary in a ZnO-Varistor (1)
charge carrier concentration at grain boundaries
band structure (no voltage applied)
microvaristor pair of grains grain boundary single barrier layer n charge carrier p concentrations acceptors 100 nm EC EF EV
[Heywang 1984 ]
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Varistor Band Structure of the Grain Boundary in a ZnO-Varistor (2)

no voltage applied voltage applied
EC
EC
thermal activation
> 3 eV acceptors
EF EV
EF EV tunneling effect
100 nm
[Fasching 1994]
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Varistor Summary
varistor effect in doped ZnO-ceramic is related to grain boundary properties, ZnO-grains exhibit a high conductivity varistor effect only at grains exhibiting a direct contact varistor effect starts at a voltage of ~ 3,0 0,5 V / grain boundary grain boundary forms a potential barrier of 0,6 eV. time constants of several nanoseconds technical varistor systems: ZnO + Bi2O3 + MnO2 + Co3O4 + Sb2O3 + Cr2O3 + additional additives (up to 10 components to optimize secondary properties)
[Ein 1982 ]
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Varistor Application: Overvoltage Protection

US = 9,8 KV UB = 200 V Ri = 10 voltage U / V I 104 100 % with SiC-varistor 103 25 % with ZnO-varistor 3% operating voltage 102 consumer the voltage peak US(t) increases the voltage U for a short time U(t) = US(t) + UB - Ri I(t)
[Heywang 1984 ]
without varistor
varistor U
10-1 101 103 current / A
logarithmic graph of U(I) at operating voltage at overvoltage US = 9,8 KV

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Varistor
ZnO-varistors
varistors for high voltage applications

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PTC Positive Temperature Coefficient Resistor
symbol PTC
[www.atpsensor.com]
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PTC Temperature Dependency of a Resistor

Rmin, Rmax minimum and maximum resistance, change of sign of the temperature coefficient Rmax/Rmin effective resistance increase max. 107 TB nominal temperature of the device at which RB = 2 Rmin TB values: -30...+250 C
Rmax 106 resistance R /
104 PTC-behavior resistance increases several orders of magnitude 100 TB 200 temperature / C 300
102 RB 100 0 Rmin
TKR: temperature coefficient of resistance
TKR =
1 dR , TKR values of 5...70% K-1 R dT


[Heywang 1984]
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PTC Defect Chemistry of Barium-Titanate (BaTiO3)
system BaTiO3 La-doping on the Ba-site oxygen ion O2 LaBa
barium vacancies
BaBa + 2e / + 1 O2 ( g ) 2
// VBa + BaO
oxygen vacancies
x OO
VO + 2e / +
barium ion Ba2+ // VBa VO
1 O2 ( g ) 2
electroneutrality
// [e] + 2 VBa 2 VO + LaBa
acceptors
donors
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PTC Electrical Properties of Grain Boundaries in Barium-Titanate

BaTiO3 insulating grain boundary area acceptor concentration barium vacancy concentration and profile is determined by the temperature profile during cooling down fast cooling down thinner insulating grain boundary area
donor concentration
grain
slow cooling down fast cooling down
[LaBa] 2[VBa]
n charge carrier concentration
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PTC Charge Carrier Transport at Grain Boundaries

grain boundary (KG) p-type doping AKG grain n-type doping grain n-type doping hight of the schottky-barrier WB at the grain boundary EB = e0 [ Agb ]2 8n 0 r [Agb]: surface charge at the grain boundary n conductivity (tunneling current)
reduced charge carrier (electrons) concentration EB EC EV
+ + - + + + + - + + + E -
~ exp
x
EB k T
grain boundary resistance

E Rgb ~ exp B k T
x
Materials and Devices in Electrical Engineering Institut fr Werkstoffe der Elektrotechnik
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PTC Phase Transition in the PTC Temperature Range

temperature dependency of the grain boundary resistance does not explain the observed temperature dependence.
E Rgb ~ exp B k T
phase transition in the PTC temperature range
resistance R /
NTC 106 104 102 100 0
PTC
NTC
100 200 temperature / C
300
[Siemens]
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PTC Compensation of the GB Potential Barrier due to spontaneous Polarization

T < TC
grain boundary
Ps + + + + + + + + Ps -
T > TC
grain boundary
-
EB
EB
negative grain boundary charge compensated by polarisation charge EB <<
TC 150
negative grain boundary charge compensated by space charge EB >>
50
250
T / C
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PTC Equivalent Circuit
equivalent circuit
summary
grain boundary
Ps + + + + + + + + Ps -
PTCs consist of polycrystalline ferroelectric compounds, mostly metal-oxides like BaTiO3. The PTC-effect is based on the insulating grain boundary (schottkybarrier) and their interaction with the temperature dependent ferroelectric porperties. The negative grain boundary charge is compensated either by a space charge (paraelectric region high resistivity) or by a polarisation charge (ferroelectric region low resistivity).
Rgrain
Rgb
Rgrain
Cgrain
Cgb
Cgrain
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PTC Application
sensors
controller
heater
heat from the environment
self heating effect
heat supply
electrical thermometer overtemperature protection
current stabilization switch time delay level monitoring current measurement
heating elements self controlled

[Schau 94 / 203]
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PTC Devices
all purpose PTC
overload protection
PTC for monitor demagnetization
heating elements temperature sensor
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PTC Nonlinear I/V-Characteristic due to Self Heating Effect
[Zinke]
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PTC Self Controlled Heating Elements for Automotive Application
PTC heating element with metallized surface
Arrangement of PTC heating elements and metallic radiators

PTC-characteristic
[Catem]
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PTC PTC for Flow Measurements

A (T Tu )
U PTC
I=
I IPTC
~ v
[Trnkler]
Pel = U I
Pth = A (T Tu )
v = flow speed A = PTC surface area Pel = electrical power U = voltage I = current Pth = thermal power = heat transfer coefficient T = temperature of PTC Tu = ambient temperature
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Hopping Conductivity Energy Band Structure in Solids
single atom vacuum potential

3p 3s 2p 2s
solid state
3p
energy band with free electrons (metal) small interaction
3s 2p 2s
orbitals: discrete energy levels a
a0
a0 discrete energy levels
a >> a0
a0 lattice parameter
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Hopping Conductivity Transport Mechanisms

place
hopping conductivity
Even if the thermal energy of the charge carriers is not sufficient for the transport in the conduction band, some materials show an electric conductivity. The transport mechanism is called hopping conductivity because the charge carriers jump from one trap to another. The conductivity depends on the concentration and energetic level of the traps.
transport in the conduction band
hopping condcutivity
[Heywang 1984]
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Hopping Conductivity Valence Exchange

Materials: Bond type: metal oxide e.g. Mn, Fe, Co, Ni, Cu, Zn (transition metals) predominantly or partially heteropolar (ionic) bond (metal: cation, oxygen: anion)
Semiconducting properties can result from valence exchange of the cations in the oxide. Charge transport through hopping-mechanism (valence exchange) elements valence states +3 +4 Ti V +2 +3 +4 +5 crystal lattice: typical compounds: A2+ B3+2 O2-4 Ni2+ Mn3+2 O2-4 (spinel) Mn2+ Cr +2 +3 +4 Mn +2 +3 +4 Fe +2 +3 +4 valence exchange hopping conduction Mn3+ Mn2+ Mn3+ Co +2 +3 Ni +2 +3 Cu +2 Zn +2
thermal activated
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Hopping Conductivity Transport of Electrons by Valence Exchange

hopping of electrons in Fe2O3
potential energy W
gradient d(eU)/dx
potential energy W
gradient d(eU)/dx
EA
Fe2+ Fe3+
Fe3+ Fe3+
EA
Fe3+ Fe3+
Fe3+ Fe2+
place x
place x
For the hopping transport, an activation energy EA is required. For a valency exchange the thermal energy of the electron has to exceed the activation energy.
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Hopping Conductivity Polarons
In case of a light orbital overlapping the electrons interact with the phonons. The electrons polarize their surrounding, which results in a lattice distortion. The electron and the surrounding distortion field are called polaron. For an electron transport this state must be broken by thermal energy supplied to the electron.
[Maier 2000]
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Hopping Conductivity Mobility of Charge Carriers

diffusion coefficient of polarons
E D = (1 c ) a 0 exp A kT
2
mobility
q (1 c ) a2 0 kT E exp A kT
EA : 1-c : a: 0 :
activation energy amount of non occupied sites jump distance Debye-frequency
q: T:
charge absolut temperature
in case of a constant concentration of point defects:
Einstein-relation:
q D k T
(T ) = ze0 n (T )
1 E exp A T kT
[Heywang 1984]
= q
(1
c T
E k
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Hopping Conductivity Conduction Mechanisms
conduction
mechanism
mobility [cm2/Vs]
EA [eV]
band
interaction with phonons and defects
D ~ T-3/2
102 .. 104
e.g. metals, semiconductors
large polaron
D ~ T-1/2
EA kT
100 .. 102
0,1
e.g. BaTiO3, SrTiO3, InSb e.g. NaCl, Fe2O3, ZnO2
hopping
small polaron*
D ~ f (T ) e
10-4 .. 10-2
0,5
* also in some insulators and ionic conductors

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NTC Negative Temperature Coefficient Resistor
symbol NTC
[www.shibako.co.kr]
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NTC Temperature Dependency of the Conductivity of different Fe-Oxides
temperature
pure magnetit
general equation for the temperature dependency of an NTC

R (T ) = h e0 n (T ) d
2
B A eT
(Scm-1)
A,B h d2 R T
material dependent constants length cross section area resistance temperature in K
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NTC Normalized R(T)-Characteristic of NTCs
temperature dependency related to RN

1 1 R (T ) = RN exp B T TN
temperature coefficient:
relative resistance
1 dR B = 2 R dT T
temperature
B R RN T TN
material constant resistance resistance at T = TN temperature in K reference temperature temperature coefficient
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NTC V/I-Characteristic including self heating effect
PK = K A0 (T TU ) = Gth (T TU )
heat losses due to convection PK
I
U2 U I = = I 2 R(T ) = Gth (T TU ) R(T )
valid for T < 350 C (heat losses due to emission not considered)
U thermal equilibrium: Pel = PK T: TU : Gth : K : A0 : temperature of the NTC temperature of the environment heat conductivity heat transference number surface area of the NTC
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NTC Nonlinear V/I-Characteristic due to self heating effect
linear temperature measurement

self heating
[Zinke 1982]
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NTC Time Dependency of the Temperature during Self Heating
th = c m
0 U
P
P: el. power (W) : time constant (s) U: environmental temperature (K) 0: final temperature (K) m: mass of the NTC (g) c: heat capacitance (Ws/gk) 0.7 Ws/gK for many NTC-materials

[Zinke 1982]
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NTC Chip Thermistor
[BetaTherm]
Chip Thermistor Features
fast response time (< 1 s in liquids) 1%, 2%, 5%, 10% accuracy 1 mW/K losses (in air at 25 C) R25C=100, 1000 ... 1 M temperature coefficient 25C= - 3,68 ; B0/50C=3263 metallization: Ag, Au
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NTC Glass Coated Chip Thermistor
Glass Coated Chip Thermistor Features
temperature range: -80 C ... 300 C long term operation up to 225 C metallization: Pt, Ir
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NTC Switch-On Delay
wo rk
ing line
time
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NTC Voltage Stabilization
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Nonlinear Resistors

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Nonlinear Resistors

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Nonlinear Resistors Introduction (1)

Materials and Devices in Electrical Engineering

Institut fr Werkstoffe der Elektrotechnik