Dielectrici si feroelectrici: notiuni

generale si metode experimentale

specifice
Dielectrici: materiale polarizabile
Polarizarea P este momentul dipolar al unitatii de volum
Legatura dintre polarizare si campul electric aplicat se
face prin intermediul susceptibilitatii dielectrice
Constanta dielectrica
E E E E P E D c c _ c _ c c c
0 0 0 0 0
) 1 ( = + = + = + =
Relatia Clausius-Mossotti leaga constanta dielectrica de polarizabilitate
In domeniul optic ramane doar
polarizabilitatea electronica, doar
electronii mai pot raspunde la
oscilatiile campului electric aplicat
=n
2

Absorbtia radiatiei electromagnetice-definitie
The process whereby the intensity of a beam of electromagnetic radiation is
attenuated in passing through a material medium by conversion of the energy of the
radiation to an equivalent amount of energy which appears within the medium; the
radiant energy is converted into heat or some other form of molecular energy.
Legea Lambert-Buguer
Legea lui Planck a densitatii spectrale de
energie pentru corpul negru
Legea Stefan-Boltzmann a densitatii totale
de energie emisa de un corp negru
Polarizare orientationala

Apare atunci cand exista molecule dipolare care se pot roti liber pentru a se orienta
paralel cu un camp electric aplicat.
Functia Langevin (a=E/kT)
E este campul electric
aplicat.
La campuri mici momentul
dipolar mediu este
proportional cu 1/T (lege
de tip Weiss)
Catastrofa de polarizare si feroelectricii
In conditii critice polarizarea devine foarte mare-deplasarea ionilor din pozitiile de
echilibru devine ireversibila, ducand la aparitia unui moment dipolar net, nenul, in
celula elementara (cazul aparitiei polarizarii in cristale cu structura perovskit).


Legea Curie-Weiss in faza
paraelectrica
) /( c T T C = c
Constanta dielectrica infinita
la tranzitia din faza
paraelectrica in faza
feroelectrica
Polarizare finita fara camp
aplicat
Teoria soft mode

Moduri de vibratie (fononi) acustice si optice
Frecventa unui mod de vibratie optic tinde la zero sub o anumita temperatura-apare
polarizare
Relatia Liddane-Sachs-Teller
Feroelectricitate
21 crystalline classes do not have a symmetry center
20 classes show piezoelectric properties
Piezoelectric crystals
32 crystalline classes
10 classes posses a polar axis-spontaneous polarization (polarization existing
without applying an electric field); show pyroelectric properties
Pyroelectric crystals
Ferroelectrics pyroelectrics in
which the spontaneous
polarization can be switched by UP
(P+) and DOWN (P-) by applying a
suitable external voltage (electric
field)
P
S

E
Hysteresis loop
P
R

E
C

Tranzitii de faza - Thermodynamic theory
First order phase transition
K is the reciprocal
permittivity

The ratio of the slopes
below and above Curie
temperature is -8
The entropy has a jump at
the Curie temperature
Thermodynamic theory
First order phase transition
K is the reciprocal
permittivity

The ratio of the slopes
below and above Curie
temperature is -4
The entropy has a jump at
the Curie temperature
Depolarization field
L is the depolarization factor
P
S
E
dep

Ferroelectric domains
Reference:
Materiale feroelectrice
Ferroelectric materials-classification
Perovskiti
ABO
3

A=Na, K, Li, Ba, Pb, Bi
B=Nb, Ta, Ti, Zr, Fe
LiNbO3 BiFeO3
LiTaO3
BaTiO3
PbTiO3
PbZrO3
Solutii solide (ex. Pb(Zr,Ti)O3)
Order-disorder ferroelectrics
Cristale cu legaturi de hidrogen.
Peste temperatura de tranzitie atomii de
hidrogen sunt uniform distribuiti inre cele doua
minime energetice deci momentul dipolar total
este nul.
Sub temperatura de tranzitie unul din minime
este preferat, deci apare polarizare.
Mecanisme de conductie in izolatori
Curent limitat de sarcina spatiala cu un singur nivel
de captura
La tensiuni mici dependenta de tensiune este de tip
ohmic, ~V
La incarcarea nivelului de captura apare o crestere
brusca a curentului
Dupa incarcare dependenta de tensiune devine ~V
2

TFL inseamna trap fill limit
Trape putin adanci
Trape adanci
Curenti limitati de sarcina spatiala (SCLC)
Distributie exponentiala de trape
l=T
t
/T
0.1 1 10
1E-13
1E-12
1E-11
1E-10
1E-9
1E-8
1E-7
1E-6
1E-5
1E-4
1E-3
0.01
C
u
r
r
e
n
t

(
A
)
Voltage (V)
150K
200K
250K
300K
350K
400K
-6 -4 -2 0 2 4 6
1E-7
1E-6
1E-5
1E-4
1E-3
0.01
0.1
1
10
100
C
u
r
r
e
n
t

d
e
n
s
i
t
y

(
A
/
c
m
2
)
Voltage (V)
30 nm
90 nm
400 K
c)
SCLC liber de centri de captura este independent de temperatura.
In regimul de camp electric mare dependenta de temperatura trebuie sa
dispara-curbele converg intr-una singura
SCLC este confirmat daca si dependenta de grosime este satisfacuta!
Emisia Pool-Frenkel
Se reprezinta Ln(J/V)~V
1/2
la T constant
Din panta se poate estima valoarea constantei dielectrice
daca valoarea este compatibila cu cea obtinuta prin alte
metode atunci mecanismul poate fi Pool-Frenkel
Se reprezinta Ln(J/V)~1/T la tensiune constanta, pentru mai
multe tensiuni si se determina un
app

Apoi
app
se reprezinta ca V
1/2
si se determina
B

Tunelare Fowler-Nordheim
Fowler-Nordheim nu are dependenta de
temperatura
Aapare la densitati mari de purtatori
liberi, si la temperaturi joase
Energia caracteristica:
FN apare atunci cand E
00
>>kT
Emisia Schottky
Ecuatia valabila daca drumul liber mediu este mai mare decat grosimea probei:
Daca drumul liber mediu este mai mic decat grosimea ecuatia valabila este:

Hopping
Hopping activat termic:
|
.
|

\
|

kT
W
T
a
exp ~
2 / 3
o
|
.
|

\
|

|
.
|

\
|
kT
W
kTw
Vqa
j
a
exp
2
sinh ~
=qa/2kTw
-80 -70 -60 -50 -40 -30 -20 -10 0 10 20 30 40 50 60 70 80
-7.0x10
-6
-6.0x10
-6
-5.0x10
-6
-4.0x10
-6
-3.0x10
-6
-2.0x10
-6
-1.0x10
-6
0.0
1.0x10
-6
0.0
2.0x10
-9
4.0x10
-9
6.0x10
-9
8.0x10
-9
1.0x10
-8
1.2x10
-8
o=1
C
u
r
r
e
n
t

(
A
)
sinh(oV)
300 K
negative side
positive side

C
u
r
r
e
n
t

(
A
)
2 3 4 5 6 7
-34
-33
-32
-31
-30
-29
-28
-27
-26
-25
-24
L
n
(
o
/
T
3
/
2
)
1000/T
3 V
3.4 V
4 V
4.4 V
5 V
positive side
1.7 1.8 1.9 2.0 2.1 2.2 2.3
0.24
0.26
0.28
0.30
0.32
0.34
0.36
0.38
0.40
0.42
W
a

(
e
V
)
V
1/2
C
F
Linear Fit of Data9_C
Linear Fit of Data9_F negative side
intercept at 0.74 eV
positive side
intercept at 0.51 eV
Mai exista si hopping cu range variabil
(unidimensional
in nanofire)
Metode experimentale specifice pentru feroelectrici
Structura de baza-capacitor
Este necesara o buna cunoastere a naturii contactelor
ohmic-transparent pentru electroni sau pentru goluri
neutru-nu exista curbura de benzi, desi poate exista bariera de potential
rectificator-bariera de potential, curbura de benzi, regiune depletata
Problema suplimentara in cazul feroelectricilor
prezenta sarcinii de polarizare in apropierea interfetei cu electrodul metalic
Masuratoarea de histerezis
V(t)
V
out
(t)
C
sample
C
0
Sawyer-Tower circuit Hysteresis loop
+P
-P
-E
C +E
C
P=V
out
C
0
/A; E=v/d
} }
+ + =
c
c
+ + =
) ( ) ( ) ( ) (
) (
) ( ) ( ) (
V D dt V j dt V j V Q
t
V D
V j V j V j
tr l
tr l
The hysteresis measurement is not static, it is dynamic
A change of the applied voltage produces:
changes in the electric displacement D
changes in the leakage current
changes in the space charge regions changes in the
occupancy state of the traps
All are current sources all are integrated on the reference
capacitor C
0

S
P E D + = c c
0
The integral over time must be converted in an integral over voltage
Triangular signal
+V
a

-V
a

T
t
dV dt t V
o
o
1
= =
with
f V
a
4 = o
-15 -10 -5 0 5 10 15
-40
-30
-20
-10
0
10
20
30
40
P
o
l
a
r
i
z
a
t
i
o
n

(

C
/
c
m
2
)
Voltage (V)
-3 -2 -1 0 1 2 3
-120
-80
-40
0
40
80
120
P
o
l
a
r
i
z
a
t
i
o
n

(

C
/
c
m
2
)
Voltage (V)
Polycrystalline : PZT40/60 (~250 nm) Epitaxial
} }
+ + =
c
c
+ + =
) ( ) ( ) ( ) (
) (
) ( ) ( ) (
V D dt V j dt V j V Q
t
V D
V j V j V j
tr l
tr l
S
P E D + = c c
0 with
5. Ideal ferroelectric
Leakage and trap contribution negligible.
f V
E
P
d
A
C I
a
S
l
|
.
|

\
|
c
c
+ = 4
) ( ) ( V P V C V Q
S l s
+ =
-6 -4 -2 0 2 4 6
-60
-40
-20
0
20
40
60
80
100
Dynamic
Frequency:
red - 10 Hz
green - 100 Hz
blue - 1000 Hz
cian - 2000 Hz
P
o
l
a
r
i
z
a
t
i
o
n

(

C
/
c
m
2
)
Voltage (V)
No frequency
dependence for
charge
-6 -4 -2 0 2 4 6
-0.008
-0.006
-0.004
-0.002
0.000
0.002
0.004
0.006
0.008
0.010
black-10 Hz
red-100 Hz
gree-1000 Hz
blue-200 Hz
C
u
r
r
e
n
t

(
A
)
Voltage (V)
D
Frequency dependence of the chargetraps, domains
|
.
|

\
|
=
t
t
N t N
T T
exp ) (
0
6. Traps
t
) (
0
t N
dt
dn
dx
dt
dn
qA I
T
w
tr
t
=
=
}
1
,
1
,
exp
exp

|
.
|

\
|

=
(

|
.
|

\
|

=
kT
E E
N v
kT
E E
N v
V T
V p th p p
T C
C n th n n
o t
o t
Emission from the traps
mobile charge carriers
changes in the space charge displacement current
Back-to-back Schottky diodes one side emission, the other side
capture the space charge variation will be of opposite sign at the
two contacts the displacement currents cancel each other
The hysteresis loop and the traps
-6 -4 -2 0 2 4 6
-800
-600
-400
-200
0
200
400
600
800
Static
Frequency:
black - 1 Hz
red - 10 Hz
green - 100 Hz
P
o
l
a
r
i
z
a
t
i
o
n

(

C
/
c
m
2
)
Voltage (V)
-6 -4 -2 0 2 4 6
-40
0
40
Frequency:
red - 10 Hz
green - 100 Hz
blue - 1000 Hz
cian - 2000 Hz
P
o
l
a
r
i
z
a
t
i
o
n

(

C
/
c
m
2
)
Voltage (V)
Ideal insulator, with negligible leakage and
constant field Q = D = c
0
cE + P
S
if P
S
is
saturated, the Q ~ c
0
cV c from the slope
1 10 100 1000
1000
10000
from dynamic
hysteresis
from static hysteresis
"
D
i
e
l
e
c
t
r
i
c

c
o
n
s
t
a
n
t
"
Frequency (Hz)
|
.
|

\
|
=
t
t
N t N
T T
exp ) (
0
t
) (
0
t N
dt
dn
dx
dt
dn
qA I
T
w
tr
t
=
=
}
dV dt t V
o
o
1
= =
with
f V
a
4 = o Triangular voltage
|
|
.
|

\
|
=
f V
V N qAw
V I
a
T t
tr
t t 4
exp ) (
0
) (
4
) (
0
0
V P E
f V
N qdw
V Q
S
a
T t
s
+
|
|
.
|

\
|
+ =
t
c c
Dielectric constant decreasing as 1/f
Masuratoarea de capacitate
Masuratoarea de capacitate este utilizata pentru a obtine informatii despre
constanta dielectrica, mecanismele de polarizare si pierderile dielectrice
Constanta dielectrica este o marime complexa.
Masuratoarea de capacitate este de fapt o masuratoare de curent in
curent alternativ.
The measured dielectric constant
Legatura dintre constanta dielectrica teoretica si cea measurata-apar pierderile
prin conductie, care pot fi foarte importante la frecvente mici
Puntile LRC actuale pot reda direct
dependenta de frecventa a partii reale
a constantei dielectrice si a tangentei
unghiului de pierderi
Tipuri de masuratori de capacitate:
-Masuratoarea simpla de capacitate, la frecventa si temperatura constanta-este
utilizata pentru a determina constanta dielectrica si pierderile.
- Masuratoarea capacitate-frecventa (C-f)-se obtine dispersia constantei
dielectrice si a pierderilor; analiza duce la obtinerea de informatii despre
mecanismele de relaxare, mecanismele de pierderi, etc.
- Masuratoarea capacitate-temperatura (C-T)-informatii despre tranzitii de faza,
energii de activare, etc. (de regula se executa masuratori complexe C-f-T sau
C-T-f)
- Masuratoarea capacitate-tensiune (C-V)-informatii despre eventuala
dependenta de tensiune a constantei dielectrice, despre tunabilitate, etc.

d
A
C
m
c c
0
=
A
d

c as a material constant
For the same composition, the values can
spread over one order of magnitude
Rareori se tine cont de efectul microstructurii asupra
masuratorii de capacitate.
-10 -5 0 5 10
0.006
0.007
0.008
0.009
0.010
0.011
0.012
S
p
e
c
i
f
i
c

C
a
p
a
c
i
t
a
n
c
e

(
F
/
m
2
)
Voltage (V)
Same composition
(PZT40/60)
-3 -2 -1 0 1 2 3
0.020
0.024
0.028
0.032
0.036
0.040
S
p
e
c
i
f
i
c

C
a
p
a
c
i
t
a
n
c
e

(
F
/
m
2
)
Voltage (V)
Polycrystalline Epitaxial
Orice defect structural poate induce sarcini suplimentare in sistem-capacitatea
masurata este afectata-distorsiuni in estimarea constantei dielectrice
Contributii intrinseci (cele legate strict de raspunsul dielectric al materialului studiat)
Contributii extrinseci (induse de defecte structurale, inclusiv interfete)
In materialele policristaline constanta dielectrica este dominata de contributii
extrinseci-pot fi partial eliminate lucrand cu straturi epitaxiale sau cu monocristale
Evidenta existentei regiunilor de sarcina spatiala asociate contactelor
Schottky la interfetele cu electrozii (strat epitaxial de PZT)
E
P
E E
D
S
f
c
c
+
c
c
+ =
c
c
=
0 0
1 1
c
c
c
c
c
S
P E D + = c c
0
tunnability switching
A
d
C C
i m
c c
0
1 1
+ =
C
i
is voltage dependent as V
1/2

Schottky contact!
-16 -12 -8 -4 0 4 8 12 16
1
2
3
4
5
6
7
8
C
a
p
a
c
i
t
a
n
c
e

(
n
F
)
Voltage (V)
Interfacial polarization
Interfacial charge
Tehnici de investigare de tip SPM (scanning probe microscopy)
Cea mai utilizata este PFM (Piezoelectric Force Microscopy)
Posibile subiecte teoretice:
1. Dielectrici: functia dielectrica, absorbtia radiatiei EM in solide, catastrofa de
polarizare, etc. (pagini 2-10)
2. Feroelectrici: notiuni generale, tranzitii de faza, exemple de materiale
feroelectrice (pagini 11-22)
3. Mecansime de conductie in izolatori: curenti limitati de sarcina spatiala, emisia
Pool-Frenkel, emisia termionica, tunelare Fowler-Nordheim, hopping (pagini 23-
29)
Charles Kittel Introduction to Solid State Physics (subiect 1)
A. M. Glass si M. E. Lines Principles and Applications of Ferroelectrics and
Related Materials (subiect 2)
S. M. Sze Physics of semiconductor devices (subiect 3)
M. A. Lampert si P. Mark Current injection in solids (pentru SCLC)
M. Pollack si B. Shklovskii Hopping transport in solids (pentru hopping)
K. C. Kao Dielectric phenomena in solids

Posibile subiecte experimentale:
1. Masuratori de histerezis (pagini 31-40)
2. Masuratori de capacitate (pagini 41-47)
A. M. Glass si M. E. Lines Principles and Applications of Ferroelectrics and
Related Materials (subiect 1)
A. K. Jonscher Dielectric relaxation in solids (subiect 2)