Domain Switching as the

Ferroelectric Tester Sees It

Joe T. Evans, Jr.
Bob C. Howard
Spencer T. Smith
Radiant Technologies, Inc.

ISFD13 October 5, 2016

Radiant Technologies, Inc.
Autonomous Memory
 Summary
Nothing electrical can move inside the volume of a
capacitor without an electron moving into or out of that
capacitor from an external circuit. Those external
electrons are the ones that ferroelectric testers keep track
of during a test and each one has a story to tell. This is
their story.

Radiant Technologies, Inc.

Autonomous Memory
 Ferroelectric Test
A ferroelectric capacitor is a 2-port system.

USB to
DRIVE RETURN SENSOR 2
host

Ferroelectric Tester

Radiant Technologies, Inc.

Autonomous Memory
 Contents
a) What does a tester see?

b) What is inside the ferroelectric hysteresis loop?

c) Ferroelectric capacitors in a circuit

d) Questions:
1. KAI vs NLS vs RC?
2. Nucleation when cold?
3. Coercive Voltage Stability?
4. Vortice annihilation everywhere?
5. Partial Switching?
Radiant Technologies, Inc.
Autonomous Memory
 Balance of Forces
Imagine a perfect capacitor whose two plates are shorted by a
perfect wire. Net movement of mass in the circuit is zero. In
this condition, the integral of force around the circuit is zero.

Since Electric Field equals Newtons per Coulomb, the electric

field integrated around the circuit is zero. The sum of forces
around the circuit averages to zero even if there may be
charged particles here and there.
Radiant Technologies, Inc.
Autonomous Memory
 Return to Zero
Starting from steady state with zero motion, if any charge
anywhere inside the capacitor changes its position or its
orientation, the sum of electrical forces will not be zero.
Charges will move around the circuit to bring those forces
back to zero.

VO+

VO+

e-
Radiant Technologies, Inc.
Autonomous Memory
 The Ferroelectric Tester
A Radiant tester simply sits in the circuit path and counts the
electrons going by each way. That count is plotted versus
time.

VO+ Tester
Count = 1 at
VO+ time = 0.1 sec

e-
Note: the comings and goings of charge at zero volts is how
the Deep Level Transient Spectroscopy (DLTS) Task works.
Radiant Technologies, Inc.
Autonomous Memory
 The Ferroelectric Tester
Adding a voltage source to the circuit simply forces charges
to move.

Voltage is optional.

Tester
Count = 1 at
time = 0.1 sec

e-

That count over a full voltage cycle is the hysteresis loop.

Radiant Technologies, Inc.

Autonomous Memory
 The Ferroelectric Tester
In summary, a ferroelectric tester will report everything that
happens inside the capacitor above the resolution of the
instrument. In Radiant’s case, that limit is a few 10’s of
femtocoulombs.

Voltage is optional.

Tester
Count = 1 at
time = 0.1 sec

e-
Radiant Technologies, Inc.
Autonomous Memory
 Contents
a) What does a tester see?

b) What is inside the ferroelectric hysteresis loop?

c) Ferroelectric capacitors in a circuit

d) Questions:
1. KAI vs NLS vs RC?
2. Nucleation when cold?
3. Coercive Voltage Stability?
4. Vortice annihilation everywhere?
5. Partial Switching?
Radiant Technologies, Inc.
Autonomous Memory
 The Components
• According to Joe:
– Linear capacitance
– Non-linear capacitance
– Remanent polarization

Ignore for now

– Remanent and non-remanent leakage

– Remanent and non-remanent small signal capacitance
– Reverse bias diode electrode interfaces
– Left-overs

Radiant Technologies, Inc.

Autonomous Memory
 Normalized CV
The normalized CV [nCV] is the mathematical derivative of
the polarization hysteresis loop. It has the formula

P/V => (Q/V)/Area

and has the units of
F/cm2

when the derivation is performed on the polarization units of

C/cm2

It is the Large Signal Instantaneous Capacitance of the

sample.
Radiant Technologies, Inc.
Autonomous Memory
Derivative of Linear Capacitance
1 n F L in e a r C a p a c it o r
12

11

10

7
u F /c m ^ 2

0
-4 -3 -2 -1 -0 1 2 3 4
Vo lt ag e

• C is a constant slope so the derivative of linear capacitance

is simply a vertical offset on the nCV plot.
Radiant Technologies, Inc.
Autonomous Memory
 Non-linear Capacitance
n C V o f 9 /6 5 /3 5 P L Z T R a d ia n t 9 /6 5 /3 5 P L Z T
10 [ 1700A ]
40
9 30

8 20

P o la r iz a tio n
10
7 0

-10
6
u F /c m ^ 2

-20
5 -30

-40
4
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
V o lt s
3
2
1
0
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
V o lt s

This device has both linear and non-linear capacitance. The linear
capacitance is the vertical offset of the nCV plot. The tips do not
touch zero.
Radiant Technologies, Inc.
Autonomous Memory
 Remanent Hysteresis
Switching and Non-switching half loops:
Switching & Non-switching Loops

70

60

50
uC/vm^2

40

30

20
Switching
10 Non-switching

0
0 1 2 Volts 3 4 5

Radiant Technologies, Inc.

Autonomous Memory
 Remanent Hysteresis
• PUND: P*r - P^r = dP = Qswitched
• Hysteresis: Switching - Non-switching = Remanence:

Remanent Hysteresis Calculation

70

60

50 Remanent
Half Loop
40
uC/vm^2

30

20
Switching
10 Difference
Non-Switching
0
0 1 2 3 4 5
-10 Volts

Radiant Technologies, Inc.

Autonomous Memory
 Domain Switching
n C V o f R e m a n e n t H y s t e r e s is L o o p
[ T ype AB ]

N o r m a l iz e d C a p a c i t a n c e ( µ F /c m 2 )
300
R em an en t Coercive Voltage

250

200

150

100

50

-6 -5 -4 -3 -2 -1 0 1 2 3 4 5 6
Vo lt ag e

• The nCV of the remanent polarization loop rests on the X-

axis because it has no capacitance on the re-trace.
Radiant Technologies, Inc.
Autonomous Memory
 Resistive Leakage in
the Hysteresis Loop
• Pure resistance is a “football”.
• The derivative of pure resistive leakage is an “X”.
Hyster esis of L in ear R esistor
[ 2.5Mohm 4V 1ms ]
n C V of L in ear R esistan ce
2.0 [ 2.5Mohm 4V 1ms ]

1.00
1.5

0.75
1.0

0.50
0.5
P o la r iz a t io n

0.25
-0.0
u F /c m ^ 2
0.00
-0.5

-0.25
-1.0

-0.50
-1.5

-2.0 -0.75

-4 -3 -2 -1 -0 1 2 3 4 -1.00
Voltage
-4 -3 -2 -1 -0 1 2 3 4
Voltage

Radiant Technologies, Inc.

Autonomous Memory
 Is this Ferroelectric?
1750

P o la r iz a t io n (µ C /c m 2 )
N o r m a liz e d C a p a c it a n c e (µ F /c m 2 )

1500

F e r r o e le c t r ic C a p a c it o r || L in e a r R e sist o r 1250
[ T e s t P e r io d = 2 s e c o n d s ] 1000

300 750

500

200 250

100 -7 .5 -5 .0 -2 .5 0 .0
V o lt ag e
2 .5 5 .0 7 .5

-100

-200

-7 .5 -5 .0 -2 .5 0 .0 2 .5 5 .0 7 .5
V o lt ag e

• Yes, it is ferroelectric! See the ferroelectric remanent polarization

switching peaks sticking out of the resistor “X”.
Radiant Technologies, Inc.
Autonomous Memory
 The Perfect Capacitor
• A perfect capacitor combines linear and non-linear
capacitance with remanent polarization.
Switched - Logic 1 Remanent

40

R e m a n e n t H y s t e r e s is 30
[ 1u 4/20/80 PNZ T ]
20

Polarization (µC/cm2)
Sw it c h ed - L o g ic 1 R em an en t 10
10
N o r m a l iz e d C a p a c i t a n c e ( µ F /c m 2 )

9 -10

8 -20

-30
7
-40

6 -40 -30 -20 -10 0 10 20 30 40

Voltage

4
This capacitor is not as square
as the one for which the
3
remanent polarization was
2 plotted as the nCV three pages
1
back. This capacitor has much
smaller peaks which allow the
0
structure at the base of the
-1 nCV to be seen in perspective.
-30 -25 -20 -15 -10 -5 0 5 10 15 20 25 30
Vo lt ag e
Radiant Technologies, Inc.
Autonomous Memory
 Contents
a) What does a tester see?

b) What is inside the ferroelectric hysteresis loop?

c) Ferroelectric capacitors in a circuit

d) Questions:
1. KAI vs NLS vs RC?
2. Nucleation when cold?
3. Coercive Voltage Stability?
4. Vortice annihilation everywhere?
5. Partial Switching?
Radiant Technologies, Inc.
Autonomous Memory
 CFE Equation
The three components identified for this disussion are
combined below to create a single equation for FE
capacitance. (Cdiode will be ignored.)
 Towards VMax:

M = 1 for switching or
M = 0 for non-switching

 Return-to-Zero:

Radiant Technologies, Inc.

Autonomous Memory
 Fitted Components
Type AD103 & Components
6

CLInear = 0.3nF
+CRem

nF
CParaelectric = 0.7nF 5

σParaelectric = 0.8v
CRemanent = 2.3nF 4

σRemanent = 0.23v
+VCoercive = 1.66v 3

Cdiode = 0.075nF
2 CParaelectric + CDiode

0
-5 -4 -3 -2 -1 0 1 2 3 4 5
Volts
+CLinear

 The derivative of a real loop (dotted) can be hand-fitted

by the components.
Radiant Technologies, Inc.
Autonomous Memory
 Fitted Components

 Summation of the fitted components against the original loop.

Radiant Technologies, Inc.
Autonomous Memory
 An FE Cap in a Circuit
The equation describing the capacitance of a ferroelectric
capacitor can now be inserted directly into the classic
Resistor-Capacitor Charging equation from electrical
engineering. This equation can be rigorously derived so the
substitution is justified.

t

Vout  Vpwr  (1  e RC FE
)

In the following pages, the impact of the ferroelectric

capacitor properties on circuit performance is demonstrated.
Radiant Technologies, Inc.
Autonomous Memory
 Classic RC
A ferroelectric capacitor will exhibit multiple capacitances when
switching. The charging of two different linear capacitors is below. They
follow the classic equation: t
Vout  Vpwr  (1  e RC )
10
CSmall
9
8
15M
7
CLarge
6
Volts

5
4 1nF
3
100pF
2
1
0
-0.010 0.000 0.010 0.020 0.030 0.040 0.050 0.060 0.070 0.080
Seconds
Radiant Technologies, Inc.
Autonomous Memory
 RCFE
Two Linear Capacitor Ferroelectric Model
To model a simple ferroelectric capacitor CFE, use a smaller capacitance
when remanent polarization is not switching and a higher capacitance
when it is switching, in this case from 2.2 volts to 2.9 volts.

10
9 Non-switching CFE Model
8
7
Switching CFE Model
6
Volts

5
15M
4 t
3 Vout  Vpwr  (1  e RC FE
)
2
1nF 100pF
1
0
0.000 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008
Seconds
Radiant Technologies, Inc.
Autonomous Memory
 A Real RCFE
Measured
A real ferroelectric capacitor follows this model exactly with its non-linear
capacitances defined by the CFE equation derived earlier.
C = 400 µm2 2600Å-thick 20/80 PZT = linear + non-linear + remanent polarization
R = 15M
R C A B 401 15M ohm 9V R C A B 401 15M ohm 9V
10
9 Non-switching
8
V o u t

7
6
Switching
5
C

4
R

3
2
1 Defined as the “Shelf Voltage”.
0
0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 3 .0 3 .5 4 .0
T im e (m s )
Radiant Technologies, Inc.
Autonomous Memory
 RCFE vs Switching Speed
The switching and non-switching curves below are the result of the
limitation of current flow by the resistor and are not ‘intrinsic’ switching
speed curves. The ferroelectric capacitor will explicitly follow the RCFE
rise time law as long as the intrinsic switching speed of the ferroelectric
capacitor is faster than RCFE.

R C A B 401 15M ohm 9V R C A B 401 15M ohm 9V

10
9 Non-switching
8
V o u t

7
6
5 Switching
C

4
R

3
2
1
0
0 .0 0 .5 1 .0 1 .5 2 .0 2 .5 3 .0 3 .5 4 .0
T im e (m s )
Radiant Technologies, Inc.
Autonomous Memory
 Contents
a) What does a tester see?

b) What is inside the ferroelectric hysteresis loop?

c) Ferroelectric capacitors in a circuit

d) Questions:
1. KAI vs NLS vs RC?
2. Nucleation when cold?
3. Coercive Voltage Stability?
4. Vortice annihilation hiding in plain sight?
5. Partial Switching?
Radiant Technologies, Inc.
Autonomous Memory
 KAI vs NLS vs RCFE
a) The Kolmogorov-Avrami-Ishibashi domain switching
theory posits nucleation-dominated switching.
−𝑡 2
𝑃 = 𝑃0 1 − 𝑒 𝑡0

a) The Nucleation-Limited Switching (NLS) model

attempts to correct KAI when there are few nucleation
sites. −𝑡
𝑃 = 𝑃0 1 − 𝑒 𝑡 𝑖

b) If the ferroelectric material is faster than the tester, the

classic electrical engineering equation applies. (RCFE)
−𝑡
𝑃 = 𝑃0 1 − 𝑒 𝑅𝐶𝐹𝐸

Gruverman, et al, Applied Physics Letters 87, 082902 (2005)

Radiant Technologies, Inc.
Autonomous Memory
 KAI vs NLS vs RCFE
This classic paper shows a Shelf Voltage!

Gruverman, et al, Applied Physics Letters 87, 082902 (2005) Pg 2.

Radiant Technologies, Inc.
Autonomous Memory
 KAI vs NLS vs RCFE
a) The presence of the shelf voltage in the Gruverman et
al data means that this test was resistance limited and
followed the RCFE rule as a circuit component.

b) The test circuit resistance slows down the capacitor

response but the ferroelectric switching mechanism(s)
define the capacitance versus voltage response of the
capacitor. −𝑡
𝑃 = 𝑃0 1 − 𝑒 𝑅𝐶𝐹𝐸

Conclusion: the shape of the ferroelectric switching function

(KAI, NLS, etc) is retained in all such measurements no
matter how slow. The intrinsic switching time constant is
not.
Radiant Technologies, Inc.
Autonomous Memory
 Correction to KAI & NLS
a) Note the asymmetry of the three equations. KAI and
NLS have only a circuit-independent time constant in
the denominator of the power of the exponential.
−𝑡 2
𝑃 = 𝑃0 1 − 𝑒 𝑡0

−𝑡
𝑃 = 𝑃0 1 − 𝑒 𝑡𝑖

−𝑡
𝑃 = 𝑃0 1 − 𝑒 𝑅𝐶𝐹𝐸

b) The RCFE Law equation ignores switching physics.

Radiant Technologies, Inc.

Autonomous Memory
 Correction to KAI & NLS
Both the circuit law and the switching physics operate
simultaneously. The slower mechanism dominates so the two
mechanisms should be treated as components in series.

The time constant should be ‘RCFE+tcharacteristic’.

This correction is
recursive since the
value of CFE depends
on tc. Simulations may
not converge if RCFE
and tc are nearly equal
in magnitude.

Radiant Technologies, Inc.

Autonomous Memory
 Cold Nucleation
All switching theories treat domain reversal as an activation
energy mediated process.
𝐸𝐴𝑐𝑡𝑖𝑣𝑎𝑡𝑖𝑜𝑛
𝑡𝑛𝑢𝑐𝑙𝑒𝑎𝑡𝑒 = 𝑡𝑎𝑡𝑡𝑒𝑚𝑝𝑡 𝑒 𝑘𝑇

Rappe et al. predict from first principles that the nucleation

activation energy for Lead Titanate should increase by a
factor of ~4 while decreasing the temperature from ambient to
200K. This should slow down the rate of reverse domain
nucleation by a factor of e4.

This does not happen in thin film PZT at normal test speeds!
Shin, et al, Nature Letters 06165.3d (4/9/2007) 13.43.34
Radiant Technologies, Inc.
Autonomous Memory
 Cold Nucleation
Hysteresis @ 20V 10k->310K
[ AB403 20/80 PZT 2600A ]

40

20
uC/cm2

-20

-40

-20 -15 -10 -5 0 5 10 15 20

Voltage

Radiant Technologies, Inc.

Autonomous Memory
 Cold Nucleation
• Switched Remanent Polarization vs Frequency from a
temperature of 250 K down to 50 K shows no change
whatsoever in switching speed with temperature.

Remanent
Polarization

Radiant Technologies, Inc.

Autonomous Memory
 Analysis
• The temperature independence of the remanent
polarization switching speed may be an indication that it
is a function of tunneling, not nucleation rates.

• The nucleation rate model is preserved if the nucleation

time constant is so fast compared to the maximum test
frequency that even an e4 slow-down in nucleation rate
would still cause domain switching to be faster than the
RCFE circuit speed limitation.

• Preserving the nucleation rate models given the

megahertz speed of the cryogenic PUND tests would thus
require PZT switching to occur with a 10 picosecond
time constant at room temperature.
Radiant Technologies, Inc.
Autonomous Memory
 What Determines Vc?
• Why does the Coercive Voltage change with voltage for
BFO and PZT? 250nm 20/80 PZT
[ Type AB WHITE ]

40

20

Polarization
0
Hysteresis vs Volts
[ BFO ]
-20
60

-40
40

20 -5 0 5
Voltage
uC/cm2

0
How can the coercive voltage
-20
for remanent polarization
-40
switching be predicted from
-60 existing models?
-4 -2 0 2 4 6 8
Voltage
Radiant Technologies, Inc.
Autonomous Memory
 Leakage Measurement
The polarization at the top of a pulse applied to a PZT
capacitor continues to climb after the pulse voltage is stable.
3/20/80 PNZT Non-switching
Polarization (µC/cm2)

This climb is
10 usually
associated with
5 current leakage
through the
0 capacitor at
4
voltage.
3
Drive Volts

0
2 4 6 8 10 12 14
Time (ms)
Radiant Technologies, Inc.
Autonomous Memory
 Vortices or Leakage?
The Leakage Measurement simply measures the change in
charge coming from the capacitor after the applied voltage
has stabilized across the capacitor.
V Soak Count

3/20/80 PNZT Non-switching VB

14.2

14.1 Soak Count

Polarization (µC/cm2)

14.0
t
13.9 I = Q / t
13.8
Might vortice
13.7 pair annihilation
13.6
be hidden in this
5 6 7
Time (ms)
8 9 10
current?
Radiant Technologies, Inc.
Autonomous Memory
 Partial Switching
The voltage applied to the capacitor can stop anywhere along
the Shelf Voltage and the capacitor will stay in that partially
switched state. It has memory. Polarization models need to
explain this property.
Plot 7V Analog Read time vs Write time RT
[ Type AB WHITE ]
7

4
Volts

0.05 0.10 0.15 0.20 0.25 0.30

Time (ms)

Radiant Technologies, Inc.

Autonomous Memory
 Conclusion
• Everything that happens inside a capacitor must appear in a
measurement when the capacitor is hooked to a tester.

• Only two limitations will prevent the tester from observing

an event:
1. Does some charge event occur in parallel with an
equal but opposite charge event that cancel each
other?
2. Is the signal too small?

• There remain many mysteries about ferroelectric capacitors.

Radiant Technologies, Inc.

Autonomous Memory