Co

re-s

hell D

om

ain

Str

uctu

re

In

vesti

gati

on

of

Lead

-free

In

cip

ien

t P

iezo

ceram

ic b

y

Pie

zo

resp

on

se F

orce M

icro

sco

py

Na L

iu1, R

ob

ert

W. S

tark

1, C

hri

sti

an

Die

tz1

Mati

as A

co

sta

2, W

oo

k J

o3, J. R

öd

el2

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

Na L

iu |

1

1D

epart

ment of M

ate

rials

Scie

nce a

nd C

ente

r of S

mart

Inte

rfaces,

Technis

che U

niv

ers

ität D

arm

sta

dt, G

erm

any

2D

epart

ment of G

eo-

and M

ate

rials

Scie

nce, Technis

che U

niv

ers

ität

Darm

sta

dt, G

erm

any

3S

chool of M

ate

rials

Scie

nce a

nd E

ngin

eering, U

lsan N

ational In

stitu

te o

f S

cie

nce a

nd T

echnolo

gy,

Republic

of K

ore

a

Ou

tlin

e

1.

Mo

tivati

on

! Bi 1

/2N

a1/2

TiO

3-2

5SrT

iO3 l

ead-f

ree incip

ient pie

zocera

mic

! C

ore

-shell

mic

rostr

uctu

re

2.

Pie

zo

resp

on

se F

orce M

icro

sco

py

!  D

om

ain

im

agin

g

!  D

om

ain

sw

itchin

g

3.

Resu

lts

!  V

isualiz

ation o

f non-e

rgodic

core

and e

rgodic

shell

dom

ain

str

uctu

re

!  H

ete

rogeneous n

ucle

ation o

f dom

ain

s a

t core

/shell

inte

rface

!  T

opogra

phic

al diffe

rence b

etw

een the c

ore

and s

hell

regio

n

4.

Co

nclu

sio

ns

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

2

Mo

tivati

on

17.0

9.1

4 |

Inte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

3

Jo, W

., e

t al.. Journ

al of E

lectr

ocera

mic

s 2

9(1

), 7

1-9

3 (

2012).

E

u-D

irective 2

011/6

5/E

u: (R

oH

S),

Off. J. E

ur. U

nio

n, L 1

74, 88-1

10 (

2011).

Kra

uss e

t al. J

EC

erS

30 (

2010)

Lead-f

ree incip

ient

pie

zocera

mic

Bi 1

/2N

a1/2

TiO

3-2

5S

rTiO

3

Poste

r: P

01 b

y M

atias A

costa

incip

ient

Lead-f

ree incip

ient

pie

zocera

mic

!"

#$

%!&!

!&'

!&"

!&(

!&#

!"

#$

%!&!

!&'

!&"

!&(

!&#

)

)

)

) *+,-./)012

')3

4

567-,.4-+.6/)089:;"2

<)0=>9;

;2

<)0=>9;

;2

)

)

)

!"

#$

%!&!

!&'

!&"

!&(

!&#

!"

#$

%!&!

!&'

!&"

!&(

!&#

)*+,-./

/0

)*+,-./

/0

*

*

* 123456*+70

'*8

9

:;<4359425;6*+=.>/"0

*

*

*

!"

#$

%!

"#

$%

!&!

!&'

!&"

!&(

!&#

)

)

)

*+,-./)012

')3

4

567-,.4-+.6/)089:;"2

<)0=>9;

;2

<)0=>9;

;2

)

)

)

Larg

e e

lectr

ic-

field

-induced s

train

Mo

tivati

on

Acosta

, M

., e

t al.. Journ

al of th

e A

merican C

era

mic

Socie

ty 9

7(6

): 1

93

7-1

943.(

2014)

XR

D

Die

lectr

ic P

ropert

ies

Macro

scopic

ally

Pseudocubic

and R

ela

xor

Bi 1

/2N

a1

/2T

iO3-2

5S

rTiO

3 le

ad-f

ree incip

ient pie

zocera

mic

Core

-shell

mic

rostr

uctu

re

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

4

Revers

ible

ele

ctr

ic-f

ield

-induced p

hase

transitio

n fro

m m

ixed r

ela

xor

sta

te t

o

ferr

oele

ctr

ic p

hase

What is

the m

echanis

m o

f la

rge s

train

in B

NT-2

5S

T?

Mo

tivati

on

Core

-shell

mic

rostr

uctu

re

TE

M

SE

M-B

SE

Co

urt

esy o

f A

co

sta

et

al. a

nd

B3

ST

EM

Non-e

rgodic

core

Erg

odic

shell

core

shell

Core

: S

r-deple

ted/(

Bi,N

a)-

rich

Sh

ell:

Sr-

rich/(

Bi,N

a)-

deple

ted

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

5

PF

M

Nanoscale

Pie

zo

resp

on

se F

orce M

icro

sco

py

Balk

e, N

., e

t al.. Journ

al of th

e A

merican C

era

mic

Socie

ty 9

2(8

): 1

629-1

647. (2

009)

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

6

Dom

ain

im

agin

g

Do

main

sw

itchin

g

DC

Vtip=

Va

cco

s(ω

t)

d=

d1ωV

acco

s(ω

t+φ

)

Function

Genera

tor

Laser

Sourc

e

PS

D

S

am

ple

Bottom

Ele

ctr

ode

Phase

Am

plit

ude

Lock-I

n

in

in

out

http://w

ww

.ntm

dt.com

/spm

-princip

les/

Re

su

lt:

vis

ualizati

on

of

co

re-s

hell

do

main

str

uctu

re

!"#"$%&#'()))*+&,#-./012))))*+#'&32)))4+&,#-./012))))4+#'&32))))))))))

Region 1

2 n

m

566)7,)

7,)

arb

.

-20°

201°

566)7,)

4 n

m

arb

.

0°

140°

arb

.

105°

285°

3 n

m

8)9,)

arb

.

-47°

132°

arb

.

arb

.

38°

116°

54°

117°

core

non-e

rgodic

core

core

erg

odic

shell

shell

shell

Region 2 Region 3

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

7

:3(2-2;<6=)

)>)?)@=)AB,

)

:C=@6!D)

>)?)=)AB,

)

Cantile

ver

):3(2-2;<6=)

)>)?)@=)AB,

)

!"#"$%&#'()))*+&,#-./012))))*+#'&32)))4+&,#-./012))))4+#'&32))))))))))

arb

.

105°

285°

arb

.

arb

.

38°

116°

54°

117°

:3(2-2;<6=)

)>)?)@=)AB,

)

:C=@6!D)

>)?)=)AB,

)

Cantile

ver

):3(2-2;<6=)

)>)?)@=)AB,

)

arb

.

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

-20

° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° ° °

201°

co

re

sssssssssssssssssssssssssssssssssssshhhhhhhhhhhhhhh

eeeeeeeeeeeeeeeeell

arb

.

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

-47

° ° ° ° ° ° ° ° ° ° ° ° ° °

132°

cooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo

rrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrreeeeeeeee

sssssssssssssssssshell

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

0°

140°

non-eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeee

rrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggggodic

cccccccccccccccoooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooooo

rrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrrreeeeeeeeeeeeee

errrrggggggggggggggggggggggggggggggggggggggggggg

ooooooooooodic

shhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhhh

eeeeeeeeeeeell

arb

201

° ° ° ° ° ° ° ° ° ° ° ° polis

hin

g?

diffe

rent

chem

ical

com

positio

n?

))))))))))!"#"$%&#'()))))))*+&,#-./012))))))))))*+#'&32)))))))))4+&,#-./012))))))))))4+#'&32)

Re

su

lt:

ele

ctr

ic-f

ield

-in

du

ced

ferr

oele

ctr

ic

do

main

evo

luti

on

arb

. -1

00

°

10

0°

arb

. -1

67

°

16

7°

15

nm

8)9,)

Virgin state After poling

45 min 15 min 90 min

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

8

8)9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,)))

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

9,

45 min 111111111115 min

Re

su

lt:

ele

ctr

ic-f

ield

-in

du

ced

ferr

oele

ctr

ic

do

main

evo

luti

on

arb

. -1

00

°

10

0°

arb

. -1

67

°

16

7°

15

nm

8)9,)

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

9

Virgin state After poling

45 min 15 min 90 min

Topogra

phy

L-a

mplit

ude

L-p

hase

V-p

hase

V-a

mplit

ude

arb

. 1

00

°

arb

. -1

67

°

16

7°

15

nm

Topogra

phy

L-a

mplit

ude

L-p

hase

V-p

hase

V-a

mplit

ude

L-p

hase

V-p

hase

Topogra

phy

8)9,)

J. E

. Z

hou, T.-

L. C

heng, Y. U

. W

ang, J. A

ppl. P

hys. 2012, 111, 024105.

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

10

" 7"7+2%$"1.;);"%2)B)2%$"1.;)3'2--)1",&.7)3/%0;/0%2)

) " '2/2%"$272"03)70;-2&E"7)"F)1",&.73)&/)/'2);"%2B3'2--)

.7/2%F&;2))

) " 2-2;/%.;+G2-1+3273.EH2)/"#"$%&#'.;&-)'"--"I).7)/'2);"%2)

Open q

uestions:

" W

hat

is t

he m

echanis

m b

ehin

d t

he t

opogra

phic

al change in t

he

core

regio

n b

efo

re/a

fter

apply

ing e

lectr

ical field

?

" A

t core

/shell inte

rface,

str

ain

mis

matc

h? C

harg

e a

ccum

ula

tion?

Co

nclu

sio

ns

Th

an

k y

ou

fo

r t

he A

tten

tio

n!

Back r

ow

(f.

l.t.

r.):

Lim

or

Zem

el, M

are

k J

an

ko

, C

hri

sti

an

Die

tz, A

gn

ieszka V

oß

, S

imo

n S

ch

iwek,

M

ari

e-C

hri

sti

n A

pfe

l; F

ron

t ro

w (

f.l.t.

r.):

Kim

Ph

uo

ng

Lie

u, A

sm

a S

idd

iqu

e,

Ro

bert

Sta

rk,

Su

man

Nara

yan

, N

a L

iu;

(Mis

sin

g:

Imke M

urs

ch

el, E

lke K

äm

mere

r, A

nd

reas P

log

, M

axim

ilia

n K

öh

n)

17.0

9.1

4

| I

nte

rnational Sym

posiu

m S

FB 5

95 |

N

a L

iu |

11