Nuc

leat

ion

mec

hani

sms

of a

tom

ic la

yer

depo

sitio

nde

posi

tion

of la

ntha

num

oxi

de o

n Si

Jinh

eeKw

onM

inD

aiEr

ikLa

nger

eis

Jinh

ee K

won

, M

in D

ai,

Erik

Lan

gere

is,

Lesz

ek W

ielu

nski

and

Yve

s J.

Cha

bal

Rut

gers

Uni

vers

ity

Kyo

ungh

aKim

and

Roy

GG

ordo

nKyo

ungh

a Kim

and

Roy

. G

. G

ordo

nH

arva

rd U

nive

rsity

Con

tent

s

•P

rope

rties

of L

a 2O

3as

a p

oten

tial h

igh-

k m

ater

ial

p2

3p

g

•In

-situ

trans

mis

sion

Fou

rier t

rans

form

infra

red

spec

trosc

opy

(FTI

R) p

erfo

rmed

durin

g at

omic

laye

r dep

ositi

on

(Pre

curs

ors

: Lan

than

um tr

is-N

,N’-d

iisop

ropy

lace

tam

idin

ate,

D2O

)

La(i P

r 2am

d)3

+N

2pu

rge

+D

2O+

N2

purg

e+

FTIR

+FT

IR+

…

•In

itial

sur

face

nuc

leat

ion

mec

hani

sms

and

post

dep

ositi

on a

nnea

ling

effe

cts

•C

oncl

usio

n

La(P

r 2am

d)3

N2

purg

e D

2O

N2

purg

e F

TIR

FTI

R …

Con

clus

ion

La2O

3on

Sili

con

& in

-situ

IR m

easu

rem

ents

La2O

3P

oten

tial m

ater

ial f

or h

igh-

gate

die

lect

rics

•Lar

ge p

erm

ittiv

ity (

~ 27

)•T

herm

al s

tabi

lity

in c

onta

ct w

ith S

i•h

igh

elec

trica

l bre

akdo

wn

field

stre

ngth

•S

uita

ble

band

gap

(Eg

~ 4.

3 eV

) and

con

duct

ion

band

offs

et

Pre

curs

ors:

Pre

curs

ors:

Lant

hanu

m tr

is-N

,N’-d

iisop

ropy

lace

tam

idin

ate

D2O

30 35

40

45 30 35

40

45

Sin

gle

beam

10

15

20

25

30

10

15

20

25

30 5

500

1

000

1

500

2

000

2

500

3

000

3

500

5

500

1

000

1

500

2

000

2

500

3

000

3

500

FTIR

of g

as p

hase

La(

i Pr 2

amd)

3

20

(x10

-8 )

H2O

+

LaL 3

Mas

s sp

ectr

omet

ry(A

LD c

ham

ber)

LaL 3

+ H

2O

La(O

H)L

x +H

L + D

2O

1015

Pressure (Torr)H

O+

010

2030

4050

05

P

Atom

icm

ass

unit

10-2

1664

.6 c

m-1

(-N

CN

-)

2970

cm

-1

(CH

3)At

omic

mas

s un

it10

(CH

3)

2874

cm

-1

(CH

3)

1492

.8 c

m-1

68

orr)

(x10

-10 )

Pres

sure

vs.

tim

epu

mpi

ng13

80.8

cm

-1

CH

3w

aggi

ng(C

H3)

24

Pressure (To

500

1000

1500

2000

2500

3000

3500

4000

060

120

180

240

300

360

0

Tim

e (s

ec)

FTIR

of g

as p

hase

La(

i Pr 2

amd)

3

20

(x10

-8 )

D2O

+

LaL 3

Mas

s sp

ectr

omet

ry

LaL 3

+ D

2O

La(O

D)L

x +D

L

1015

Pressure (Torr)

10-2

010

2030

4050

05

P

Atom

icm

ass

unit

1659

.2 c

m-1

(-N

CN

-)D

10At

omic

mas

s un

it

HL

1664

.6 c

m-1

DL

1659

.2 c

m-1

(-N

CN

-)

500

1000

1500

2000

2500

3000

3500

4000

Wav

enum

bers

(cm

-1)

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

200o

C

Si-H

2083

cm

-1Si

-H62

7 cm

-1

9020

0o C p

rean

neal

%)90

%)

3c_D

2O

6090

H coverage (%

H/S

i(111

)

6090

H coverage (%

2c_D

2O

2.5c

_La

1.5c

_La

1cD

O

ce (arb. unit)

030 Normalized H

Si-H

ben

ding

Si-H

stre

tchi

ng

030 Normalized H

2 x

10-2

10-3

0.5c

_La

1c_D

2O

absorbanc

-10

12

3N

umbe

r of A

LD c

ycle

s

refe

renc

ed to

SiO

2/Si(1

11)

05

1015

20N

umbe

r of A

LD c

ycle

s60

062

064

020

5021

00w

aven

umbe

r (cm

-1)

H/S

i(111

)

600

620

640

2050

2100

•40

% (7

0 %

) H lo

ss a

fter 1

(3) c

ycle

•D

ensi

ty o

f Si-H

on

Si(1

11) =

7.8

x 1

014

cm-2

2(

)

HLa

HH

HH

LaH

LaH

RR

RR

R

HLa

HH

R

LaH

R

LaH

R

40 %

H lo

ss =

3.1

x 1

014

cm-2

La a

tom

s/cm

2(R

BS)

afte

r 1 c

ycle

= ~3

x 1

014 cm

-2(±

7%)

Rea

ctio

n be

twee

n 1s

tLa

(i Pr 2

amd)

3an

d H

/Si(1

11) a

t Ts

= 20

0oC

10-4

2964

cm

-1

asym

:C

-CH

3

refe

renc

ed to

H/S

i(111

)

960

cm-1

(arb. unit)28

72 c

m-1

sym

:C

-CH

3

2.5c

La3c

_D2O

5c_D

2O

Absorbance

928

cm-1

gas

phas

e

928

cm-1

05

L

1.5c

_La

_

1c_D

2O

2c_D

2O

1000

1500

2000

2500

3000

A

La-O

-Si

2083

cm

-1

Si-H

928

cm0.

5c_L

a

ht (arb. unit)

6

(10-4

)

HH

HH

H?

H?

1000

1500

2000

2500

3000

Wav

enum

ber (

cm-1)

LaL

L

O

LaL

L

O0

510

1520

Peak heigh

Num

ber o

f ALD

cyc

les

03

SiSi

SiSi

SiSi

SiSi

Si

SiSi

SiSi

SiSi

SiSi

Si

LaL 3

+

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

200o

C

2872

cm

-1

sym

:C-C

H3

3c_D

2O

2964

cm

-1

asym

:C-C

H3

2694

cm

-1

(La 2

O3)

OD

2583

cm

-1

(La 2

O3)

D2O

5x10

-5

2.5c

La5c

D2O

11c_

D2O

20c_

D2O

2c_D

2O

2.5c

_La

2.5c

_La

3c_D

2O

_2

1.5c

_La

5x10

-5

2c_D

2O

1c_D

2O1.

5c_L

a

1c_D

2O

0.5c

_La

2500

2800

3100

Diff

eren

tial

2500

2700

0.5c

_La

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

200o

C

1458

1416

991

930

*car

bona

te s

peci

esas

CO

La-s

ilicat

e78

0 –

1020

cm

-153

5

452

La2O

3La

-O

4 x

10-4

2694

SiO

x11

41

86293

0

0.35

50 cm-1

y =

0.01

7 x

- 0.0

15

2712

2694 O-D

2583

1141

0.07

0.14

0.21

0.28

between 1250 - 165

D2O

05

1015

20

0.00

Area b

ALD

cyc

le

5c11c

20c

1.5c

2c2.5c

3c

2 x1

0-3

1000

1500

2000

2500

3000

0.5c

1c

refe

renc

ed to

H/S

i(111

)40

060

0

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

200o

C

1458

1416

991

930

*car

bona

te s

peci

esas

CO

La-s

ilicat

e78

0 –

1020

cm

-153

5

452

La2O

3La

-O

20c

151714

64 1419

Diff

eren

tial

4 x

10-4

2694

SiO

x11

41

86293

019

.5

19c

2712

2694 O-D

2583

1141

D2O

18.5

c

5c11c

20c

2x10

-4

1.5c

2c2.5c

3c

2 x1

0-3

18c

:: H

/Si(1

11)

1000

1500

2000

2500

3000

0.5c

1c

refe

renc

ed to

H/S

i(111

)40

060

015

0017

0013

00

Pos

t dep

ositi

on a

nnea

ling

refe

renc

ed to

H/S

i(111

)

2x10

-312

5010

5312

40

m-1)

0.6

unit)

LOTO

)

530

1200

avenumbers (cm

0.2

0.4

mode area (arb.

ance (arb. unit)

700o

C80

0oC

200

400

600

800

1160

Wa

Ann

ealin

g te

mpe

ratu

re (o C

)

0.0

LO m

Absorba50

0oC

600o

C

700

C

1467

1392

860

gp

()

1020

1050

cm-1)

1.2

1.6

b. unit)

@C

300o

C

400o

C

1392

1140

990

1020

Wavenumbers (c

0.4

0.8

O mode area (arb

500

1000

1500

Wav

enum

ber (

cm-1

)

20c

@20

0oC

200

400

600

800

960

W

Ann

ealin

g te

mpe

ratu

re (o C

)

0.0

TO

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

300o

C

1186

990

10-3

La-s

ilicat

e

SiO

x

La2O

353

06090

mode area (%)

1420

1550

1990

O-D

(La 2

O3)

2695

20c

Car

bona

te s

peci

es

030

Si-H 2083 cm-1 m

11c

20c

10.5

c11

c

20c

105

•La

2O3

LOm

ode

at53

0cm

-1

05

1015

20N

umbe

r of A

LD c

ycle

s

•~1

00%

H lo

ss b

y th

e en

d of

5th

cycl

e

25c

3c5c10c

5c10.5

c

10c

•Le

ss c

arbo

nate

spe

cies

in th

e fil

m

(140

0 –

1600

cm

-1)

La2O

3LO

mod

e at

530

cm

1c1.5c

2c2.5c

3c•

Inte

rfac

ial S

iOx

form

atio

n

(110

0 –

1200

cm

-1)

•La

silic

ate

form

atio

n

1000

1500

2000

2500

3000

600

400

0.5c

1c

2x10

-3•

La-s

ilica

te fo

rmat

ion

(800

–11

00 c

m-1

)

•19

90 –

2100

cm

-1m

odes

refe

renc

ed to

H/S

i(111

)

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

300o

C

1180

)

Peak

pos

ition

s

1160

1020

venumbers (cm-1

05

1015

20

1140

ALD

cyc

les

05

1015

20

990

Wav

ALD

cyc

les

1186

cm

-1

990

cm-1

70o C

990c

m-1

865c

m-1

10c

10.5

c11

c20

c10

-320

o C

20cy

cle_

70o

20cy

cle

20o

865c

m

0.5c

1c1.5c

2c2.5c

3c5c10

-320

cycl

e_20

19.5

cycl

e_70

o

19.5

cycl

e_20

o

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

300o

C

4c_D

2O19

9821

13

Diff

eren

tial

Dec

ompo

sitio

n of

La-

prec

urso

r cy

anam

ide

[N-C

N]2

-(o

r car

bodi

imid

e [N

=C=N

]2- )

(CN

)C

N

3.5c

_La

as(C

N2)

1900

~ 2

120

cm-1

2x10

-4

La

CN

2.5c

_La

3c_D

2O

1D

O

1.5c

_La

2c_D

2O

1c_D

2O

1800

2000

2200

2400

0.5c

_La

Wav

enum

bers

(cm

-1)

Z. N

atur

fors

ch 5

8, 1

097

(200

3)

ALD

of L

a 2O

3on

H/S

i(111

) at T

s=

300o

C

4c_D

2O19

9821

13

Diff

eren

tial

-H

3.5c

_La

2x10

-4

-H(g

)-H

2.5c

_La

3c_D

2O

(g)

-H

1D

O

1.5c

_La

2c_D

2O-H

1c_D

2O(g

)

1800

2000

2200

2400

0.5c

_La

Wav

enum

bers

(cm

-1)

Sum

mar

y

•La(

i Pr 2

amd)

3is

hyd

roly

zed

by re

sidu

al w

ater

in th

e A

LD c

ham

ber

• Com

plet

eH

loss

byth

een

dof

5th

cycl

e(T

s=

300o

C)

Com

plet

e H

loss

by

the

end

of 5

cycl

e (T

s 3

00C

)

•La-

silic

ate

and

SiO

2fo

rmat

ion

alon

g w

ith L

a 2O

3

Cb

ti

itii

thfil

db

lit5

00o C

•Car

bona

te im

purit

ies

in th

e fil

ms

re

mov

ed b

y an

neal

ing

at 5

00o C

•La(

i Pr 2

amd)

3de

com

pose

d to

cya

nam

ide

at T

s=

300o

C