Des

igni

ng S

uita

ble

Met

al A

mid

inat

e So

urce

sfo

r TiN

and

Ba/

Sr-c

onta

inin

g Th

in F

ilms

Jean

-Séb

astie

n M

. Leh

n, Q

ing

Min

Wan

gD

aew

on H

ong

and

Deo

V. S

hena

i*A

dvan

ced

Thin

-Film

Tec

hnol

ogie

s,R

ohm

and

Haa

s El

ectr

onic

Mat

eria

ls L

LC,

Nor

th A

ndov

er, M

A 0

1845

.

Hon

gtao

Wan

g an

d R

oy G

. Gor

don*

Dep

artm

ent o

f Che

mis

try

and

Che

mic

al B

iolo

gy, H

arva

rd U

nive

rsity

, C

ambr

idge

, MA

021

38.

Sele

ctio

n of

Sui

tabl

e Pl

atfo

rms

for A

LDSe

lect

ion

of S

uita

ble

Plat

form

s fo

r ALD

OOR

1

R3

MR

2

MR

MX

MO

R

MN

R1

R2

N NR

2

R1

R3

M

M

O O R

M

MR

1 R2

NR

8

R7

R6

R5

R3

R4

NNR

2

R4

MR

3

R1

R5

O NR

M

R

Met

al a

lkyl

Met

al h

alid

e

Met

al a

lkox

ide

Met

al �

-dik

eton

ate

Met

al d

ialk

ylam

ide

Met

al a

mid

inat

e

Met

al c

yclo

pent

adie

nide

Met

al d

ialk

ylam

inoa

lkyl

Met

al �

-dik

etim

inat

e

Met

al a

lkox

yalk

oxid

e

Met

al d

ialk

ylam

inoa

lkox

ide

Met

al A

mid

inat

es

•Bid

enta

te “

chel

atin

g” e

ffect

sIm

prov

ed th

erm

al s

tabi

lity

•R1,

2,3 t

unin

g in

am

idin

ate

Vol

atilit

y an

d re

activ

ity c

ontro

l •N

o di

rect

M-C

bon

dsLe

ss c

arbo

n in

corp

orat

ion

in fi

lms

•Am

idin

ates

of L

a, C

u, C

o, R

u, N

i, E

r, G

d, Z

r, H

f, Y

are

use

d ef

ficie

ntly

in A

LD.

New

Am

idin

ate

Sour

ces

for B

a, S

r and

Ti

�Ti

N is

an

exce

llent

bar

rier a

nd a

lso

a go

od e

lect

rode

mat

eria

l.

�Th

e cu

rren

t tita

nium

sou

rces

(TD

MA

Ti a

nd T

DEA

Ti)

� la

ck th

erm

al s

tabi

lity

and

deco

mpo

se a

t ele

vate

d te

mpe

ratu

res

� m

ay le

ad to

infe

rior q

ualit

y Ti

N fi

lms.

�N

ew T

i (III

) Am

idin

ate

is d

esig

ned

to o

verc

ome

thes

elim

itatio

ns

�ST

O, B

TO a

nd B

ST fi

nd a

pplic

atio

ns in

� N

VFeR

AM

, mic

row

ave,

DR

AM

, MEM

s.

�B

a an

d Sr

am

idin

ates

are

als

o de

velo

ped

as a

ltern

ativ

e so

urce

s.

New

Ti

New

Ti ,,

SrSr,, a

nd B

a So

urce

s fr

om R

ohm

and

Haa

s an

d B

a So

urce

s fr

om R

ohm

and

Haa

s

Ti-F

AM

D

Ba-

AM

D

Sr-A

MD

TGA

and

Vap

or P

ress

ure

Cur

ve fo

r Ti

TGA

and

Vap

or P

ress

ure

Cur

ve fo

r Ti -- F

AM

DFA

MD

Cle

an e

vapo

ratio

n

with

<1%

resi

due

T 1/2

= 1

55o C

log

P(m

mHg

) = 7

.872

- 31

29 /

T (K

)

10.0

0

100.

00

1000

.00

1000

0.00

8090

100

110

120

130

140

Temp

erat

ure

Cent

igra

de

Vapor Pressure (mTorr) Ti-F

AM

Dof

fers

:•h

ighl

y vo

latil

e liq

uid

Ti (I

II) p

recu

rsor

• Cle

an e

vapo

ratio

n w

ith n

eglig

ible

resi

dues

• V

P =

0.1

Torr

at 8

0 OC

, sui

tabl

e fo

r ALD

TiN

Thi

n Fi

lm P

roce

ssin

g fr

om T

i Ti

N T

hin

Film

Pro

cess

ing

from

Ti ((

IIIIII)) F

AM

DFA

MD

Sour

ce T

emp:

85 �C

ALD

TiN

: 28

0 <

T <

310

o C

CVD

TiN

: 31

0 <

T <

335

o C

CVD

TiC

N:

T >

335

o C

Ti F

AM

DA

LD p

roce

ss w

indo

w is

280

< T

< 3

10 o C

0

0.51

1.52

2.53

3.54

4.55 25

030

035

040

0

Tem

p (º

C)

Growth rate (Å/cycle)

With

Am

mon

ia

With

out A

mm

onia

TEM

of A

LD T

iNTE

M o

f ALD

TiN

10 1/nm

10 1/nm

5 nm

5 nm

Plan

e vi

ew

Cro

ss-s

ectio

n

Epox

y

TiN

SiO

2

Rea

l spa

ce im

age

Diff

ract

ion

patte

rn

Am

orph

ous

with

som

e tin

y na

nocr

ysta

lline

regi

ons

AFM

of A

LD T

iNA

FM o

f ALD

TiN

Smoo

th fi

lms

(with

RM

S =

0.46

nm) w

ere

obta

ined

.

11

2

2

3

3

Con

form

al in

80:

1 as

pect

ratio

hol

e,

ALD

at 3

35 ºC

with

am

mon

ia

No

C in

the

film

s at

< 3

35 ºC

by

XPS

TiN

ALD

TiN

ALD

:: Ste

p C

over

age

by T

EM

Step

Cov

erag

e by

TEM

Ti-F

AM

D

Vapo

r Pre

ssur

e of

Sr A

MD

Vapo

r Pre

ssur

e of

Sr A

MD

Enha

nced

Tra

nspo

rt b

y Tr

imet

hyla

min

e En

hanc

ed T

rans

port

by

Trim

ethy

lam

ine

�U

sing

Me 3

N a

s a

carr

ier g

as in

crea

ses

the

TG v

apor

tran

spor

t rat

e of

Sr

(thd)

2 and

Sr(

amd)

2

140

150

160

170

180

190

200

210

220

230

0

100

200

300

400

500

Evaporation rate, nmol min-1 cm-2

Evap

orat

ion

Tem

pera

ture

, oC

Sr(th

d)2/

N2

Sr(

thd)

2/M

e 3N

Sr(

amd)

2/N 2

Sr(

amd)

2/M

e 3N

>3 x

fast

er fo

r Sr(

thd)

2

>6 x

fast

er fo

r Sr(

amd)

2

Sr(a

md)

2/Me 3

N >

20 x

fa

ster

than

Sr(

thd)

2/N2

Hig

h Th

erm

al S

tabi

lity

of S

rH

igh

Ther

mal

Sta

bilit

y of

Sr //

Ba

Ba --

AM

DA

MD

Ther

mal

sta

bilit

y st

udie

s by

Acc

eler

ated

Rat

e C

alor

imet

ry a

naly

sis

(AR

C)

Sr-A

MD

Ba-

AM

D

Sta

ble

up to

250

o C

Sta

ble

up to

250

o C

Sta

ble

up to

220

o C

Sta

ble

up to

220

o C

Prop

ertie

s of

the

New

Ti

Prop

ertie

s of

the

New

Ti ,,

SrSr,, a

nd B

a Pr

ecur

sors

and

Ba

Prec

urso

rsN

ame

Ti-F

AM

DSr

-AM

DB

a-A

MD

M. W

. (g/

mol

)28

9.37

852

.38

951.

79

App

eara

nce

Dee

p Br

own

liqui

d W

hite

sol

idW

hite

sol

id

M.P

. (ºC

)N

/A >

200

ºC>

200

ºC

Den

sity

(g/m

L)0.

90 0

.50

0.5

4

Vapo

r Pre

ssur

e lo

g P

(Tor

r) =

7.87

2–31

29/T

(K)

log

P(T

orr)

= 10

.41-

3887

/T(K

)D

ata

colle

ctio

n in

pro

gres

s

Ther

mal

St

abili

tyD

ata

colle

ctio

n in

pro

gres

sSt

able

to 2

50 ºC

by

ARC

St

able

to 2

20 ºC

by

ARC

1 H N

MR

Org

anic

impu

rity

N.D

.O

rgan

ic im

purit

y N

.D.

Org

anic

impu

rity

N.D

.

Solu

bilit

ySo

lubl

e in

hyd

roca

rbon

so

lven

ts (>

0.1

M)

Solu

ble

in h

ydro

carb

on

solv

ents

(0.1

M)

Solu

ble

in h

ydro

carb

on

solv

ents

(0.1

M)

Shel

f life

St

able

ove

r 3 m

onth

s St

able

ove

r 6 m

onth

s St

able

ove

r 4 m

onth

s

TGA

Cle

an e

vapo

ratio

n C

lean

eva

pora

tion

Cle

an e

vapo

ratio

n

Sum

mar

ySu

mm

ary

�N

ew s

ourc

es o

f Ti,

Sr a

nd B

a ar

e ne

eded

for T

iN, S

TO a

nd B

ST

appl

icat

ions

.

�Ti

-FA

MD

, Sr-

AM

D a

nd B

a-A

MD

with

gr

eate

r the

rmal

sta

bilit

y ar

e de

velo

ped.

�P

relim

inar

y A

LD re

sults

for T

iN u

sing

liq

uid

Ti (I

II) s

ourc

e ar

e re

porte

d.

�Fu

rther

gro

wth

stu

dies

on

BS

T an

d S

TO

ar

e to

be

cond

ucte

d.