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Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Des
igni
ng S
uita
ble
ALD
Pre
curs
ors
for H
igh-
k D
iele
ctric
s, B
arrie
rs a
nd
Met
als
App
licat
ions
Deo
V. S
hena
i, H
uazh
iLi,
Qin
gM
in W
ang,
and
Yos
hiSe
nzak
i,R
ohm
and
Haa
s El
ectr
onic
Mat
eria
ls L
LCR
oy G
. Gor
don ,
Har
vard
Uni
vers
ity
Des
igni
ng S
uita
ble
ALD
Pre
curs
ors
for H
igh-
k D
iele
ctric
s, B
arrie
rs a
nd
Met
als
App
licat
ions
Deo
V. S
hena
i, H
uazh
iLi,
Qin
gM
in W
ang,
and
Yos
hiSe
nzak
i,R
ohm
and
Haa
s El
ectr
onic
Mat
eria
ls L
LCR
oy G
. Gor
don ,
Har
vard
Uni
vers
ity
Sour
ces
for S
uper
ior D
evic
esSM
2007
, Roh
m a
nd H
aas
Elec
tron
ic M
ater
ials
LLC
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Out
line
ALD
Pre
curs
or S
elec
tion
Crit
eria
Met
al A
mid
inat
es=>
Bes
t The
rmal
Sta
bilit
y vi
s-à-
vis
Am
ides
ZrA
mid
inat
efo
r ALD
of Z
rO2
Ru
Am
idin
ate
for A
LD o
f Ru
La F
orm
amid
inat
e=>
Nov
el s
ourc
e fo
r ALD
of L
aAlO
3P
recu
rsor
Dev
elop
men
t for
Impr
oved
The
rmal
Sta
bilit
y
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
ALD
Pre
curs
orS
elec
tion
Crit
eria
1) A
dequ
ate
vapo
r pre
ssur
e (>
~0.
1 To
rrat
< 2
00 ºC
)-m
onon
ucle
ar m
etal
com
plex
es p
refe
rred
2) A
ccep
tabl
e Th
erm
al s
tabi
lity
durin
g va
poriz
atio
n3)
Rea
dily
reac
ts w
ith 2
ndre
acta
nt a
t a lo
w te
mpe
ratu
re4)
Exh
ibits
low
impu
rity
inco
rpor
atio
n in
the
film
s5)
Liq
uid
sour
ces
are
pref
erre
d fo
r con
sist
ent v
apor
del
iver
y
Prec
urso
r Des
ign:
Pra
ctic
al fo
r com
mer
cial
app
licat
ion,
i.e. S
afet
y, S
tabi
lity,
She
lf-lif
e, T
hrou
ghpu
t, an
d Pr
ice.
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Sel
ectio
n of
Sui
tabl
e P
recu
rsor
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-d
iket
onat
e
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-d
iket
imin
ate
Met
al a
lkox
yalk
oxid
e
Met
al d
ialk
ylam
inoa
lkox
ide
Met
al A
mid
inat
es: N
o di
rect
M-C
bon
ds, a
nd e
xhib
it si
gnifi
cant
ly b
ette
r th
erm
al s
tabi
lity
than
am
ides
, as
a re
sult
of “c
hela
ting”
amid
inat
elig
and.
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Zr(a
mid
inat
e)4
for H
igh-
k A
pplic
atio
n
Hig
h th
erm
al s
tabi
lity:
No
resi
due
afte
r TG
No
chan
ge in
NM
R a
fter h
eatin
g at
250
o Cfo
r 1 w
eek
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Dec
ompo
sitio
n P
rofil
es
for T
EM
AZr
and
Zr(a
mid
inat
e)4
Vap
or P
ress
ure
Cur
vefo
r Zr(a
mid
inat
e)4
05
1015
20
0.00
674
0.01
832
0.04
979
0.13
534
0.36
7881
2.71
828
05
1015
20Ti
me
(day
)
Ln ratio
Tim
e (h
r)
0.01
0.10
1.00
10.0
0
4060
8010
012
014
016
018
0Te
mpe
ratu
re C
entig
rade
Vapor Pressure(torr
Zr(M
e 2-a
md)
4
log
P =
3.4
85-1
762/
TZr
(AM
D) 4,
t 1/2
= 46
8 da
ys
TEM
AZr
, t1/
2=
1.8
Hou
rs
No
deco
mpo
sitio
n of
Zra
mid
inat
esfo
r > 1
000
Hou
rs a
t 200
ºCSo
lid s
ourc
e w
ith re
ason
able
vap
or p
ress
ure
for A
LD a
pplic
atio
nB
est c
andi
date
for p
oten
tial d
irect
liqu
id in
ject
ion
deliv
ery
inA
LDFu
rthe
r DLI
form
ulat
ion
wor
k is
ong
oing
, and
will
be
pres
ente
d in
due
cou
rse
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
ALD
of Z
rO2U
sing
Zr(
amid
inat
e)4&
TE
MA
Zrat
UT
Dal
las
150
200
250
300
350
46810121416 Thickness [nm]
Prog
ram
min
g su
bstra
te te
mpe
ratu
re [C
]
TEM
A-Zr
Zr-A
MD
•Fo
rTEM
A-Z
r, th
e gr
owth
rate
incr
ease
d ra
pidl
y ab
ove
300C
and
poo
r uni
form
ity w
as o
bser
ved.
•Fo
rZr-
AM
D, t
he g
row
th ra
te d
oes
not v
ary
sign
ifica
ntly
eve
n at
a d
epos
ition
tem
pera
ture
of
high
er th
an 3
00C
and
a g
ood
unifo
rmity
was
obs
erve
d as
wel
l.
# of
cyc
les
: 40c
y (T
EM
A-Z
r)18
0cy
(Zr-
AM
D)
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Sat
urat
ion
Cur
ve :
ZrO
2U
sing
Zr(
amid
inat
e)4
at U
T D
alla
s
0.0
0.3
0.6
0.9
1.2
1.5
0.0
0.1
0.2
0.3
0.4
0.5
Growth rate[A(cycle)-1
]
Puls
e tim
e [s
ec]
Gro
wth
rate
: ~0
.24A
/cy
The
self-
limiti
ng g
row
th w
as v
erifi
ed fo
r the
ZrO
2de
posi
tion
proc
ess
usin
g th
e Zr
-AM
D
prec
urso
r by
incr
easi
ng th
e pu
lse
time
at 3
00C
.A
line
ar d
epos
ition
rate
, cha
ract
eris
tics
of A
LD, w
as a
lso
obse
rved
with
Zr-
AM
D a
nd H
2O.
•Sub
stra
te :
HF-
treat
ed S
i•P
rogr
amm
ing
subs
trate
tem
p :3
00C
010
020
030
040
050
060
070
0024681012141618 Thickness [nm]
Num
ber o
f cyc
les
Gro
wth
rate
: ~0
.25A
/cy
Inte
rfaci
al o
xide
: ~1
nm
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
XR
D: Z
rO2A
LD U
sing
Zr(
amid
inat
e)4
at U
T D
alla
s
Sam
ple
: ZrO
2fil
m (3
.7nm
)
Sub
stra
te :
SiO
2(1n
m)/p
-Si
Anne
alin
g : R
TA 7
00ºC
for 3
0s
Gla
ncin
g A
ngle
: 0.
5º
As-
dep
O2-
700C
N2-
700C
2024
2832
3640
4448
52
Intensity (a.u.)
2 Th
eta
011
-111101
111
200
200
: tet
rago
nal
: mon
oclin
ic
As-
depo
site
d on
eam
orph
ous
phas
eA
s-an
neal
ed o
ne in
N2/O
2
tetra
gona
l pha
se
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Sum
mar
y: Z
rO2
ALD
usi
ng Z
r(am
idin
ate)
4an
d O
zone
at A
SM
Rea
ctor
s : F
-120
and
F-45
0fro
m A
SM
Si S
ubst
rate
and
Rea
ctio
n te
mpe
ratu
re 2
00-3
50 °
CTh
e hi
gher
ther
mal
sta
bilit
y of
Zr(
amid
inat
e)4
is d
emon
stra
ted,
and
no
ther
mal
dec
ompo
stio
n is
foun
d to
occ
ur d
urin
g th
e pr
ecur
sor
deliv
ery
at 1
00-1
20
C u
sing
F-1
20 re
acto
r.A
LD m
ode
thin
film
gro
wth
is d
emon
stra
ted
betw
een
200-
250C
. A
t 200
-250
C
, the
film
gro
wth
rate
was
foun
d to
be
ca. 0
.23
A/c
ycle
und
er u
nopt
imiz
ed c
ondi
tions
, and
can
be
expe
cted
to b
e gr
eate
r with
furth
er p
roce
ss o
ptim
izat
ion,
as
high
as
1.4
A/c
ycle
base
d on
pre
limin
ary
cust
omer
eva
luat
ion
resu
lts.
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Rut
heni
um (C
arbo
nyl)
Am
idin
ates
for A
LD A
pplic
atio
n
Ru(
amd)
Ru(
amd)
22(C
O)
(CO
) 22
Ru(
tBu 2
-AM
D) 2
(CO
) 2is
an
air &
moi
stur
e st
able
sol
idVa
por p
ress
ure>
0.05
Tor
r@13
0°C
Low
eva
pora
tion
resi
due
0.14
% b
y TG
A
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Ru(
CO
) 2(a
mid
inat
e)2
: ALD
and
CV
D G
row
th R
ates
Ru(
amd)
Ru(
amd)
22(C
O)
(CO
) 22
Adv
anta
ge: O
xyge
n-fr
ee A
LD P
roce
ss !!
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Ste
p co
vera
ge: R
ufil
mus
ing
Ru(
CO
) 2(a
mid
inat
e)2
Top
of tr
ench
45 n
m
Mid
dle
of tr
ench
40 n
m
Bot
tom
of t
renc
h40
nm
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
New
La
Sou
rce
from
Roh
m a
nd H
aas
Com
pany
: La
ntha
num
For
mam
idin
ate,
La(
FAM
D) 3
Ther
mal
Sta
bilit
y at
200
C
Exce
llent
The
rmal
Sta
bilit
yTG
A: t
1/2
= 20
9°C
with
neg
ligib
le re
sidu
e M
ost V
olat
ile L
a So
urce
so
far
Hig
her V
apor
Pre
ssur
e th
an L
a(C
p)3
and
La(th
d)3
020406080100
120
050
100
150
200
Tim
e (h
r)
% Precursorsremaining
TD
IPA
LaT
DIP
FLa
HN NR
1
R3
La 3
Lant
hanu
mFo
rmam
idin
ate
TGA
of L
a(FA
MD
) 3
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Vap
or P
ress
ures
for L
a(am
d)3
and
La(fo
rmam
idin
ate)
3
0.10
00
1.00
00
10.0
000
100.
0000
1000
.000
0
4060
8010
012
014
016
018
0Te
mp
erat
ure
Cen
tig
rad
e
Vapor Pressure (mtorr)
La(iP
r2-f
md)
3lo
g P
= 1
.840
8 -
1151
/T
La(t
hd)3
log
P =
2.4
732
- 19
03/T
La(iP
r2-a
md)
3lo
gP
= 2
.477
4 -
1456
/T
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
ALD
of L
a 2O
3an
d La
xAl 2-
xO3
Usi
ng L
a(FM
D) 3
at H
arva
rd U
nive
rsity
020
4060
8010
012
014
005101520
Y =
A +
B *
XP
aram
eter
Val
ueE
rror
----
-----
----
-----
-----
----
-----
-- --
-A
-0.1
2272
0.15
751
B0.
1597
90.
0027
4--
----
-----
-----
----
-----
-----
----
-----
-R
= 0
.999
71
Thickness (nm)
cycl
es
La2O
3
LaxA
l 2-xO
3
Co-
reac
tant
s: T
rimet
hyla
lum
inum
(Me 3
Al)
and
H2O
Subs
trat
e Te
mpe
ratu
re: 3
00 ºC
, Bub
bler
Tem
pera
ture
: 120
ºCR
efer
ence
: Res
ults
pre
sent
ed b
y G
ordo
n et
al.
at th
is C
onfe
renc
e
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Zr(M
e 2-A
MD
) 4, X
P-07
226
and
XP-0
7227
New
ZrS
ourc
es w
ith Im
prov
ed T
herm
al S
tabi
lity
From
Roh
m a
nd H
aas
Com
pany
050
100
150
200
250
300
350
020406080100
Weight Percentage%
Tem
pera
ture
(C)
TGA
of T
EMA
Zran
d Zr
(Me 2
-AM
D) 4
•Mot
ivat
ion:
Gre
ater
The
rmal
Sta
bilit
y th
an c
onve
ntio
nal p
recu
rsor
s.•D
esira
ble:
Acc
epta
ble
vola
tility
(ca
0.1
Torr
at <
200
C) a
nd p
refe
rabl
y a
liqui
d pr
ecur
sor.
•Zr(
AM
D) 4,
XP-
0722
6 an
d XP
-072
27 e
xhib
it be
tter t
herm
al s
tabi
lity
vis-
à-vi
s TE
MA
Zr.
•XP-
0722
7 is
a li
quid
with
hig
her v
apor
pre
ssur
e th
an T
EMA
Zr(1
60 m
Torr
and
28 m
Torr
at 4
0 C
resp
) tha
t is
desi
rabl
e fo
r hig
her t
hrou
ghpu
t in
ALD
.
TGA
Dat
a fo
r Zr S
ourc
es
120
140
160
180
200
220
240
TEM
AZr
Zr(M
eCp)
2(O
Me)
(Me)
XP-
0722
7X
P-07
226
Zr(M
e2-A
MD
)4
Temp for 50%Mass Loss(Deg C)
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Acc
eler
ated
Rat
e C
alor
imet
ry(A
RC
) and
Impr
oved
The
rmal
Sta
bilit
y
ARC
Resu
lts:
TEM
AZr
050100
150
200
250
300
050
010
0015
0020
0025
0030
00
Tim
e (M
inut
es)
SampleTemp. (Degrees C)
0100
200
300
400
500
600
700
800
Pressure (psia)
onse
t at 1
39 d
eg C
ARC
Resu
lts:
XP-
0722
7
020406080100
120
140
160
180
010
020
030
040
050
060
070
080
0
Tim
e (M
inut
es)
Sample Temp. (Degrees C)
010203040506070
Pressure (psia)
onse
t at >
160
C
•Com
para
tive
AR
C b
ench
mar
king
of X
P-07
227
and
TEM
AZr
conf
irms
impr
ovem
ent i
n th
erm
al s
tabi
lity.
•Zr(
Me 2
-AM
D) 4
and
La(F
MD
) 3sh
ow n
o de
com
posi
tion
upto
250
C(e
xper
imen
t ter
min
atio
n po
int).
•Mor
e re
sults
on
ALD
and
film
cha
ract
eriz
atio
n us
ing
new
pre
curs
ors
will
be
repo
rted
in fu
ture
.
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Sum
mar
y
Met
al A
mid
inat
esar
e fo
und
to b
e m
ore
stab
le th
an c
onve
ntio
nal M
etal
A
mid
es a
s pr
ecur
sors
for A
LD a
pplic
atio
ns.
Am
idin
ates
of Z
r, R
uan
d La
are
dem
onst
rate
d as
sui
tabl
e pr
ecur
sors
fo
r ALD
of Z
rO2,
Ru,
La 2
O3
and
LaxA
l 2-xO
3
La F
orm
amid
inat
e=>
a n
ovel
vol
atile
La
sour
ce fr
om R
ohm
and
Haa
s C
ompa
ny fo
r ALD
of L
a 2O
3an
d La
xAl 2-
xO3.
Ong
oing
dev
elop
men
t of n
ew s
ourc
es fo
r ALD
app
licat
ion
at R
ohm
an
d H
aas
Com
pany
and
in c
olla
bora
tion
with
Gor
don
Gro
up a
t H
arva
rd U
nive
rsity
.
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
Ack
now
ledg
emen
ts
Roh
m a
nd H
aas
Com
pany
:A
rt A
mam
chya
n, R
on D
iCar
lo, J
osep
h M
agee
, S
teph
en M
anzi
k, M
icha
el P
ower
, Ral
ph P
ugh,
M
icha
el R
ouss
eau,
John
Suy
dam
Uni
vers
ity o
f Tex
as a
t Dal
las:
D
r. J.
Kim
et a
l.
ASM
Mic
roch
emis
try,
Fin
land
Gor
don
Gro
up, H
arva
rd U
nive
rsity
Roh
m a
nd H
aas E
lect
roni
c M
ater
ials
LL
C
