Designing Suitable Metal Amidinate Sources for TiN and Ba...
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Transcript of Designing Suitable Metal Amidinate Sources for TiN and Ba...
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.