nucleation mechanisms of atomic layer deposition of...
TRANSCRIPT
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