Supplementary Information for:
Nanoporous SiCOH/CxHy dual phase films with an ultralow dielectric
constant and a high Young’s modulus
Jong-Min Parka, Jong Kil Choia, Cheng Jin Ana, Ming Liang Jina, Sangwoo Kangc, Juyoung
Yunc, Byung-Seon Kong*b and Hee-Tae Jung*a
a National Research Lab. For Organic Opto-Electronic Materials, Department of Chemical and
Biomolecular Eng. (BK-21), Korea Advanced Institute of Science and Technology, Daejeon 305-701,
Korea. Fax: +82 42 350 3910; Tel: +82 42 350 3931; E-mail: [email protected]
b KCC Central Research Institute, 83 Mabook-dong, Giheung-gu, Yonginsi,Gyunggi-do 446-912,
Korea E-mail: [email protected]
c Vacuum Center, Division of Advanced Technology, Korea Research Institute of Standards and
Science, Daejeon 305-340, Korea
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Scheme S1
We insta
used to gen
were mixed
on silicon s
1 A schemat
alled the PE
nerate radica
d in the mai
substrates.
tic represen
ECVD reac
al oxygen in
instream of
tation of the
ctor (Schem
n between t
the plasma
e PECVD r
me S1) for c
the shower
a, and flowe
reactor setup
coating two
head and th
ed toward th
p for coating
o precursors
he substrate
he substrate
g on flat sub
s. A plasm
e. ATMS an
e. The film w
bstrates.
a reactor w
nd CHO gas
was deposit
was
ses
ted
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Fig. S1 AdCHO/ATM
annealed at
dditional PMS ratio at
t 420 °C.
orosity of each depos
the ATMSsition tempe
S and ATMerature. The
MS/CHO diee O2/ATMS
electric filmS ratio was
ms as a fus 2.5 and th
unction of the films we
the ere
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
(S1)
(S2)
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Fig. S2 Thefunction of
films were
For the fi
deposited f
atmosphere
0.06 after a
thermally l
content as w
groups such
The value
relatively h
deposited fi
e Si-CH3/Sif the CHO/A
annealed at
ilms deposi
films, and
e for 2 hr. T
annealing as
labile group
well as the
h as CH3 an
of Si-CH3/
higher than t
films at 120
i-O and CHATMS ratio
t 420 °C.
ited at 120 o
the peak
The CHm/Si
s well. This
ps (CxHy) a
CHm conten
nd CHm can
/Si-O and C
those for 21
oC is lower
Hm/Si-O peako at each dep
oC, the rang
ratio was r
-O peak rat
s trend is si
and Si-CH3
nt decreased
n increase th
CHm/Si-O p
10 oC. For th
r than that o
k ratio in thposition tem
ge of the Si
reduced to
tio, 0.08-0.2
imilar to the
3 were rem
d after anne
he porosity o
peak ratios
his reason,
of the films
he ATMS anmperature. T
i-CH3/Si-O
0.06-0.12
23, of the as
e films dep
moved after
ealing at 42
of the film
for the dep
it is estimat
at 210 oC.
nd ATMS/CThe O2/ATM
peak ratio
after anne
s-deposited
osited at 21
annealing
20 oC.22, 34 T
and decreas
position tem
ted that the
CHO dielecMS ratio wa
was 0.10-0
ealing at 4
d films decre
10 oC. It se
at 420 oC
The desorpt
se the dielec
mperature o
dielectric c
ctric films asas 2.5 and t
0.18 in the a
420 oC in A
eased to 0.0
ems that bo
. The Si-C
tion of carb
ctric consta
of 120 oC a
constant of t
s a the
as-
Ar
04-
oth
H3
bon
ant.
are
the
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Table S1. The effect of substrate temperature and annealing on the amount of each chemical component in the ATMS/CHO dielectric film. The O2/ATMS ratio was 2.5, the CHO/ATMS ratio was
0.5, and the dielectric films were annealed at 420 °C.
Deposition Temp. = 120 °C Deposition Temp. = 210 °C
As-deposited[%]
Annealed[%]
Annealed[%]
SiO0 10.69 5.06 1.04
SiO1 38.73 18.83 6.07
SiO2 38.58 43.08 42.06
SiO3 12 31.37 46.37
SiO4 0 1.67 4.45
Sub-total 100 100 100
C(Si)n 29.7 30.04 21.99
Si-CH3 55.49 50.7 58.53
CO1 9.36 13.55 12.43
CO2 5.45 5.71 7.05
Sub-total 100 100 100
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Table S2. A comparison table between this study and previously reported dielectric constants and moduli of low-k SiCOH films.18-22,62-64
Dielectric constant Modulus [GPa] Ref.
2.6 6.4 Jousseaume et al., J. Electrochem. Soc., 2007.
2.4 3.5 Burkey et al., J. Electrochem. Soc., 2004.
2.4 9 Frot et al., Adv. Funct. Mater., 2012.
2.4 8.4 This work
2.3 5.9 Rathore et al., Adv. Funct. Mater., 2008.
2.3 4.1 Dubois et al., Proc. IEEE Int. Interconnect Technol. Conf.,
2005.
2.2 5.4 Trujillo et al., Adv. Funct. Mater., 2010.
2.2 6~7 Eslava et al., J. Am. Chem. Soc., 2008.
2.2 11 Eslava et al., J. Am. Chem. Soc., 2007
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Fig. S3 XP
spectra. Th
PS analysis o
e peak shift
of ATMS/C
t and the int
CHO dielect
tensity chan
tric films de
nge after ann
eposited at 2
nealing at 4
210 °C; (a)
420 °C are re
Si2p spectr
epresented
ra and (b) C
in (a) and (b
C1s
b).
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Fig. S4 Th
ATMS/CH
and dielectr
When w
S4), with th
were reduc
to that of
substrate te
ATMS/CH
dielectric c
annealing (
SiO4.
he atomic r
O dielectric
ric films we
e calculated
he increase
ed from 0.8
V4D4 (tet
emperature,
O dielectric
constant aft
Fig. 4c, 4e,
ratio (a) O/
c films as a
ere annealed
d the overa
e of the sub
86 and 0.84
travinyltetra
the higher
c films depo
ter annealin
S2a). This
/Si, (b) C/S
function of
d at 420 °C.
ll atomic ra
bstrate temp
to 0.46 and
amethylcycl
the oxygen
osited at 12
ng. The Si
indicates th
Si and (c)
f the deposi
.
atio of O/Si
perature fro
d 0.61 after
lotetrasilox
n content an
20 °C shows
2p peak w
hat Si-O mo
C/O that w
ition temper
i, C/Si, and
m 120 °C t
annealing,
ane) low-k
nd the lowe
s a higher c
was shifted
oieties chang
were obtain
rature. The
d C/O based
to 210 °C,
respectively
k films.22 I
r the carbon
carbon cont
from 101.
ged from Si
ned from X
O2/ATMS
d on the pea
the C/O an
y. This is a
In short, th
n content. T
tent, followe
7 eV to 10
iO0 and SiO
XPS charts
ratio was 2
ak areas (F
nd C/Si rati
similar resu
he higher t
Therefore, t
ed by a low
02.6 eV aft
O1 to SiO3 a
of
2.5
ig.
ios
ult
the
the
wer
fter
and
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Fig. S5 Ty
image, (c) A
Fig. S5 sh
is amorpho
amorphous
smooth, un
(Fig. S5c) a
Square) of
ypical image
AFM image
hows a typi
us in structu
structure i
niform, and
and its corre
0.293 nm an
es of the A
e, and (d) cr
ical FE-SEM
ure with a t
in SiCOH
defect free
esponding h
nd small rid
TMS/CHO
ross-section
M cross-sec
thickness of
films (Fig.
e in both th
height profil
dges with a
dielectric f
nal AFM pro
ctional imag
f ~ 300 nm.
S5b). The
he as-deposi
le (Fig. S5d
maximum h
film; (a) cro
ofile measur
ge of the AT
It was obse
e surface m
ited and ann
d), the film
height of 1.
oss-sectiona
red along th
TMS/CHO
erved in the
microstructur
nealed sam
shows a ver
8 nm.
al SEM ima
he indicated
dielectric f
e TEM imag
re of the f
mples. In the
ry low RMS
age, (b) TE
d plane.
film. The fi
ge of a typic
film was ve
e AFM ima
S (Root Me
EM
lm
cal
ery
age
ean
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Fig. S6 EF
precursor-s
ATMS/CH
We meas
(EFM) anal
/semicondu
uniformity
capacitance
difference o
using oscil
applied by
composite f
deposited),
the films w
(annealed)
M images o
selection an
O (annealed
sured the di
lysis, which
uctor (MIS)
of the diele
e, which is
of the elect
lation and
an externa
films, we fo
ATMS (an
were 2.1 V, 0
films was lo
of ATMS a
nd post-tre
d). The O2/A
ielectric con
h is easier th
) structure
ectric const
s evaluated
tric potentia
non-contac
al battery, f
found that th
nnealed), an
0.7 V, and 0
ower than th
and ATMS/C
eatment. (a
ATMS ratio
nstants of th
han the capa
(Fig. S6).
tant in the f
from the
al or the ele
t mode. A
forming a c
he distributi
nd ATMS/C
0.2 V, respe
hat of ATM
CHO dielec
a) ATMS
o was 2.5 an
he dielectric
acitance-vo
An additio
films. The d
surface ch
ectrostatic c
bias voltag
capacitor. F
ion of the e
CHO (annea
ectively. Th
MS alone.
ctric films d
(as-deposi
nd the annea
c materials u
ltage (C-V)
onal benefit
dielectric pr
harge. The
capacitance.
ge (7 V) be
From EFM
electric pote
led) films w
herefore, the
deposited at
ited), (b)
aling tempe
using electr
measureme
t of EFM i
roperty of th
surface ch1–3 The sca
etween the
results of A
entials on th
were very un
e dielectric
t 120 °C as
ATMS (an
erature was
rostatic forc
ent of the m
is that it c
the films is
harge is fou
an rate was
tip and the
ATMS and
he surface i
uniform, and
constant of
a function
nnealed), (
420 °C.
ce microsco
metal/insulat
can check t
related to t
und from t
fixed at 1 H
e sample w
ATMS/CH
in ATMS (a
d that those
f ATMS/CH
of
(c)
ope
tor
the
the
the
Hz
was
HO
as-
of
HO
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
Fig. S7 Tol
and ATMS
only (b, d)
was 420 °C
luene adsor
/CHO diele
ATMS/CH
C.
rption-desor
ectric films
HO dielectri
rption isothe
deposited a
ic films. Th
erm plots (a
at 210 °C as
he O2/ATM
a, b) and po
s a function
MS ratio was
ore size dist
of precurso
s 2.5 and th
tributions (c
or-selection
he annealing
c-f) of ATM
. (a, c) ATM
g temperatu
MS
MS
ure
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013
The standard measurement protocol is as follows: Samples was heated up to 150 °C for 5 min before
porosimetry measurement on a separate hot plate. Wafers was placed in vacuum chamber, then
porosimetry cycle with toluene as solvent chemical. Spectroscopic ellipsometric porosimetry
measurements was evaluated automatically. Samples were located in an adaptation plate on the robot
loader arm of the PS-2000 ellipsometric porosimeter system.
The porosity and average pore radius of ATMS only films were 7.4 % and 0.61 nm, respectively.
Those of ATMS/CHO dielectric films were 14 % and 0.58 nm using EP data (Fig. S7). Pore Radius
Distribution (PRD) were desirably narrow and microporous below 1.6 nm (Fig. S7 c, d). In ATMS only
and ATMS/CHO system, the main pore size was about 0.5~0.6 nm, of which the main portion was
microporous rather than mesoporous. Also, the region of mesoporus part in ATMS/CHO system was
relatively higher than ATMS only films. EP measures the change of the optical properties and
thickness of the materials during an adsorption experiment. During the experiment, the pores in the
layer are filled gradually by adsorptive (solvent) material such as toluene. Change of optical properties,
detected by spectroscopic ellipsometry (an optical technique). Pore analysis is considered Dubinin-
Radushkevich (DR) model and modified Kelvin equation. Pore size distribution (PSD) calculated from
refractive index/volume adsorbed isotherm. First, the volume adsorbed isotherm is calculated from the
refractive index isotherm (Lorentz-Lorenz equation).4
1 M. Nonnenmacher, M. P. O'Boyle and H. K. Wickramasinghe, Appl. Phys. Lett., 1991, 58, 2921. 2 R. M. Nyffenegger, R. M. Penner and R. Schierle, Appl. Phys. Lett., 1997, 71, 1878. 3 D. M. Chiang, W. L. Liu, J. L. Chen and R. Susuki, Chem. Phys. Lett., 2005, 412, 50. 4 F. Rouquerol, J. Rouquerol and K. S. W. Sing, Adsorption by Powders and Porous Solids, Academic Press Inc., 1999.
Electronic Supplementary Material (ESI) for Journal of Materials Chemistry CThis journal is © The Royal Society of Chemistry 2013