yunc, byung-seon kongb and hee-tae jung · b kcc central research institute, 83 mabook-dong,...

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


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


(S1)

(S2)


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


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


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


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).


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


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


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


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


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.


yunc, byung-seon kong*b and hee-tae jung* · b kcc central research institute, 83 mabook-dong,...

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yunc, byung-seon kongb and hee-tae jung · b kcc central research institute, 83 mabook-dong,...