1/12/2013
1
New Class of ULow-k for Advanced Interconnects:Fundamentals and Application of Silicon Carbide
Hybrid Glasses
Yusuke Matsuda Lecturer and Ph.D. Candidate
Department of Materials Science and Engineering Stanford University
Advisor: Professor Reinhold Dauskardt
January 9th, 2013
Motivation
Experimental Methods
Mechanical Properties of Silicon Carbide Hybrid Glasses – role of glass network connectivity and plasticity – toughening interface by adjacent plasticity – moisture-assisted cracking
Silicon Carbide Hybrid Glasses as new Low-k Dielectrics
Summary
Outline
Sant Clara Valley Section, Components, Packagingand Manufacturing Technology Society Chapterwww.cpmt.org/scv
1/12/2013
2
Low-k Dielectrics in Microelectronic Interconnects
Cu
silica-based low-k dielectrics
- to avoid RC delay - to reduce power consumption
Silica-Based Low-k Dielectrics and Challenges
1997 2002 2004 2006 2008
SiO2
k=4.3
F-SiO2
k=3.8
SiCOH
k=3.0 SiCOH
k=2.7 p-SiCOH
k=2.4
IBM volume manufacturing of CMOS microprocessors (Dubois, et al. Chem. Rev. 2010, 110, 56–110 )
mechanically weaker
Kim, et al, 2011 IITC proc. p911 Susko et al, ECS Trans. 16 (19) 51-60 (2009)
Window glass Hybrid glass0
2
4
6
8
Mech
an
ica
l to
ugh
ne
ss (
J m
-2)
SiO2 low-k (k=2.5)
~1/3
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3
Challenge: Moisture-Assisted Cracking
Michalske, Nature p511, 1982
mechanochemistry between Si-O and H2O
dramatically reduces fracture resistance of silica-based ULK
Device Aqueous solution
Pressure
Wet processes (CMP)
Impact on Chip Packaging Interaction
Shearing direction
Cu bump
interconnect layers
polyimide
passivation UBM
Courtesy of Alex Hsing at Dauskardt group
Stack 1 Stack 2 Stack 30
2
4
6
8
10
12
14
Failu
re E
ne
rgy,
f (J)
Dielectric Stack
decreasing k
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Solution: Non Silica-Based ULK
DSV-BCB
F-DLC polyimid
a few examples of unsuccessful attempts
SiLK
Can we make ULKs with silicon carbide hybrid glasses?
Hybrid structure – inorganic network: Si-C, C-C, Si-Si – terminal bonds: Si-Hx, C-Hx
Nanostructures – nanoporosity
Tunable multi-functionality – optical and electrical
Silicon Carbide Hybrid Glass Films
Si
H
C
CH3
• little bond polarity • excellent chemical/thermal stability • no moisture-sensitive bonds limited “moisture-assisted cracking”
significant advantages
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Applications of Silicon Carbide Hybrid Glass
water filter micro/nano machine (Sandia National Lab)
semiconductor solar cell
optics
optical waveguide (Shoji, App. Phy. Exp. 2010)
Brittle inorganic network
Reduced network connectivity
Actual sensitivity to moisture-assisted cracking has not been reported.
Fundamental Challenge: Mechanically Fragile
Effects of glass network connectivity on mechanical properties are unknown…
Si
H
C
CH3
reduced connectivity
Si C
fully connected (crystalline)
hydrogenation
Is it possible to confer plasticity to the glasses?
Gc = G0 + Gplasticity ~ negligible
fracture resistance
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6
To understand the fundamental connections between the molecular structure and mechanical properties – network connectivity – plasticity – moisture-assisted cracking
To improve their mechanical properties and create new
hybrid materials
Objective
Motivation
Experimental Methods
Mechanical Properties of Silicon Carbide Hybrid Glasses – role of glass network connectivity and plasticity – toughening interface by adjacent plasticity – moisture-assisted cracking
Silicon Carbide Hybrid Glasses as New Low-k Dielectrics
Summary
Outline
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Experimental Methods
Elemental Analysis and Glass Structure • 13C solid state NMR • Nuclear reaction analysis/Rutherford backscattering • FTIR, X-ray photoelectron spectroscopy
Mechanics Characterization • Four Point Bend (FPB) and Double Cantilever Beam (DCB) geometries
• Nanoindentation, Surface Acoustic Wave (SAW)
FPB adhesion
DCB cohesion Silicon
barrier film
barrier film film of interests
thin film
adhesion
cohesion
Motivation
Experimental Methods
Mechanical Properties of Silicon Carbide Hybrid Glasses – role of glass network connectivity and plasticity – toughening interface by adjacent plasticity – moisture-assisted cracking
Silicon carbide hybrid glasses as New Low-k Dielectrics
Summary
Outline
1/12/2013
8
Plasma enhanced chemical vapor deposition (PECVD) Hydrogenation up to 60 at.%
– connectivity – k: 2.8-7.2
A wide variety of chemical compositions – Stoichiometric (Si/C ~ 1) – Non-stoichiometric (C/Si > 1)
Nanoporosity by second organic phases
Hydrogenated Amorphous Silicon Carbide (a-SiC:H)
Si
H
C
CH3
Silicon barrier film
barrier film
a-SiC:H (500 nm)
Mechanical Properties and Glass Network Connectivity
bond
energy
area
bonds
area
energyGc
connectivity
Fracture properties (brittle materials)
rm
Nstiffness
m
NE
12
connectivity
Elastic properties
r
Si
H
C
CH3
“The deepest and most interesting unsolved problem in solid state theory is probably the theory of the nature of glass and the glass transition” P. W. Anderson (Novel-Prize Laureate), 1995
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Mean Field Approach for Connectivity
H
Hii
x
xxNr
1
2'
C Si
Si
Si
Si
C Si
H
Si
H
Ni: number of bonds in element i NSi: 4, NC: 3 or 4, NH = 1
xi: atomic fraction of element i
max <r’>=4 crystalline SiC
<r’>=2 a-SiC:H
- Rutherford backscattering - 13C NMR sp2 and sp3 C
average network bond number (per atom)
simply count number of network bonds
Effects of Connectivity on Elastic Properties
2.0 2.5 3.0 3.5 4.00
100
200
300
400
500 Stoichiometric films (Si/C~1)
Non-stoichiometric films (Si/C>5)
Fitting
SiO2
Yo
un
g's
mo
du
lus,
E (
GP
a)
Average network bond number, <r'>
C Si
H
Si
H
<r’> = 2
Bulk SiC
<r’> = 4
C Si
Si
Si
Si
rigidity percolation <r’c> ~ 2.4
rm
Nstiffness
m
NE
12
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Effects of Connectivity on Fracture Energy
2.0 2.5 3.0 3.5 4.00
2
4
6
8
10
12
Co
he
siv
e f
ractu
re e
ne
rgy,
Gc (
J/m
2)
Average network bond number, <r'>
stoichiometric Si/C~1
bond
energy
area
bonds
area
energyGc
connectivity
Matsuda, Kim, Stebbins, Dauskardt, et al., in review
Effects of Connectivity on Fracture Energy
2.0 2.5 3.0 3.5 4.00
2
4
6
8
10
12
Co
he
siv
e f
ractu
re e
ne
rgy,
Gc (
J/m
2)
Average network bond number, <r'>
non-stoichiometric (C/Si ~5) porous (12% porosity)
plasticity? Gc=G0 + Gplasticity
crystalline SiC (Lawn,1993)
C/Si ~5 non-porous
stoichiometric Si/C~1
Matsuda, Kim, Stebbins, Dauskardt, et al., in review
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stoichiometric Si/C~1
Effects of Connectivity on Fracture Energy
250 150 100 50 0 -50 PPM
200 2.0 2.5 3.0 3.5 4.00
2
4
6
8
10
12
Co
he
siv
e f
ractu
re e
ne
rgy,
Gc (
J/m
2)
Average network bond number, <r'>
non-stoichiometric (C/Si ~5) porous (12% porosity)
plasticity? Gc=G0 + Gplasticity
C/Si ~5 non-porous
C=C
CHx (-C-C-C-C-)
C-Si
13C NMR
porous
non-porous
Matsuda, Kim, Stebbins, Dauskardt, et al., in review
crystalline SiC (Lawn, 1993)
Plasticity in Non-Stoichiometric a-SiC:H
0 2 4 6 8 10-500
-400
-300
-200
-100
0
100
Vert
ica
l D
ispla
ce
men
t, z
(nm
)
Horizontal Displacement, x (m)
porous load=3mg σys=104MPa
non-porous load=5mg σys=792MPa
pileup
nanoindentation
0 500 1000 1500 2000 25000
3
6
9
12
15
Fra
ctu
re E
ne
rgy, G
c (
J/m
2)
Film Thickness, h(nm)
thickness dependence of Gc
non porous
porous crack tip
plastic zone 2rp
215nm
3nm
porous
p2r
plasticity
Matsuda, Dauskardt, et al., Acta Materialia, 2012
HxSi(CH 3)1-x R SiSi
+
400 oC E-beam
methylsilane phenyl porogen sp3 CHx chain
Origin of plasticity
Matsuda, Kim, Stebbins, Dauskardt, et al., in review
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Tunable Plasticity Contribution to Gc phenyl porogen
Matsuda, Stebbins, Dauskardt, et al., in review
400 200 100 0 -200 -300 -400
chemical shift (ppm)
sp2 C CHx Si-CH3
300 PPM
0%
68%
34%
17%
100%
-100
R
0%
68%
34%
17%
100%
0 25 50 75 1000
2
4
6
8
10
12
Co
he
siv
e f
ractu
re e
ne
rgy,
Gc (
J m
-2)
Porogen amount relative to SiC-15, %
R
Plasticity contribution is tunable!
Chemical/Thermal stability ~ 400 oC
Motivation
Experimental Methods
Mechanical Properties of Silicon Carbide Hybrid Glasses – role of glass network connectivity and plasticity – toughening interface by adjacent plasticity – moisture-assisted cracking
Silicon carbide hybrid glasses as New Low-k Dielectrics
Summary
Outline
1/12/2013
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Toughening Interface by Adjacent Plasticity
GC = G0 + Gplasticity
silicon substrate
brittle film weak interface
G0
a-SiC:H with plasticity plastic
zone, Gplasticity
fragile materials σ
r
Limitations of Metal and Polymers for Toughening
limited metal plasticity at the nanoscale
• low dislocation mobility
• small grain size (Hall-Petch)
(Lane, Dauskardt, 2000)
limitations of polymer • thermal stability
• too soft
0 50 100 150 200 250 0 2 4 6 8
10 12 14 16 18
Frac
ture
Ene
rgy,
Gc (
J.m
2 )
Film Thickness, h (nm)
SiO2
SiCN Gpl h polymer
(Kearney, Dauskardt, 2004)
Polymer films
10 -2 10 -1 1 10 0
20
40
60
80
100
20
Copper Layer Thickness, h (m)
Inte
rface
Fra
ctur
e E
nerg
y, G
c (J/
m2 )
substrate dielectric glass
metal
thickness limit ~300 nm
separation25nm
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Toughening Interface by Adjacent Plasticity
GC = G0 + Gplasticity
a-SiC:H (25-250 nm)
fragile dielectrics
silicon substrate
brittle film (25 nm) fracture, G0 (1.6 J/m2)
< 250 nm
25 - 1000 nm
Limited Film Thickness
a-SiC:H with plasticity
mimicking a typical device structure
excellent thermal & chemical stability
Effects of a-SiC:H Film Thickness
0 50 100 150 200 2500
1
2
3
4
5
6
7
Ad
he
sio
n e
ne
rgy,
GC (
J m
-2)
a-SiC:H film thickness, ha-SiC:H
(nm)
Gpl
G0
Gc = G0 + Gplasticity
fragile dielectrics (100 nm)
Si
Plastic a-SiC:H (25-250 nm)
brittle film (25 nm)
Matsuda, Ryu, Dauskardt et al., To be submitted to Small
0 50 100 150 200 250
0.00
0.25
0.50
0.75
a-SiC:H film thickness, ha-SiC:H
(nm)
Pla
stic z
on
e s
ize
, (
m2)
FEA simulation
Fragile dielectrics
Si
brittle film
1/12/2013
15
0 200 400 600 800 10000
4
8
12
16
Adh
esio
n E
ne
rgy G
C (
J m
-2)
Dielectrics thickness (nm)
Effects of Separation Thickness
Si
Plastic a-SiC:H (250 nm)
brittle films
fragile dielectrics (25 - 1000nm)
Motivation
Experimental Methods
Mechanical Properties of Silicon Carbide Hybrid Glasses – role of glass network connectivity and plasticity – toughening interface by adjacent plasticity – moisture-assisted cracking
Silicon carbide hybrid glasses as New Low-k Dielectrics
Summary
Outline
1/12/2013
16
Moisture-Assisted Cracking
Guyer, Dauskardt (unpublished results)
30% RH
Gc
Organosilicate low-k
Gth 30%
Cra
ck g
row
th v
elo
city, v (m
s-1
)
Moisture-Assisted Cracking
Guyer, Dauskardt (unpublished results)
30% RH
85% RH
Gc
Organosilicate low-k
Gth
Cra
ck g
row
th v
elo
city, v (m
s-1
)
Gth 85%
30%
ΔGth
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Moisture-Assisted Cracking in a-SiC:H Films
Silicon carbide hybrid glasses
0.5 1.0 1.5 2.0 2.510
-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
10-3
N2
90% RH
N2
Cra
ck G
row
th V
elo
city, v (
ms
-1)
Applied Strain Energy Release Rate, G (J m-2)
E: 11.5GPa
k: 4.0
Temp: 25oC
90%RH
Matsuda, Dauskardt, et al., Acta Materialia, 2012
Much less sensitivity, but still exhibit crack growth below Gc
ΔGth~ 0
Moisture-Assisted Cracking in a-SiC:H Films
0.5 1.0 1.5 2.0 2.510
-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
10-3
N2
90% RH
N2
Cra
ck G
row
th V
elo
city, v (
ms
-1)
Applied Strain Energy Release Rate, G (J m-2)
E: 11.5GPa
k: 4.0
Temp: 25oC
90%RH
Matsuda, Dauskardt, et al., Acta Materialia, 2012
Si-CH2-Si Si-O-Si
Abs
orba
nce
(a.u
.)
(King, et al. J. Non. Crys. sol. 2011)
formation of Si-O-Si bonds
Si − H + H2O → SiOH + H2 Si − OH + Si − OH → Si − O − Si + H2O
Silicon carbide hybrid glasses
ΔGth~ 0
Si
Si
H
H
removing Si-Hx groups can result in total insensitivity
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Moisture-Assisted Cracking in a-SiC:H Films
0.5 1.0 1.5 2.0 2.510
-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
10-3
N2
90% RH
N2
Cra
ck G
row
th V
elo
city, v (
ms
-1)
Applied Strain Energy Release Rate, G (J m-2)
E: 11.5GPa
k: 4.0
Temp: 25oC
90%RH
Matsuda, Dauskardt, et al., Acta Materialia, 2012
Silicon carbide hybrid glasses
G = GSi-C + GSi-O
separation of strain energy G
crack plane
unruptured plane
moisture sensitive
insensitive
crack front
ΔGth~ 0
Moisture-Assisted Cracking in a-SiC:H Films
0.5 1.0 1.5 2.0 2.510
-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
10-3
N2
90% RH
N2
Cra
ck G
row
th V
elo
city, v (
ms
-1)
Applied Strain Energy Release Rate, G (J m-2)
E: 11.5GPa
k: 4.0
Temp: 25oC
90%RH
Silicon carbide hybrid glasses
crack plane
unruptured plane
moisture sensitive
insensitive
crack front
threshold, Gth
Gth = GcSi-C + 2g Si-O
ΔGth~ 0
Matsuda, Dauskardt, et al., Acta Materialia, 2012
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Moisture-Assisted Cracking in a-SiC:H Films
0.5 1.0 1.5 2.0 2.510
-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
10-3
N2
90% RH
N2
Cra
ck G
row
th V
elo
city, v (
ms
-1)
Applied Strain Energy Release Rate, G (J m-2)
E: 11.5GPa
k: 4.0
Temp: 25oC
90%RH
Matsuda, Dauskardt, et al., Acta Materialia, 2012
Silicon carbide hybrid glasses
crack plane
unruptured plane
crack front
humiditylow
humidity high
OH
OH
SiOSithP
PkTNG
2
2ln
# Si-O-Si ruptured bonds
vapor pressure
ΔGth~ 0
Model Prediction: ΔGth
0.5 1.0 1.5 2.0 2.510
-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
10-3
N2
90% RH
N2
Cra
ck G
row
th V
elo
city, v (
ms
-1)
Applied Strain Energy Release Rate, G (J m-2)
E: 11.5GPa
k: 4.0
Temp: 25oC
90%RH
Humidity range Gth [J/m2]
20 – 70% RH 0.005
1-90% RH 0.019
0.1-90% RH 0.028
predictions
consistent with measurements
~1018 bonds/m2
humidity low
humidityhigh
2
2lnOH
OH
SiOSithP
PkTNG
ΔGth~ 0
Matsuda, Dauskardt, et al., Acta Materialia, 2012
Silicon carbide hybrid glasses
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How Sensitivity to Moisture-Assisted Cracking Change with Si-O-Si Bond Density?
O
H
Si
Si
C
C
Matsuda, King, Dauskardt, to appear in Thin Solid Films
600 800 1000 1200
Absorb
ance (
a.u
.)
Wavenumber (cm-1)
O
divalent
Si-O-Si/Si-CH2-Si Si-C
oxygen at.%
oxygen to ~ 20 at.% moisture sensitive
Oxidized a-SiC:H films
Technological motivation O-doping for tailoring electrical/optical properties
1.0 1.5 2.0 2.5 3.0 3.510
-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
20% RH
70% RH
a-SiCO:H-1
xXPS
oxygen: 10.3 at.%
E: 15.2 GPa
25 oC
Cra
ck g
row
th v
elo
city, v (
m s
-1)
Applied strain energy release rate, G (J m-2)
Gth 1.0 1.5 2.0 2.5 3.0 3.5
10-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
20% RH
70% RH
a-SiCO:H-6
xXPS
oxygen: 20.0 at.%
E: 30.3 GPa
25 oC
Cra
ck g
row
th v
elo
city,
v (
m s
-1)
Applied strain energy release rate, G (J m-2)
Gth 1.0 1.5 2.0 2.5 3.0 3.5
10-12
10-11
10-10
10-9
10-8
10-7
10-6
10-5
10-4
20% RH
70% RH
a-SiCO:H-3
xXPS
oxygen: 11.1 at.%
E: 15.5 GPa
25 oC
Cra
ck g
row
th v
elo
city,
v (
m s
-1)
Applied strain energy release rate, G (J m-2)
Gth
increasing sensitivity
ρSi-O-Si: 5.8 nm-3 ρSi-O-Si: 8.6 nm-3 ρSi-O-Si: 23.9 nm-3
Matsuda, King, Oliver, Dauskardt, in review
Moisture Sensitivity and Si-O-Si Bond Density
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0 5 10 15 20 25 30
0.0
0.1
0.2
0.3
0.4
0.5
G
th (
J m
-2)
Si-O-Si bond density, Si-O-Si
(bond nm-3)
Gth
= 0.0225exp(0.1038Si-O-Si
)
humidity low
humidityhigh
2
2lnOH
OH
SiOSithP
PkTNG
new atomistic model
0 5 10 15 20 25 30
0
20
40
60
80
new atomistic model
NS
i-O
-Si (
bonds n
m-2)
Si-O-Si Bond Density, Si-O-Si
(bonds nm-3)
NSi-O-Si
Moisture Sensitivity and Si-O-Si Bond Density
Matsuda, King, Oliver, Dauskardt, in review
0 5 10 15 20 25 30
0
20
40
60
80
planar crack model
NSi-O-Si
= 2/3
Si-O-Si
new atomistic model
NS
i-O
-Si (
bonds n
m-2)
Si-O-Si Bond Density, Si-O-Si
(bonds nm-3)
Matsuda, King, Oliver, Dauskardt, in review
Si SiCN
SiCN
film
Si SiCN
SiCN
…disproportionate number of Si-O-Si bonds ruptured in moisture-assisted cracking…
humidity low
humidityhigh
2
2lnOH
OH
SiOSithP
PkTNG
new atomistic model
0 5 10 15 20 25 30
0.0
0.1
0.2
0.3
0.4
0.5
G
th (
J m
-2)
Si-O-Si bond density, Si-O-Si
(bond nm-3)
Gth
= 0.0225exp(0.1038Si-O-Si
)
NSi-O-Si
Moisture Sensitivity and Si-O-Si Bond Density
1/12/2013
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0 5 10 15 20 25 30
0
20
40
60
80
planar crack model
NSi-O-Si
= 2/3
Si-O-Si
new atomistic model
NS
i-O
-Si (
bonds n
m-2)
Si-O-Si Bond Density, Si-O-Si
(bonds nm-3)
Si SiCN
SiCN
film
Si SiCN
SiCN
…disproportionate number of Si-O-Si bonds ruptured in moisture-assisted cracking…
Si
O
C
O
O
O
Si
crack path meandering
5.76 eV
planer path 7.54 eV
bond energies (Wiederhorn 1980) • Si-C: 4.66eV
• Si-O (moist) : 1.44 eV
Moisture Sensitivity and Si-O-Si Bond Density
NSi-O-Si
Matsuda, King, Oliver, Dauskardt, in review
Atomistic Crack Path Meandering in MD
Matsuda, Oliver, King, Dauskardt, in review
max-flow min-cut theorem (Ford, 1956), Oliver (2010)
generate molecular structure
mathematically count ruptured bonds
O
H
Si
Si
C
C
bond length & angles: crystalline SiC oxygen: ~17 at.%
1/12/2013
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Atomistic Crack Path Meandering in MD
Matsuda, Oliver, King, Dauskardt, in review
max-flow min-cut theorem (Ford, 1956), Oliver (2010)
generate molecular structure
mathematically count ruptured bonds
O
H
Si
Si
C
C
bond length & angles: crystalline SiC oxygen: ~17 at.%
change bond strength
Si-O Si-C
Atomistic Crack Path Meandering in MD
0.0 0.5 1.0 1.5 2.00
1
2
3
4
5total bond ruptured
Si-C bonds ruptured
Ru
ptu
red
bo
nd
s (
bo
nd
s n
m-2)
Ratio of Si-O to Si-C bond strength
Si-O bonds ruptured
moist environment
reducing Si-O bond strength
Matsuda, Oliver, King, Dauskardt, in review
change bond strength
Si-O Si-C
max-flow min-cut theorem (Ford, 1956), Oliver (2010)
generate molecular structure
mathematically count ruptured bonds
1/12/2013
24
Plasticity can be conferred to silicon carbide hybrid glasses by incorporating sp3 C chains. – plasticity is tunable. – plasticity improves adhesion at adjacent interfaces.
Silicon carbide hybrid glasses still exhibit low sensitivity to moisture-assisted cracking. – trace Si-O-Si bonds were responsible for this little sensitivity. eliminating Si-Hx bonds can lead to a complete insensitivity.
Key Findings
Motivation
Experimental Methods
Mechanical Properties of Silicon Carbide Hybrid Glasses – role of glass network connectivity and plasticity – toughening interface by adjacent plasticity – moisture-assisted cracking
Silicon carbide hybrid glasses as New Low-k Dielectrics
Summary
Outline
1/12/2013
25
Leveraging from fundamental research to develop new low-k Moisture-insensitivity
no Si-O and Si-Hx bonds total insensitivity
sp3 CHx chains toughness
Mechanically stiffer Thermally and chemically stable
process compatible (up to 400oC)
Little bond polarity lower dielectric constant using less porosity
Silicon Carbide Based Low-k Dielectrics
Silicon Carbide Based Low-Dielectrics
• sp3 C chains • no Si-O bonds • no Si-Hx bonds • k=as low as 2.3 without additional porosity • thermal/chemical stability • hydrophobic (>110o) • a low-leakage current < 2 x 10-9 Amp/cm2 at 1MV/cm • high breakdown voltage > 5MV/cm • good adhesion with Cu and SiO2
Matsuda, Interrante, Dauskardt, Dubois, et al., ACS Applied Materials & Interfaces Interrante, Ramanath, et al. Phys Chem Lett 2010, 1, 336 Interrante, Ramanath, Acs Appl Mater Inter 2010, 2, 1275. Interrante et al., Dalton Trans., 39, 9193, 2010
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26
process
Silicon Carbide Based Low-Dielectrics
ring opening reaction
disilacyclobutane (DSCB) rings
250-300oC
3500 3000 2500 2000 1500 1000
Ab
so
rba
nce
(a
.u.)
Wavenumber (cm-1)
Cure time: 1h
Si-Hx 400 oC
DSCB ring
C-Hx
Si-CH2-Si
300 oC
200 oC
FTIR
good thermal stability ~ 400 oC
solution process
Matsuda, Interrante, Dauskardt, Dubois, et al., ACS Applied Materials & Interfaces
Excellent Mechanical Properties
2 3 4 5 6 7 8 9 10 110
1
2
3
4
Me
ch
an
ica
l T
ou
gh
ne
ss (
J/m
2)
Mechanical Stiffness (GPa)
Our new low-k
CDO low-k
MSSQ low-k
Matsuda, Interrante, Dauskardt, Dubois, et al., ACS Applied Materials & Interfaces
Young’s modulus, E (GPa)
Fra
ctu
re e
nerg
y, G
c (J m
-2)
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27
Sensitivity to Moisture-Assisted Cracking
1.5 2.0 2.5 3.0 3.5 4.010
-10
10-9
10-8
10-7
10-6
10-5
10-4
Cra
ck G
row
th R
ate
, da/d
t (m
s-1)
Crack Driving Force, G (J m-2)
25oC
85%
30%
silica-based low-k
Matsuda, Interrante, Dauskardt, Dubois, et al., ACS Applied Materials & Interfaces
1.5 2.0 2.5 3.0 3.5 4.010
-10
10-9
10-8
10-7
10-6
10-5
10-4
Cra
ck G
row
th R
ate
, da/d
t (m
s-1)
Crack Driving Force, G (J m-2)
25oC
new low-k
20% 70%
85%
30%
silica-based low-k
Silica-based low-k • high sensitivity to moisture-
assisted cracking
Silicon carbide low-k • insensitivity to moisture-
assisted cracking • crack growth is due to
viscoelastic relaxation of sp3 C-C chains
water molecule
crack tip stress
chain slip and disentanglement
Sensitivity to Moisture-Assisted Cracking
Matsuda, Interrante, Dauskardt, Dubois, et al., ACS Applied Materials & Interfaces
1/12/2013
28
Important roles of connectivity and plasticity in mechanical properties of silicon carbide hybrid glasses
Summary
Fracture properties/toughening Elastic properties
Toughening interface using adjacent plasticity
Moisture-assisted cracking in silicon carbide hybrid glasses
Summary
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New material development leveraging from fundamental research.
Summary
2 3 4 5 6 7 8 9 10 110
1
2
3
4
Mech
an
ica
l T
oug
hn
ess (
J/m
2)
Mechanical Stiffness (GPa)
Advisor: Prof. Reinhold H. Dauskardt
Collaborators: – Drs. Sean King, Jessica Xu, Jeff Bielefeld (Intel) – Drs. Geraud Dubois, Theo Frot, Willi Volksen (IBM Almaden) – Prof. Jonathan Stebbins, Dr. Namjun Kim, Ill Ryu (Stanford) – Prof. Leonard Interrante (Rensselaer Polytechnic Institute)
Dauskardt group: – Mark Oliver (Dow Electronic Materials), Taek-Soo Kim (KAIST), Jeff
Yang, Tissa Mirfakhrai, Scott Issacson
Supports – Department of Energy, Semiconductor Research Corporation – Stanford Graduate Fellowship, Heiwa Nakajima Foundation,
Nakagawa/Mitani Fellowship
Acknowledgement