SP 2005 Lecture19

Outline
6.12J / 3.155J Micr oelectr onic pr ocessing
Electro-chemical deposition
Why electro-chemical deposition?
How does it compare with sputtering, CVD, evaporation?
Excellent step coverage, esp. for small features
Reliability
Yield, Y ∝ e-AD
Failure Probability Density , Meant time to failure
“Infant mortality”, “steady state”, “wear out”
Electromigration
Manifestations of elecro-migration
Causes
Cures
Ap r i l 25 , 2005
ELECTRO-CHEMICAL DEPOSITION
 We saw CVD Gas phase reactants: pg ≈ 1 mTorr to 1 atm.

Good step coverage, T > 350 K
 We saw sputtering Noble (+ reactive gas) p ≈ 10 mTorr; ionized particles

Industrial process, high rate, reasonable step coverage
Extensively used in electrical, optical, magnetic devices.
 We saw evaporation: Source material heated, peq.vap. = ~ 10-3 Torr, pg < 10-6 Torr
Generally no chemical reaction (except in “reactive deposition),
λ = 10’s of meters, Knudsen number NK >> 1
Poor step coverage, alloy fractionation: Δ pvapor
Historical (optical, electrical)
Ap r i l 25 , 2005
ELECTRO-CHEMICAL DEPOSITION
See: Madou, Fundamentals of Microfabrication; Plummer, Sec. 9.3.10
Cathode Anode
Electro-chemical plating: -V +V
Reduction of metallic ions
from aqueous,
Cu+
inorganic salt electrolytes.
Mz+(solution) + ze- ⇒ M(lattice) e-
z electrons supplied
by external power supply
Electroless (autocatalytic) deposition process This is a

(no power supply) battery
reducing agent in the solution is the electron source
Ap r i l 25 , 2005
Why ELECTRO DEPOSITION?
IC processing generally avoids wet processes

Increased use of Electro-depostion
driven by:
1) Cu replacing Al in metallization
Cu is difficult to remove by dry etch,
but is readily deposited electro-chemically
2) MEMS, need for high aspect ratio structures.
Ap r i l 25 , 2005
How ELECTRO DEPOSITION?
Spin-coat
Expose
Photoresist Develop
Seed layer (15-30 nm) Au, Pt, Cu, Ni…
Adhesion layer (5-10 nm) Ti, Cr
(good oxides)
Dielectric substrate
Seed layer becomes cathode;

attracts M+ , coated with M layer
Ap r i l 25 , 2005
ELECTRO DEPOSITION
Cathode Anode
-V +V CuSO4.5H2O
Cu+
At 0.377 V
e-
Film
Ap r i l 25 , 2005
Aside: ELECTRO DEPOSITION vs. SPUTTERING
Cathode
is “target”,
Cathode Anode source material
-V +V P ≈ 10-100 m Torr
cathode anode
Ex
Cu+ - v Ar + v e!
⊕
V ≈ 1 kV
P ≈ 10-100 m Torr
e-
- ⊕
Film
Film
Ap r i l 25 , 2005
Physical process
Cathode Anode dc c(!) " c(0)

-V +V =
dx #
c(") ! c(0)
Cu+ J = ! NqDF
#
e- Faraday Const
Diffusion const.
# electrons in reaction
1-D potential due to concentration diff Cu+ concentration

RT # c(0) & c(x)
! = ln % c∞ Cu+
NF $ c(") ('
At φc, all Cu+ at x = 0 are consumed
c(0) !
Jc is limited by
c"
J c = ! NqDF diffusion and x
# bulk concentration δ
Ap r i l 25 , 2005
Physical process
c"
cCu+(x) J c = ! NqDF
c∞Cu+ #
c0 RT # c(0) &
!c = ln %
NF $ c(") ('
x
! = 2 Dt
) # NF"c & , J
J = J c +1 ! exp % ( . Activation
+* $ RT ' .-
!c current
!
Increased
stirring
Diffusion limited
Electro-deposition
Ap r i l 25 , 2005
ELECTRO DEPOSITION vs. SPUTTERING
Cathode
is “target”,
Cathode Anode source material
-V +V P ≈ 10-100 m Torr
cathode anode
Ex
Cu+ - v Ar + v e!
⊕
V ≈ 1 kV
e-
+ VD.C. + VD.C.
Cu+ Ar+
e- e-
Plasma
High conductivity
Ap r i l 25 , 2005
Feature size dependence
J
Activation This applies to
!c current large substrates: δ/L << 1
! L
δ
Diffusion limited
Electro-deposition
δ
But for small features: δ/L >> 1 L
Ap r i l 25 , 2005
Small features
+V
++++
δ
But for small features: δ/L >> 1 - - - -
+ + + +
-V
L
Electro-deposition is faster,
+V
the smaller the feature
great for vias, step coverage… δ
-V
L
Ap r i l 25 , 2005
Leveling agents
Small organic and inorganic molecules

control Cu interaction with substrate.
These molecules are known generically as
‘accelerators’, ‘levelers’ or ‘inhibitors’.
“Leveling agents” preferentially adhere

on high, convex surfaces,
(not in trenches),
inhibit high-point deposition,
level the film surface.
Ap r i l 25 , 2005
Leveling agents, accelerators, inhibitors
Little is understood concerning how these molecules

affect growing Cu surface, nor with Cu ions in solution.
Polyethylene glycol (PEG)

works via synergy with Cu+ and Cl-.
Most common accelerator, bis(3-sulfopropyol) disulfide (SPS),

interacts with the surface,
increases electron transfer rate across the interface.
Ap r i l 25 , 2005
Applications of electrochemical deposition
printed circuit boards,

magnetic alloys for computer memories,
coatings for hard disk drives,
wear resistant coatings,
corrosion resistant alloys,
metal matrix composites ,
electroreformed laser mirrors,
electrochromic materials,
decorative coatings,
oxides,
organic polymers.
Ap r i l 25 , 2005
Outlook
As the feature size decreases,

present methodology of depositing Cu on Si will change.
Use of a seed layer, deposited by PVD or CVD

will likely be eliminated.
Cu will be directly deposited onto the diffusion barrier,
need development of new bath chemistries.
Possible: direct deposition of Cu onto oxide and nitrides

in various environments.
Ap r i l 25 , 2005
Reliability of semiconductor I Cs
plus Electrodeposition
Read Campbell, p. 425 -428 and Ch. 20. Sec. 20.1, 20.2; Plummer, Sec. 11.5.6
1. IC reliability:
Yield = (# operating parts) / (total # produced)
Failure of devices occurs by various mechanisms:

 Particles on surface interrupt depositions, flaw devices
 Oxides, dielectrics fail by charging or dielectric breakdown,
 Metals fail by corrosion and
Electro-migration:
2. Electromigration:
 Manifestation Hillocks and voids
 Modeling Currents, Thermal gradients, electric fields
Ap r i l 25 , 2005
Reliability of semiconductor I Cs
Why is this an issue?
Net yield is product: Y1 x Y2 x Y3… (e.g., a 10-step process each 95% =>60% yield)
Defect density, D, has decreased

“Learning curve”: yield vs. lot number with succeeding higher-density
dynamic random access memories …
and average over last 7 lots.
Ap r i l 25 , 2005
Killer defects
Defect area density
Simplest yield model assumes independent, randomly-distributed defects,

(Poisson distribution):
A = chip area AD = probability

Yield of defect
Y ! e"AD D = defects/area overlapping
chip
AD Y = (1! G)e!AD(" )
Fraction of disk area
in which all circuits fail
Particle control: Class (Max #/ft3) > 0.5 µm

1 1
10 10
100 100
1000 1000
Ap r i l 25 , 2005
Killer defects
Defect size
Defects are not randomly distributed spatially

(e.g. stress concentrations generate dislocations, stacking faults),
nor randomly distributed by size, δ, i.e. D = D(δ):
Empirical distribution of defect sizes: 1
All fail
!q
1! G
D(! ) = c , 0 < ! < !0
!0q +1
!0p"1
D(! ) = c p , !0 < ! < !max
!
Hard to measure,
Therefore Y ≈ (1-G) exp(-AD)
G is fractional area where all fail
Meander-line
process control
module
Ap r i l 25 , 2005
Wafer size and reliability challenges
Wafers now 300 mm,

soon 450 mm.
Now 5 billion square in. of ckts/yr,

at $25/sq in. => $125 billion/yr
That’s 800 acres, 1 sq. mile
Ckts/wafer
Moore’s law
Ckts/area doubles every 18 mos.
More chips/wafer => more chips

per process cycle
Now 3 yrs
greater demands on deposition uniformity
Ap r i l 25 , 2005
“Perfect storm” in microfabrication
Convergence of 3 simultaneous disruptive events (all on larger wafers):

1) Smaller line-width, conductors, capacitors…
Now λ = 248 nm, KrF excimer => 130 nm lines (Pentium 4)
λ = 193 nm, ArF excimer => 110 nm lines
Soon λ = 157 nm, Ar excimer => 70 nm lines
T < 100 C
2) New materials
Al conductors => Cu (TaN buffer) T < 1000 C
SiO2 dielectrics (3 GHz)
=> lower κ, C-doped SiO2 (5 GHz)
T < 500 C
3) New deposition processes

CVD, PVD now being joined/replaced by
“atomic layer deposition” (ALD)
Ap r i l 25 , 2005
Reliability definitions
Cumulative failure distribution function, F (t): R (t )

1
F (t) = fraction of failures up to time, t. F ( t)
Survival or reliability distribution function, R (t):
R (t )= 1 - F (t ) 0
0 t
Failure probability density function, f (t): f ( t)
f (t) = dF/dt 0
(This is key to predicting failure rates) 0 t
"
Mean time to failure, MTTF: MTTF = # t ! f (t)dt

0
Median time to failure, t50: time after which half of devices have failed.
Ap r i l 25 , 2005
Reliability definitions
1
λ(t)
Failure probability density/number remaining:
λ(t) = f(t)/R(t)
0
0 t
Failure rate during time δt, λ(t):
R(t) " R(t + #t) 1 dR(t) 1 dF(t)
! (t) = =" =
#tR(t) R(t) dt R(t) dt
Failure rate ! (t) = "

1 dR(t)
= const. = ! 0 (fractional failure frequency)
in steady state: R(t) dt
Steady-state survival
Hence: or reliability drops off
R(t) ! e" #0 t exponentially with time
steady state: "
1
f ss (t) =
dF
dt
=!
dR
dt
" #0e! #0 t MTTFss = # t ! f (t)dt = $0
0
Ap r i l 25 , 2005
Different failure processes
Failure rate:
λ (t )
!(t) = !0
0
t
“Infant Steady
mortality” state Wearout
Ea
!
Different failure processes have
different thermally activated rates: r = r0 e kBT
Ap r i l 25 , 2005
Mean time to failure
The mean time to failure (MTTF)

(related to inverse of rate): "n + Ea / kB T
MTTF ! J e
n ≈ 2 to 3.
(Most activated mechanisms of f ailur e have a f or m like this)

Expressed in log form as:
En
ln < t fail >= ln(A) ! nln(J) +
kBT
Plotted vs Log(J), right Log(MTTF)

in which case the slope gives the power, -n.
For increased operating current,

MTTF drops off as the -nth power of J.
For higher operating temperatures,
lifetime curve is shifted down, quicker failure.
log(J)
Or, ln(MTTF -1), mean failure rate, could be plotted vs. 1/T (Arrhenius plot)…
Ap r i l 25 , 2005
Mitigating thermally activated failure
Thermally activated failure rates: Caution on accelerated aging:

Ea
!
r = r0 e kBT Accel. aging
test
Ln(r)
RT
Operate at lower temp.,
Operating
lower current density temperature
Use “burn-out” to elim. early fails

1/kBT
…you may get

wrong activation energy.
Example: electromigration. ..
Ap r i l 25 , 2005
Electromigration: Manifestation
Hillock formation Whisker bridging

two interconnects
4 microns
! = "y E # 10 9 Pa # 2 $10%4 lbs /micron 2 Hillocks and voids
(Current flow )
(Pics: Aluminum films, Bell Labs)
Ap r i l 25 , 2005
Electromigration: electron wind moves atoms
Electromigration: mode of failure in high-current-density heterostructures.

(Most literature on electromigration deals with metallic conductors in semiconductor devices)
J = nqv
Large current density, J => not only charge transport
but also mass transport of
charged particles, e’s or h’s.
When charge carriers collide with atoms (“electron wind”),

they impart a small momentum to atoms,
sweeping them in the direction of the carrier drift.
Ap r i l 25 , 2005
Electromigration: electron wind moves atoms
Electromigration flux of species A, jA = cAvdrift,

requires the force on an ion A
J = nqv
due to the electric current:
F = qZA E = qZA J !
* *
(Z*q . nq v ) ρ
Ion - carrier
interaction
Here q is the electronic charge, ZA* is the effective ion valence

and E is the electric field (force per unit charge)
producing the electric current density, J = E/ρ
Yield stress
of Al is about
! = F / area " 100 GPa
70 GPa
Ap r i l 25 , 2005
Electromigration: grain-boundary diffusion
Most electromigration takes place along grain boundaries.
DA = DA exp[!Ea /(k BT)]

o
DA is the grain boundary diffusion coefficient of A .
(EA typically ≈ 0.5 - 0.8 eV vs. bulk about 1.4 eV)
Flux of species A, JA, is proportional to the product

F = qZA J! ):
*
(volume concentration of A) x (velocity of A resulting from
DA F DA qZA* J!
J A = cA v A = cA = cA
RT RT
Here use Nernst-Einstein equation for drift velocity of a particle

at temperature T under influence of force F: v = DAF/RT.
Ap r i l 25 , 2005
Electromigration: grain-boundary diffusion
DA F DA qZA* J!
J A = cA v A = cA = cA
RT RT
Electromigration is problematic
• at high current density, J
• high resistivity, ρ (many electron-atom collisions),
• for large grain-boundary diffusion, D
• at high T (which is in exponent of DA),
• for light metals (DA0 is inverse function of mass of A)
Ap r i l 25 , 2005
Electromigration damage: due to flux divergence or temperature gradients
Fick's second law of diffusion states that change in concentration of species A

occurs as a result of a divergence in JA, i.e. a variable concentration gradient:
!cA !J A ! 2 cA
=" = DA 2
!t !x !x
Add temperature-dependent term to time rate of change of concentration as follows:
dc A "J A "J A dT
=! !
dt "x "T dx
Isothermal mass transport temperature gradients

due to flux divergence associated with
jA such as at local hot or cold spots
grain boundary junctions. couple with temperature
dependence of JA.
Ap r i l 25 , 2005
Electromigration vs. linewidth/grain size
(Thompson-Frost model)
Yield
w/d50 ≈ 3.0 d50
w/d50
DAc A d#
JA = (qZ*A J ! + " ) w/d50 ≈ 1.3
k BT dx Voids hillocks
Equilibrium: Mass flow
d! qZA* J# , ! = "ax + b
="
dx $ Lp
$& Z* qJ" ' Lp
! max = ±
% # ( 2 w/d50 ≈ 0.3
! crit 2"
JLp <
Z * q#
Ap r i l 25 , 2005
Electromigration summary
electron wind,
mass transport
Voids, depletion
Accumulation, hillocks
Most electromigration takes place 4 microns

along grain boundaries.
Grain boundaries that run parallel to current direction
are most problematic.
A factor cos (θ) is often attached to the atomic flux expression to reflect this fact;
a is the angle between the current and the grain boundary.
Ap r i l 25 , 2005
Summary
Electro-chemical deposition
Need driven by Cu and MEMS
Potential initiates M+ diffusion; diffusion limited
Excellent step coverage, esp. for small features
Reliability
Yield, Y ∝ e-AD
F (t) = fraction of failures up to time, t. Prob. Den: f (t) = dF/dt
Infant mortality, steady state, wear out; different processes
Electromigration
Momentum transfer from charge carriers to atoms
Aggrevated by large J, high T, small mass (Al)
Role of grain boundaries and T gradients
Ap r i l 25 , 2005

SP 2005 Lecture19

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Outline

6.12J / 3.155J Micr oelectr onic pr ocessing

 We saw CVD Gas phase reactants: pg ≈ 1 mTorr to 1 atm.

 We saw sputtering Noble (+ reactive gas) p ≈ 10 mTorr; ionized particles

Electroless (autocatalytic) deposition process This is a

IC processing generally avoids wet processes

but is readily deposited electro-chemically

2) MEMS, need for high aspect ratio structures.

Seed layer becomes cathode;

Cathode Anode dc c(!) " c(0)

1-D potential due to concentration diff Cu+ concentration

Small organic and inorganic molecules

“Leveling agents” preferentially adhere

Little is understood concerning how these molecules

Polyethylene glycol (PEG)

Most common accelerator, bis(3-sulfopropyol) disulfide (SPS),

printed circuit boards,

As the feature size decreases,

Use of a seed layer, deposited by PVD or CVD

Possible: direct deposition of Cu onto oxide and nitrides

Failure of devices occurs by various mechanisms:

Defect density, D, has decreased

Simplest yield model assumes independent, randomly-distributed defects,

A = chip area AD = probability

Particle control: Class (Max #/ft3) > 0.5 µm

Defects are not randomly distributed spatially

Wafers now 300 mm,

Now 5 billion square in. of ckts/yr,

That’s 800 acres, 1 sq. mile

More chips/wafer => more chips

Convergence of 3 simultaneous disruptive events (all on larger wafers):

Soon λ = 157 nm, Ar excimer => 70 nm lines

3) New deposition processes

Cumulative failure distribution function, F (t): R (t )

Failure probability density function, f (t): f ( t)

Mean time to failure, MTTF: MTTF = # t ! f (t)dt

Failure rate ! (t) = "

The mean time to failure (MTTF)

(Most activated mechanisms of f ailur e have a f or m like this)

Plotted vs Log(J), right Log(MTTF)

For increased operating current,

Thermally activated failure rates: Caution on accelerated aging:

Use “burn-out” to elim. early fails

…you may get

Hillock formation Whisker bridging

Electromigration: mode of failure in high-current-density heterostructures.

When charge carriers collide with atoms (“electron wind”),

Electromigration flux of species A, jA = cAvdrift,

Here q is the electronic charge, ZA* is the effective ion valence

Most electromigration takes place along grain boundaries.

DA = DA exp[!Ea /(k BT)]

DA is the grain boundary diffusion coefficient of A .

(EA typically ≈ 0.5 - 0.8 eV vs. bulk about 1.4 eV)

Flux of species A, JA, is proportional to the product

Here use Nernst-Einstein equation for drift velocity of a particle

Fick's second law of diffusion states that change in concentration of species A

Isothermal mass transport temperature gradients

Most electromigration takes place 4 microns

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