Lecture 13.

Chemical Mechanical Polishing

What is CMP?
 Polishing of Layer
to Remove a
Specific Material,
e.g. Metal,
dielectric
 Planarization of IC
Surface Topology
CMP Tooling
 Rotating Multi-head
Wafer Carriage
 Rotating Pad
 Wafer Rests on Film
of Slurry
 Velocity= -
(WtRcc)–[Rh(Wh –Wt)]
 when Wh=Wt
Velocity = const.
Slurry
 Aqueous Chemical Mixture
– Material to be removed is soluble in liquid
– Material to be removed reacts to form an oxide
layer which is abraded by abrasive
 Abrasive
– 5-20% wgt of ~200±50nm particles
• Narrow PSD, high purity(<100ppm)
• Fumed particle = fractal aggregates of spherical
primary particles (15-30nm)
Pad Properties
 Rodel Suba IV
 Polyurethane
– tough polymer
• Hardness = 55
– Fiber Pile
• Specific Gravity = 0.3
• Compressibility=16%
• rms Roughness =
30μm
– Conditioned
 Heuristic Understanding of CMP
 Preston Equation(Preston, F., J. Soc. Glass Technol., 11,247,(1927).

– Removal Rate = Kp*V*P

• V = Velocity, P = pressure and Kp is the proportionality constant.
CMP Pad Modeling
 Pad Mechanical Model - Planar Pad
• Warnock,J.,J. Electrochemical Soc.138(8)2398-
402(1991).

 Does not account for Pad Microstructure

CMP Modeling y
Papplied
D

Wafer

Slurry h(x)
x
Pad
U

 Numerical Model of Flow under

Wafer
– 3D-Runnels, S.R. and Eyman, L.M., J. Electrochemical
Soc. 141,1698(1994).
– 2-D-Sundararajan, S., Thakurta, D.G., Schwendeman,
D.W., Muraraka, S.P. and Gill, W.N., J. Electrochemical
Soc. 146(2),761-766(1999).
Abrasive in 2D Flow Model
 In the 2-D approach the effect of the slurry and
specifically the particles in the slurry is reduced
to that of an unknown constant, , determined by
experimental measurements
Polishing Rate with Abrasive
 1    w CA
Polishing Rate without Abrasive
 where w is the shear stress at the wafer surface
and CA is the concentration of abrasive.

Sundararajan, Thakurta, Schwendeman, Mararka and Gill,

J. Electro Chemical Soc. 146(2),761-766(1999).
Copper Dissolution

 Solution Chemistry
– Must Dissolve
Surface Slowly
without Pitting
 Supersaturation
Effect of Particles on CMP is Unknown.

 Effect of Particles on
CMP
– Particle Density
– Particle Shape &
Morphology
– Crystal Phase
– Particle Hardness &
Mechanical Properties
– Particle Size Distribution
– Particle Concentration
– Colloid Stability
Particle Effects
-Aggregated Particles are used

SSA(m2/gm) Phase(%alpha)Primary Diameter(nm)Agg. Diameter(nm)W Rate(nm/min.) Selectivity(W/SiO2)

55 80% 27.5 86 485 50
85 40% 17.8 88 390 110
100 20% 15.1 87 370 NA
Indentation

CL
CR

Plastic Damage
Elastic Behavior Brittle Damage
Layer Hardness Effects
 Effect of Mechanical
Properties of
Materials to be
polished

 Relationship of pad,
abrasive and slurry
chemistry needed for
the materials being
polished.
Pad Conditioning
 Effect of Pad on CMP
• Roughness
increases Polishing
Rate
– Effect of Pad
Hardness
&Mechanical
Properties
– Effect of
Conditioning
– Reason for Wear-out
Rate
Mass Transfer-
Bohner, M. Lemaitre, J. and Ring, T.A., "Kinetics of Dissolution of -
tricalcium phosphate," J. Colloid Interface Sci. 190,37-48(1997).

 Driving Force for dissolution,

– C-Ceq=Ceq(1-S)
– S=C/Ceq
 Different Rate Determining Steps
– Diffusion - J(Flux) = kcCeq (1-S)
– Surface Nucleation
• Mono - J  exp(1-S)
• Poly - J  (1-S)2/3 exp(1-S)
– Spiral(Screw Dislocation) - J  (1-S)2
Macro Fluid Flow
 Continuity Equation
 Navier Stokes Equation (Newtonian Fluid)
– Rotation of Wafer (flat)
– Rotation of Pad (flat)
• Sohn, I.-S., Moudgil, B., Singh, R. and Park, C.-W., Mat. Res. Soc.
Symp. Proc. v 566, p.181-86(2000)
Velocity Vector Field Velocity Vector Field
Near Wafer Surface

( Ux, Uy ) Wafer Surface ( Ux, Uy ) Pad Surface

Tufts University
Expt. Results
 Pseudo-2D Macro Flow Model
x = Rw - r
 Velocity field in the
gap near edge of
wafer
Velocity Field
 y  y  y 
cerf ( )  cerf (  )  cerf (  ) 
x x x x x
 2   2   2  
 V V  V  V  V 
Vx  V  
cerf ( 2  y
)  cerf (
2

y
)  ... 
 x x x x 
  2   2  
 V V V V 
y 
 and 1 
x x
2 2
V V

Shear Rate
1/ 2
Rww  r  p r  
2 2
L   p L
   (  cos )    sin   
  Rw w Rw Rw   w Rw   Across Gap

Solution Complexation-
Chen, Y. and Ring, T.A., "Forced Hydrolysis of In(OH)3- Comparison of
Model with Experiments" J. Dispersion Sci. Tech., 19,229-247(1998).

 Solutions are Not Simple but Complex

 Complexation Equilibria
– i M+m + j A-a  [Mi Aj](im-ja)
– Kij ={[Mi Aj](im-ja)}/{M+m}i {A-a }j {}=Activity
– Multiple Anions - A, e.g. NO3-, OH-
– Multiple Metals - M, e.g. M+m, NH4+, H+
 Complexation Needed to Determine the
Equilibrium and Species Activity,{}i=ai
 Silica Dissolution - Solution Complexation

SiO2(c) + H2O <---> Si(OH)4 Amorphous SiO2 dissolution

Si(OH)4 + H+1 <---> Si(OH)3·H2O+1 pKo= -2.44 ΔHo= -16.9 kJ/mole

Si(OH)4 + OH-1 <---> H3SiO4-1 + H2O pK1= -4.2 ΔH1= -5.6 kJ/mole

Si(OH)4 + 2 OH-1 <---> H2SiO4-2 + 2 H2O pK2= -7.1 ΔH2= -6.3 kJ/mole

4Si(OH)4 + 2 OH-1 <---> Si4O6(OH)6-2 + 6 H2O pK3= -12.0 ΔH3= -12 kJ/mole

4Si(OH)4 + 4 OH-1 <---> Si4O4(OH)4-4 + 8 H2O pK4=~ -27

Solution Complexation

H3SiO4-1

Si(OH)3·H2O+1 Si(OH)40
Copper CMP uses a More
Complex Solution Chemistry
 K3Fe(CN)6 + NH4OH
– Cu+2 Complexes
• OH- - i:j= 1:1, 1:2, 1:3, 1:4, 2:2, 3:4
• NO3- -weak
• NH3 - i:j= 1:1, 1:2, 1:3, 1:4, 2:2, 2:4
• Fe(CN)6-3 - i:j=1:1(weak)
• Fe(CN)6-4 - i:j=1:1(weak)
– Cu+1 Complexes
Copper Electro-Chemistry
 Reaction-Sainio, C.A., Duquette, D.J., Steigerwald, J.M., Murarka, J.
Electron. Mater., 25,1593(1996).

Cu  Fe(CN )36  2 NH3 

  Cu( NH3 )2  Fe(CN )64
EQ K

 Activity Based Reaction Rate-Gutman, E.M.,

“Mechanochemistry at Solid Surfaces,” World Scientific Publishing, Singapore, 1994.
~
A
 a j j  k2  a j j  k2 a j
  j
J ( Flux )  k1 exp(  1)
j  reac tan ts j  products j Rg T
– k”=reaction rate constant 1=forward,2=reverse
– aj=activity, j=stociometry, μj =chemical
potential
– Ã =Σνjμj =Overall Reaction Affinity
 Chemical Potential

 Mineral Dissolution
 i   io  Rg T ln ai   io  Rg T ln  i ci
 Metal Dissolution
 i   io  Rg T ln ai  zi    io  RgT ln  i ci  zi 
 ø=Electrode Potential
 =Faraday’s Constant
Fluid Flow y
Papplied
D

Wafer

Momentum Balance Slurry h(x)

x

 Newtonian U
Pad

Lubrication Theory

0   P   u( x, y)
2

 Non-Newtonian
Fluids
0   P    ( )u( x, y)
2
CMP Flow Analogous to Tape Casting
-RING T.A., Advances in Ceramics vol. 26", M.F. Yan, K. Niwa, H.M. O'Bryan and W. S. Young, editors ,p. 269-576,
(1988).

 Newtonian Yc=0,
– Flow Profile depends upon Pressure
 Bingham Plastic, Yc0
Wall Shear Rate, w
 Product of
– Viscosity at wall shear stress
– Velocity Gradient at wall
Slurries are Non-Newtonian Fluids

 Crossian Fluid- Shear Thinning

Mass Transfer into Slurries
 No Known Theories!

 2-D CMP Model gives this Heuristic

PolishingR atewithAbrasive
 1   wC A
PolishingR atewithoutAbrasive

 Wall Shear Stress, w and Abrasive

Concentration, CA are Important!
Mechanical Properties
 Elastic Deformation
 Plastic Damage
 Plastic Deformation
– Scratching
 Abrasive Particles Cause Surface Stress
A. Evans “Mechanical Abrasion”

 Collisions with Wafer Surface

Cause Hertzian Stress Hertzian Stress, sigma/Po

 Collision Rate ?

 Stress Due To Collision

 P[ =(H tan2 )1/3 Uk2/3] is the peak load (N) due to the
N
incident kinetic energy of the particles, Uk,The load is
spread over the contact area
Mechanical Effects on Mass
Transfer
 Chemical Potential-Gutman, E.M., “Mechanochemistry at
Solid Surfaces,” World Scientific Publishing, Singapore, 1994.

– Mineral Dissolution
 i   io  Rg T ln ai  Vm
  ln( X i )   (Vˆi  Vi ,m )
  
  T Rg T
– Metal Dissolution
 i   io  Rg T ln ai  zi   Vm
Effect of Stress on Dissolution
Metals Mineral-CaCO3
Mechano-Chemical Effect
– Effect on Chemical Potential of solid
– Effect of Activity of Solid
 As a result, Dissolution Rate of Metal
and Mineral are Enhanced by Stress.
Oxidation of Metal Causes Stress
 Stress, i = E i (P-B i – 1)/(1 - i)
• P-Bi is the Pilling-Bedworth ratio for the
oxide
Hertzian Hertzian Shear Stres s , T au/Po

Shear Stress

 Delatches the Oxide Layer M

 Weak Interface Bond

CL h

b
Lateral
Cracks

 CL=0.096 (E/H)2/5 Kc-1/2 H-1/8 [ 1- (Po/P)1/4]1/2 P5/8

• A. Evans, UC Berkeley.
CMP Problems
 Defectivity
– WIWNU
– Dishing and Erosion
– Line Erosion
– Scratching
Scratching Cases

 Rolling Indenter
 Line Scratches
– Copper Only
– Copper & ILD
 Chatter Scratches
 Uncovery of Pores 120 microns