1. Introduction and application.

2. Dopant solid solubility and sheet resistance.

3. Microscopic view point: diffusion equations.
4. Physical basis for diffusion.
5. Non-ideal and extrinsic diffusion.
6. Dopant segregation and effect of oxidation.
7. Manufacturing and measurement methods.
Chapter 7 Dopant Diffusion
1
NE 343: Microfabrication and thin film technology
Instructor: Bo Cui, ECE, University of Waterloo; http://ece.uwaterloo.ca/~bcui/
Textbook: Silicon VLSI Technology by Plummer, Deal and Griffin
Base Emitter Collector
p
p
n+
n-
p+ p+
n+ n+
BJT
p well
NMOS
Doping in MOS and bipolar junction transistors
Doping is realized by:
Diffusion from a gas, liquid or solid source, on or above surface. (no longer popular)
Ion implantation. (choice for todays IC)
Nowadays diffusion often takes place unintentionally during damage annealing
Thermal budget thus needs to be controlled to minimize this unwanted diffusion.
2
In this chapter, diffusion means two very different concepts: one is to dope the substrate from
source on or above surface the purpose is doping; one is diffusion inside the substrate the
purpose is re-distribute the dopant.
Application of diffusion
In the beginning of semiconductor processing, diffusion (from gas/solid phase
above surface) was the only doping process except growing doped epitaxial layers.
Now, diffusion is performed to:
Obtain steep profiles after ion implantation due to concentration dependent
diffusion.
Drive-in dopant for wells (alternative: high-energy implantation), for deep p-n
junctions in power semiconductors, or to redistribute dopants homogeneously
in polysilicon layers.
Denude near-surface layer from oxygen, to nucleate and to grow oxygen
precipitates.
Getter undesired impurities.
Diffusion is the redistribution of atoms from regions of high concentration of mobile
species to regions of low concentration.
It occurs at all temperatures, but the diffusivity has an exponential dependence on T.
3
Doping profile for a p-n junction
4
Diffusion from gas, liquid or solid source
Pre-deposition (dose control) Drive-in (profile control)
Silicon dioxide is used as a mask against impurity diffusion in Silicon.
The mixture of dopant species, oxygen and inert gas like nitrogen, is passed over the
wafers at order of 1000
o
C (900
o
C to 1100
o
C) in the diffusion furnace.
The dopant concentration in the gas stream is sufficient to reach the solid solubility
limit for the dopant species in silicon at that temperature.
The impurities can be introduced into the carrier gas from solid (evaporate), liquid
(vapor) or gas source.
5
Pre-deposition
Drive-in
Comparison of ion implantation with solid/gas phase diffusion
6
1. Introduction and application.
2. Dopant solid solubility and sheet resistance.
3. Microscopic view point: diffusion equations.
4. Physical basis for diffusion.
5. Non-ideal and extrinsic diffusion.
6. Dopant segregation and effect of oxidation.
7. Manufacturing and measurement methods.
Chapter 7 Dopant Diffusion
NE 343 Microfabrication and thin film technology
Instructor: Bo Cui, ECE, University of Waterloo
Textbook: Silicon VLSI Technology by Plummer, Deal and Griffin
7
Dopant solid solubility
Solid solubility: at equilibrium, the maximum concentration for an impurity
before precipitation to form a separate phase.
Figure 7-4
8
Solid solubility of common impurities in Silicon
9
Solubility vs. electrically active dopant concentration
Not all impurities are electrically active.
As has solid solubility of 210
21
cm
-3
.
But its maximum electrically active dopant concentration is only 210
20
cm
-3
.
V: vacancy
Figure 7-5
10
As in
substitutional
site, active
Inactive
Resistance in a MOS
For thin doping layers, it is convenient to find the resistance from sheet resistance.
Figure 7-1
11
A
l
R =
A
l
j
S
x
R R

= =
w
x
j
j
S
x
R

=
Sheet resistance R
S
: (bulk) resistivity
x
j
: junction depth, or film thickness
w
l
R
w
l
x wx
l
A
l
R
S
j j
= = = =


R=R
s
when l=w (square)
Figure 7-2
Ohms law:
Mobility :
By definition:
Therefore:
Finally:
Where:
E J

o =
( )
p n
p n q o + =
J E

=
E v

=
( )
n h
v n v p q J

=
|
|
.
|

\
|
+ =
|
.
|

\
|
=
x
nx
x
hx n h
E
v
n
E
v
p q
E
v
n
E
v
p q

o
x
hx
p
E
v
=
x
nx
n
E
v
=
Important formulas
o: conductivity; : resistivity; J: current density; E: electrical field
v: velocity; q: charge; n, p: carrier concentration.
13
Sheet resistance
Q q Nx q x x
R
j j j
S
o
1 1 1
= = = =
N is carrier density, Q is total carrier per unit area, x
j
is junction depth
( ) | | ( ) | |
}

= = =
j
x
B
j j
S
dx x n N x n q
x x
R
0
1 1

For non-uniform doping:

This relation is calculated to generate the so-called Irvins curves.
See near the end of this slide set.
14
1. Introduction and application.
2. Dopant solid solubility and sheet resistance.
3. Microscopic view point: diffusion equations.
4. Physical basis for diffusion.
5. Non-ideal and extrinsic diffusion.
6. Dopant segregation and effect of oxidation.
7. Manufacturing and measurement methods.
Chapter 7 Dopant Diffusion
NE 343 Microfabrication and thin film technology
Instructor: Bo Cui, ECE, University of Waterloo
Textbook: Silicon VLSI Technology by Plummer, Deal and Griffin
15
Diffusion from a macroscopic viewpoint
Ficks first law of diffusion
F is net flux.
( )
( )
x
t x C
D t x F
c
c
=
,
,
C is impurity concentration (number/cm
3
), D is diffusivity (cm
2
/sec).
D is related to atomic hops over an energy barrier (formation and migration of mobile
species) and is exponentially activated.
Negative sign indicates that the flow is down the concentration gradient.
This is similar to other laws
where cause is proportional to
effect (Fouriers law of heat flow,
Ohms law for current flow).
Figure 7-6
16
) exp(
0
kT
E
D D
a
i
=
Intrinsic diffusivity D
i
Intrinsic: impurity concentration N
A
, N
D
< n
i
(intrinsic carrier density).
Note that n
i
is quite high at typical diffusion temperatures, so "intrinsic" actually
applies under many conditions. E.g. at 1000
o
C, n
i
=7.1410
18
/cm
3
.
E
a
: activation energy
D
0
(cm
2
/s) E
a
(eV)
B 1.0 3.46
In 1.2 3.50
P 4.70 3.68
As 9.17 3.99
Sb 4.58 3.88
Figure 7-15, page 387
17
A
( ) ( ) | | x A t x C t t x C A A + , ,
( ) ( ) | | ( ) ( ) | | t A t x F t x x F t A t x x F t x F A A + = A A + , , , ,
( ) ( ) | | ( ) ( ) | | t A t x F t x x F x A t x C t t x C A A + = A A + , , , ,
Ficks second law
The change in concentration in a volume element
is determined by the change in fluxes in and out
of the volume.
Within time At, impurity number change by:


During the same period, impurity diffuses in and
out of the volume by:


Therefore:


Or,


Since:


We have:
x
t x F
t
t x C
c
c
=
c
c ) , ( ) , (
( )
( )
x
t x C
D t x F
c
c
=
,
,
( ) ( ) ( )
(

c
c
c
c
=
c
c
=
c
c
x
t x C
D
x x
t x F
t
t x C , , ,
If D is constant:
( ) ( )
2
2
, ,
x
t x C
D
t
t x C
c
c
=
c
c
Figure 7-7
18
x
C
I
=0
C
*
C
s
C
g
SiO
2
Si
0
2
2
=
c
c
=
c
c
x
C
D
t
C
bx a C + =
Solution to diffusion equation
( ) ( )
2
2
, ,
x
t x C
D
t
t x C
c
c
=
c
c
At equilibrium state, C doesnt change with time.
Diffusion of oxidant (O
2
or H
2
O)
through SiO
2
during thermal
oxidation.
19
Gaussian solution in an infinite medium
C0 as t 0 for x>0
C as t 0 for x=0
}C(x,t)dx=Q (limited source)
This corresponds to, e.g. implant a very
narrow peak of dopant at a particular depth,
which approximates a delta function.
( ) ( )
|
|
.
|

\
|
=
|
|
.
|

\
|
=
Dt
x
t C
Dt
x
Dt
Q
t x C
4
exp , 0
4
exp
2
,
2 2
t
Important consequences:
Dose Q remains constant
Peak concentration (at x=0) decreases as 1/ \t
Diffusion distance from origin increases as 2 \Dt
Figure 7-9
20
At t=0, delta
function dopant
distribution.
At t>0
21
( )
|
|
.
|

\
|
=
Dt
x
Dt
Q
t x C
4
exp ,
2
t
Gaussian solution near a surface
A surface Gaussian diffusion can be
treated as a Gaussian diffusion with
dose 2Q in an infinite bulk medium.
Note: Pre-deposition by diffusion can also
be replaced by a shallow implantation step.
1. Pre-deposition
for dose control
2. Drive in for
profile control
Figure 7-10
22
|
|
.
|

\
|
=
|
|
.
|

\
|
=
Dt C
Q
Dt
C
C
Dt x
B
T
B
s
j
t
ln 2
ln 2
( )
Dt
Q
t C C
T
S
t
= = , 0
( )
( ) t x C
Dt
x
x
t x C
,
2
,
=
c
c
( )
|
|
.
|

\
|
=
c
c
B
s
j
B
x
C
C
x
C
x
t x C
j
ln
2
,
Gaussian solution near a surface
Surface concentration
decreases with time
Concentration gradient
Junction depth At p-n junction
Error function solution in an infinite medium
An infinite source of material in the half-
plane can be considered to be made up of
a sum of Gaussians. The diffused solution
is also given by a sum of Gaussians,
known as the error-function solution.
This corresponds to, e.g. putting a
thick heavily doped epitaxial layer on a
lightly doped wafer.
At t=0
C=0 for x>0
C=C for x<0.
( )
( )
( )
( )
( )
( ) | | q q
t
q
o
o
o
t
t
d
C
t x C
Dt
x
d
Dt
x
Dt
C
t x C
Dt
x x
x
Dt
C
t x C
Dt x
n
i
i
i
}
}

+

=
=
=

=
(

A =
2
2
0
2
1
2
exp ,
2
4
exp
2
,
4
exp
2
,
( ) ( )
( )
( ) ( )
( )
(

|
.
|

\
|
=

(

|
.
|

\
|
=

}
Dt
x
erf c
C
t x C
x erf x erf c
Dt
x
erf
C
t x C
d z erf
z
2
2
,
1
2
1
2
,
exp
2
0
2
q q
t
erfc: complementary error function
Figure 7-11
23
Error function solution in an infinite medium
Evolution of erfc diffused profile
Important consequences of error function solution:
Symmetry about mid-point allows solution for constant surface concentration to be derived.
Error function solution is made up of a sum of Gaussian delta function solutions.
Dose beyond x=0 continues to increase with annealing time.
Figure 7-12
24
Error function solution in an infinite medium
Properties of Error Function erf(z) and Complementary Error Function erfc(z)
x x
t
2
) ( erf ~
For x << 1
( )
( )
x
x
x
2
exp 1
erfc

=
t
For x >> 1
( ) 0 0 erf =
( ) 1 erf =
( ) ( )
}
=
x
du u x
0
2
- exp
2
erf
t
( ) | |
( )
2
exp
2 erf
x
dx
x d
=
t
( ) | |
( )
2
2
2
exp
4 erf
x x
dx
x d
=
t
( ) ( ) ( )
}

= =
x
du -u x x
2
exp
2
erf 1 erfc
t
}

=
0
1
) ( erfc
t
dx x
( ) 1 0 erfc =
( ) 0 erfc =
25
Boundary condition: C(x,0)=0, x=0; C(0,t)=C
s
; C(,t)=0
Error function solution near a surface
Constant surface concentration at all times, corresponding to, e.g., the situation of
diffusion from a gas ambient, where dopants saturate at the surface (solid solubility).

Constant 1/2
( )
}

= |
.
|

\
|
=
Dt x
u
s
s
du e
C
Dt
x
C t x C
2
2
2
2
erfc ,
t
}

= |
.
|

\
|
=
0
2
2
erfc Dt
C
dx
Dt
x
C Q
s
s
t
Pre-deposition dose
Cs is surface concentration,
limited by solid solubility,
which doesnt change too
fast with temperature.
26

Dt
( )
tot
= D
i
i

t
i
Successive diffusions
Successive diffusions using different times and temperatures
Final result depends upon the total Dt product
( ) ( )
n eff
t t t D Dt + + + = ...
2 1
( ) ... ...
1
2
2 1 1 1 2 2 1 1
+
|
|
.
|

\
|
+ = + + =
D
D
t D t D t D t D Dt
eff
When D is the same (same temperature)
When diffused at different temperatures
As D increases exponentially with temperature, total diffusion (thermal
budget) is mainly determined by the higher temperature processes.
For example, the profile is a Gaussian
function at time t=t
0
, then after further
diffusion for another 3t
0
, the final profile is
still a Gaussian with t=4t
0
=t
0
+3t
0
.
(The Gaussian solution holds only if the Dt used to
introduce the dopant is small compared with the
final Dt for the drive-in i.e. if an initial o/delta
function approximation is reasonable)
27
( ) | | ( ) | |
}

= = =
j
x
B
j j
S
dx x n N x n q
x x
R
0
1 1

Irvins curves
Motivation to generate Irvins curves: both N
B
(background carrier concentration), R
s

(sheet resistance) and x
j
can be conveniently measured experimentally but not N
0
(surface
concentration). However, these four parameters are related by:




Irvins curves are plots of N
0
versus (R
s
, x
j
) for various N
B
, assuming erfc or half-Gaussian
profile. There are four sets of curves for (n-type and p-type) and (Gaussian and erfc).
( )
}
=
j
x
j
dx x
x
0
1
o o
1-
Irvins curves
Four sets of curves: p-type erfc, n-type erfc, p-type half-Gaussian, n-type half-Gaussian
Explicit relationship between: N
0
, x
j
, N
B
and R
S
.
Once any three parameters are know, the fourth one can be determined.
Figure 7-17
1-
Example
Design a boron diffusion process (say for the well or tub of a CMOS process) such that

s
=900O/square, x
j
=3m, with C
B
=110
15
/cm
3
.
From (half-Gaussian) Irvins curve, we find
C
s
<< solubility of B in Si, so it is correct to assume pre-deposition (here by ion
implantation) plus drive-in, which indeed gives a Gaussian profile.
The average conductivity of the layer is
30
( )
|
|
.
|

\
|
=
Dt
x
Dt
Q
t x C
4
exp ,
2
t
( )
2 9
15
17
2
4
2
cm 10 7 . 3
10
10 4
ln 4
10 3
ln 4

=
|
|
.
|

\
|

=
|
|
.
|

\
|
=
B
s
j
C
C
x
Dt
|
|
.
|

\
|
=
Dt
x
C C
j
s B
4
exp
2
Example (cont.)
hours 8 . 6
sec cm 10 5 . 1
cm 10 7 . 3
2 13
2 9
in drive
=

t
2 13 9 17
cm 10 3 . 4 10 7 . 3 10 4

= = = t tDt C Q
s
Assume drive-in at 1100
o
C, then D=1.510
-13
cm
2
/s.
Pre-deposition dose
31
t
Dt
C Q
s
2 =
sec 5 . 5
10 2 . 4 10 5 . 2 2
10 3 . 4
15
2
20
13
dep pre
=

|
|
.
|

\
|


=

t
t
( ) ( )
9
in drive
14
dep pre
10 7 . 3 10 3 . 2

<< Dt Dt
Now if we assume pre-deposition by diffusion from a gas or solid phase at 950
o
C, solid
solubility of B in Si is C
s
=2.510
20
/cm
3
, and D=4.210
-15
cm
2
/s.
The profile of this pre-deposition is erfc function.
However, the pre-deposition time is too short for real processing,
so ion-implantation is more realistic for pre-deposition.
Example (cont.)
32