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Doping techniques

Doping by diffusion

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Introduction to doping techniques


In the whole ingot (bulk):
During the fabrication (Czochralsky), adding impurities to the melt
In the epitaxial layer:
D i th
During
the epitaxial
it i l process, adding
ddi d
doping
i species
i (b
(beam, gas, etc)
t )

After epitaxial growth, in selected areas:


Doping
p g by
y diffusion
Doping by ion implantation

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Need of selective doping


Example: fabrication of a device (p-n junction)
UV light
SiO2

n-type Si

SiO2

n-type Si

SiO2

n-type Si

6. Resist removal

3. Exposure
SiO2

SiO2
SiO2

n-type Si
1. Oxidation

n-type Si

n-type Si
4. Developing

Resist
SiO2

n-type Si
2 Photoresist
2.

SiO2

n-type Si
5. Etching

SiO2

7. Selective doping

SiO2
SiO2

Si:p
p

n-type Si

Si:p

SiO2

8. Metallization

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Doping by diffusion
General technique for diffusion
The wafers are introduced in a furnace where an inert gas containing the
doping species is flowing
Case of Silicon: B for p type and As or P for n type:
Solid sources: BN,

As2O3, P2O5

(Spin-on-glass, SiO2+dopant oxide)

Liquid sources: BBr3, AsCl3, POCl3 ((Phosphrous Oxychloride)


y
)
Gas sources:

B2H6, AsH3,

PH3

The dopant atoms diffuse into the silicon due to their high solubility and
the substrate temperature (diffusivity).

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Doping by diffusion
Doping
p g from a p
powder using
g
a source furnace (solid source)

Doping from a liquid source

Doping from a gaseous source

Flow meter
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Doping by diffusion

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Doping by diffusion
Industrial furnaces for production

Horizontal furnace
Vertical furnace
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Doping by diffusion

Comparison

Feature

Horizontal

Vertical

Heat up speed

slower

faster

Quartz boat loading time

slower

faster

Cool down speed

equal

equal

Maximum Temperature

1100C

1250C

Temperature uniformity

lower

higher

Flexibility: Run mixed diameter of wafers in one run

possible

not possible

Flexibility:
y Rungdifferent diameter of wafers run to run
processed

possible

not possible

St k wafer
Stock
f cassettes
tt

3" - 6" (8")

4" - 300mm 12

no

yes

lower

very high

>150 wafer

100 - 150 wafer

Power consumption

high

lower

Price

low

high

Automation level
Capacity

In general vertical furnaces are used for mass production


Horizontal furnaces are used for research

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Diffusion Theory
In a concentration gradient, particles flow along the direction where the
particle density is lower (statistical process)

In the region with lower concentration the


atoms mean free path is higher.

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Diffusion Theory
Flux (F) : number of dopant atoms
passing through a unit area per unit
time.
The number of atoms inside the
differential volume (dV) per unit time is
expressed as:
[F( x ) F( x dx
d )] A
dV

This can also be expressed as:


dn
(A dx )
dt
n = dopant concentration per unit volume

Therefore:

dn
(A dx ) A [F( x ) F( x dx )]
dt

dn
dF

dt
dx

One dimensional
continuity equation
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Diffusion Theory
1st Ficks diffusion law

o
o
o
o

n
F D
x

Negative sign because flux goes


in the direction in which the
concentration decreases

The driving force for the atoms to diffuse is the concentration gradient
The flux is proportional to this gradient
The proportionality constant is the diffusion coeficient (D) expressed in cm2 /sec.
/sec
The atoms move (diffuse) from a high concentration region towards a lower concentration region

D is the difussion coefficient which depends on:


Material (substrate)
Crystal orientation (substrate)
Species to be diffused (dopant)
Temperature of the substrate

Ea
D D 0 exp

kT

g 1st Ficks law into continuityy equation,


q
, we obtain:
Introducing

dn
dF

d
dt
dx
d

dn
d 2n
D 2
d
dt
d
dx

2nd
d Ficks
c sd
diffusion
us o law
a
(assumes that D is independent of x)
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Diffusivity in Si and GaAs

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Doping by diffusion

Interstitial

Vacancy driven

Low activation energy (lower temperatures)

Higher activation energy (higher temperature)

Dopants at interstitial positions may not be


electrically active

High probability to be electrically active

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Doping by diffusion
Diffusion profiles:
The final diffusion profile is obtained solving the 2nd Ficks
law taking into account the right boundary conditions.

x = depth

wafer
f
There are 2 important cases:

Diffusion
profile

Constant surface concentration (predeposition): The wafer is heated in an


atmosphere with a constant concentration of doping species at the surface.
(infinite source)
Constant total dopant amount (drive-in or redistribution): This process is
carried out after the predeposition. Source is just the material predeposited.
Dopants get deeper into the substrate. (finite source)

Universidad Politcnica de Madrid

Doping by diffusion
Constant surface concentration (infinite source)
Flux of doping species

Boundaryy conditions:
C(x,t) Impurity concentration into the semiconductor

Semiconductor

C(x,0) = 0 At t=0 there are no dopants inside the wafer


C(0,t) = Cs The surface concentration is constant (Cs)
C(,t) = 0 Far from the surface the impurity conc. is equal to 0

Notice that Cs has units of atoms per cm-3

Solution of Ficks equation:


x

2
x
y2

C( x , t ) C S 1
e dy
d CS erfc
f

0
2 Dt

Concentration profile as a
function of depth (x) and time (t)

The total amount of impurities introduced at a time = t:

2
Total amount of impurities as a
CS D t
function of time [atomscm-2]

Notice that Q(t) has units of atoms per cm-2

Q( t ) C( x , t ) dx
0

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Doping by diffusion
Constant surface concentration (predeposition)

x
C ( x, t ) C S erfc

2 D t

2
Q( t ) C( x , t ) dx
d
CS D t

0
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Doping by diffusion
Constant total dopant (drive-in, finite source)
Dopant amount previously established by predeposition (shallow diffusion)

Semiconductor

QT is now constant. Heating the semiconductor will change


the distribution profile but not the total amount of dopants.
Boundary conditions:

QT C ( x, t ) dx

Now Cs changes with time (decreases)

Cs

Total amount of impurities constant at ANY time

QT
Dt

C (
( , t ) 0

Far from the surface the impurity


p y conc. is equal
q
to 0

Notice that QT has units of atoms per cm-2


Solution of Ficks equation:

x2
QT

C( x , t )
exp
Dt
4Dt

Concentration profile (Gaussian) as a


function of depth (x) and time (t).

Notice that C(x,t) has units of atoms per cm-3

Universidad Politcnica de Madrid

Doping by diffusion
Constant total dopant (drive-in, finite source)

x2
QT

C( x , t )
exp
Dt
4Dt

QT
Cs
Dt

Universidad Politcnica de Madrid

Doping by diffusion
Finite source

Diffusion profiles versus


normalized depth.
Example with either source:
Given the C/Cs value and g
get
depth x once D and t are known

Infinite source

QT

or
Give temperature
temperature, time and depth
(x) and determine C/Cs value.
Then determine C, given Cs or QT

QT
Cs
Dt

or

Cs = constant

Universidad Politcnica de Madrid

Doping by diffusion
x

erfc(x)

erfc(x)

21
2,1

0 00297947
0,00297947

0,1

0,887537084

2,2

0,00186285

0,2

0,777297411

2,3

0,00114318

0,3

0,671373241

2,4

0,00068851

04
0,4

0 571607648
0,571607648

25
2,5

0 00040695
0,00040695

0,5

0,479500124

2,6

0,00023603

0,6

0,39614391

2,7

0,00013433

0,7

0,322198807

2,8

7,5013E05

0,8

0,25789921

2,9

4,1098E05

0,9

0,203091887

2,209E05

0,157299265

3,1

1,1649E05

1,1

0,119794959

3,2

6,0258E06

1,2

0,08968604

3,3

3,0577E06

1,3

0,065992071

3,4

1,522E06

1,4

0,047714888

3,5

7,431E07

1,5

0,033894858

3,6

3,5586E07

1,6

0,02365162

3,7

1,6715E07

1,7

0,016209542

3,8

7,7004E08

1,8

0,010909499

3,9

3,4792E08

1,9

0,007209571

1,5417E08

0,004677735

4,1

6,7E09

Tables and useful relationships


p

Diffusion length

LD D t

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Predeposition:
p
an example
p
Carrier concentration profile in a p-n junction.

ND = CB

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Doping by diffusion

Tables and useful relationships

Junction depth:

CB is C bulk

CS is C at the surface

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Intrinsic and extrinsic diffusion


Previous results hold if D is NOT dependent on position (x), what allows
an easy solving of the 2nd Fick equation. This is called intrinsic diffusion.
What determines the change from
intrinsic to extrinsic regime?
Compare dopant concentration with
the INTRINSIC CARRIER density
y
at the diffusion temperature: C(x,t)
with ni (Tdiff)
ni (Tdiff) > C(x,t)

Intrinsic

ni (Tdiff) < C(x,t)

Extrinsic

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Intrinsic and extrinsic diffusion


ni > C(x,t)

Intrinsic

ni < C(x,t)

Extrinsic

D/D
D/D
/Dss(T)
(T)

D dependent on position means


dependent on concentration C(x,t)

C/ni(T)

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Extrinsic diffusion

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Extrinsic diffusion
D ~ C2

Phosporous

D~C

D constant

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Extrinsic diffusion
Junction depth for extrinsic diffusion

Ds t

for D ~ C (

XJ = 1.1

Ds t

for D ~ C2 (

= 2)

XJ = 0.87

Ds t

for D ~ C3 (

= 3)

XJ = 1.6

= 1)

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Use of masks for diffusion


Need of masks to define the diffusion window:
Material
Thickness
Temperature

Problems:
Isotropical diffusion
((lateral and vertical))
Affects design rules

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Use of masks for diffusion

SiO2

Minimum mask thickness?


Depends on :
Mask material
Diffusion species
Diffusion temperature
Diffusion time

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Doping techniques
Doping by ion implantation

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Doping by Ion Implantation


Produce an accelerated beam of dopant ions and bombard the substrate

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Doping by Ion Implantation

300 mm
Si wafers

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Doping by Ion Implantation


Lorentz Law: F = q V x B

Deviation

R = mV/qB

Dose:

Ions/cm2

Penetration depth depends on:


Ion kinetic energy
Ion mass
Energy
E
loss
l
mechanism
h i
Substrate material
Incidence angle (channeling)
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Doping by Ion Implantation


Advantages of Ion Implantation:
Very precise control of dose
Independent control of impurity dose and penetration depth
Very fast process (one 6 wafer takes 6 sec for moderate doses)
Complex profiles can be achieved with multi-energy implants
Less Lateral spreading than diffusion
Wide Range of Dopants Can Be Selected
Room Temperature process (*).
(*) Mask of photoresist
Disadvantages of Ion Implantation:
Very
V
deep
d
and
d very shallow
h ll
profiles
fil are diffi
difficult
l
Not all damage can be removed by annealing
Typically has higher impurity content than diffusion does
Expensive
Safety Hazards - Toxic Gases (AsH3, PH3), High Voltage, Radiation,

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Doping by Implantation
Multi-energy implantation

Mn on ZnO

The impurity profile maximum does nor occur at the surface


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Doping by Ion Implantation

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Doping by Ion Implantation


The ion statistical distribution is:

x R p 2

C ( x)
exp
2

2 p
2 p

Rp
C(Rp)

C(Rp )

0 6 C(Rp)
0.6

S
2 p

C(x)

S = dose (at/cm2)
Rp

Projected range

p (Rp) Projected straggle (std.deviation)


(R) Lateral
L t l straggle
t
l

x = Rp p

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Doping by Ion Implantation

400

Stopping power, S = energy loss per unit length

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Energy loss of the projected ions


R

dE
dE
dx

R dx
Sn ( E ) Se ( E )
S
Sn ( E ) Se ( E )
dx
0

E0

dE
0 S n ( E ) Se ( E )

Collision between nuclei (Coulomb or Rutherford)

snooker
k game
E0
M1

v1

v0
M2

M1

4 M 1M 2
1
2
E for = 0
M 2 v 2
2 0
2
M1 M 2

Sn ( E ) kn E

v2

for low E

M2

Interaction with clouds of electrons (drag)

S e ( E ) ke E 10 (eV )
7

1/ 2

/ cm
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Energy loss of the projected ions

Sn ( E ) kn E

for low E

En
nergy Losss (ev/nm)

Coulomb interaction

S n (E )
Implantation
region

Reduced for high E

Rutherford interaction

At high E, Se dominates (low mass)


At low E Sn dominates

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Energy loss of the projected ions

Electronic
Stopping

Ion Energy
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Doping by ion implantation


R

E0

dE
R dx
S ( E ) Se ( E )
0
0 n

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Doping by ion implantation

Universidad Politcnica de Madrid

Channeling effects
Crystals have directions with low atomic density where the ions penetrate deeper.
The only stopping mechanism is the electronic interaction
How to reduce channeling:
Angle
g of incidence
Surface amorphization

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Energy loss of the projected ions

Sn ( E ) kn E

for low E

Coulomb interaction

S n (E )
Implantation
region

Reduced for high E

Rutherford interaction

At high E Se dominates
dominates***
At low E Sn dominates

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Crystal Damage

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Crystal Damage

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Crystal Damage recovery by RTA


p = Rp

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Crystal Damage recovery by RTA

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Masking

Transmitted fraction of ions beyond a depth d

Rp and Rp refer now to the MASK MATERIAL


If we want 99,99%
99 99% of ions within the mask thickness d

T = 1 0.9999
0 9999 = 10-44
Rp

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We want to implant B in Si to obtain a concentration doping of 21018 cm-3 at a depth of 300


nm. Calculate the dose.

We have a GaAs wafer with a diameter of 100 mm where we implant uniformly Zn ions using
an implantation
p
energy
gy of 100 KeV during
g 5 min with a constant ion current of 10
A.
Calculate the dose and the maximum concentration of ions

Universidad Politcnica de Madrid

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