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 IMPURITY DIFFUSION IN SEMICONDUCTORS
• Diffusion provides a powerful means of
introducing controlled amounts of chemical
impurities into silicon lattice.

• Diffusion techniques are ideally suited to batch

processing.

Pre-deposition Drive-in (Profile control)

(dose control) [junction depth &
concentration] 6
 Source of Dopant diffusion

✓ Diffusion from a chemical Liquid Source

source in a vapor form at
high temperature
✓ Diffusion from a doped
oxide source
✓ Diffusion & annealing from
an ion implanted source
Solid Source

Gas Source Spin-on-glass

AsH3, PH3, SiO2 + dopant
B2H6 oxide
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 Interstitial–
Vacancy Interstitialcy
Substitution
Feature Interstitial Diffusion (Substitutional) (Interchange)
(Combination)
Diffusion Diffusion
Diffusion
Interstitial atom Dopant alternates
Atom moves through Substitutional atom
Basic displaces a lattice between interstitial
interstitial sites between moves by exchanging
Mechanism atom; lattice atom and substitutional
lattice atoms with a vacancy
becomes interstitial positions
Atom Position Substitutional (lattice Both interstitial and
Interstitial site Interstitial site
Before Diffusion site) substitutional
Need for No (but involves
No Yes Yes (partly)
Vacancy? lattice displacement)
Atoms Typically Small atoms (H, Li, B in Larger dopants (P, As, Self-interstitials, some B, P (in Si under
Involved some cases) Sb) dopants certain conditions)
Activation Variable (depends on
Low High Moderate
Energy dominant path)
Diffusion Rate Fast Slow Moderate Intermediate to fast
Temperature Strongly temperature Strongly temperature
Less sensitive Moderate
Dependence dependent dependent
Lattice Significant during
Minimal Moderate Moderate
Distortion exchange
Boron diffusion in Si
Example in Self-interstitial
Hydrogen diffusion in Si Antimony in Si (via interstitial-
Silicon mediated diffusion
substitution pairs)
Controlling Availability of interstitial Self-interstitial Balance of vacancies
Vacancy concentration
Factor sites concentration and interstitials
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 Diffusion
Diffusion Mechanisms:
1. Interstitial Diffusion
 = 40 exp (-Em / kT)
0 = Frequency of lattice
vibration
= ~ 1013 – 1014 / sec
Em= interaction energy
~ 0.6 – 1.2 eV
• jump rate once every minute
at room temperature,
• Smaller atomic diameter than
host atom.
• Green circles are Si-lattice
points.
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 Diffusion

2. Vacancy or Substitutional Diffusion

 = Frequency of jumping
= 40 exp -(En+ Es ) / kT
0= Frequency of lattice
vibration
~1013 – 1014 / sec
Es = Energy of formation,
En= Potential barrier to break
certain covalent bond,
✓jump rate is once every 1045 years at room temperature.
✓Vacancy sites are Schottky defects (Group III & Group V
elements)
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 Diffusion
3. Interstitialcy Diffusion( Interchange
Diffusion )
A host or an impurity atom
displaces a lattice atom,
which in turn becomes an
interstitial atom. This type of
diffusion is dependent on the
availability of vacant sites and
occurs at a slower rate than
interstitial diffusion. In this
mechanism two or more
atoms diffuse by interchange
process.

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 Diffusion
[Link]-Substitution Diffusion (Combination Effects)
Combination of interstitial and substitutional mecha-
nisms may occur within a crystal. Some of diffusion
atoms may finally end in substitutional sites with
others in interstitial sites.

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In present VLSI process pre-deposition diffusion is totally replaced
by ion implantation. Why?

Implant Pre-deposition

diffusion
a. Control of doping Excellent Good
profile 0
b. Shallow junction Min. 100 A No
c. Max. doping > Solid solubility Solubility limit
d. Control parameter Electrical Thermodynamic
(Ion energy,dose, ( Temp, time )
ion current)
e. Elec. conductivity Poor (requires Good
annealing)
f. Damages High (requires Low
annealing)
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 Diffusion

Diffusion Theory
In 1855 Fick published his theory on
diffusion. The theory is based on the
analogy between material transfer in a
solution and heat transfer by conduction.
Fick’s First Law
Diffusion occurs due to the concentration
gradient of dopants. In addition to
diffusion, ionised impurities can move in
presence of a drift field. In steady state,
drift velocity, vd = E.
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 Diffusion
Fick’s First Law
In the presence of electric field E, flux density is given by

j = - D C(x,t)/x + EN … (1)

j → flux density (atom/cm2 . sec),
E → electric field,
 → mobility of impurity ions (cm2/Vs),
D → diffusion coefficient (cm2/sec),
C → volume concentration (atoms/cc),
x → distance in cm

For constant D and no field, j = - D C(x,t)/x

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Diffusion Coefficients of Impurities in Si
− EA
D = D0 e kT

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 Diffusion
Fick’s First Law

Rate of increase of dopants inside microscopic

volume ([Link])
= A. j(x) – A. j(x + dx) = ([Link]) C (x,t)/t
(flux in) (flux out)
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 Diffusion

or, C (x,t)/t = - [ j(x+dx) – j(x) ] / dx = - j/x

Thus, Fick’s second law :

C(x,t)/t = /x ( D C(x,t)/x)

= D 2C(x,t)/x2 … (2) ( const. D)

Equation (2) gives C (x,t) with proper boundary

condition and initial condition.

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 Diffusion
A. Diffusion from a constant source
[ infinite source diffusion]
➢ Corresponds to pre-deposition where,
C0  Csurface = Csolid sol.
( wafer is exposed to an impurity source of
constant concentration during the diffusion
period)
➢ Examples : emitter diffusion, ohmic contact
diffusion etc.
Initial condition :
At t = 0, C(x,t) = C(x,0) = 0 ; ( x > 0)
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Solid Solubility Limit

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 Diffusion
A. Diffusion from a constant source
Boundary conditions : a) C ( 0, t) = C0
b) C ( , t ) = 0

Then, C (x,t) = C0 erfc ( x / 2(Dt) ) …. (3)

where erfc (z) = 1 – erf (z)
Complementary error function :
erfc (z) = 2 /    e-x2 dx 
erf (z) or erfc (z) are not in closed form. Follow
look up table or curves`

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Error Function vs Gaussian

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Properties of Error Function erf(z) and
Complementary Error Function erfc(z)

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 Diffusion

Concentration profile of a constant source diffusion

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Total Amount of Charge diffused/deposited

Q=  C ( x, t )dx
0

x
Q=  C0 erfc
0 2 Dt
dx


Q = 2C0 Dt  erfc ( z ) dz
0


1
 erfc ( z )dz =
0 

Dt
Q = 2C0


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 Diffusion

B. Limited Source Diffusion

(Constant Total Dopant)

❖Corresponds to drive in diffusion

(redistribution); examples - base diffusion,
low surface concentration deep diffusion

❖A finite quantity of the diffusing material is

first placed on the wafer. Diffusion proceeds
from this limited source, and is assumed that
all of this matter is consumed.

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 Diffusion

Initial condition : At t = 0,
C (x,0) = Q (x)
Boundary conditions : b)  C (x ,t) dx = Q ( const.)
c) C (, t ) = 0
Solving the Fick’s 2nd law using these initial and
boundary conditions, we get

C (x,t) = exp { - ( x/2 Dt )2 } . Q /  (Dt) ….(4) (Gaussian)

where Q = 2 C0 ( D1t1/ ) 1/2
C0 = surface concentration at predeposition
CS = C (0,t) = Q /  (Dt)
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 Diffusion
Limited Source Diffusion
✓ Both erfc and Gaussian
profile depend on 2 Dt
= 2. Diffusion length
✓ Q0 = total integrated
dose = ( # / unit area )
✓ Ion implanted profiles
( full Gaussian) are
similar to drive-in
profiles (half Gaussian)

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 2C0 D1t1
CS =
 D2 t 2

Junction Depth

 − xj2 
CB = CS exp 
 4 Dt 
 

 − xj2 
exp  = CB
 4 Dt  CS
 

•30
  − xj2 
  = CB
 4 Dt  CS
 

− xj
2
CB
= ln
4 Dt CS

2
xj CS
= ln
4 Dt CB

CS
xj = 2 Dt ln
CB

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 Diffusion
Impurity behavior in Silicon
❑ Impurities belonging to groups III & V are substitutional
diffusers in Si. Examples are Al, B, Ga, In (p-type) and
As, Sb, P (n-type). Their motion is influenced by the
number and the charge state of lattice defects.
❑ Impurities belonging to groups I & VIII move
Interstitially in Si. These include alkali metals such as
lithium, Na, K and Ar, He, H. They are electronically
active.
❑ Most transition elements (cobalt, copper, gold, iron,
nickel, silver) diffuse by an Interstitial – Substitutional
mechanism. These impurities reduce the minority
carrier life-time in Si.

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 Diffusion
DOPANTS
For Silicon , p-type dopants → Al, B, Ga, In ( Gr- III )
n-type dopants → As, Sb, P ( Gr-V )

For GaAs, p-type dopants → Be, cd, Mg, Hg, Zn

(Gr-II elements, move along Ga sublattice )
n-type dopants → Se, S, Te
( Gr-VI elements,move along As sublattice )
n- & p- dopants → C, Ge, Si, Sn
( Gr-IV elements, can be either n- or p- type
depending on the sublattice on which they
are preferentially located. They move on
both lattices.
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 22
Diffusion
Choice of Dopants
➢ Painting a slurry of dopant source and inert oxide (
BaO, CaO, MgO, SiO2 ) in ployvinyl alcohol on semi-
conductor surface
➢ Spin-on source [ inert oxide & binder ], 2500 – 5000
rpm, thickness ~ 5000 A, baking at 200oC
➢ Gaseous source
➢ Solid source → (a) source of dopant oxide is kept in
a platinum boat. Carrier gas transports vapor from this
source and deposit them on semiconductor slice. (b)
Solid source can also be directly placed on the
semiconductor slice by CVD technique.
➢ Liquid source → Bubbler arrangements (halogen
dopant compounds are available in liquid form)
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 23
Diffusion
Diffusion Systems
1. Sealed Tube Diffusion → (a) free from contamination,
(b) can attain solid solubility at diffusion temperature,
(c) pressure ~ 1 torr is used
2. Open Tube Diffusion → (a) mechanical puller (10
cm/min. ), better approach is ramp up and ramp down
3 – 10 deg C per minute for higher diffusion temp.
Ramp down : T = To – C . t, T0 → initial temp., C →ramp
rate, t→time. Ramp down is equivalent to an extra
diffusion time of kT02 /CE0, where E0 is activation
energy of diffusion
Flat zone Furnace : temperature range → 600 – 1200oC,
0.50C tolerance, 10 cm for lab. furnace, 25 cm for
industrial unit
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 Diffusion 24

Some Features of Diffusion System

❖Surface concentration should be capable of
being controlled over a wide range of values,
up to solid solubility limit.
❖Diffusion process should not result in damage
to the surface of the slice.
❖After diffusion, material residing on the
surface of the slice should be capable of easy
removal.
❖The system should give reproducible results.
❖The system should be capable of processing a
number of slices at a time.
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 25
Diffusion
Contamination Control
✓ Quartz tube is cleaned by HCl vapor, remove
impurities by converting to their halides.
✓ Firebricks are major source of alkali ion
contamination.
✓ Heavy metallic impurities ( iron, Cu, Au)
reduce the minority carrier life time.
Halogenic compound is used as dopant
source for backside gettering i.e. damaging
of surface so that it can be used as a sink
for metallic impurities.
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 26
Diffusion

P-type and N-type impurities in Silicon

P-type impurity:
➢ Al, Ga → cannot be masked by SiO2.
➢ In → moderately deep lying impurity in silicon.
➢ B → more practical and widely used p-type
dopant.

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 Diffusion 27

N-type impurities in Silicon

➢ As, Sb → both has low diffusion constant
compared to phosphorus, recommended for
early stages of diffusion,
➢ Arsenic is better than antimony because it
provides an excellent fit to the Si lattice,
➢ Arsenic is poisonous and safe handling is
required but antimony has low vapor pressure.
➢ P → diffusion constant of P is almost same as
boron, but 10 times larger than that of arsenic
and antimony. More practical. In VLSI phos-
phorus is used as Base dopant of pnp.

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 28
Diffusion

BORON
Solid sources:
❑Boron trioxide → 2 B2O3 + 3 Si  4B + 3 SiO2
Boron skin causes a dark boron stain which is
difficult to remove in any acid. Perform
wet oxidation to form borosilicate glass which
dissolves in HF.
❑Boron nitride → Pre-oxidised at 750 – 11000C
for 30 min in order to form thin skin of B2O3
on their surface which serves as diffusion
source.

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 Diffusion 29

Liquid sources (Boron) : 9000C

TMB (trimethyl borate) → 2 (CH3O)3 B + 9O2 →
B2O3 + 6CO2 + H2O
Boron tribromide → 4BBr3 + 3O2 → 2B2O3 +
6Br2
Gaseous sources :
Diborane ( B2H6) → B2H6 + 3 O2 → B2O3 +
3H2O [ at 3000C ]
It is highly poisonous and explosive gas and is
used in 99.9% argon dilution
Boron trichloride : → 4BCl3 + 3O2 → 2B2O3 +
6 Cl2
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 30
Diffusion

Phosphorus
Solid source: Phosphorus pentoxide (P2O5)
2 P2O5 + Si  4P + 5 SiO2
P2O5 is hygroscopic. Another solid source is
formed by hot - pressing ammonium mono –
phosphate ( NH4H2PO4 ) with organic binder.

Gaseous source: Phosphine ( PH3 )

( toxic and explosive gas )
2PH3 + 4 O2 → P2O5 + 3 H2O
[ PH3 in 99.9% Ar / N2]
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 Diffusion 31

Liquid source: Phosphorus oxychloride ( PoCl3 )

( require bubbler )
4 PoCl3 + 3 O2 → 2P2O5 + 6 Cl2 ( 0 – 400C )

A typical bubbler arrangement

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 32
Diffusion
Arsenic (As)
Solid source : Arsenic trioxide (As2O3),
2As2O3 + 3Si  3SiO2 + 4 As
Liquid spin – on source : Arsenosiloxanes in
organic binder at 2500C
form arsenosilicate
glass.
Gaseous source : Arsine ( AsH3 ) → poisonous
gas, dilute before use.
✓ NPN BJT with As emitter has better low current gain.
✓ Arsenic is more frequently used for source and drain
diffusion of n – MOSFET.
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 Diffusion 33

High concentration effects ( n >> ni )

Arsenic
❖When nD > 1020 cm- 3, measured profile shows
a nearly flat portion near the surface region.
Arsenic diffusivities is then expressed as
DAs = (2 n/ni)( Di ) As
❖Arsenic atoms form cluster when the
concentration exceeds 1020 / cc.
Boron
➢ The diffusivity of boron in high concentration
region reduces considerably – almost to zero.

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 34
Diffusion

Anomalous Behavior of Shallow Phosphorus

Diffusion
It is observed in case of high concentration
diffusion in the depth of 0.5-1.0 m range
Essential feature of electronically active
phosphorus profile are an initial flat-top region
followed by a kink at around 1020/cc and then
by an extensive tail beyond this point. Small
fraction of phosphorus is electronically active
at higher concentration.

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 35
Diffusion

Anomalous feature
can be explained by
considering phos -
phorus interactions
with vacancies in the
silicon lattice which
bring about enhanced
diffusion effects. pair
dissociation
mechanism is seen in
case of P-diffusion.
Typical profile for a high con-
centration phosphorus diffusion
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 Diffusion 36

Band Gap Narrowing Effect

At high impurity doping concentration, the energy band
gap will deviate from its original value. This effect is due
to misfit strain effect, attributed to the phosphorus
diffusion in Si at high concentration (~ 1021/cc). The strain
is the result of mismatch between phosphorus atom and
Si lattice, as radius of phosphorus atom is smaller than
that of Si.
For ion-implanted layers, an additional cause of stress in
silicon lattice is from ion-implant damage.
Due to band gap narrowing effect the effective intrinsic
electron density is given by
nieff = ni exp ( −  Eg / 2 KT )

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Diffusion 37

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 Diffusion 38

Line source diffusion

Isoconcentration contours at the edge of diffusion mask.

N (r,t) = (/2Dt) exp ( - r2 /4Dt),  = impurity / unit length
of slot.
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 Diffusion 39

Limited source diffusion

Isoconcentration contours ( for different C2 ) at the

edge of diffusion mask. C2 = N / Nsurface
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 Diffusion 40

Fixed surface concentration diffusion

Isoconcentration
contours ( for different
C2) at edge of diffusion
mask. C2 = N / Nsurface .
Lateral penetration ~
75 – 85 % of Xj

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[Link], IIT- KHARAGPUR
 Diffusion 41

Evaluation of diffused layer

A. Junction depth measurement:
1. Angle lap & staining

tan  = t / d or t = d tan   ~ few degrees (1 – 50)

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 42
Diffusion

Angle lapping:
Abrasive powder ( carborundum, alumina,
boron carbide etc.) 100 – 200 mesh / grit

Staining: p-stain → 100 cc cons. HF ( 49%) +

few drops of HNO3 (0.1%)
n-stain → 200 gm CuSo4 + 1000 cc
H2O + 10 cc HF
p - diffused layer becomes black because of
formation of SiH4 , H2 SiF6, SiO etc.

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 43
Diffusion

Junction depth measurement: ( Angle lap & staining )

A cylinder is used to
groove the wafer. A
doping sensitive etch
then removes the part
of the top layer. The
junction depth can be
found from the known
diameter and the
measured width of the
lower abraded groove.

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Diffusion
2. Interference method
An optical flat is placed on the chip and is vertically
illuminated by collimated monochromatic light. The
resulting fringe pattern gives a direct measure of the
vertical depth in wavelengths of the illuminating source.
For sodium the distance between the fringes is 0.29 m
approximately.

Monochromatic light (sodium lamp, 5896 A0 )

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 45
Diffusion
B. Sheet Resistance
A simple technique to obtain information
about the impurity profile in semiconductor.
Xj

Rs = [  q N (x)dx ] –1
0

Xj

= [ q eff  N (x)dx ] –1
0

Four point probe

Resistivity () = Rsxj
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Diffusion
Four point probe resistivity measurement
✓ Current (I) is passed between the two outer
probes and the voltage (V) is measured across
the inner pair.
✓ Rs = (V / I) × correction factor (C.F)
✓ Correction factor depends on probe geometry,
ratio of probe spacing to thickness of diffusion.
✓ For co-linear probes, where probe spacing is
much larger than the junction depth, the factor
is 4.5325.

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Diffusion
C. Measurement of Impurity Profile
1. Secondary Ion Mass Spectroscopy ( SIMS )
The sample is
bombarded by high
energy ions. The
sputtered material
is mass analyzed
to determine the
composition of the
substrate.
A typical SIMS arrangement.

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 Diffusion 48

SIMS Measurement
✓ Energetic ions strike the surface of the sample
where they destroy the crystal lattice and eject
material by sputtering. Striking energy is 1 to 5
keV.
✓ A fraction of ejected material is ionized,
collected and accelerated towards a mass
spectrometer.
✓ Sputter rate can be increased and the
concentration of several impurities can be
measured as a function of depth.
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 Diffusion 49

Problems of SIMS analysis

➢ Takes larger time
➢ Requires high vacuum (~ 10-9 torr)
➢ Expensive
➢ Destructive
(Samples thicker than 1 m may take 4 to 8
hours to profile)
➢ Abrupt interface is difficult to measure,
particularly if they are buried.
➢ SIMS is nevertheless, a powerful and widely
used tool.
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 50
Diffusion
2. Rutherford Back Scattering ( RBS )

In RBS, the
energy of the
back-scattered
helium ions
can be used to
determine the
depth profile of
the chemical
composition of
the wafer.

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 Diffusion 51

Rutherford Back Scattering ( RBS )

❑Helium ions with energies in excess of 1 MeV
are incident on the sample at near normal
incidence and the ions penetrate deeply into
the sample.
❑Impurities will back scatter the ions with a
characteristic energy that depends on the mass
of the impurity and its depth into the crystal.
❑The back scattered helium ions are collected
and energy analyzed.
❑The raw data from RBS system consist of
counts versus energy.
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 52
Diffusion
Problems of RBS
❖Backscattered signal from an impurity atom
must be larger than the signal from the host
material atom for reasonable sensitivity of RBS
measurement.
❖This technique is limited to high mass
impurities such as antimony and arsenic.
❖As RBS technique does not require a sputter
erosion of the sample to be measured, RBS is
quick and nondestructive.
❖However, its sensitivity is less than SIMS.
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