Diffusion in

semiconductor
fabrication
Presentation by:
Akib Zaved,
Hiranmoi Dev Goswami,
Kritiraj Kalita &
Kingkan Talukdar
Let’s see semiconductor fabrication steps before we
diffuse:
• Oxidation
• Photolithography
• Etching
• Diffusion
• Evaporation Basic steps in
• Chemical vapor fabrication
deposition’
• Ion implantation
• Epitaxy
• Annealing
What is diffusion ?
It is a doping process(post-growth) where impurity atoms are
diffused in the semiconductor substrate .
Diffusion of what ? Interesting…
N-type and P-type impurity atoms
Why diffuse ?
To make desired device junctions .
Aren’t there other processes? Yes It is.
Yes, there are, like ion implantation.
How to diffuse impurities?
Ufff……..
Let’s find out everything one by one .
 Before diffusion, the desired diffusion region is selected and other
regions are masked by materials through which impurity atoms cannot
penetrate.(See oxidation, photolithography and epitaxy)

Dopant entry is
permitted

SiO2 SiO2 Dopant entry

Just an is prohibited
example
P-Substrate
How SiO2 prevents diffusion?(Diffusion in SiO2)
The diffusivities (diffusion coefficient) of common dopants are considerably smaller
in SiO2 .
Diffusion in SiO2 occurs in two steps: SiO2 is effective
1) Dopants reacts with SiO2 to form a glass until entire SiO2 film is only during the
consumed. first step
2) After the glass forms, the dopant diffuses into the silicon substrate.

103
Thickness of SiO2 is determined by
Rate of formation of the glass B
Which in turn depends on
P

Time ,t(min)
Temperature and time duration of the diffusion process.

102
For a given temperature minimum
thickness, d of SiO2 varies as 𝑡 , as
diffusion length is given by 𝐷𝑡 .

10
10-3 10-2 10-1 1 10
Thickness ,d(μm)
What’s happening inside the wafer ?
Diffusion in a semiconductor
can be envisaged as a series
of atomic movement of the
diffusant( dopant) in the
crystal lattice.
There are two diffusion
mechanisms:
(a) Interstitial diffusion
(b) Vacancy diffusion
(a) Interstitial diffusion
Host atom
Interstitial
atom(dopant)
a
Dopants take position of interstitial sites
and move from one place to another
without occupying a lattice site.
(b) Vacancy diffusion:

Host atom Host atom

vacancy dopant

a a
dopant

At high temperature, lattice atoms vibrate Here dopant atom takes the vacancy site.
about the equilibrium lattice sites. Here a host
atom acquires sufficient energy to leave the
lattice site and become an interstitial atom
thereby creating a vacancy.
Let’s take an example:
We want to make a P-N junction diode. Window opened for
SiO2 diffusion
(protective layer)

N-Substrate N
N

Diffusion of P-
type impurity

N N
Diffusion equations:
Fick’s 1st law:
Flux is directly proportional to concentration gradient. Diffusion flux direction

𝝏𝑪
F = −𝐃 (1)
𝝏𝒙 Silicon
Where, F = Flux of dopant atoms substrate
(host medium)
C = dopant concentration
D = diffusion coefficient
Low
𝝏𝑪 High
= concentration gradient along x dopant concentration
𝝏𝒙 concentration
Fick’s 2nd law:
Flux gradient is equal to the rate of change in concentration of
impurity atoms.
According to the conservation of matter, the change of the
dopant concentration with time must be equivalent to the local
decrease of the diffusion flux, in the absence of a source or a
sink.
𝜕𝐶 𝜕𝐹 𝜕 𝜕𝐶
=- = D [ from (1) ]
𝜕𝑡 𝜕𝑥 𝜕𝑥 𝜕𝑥

𝜕𝐶 𝜕2𝑐
=𝐷 2
𝜕𝑡 𝜕𝑥
 Decreasing

Diffusion coefficient
temperature
Diffusion coefficient(Diffusivity):
T>T>T
Diffusion coefficient can be expressed as:
𝐸𝑎
D = D0 exp(− )
𝑘𝑇 Activation energy
Here, 𝐷0 = diffusion coefficient at infinite temperature
𝐸𝑎 = Arrhenius activation energy

𝐸𝑎
(a) For interstitial diffusion, 𝑬𝒂 is related to energy required to
move a dopant atom from one interstitial site to another.
For Si and GaAs, the value of 𝑬𝒂 are between 0.5 to 1.5 eV.
𝑬𝒂 for vacancy 𝑬𝒂 for interstitial
diffusion diffusion
(b) For vacancy diffusion, 𝑬𝒂 is related to both the energies of
motion and formation of vacancies. Ranges between 3 to 5 eV.
Vacancy diffusion is slower
than interstitial diffusion
Diffusion occurs in two steps:
(a) Pre-deposition diffusion (b) Drive-in diffusion

Pre-deposition diffusion
(constant surface concentration):
A high concentration of dopant atoms introduced Predeposition diffusion
at the silicon surface by a vapor that contains the

Impurity concentration
dopant at a temperature about 1000o C.
Drive-in diffusion
Drive-in diffusion(Constant total dopant):
The impurity atoms are driven deeper
into the surface , without adding any more
impurities, thus reducing the surface Depth into the substate
concentration of the dopant.
 𝒙
Diffusion profiles:

Impurity concentration ,N(x)

Cs erfc (𝟐 𝑫𝟑𝒕𝟑
)
Cs

a) Constant- Surface-concentration diffusion(infinite source diffusion): 𝐷3 𝑡3 >𝐷2 𝑡2 >𝐷1 𝑡1

Initial condition : Concentration, C(x,0)=0 at t=0
Boundary condition: C(0,t) = Cs and C(∞,t) = 0 3
1 2
Cs = surface concentration at x=0(time independent)
𝒙
Solution : C(x ,t ) = Cs erfc ( ), 𝑫𝒕 is diffusion length 0 Distance from surface ,x
𝟐 𝑫𝒕
erfc = complementary error function
(b) Constant-total-dopant diffusion( limited source diffusion):

Impurity concentration ,N(x)

𝑺 −𝒙𝟐
Initial condition : C(x,0)=0 at t=0 exp{ }
𝝅𝐷3 𝑡3 4𝐷3 𝑡3
∞
Boundary condition : ‫ 𝟎׬‬C(x ,t) dx = S
S = total amount of dopant per unit area. 𝐷3 𝑡3 >𝐷2 𝑡2 >𝐷1 𝑡1
𝑺 −𝒙𝟐
Solution : C(x ,t ) = exp{ }
𝝅𝑫𝒕 𝟒𝑫𝒕
1 3
2

0 Distance from surface ,x

Intrinsic and extrinsic diffusion:

100
Intrinsic diffusion:

10
D/Di(T)
Doping concentration(n) intrinsic carrier concentration(𝑛𝑖 )
Extrinsic diffusion:

1
Intrinsic extrinsic
Doping concentration(n) intrinsic carrier concentration(𝑛𝑖 )
diffusion diffusion

0.1
0.01 0.1 1.0 10 100
Temperature dependance of vacancy density can be expressed as: 𝑛Τ𝑛𝑖
EF −Ei
C𝑣 = Ci exp( ) Fig: Donor impurity diffusion coefficient
kT
Ci = intrinsic vacancy density versus electron concentration
EF = Fermi level ; Ei = intrinsic Fermi level

When, n< ni vacancy density and hence diffusion coefficient is dopant concentration independent.
n> ni vacancy density and hence diffusion coefficient is dopant concentration dependent
−Ea
n
Diffusion coefficient for 𝑛 > 𝑛𝑖 is : D = D0 e kT
ni
Lateral diffusion:
Diffusion mask

Previously we considered only one dimensional

diffusion. It is valid till the horizontal dimensions are
much larger than the vertical diffusion depth.

x/ 2 Dt
The impurities can diffuse laterally below the oxide
mask. The ratio of lateral to vertical diffusion is
between 65-70%.

Drawback : This limits the proximity between adjacent

windows in the mask and device miniaturization is y/2 Dt
difficult.
Different dopant sources:
Pure elements are rarely used for diffusion.
Rather, compounds of the elements are used as they form bonds with silicon easily.
Impurities may be introduced from either solid, liquid or gaseous sources.

For p-type dopants boron is preferred and for

n-type dopants phosphorus or arsenic is Dopant medium
preferred. Why ? Atom
Phase B P As

1) They have a high diffusion rate into Solid BN P2O5 As2O3

silicon and very low diffusion rate in
SiO2 Liquid BBr3 POCl3 AsCl3
2) They are highly soluble in
silicon(solubilities exceeding 5× 1020 Gas B2H6 PH₃ AsH3
atoms/cm3)
Little bit chemistry:
Boron diffusion:
Elemental boron is inert up to temperature exceeding the melting point of
silicon.
A surface reaction with boron trioxide(B2 O3 ) is used to introduce boron to the
silicon surface:
2 B2 O3 + Si 4 B + 3SiO2
Excess B2 O3 forms brown boron skin on surface. So, Diffusion is done in oxidizing
atmosphere of 3-10% oxygen.

Solid source: BN(boron nitride) is oxidized and B2 O3 is transferred directly to

wafer surface.(I didn’t find the reaction)

Liquid source: Boron tribromide(BBr3) is most common.

4 BBr3 + 3O2 2 B2 O3 + 6 Br2

Gas Source: Diborane(B2 H6 ) in either oxygen or carbon dioxide forms B2 O3

B2 H6 + 3 O2 B2 O3 + 3H2 O
and B2 H6 + 6 CO2 B2 O3 + 6 CO + 3H2 O
Phosphorus diffusion:

Solubility
Solid source: Solid P2 O5 wafers can be used as a solid source.
2 P2 O5 + 5 Si 4 P + 5 SiO2

Liquid source:
4 POCl3 + 3O2 2 P2 O5 + 6Cl2
Br P As
Liberated Cl2 serves as a gettering agent

Gaseous source: Phosphine(PH3 ) is highly toxic, explosive gas, so is diluted in 99.9% argon or
nitrogen.
2PH3 + 4 O2 P2 O5 + 3H2 O

Arsenic diffusion:
Diffusion of arsenic is problematic (it’s is highly toxic). Ion implantation is the preferred technique
for introducing arsenic into silicon. If it is diffused the surface reaction involves arsenic trioxide:
2As2 O3 + 3 Si 3 SiO2 + 4 As
Thank God!
I didn’t choose chemistry
 Quartz furnace tube Resistance heaters

Quartz tube

vent

end cap

Liquid impurity Quartz boat

source Silicon wafers

Fig: Physical layout of equipment used in diffusion

Fast diffusants and contaminants:
Some elements are fast diffusants in silicon. They include the groups I
and VII elements, and some heavy metals such as Au, Cu, Pt and so on.
They are undesirable contaminants in VLSI .
Why are they undesirable ?
They degrade the performance of semiconductor devices.
They are usually gettered away from the active device regions by
internal gettering technique.

Gettering process : It removes unwanted impurities, particularly metals

or other contaminants and helps to enhance the purity of semiconductor
material and improve the electrical properties of the devices.

.
How to control the diffusion depth ? CAUTION !
DON’T GET MISLED BY PICTURES
1) Temperature: Higher temperature generally
increases the diffusion rate of dopant atom.
2) Time : Longer diffusion times allow more
dopant atoms to penetrate deeper into the
semiconductor.

3) Dopant concentration: Higher concentration

at the surface leads to deeper penetration and
Remember….Time is longer diffusion lengths.
crucial in diffusion
4) Crystal orientation : Different crystal
orientations may exhibit varying diffusion rates
for specific dopants.

By precise control of the time and temperature(to within 0.250c)

accurate junction depths of fraction of a micron can be obtained.
Why precise distribution and depth control necessary in
diffusion?
• Device performance: Precise control ensures that the intended electrical
characteristics, such as conductivity and carrier concentration are achieve.
• Uniformity and consistency: consistent diffusion depth lead to consistent
electrical characteristics, resulting in predictable device behavior and
reliability.
• Miniaturization and integration: Precise depth control allows for the creation
of intricate structures and smaller feature sizes required in modern
semiconductor fabrication.
• Performance optimization : optimization of device parameters such as speed,
power consumption and efficiency. For instance, transistor’s switching speed
and and leakage current.
• Preventing crosstalk and leakage: Precise depth control minimizes crosstalk
between adjacent components and reduces leakage currents by insuring
proper isolation.
 Comparing with ion implantation:
• Ion implantation can be done at low temperature but diffusion
requires high temperatures.
• Amount of dopant can be controlled in ion implantation whereas in
diffusion dopant amount can’t be controlled easily.
• There is lateral doping in both the processes. Lateral diffusion in
case of diffusions and transverse straggle in case of ion
implantation.
• Diffusion creates very little damages to the crystal structure but ion
implantation damages the crystal lattice heavily.
• Diffusion is used to form a deep junction, such as an n-tub in a
CMOS device. Whereas ion implantation is utilized to form a shallow
junction, like a source/drain junction of a MOSFET.
• Diffusion is preferred in gradual doping profiles whereas ion
implantation used for faster and precise doping.
 Conclusion
The diffusion process in semiconductor fabrication involves the
movement of dopant atoms to alter the conductivity of a
material. This controlled diffusion is crucial for creating
semiconductor devices with specific electrical properties. By
carefully introducing dopants like boron or phosphorus,
manufacturers can manipulate the conductivity of
semiconductors, enabling the creation of transistors and other
electronic components essential for modern technology.
References:
1) Kanaan Kano, Semiconductor Physics.
2)
 Please don’t ask
anything……

Any questions?
Thank you!!!!