Diffusion

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Organization of the course
Crystal growth and wafer preparation

Oxidation
Diffusion
Ion Implantation
Lithography
Etching
Deposition
Epitaxy

Process Integration and Characterization Techniques

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3.2. A boron-doped crystal pulled by the Czochralski technique is required to
have a resistivity of 10 Ω cm when half the crystal is grown. Assuming that a 100
gm pure silicon charge is used, how much 0.01 Ω cm boron doped silicon must
be added to the melt? For this crystal, plot resistivity as a function of the fraction
of the melt solidified. Assume k0 = 0.8 and the hole mobility μp = 550 cm2 volt-1
sec-1.

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Where NA of 10
ohm cm
corresponds to Cs.

and NA of 0.01
ohm cm
corresponds to
concentration in
the melt.

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What are the different processes through which impurity/dopants can be
incorporated in Si crystal?

1. During CZ process, we add fixed amount of impurities atoms in the melt.

2. During FZ process, crystal can be doped by zone labelling technique.

3. Solid state diffusion.

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Doping

Doping Methods

Diffusion Ion Implantation

Doping : The introduction of dopants onto the silicon wafer. The dopants are
deposited from a gas phase or by ion implantation

Diffusion: In diffusion, dopant atoms move from surface into Silicon by means
of the concentration gradient.

Ion Implantation: This is considered as an alternative to high-temperature

diffusion for introducing dopants. In this process, a beam of
highly energetic ions is aimed at the target semiconductor.

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Why ?
collector base emitter

p
Base p+
+
p+ p+ n+ buried layer

Substrate : n type Si

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Diffusion
Diffusion is a process by which controlled amount of impurity is
introduced into the semiconductor.

To increase the conductivity of the semiconductor material.

In a doped semiconductor, The conduction current density is given by

J = (nµe + pµh) q

J= σ E
where n is the electron concentration and p is the hole concentration.

σ = (nµe + pµh) q

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Impurities used in Si shows energy level in bandgap.

 N-type impurities shows energy level close to but below the conduction
band edge.

 P-type impurities shows energy level close to the valance band edge.

σ = (nµe + pµh) q

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Diffusion : Example

Diffusion: a molecular kinetic process that leads to homogenization,

or mixing, of the chemical components in a phase.

water

adding dye partial mixing homogenization

time
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 We subject the semiconductor at high temperature to an ambient
containing the dopant impurity.

Why Diffusion ?

 Real crystal is not a perfect crystal.

 There are point defects in it i.e., vacancies and interstitials.

 So, when this practical crystal is being subjected to an ambient containing the
impurity atom, the impurity atoms will move inside the crystal, because a
concentration gradient exists.

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Point Imperfections

Imperfect point- like regions, one or two atomic diameters in size and
hence referred to as
‘zero dimensional imperfections’

a. Vacancy defect
Interstitial
b. Impurity defects
Substitutional

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Vacancy defect

If an atom is missing from its normal

site in the crystal, the defect is called a
vacancy defect.

It may be a single vacancy, divacancy

or a trivacancy.

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Impurity defects

a. SUBSTITUTIONAL IMPURITY

 It refers to a foreign atom that substitutes for or

replaces a parent atom in the crystal.

 Pentavalent or trivalent impurity atoms doped

in Silicon or Germanium are also substitutional
impurities in the crystal.

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Impurity defects

b. INTERSTITIAL IMPURITY

An interstitial defect arises when an atom occupies a

position in the lattice that is not normally occupied
in the perfect crystal.

If atom occupies the void space in the parent

crystal without disturbing the parent atoms from their
regular sites, then it is called as ‘interstitial impurity’.

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Point defects

Ref: Wiki

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Three basic mechanisms by which an impurity atom can move inside
silicon.

1. Substitutional:

It substitutes for a host atom.

2. Interstitial:

Movement is through the interstitial spaces

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Interstitialcy:

The dopant atom starts out with being an interstitial, pushes the host atom from its
regular lattice site into the interstitial space and itself occupies the substitutional.

Diffusion mechanism of common dopants

 Boron ( vacancy and interstitialcy) with interstitialcy component dominating.

 Phosphorous (vacancy and interstitialcy) with interstitialcy component dominating.

 As – vacancy-type mechanism

 Sb – vacancy-type mechanism

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 Silicon impurities

Substitutional ( impurity P,B,As,Al, Ga, Sb, Ge

atoms are at lattice
point)
Interstitials (impurity O, Au, Fe, Cu, Ni, Zn, Mg
atoms are at interstitial
sites )

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Diffusivity of groups III and V atoms in Si
Slow diffuser in Si: As and Sb
Fast diffuser :P,B, and In.

As junction becomes
shallower, the need for slow
diffusers has become more
important.

For n-type regions : ‘As’ has

small D and high solid
solubility limit.

For p-type: ‘B’ is only dopant

with high solid solubility but
with high diffusivity. Means
shallow p-type region is more
difficult to form.

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Interstitial Diffusion: Ea is related to the energies required to
move dopant atoms from one interstitial site to another.

Vacancy Diffusion: Ea is related to both the energies of motion

and the energies of formation of vacancies.

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Diffusion System

1. Solid Source
2. Liquid Source
3. Gas Source

duty of carrier gas is to transport vapor from the source to silicon wafer

Solid Sources: BN, As2O3 , P2O5

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Liquid Source

POCl3

Liquid Sources: BBr3, AsCl3,

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Gas Source

Gaseous Sources: B2H6, AsH3, PH3

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Mathematical analysis
Fick's first law :
F = - D dN/dx
Where
 F is the "diffusion flux," of which the dimension is amount of
substance per unit area per unit time, so it is expressed in such units as
mol m−2 s−1. J measures the amount of substance that will flow through a
unit area during a unit time interval.

 D is the diffusion coefficient or diffusivity. Its dimension is area per

unit time, so typical units for expressing it would be m2/s.

 N (for ideal mixtures) is the concentration, of which the dimension is

F1  DCG  C S  /
amount of substance per unit volume. It might be expressed in units of
mol/m3.
x is position, the dimension of which is length. It might thus be
expressed in the unit m.

 Minus sign due to flow of dopants from higher concentration to lower

concentration.
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Fick’s First Law

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BITS Pilani, Pilani Campus
Arrhenius relationship

The Arrhenius relationship describes the temperature dependence of

many thermally induced processes, like: chemical reactions, particle
diffusion, evaporation rates, lattice vibrations etc.

The Arrhenius equation says that a given quantity, “α”, has an

exponential dependence on temperature,

𝐸𝐴
𝛼 𝑇 = 𝐴𝑜𝑒𝑥𝑝(− )
𝐾𝐵 𝑇
where
Αo is a pre-factor
EA is the activation energy for the process.

The activation energy represents the energy that must be overcome in

order for a reaction to occur.
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 𝐸𝐴
𝐷 = 𝐷𝑜𝑒𝑥𝑝(− )
𝐾𝑇

Plot D versus 1/T in a log scale,

From slope we can find the activation energy.

This is called the activation energy of diffusion.

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 EA substitutional = 3 to 5 eV.

EA _interstitial = 0.5 to 2 eV.

Movement through interstitial sites is a fast process.

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Fick's second law

This law predicts how diffusion causes the concentration to

change with time. It is a partial differential equation which in
one dimension reads:

where
• Φ is the concentration , Φ (x,t) is a function that depends on
location x and time t
•t is time [s]

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 Law of conservation
Fick first law of mass
¶C ¶C ¶F
F = -D =-
¶x ¶t ¶x

C   C  C 2
 D D 2
t x  x  x
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 𝜕𝑁 𝜕𝐹 𝜕 𝜕𝑁
=- = (𝐷 )
𝜕𝑡 𝜕𝑥 𝜕𝑥 𝜕𝑥

y
x
z
𝜕𝑁 𝜕2 𝑁
=D 2 This is Fick’s second Law.
𝜕𝑡 𝜕𝑥 J1

dz

If flux is changing with the distance means there J2

is some net storage of atoms, so concentration
will change with time

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Under steady state :

𝜕𝑁 𝜕2 𝑁 𝜕𝑁
=D 2 , = 0 with change in time there is no change
𝜕𝑡 𝜕𝑥 𝜕𝑡
in concentration.

So, We have

𝜕2 𝑁
D 2 =0
𝜕𝑥

Integration twice gives,

C = a+bx so under steady state we will have linear
concentration profile over distance like during oxidation,
if D is not changing with position.

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Diffusion Profile

Constant Surface-concentration diffusion Constant total dopant diffusion

Also known as Also known as

Diffusion from an unlimited source Diffusion from a limited source

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The general approach for using diffusion for getting dopants into a
semiconductor crystal is to introduce a large amount of the dopant
material at the surface of a wafer (create a concentration gradient

We can treat the problem in a 1-D fashion. Also, we generally assume

that initially there is no dopant within the bulk of the wafer [i.e. N(x≠0,
t=0) = 0] and the wafer is so thick that no dopant will ever diffuse to
the back surface (i.e. that the wafer is effectively infinitely thick).

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 Constant Surface-concentration diffusion

Diffusion from an unlimited source

Impurity atoms are transported from a vapor source onto the semiconductor surface
and diffused into the semiconductor wafers.

The vapor source maintains a constant level of surface concentration during the
entire diffusion process.

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 Initial condition :

N(x >0, t=0)=0 (no dopant in the wafer before the diffusion)

The boundary conditions are:

N(x =0, t) =Ns (surface concentration is held constant

N(x ∞, t) =0 (nothing gets to backside)

𝜕𝑁 𝜕2 𝑁
=D 2
𝜕𝑡 𝜕𝑥

The solution of the Fick's law that satisfy the above initial and boundary
condition is given by:

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 𝑥
𝑁 𝑥, 𝑡 = 𝑁𝑜[1 − erf ]
2 𝐷𝑡

𝑥
𝑁 𝑥, 𝑡 = 𝑁𝑜 erfc( )
2 𝐷𝑡

𝐷𝑡 Diffusion length

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 Error Function

2 𝑥 −𝑧 2
erf 𝑥 = න 𝑒 𝑑𝑧
𝜋 0

erfc(x) = 1-erf(x)

erf (0) = 0

erf (−x) = −erf x

erf( ∞ ) = 1

erf (−∞) = −1

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The quantity Dt determines the shape of the profile. The units of Dt is m2.
(Dt)1/2 has dimension of length, and it represents the characteristic scale of the
diffusion. If (Dt)1/2 is small, the diffusion is shallow, and if (Dt)1/2 is big the
diffusion is deeper.

Of course, (Dt)1/2 is determined by the temperature and time of the diffusion.

So diffusion can be characterized in terms of a time and a temperature.

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Dose

We can define a quantity called the dose, which is the total amount of
a dopant diffused into a wafer. Mathematically,

units of dose are m–2 (or μm–2)

∞
𝑄 𝑡 = න 𝑁 𝑥, 𝑡 𝑑𝑥 𝑥
𝑁 𝑥, 𝑡 = 𝑁𝑜[1 − erf ]
0 2 𝐷𝑡
𝑥
𝑁 𝑥, 𝑡 = 𝑁𝑜 erfc( )
2 𝐷𝑡

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Constant total dopant diffusion

Diffusion from a limited source

A fixed amount of dopant is deposited onto the semiconductor

surface and is then diffused into the material from the surface.

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 The initial condition is :

N(x > 0, t=0) =0 (no dopant in the wafer before the diffusion)

The boundary conditions are:

The constant dose boundary condition is

∞
𝑄 = න 𝑁 𝑥 𝑑𝑥 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 ( 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑎𝑡𝑒𝑟𝑖𝑎𝑙 𝑝𝑙𝑎𝑐𝑒𝑑 𝑜𝑛 𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑝𝑟𝑖𝑜𝑟
0
𝑡𝑜 𝑑𝑖𝑓𝑓𝑢𝑠𝑖𝑜𝑛 𝑖𝑠 𝑓𝑖𝑥𝑒𝑑)

N(x ∞, t) =0 (nothing gets to backside)

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The diffusion equation solution under these conditions is a
Gaussian function:
𝑄 𝑥2
𝑁 𝑥, 𝑡 = exp(− )
𝜋𝐷𝑡 4𝐷𝑡

The surface concentration for the Gaussian profile by putting x=0 in

the above equation:
𝑄
𝑁 0, 𝑡 =
𝜋𝐷𝑡

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Again, we see that the Dt-product determines the shape of the profile.
With a bigger Dt more dopant moves deeper into the wafer.

Since there is a fixed dose of dopant, as more atoms move deeper into
the wafer, the surface concentration must decrease. The expression for
N(0) confirms that expectation – as Dt increases, the surface
concentration decreases.

The surface concentration for the Gaussian profile is

𝑄
𝑁 0, 𝑡 =
𝜋𝐷𝑡

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The major difference between these solutions is:

 The error function solution applies when there is an infinite supply of

dopant, which implies that an increasing dose of dopant is introduced
into the substrate during the diffusion process to maintain a constant
surface concentration .

 The Gaussian solution applies when the initial dose of dopant is fixed
and consequently, the surface concentration must drop as the dopant
diffuses deeper into the bulk.

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Junction depth

When we perform a diffusion, dopant is

generally diffusing into a region where
some dopant (opposite type) already
exists.

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we can determine the junction depth with the background doping of the Si
substrate, by setting the doping the profile equal to the background doping at
the junction as given below:

Junction depth for the constant-source (error function) diffusion:

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Junction depth for the constant-dose (Gaussian) diffusion:

𝑄
𝑁 0, 𝑡 =
𝜋𝐷𝑡

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Numerical -1

A constant-source boron diffusion is performed into an n-type silicon

wafer. The diffusion temperature is 1050°C and the diffusion time is 1 hour.
Assume that the surface concentration is limited by the solid solubility
limit. If the n-type background doping of the silicon is 5x1016 cm–3, find the
junction depth. Activation energy ( EA) = 3.5 eV. erf( 2.63) = 0.9998. solid
solubility limit for boron in silicon is = 2.4*1020 cm-3, Do = 1 cm2/s

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Two step diffusion
How to get a dose during constant-dose ?

 One method would be to use ion implantation.

 Another approach is to use a constant-source (error function) diffusion to introduce

the dose. We know that the dose of a constant-source diffusion is given by:

• Pre-deposition:
• Diffusion from a constant source,
– at temp T1 and time t1
• Or using Ion implantation

• Drive-in step

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If the time is kept short and the temperature kept low, (so that the Dt product
is small), none of the dopant will have diffused far from the
surface. As an approximation, we can assume that all of the dopant is right at the
surface.

Then we can remove the dopant source (thus fixing the dose) and
follow up with constant-dose diffusion step.

Inserting the dose from the constant-source step into the equation for
the Gaussian diffusion profile, we obtain the two-step diffusion
equation.
𝑄 𝑥2
𝑁 𝑥, 𝑡 = exp(− )
𝜋𝐷𝑡 4𝐷𝑡

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where D1t1 refers to the constant-source step ( pre-deposition) and D2t2
are the parameters for the constant-dose step ( drive –in).

 Gaussian diffusion results if D1t1 ˂˂ D2t2

 Erfc diffusion results if D1t1 ˃˃ D2t2

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Diffusion and junction depth

Dt equivalency plot for P.

Any point on the fitted line

has the same
XJ 2 = Dt =(1um)2

Thus: 0.000001 minutes at

1150oC is equivalent to 1
minute at 700oC.

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 collector base emitter

 Gaussian diffusion profile is ideally suited for those

p
cases Where low value of surface concentration is + Base p+
required in conjunction with high diffusion depth n+ buried layer

 The base diffusion of BJT presents this type of

situation

 Where emitter can be doped with erfc diffusion

profile as surface concentration is higher with
shallow junction.

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Successive Diffusion

For this , let us consider the case of base and emitter diffusion in BJT.

first We have to diffuse the base and then we have to diffuse the emitter.

To obtain certain junction depth, we go for pre deposition and drive-in during
base diffusion, Now, during emitter diffusion, the base is also being subjected to
further drive-in.

So, even though we are not putting any new base dopant, the already present
base dopants are being subjected to a further drive-in process and therefore,
both the junction depth as well as the surface concentration of the base region
is going to change.

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Dt , which represents how deep the dopants have gone inside.

First consider the drive-in for base. Drive-in was carried out for a time of t1 at a particular
temperature, so that the diffusion coefficient was D1

In the next instance, the emitter diffusion was carried out, emitter drive-in was done for a
time of t2 and at a temperature corresponding to which the diffusion coefficient of boron
was D2 .

So, in that case the effective Dt will be given

D1t1+D2t2

So, this is called successive diffusion.

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Other effects

 Transient enhanced diffusion

 Electric field effect

 Doping effect

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Solid Solubility and “maximum” activation

• Dopants are soluble in bulk silicon up to

a maximum value before they
precipitate into another phase.

• Dopants may have an “electrical”

solubility that is different than the solid
solubility defined above

• When in a cluster, As atoms keep their

“extra” electrons and do not result in
doping.
• Solid solubility of As in silicon: 2x1021
cm-3
• Electrically-activated concentration of As:
2x1020 cm-3

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Transient enhanced diffusion

 Due to ion implantation

,point defects ( vacancy )
will be more and hence
diffusivity will be more
near the surface where we
implanted the dose.

 Now diffusivity is more

near the surface and then
diffusivity is decreasing
because defects are
absent.

 So more accumulation in
the area where diffusivity
is less, thus we will get
box like profile.
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Electric field effects

• The field comes from higher mobility of electrons

and holes compared to dopant atoms.

N-type dopants are positively charged. We have to change the fick’s law and
need to add a factor of electric field ( drift component).now two factors are
responsible for generation of flux.

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 diffusion coefficient = constant

If D is not a constant and it is a function of doping concentration

Where N = concentration of dopant atoms.

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At high doping concentrations (n
> ni), the Fermi level will move
toward the conduction band edge
for donor-type vacancies, and the
term e (EF-Ei /kT) becomes larger
than unity. This causes Cv to
increase, which in turn gives rise
to enhanced diffusion.
 The number of vacancies per unit
volume) has a temperature dependence
similar to that of the carrier density.
 where Cv is the vacancy density, Ci is
the intrinsic vacancy density, EF is the
Fermi level, and Ei is the intrinsic Fermi
level.
 At low doping concentrations (n < ni),
the Fermi level coincides with the
intrinsic Fermi level (i.e., EF = Ei). The
vacancy density is equal to Ci and
independent of the dopant
concentration. The diffusion coefficient,
which is proportional to Ci, will also be
independent of doping concentration.
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First of all we will see what happens if D is a function of the doping concentration (C).

D∝ C Ds = K Cs D = Ds( C / Cs )
K = Ds/ Cs
D=KC

Ds = K Cs2 D = Ds(C/ Cs )2
D∝ C2
K = Ds/ Cs2

Ds = K Cs3 D = Ds(C/ Cs )3
D ∝ C3
K = Ds/ Cs3

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In the complementary error
function profile, you see the
junction is much deeper compared
to the other three cases and the
doping concentration is falling;
right from the surface it is falling
gradually.

whereas D ∝ C3 ,
junction is much shallower and it
remains at the surface concentration
level for a much larger part of this
junction and then falls more steeply.

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xj =

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In a two-step process, phosphorus was diffused into a p-type
silicon wafer (NB = 1017 cm -3). In the deposition step, the temperature
was 900°C and the diffusion time was 45 minutes. Ns = 7 * 1020 cm-3
( solid solubility limit at 900oc). In the drive-in step, the temperature
was 1100°C and the time was 60 minutes. Find the surface
concentration and junction depth. Activation energy ( EA) = 3.68 eV.
Do = 4.70 cm2/s.

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Irvin’s curves

Irvin’s curves: Irvin’s curves are plots of N0 versus (Rs xj) for various NB,
assuming erfc or Gaussian profile. There are four sets of curves for (n-type
and p-type) and (Gaussian and erfc).

Why?

xj

    x dx
1
xj 0
 1 1
RS   
x j x j xj

q  nx   N B  nx dx

We need Irvin’s curves to find: 0

The surface concentration

The junction depth
The sheet resistance
Backward Concentration
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Sheet resistance (RS)

 : (bulk) resistivity
RS  xj: junction depth, or film thickness…
xj

l l  l l
R    RS
A wx j x j w w

R=Rs when l=w (square)

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   qnn  p p 
For non-uniform doping:

This relation is calculated to generate the so-called Irvin’s curves.

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Irvin’s Curves

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Irvin’s Curves

• An alternative way of presenting the data may be found if we set

eff=1/sxj

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Design and Evaluation
• There are four parameters in a irvin’s curve.

The surface concentration

The junction depth
The sheet resistance
Backward Concentration

These parameters are not independent

• Irvin developed a relationship that describes these parameters

1 1
S  
 xj xj

q  n( x)  N B  n( x)dx

0
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 Example
Design a boron diffusion process (say for the well or tub of a CMOS process)
such that Rs= s=900/square, xj=3m, with CB=11015/cm3. Assuming two
step diffusion.

The average conductivity of the layer is

Why Gaussian
because in cmos process p or n well are moderately doped.
From (Gaussian) Irvin’s curve, we find
Cs << solubility of B in Si.
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  x  2  x 2j 
C  x, t  
Q
exp   C B  C s exp  
Dt  4 Dt   4 Dt 
 
Dt 
x 2j

3 10 4 2
 3.7 10 9 cm2
 Cs   4 1017 
4 ln   4 ln  15

 CB   10 

Assume drive-in at 1100oC, then D=1.5×10-13cm2/s.

3.7 10 9 cm2

tdrivein  13
 6.8 hours
1.5 10 cm sec2

Pre-deposition dose
Q  Cs Dt  4 1017    3.7 10 9  4.3 1013 cm2
BITS Pilani, Pilani Campus
Now if we assume pre-deposition by diffusion from a gas or solid phase at
950oC, solid solubility of B in Si is Cs=2.5×1020/cm3, and D=4.2×10-15cm2/s.
The profile of this pre-deposition is erfc function.

Dt
Q  2C s

2
 4.3  10 13
 
tpredep    
20  15
 5.5 sec
 2  2.5  10  4.2  10

  
Dtpredep 2.3 10 14  Dtdrivein 3.7 10 9 

BITS Pilani, Pilani Campus