Diffusion Process

Diffusion
• Diffusion is the phenomenon of atomic movement of diffusant into
crystal through vacancy or interstitial site.
• The higher the temperature, the faster diffusion will occur
• The net drift of atoms will happen from higher to lower
concentration regions.
• Diffusion depends on five main variables.
initial concentration,
surface concentration,
diffusivity:- the rate at which the impurity penetrates
into the solid
time, and
temperature
Goals of diffusion methods

• Control of
dopant distribution
 total dopant concentration
its uniformity and reproducibility
• Allow Batch Processing to reduce manufacturing cost
Substitutional

– Ex:P,As,Sb
– Electronically Active
– Modulate the conductivity
of
– semiconductor due to
donors
Interstitial

– Ex: Group-1 & 8 element

– (Lithium, Argon, Helium
etc.,)
– Cu,Au,Ni has both
substitutional
– and Interstitial
Interstitialcy

• Ex: Boron
Diffusion - Fick’s First Law

Particle flux J is proportional to the negative

of the gradient of the particle concentration

N
J  D
x

D = diffusion coefficient
J – Flux : rate of transfer of solute dopant per unit ) area.
(dilute solution: No. of dopant atoms is less than host atom)
N – Concentration of dopant
x – Movement of dopant
= exp

EA (Sub) >> EA (Inter)

Diffusion - Fick’s Second Law

dx = A[j x) − j x + ]

/ – rate at which dopant concn.

changing

dx – rate of accumulation of dopant

between P1 and P2

[j x + dx − j x ]
=−
Diffusion - Fick’s Second Law

[j x + dx − j x ]
=−

As lim =−
→

=
 Diffusion Co-efficient - Constant

=
= (Fick’s Simple Law of diffusion)

Doping Profile:
1. Infinite Source of diffusion or Constant Source diffusion
(Surface Concn. is constant)

Boundary Condition: Initial Condition:

N(0,t) = N0 N(x,0) = 0
where, N0 = Solid solubility limit
N(∞,t) = 0
Constant Source Diffusion
Complementary Error Function Profiles
 x 
Concentration : N x,t   N 0erfc 
2 Dt 


Dt
Total Dose : Q  N x,t dt  2N 0

0

N 0  Surface Concentration

D  Diffusion Coefficient

erfc = Complementary Error Function

erfc z  1 erf z 

z
2
erf z 

 expx  dx
2

0
Constant Source Diffusion -
Complementary Error Function Profiles
(Predeposition)

= ,

= ∫ erfc dx Note: z = dz = dx/2

= No 2 ∫ erfc

=2 0

At the Junction N = NB
= erfc
2
 Limited Source Diffusion- Constant Total Impurity
Gaussian Profiles
Boundary condition:

Initial Impulse with Dose Q =

∞, = 0
Initial Condition
N(x,0) =0
Concentration :
2 2
  x   Q   x  
N  x, t   N 0 exp     exp    
  2 Dt   Dt   2 Dt  

Q
N s  Surface Concentration N(0, t) N s 
Dt

D  Diffusion Coefficient
At xj N=NB
Gaussian Profile
= exp −
Example Problem:

Phosphorus is diffused into a uniformly doped p-type silicon with original

doping concentration of the sample being 1016/cm3 at 1150°C. Given that the
solid solubility of phosphorous in silicon at 1150°C is 1020/cm3 and diffusion
co-efficient at this temperature is 1 x 10-12 cm2/s.

(a) Calculate the total number of phosphorus atoms per unit area of silicon
surface after predeposition time of 1 hour.
(b) If After this , drive-in is carried out for 2 hours at same temperature,
what will be the final junction depth and surface concentration?
Example Problem:

Sol:
(a) The total amount of phosphorus introduced in silicon per unit area after
predeposition as
=2 0 = 6.77 X 1015 /cm2

(b) Now after drive in the surface concentration is given by setting x=0 in the following
equation , = exp − + NB so if the drive-in carried out for 2 hours at the
.
same temperature, we have = - 1016 =4.5x 1019 /cm3
. .
Example Problem:

In order to obtain the junction depth, we note that at the junction the
phosphorus concentration becomes equal to the original background doping
concentration of the sample

At xj , x=xj and N=NB

= exp −

Xj = 4.92µm
D as a function of Concentration

Dα N
D=KN
Ds=KNs
D= (N/Ns)Ds
Dα N = (N/Ns)Ds
Dα N2 = (N/Ns)2Ds
Dα N3 = (N/Ns)3Ds
D as a function of Concentration

D= (N/Ns)Ds
N/Ns

D=Ds

D=(N/Ns)2Ds

D=(N/Ns)3Ds

Y=x/2
Junction Depth

= 1.616 t -> D α N

= 1.019 t -> D α N2

= 0.87 t -> D α N3

Same surface concentration and same time

 D shows higher power concentration dependent
Diffusion
D is constant or function of concentration?
Diffusion happens at higher temperature
At diffusion temperature
ni > Impurity concentration then D is constant
ni < Impurity concentration then Dα N

For substitutional dopant replaces Si atoms  vacancy available

in lattice
Point defect have to interact with dopants- depends on charge
state.
Diffusion co-efficient can be function of concn.
D as a function of Concentration

Predeposition:
2
=

Drive In:
=

= D1t1<<D2t2
After drive in Ns<<No
Bipolar Transistor Fabrication

Emitter Base Collector

SiO2
n+ p n+
p+ p+
n-Epi

n + Buried Layer

P-substrate

Dteff = D1t1 + D2t2 + …. (Successive Diffusion)

High temp. process modify the diffusion profile

22
Diffusion system

• Open furnace tube system using solid, liquid or gaseous

source.

• Three zone horizontal furnace is used for diffusion.

• Wafers are placed in a quartz boat and are heated to high

temperature.

• Impurities are transported to silicon surface and then diffuse

into wafer.
Diffusion System

Open Furnace Tube Systems

(a) Solid source in platinum
source boat
(b) Liquid Source - carrier
gas passing through
bubbler
(c) Gaseous impurity source
Wafers in Quartz Boat
Scrubber at Output
Boron Diffusion – Solid Source
• Diffusion Co-efficient 10-12 cm2/sec at 1150ºC
• Boron has high solubility in silicon and can achieve active surface
concentration up to 4X1020 cm-3.. NA = 5x1019/cm3 due to misfit
factor.
• Elemental boron is inert up to temperature exceeding melting point
of silicon.
• A surface reaction with boron trioxide is used to introduce boron to
silicon surface.
2B2O3 +3Si 4B + 3 SiO2
 Excess boron trioxide – brown boron skin – difficult to remove with
acids
 Diffusion at oxidizing atmosphere containing 3 to 10 % oxygen.
Boron Diffusion – Solid Source
• Solid Sources of boron- trimethylborate (TMB) and boron nitride
wafers.
• TMB should kept below room temperature.
• TMB vapor reacts in furnace tube with oxygen to form boron
trioxide, water and carbon dioxide.

2 (CH3O)3 B + 9O2  B2O3 + 6CO2 + 9H2O

Unreacted TMB must be scrubbed from exhaust system.

Boron Diffusion
• Most common liquid source for boron is boron tribromide (BBr3). The
reaction is
4BBr3 + 3O2  2B2O3 +6Br2
 free bromine combines easily with metallic impurities and is useful
removing metallic impurities during diffusion.
 gaseous source of boron is diborane (B2H6).
 Diborane is highly poisonous and explosive gas.
 Excessive diborane cause pitting
 To reduce risk of handling, diborane is usually diluted with 99.9 % argon
or nitrogen volume.
Diborane oxidizes in either oxygen or carbon dioxide to form boron trioxide :
B2H6 + 3O2  B2O3 +3H2O
B2H6 is highly explosive, alternate BCl3
Phosphorous Diffusion – Solid Source
• Diffusion Co-efficient 10-12 cm2/sec at 1150ºC
• Phosphorus has high solubility in silicon and can achieve active
surface concentration up to 4X1020 cm-3.. NA = 5x1021/cm3 due to
misfit factor.
Phosphorus Diffusion

Surface Reaction : Gaseous Source : Phosphine PH 3 (Extremely Toxic)

2 P2 O5  5Si  4 P  5SiO2
2PH 3  4O2  P2O5  3H 2O

Solid Sources :
Phosphorus Pentoxide All systems need careful scrubbing!
Ammonium monophosphate NH 4 H 2 PO 4
Ammonium diphosphate NH 4 2 H 2 PO 4 P2O 5 POCl3 Cl2

Liquid Source : Phosphorus Oxychloride POCl3

4 POCl3  3O2  3P2 O5  6Cl 2

Arsenic & Antimony Diffusion

Arsenic Surface Reaction Antimony Surface Reaction

2As2O3  3Si  3SiO2  4 As 2Sb2O3  3Si  3SiO2  4Sb

Solid Sources : Possible - Low Surface Concentations Liquid Source : Antimony Pentachloride Sb 3Cl5

Gaseous Source : Arsine AsH 3 (Extremely Toxic)

Ion  Implantation Is Normally Used for Deposition Ion  Implantation Is Normally Used for Deposition
Ion Implantation

1. Ion Source
2. Mass Separator
3. High-Voltage Accelerator (Up to 5 MeV)
4. Scanning System
5. Target Chamber
 Implantation Technology
• Ion source:
– operates at 25kV
– produces a plasma contain desired impurity + undesired species
– arsine-phosphine and diborane as well other gas used as source
• Mass Separator (Homogenous field Magnetic analyzer)
– Analyzer magnet bends ion beam through right angle to select desired impurity.
– Selected ion passes through an aperture slit into main accelerator column.
• High Voltage Accelerator:
– Adds energy to the beam and accelerate ions to their final velocity.
– Accelerator column and ion source operated at high voltage relative to target.
– Ion source and accelerator are mounted within protective shield.
• Scanning system:
– X- and Y axis deflection plate is used to scan beam across wafer- uniform
implant & desired dose.
– Beam is bent slightly to prevent neutral particle from hitting target.
• Target Chamber
– Silicon wafer serves as target and maintained near ground potential for safety.
– Vaccum condition
 Implantation
Force on charged particle 
F  q v x B 
2 mV
Magnetic Field B 
qr 2

m  mass
v = velocity
V  accelerati on potential
A = wafer area
Diffusion Vs Ion Implantation
• Diffusion is more prone to
contamination (Furnace, Quartz
Boat, Source Push Rod).
• Control of doping is 5 to 10%
• High temperature process. (Oxide
serves as Mask)
• Shallower Junction is difficult at
lower concentration
• Ion Implantation is clean system
(High Vaccum)
• Control of doping is 1 to 2%
• Low temperature process. (PR serves
as mask)
• Better flexibility
 Lattice Damage and Annealing
• Conductivity: Most of the impurity are not sitting in
substitutional sites. Region will become semi insulating
• Mobility: Highly disorder region
• Lif time : Higher Temperature
Lattice Damage and Annealing
• Implantation damage can be removed by an “annealing” step.

• Typically heated to temperature between 800-1000o C for 30

min.
• At these temperature Si atoms move back into the lattice sites
and impurity atoms can enter into the substitutional sites in
the lattice.
• After the annealing all implanted dose becomes electrically
active, except impurity concentration exceeding 1019/cm3.

Unfortunately, annealing for 30 min approaching 800-1000o C

can cause considerable spreading of the implant by diffusion.
Rapid Thermal Annealing
• In addition to removing the damage caused by implantation,
annealing step is required to electrically activate the
implanted impurities.

• In order to minimize the diffusion of shallow implanted profile

Dt must be kept small.

• RTA can achieve desired results with annealing times that

range from few min to few sec.
Rapid Thermal Annealing

•Rapid Heating

•950-1050o C

•50o C/sec

•Very Low Dt
•RTO
•RTN

(b)
Figure 5.12
(a) Concept for a rapid thermal annealing (RTP) system. (b) Applied Materials 300 mm RTP System (Courtesy Applied Materials)