EE-527: MicroFabrication

Solid-State Diffusion

R. B. Darling / EE-527 / Winter 2013

 The Process of Diffusion
• Diffusion is a process driven by temperature and described
by statistical thermodynamics.
• It occurs in numerous circumstances and it is responsible
for many important physical transport effects in all fields
of science and engineering.
• In the field of microfabrication, solid-state diffusion is the
process by which dopant impurity atoms are introduced
into semiconductors to form localized n-type and p-type
regions, and where these regions adjoin, pn-junctions.

R. B. Darling / EE-527 / Winter 2013

 Fick’s Laws
• Fick’s First Law: the diffusive flux is proportional to the
concentration gradient:

F   DC
• Particle Continuity Equation: conservation of matter:

C 
  F
t
• Fick’s Second Law: combine the above two:
C
  DC 
t
R. B. Darling / EE-527 / Winter 2013
 The Diffusion Coefficient
• The diffusion coefficient or “diffusivity” usually follows
an Arrhenius relationship:
D
log
  Ea  D0
D  D0 exp  
k T
 B 
• Ea is the activation energy.  Ea  slope
• The activation energy is the
slope of the line on a plot of
log(D) versus 1/kBT.
• Typical activation energies
for solid-state diffusion are 1
~ 3.3 to 4.4 eV. k BT
R. B. Darling / EE-527 / Winter 2013
 Atomic Mechanisms of Diffusion – 1
• Impurity atoms may reside on a normal lattice site; this is a
substitutional impurity.
• Or they may reside in an open space of the lattice; this is
an interstitial impurity.
• For an impurity atom to behave as a dopant, it must be
substitutional so that it can ionize and either donate or
accept electrons.
• Interstitial impurity atoms can diffuse fairly quickly
because they do not need to break any bonds.
• Substitutional impurity atoms diffuse fairly slowly because
they must break and make bonds in order to propagate.
• Moving an impurity atom from an interstitial into a
substitutional position is termed dopant activation.
R. B. Darling / EE-527 / Winter 2013
 Atomic Mechanisms of Diffusion – 2

interstitial transport direct exchange vacancy exchange

interstitial transfer Frank-Turnbull kick-out

R. B. Darling / EE-527 / Winter 2013

 Atomic Mechanisms of Diffusion – 3
• Diffusion of substitutional impurities can occur through:
– Direct exchange: The impurity atom an adjacent host lattice atom
simply trade places. This requires breaking ~6 bonds.
– Vacancy exchange: The impurity atom moves into a lattice
location which is vacant. The vacancy and the impurity effectively
trade places. This requires breaking only ~3 bonds.
– Interstitial transfer: The impurity atom can get knocked out of a
substitutional position and become an interstitial. As an interstitial,
the impurity atom can move much more rapidly through the lattice.
The impurity atom can then come to rest by becoming a
substitutional atom again. This can occur through:
• Frank-Turnbull process: The interstitial impurity atom falls into and
fills a vacancy.
• Kick-out process: The interstitital impurity displaces a host lattice
atom and takes its place.
R. B. Darling / EE-527 / Winter 2013
 Dopant Atoms for Silicon
• Boron (P-type)
– A relatively fast diffuser.
• Phosphorous (N-type)
– A relatively fast diffuser, almost identical to B.
• Arsenic (N-type)
– A relatively slow diffuser, about 10X slower than B or P.
• Aluminum (P-type)
– An extremely fast diffuser, 10X faster than B or P.
– Important for making p-type contacts.
• Gallium (P-type)
– A relatively fast diffuser, about the same as B or P.
• Antimony (N-type)
– A relatively slow diffuser, about the same as As.
R. B. Darling / EE-527 / Winter 2013
 Common Interstitial Elements in Silicon
• Oxygen
– High concentrations in Czochralski (CZ) grown wafers.
– Almost none in float-zone (FZ) grown wafers.
• Iron
• Copper
– An extremely fast diffuser and precipitate in silicon.
– Can be used to decorate point defects.
• Nickel
• Zinc
• Manganese
• Gold
– A fast diffuser and a carrier lifetime killer.
R. B. Darling / EE-527 / Winter 2013
 Diffusion by Vacancy Exchange
• This is the predominant mechanism for most dopants in Si.
• Consider the example for boron (B):
• As a substitutional impurity, boron is an acceptor and it
will be singly negative charged (−1) when ionized.
• Vacancies have the ability to take on nearly any charge
state: {…, −2, −1, 0, +1, +2, …}.
• Singly positive charged vacancies will interact strongly
with boron, because the resulting pair is neutral.
• Diffusion of boron can be achieved through the movement
of (B−V0) pairs or (B−V+) pairs.
• The neutral (B−V+) pairs have more than 10X higher
diffusivity.
R. B. Darling / EE-527 / Winter 2013
 Ionization of Vacancies
• Vacancies can take on different charge states by providing
a point defect site that can trap a free electron or hole.
• This can be viewed as a reaction: e.g. hole capture:

N
V 0  h  V  K e  V 0 equilibrium rate constant
pNV
 
• Intrinsic case: n = p = ni, N N p ni
K e  Vi0 V

 
ni NV NVi ni n
• When p rises above ni, then NV+ will also rise above NVi+ in
the same proportion.
• The combined diffusion coefficient becomes
  E 0
 p    E 

DV  Do exp 
o a
  D0 exp 
a

k T
 B  i n k
 B  T
R. B. Darling / EE-527 / Winter 2013
 Diffusion by Vacancy Exchange
• Example: boron in silicon:
– D00 = 0.037 cm2/V-s, Ea0 = 3.46 eV
– D0+ = 0.41 cm2/V-s, Ea+ = 3.46 eV
• In general,
2 2
 p  p n  *  n  *
DV  D*0    D*    D*    D    D  ...
 ni   ni   ni   ni 

• Because n and p depend upon the local doping level, the

diffusion coefficient becomes concentration dependent.
• For the majority of cases, the high temperatures of a
diffusion furnace make ni quite large, and the sample is for
the most part under intrinsic conditions, n = p = ni.

R. B. Darling / EE-527 / Winter 2013

 Donor Impurity Diffusion Coefficients
• Phosphorous in silicon:
– D00 = 3.85 cm2/V-s, Ea0 = 3.66 eV
– D0− = 4.44 cm2/V-s, Ea− = 4.0 eV
– D0−− = 44.2 cm2/V-s, Ea−− = 4.37 eV
• Arsenic in silicon:
– D00 = 0.066 cm2/V-s, Ea0 = 3.44 eV
– D0− = 12 cm2/V-s, Ea− = 4.05 eV
• Antimony in silicon:
– D00 = 0.214 cm2/V-s, Ea0 = 3.65 eV
– D0− = 15 cm2/V-s, Ea− = 4.08 eV

Data from R. B. Fair, S. K. Ghandhi; Runyan and Bean - SICPT

R. B. Darling / EE-527 / Winter 2013
 Acceptor Impurity Diffusion Coefficients
• Boron in silicon:
– D00 = 0.037 cm2/V-s, Ea0 = 3.46 eV
– D0+ = 0.41 cm2/V-s, Ea+ = 3.46 eV
• Aluminum in silicon:
– D00 = 1.385 cm2/V-s, Ea0 = 3.41 eV
– D0+ = 2480 cm2/V-s, Ea+ = 4.20 eV
• Gallium in silicon:
– D00 = 0.374 cm2/V-s, Ea0 = 3.39 eV
– D0+ = 28.5 cm2/V-s, Ea+ = 3.92 eV

Data from R. B. Fair, S. K. Ghandhi; Runyan and Bean - SICPT

R. B. Darling / EE-527 / Winter 2013
 Diffusion Coefficients for Dopants in Silicon
Al
 11
110

2 Ga
DP T d   cm  s P
 i  12
110 B
2
DAs  T d   cm  s
 i
 13
110
As
2 Sb
DSb T d   cm s
 i

2  14
DB T d   cm  s 110
 i
Three
2 Speed
DAl T d   cm  s  15
110
 i Groups
2
DGa T d   cm  s
 i  16
110

 17
110
900 1000 1100 1200
1
Td  K  273.15
i
R. B. Darling / EE-527 / Winter 2013
Diffusion Coefficients for Dopants in Silicon
Diffusion Coefficients in Silicon
‐10

‐12
Log10 of Diffusion Coefficient, cm2/sec

‐14
Phosphorous
Arsenic
‐16
Antimony
Boron
‐18 Aluminum
Gallium

‐20

‐22
0.6 0.7 0.8 0.9 1.0 1.1 1.2
1000/T, degrees K

R. B. Darling / EE-527 / Winter 2013

Diffusion Coefficients for Dopants in Silicon
Diffusion Coefficients in Silicon
1.E‐10

1.E‐11

1.E‐12

1.E‐13
Diffusion Coefficient, cm2/sec

1.E‐14
Phosphorous
1.E‐15
Arsenic
1.E‐16
Antimony
1.E‐17 Boron
1.E‐18 Aluminum
1.E‐19 Gallium

1.E‐20

1.E‐21

1.E‐22
600 700 800 900 1000 1100 1200
Temperature, degrees C

R. B. Darling / EE-527 / Winter 2013

Diffusion Coefficients for Dopants in Silicon
Diffusion Coefficients in Silicon
1.E‐11

1.E‐12
Diffusion Coefficient, cm2/sec

1.E‐13
Phosphorous
Arsenic
1.E‐14
Antimony
Boron
1.E‐15 Aluminum
Gallium

1.E‐16

1.E‐17
900 1000 1100 1200
Temperature, degrees C

R. B. Darling / EE-527 / Winter 2013

 Electric Field Enhanced Diffusion – 1
• Equilibrium electric field in a doped region:
 k T n k T p
E B  B
q n q p
• This electric field can produce ionic drift which can enhance
or retard the diffusion of charged impurity atoms (ions).
• Drift and diffusion together give an ion flux of
  qZ 
F   DC   C E   DC  D CE
k BT
• Here, μ is the mobility of the diffusing ions, Z is the charge
state of the ions, and the Einstein relationship for this is
D k BT

 qZ
R. B. Darling / EE-527 / Winter 2013
 Electric Field Enhanced Diffusion – 2
• If the impurity is a donor, the electron density will be
related to the impurity concentration as

n
1
2
 C 2  4ni2  C 
• The built-in electric field is then
 kT 1 k T 1 n
E B n   B C
q n q n C
• Performing the calculus,
1 n 1

n C C 2  4ni2
• Giving:  k BT C
E
q C 2  4ni2 R. B. Darling / EE-527 / Winter 2013
 Electric Field Enhanced Diffusion – 3
• The ion diffusion flux can then be simplified to the form:

F   gDC
• The electric field enhancement factor is
ZC
g  1  donors
C  4ni
2 2

• For a singly charged donor ion (Z = +1), this is maximized

for C >> ni, for which gmax = 2.
• For acceptor ions (Z = −1), the analogous result is
ZC
g  1  acceptors
C  4ni
2 2

• However, field retardation can occur then a charged

impurity is diffusing through an electric field region
caused by the opposite type impurity. R. B. Darling / EE-527 / Winter 2013
Intrinsic Carrier Concentration at High Temperatures
• High concentration and electric field enhanced diffusion
occur when the dopant and carrier density exceed the
intrinsic carrier density:
20
110

18
110

16
110
ni T i  cm
3

14
110

12
110

10
110
0 200 400 600 800 1000 1200
1
T i K  273.15 R. B. Darling / EE-527 / Winter 2013
 Constant Surface Concentration – 1
• The concentration of the dopant is held constant at the
surface of the wafer throughout the diffusion process.

C ( x, 0)  0 initial condition
C C 2
D 2 C (0, t )  CS boundary condition
t x
C ( , t )  0 boundary condition
• The solution is a complementary error function profile:
 x 
C ( x, t )  CS erfc  
erfc(0)  1  2 Dt 
2 x


u 2
erfc()  0 erf ( x)  e du
0
erfc( x)  1  erf ( x)
R. B. Darling / EE-527 / Winter 2013
 Constant Surface Concentration – 2
• The dose is the diffused concentration integrated over
depth:

S (t )   C ( x, t ) dx
0

• For the constant surface concentration case, the dose

increases as the square root of time:
2
S (t )  CS Dt


R. B. Darling / EE-527 / Winter 2013

 Constant Dose – 1
• The fixed dose S of the dopant is introduced and held
constant throughout the diffusion process.
C ( x, 0)  0 initial condition
C  2C 

t
D 2
x 0
C ( x, t ) dx  S boundary condition
C ( , t )  0 boundary condition
• The solution is a Gaussian profile:
S   x2 
C ( x, t )  exp  
 Dt  4 Dt 

R. B. Darling / EE-527 / Winter 2013

 Constant Dose – 2
• The dose is the diffused concentration integrated over
depth:

S (t )   C ( x, t ) dx
0

• For the constant dose case, the surface concentration

decreases as the square root of time:

S
C (0, t )  CS (t ) 
 Dt

R. B. Darling / EE-527 / Winter 2013

 Predeposit – Drive-In Processing – 1
• A common two-step diffusion process which is used to
create deeper diffusions with a smaller surface
concentration.
– This allows another diffusion of opposite type to be more easily
performed. (Double-diffused and triple-diffused structures)
• The predeposit step introduces the dose.
– Diffusion with a constant surface concentration.
– Ion implantation to a prescribed dose and range.
• The drive-in step diffuses this dose deeper into the
substrate while diluting the peak concentration.
– Diffusion with a constant dose.
– The drive-in step will also anneal (activate) the implanted ions.

R. B. Darling / EE-527 / Winter 2013

Predeposit – Drive-In Processing – 2

Boron into Si:

T = 1000°C
D = 10−14 cm2/s
tpd = 1 hour
tdi = 3 hours
∆t = 10 mins
CS = 1018 cm−3

R. B. Darling / EE-527 / Winter 2013

 Junction Depth
• The metallurgical junction depth is defined as where the
doping polarity changes from n-type to p-type.
• Computationally, it is where the diffused dopant
concentration becomes equal to the background doping of
the substrate, CB.
• For the constant surface concentration case:
 CB 
1
x j  2 Dt erfc  
C
 S
• For the constant dose case:
 S 
x j  4 Dt ln  
 CB  Dt 
R. B. Darling / EE-527 / Winter 2013
 Multiple Thermal Cycles
• The time-temperature profile of the overall thermal
processing schedule can be accounted for by using an
effective diffusivity-time product:

 Dt eff   Diti   D(t ) dt

i

• Noting that,
D(t )  D(T (t ))
• Note that increasing the temperature has a much more
significant effect on the diffusion depths than does
lengthening the time.

R. B. Darling / EE-527 / Winter 2013

 Double Diffused BJT Structure
3
20 N(x), cm
10

10
19 Emitter
Net doping (Nd+ − Na−) near junctions is
reduced from diffused impurity profiles
18
10 N E(x) because of partial dopant compensation.

17
10 Base
16
10 N B(x)
15
10
14 Collector NC
10
13
10
12
10 x, m
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
x jE xjC R. B. Darling / EE-527 / Winter 2013
 Emitter Push Effect
• Emitter push is a two-dimensional diffusion effect where a
second high concentration diffusion (an emitter)
effectively increases the junction depth of a preceding
diffusion (a base).

base emitter

collector

R. B. Darling / EE-527 / Winter 2013

 Emitter Pull Effect
• Emitter pull is a two-dimensional diffusion effect where a
second high concentration diffusion (an emitter)
effectively decreases the junction depth of a preceding
diffusion (a base).

base emitter

collector

R. B. Darling / EE-527 / Winter 2013

 Diffusion Spiking or Piping
• Some impurity atoms, in very high surface concentrations,
can diffuse along preferential crystal directions much faster
than at lower concentrations.
• This can lead to dopant spikes which penetrate deep into
the substrate and which can short out shallow diffusions.
• A good example is aluminum:
Al contact

n-type

shorted
junction
p-type

R. B. Darling / EE-527 / Winter 2013

 Dopant Sources for Silicon
• Gaseous – metered out into the diffusion tube
– diborane, B2H6
– phospine, PH3
– arsine, AsH3
• Liquid – vaporized and carried into the diffusion tube
– boron bromide, BBr3
– phosphorous oxychloride, POCl3 (“pockel”)
– arsenic trichloride, AsCl3
• Solid – wafers that are loaded along beside the silicon wafers
– boron nitride, BN
– phosphorous pentoxide, P2O5
– arsenic trioxide, As2O3
– These are known as “planar solid sources.”
R. B. Darling / EE-527 / Winter 2013
 Boron Surface Chemistry
• All dopant sources for boron first create a boron oxide on
the surface of the silicon wafer:
– Gaseous: Diborane: B2H6 + 2O2 → B2O3 + 3H2O
– Liquid: Boron bromide: 2BBr3 → 2B + 3Br2, 4B + 3O2 → 2B2O3
– Solid planar sources: Boron nitride: 4BN + 3O2 → 2B2O3 + 2N2
– The oxide is necessary to create a boron phase which will
condense and adhere to the silicon wafer surface.
• Simultaneous oxidation of the Si will create a mixed oxide
on the surface: SiO2 + B2O3.
• The boron oxide will decompose with high heat, yielding
free boron at the surface of the wafer:
– 2B2O3 + 3Si → 4B + 3SiO2.
• Excess boron will create tenacious silicon borides:
– Excess B + Si → SiB4 or SiB6. R. B. Darling / EE-527 / Winter 2013
 Phosphorous Surface Chemistry
• Phosphorous sources must also create an oxide on the
surface of the silicon wafer:
– Gaseous: Phosphine: 2PH3 + 4O2 → P2O5 + 3H2O
– Liquid: “Pockel”: 2POCl3 + 2O2 → P2O5 + 3Cl2
– Solid planar source: Phosphorous pentoxide: P2O5
• Simultaneous oxidation of the Si will create a mixed oxide
on the surface: SiO2 + P2O5.
• The phosphorous oxide will decompose with high heat,
yielding free phosphorous at the surface of the wafer:
– 2P2O5 + 5Si → 4P + 5SiO2.
• Excess phosphorous will create silicon phosphides:
– Excess P + Si → SiP or SiP2.
– Unlike SiB4 and SiB6, the SiP and SiP2 are easy to remove.
R. B. Darling / EE-527 / Winter 2013
 Spin-On Dopants for Silicon
• Spin-on dopants are the least expensive and easiest to
handle dopant source.
– They likewise have the least controllability and reproducibility.
– They can be a good, economical solution when only a highly
doped contact region is required, such as in solar cells, and some
rectifier applications.
• Typical composition:
– Dopant oxide: e.g. B2O3, P2O5, As2O3, SnO, ZnO
– Siloxane polymer: – O – Si – O –
– Coating solvent: e.g. EtOH, MeOH, C6H13OH (hexanol)
• Typical processing:
– Spin coat at 3000 rpm for a thickness of 150 to 250 nm.
– Bake at 200°C for 15 min. to evaporate the solvent and cross-link
the siloxane into SiO2 which also incorporates the dopant oxide.
– Furnace tube diffusion cycle and deglaze. R. B. Darling / EE-527 / Winter 2013
 Diffusion Modeling and Simulation
• Diffusion is perhaps the easiest physical process to
simulate because it is inherently stable.
– Time evolution tends to smooth out profiles, reducing or
eliminating singularities.
– Dependent variables remain everywhere differentiable.
– Highly efficient solver routines can be applied.
• Commercial and academic diffusion process simulators:
– SUPREM IV (the original from Stanford University)
– TSUPREM IV (Avant!, Inc.)
– ATHENA (Silvaco, Inc.)
– Sentaurus (Synopsys, Inc.)
– COMSOL – write it yourself, but obtain greater flexibility – good
for including the physics that other TCAD programs leave out.

R. B. Darling / EE-527 / Winter 2013