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https://www.scribd.com/doc/162874824/DefectsIVRKRDiffusion
08/25/2013
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Defect Phenomena: Diffusion
· structures are getting smaller in all
technological developments (e.g.
nanodesign)
· especially in semiconductor
technology: device structures are
even smaller than diffusion length
of dopants (45 nm technology of
CPUs)
· diffusion starts to become a problem
when device is exposed to high
temperatures e.g. after ion
implantation (annealing at
900.1000°C for 30 s)
· diffusion can strongly be influenced
by coimplantation of electrically
ineffective ions (e.g. carbon co
implantation in B:SiC)
2
Atomic change of sites & diffusion
· diffusion in solids = material transport in
lattice as a result of atomic change of sites
· for a single atom: random path
· diffusion always important for processes at
elevated temperatures, such as:
 ordering and disordering processes in
alloys (formation of precipitation)
 doping of semiconductors
 defect annealing after plastic
deformation and ion implantation
 sintering
 layer growth at surIaces, .
· proved: diffusion is realized by jumps of
interstitials or vacancies/divacancies
· simultaneous change of a ring of atoms
needs too high energy. It has never been
observed.
3
Most simple mechanism: j ump of a vacancy
· jump of a vacancy (Leerstelle) =
movements of an atom to the vacancy site
· jump rate v
v
= reciprocal mean duration of
stay of a vacancy at a given lattice site
· the jump rate follows an Arrhenius law:
Z . number oI next neighbors
I
0
. jump attempt Irequency
E
v
m
... migration energy
k . Boltzmann constant
v 0 v
exp( / )
m
Z E kT v = · I · ÷
· typical frequency I
0
~ 10
12
s
1
· thus temperature T
1
where 1 step per
second is observed:
· for metals with T
melt
=1300 K: already at
300K vacancy mechanism of diffusion
works well
1 v
/ K 380 / eV
m
T E = ·
4
Vacancy model of diffusion
· selfdiffusion in metals and alloys, in many ionic crystals, and in ceramic materials often occurs
via vacancy mechanism
· atomic fraction of vacancies in thermal equilibrium
· typical values of C
v
in metals are 10
4
. 10
3
near the melting point (not in semiconductors)
F F
v F F
exp( ) exp( ) , ... vacancy formation entropy and enthalpy
S H
C S H
kT kT
= ÷ ÷
5
divacancy mechanism of diffusion
· at very high temperatures (near melting point) number of divacancies becomes
considerably large
· vacancy mechanism of diffusion is accompanied by divacancy mechanism
· however vacancy mechanism dominates below 2/3 T
m
6
I nterstitial diffusion
· interstitial (Zwischengitteratom) diffusion is more
complicated
· structure of lattice and size of atoms is obviously
important for jump
· difference: self and impurity diffusion
· interstitial diffusion is often activated already at
very low temperatures, i.e.
· migration energy extremely low  in Au and Nb:
selfinterstitials move below 1K !
· selfinterstitial annealing after lowtemperature
electron irradiation of Cu:
v i
>>
m m
E E
r
e
s
i
d
u
a
l
R
e
s
i
s
t
i
v
i
t
y
dR
dT
7
I nterstitial diffusion
· when interstitials exist in a large concentration: interstitial diffusion
· especially important when small atoms diffuse: e.g. hydrogen in metals
· but also selfdiffusion (e.g. in Si, since diamond lattice is relatively open)
ring vacancy interstitial
mechanism
· not important for selfdiffusion in dense
metallic lattice (there: vacancy mechanism)
· selfinterstitials in metals have a much larger
formation enthalpy compared to vacancies
8
Hydrogen diffusion in metals
· hydrogen is very small: rapid diffusion
· technological application: storage of
hydrogen in metals for use in fuel cells
(e.g. in Ti)
· permeation of hydrogen through Pd
membrane: method for purification
· isotopic effects are found: D
H
>D
D
>D
T
· deviation of D
H
below RT from
Arrhenius low was explained by
quantum effects (tunneling)
9
I nterstitial diffusion in metals
· C, N, and O often dissolve
interstitially in metals (e.g. in
Nb)
· comparison with Nb self
diffusion shows orders of
magnitude difference
· interstitial diffusivity near
melting point may be as high
as in liquids
10
I nterstitial diffusion in metals
· diffusivity of interstitially dissolved atoms can be very different
· D differs by 20 orders of magnitude
· slope is determined by migration enthalpy (Wanderungsenthalpie)
11
Dissociative interstitialsubstitutional exchange mechanism:
F rankTurnbull mechanism
· atom starts from regular lattice site, moves to interstitial position, and diffuses as
interstitial relatively fast (B in Si)
· vacancy is required; diffusion ends at the vacancy site
· also called: dissociative mechanism
· example: fast diffusion of Cu in Ge
i s
B V=B +
12
I nterstitialsubstitutional exchange mechanism without vacancies:
Kickout mechanism
· impurity atom B starts from interstitial site, diffuses there and kicks out an atom
at regular lattice site, which by itself starts interstitial diffusion
· diffusion of B ends at a regular lattice site, but can start there again, after being
kicked out again
· example: rapid diffusion of Au, Pt, and Zn in Si; also several dopants in Si
A i A i i
A +B =B A A ... selfinterstitials +
13
Abnormal fast
diffusion in Si
· abnormal fast diffusivity in Si is due
to interstitialsubstitutional exchange
mechanism (kickout mechanism)
14
Summary of diffusion mechanisms
1. direct interstitial mechanism (video)
2. vacancy mechanism (video)
3. FrankThurnbull mechanism (video)
4. Kickout mechanism (video)
15
Macroscopic description: Fick`s laws
· 1. Fick`s law (A. Fick 1855) describes diIIusion
('current¨ I of atoms) along a concentration
derivation/gradient dn/dx:
· 2. Fick`s law (diIIusion equation) describes in
addition time dependence
· is second order, linear partial differential equation
· solution requires starting and boundary conditions
d
D ... diffusion coefficient
d
n
I D
x
= ÷
2
2
n n
D
t x
c c
=
c c
· D is measured in m
2
/s (often in cm
2
/s)
· typical values:
· gases (normal conditions): 10
5
. 10
4
m
2
/s
· liquids (RT): 10
9
m
2
/s
· solids: 10
9
. 10
24
m
2
/s
· example: Au selfdiffusion at RT: D =10
24
m
2
/s
· this means about 10
10
m/day: 1 atomic distance
16
· description of temperature behavior can
often be described by an Arrhenius
relation
· the preexponential factor D
0
can be
written as:
· the socalled Arrhenius plot of diffusion
shows log (diffusivity) = f (1/T); when
Q is temperature independent, a straight
line with slope Q k
B
1
is found
Diffusion is strongly temperaturedependent
0
exp( )
... activation enthalphy of diffusion
B
Q
D D
k T
Q
= ÷
0
0
'
0
'
exp( )
... diffusion entrophy
... geometry factors, jump frequency
B
S
D D
k
S
D
A
=
A
17
Thinfilm solution
· thin layer of diffusing species (amount M per unit area) is located at x=0 of a semiinfinite
sample (selfexhausting source)
· concentration after time t is then described as
· the quantity is the typical diffusion length Dt
Special solutions of the diffusion equation
2
( , ) exp( )
4
M x
c x t
Dt
Dt
= ÷
t
The er ror function solution
· if at t = 0 the concentration of diffusing species is c(x,0) = 0 and if for t > 0 the
concentration at x = 0 maintained to be c (0, t) = c
s
= const., the solution of the diffusion
equation is:
· these conditions describe the indiffusion of a diffusor into semiinfinite solid with a non
volatile (nonexhausting) source (e.g. diffusor from gas phase)
( , ) where 1
2
s
x
c x t c erfc erfc z erf z
Dt
 
= · = ÷

\ .
18
Tracer method
· Only method for selfdiffusion, but works in general
· radioisotopic tracer atoms are deposited at surface of solid by e.g. electrodeposition
· isothermal diffusion is performed for a given time t
· often quartz ampoules are used (T<1600°C)
· sample is then divided in small slices either mechanically, chemically or by sputtering
techniques
· mechanically: for diffusion length of > 10 µm; D>10
11
cm
2
/s
· sputtering oI surIace: Ior small diIIusion length (at low temperatures) 2nm . 10µm
· for the range D = 10
21
. 10
12
cm
2
/s
Experimental determination of diffusion coefficient
19
· example: diffusion of Fe in
Fe
3
Si
· from such figures the
diffusion constant can be
determined with an accuracy
of a few percent
· stable isotopes can be used as
well, when highresolution
SIMS is used
· this technique is more
difficult
Experimental determination of diffusion coefficient
20
· sophisticated method: growth of
layer structure of material of
interest including olayers of
diffusing impurity
· example: B diffusion in Si with
and without Si implantation
(upper panel)
· after implantation: strong
enhancement of diffusion due to
implantationinduced defects
· lower panel: enhancement of
diffusion by implantation defects
is suppressed when C is present
at high concentration
· Si selfinterstitials are strongly
suppressed due to presence of C
· B diffusion is impeded (diffuses
via kickout mechanism)
· diffusion profiles were analyzed
numerically by MC methods
· different diffusion mechanism
can be separated this way
Diffusion studies using MBE olayers and SI MS
Rene Scholz, Ph.D. Thesis, Halle 1999
21
Typical schematic of a
dynamical SI MS instrument.
High energy ions are
supplied by an ion gun (1 or
2) and
focused on to the target
sample (3), which ionizes
and sputters some atoms off
the surface.
These secondary ions are
then collected by ion lenses
(5) and filtered according to
atomic mass (6), then
projected onto an electron
multiplier (7, top), Faraday
cup (7, bottom), or CCD
screen (8).
SI MS: Secondary Ion Mass Spectroscopy
22
Tabletop SI MS System
23
Diffusion depends on lattice structure and defect density
· diffusivity is much higher along grain boundaries and dislocations
· diffusion also depends on crystal lattice structure, i.e. the phase of an alloy (fcc and bcc Fe)
24
The Ki r kendall effect
· when two metals A and B are in direct contact, A atoms diffuse into B, and vise versa
· diffusion may be different, so at one side vacancy clusters are formed, the other material swells
welding
copper
brass
25
26
Zn diffusion in GaP
· Zn diffusion in GaP (also in GaAs) creates a large number of monovacancies
· in contradiction to all existing diffusion models
· further research required to fully understand diffusion
Positron annihilation result
27
Literature
· 'DiIIusion in Condensed Matter¨, J. Kärger, P. Heitjans, R. Haberlandt
Friedr. Vieweg & Sohn Verlagsgesell. mbH Braunschweig 1998
Analytical solutions of diffusion equation
,The Mathematics of DiIIusion', John Crank, Oxford University Press; 2. Ed. (1979, Reprint
2004.
,DiIIusion  Methoden der Messung und Auswertung', W. Jost, Verlag von Dr. Dietrich
Steinkopff, Darmstadt 1957
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