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Defects IV - RKR Diffusion

Defects IV - RKR Diffusion

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Defect Phenomena: Diffusion
· structures are getting smaller in all
technological developments (e.g.
nano-design)
· 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 co-implantation 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
· self-diffusion 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:
self-interstitials move below 1K !
· self-interstitial annealing after low-temperature
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 self-diffusion (e.g. in Si, since diamond lattice is relatively open)
ring vacancy interstitial
mechanism
· not important for self-diffusion in dense
metallic lattice (there: vacancy mechanism)
· self-interstitials 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 interstitial-substitutional exchange mechanism:
F rank-Turnbull 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 nterstitial-substitutional exchange mechanism without vacancies:
Kick-out 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 ... self-interstitials +
13
Abnormal fast
diffusion in Si
· abnormal fast diffusivity in Si is due
to interstitial-substitutional exchange
mechanism (kick-out mechanism)
14
Summary of diffusion mechanisms
1. direct interstitial mechanism (video)
2. vacancy mechanism (video)
3. Frank-Thurnbull mechanism (video)
4. Kick-out 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 self-diffusion 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 pre-exponential factor D
0
can be
written as:
· the so-called 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 temperature-dependent
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
Thin-film solution
· thin layer of diffusing species (amount M per unit area) is located at x=0 of a semi-infinite
sample (self-exhausting 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 in-diffusion of a diffusor into semi-infinite solid with a non-
volatile (non-exhausting) 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 self-diffusion, but works in general
· radioisotopic tracer atoms are deposited at surface of solid by e.g. electro-deposition
· 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 high-resolution
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 o-layers of
diffusing impurity
· example: B diffusion in Si with
and without Si implantation
(upper panel)
· after implantation: strong
enhancement of diffusion due to
implantation-induced defects
· lower panel: enhancement of
diffusion by implantation defects
is suppressed when C is present
at high concentration
· Si self-interstitials are strongly
suppressed due to presence of C
· B diffusion is impeded (diffuses
via kick-out mechanism)
· diffusion profiles were analyzed
numerically by MC methods
· different diffusion mechanism
can be separated this way
Diffusion studies using MBE o-layers 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
Table-top 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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