Professional Documents
Culture Documents
1. Thermal accommodation
2 Adsorption (physisorption) of
2.
atoms/molecules
3. surface diffusion
4. formation of molecule-molecule and
substrate-molecule bondings
( h i
(chemisorption)
ti )
5. nucleation: aggregation of single
atoms/molecules
6. structure and microstructure formation
((amorphous-
p polycrystalline
p y y -single-
g
crystalline, defects, roughness, etc.)
7. changes within the bulk of the film, e.g.
diff i
diffusion, grain
i growthth etc.
t
Adsorption Process
vapor desorption
molecule reflection
z
1
Ji
x
, c
Sc
substrate
surface
physisorption chemisorption incorporation utilization
Ts L
substrate temp.
a
Ref: D. L. Smith, Thin-Film deposition Principles & Practice, 1995, McGrawHill, Boston
Thermal Accommodation
Impinging atoms must lose enough Reflected Incident
energy thermally to stay on surface Er,Tr Ev,Tv
i i
impinge
ko ko k
rebound
H- passivated surface:
Si (g) + H (c) Si (p)
chemisorption only on non-passivated
non passivated sites Si (g) + Si (c) Si (c)
b Erb
-40 1kJ/mol ~ 1eV/atom
precursor physisorption
-400
advantageous:
d t condensation
d ti didirectly
tl iinto
t
chemisorbed state
high kinetic energy and molecule dissociation
in the vapor phase required (sputtering, PLD)
-600
600 dissociative chemisorption
Ref: D. L. Smith, Thin-Film deposition Principles & Practice, 1995, McGrawHill, Boston
Adsorption
Ei
R t are thermally
Rates th ll activated
ti t d (A
(Arrhenius
h i llaws)) k i = vi 0 exp
RTs
J i (1 ) = Rr + Rd (conservation of mass)
# of physisorbed species that
can chemisorb
h i b or d desorb
b
J i / nS 0 = J
= Rr = k r n S 0 = J i
J i / nS 0 + k r + k d v Er Ed
1
1 + 0d
exp
v0 r RTS
( : Chemisorption coefficient)
Adsorption
E
Molecular hopping rate: k s = v0 s exp (influence of substrate temperature
temperature, TS)
R Ts
(v0s=10131016 Hz: attempt frequency)
Diff i
Diffusion: random
d walk,
lk not di
directed.
d
Equal hopping probabilities for forward and backward motion
th : = r N 0 a N 0 = a k s t
Diff i llength,
Diffusion
(r: rms change in distance per hopping event, N0: number of hops, a: lattice constant,
t: diffusion time))
v0 s = 1013 S 1
E s = 20meV
E s = 200meV = 300 m (physisorbed)
= 5nm
T = 1000 K (chemisorbed)
t = 1s
Strong influence of bonding conditions!
a = 0.3nm
Diffusion
diffusing molecules may desorb or be buried
average time between adsorption and burial by incident molecules: tb=n0/Ji
n0: adsorption site density (#cm-2), Ji: incident flux (#cm-2s-1)
E
Molecular hopping rate: k s = v0 s exp (influence of substrate temperature
temperature, TS)
R Ts
(v0s=10131016 Hz: attempt frequency)
Diff i
Diffusion: random
d walk,
lk not di
directed.
d
Equal hopping probabilities for forward and backward motion
th : = r N 0 a N 0 = a k s t
Diff i llength,
Diffusion
(r: rms change in distance per hopping event, N0: number of hops, a: lattice constant,
t: diffusion time))
v0 s = 1013 S 1
E s = 20meV
E s = 200meV = 300 m (physisorbed)
= 5nm
T = 1000 K (chemisorbed)
t = 1s
Strong influence of bonding conditions!
a = 0.3nm
Nucleation
surface energy per unit area, : energy per unit area needed to create or increase a
surface
(non constant number of surface atoms) unit: Jm-22
(non-
surface stress: force per unit length needed to increase a surface
(constant number of surface atoms, solids only) unit: Nm-1, includes strain
contribution
Nucleation
W = 2 A = 2 x b
F W Force acts tangentially
= = 2
b x b Tends to decrease surface area
Surface energy exists because bonds are broken to create/increase the surface
(surface stress: bonds are elastically strained)
Strong driving force: minimization of surface energy (spherical soap bubble)
A min
Chemical composition
crystallographic orientation Surface totpgraphy
atomic reconstruction
Nucleation
usually is anisotropic, i.e. differently oriented surfaces have different
(differences in metals are of the order of % - larger in covalent or ionic systems)
fcc crystal (Au, Al): {111} surfaces have lowest surface energy atoms in closed
packed (111) lattice planes have most in-plane bonding partners and smallest
interplanar bonding
bcc (Cr,Fe):
(Cr Fe): {110}
hcp (Zn, Mg): {0001}
diamond (Si
(Si, Ge): {111} polar/ionic bonding
bonding,
Zinc blende (GaAs, ZnSe): {110} planes with lowest have
CaF2: {110} same number of cations
NaCl: {100} and anions
surface reconstruction: atomic positions and surface bonds are different from those
in the bulk in order to decrease ( 50 %!) can increase Er (PSCS)
surface passivation: addition of a ML of an element, dangling bonds react to
terminated bonds prevents reconstruction
reconstruction, often more effective than
reconstruction.
Nucleation
thin film nucleation: interplay of 3 surface energies per unit area
s: substrate free surface
f : film free surface j A j min
I : substrate/film interface
relative magnitudes of these quantities strongly influence nucleation
(provided that nucleation is not kinetically limited and can approach equilibrium)
Smith 5.8
5 8 or Ohring 5.2
52
f
few ML llayer-by-layer,
b l th
then crossover tto iisland
l d growth
th
(not only a -effect, see Ch,7 - Epitaxy) (Stranski-Krastanov)
Nucleation
3D- nucleation (islands) is usually undesirable
mitigation strategy: change one or more of the j such that i + f > s
- i is lower for materials with same type of bonding (metallic/covalent/ionic)
- i is lower in case of chemical reactivity
Auu/C Cr / g
glass
ass layer-by-layer,
aye by aye , wetting
ett g
Cr is an intermediate glue layer; 3-10nm sufficient
(continuous layer)
Ti: similar ggood bondingg material
Nucleation
alternative methods to prevent island growth:
i + f > s
i + f < s
Classical Nucleation
heterogeneous nucleation
takes place at "active" surface sites (steps, defects, contamination); low local i
atoms
t reachh these
th sites
it byb diffusion
diff i or di
directly
tl ffrom th
the vapor phase
h
homogeneous nucleation
at random positions
if ssufficient
fficient high n
number
mber of atoms meet thro
through
gh diff
diffusion
sion to form a stable n
nucleus
cle s
surface energy critical radius for nucleation
Nucleation
formation of a nucleus:
1 ) Gibbi
1.) Gibbis
s free enthalpy of the nucleus,
nucleus GV, decreases if JC/JV > 1
(JC: condensing molecular flux, JV: evaporating molecular flux)
V p a3 r 3 p
GV = ( V C ) = RT ln :
Vmol V Vmol
p pV supersaturation
G = GV + G S
Nucleation on
nonwetting substrate
Ji
p J
v c = RT ln = RT ln c ; c = v
pv Jv
Ji Jv Af,f
Gibb free
Gibbs f energy change
h per nucleus
l
r V
G = ( v c ) + f Af
s Vmc
p 43 r 3
= RT ln . + f 4r 2
pv Vmc
Ai,i c = chemical potential of condensate
v = chemical potential of vapor
pv = saturation vapor pressure
Ji= incoming particle flux
p = vapor pressure
Jv=evaporating particle flux
Jc = condensing molecular flux
A = area (i:interface, f:film, s:substrate)
Jv = evaporating molecular flux
= surface energy
Vmc= molar volume of the condensate
Surface Energy Balance and critical radius
Gs = a1r 2 f + a2 r 2 i + a3 r 2 s
= curved surface of nucleus
+ interface
+ substrate
G = GV + GS
2(a1 f + a2 i a3 s ) 4(a1 f + a2 i a3 s )
r* = G (r*) = 2
RT p RT p
3a3 ln( ) 27 a32 ln( )
Vmol pv
Vmol pv
a1 = 2 (1 cos )
a 2 = sin 2 for a spherical nucleus
a3 = (2 3 cos + cos 3 ) / 3
balance of surface forces
Smith 5.12 (acting tangentially)
S = i + f cos
16 3f 2 3 cos + cos 3
G (r ) =
RT p 4
3 ln
Vmol pV
= 0: G(r*) = 0 ideal wetting, layer-by-layer growth, no nucleation barrier
nucleation even if p < pV (oxidation of metals at very low oxygen partial pressure)
= 180: G(r*) = max corresponds to bulk homogeneous nucleation
Precursor adsorption model
b a
2Y(g) Y2(g) = gas-phase molecule
40 c Y(g) = gas-phase atom
Ea = activation energy
Ep=0: enthalpy in the vapor phase,
fH of Y2(g)
no kinetic energy
Ep, Era fH: enthalpy off formation
f off Y2
Ea Y2(g)
kJ/mol Ed: desorption barrier (physisorbed)
Er: reaction barrier (p) (c)
a Eda
Ea: reaction barrier vapor (c)
Edb Ec: enthalpy
th l iin chemisorbed
h i b d state t t
b Erb
-40 1kJ/mol ~ 1eV/atom
precursor physisorption
-400
advantageous:
d t condensation
d ti didirectly
tl iinto
t
chemisorbed state
high kinetic energy and molecule dissociation
in the vapor phase required (sputtering, PLD)
-600
600 dissociative chemisorption
Ref: D. L. Smith, Thin-Film deposition Principles & Practice, 1995, McGrawHill, Boston
Adsorption
h
homogeneous nucleation
l i on terrace
2
r* = G (r*) = 2
RT n RT n
a ln( s ) a 2 ln( s )
Vmol nV
Vmol nV
2D nucleation (2)
Spiral growth of thin films (only if surface diffusion is strong):
No homogeneous nucleation necessary, always steps present
2D nucleation (3)
Nucleation rate
nucleation rate = d/dt (surface density of stable nuclei)
early stages: nuclei dont grow through direct impingement of gas phase atoms
more important:
p rate at which adsorbed atoms attach a critical nucleus
adsorbed atoms remain until desorption for (adatom lifetime)
Ec
C = 0c1 exp
RT
Ec is
i hi
highest
h at steps, contaminations,
i i etc. - higher
hi h d density
i off nuclei
l i
nucleation rate: N = N * A *
: equilibrium
ilib i concentration
t ti off critical
iti l nuclei,
l i
N * = ns e G*/ kT nS: total nucleation site density
r G (r )
< 0, < 0 hi
higher
h d deposition
iti rate
t smaller
ll r*, faster
f t increase
i off
p T
p T
density of nuclei
Cluster Coalescence
coalescence of nuclei
driving force: minimization of surface energy
a. cluster migration & rotation, coalescence results from random collisions of clusters
1 EC
D(r ) S exp EC related to ES, s = 13
r RT
Cluster Coalescence
pi
i (r ) = 0 + RT ln vapor pressure pi
p
2
pi (r ) = p exp
rRT
b. mass transport
b f
c. convex surface (r
( > 0):
0)
by evaporation
growth of large atoms evaporate
nucleus at the concave
co ca e su
surface
ace ((r < 0)
0):
expense of the
small one atoms condense
Cluster Coalescence
Zone Model
Evaporation:
TS/TM < 0.3 surface diffusion can be neglected ( < a)
highly
g y disordered columnar small diameter ((~ 10 nm)) crystals
y
tapers columns, dome tops, voided boundaries
promoted by substrate roughness and oblique deposition
Sputtering:
TS/TM < 0.1 (0.15 Pa) TS/TM < 0.1 (0.15 Pa)
kinetic energy of depositing atoms compensates low thermal mobility
Sputtering:
0.1 < TS/TM<0.4 ((0.15 Pa)) 0.4 < TS/TM<0.5 ((4 Pa))
fibrous grains, dense grain boundaries
Wide columns
Wid l ((smallll surface
f curvature)
t )
Widen at the expense of narrow columns (large surface curvature)
Lateral growth
gro th until
ntil col mn diameter >>
column
TM
exp
Ts
1 1
=
r1 r2
Evaporation:
TS/TM>0.5
0.5 - significant surface and bulk diffusion
recrystallization/grain growth, Oswald ripening during thin film growth
large equiaxed grain, grain size film thickness
relativelyy smooth surfaces,, grain
g boundaryyggrooving
g
Sputtering:
0.6 < TS/TM<1.0
Zone 2
Zone1
Evaporation
Ts//TM
0 0.5 0.9
Sputtering
Zone1
Zone T
Zone 2
Zone 3
Zone example
Kinetically Restricted Growth
ballistic deposition
statistic roughening due to fluctuations in the deposition rate
& shadowing: g
models used here ("capillarity theory") give a simple picture and correct tendencies
but: results are not exact
calculations often result in too small r*, even if correct parameters (j,...) are used
validity of macroscopic concepts (like j) is questionable
everything is based on the assumption of a system in thermodynamical equilibrium
but: most preparation processes are subject to kinetic constraints
Kinetic nucleation theories can be found in the books by Smith and Ohring