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Basic steps of thin film growth

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

Ji=impinging flux = accommodation coefficient =trapping probability


= chemisorption reaction probability c=condensation coefficient Sc = sticking coefficient
= utilization fraction

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

assume Equivalence between energy


and temperature; E = kT. Substrate; Ts

Thermal accommodation coefficient Thermal accommodation coefficient


T=0 Er=Ev elastic collision (no
energy loss) Ev Er Tv Tr
T=1 Er>Ev all excess energy
T = =
Ev Es Tv Ts
loss
Examine energy transfer to lattice:
one dimensional model from B.McCarrol
and G. Ehrlich, J. Chem. Phys. 38, 523
(1963).
Consider
C id a chain
h i off atoms
t connectedt dbby impinge
ko ko k
springs
if rebound is strong enough - atom
rebound
ebou d
escapes
if not - atom is trapped - oscillates
and loses energy to lattice
Thermal Accommodation

i i
impinge
ko ko k

rebound

atom is trapped if Ev < 25 Edesorb


Edesorb ~ 1-4 eV
Ev < 25 - 100 eV or Tv < 2500 - 10,000 K
ptrapped
most
most deposition processes have Ev < 10 eV
Most atoms are trapped
Thermal accommodation is very
f t around
fast; d 10-14
14 seconds
d
Adsorption Process
molecule arrives from the vapor phase:
attractive force at distance of a few atomic diameters from the substrate
non-polar
l molecules:
l l van-der-Waals
d W l forces
f
polar molecules: stronger forces
transfer of kinetic energy to the substrate, adsorption
prec rsor adsorption
precursor adsorption: weak
eak bonding as a prec
precursor
rsor to strong bonding
SiH4 (g) ... SiH4 (p) Si (c) + 2H2 (g) ; p=physisorption; (c) chemisorption

alloy films: 2 components in the vapor phase


Zn (g) + Zn (c) Zn2 (p)
Zn (g) + Se (c) ZnSe (c)

H- passivated surface:
Si (g) + H (c) Si (p)
chemisorption only on non-passivated
non passivated sites Si (g) + Si (c) Si (c)

stronger bonding at surface steps

metal atoms on non-metallic substrates:


metal-metal bondings stronger than metal-substrate bondings
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

Rate of chemisorption Rr = rate constant kr ML concentration nS0 coverage


Rate of desorption Rd = rate constant kd ML concentration nS0 coverage
ns0: number density of surface atoms in a ML

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

assumption: ki independent of surface site (no surface steps etc.)


TS low enough to avoid thermal decomposition

(Er-Ed) > 0: activation energy for chemisorption, Rr if TS


((e.g.
g CVD,, decomposition
p of SiH4 - can also be induced byy
nucleation at nucleation sites like steps or non-passivated surface
atoms)

(Er-Ed) < 0: Rr if TS , desorption rate increases stronger than reaction rate


(e. g. CVD at too high TS)

nucleation is problematic if precursor-precursor bonding is stronger than


precursor-substrate bonding island growth, inhomogeneous coverage
e.g. Zn/Cd on glass or NaCl

high Ea : metal atoms stay physisorbed, desorb or nucleate to islands


Diffusion
extremely important for thin film formation
allows adsorbed species to form clusters (homogeneous nucleation)
allows adsorbed species to find heterogeneous nucleation sites (steps etc
etc.))
adsorbed atoms move in potential energy "landscape"
generated by substrate or thin film surface atoms: diffusion, hopping
Diffusion
ES < Ed , Ec : only partial breaking of bonds

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)

desorption from chemisorbed state after

maximum in close to re-evaporation


re evaporation temperature
best film quality (smoother, less defects, more homogeneous)
Diffusion
ES < Ed , Ec : only partial breaking of bonds

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)

Fundamental to thin film growth:


Surface energy can be minimized by surface diffusion

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

i + f < s layer-by-layer growth (Frank-van der Merwe)

i s + f island growth (Volmer-Weber)


minimization of total surface energy:
i > s + f
low- facets of islands

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

Au on glass 3D- nucleation


Cr on glass 2D- nucleation O-Si Si-Cr/O-Cr bondings
Au on Cr 2D 2D- nucleation,
nucleation strong metallic bonding
--------------------------------------------------------------------------------------------------

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:

ion beam irradiation of the substrate surface


(breaks bonds, enhances reactivity, destroys islands i.e. disturbs equilibrium - ion
beam irradiation is often very effective)

apply a surfactant reduces f more than S


(water on glass: drops - soapy water on glass: layers)

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

2.) surface energy balance:

G S = a1 r 2 f curved surface of the nucleus


+ a2 r 2 i interface
a 2 r 2 S substrate surface

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

Growth of nuclei with r>r*


r r to lower total enthalpy more stable nuclei
Nuclei with r< r* spontaneously disintegrate
Critical radius r* and nucleation barrier decrease with increasing supersaturation
Contact Angle

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

assumption: ki independent of surface site (no surface steps etc.)


TS low enough to avoid thermal decomposition

(Er-Ed) > 0: activation energy for chemisorption, Rr if TS


((e.g.
g CVD,, decomposition
p of SiH4 - can also be induced byy
nucleation at nucleation sites like steps or non-passivated surface
atoms)

(Er-Ed) < 0: Rr if TS , desorption rate increases stronger than reaction rate


(e. g. CVD at too high TS)

nucleation is problematic if precursor-precursor bonding is stronger than


precursor-substrate bonding island growth, inhomogeneous coverage
e.g. Zn/Cd on glass or NaCl

high Ea : metal atoms stay physisorbed, desorb or nucleate to islands


2D-Nucleation
= 0: no nucleation barrier?

Sufficient surface diffusion: adsorbed


atoms form 2D-gas at the surface
Replace surface energy by step energy
(bonding partners are missing)

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

if atoms aggregate during tc they stay on the substrate

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

A* = 4 (r*) 2 : attachment area of the critical nucleus

( PV PS ) N A : rate at which adatoms impinge onto


=
2MRT
c=condensation coefficient
Nucleation rate
= jump rate surface density of adatoms = jump rate vapor impingement rate
E S pN A E
= v0 s exp v0c1 exp c
RT 2MRT RT
assume vos v0c :
E c E s G (r )
NA
pN
N = C r n s exp


2MRT RT
complex
p expression,
p but exponential
p dominates:
nucleation strongly depends on G(r*), thus can be influenced by T, p

r r* increases with TS because supersaturation decreases


>0 late film coalescence (@ high average thickness)
T p

G (r ) density of stable nuclei increases slower with increasing


>0
T T late film coalescence (@ high average thickness)
p

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

kinetic theories of nucleation :


number density of stable nuclei
decreases after a certain time

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

chemical potential, I, of a spherical nucleus consisting of i atoms (:atomic volume):

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

Structure Zone model


Valid for many deposition techniques
Valid for metals semiconductors
and insulators

Superposition of physical processes


which establish structural zones
Z1 zone

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

High disorder density, hard


ZT (transition) zone

Sputtering:
0.1 < TS/TM<0.4 ((0.15 Pa)) 0.4 < TS/TM<0.5 ((4 Pa))
fibrous grains, dense grain boundaries

High disorder density, hard, high strength, low ductility


Z2 zone

Evaporation: 0.3 < TS/TM<0.5 Sputtering: 0.4 < TS/TM<0.7


surface diffusion increasingly important
Many materials: sharp transition Z1Z2 @ TS/TM = 0.3
Ec
Ds exp( ), Ec TM , Ds exp(TM / Ts )
k BTs
correlation Ec & TM: bonding strength
columns, dense g grain boundaries ((voids are filled by
y surface
diffusion)
Less defects than in Z1,ZT
Transition temperature Z1Z2 increase with deposition rate, Ji
1 Es
exp
Ji 2 RT
Z2 zone

Column tops often facetted hard, low ductility

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

Diffusion sufficiently high to establish


mechanical equilibrium at the interface
(thermal grooving)
Z3 zone

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

Low distortion density, soft


Zone vs Substrate Temperature
Zone 3

Zone 2

Zone1

Evaporation

Ts//TM
0 0.5 0.9
Sputtering

Zone1
Zone T
Zone 2

Zone 3
Zone example
Kinetically Restricted Growth

low TS/TM: surface diffusion can be neglected


g

atoms stick immediately to the surface


and
d gett b
buried
i dbbefore
f ah
hopping
i process occurs

ballistic deposition
statistic roughening due to fluctuations in the deposition rate
& shadowing: g

columnar growth, void formation


In or Out

in most cases: Z1 undesired


optical applications: absorption
absorption, diffuse scattering
isolators: defect induced conductivity
semiconductors: trapping sites

If high Ts cannot be applied: ion beam assisted deposition (IBAD) ZT

Z1 porosity is of advantage for


gas detectors (adsorption of gas changes property, e.g. electrical
resistance)
catalytic applications, e.g. fuel cells
coatings that are subject to large T-changes
(missing lateral stability prevents delamination due to differential
thermal expansion)
p )
Summary
high deposition rate & low substrate temperature:
fine- grained polycrystalline or amorphous film, coalescence
at small average thickness
thickness, relatively smooth

low deposition rate & high substrate temperature:


coarse- g
grained p
polycrystalline
y y ((or single-
g crystalline
y film),
),
coalescence at high average thickness, relatively rough
Summary

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