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 -singleg crystalline, defects, roughness, etc.) 7. changes within the bulk of the film, e.g. diff i diffusion, grain i growth th etc. t

Adsorption Process
vapor molecule reflection desorption

z x
substrate surface

Ji 1 , c Sc
physisorption chemisorption incorporation utilization

Ts
substrate temp.

L a

Ji=impinging flux = accommodation coefficient = chemisorption reaction probability c=condensation coefficient = utilization fraction

=trapping probability
Sc = sticking coefficient

Ref: D. L. Smith, Thin-Film deposition Principles & Practice, 1995, McGrawHill, Boston

Thermal Accommodation
Impinging atoms must lose enough energy thermally to stay on surface assume Equivalence between energy and temperature; E = kT. Thermal accommodation coefficient T=0 Er=Ev elastic collision (no energy loss) T=1 Er>Ev all excess energy 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 of f atoms t connected t db by springs if rebound is strong enough - atom escapes if not - atom is trapped - oscillates and loses energy to lattice Reflected Er,Tr Substrate; Ts Incident Ev,Tv

Thermal accommodation coefficient Ev Er Tv Tr T = = Ev Es Tv Ts

ko

ko

impinge rebound ebou d

Thermal Accommodation
ko ko k i i impinge 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 14 seconds f t around fast; d 10-14 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
40

2Y(g)

fH of Y2(g) Ep, kJ/mol Ea a Era Y2(g) Eda Edb Erb

Y2(g) = gas-phase molecule Y(g) = gas-phase atom Ea = activation energy Ep=0: enthalpy in the vapor phase, no kinetic energy fH: enthalpy of f formation f of f Y2 Ed: desorption barrier (physisorbed) Er: reaction barrier (p) (c) Ea: reaction barrier vapor (c) Ec: enthalpy th l i in chemisorbed h i b d state t t

-40

1kJ/mol ~ 1eV/atom

precursor physisorption
-400 advantageous: d t condensation d ti di directly tl i into 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

R t are thermally Rates th ll activated ti t d (A (Arrhenius h i l laws) )

Ei k i = vi 0 exp RT s

J i (1 ) = Rr + Rd   

# of physisorbed species that can chemisorb h i b or d desorb b

(conservation of mass)

J i / nS 0 = Rr = k r n S 0 = J i v J i / nS 0 + k r + k d Er Ed 0d 1 + exp RTS v0 r ( : Chemisorption coefficient)

= J 1

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 by y nucleation at nucleation sites like steps or non-passivated surface atoms) Rr if TS , desorption rate increases stronger than reaction rate (e. g. CVD at too high TS)

(Er-Ed) < 0:

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 Molecular hopping rate: k s = v0 s exp
E R Ts temperature, TS) (influence of substrate temperature

(v0s=10131016 Hz: attempt frequency) Diff i Diffusion: random d walk, lk not di directed. d Equal hopping probabilities for forward and backward motion Diff i l Diffusion length, th : = r N 0 a N 0 = a k s t (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 (physisorbed) E s = 200meV = 300 m = 5nm (chemisorbed) T = 1000 K 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 Molecular hopping rate: k s = v0 s exp
E R Ts temperature, TS) (influence of substrate temperature

(v0s=10131016 Hz: attempt frequency) Diff i Diffusion: random d walk, lk not di directed. d Equal hopping probabilities for forward and backward motion Diff i l Diffusion length, th : = r N 0 a N 0 = a k s t (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 (physisorbed) E s = 200meV = 300 m = 5nm (chemisorbed) T = 1000 K 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 2 (non constant number of surface atoms) unit: Jm-2 (nonsurface 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 atomic reconstruction Surface totpgraphy

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): hcp (Zn, Mg): diamond (Si (Si, Ge): CaF2: NaCl: {110} {0001} {111} {110} {100} polar/ionic bonding bonding, planes with lowest have same number of cations and anions

Zinc blende (GaAs, ZnSe): {110}

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 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

A j min

i + f < s

layer-by-layer growth (Frank-van der Merwe)

i s + f i > s + f

island growth (Volmer-Weber) minimization of total surface energy: low- facets of islands

f few ML l layer-by-layer, b l th then crossover t to i island 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 -------------------------------------------------------------------------------------------------Au u/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 g good bonding g 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 reach h these th sites it by b diffusion diff i or di directly tl f from th the vapor phase h homogeneous nucleation at random positions if s sufficient 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)
p a3 r 3 V GV = ( V C ) = RT ln p V Vmol V mol

p : pV supersaturation

2.) surface energy balance:

G S = a1 r 2 f + a2 r 2 i a 2 r 2 S

curved surface of the nucleus interface substrate surface

G = GV + G S

Nucleation on nonwetting substrate

Ji Ji Jv r s Af,f

v c = RT ln

J p = RT ln c ; pv Jv

c = v

Gibb free Gibbs f energy change h per nucleus l V G = ( v c ) + f Af Vmc

3 p 4 3 r = RT ln . + f 4r 2 pv Vmc

Ai,i Ji= incoming particle flux Jv=evaporating particle flux A = area (i:interface, f:film, s:substrate) = surface energy

c = chemical potential of condensate v = chemical potential of vapor pv = saturation vapor pressure p = vapor pressure Jc = condensing molecular flux Jv = evaporating molecular flux 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

r* =

2(a1 f + a2 i a3 s ) RT p 3a3 ln( ) Vmol pv

G (r*) =

4(a1 f + a2 i a3 s ) p 2 RT 27 a3 ln( ) V pv mol

2

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 a3 = (2 3 cos + cos 3 ) / 3
Smith 5.12 balance of surface forces (acting tangentially) for a spherical nucleus

S = i + f cos
2 3 cos + cos 3 G (r ) = 4 RT p 3 ln Vmol pV

16 3 f

= 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
40

2Y(g)

fH of Y2(g) Ep, kJ/mol Ea a Era Y2(g) Eda Edb Erb

Y2(g) = gas-phase molecule Y(g) = gas-phase atom Ea = activation energy Ep=0: enthalpy in the vapor phase, no kinetic energy fH: enthalpy of f formation f of f Y2 Ed: desorption barrier (physisorbed) Er: reaction barrier (p) (c) Ea: reaction barrier vapor (c) Ec: enthalpy th l i in chemisorbed h i b d state t t

-40

1kJ/mol ~ 1eV/atom

precursor physisorption
-400 advantageous: d t condensation d ti di directly tl i into 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 by y nucleation at nucleation sites like steps or non-passivated surface atoms) Rr if TS , desorption rate increases stronger than reaction rate (e. g. CVD at too high TS)

(Er-Ed) < 0:

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 homogeneou s nucleation l i on terrace r* =

RT n ln( s ) a nV Vmol

G (r*) =

2
RT ns a2 ln( ) V nV mol
2

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)

C = 0c1 exp
if atoms aggregate during tc they stay on the substrate

Ec RT

Ec is i hi highest h at steps, contaminations, i i etc. - higher hi h d density i of f nuclei l i nucleation rate: N = N * A *

N * = ns e G*/ kT

: equilibrium ilib i concentration t ti of f critical iti l nuclei, l i nS: total nucleation site density : attachment area of the critical nucleus : rate at which adatoms impinge onto
c=condensation coefficient

A* = 4 (r*) 2
( PV PS ) N A = 2MRT

Nucleation rate
= jump rate surface density of adatoms = jump rate vapor impingement rate

= v0 s exp
assume

E S pN A Ec 1 v0 exp c RT 2MRT RT

vos v0c :

E c E s G (r ) N = C r n s exp RT 2MRT NA pN
complex p expression, p but exponential p dominates: nucleation strongly depends on G(r*), thus can be influenced by T, p

r T

>0
p

r* increases with TS because supersaturation decreases late film coalescence (@ high average thickness)

G (r ) T r p

>0
p

density of stable nuclei increases slower with increasing T late film coalescence (@ high average thickness)

G (r ) higher h d deposition iti rate t smaller ll r*, faster f t increase i of f < 0, < 0 hi density of nuclei p T

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 RT r

EC related to ES, s = 13

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

i (r ) = 0 + RT ln

pi p

vapor pressure pi

2 pi (r ) = p exp rRT

b. mass transport b by evaporation growth of large nucleus at the expense of the small one

f (r ( > 0): 0) c. convex surface atoms evaporate concave co ca e su surface ace ( (r < 0) 0): 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

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

Ec Ds exp( ), Ec TM , Ds exp(TM / Ts ) k BTs

1 Es exp Ji 2 RT

Z2 zone
Column tops often facetted hard, low ductility Wide columns Wid l ( (small ll surface f curvature) t ) Widen at the expense of narrow columns (large surface curvature) Lateral growth gro th until ntil col column mn diameter >>

1 1 = r r 1 2

TM exp T s

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 y smooth surfaces, , grain g boundary yg grooving g relatively Sputtering: 0.6 < TS/TM<1.0 Low distortion density, soft

Zone vs Substrate Temperature

Zone 3 Zone 2 Zone1 Evaporation

Ts/ /TM
0 Sputtering Zone1 Zone T 0.5 0.9

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 get tb buried i db before 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 singleg 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