PHYSICAL VAPOR DEPOSITION (PVD)

PVD II: Evaporation

We saw CVD Gas phase reactants: pg 1 mTorr to 1 atm.
Good step coverage, T > 350 K

We saw sputtering

Noble (+ reactive gas) p 10 mTorr; ionized particles Industrial process, high rate, reasonable step coverage Extensively used in electrical, optical, magnetic devices.

Now see evaporation: Source material heated, peq.vap. =~ 10-3 Torr, pg < 10-6 Torr Generally no chemical reaction (except in reactive deposn),

= 10s of meters, Knudsen number NK >> 1

Poor step coverage, alloy fractionation: pvapor Historical (optical, electrical)
Campbell, Ch. 12 is more extensive than Plummer on evaporation
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Standard vacuum chambers

pi 10-6 Torr (1.3 10-4 N / m2)

Mostly H2O, hydrocarbons, N2 He by residual gas analysis (RGA = mass spec.)

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Ultra-high vacuum chambers

p < 10-8 Torr demands: Stainless steel chamber Bakeable to 150oC Turbo, ion, cryo pumps

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Knudson number 1

=
p = 10-10 25 23 Log[n (#/m3)] 21 19 17 10-8 10-6 10-4

10 10-2

0.01 cm 100 Torr

Sputtering CVD

1 Atm= 0.1 MPa 760 mm 14 lb/in2

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Evaporation -6 -4 -2 0 Log[P (N/m2)] 2 4

Ballistic, molecular flow, /L >> 1 High purity films Epitaxy

Generally /L < 1 Films less pure Epitaxy is rare

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Atomic flux on surface due to residual gas

p atoms nv x p 2kB T =J J = = = 2mk B T area t 2 2k B T m

Given 10-6 Torr of water vapor @ room temp, find flux

1atm 10 5 Pa p = 10 Torr , 760 T atm
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kB T (RT ) = 0.025eV = 4 1021 J

N p = 1.3 10 m2
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mH 2 O =

18 26 = 3 10 kg NA

atoms/molecules J = 4.8 1014 2 cm sec

What is atomic density in 1 monolayer (ML) of Si? N = 5 x 1022 cm-3 => 1.3 x 1015 cm-2. So at 10-6 Torr, 1 ML of residual gas hits surface every 3 seconds! Epitaxy requires slow deposition, surface mobility, So you must keep pressure low to maintain pure film
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Now add evaporation source

e-beam I Resistive heater Equilibrium vapor pressure: RF-induction heater _ B field

e+

H = heat of vaporization

H pv = p0 exp kB T
Strong T dependence
Work function

free

V(x)

eHeat of vaporization solid

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Vapor pressure of elements employed in semiconductor materials. Dots correspond to melting points

Rely on tables, attached: pvapor > > pvac,

Elemental metals easy to evaporate, but alloys compounds Differential pvapor so use 2 crucibles or deposit multilayers and diffuse Oxides, nitrides deposit in oxygen (or other) partial p

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(note W, Mo can be used as crucibles.)

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We expressed flux of residual gas: p J= Chamber p = 10-6 Torr 2mkB T

14 J 5 10 molecules

cm2s

The source also flux

J= pvap 2msource kB Tsource
For Al at 1000 K, pvap = 10 -7 Torr (from figure) m = species to be evaporated, = 27 amu for Al JAl 2 x 1013 Al/cm2-s just above crucible Therefore heat Al to T > 800 C but thats not all Net flow out of crucible ~ J Ac (# / t) Mass flow out of crucible ~ J Ac m ( mass / t) Note: 3 different temperatures: Tsource Tevaporant >> Tsubstrate > Tchamber = Tresid gas RT. System not in thermal equilibrium; only thermal interaction among them is by radiation and/or conduction through solid connects (weak contact). No convection when NK << 1.
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Ac

How much evaporant strikes substrate? At 10-6 Torr, trajectories are uninterrupted.
While a point source deposits uniformly on a sphere about it, a planar source does not: J

cos1
1

substrate

r r 1

substrate

R Convenient geometry

Ac Geometric factor = 2 cos 1 cos 2 2 R

Geometric factor = Deposition rate = Jm

cos1 = cos 2 = Ac 2 4 r

R 2r

Ac m or 2 4 r area t

Ac # 2 4 r area t

Ac 1 thick Film growth rate = Jm 2 4 r f t

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Film growth rate for evaporation

v=

Ac 1 thick = Jm 2 t 4 r f

pvap 2msource kB Tsource

Cg

pvap Ac Ac = 2 m 4 r m 4 r 2 m

msource 2k B Tsource

Cf. CVD

vf =

N 1 1 + ng k

oxide

v ox =

H pg N 1 t ox 1 + + h D ks

In PVD growth, strike balance R= deposition rate Surface diffusion rate R > 1 R < 1 stochastic growth, rough layer by layer, smooth (can heat substrate)

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Exercise Deposit Al (2.7 g/cm3) at r = 40 cm from 5 cm diam. crucible heated to 1100C (cf Tmelt) pAl vap 10-3 Torr,

pH 2 O = 106 Torr
(this is not good)

5 2 Ac = 2

Compare arrival rate of Al and H2O at substrateand calculate film growth rate (106 760)10 5 18 molecules J H2 O = = 4.8 10 2 ms 2 (0.025eV e) (18 N A )
Ac 18 atoms = 1.76 10 J Al = 2 2 ms 2 (1373k B ) (27 N A ) 4 r
3

(10

105 760)

pvap Ac v= m 4 r 2

msource 1011 m /s 2k B Tsource

slow!

Leave shutter closed so initial Al deposition can getter O2 and H2O. Also, better done at lower
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pH 2 O

or higher deposition rate.

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Step coverage is poor in evaporation (ballistic) - Shadow effects

Heat substrate to increase surface diffusion.

E Surf D = D exp a kT
S S 0

S E a << E a

bulk

By contrast, metal CVD and sputtering => better step coverage

e.g. WF6 + 3H2 W + 6HF G 70 kJ (0.73eV) mole W

Can do below 400C

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Other methods of heating charge. e-beam I Resistive heater RF-induction heater _ B field

e+

Can you suggest other methods? Laser: Pulsed Laser Deposition (PLD), laser ablation Ion beam deposition (IB)D:
keep substrate chamber at low P, bring in ion beam through differentially pumped path. Can also use ion beam on film to add energy (ion beam assisted deposition, IBAD)
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Ion beam Source, target

Substrate, film Ion beam

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Surface energy in a growing film depends on the number of bonds the adsorbed atom forms with the substrate (or number unsatisfied). This depends on the crystallography of the surface face and on the type of site occupied (face, edge, corner, crevice). Macroscopically, a curved surface has higher surface energy (more dangling bonds) than a flat surface.

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Microstructure types observed in sputtered films with increasing substrate temperature normalized to melting temperature of deposited species.

Quenched growth

Thermally activated growth

<a

<a

Ts/Tm > 0.3

Ts/Tm > 0.5

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Interfaces between dissimilar materials

Four characteristic equilibrium, binary phase diagrams, above, and the types of interface structures they may lead to, below (non-equilibrium). The first-column figures would apply to Ga-As, the second to Si-Ge. Third case, B diffuses into A causing swelling; A is forced by swelling into B as a second phase.
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Schematic stress strain curve showing plastic deformation beyond the yield point.

Upon thermal cycling, a film deposited under conditions that leave it in tensile stress may evolve through compression then even greater tension .

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