What does

Materials Science have to do with

Microelectronic Processing?
• Need to understand
Differences: metals, oxides and semiconductors
Atomic bonding, Oxidation rates, compound formation (GaAs)
chemical reactions Solubility of impurities in Si
Chemical reactions for CVD precursors, byproducts

• Need to understand
Gas concentration (critical to CVD reaction rates)
Gas diffusivity, Surface mobility (key to quality film growth)
Solid-state What controls interfaces (e.g. SiO2/Al)
diffusion crystal growth, and impurities
How manage grain growth, film microstructure

Electrical, mechanical properties depend on all of the above

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Vacuum Technology and film growth

p-channel

Poly Gate pMOS

Metal-Oxide-Semiconductor (MOSFET)
Polycrystaline Silicon
polysilicon
Source Gate Drain

Poly Si
ion-implanted Diffusion Resistor
n-Si Resistor

Oxide grown in steam, p-regions ion-implanted,

Al sputter deposited, others made by CVD

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 What will we cover in upcoming lectures?
• Chemical vapor deposition (CVD) Feb 14
Most widely used method for growth of high-grade
semiconductor, metals, oxide films,
• Oxidation Feb 16
Key advantage of Si: stable uniform oxide
How control its growth, thickness, quality

• Ion implantation and diffusion Feb 22

How semiconductor surfaces are doped Feb. 23

• IC testing Feb 28
How semiconductor surfaces are doped

• Physical vapor deposition (PVD) April 6, 13

Growth of quality films by sputter deposition or evaporation

These processes (ex IC test) done in vacuum or controlled environment.

Therefore, need to understand
vacuum technology,… gas kinetics.
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Gas Kinetics and Vacuum Technology

How far does a molecule travel between collisions?

m ≈ 5 x 10-26 kg
Consider a volume V of gas (e.g. N2)
L velocity
“Snap shot” N N
number N, n= =
V L3

d molecule impact parameter, scattering

=>
cross section = π d 2
d
“Movie”
Mean free path ≡ λ λ

πd2
Volume swept out by 1 molecule
between collisions = λπd 2
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 Volume swept out by 1 molecule
between collisions = λπd 2
Total volume of sample
λ
L3 = V ≈ Nλπd 2
πd2

V 1 2
"# $ = More accurately: "=
N%d 2 n%d 2 2n#d 2

Use 2 kB T
! "# = p λ (cm)
Ideal gas: 2$d 2 p !
1 atm 10-5
1 Torr 10-2
! 1 mT 10

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What is flux of atoms hitting surface per unit time?

vx nvx
area J ( # / area time)
= 2

# / vol. We need v x , v

Calculating gas velocities

P(v)
Maxwell speed distribution:
!
# m &3 / 2 2 # mv 2 &
P(v) = 4 " % ( v exp%) ( v vvms
$ 2"kT ' $ 2kT '
speed

v= " vP (v)dv
! 2kT 8kT , 3kT
vx = v= v rms =
1 2 3 "m "m m
Generally: mv " k B T
2 2 v x = v /2 vrms ≈ 500 m/s
!

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! !

3
!
 So flux of atoms hitting surface per unit time

vx area nv x n 2kT ideal p

Jx = = gas = Jx
2 2 "m 2"mkT
# / vol.

Compare:
2kB T
"=
2#d 2 p
!
2
E mv
Dimensional analysis: (force/area = en/vol.): p = kin = n = Jmv
Vol 2
!
p(Torr)
Numerically, J x = 3.5 "10 22 (atoms /cm 2 sec)
! /mole # K)
MT(g

This gives
! a flux at 10-6 Torr of 1 monolayer (ML) arriving per sec

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Diffusivity
ΔG
Recall diffusion $ #G'
in solids: D = D0 exp&" )
% kT (
Debye ν ≈ 1013 s -1

For gas, no energy barrier, just collisions.

dc n n J λ
J gas = "Dgas # "D
dx $ #v x
Dgas "
nvx 2
2 (cm2/s)
!
2kT T 3/2
recall "= " Dgas #
2#d 2 p p
vx " T or Dgas " T1/ 2

!
!
!
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!
 Review
2kB T
Ideal gas: pV = NkBT, "# = ≈ 10 cm at p = 1 mT
2$d 2 p

1 2 3
Generally: mv " k B T
2 2
!
nv x n 2kT ideal p E kin mv
2
Jx = = gas = Jx p= =n = Jmv
! 2 2 "m 2"mkT Vol 2

dc n #v x !
J gas = Dgas "D Dgas!" Weak temperature dependence
dx # 2
relative to solid state diffusion
(cm2/s)

! Lec. 3, Wed., Feb. 9, 2005 6.152J/3.155J 9

Knudsen number
L = dimension of chamber or reactor p λ (cm)
1 atm 10-5
2kB T
Recall: "= 1 Torr 10-2
2#d 2 p
1 mT 10

Flow is viscous; p > 1 mT

λ/L < 1 Pump power > viscosity;
!
Knudsen Must transport large # of molecules
number, N0 = λ/L
Molecular, ballistic flow;
λ/L > 1 p < 1 mT
Pump efficiency is critical;
Must attract and hold molecules

What does this imply for pumping?

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 Gas flow and pump speed
Gases are compressible, unlike liquids.
∴ express flow as number of molecules/time, not volume/t.
dN 1 " dp dV %
Q= = $V +p '
dt kB T # dt dt &

Conductance of
Pump throughput, Q:
vacuum component:
! pp
p1 p2
pump

" Q = C( p # p p ) Q " pS
Pump speed units, S = V /(k BT t )
Units of conductance = 1/(sec-Pa)
sccm or L/s
C ∝ area/length
! ! Std. cc/min Liters/sec
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Gas flow and pump speed

(pp is pressure
Conductance of vacuum component: " Q = C( p # p p )
nearer pump)

Q Q
But throughput: Q " pS, p = pp =
eff

S eff Sp
!
p chamber
# Q Q& CS p 1
Q = C%% eff " (( " S eff = =
! $S !S p ' C + Sp 1 + 1
C Sp
pp
pump
!S
p
Seff !

C
Effective pump speed, S , never exceeds
conductance of worst component or pump speed, S p .
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 Vacuum technology: Generating low pressure

Two classes of vacuum pumps: 1 dV

1) Molecules physically removed from chamber
S=
kT dt
a) mechanical pump

b) Turbo molecular pump

!
c) Oil diffusion pump p

2) Molecules adsorbed on a surface,

or buried in a layer
a) Sputter/ion pump (with Ti sublimation)

b) Cryo pump

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1) Molecules physically removed from chamber

a) Mechanical pump b) Oil diffusion pump c) Turbo molecular pump
1 atm
Oil contamination, Hot Si oil vaporized, Rotating (25 krpm) vanes (760 Torr)
Vibrations. jetted toward fore pump, impart momentum to gas,
But pumps from momentum transfer to gas, pres’re incr’s away from chamber,
1 atm to mT. 1 Torr
which is pumped out. gas pumped by backing pump.
S ≈ 2 x 104 L/s S = 12A L/s No oil. S = 10 L/s
3

1 milliT

10-6 T

10-9 T

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 2) Molecules adsorbed on a surface, or buried in a layer
a) Sputter/ion pump (with Ti sublimation) b) Cryo pump
1 atm

Gas is ionized (760 Torr)

by hi-V ,
ions spiral in B field, 1 Torr
embed in anode,
Coated by Ti.
No moving parts,
no oil.
S depends on Very clean, 1 milliT
pump size and molecules condense
S(H) >>S(O,N,H2O) on cold (120 K) surfaces,
No moving parts. S ≈ 3A (cm2)L/s

10-6 T
v

B
10-9 T

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PUMP SUMMARY

Two classes of vacuum pumps:

1) Molecules physically removed from chamber
a) mechanical pump Pumps from 1 atm; moving parts, oil

b) Turbo molecular pump Clean, pumps lg. M well, from 1 atm;

low pump speed, moving parts
c) Oil diffusion pump No moving parts; oil in vac

2) Molecules adsorbed on a surface,

or buried in a layer
a) Sputter/ion pump Clean, pumps reactants, no moving parts;
(with Ti sublimation) pumps from 10-4 T.

b) Cryo pump Clean, no moving parts;

pumps from 10-4 T.

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 Vacuum technology: Deposition chambers

Standard vacuum, p ≈ 10-5 -10-6 Torr Ultrahigh vacuum, p ≈ 10-8 -10- 11 Torr;
Glass or stainless steel, Stainless steel (bakeable);
usually diffusion pumped, Ion and/or turbo pumped
CVD, thermal evap. or sputter dep. thermal evap. Sputter deposition
=> polycrystalline films => better quality films, epitaxial

1. Get
p < 1 mT;
close valve

2. Open
backing valve,
Turn on diff’n
pump

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Vacuum technology: Deposition chambers

Ultrahigh vacuum, p > 10-11 Torr;

Stainless steel (bakeable);
Ion and/or turbo pumped
thermal evap. Sputter deposition
=> better quality films, epitaxial

Baking a stainless-steel uhv system

(T up to 200 C for 10’s of hrs)
desorbs water vapor, organics
from chamber walls;
these are ion-pumped out;
pressure drops as T returns to RT.

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 Thin film growth general Bonds on 3 sides

3 bonds with substrate

Arrival, sticking,
surface diffusion,
More bonds bonding
Bonds on 1 side

Rate of arrival arrival

R≡ Film growth
Diffusion rate competes with gas arrival. growth
diffusion

1) R > 1 ⇒ Non-equilibrium, fast growth, many misaligned islands form,

leading to defective (high-surface-en), polycrystalline film, columnar
grains, This 3-D growth is “Volmer-Weber” mode; Can ⇒ amorphous film.

2) R < 1 => Slower, more equilibrium, layer-by-layer growth, larger grains

(raise surface temperature to ↑ mobility ⇒ ↑ g.s. ). If film and substrate
have same crystal structure, film may grow in perfect alignment with
substrate (“epitaxy”). This 2-D growth is “Frank-van der Merwe” mode.
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Thin film growth details (R < 1)

Rate of arrival
R≡
Diffusion rate

1) Arrival rate, 3) Chemical

physical reaction 5) Growth
adsorption

4) Nucleation 6) Bulk diffusion

Better quality films;

2) Surface layer-by-layer growth
diffusion

If R > 1, processes 2) - 6) have reduced probability;

=> poor quality, rough films
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 Looking ahead…

Thin films made by a variety of means:

thermal vapor deposition (evaporation)
- for metals Physical vapor deposition
(PVD)
sputter deposition
DC-magnetron- for metals
-RF for oxides

chemical vapor deposition Chemical vapor deposition

- for metals, semiconductors (CVD)

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