Chemical Vapor Deposition (CVD)

Processes: gift of SiO2 - Expose Si to steam => uniform insulating layer

or metal film growth :
Contrast with

CVD:

high vacuum, single element

toxic, corrosive gas flowing through valves,

T up to 1000C, multiple simultaneous reactions,

gas dynamics, dead layers whose idea was it?

All layers above poly-Si made by CVD, except gate oxide and aluminum
Mon., Sept. 15, 2003

CVD
reactors
Four
reaction
chambers
(similar to those
for Si oxidation)

Control
module

Control T,
gas mixture,
pressure,
flow rate

Mon., Sept. 15, 2003

CVD is film growth from vapor/gas phase via chemical reactions

in gas and on substrate:
e.g. SiH4 (g) Si (s) + 2H2 (g)
Do not want Si to nucleate above substrate (homogeneous nucleation),
but on substrate surface (heterogeneous nucleation).

Twall
Reactor

Transport
of precursors
across
dead layer to
substrate

Susceptor
Pyrolysis: thermal
decomposition
at substrate

film

sub>

Mon., Sept. 15, 2003

Twall

Removal of
by-products
Chemical reaction:
Decomposed species
bond to substrate

More details
3

CVD Processes

8
1

Bulk transport
of byproduct

Bulk
transport

Reactant
molecule
Carrier gas
(Maintain hi p,
slow reaction)

J1 Dg DC

2 Transport

across bndry
layer
3

Diffusion of
(g) byproduct

Decomposition

6 Desorption

Adsorption

Reaction with film

J 2 ~ k iCi
Surface diffusion
Mon., Sept. 15, 2003

Gas transport
2 Transport

across
boundary
layer

J1 Dg DC

Knudsen NK

l
<1
L

Viscous flow

lv x
Dgas
2

Mon., Sept. 15, 2003

Revisit gas J = h C - C
1
g( g
s)
dynamics:

Boundary layer

l vx
D=
2

And we saw gas diffusivity

dC
D
J1 = D
=
Cg - Cs)
(
dx d(x)
Layer thickness, d(x)
(unlike solid)

boundary layer

gas vel: u0

d (x)

Cg

us = 0
wafer

wafer

Fluid dynamics:

1
d =
L

d( x ) =

hx
ru0

d (x)

Cs

x=L

r = mass density, h = viscosity

h
2 L
2
d (x )dx = 3 L ru L 3 Re
0
0

D
3D
So: hg = d 2 L Re

Mon., Sept. 15, 2003

uL

Reynolds #: Re = r 0
h
ease of gas flow

Several processes in series

Simplify CVD to 2 steps:
Boundary
layer

AB

Dg
J1 =
DC
d

J2

J 2 = ksCs
Sticking coefficient gAB,
0 gAB 1
AB bounces
off surface

Good
adhesion

Reaction rate constant, ks

as in oxidation, but no
sold-state diffusion here,
reaction occurs at surface.
Lets analyze, solve for J2
Mon., Sept. 15, 2003

Two main CVD

process:
AB

J1 =

Dg

Boundary
layer

J1 = hg (Cg - Cs)

DC

J2

B
A

J 2 = k sCs
In steady state:

J 1 = J2 ,

hg ( Cg - C s ) = k sC s
Electrical analogy:

Cs =

hg
hg + k s

Cg

J 2 = k sCs =

hg k s
hg + k s

J1 = J2,

R = R1+R2
G = 1/R= G1G2 /(G1+G2)
Two processes in series; slowest one limits film growth
Mon., Sept. 15, 2003

Cg

Two main CVD

process:
AB

J1 =

Dg

DC

Boundary
layer

J1 = hg (Cg - Cs)

J2

B
A

J 2 = k sCs
J 2 = k sCs =

hg k s
hg + k s

Cg
Cg N f
=
v=
1 1
hg + k s N f
+
hg k s
hg k s C g

# 1

,
Film growth rate v = J
area - t #
N

vol

Slower process controls growth

Mon., Sept. 15, 2003

Two main CVD

process:
AB

Boundary
layer

J1 = hg (Cg - Cs)

J2

B
A

J 2 = k sCs

Cg N f
v=
1 1
+
hg ks

Examine these 2 limits of growth,

hg or ks limited
Reaction limited growth,
Transport limited growth,
ks<< hg:
hg << ks:

v=

hg Cg
Nf

3DCg
3lv xCg Re

Re =
2LN f
4LN f

DG
k sCg Cg
v=
=
k 0e kT
Nf
Nf

ease of gas flow

Mon., Sept. 15, 2003

10

Transport limited growth :

v=

hg Cg
Nf

3DCg
2LN f

Re =

Reaction limited growth :

3lv xCg Re

DG
k sCg
Cg
v=
=
k 0e kT
Nf
Nf

4LN f

Most CVD is done in this limit

where gas dynamics,
reactor design are important.

G = free energy change in reaction

(G @ H for gas
becasue gas reaction no S)

Remedy for boundary layer

J2

A
Susceptor, 3o -10o

More uniform ug, Cg fi

uniform film growth rate , v

Choice of reactants and

temperature are critical
Mon., Sept. 15, 2003

11

CVD FILM GROWTH

GAS TRANSPORT-LIMITED

REACTION-RATE LIMITED

3lvx Cg
v=
Re
4N f L

l=
Cg
Pg

kBT
,
2
2pd Pg
=

v=

2k B T
vx =
,
pm

Nf

Cg
Nf

Re ~ u0

DG
kT

(G @ H for gas no S for

gas reaction)

- DH

k 0e

G = free energy change in reaction

1
kBT

v T

k sCg

v~e

u0
Mon., Sept. 15, 2003

kT

12

Transport
limited

v T

ln (v)
1

high T

u0

low T

gas - vel ,

Most CVD is transportlimited. Slow, layer-by-layer ln (v)

growth, epitaxy. Requires
high T, low pressure, low gas
viscosity. Chamber design,
gas dynamics control
process.
To reduce nucleation of
products in gas phase, use
low partial pressure (LPCVD).

u0

Reaction
limited

- DH

v~e

Rate:

T 1/2
fi DH
Arrhenius-like
1/T
1000K

Mon., Sept. 15, 2003

400K

T
13

kT

Review CVD
We saw
CVD is film growth from vapor/gas phase via chemical reactions
in gas and at substrate:
e.g. SiH4 (g) Si (s) + 2H2 (g)

Twall
Reactor

Transport
of precursors
across
dead layer to
substrate

Susceptor

film

sub>

Removal of
by-products

Twall

Pyrolysis:

Chemical reaction:

thermal decomposition
at substrate

Decomposed species
bond to substrate

Mon., Sept. 15, 2003

14

Gas transport
limited
ln (v)

Reaction
limited
high T

v T 1/ 2 u0

low T

Transport-limited CVD.
Chamber design, gas dynamics
control film growth.
Non uniform film growth.
ln (v)
Slow, layer-by-layer growth,
epitaxy, require high T,
low pressure,
l/L = NK >> 1.
That puts you in the
Reaction-limited regime

u0

T 1/2

Rate:

- DH

v~e

Arrhenius-like
fi DH

1/T
1000K
Mon., Sept. 15, 2003

400K

T
15

kT

Some CVD reactions

Silane pyrolysis

Silane oxidation

(heat induced reaction)

(450C)

SiH4 (g) + O2(g) SiO2 (s) + 2H2 (g)

(by LPCVD for gate oxide)

SiH 4 (g) Si (s) + 2H2 (g) ( 650C)

This fi poor Si at 1 atm, so use low pressure

Poly Si

Si - tetrachloride reduction

SiCl4 (g) + 2H2 (g)

Si (s) + 4HCl (g) (1200C)

PSiCl4
PH 2

Crystalline

(Si-tetraactually much more complex than this;

etch

8 different compounds are formed, detected by RGA)

Mon., Sept. 15, 2003

16

Some CVD reactions (cont.)

Doping
Phosphine

Diborane

2PH3 (g) 2P (s) + 3H2 (g)

B2H6 (g) 2B (s) + 3H2 (g)

GaAs growth
Trimethyl Ga (TMG) reduction
(CH3)3 Ga + H2 Ga (s) + 3CH4
Arsene
Or

2AsH3 2As (s) + 3H2

Least abundant
element on surface
limits growth velocity

7 5 0C

6 GaAs (s) + 6 HCl g

As4 (g) + As2 (g) + 6 GaCl (g) + 3 H2 (g)

8 5 0C

Si-nitride compound formation

3 SiCl2H2 (g) + 4NH3 (g) Si3N4 (s) + 6H2(g) + 6HCl (g) (750 C)
Mon., Sept. 15, 2003

17

How can you select process parameters to get

desired product and growth characteristics?
Consider:
1)

SiH4 (g) SiH2 (g) + H2 (g)

Total pressure = partial Ps

Three unknown pressures

Ptot = PSiH4 + PH2 + PSiH2

still have 2 unknown Ps

2) Conservation of ratio

Si
=>
H

PSiH2 + PSiH4
4PSiH4 + 2PSiH 2 + 2PH 2

= const

still have 1 unknown P

3)

Equilibrium constant, K (cf. Law of mass action)

= H for gas

PH 2 PSiH2
PSiH4

= K0 e

DG
kT

And similarly for

each reaction.

These equations provide a starting place for growth parameters. (Many

eqs. for real systems; done on computer)
Do a run, analyze results,
tweak process.
Mon., Sept. 15, 2003

18

Where does

DG
PH 2 PSiH2
K
= K0 e kT come from?
PSiH4
Consider mass action for class groups

Consider mass action for electrons and holes:

N-type semiconductor

Intrinsic semiconductor
Conduction
band

ni
EF
pi

Valence
band
Recombination
2
probability set
i
i
by energy gap and
number of each species

p
n

2
i

n = n pi

PH2 PSiH2 = K PSiH4

Donor
levels

EF

n = np

More free electrons

=> more recombination,
fewer holes (Eg same)
K indicates a bias at equilibrium in the reaction
toward the products(different molecular species)
p

Mon., Sept. 15, 2003

19

Exercise

Ptot = 1 atm, T = 1000 K,

Assume reaction: AB
A+B
K = 1.8 109 Torr exp ( - 2 eV / kB T )
Assume PA PB find PAB
Solution:

K=

PAPB
PAB

and Ptot = PA + PB + PAB ,

and at 1000 Kelvin,

K = 0.153 Torr,

PA PB. \ 760 T = 2PA + PAB

PA2 = 0.153 PAB = 0.153 (760 - 2 PA) PA = PB = 10.9 Torr, PAB = 738 Torr
Small value of K, 0.153 Torr, implies that at equilibrium,
the product of the right-hand side partial pressures
Is but 15% of the reactant (left-hand-side) partial pressure;
the reaction may not produce much in equilibrium. What if lower T?
Mon., Sept. 15, 2003

20

Atmospheric Pressure CVD: APCVD

(little used today, but illustrative)
High P, small l => slow mass transport, large reaction rates;
film growth limited by mass transfer, boundary layer;
(quality of APCVD Si from silane is poor, better for dielectrics).

Example:
SiH4 + 2O2 SiO2 + 2H2O

T = 240 - 450C

Done in N2 ambient (llow partial pressure of active gas, reduces reaction rate)
add 4 - 12% PH3 to make silica flow, planarize.
ln v

Transprt ltd APCVD

low T,
reaction rate
limited

1/ T
21
Mon., Sept. 15, 2003

Low Pressure CVD (LPCVD) for dielectrics and semiconductors

Equilibrium not achieved at low P where
(molecular flow, few collisions).

l
= Kn > 1
L

kB T
l=
2pd 2 P

lower P => higher Dg, hg improves transport

reduces boundary layer,
extends reaction-limited regime

ks term

hg at 1 Torr

LPCVD

ln v

hg at 760 Torr

Transport
limited

Reaction limited

F.9.13

1/ T

Mon., Sept. 15, 2003

22

Low Pressure CVD (LPCVD) for dielectrics and semiconductors

Hot wall reactor
Cold wall reactor
fi uniform T distribution but
Reduce reaction rate,
surface of reactor gets coated.
deposition on
So system must be dedicated to
surfaces. For epi Si.
1 species to avoid contamination.
All poly-Si is done by hot-walled LPCVD;
good for low pin-hole SiO2 , conformality

23
Mon., Sept. 15, 2003

Low Pressure CVD (LPCVD) for dielectrics and semiconductors

In such non-equilibrium, large l cases,
growth rate is reaction limited,
Low P

LPCVD

kinetically controlled,reaction-rate limited.

Silane pyrolysis

SiH4 (g) Si (s) + 2H2 (g) ( 575 - 650C)

10 - 100 nm/min

(Atm. P

APCVD

equilibrium, transport ltd.)

LPCVD
+ requires no carrier gas
+ fewer gas-phase reactions, fewer particulates
+ eliminates boundary layer problem
+ lower P => higher Dg, extends reaction-limited regime
+ good conformal growth (unlike sputtering or other PVD methods
-

which are directional)

strong temperature dependence to growth rate

+ easier to control T with hot-wall furnace
Mon., Sept. 15, 2003

24

R.F. Plasma-enhanced CVD (PECVD) for dielectric

MOS metallization: avoid contact interaction betw. Al & Si, SiO2, T < 450C
At low T, surface diffusion is slow,
must supply kinetic energy for surface diffusion.
Plasma provides that energyand enhances step coverage.
What is a plasma? Ionized noble gas, accelerated by AC (RF) or DC
voltage, collides with active species in gas and at surface, importing Ekin
Metal CVD
Step coverage is important for electric
contacts.
oxide

WF6 + 3H2 W + 6 HF
DG 70 kJ / mole (0.73 eV/atom)

oxide
semi

below 400C
Mon., Sept. 15, 2003

25