Chemical Vapor Deposition (CVD)

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

clean and simple
or metal film growth : high vacuum, single element… clean and simple

… Contrast with CVD: toxic, corrosive gas flowing through valves,

T up to 1000°C, multiple, simultaneous chemical reactions,
gas dynamics, dead layers… whose idea was it?

(Dr. Estis
Zmaart?)

CVD is the single most widely used deposition method in IC manufacture

Lec. 4 Mon., Feb. 14, 2005 1

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

Control T,
gas mixture,
pressure,
flow rate

Lec. 4 Mon., Feb. 14, 2005 2

1
 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

Removal of
by-products
Transport
of precursors
across
dead layer to film
Susceptor Chemical reaction:
substrate T sub> Twall Decomposed species
Pyrolysis: thermal bond to substrate
decomposition
at substrate More details…
Lec. 4 Mon., Feb. 14, 2005 3

CVD Processes

8
1 Bulk Bulk transport
transport of by-product

Reactant
molecule 7 Diffusion of (g)
2 Transport by-product
Carrier gas across bndry 4
(Maintain hi p,
layer Decomposition
slow r eaction)
5 6 Desorption
J1 " Dg #C 3
Adsorption
Reaction with film
J 2 ~ k iCi
Surface diffusion
Lec. 4 Mon., Feb. 14, 2005 4

2
 Hi vel, low P

Gas transport
Low vel, hi P
Laminar flow across plate:
2
Transport across Hi vel, low py
“boundary layer”
Low vel, hi py…
…shorter λ
J1 " Dg #C
kB T
"=
2#d 2 P
"
Knudsen NK ≡ <1
L
L
Viscous flow

#v x
Dgas "
2
Laminar flow pipe. Conductance ∝ A/L
Lec. 4 Mon., Feb. 14, 2005 5

Revisit dC D
gas
J1 = "D
dx
="
# (x)
(Cg " Cs ) J1 = "hg (Cg " Cs )
Boundary layer
dynamics: Layer thickness, δ(x)
"v
And we saw gas diffusivity D = x (unlike solid) z u
2 !
!
gas vel: u0 boundary layer
Cg
δ (x)
Cs
δ (x) us = 0 wafer
x x=L
wafer

#x
! Fluid dynamics: "( x ) = ρ = mass density, η = viscosity
$u0
L uL
1
# " (x )dx = 23 L %u$ L & 23 LRe
Reynolds #: Re = " 0
" = ease of gas flow #
L 0 0
D 3D
So: hg = " # 2 L Re
Lec. 4 Mon., Feb. 14, 2005 6

3
 Several processes in series
Simplify CVD to 2 steps:
Boundary
AB layer
Dg
J1 = #C J2
" B
A

J 2 = ksCs
Reaction rate constant, ks
! coefficient γAB,
Sticking
…no sold-state diffusion here,
0 ≤ γAB ≤ 1
reaction occurs at surface.

AB bounces Good !
off surface adhesion
Let’s analyze, solve for J2…

Lec. 4 Mon., Feb. 14, 2005 7

Two main CVD

Boundary
process: AB layer
Dg
J1 = #C J1 = hg (Cg " Cs)
" J2 B
A

J 2 = k sCs
!
In steady state: J1 = J2, hg hg k s
hg ( Cg - Cs ) = ksCs
Cs = C , J 2 = k sCs = C
hg + k s g hg + k s g
Electrical analogy: J1 = J2,
R = R1+R2
G = 1/R= G1 G2 /(G1+G2)

Two processes in series; slowest one limits film growth

Lec. 4 Mon., Feb. 14, 2005 8

4
 Two main CVD
Boundary
process: AB layer
Dg
J1 = #C J1 = hg (Cg " Cs)
" J2 B
A

J 2 = k sCs
! hg k s
J 2 = k sCs = C
hg + k s g

$ # ' 1 hg k s C g C g N f
Film growth rate " v = J& ) , v= =
% area # t ( $ # ' hg + k s N f 1 1
Nf& ) +
% vol ( hg k s
v (thickness/time)
Slower process controls growth
!
Lec. 4 ! 14, 2005
Mon., Feb. 9

Two main CVD

Boundary
process: AB layer
J1 = hg (Cg " Cs)
J2 B
A

J 2 = k sCs
C N
v= g f
1 1 Examine these 2 limits of growth:
+
hg ks hg limited or ks limited…
Reaction limited growth,
Transport limited growth,
ks<< hg:
hg << ks:
#G
hC 3DCg 3#v xCg Re k sCg Cg "

v= g g " Re = v= = k 0e kT
Nf 2LN f 4LN f Nf Nf
ease of gas flow

Lec. 4 Mon., Feb. 14, 2005 10

5
 Transport limited growth : Reaction limited growth :
hg Cg 3DCg 3#v xCg Re k sCg C "
#G
v= " Re = v= = g k 0e kT
Nf 2LN f 4LN f Nf Nf
Most CVD is done in this limit
where gas dynamics, ∆G = free energy change in reaction
reactor design are important.
(∆G ≅ ∆H for gas

Remedy for boundary layer becasue gas reaction no ∆S)

J2 B
A

Susceptor, 3o -10o

More uniform ug, Cg ⇒ Choice of reactants and

uniform film growth rate , v temperature are critical

Lec. 4 Mon., Feb. 14, 2005 11

CVD FILM GROWTH

GAS TRANSPORT-LIMITED REACTION-RATE LIMITED

3"vx Cg #G
v= Re k sCg Cg "
4N f L v= = k 0e kT
Nf Nf
2k B T
vx = ,
"m ∆G = free energy change in reaction
kBT ∆G = ∆H - T∆S
"= ,
2#d 2 Pg
Re ~ u0 (∆G ≅ ∆H for gas → no ∆S for
Cg 1 gas reaction)
=
Pg k B T
" #H
kT
v "T
1
2
u0 v~e

Lec. 4 Mon., Feb. 14, 2005 12

6
 Transport ln (v) high T
limited 1
v "T 2
u0
low T
Reaction
limited

gas " vel , " #H

u0 Rate: v~e kT

Most CVD is transport-

ln (v)
limited. Slow, layer-by-layer
growth, epitaxy. Requires
high T, low pressure, low gas T 1/2
viscosity. Chamber design, ⇒ ΔH
gas dynamics control
process. Arrhenius-like
To reduce nucleation of 1/T
products in gas phase, use T
1000K 400K
low partial pressure (LPCVD).
Lec. 4 Mon., Feb. 14, 2005 13

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 Removal of
across by-products
dead layer to film
Susceptor
substrate T sub> Twall

Pyrolysis: Chemical reaction:

thermal decomposition Decomposed species
at substrate bond to substrate

Lec. 4 Mon., Feb. 14, 2005 14

7
 Gas Reaction
transport limited
ln (v) limited high T
1/ 2
v "T u0
low T

Transport-limited CVD.
Chamber design, gas dynamics " #H
u0 Rate: v~e kT
control film growth.
Non uniform film growth.
ln (v)

Slow, layer-by-layer growth, T 1/2

epitaxy, require high T, Arrhenius-like
low pressure, ⇒ ΔH
λ/L = NK >> 1.
That puts you in the
Reaction-limited regime 1/T
T
1000K 400K

Lec. 4 Mon., Feb. 14, 2005 15

Some CVD reactions

Silane pyrolysis Silane oxidation (450°C)

(heat induced reaction) SiH4 (g) + O2(g) → SiO2 (s) + 2H2 (g)
SiH4 (g) → Si (s) + 2H2 (g) ( 650°C) (by LPCVD for gate oxide)
This ⇒ poor Si at 1 atm, so use low pressure

rate v
Si - tetrachloride reduction c1 c2 Poly Si
SiCl4 (g) + 2H2 (g) →
PSiCl4
SiCl4 H2
Si (s) + 4HCl (g) (1200°C) Crystalline
PH 2

etch
(Si-tetrachloride actually much more complex than this;
8 different compounds are formed, detected by RGA)

Lec. 4 Mon., Feb. 14, 2005 16

8
 Some CVD reactions (cont.)
Doping
Phosphine Diborane
2PH3 (g) →2P (s) + 3H2 (g) B2H6 (g) →2B (s) + 3H2 (g)

Si-nitride compound formation

3 SiCl2H2 (g) + 4NH3 (g) → Si3N4 (s) + 6H2(g) + 6HCl (g) (750° C)

GaAs growth
Trimethyl Ga (TMG) reduction
(CH3)3 Ga + H2 → Ga (s) + 3CH4 Least abundant
element on surface
Arsene 2AsH3 → 2As (s) + 3H2 limits growth velocity
7 5 0°C
Or "#
As4 (g) + As2 (g) + 6 GaCl (g) + 3 H2 (g)" "
"#
# # 6 GaAs (s) + 6 HCl g
8 5 0°C

Lec. 4 Mon., Feb. 14, 2005 17

How can you select process parameters to get

desired product and growth characteristics?
Consider: SiH4 (g) → SiH2 (g) + H2 (g) Three unknown pressures

1) Total pressure = ∑ partial Ps Ptot = PSiH4 + PH2 + PSiH2

…still have 2 unknown Ps

Si PSiH2 + PSiH4
2) Conservation of ratio => = const
H 4PSiH4 + 2PSiH 2 + 2PH 2
…still have 1 unknown P
3) “Equilibrium constant”, K (cf. Law of mass action)
rate
%G
PH 2 # PSiH2 $ c1 c2 And similarly for
K" = K0 e kT each reaction.
PSiH4
SiCl4 H2
These 3 equations provide a starting place for growth parameters.
(Many equations for real systems; done on computer)
Do a run, analyze results, …tweak process.
Lec. 4 Mon., Feb. 14, 2005 18

9
 %G
PH 2 # PSiH2 $
Where does K" = K0 e kT come from?
PSiH4 Consider “mass action” for class groups…

Consider “mass action” for electrons and holes:

Intrinsic semiconductor N-type semiconductor

Conduction n
ni Donor
band EF levels
EF

Valence pi p
band
Recombination
n
2 2
probability set i n = n pi
i ni = np
by energy gap and
number of each species
More free electrons
p
=> more recombination,
fewer holes ( Eg same)
K indicates a bias at equilibrium in the reaction
toward the products(different molecular species) K PSiH4 = PH 2 " PSiH 2
Lec. 4 Mon., Feb. 14, 2005 19

When a system undergoes a process in which

only heat energy, dQ, and pV work occur at constant T, then dG = Vdp

dp dp
dG = NkB T or RT
dQ = TdS Vdp p p
!

B B
# dG & pB
" dG = RT " d ln( p) # G B ! ln( pB / pA )
$ GA = RT exp%" ()
$ RT ' pA
A A

Define this ratio pB/pA, as K

%G
! PH 2 # P!
SiH2
$
For multiple reagents: K" = K0 e kT
PSiH4

Entropy of mixing, dSmix = "RN i ln(N i ) , leads to similar result

Lec. 4 Mon., Feb. 14, 2005 20

10
 Exercise
Assume reaction: AB ←→ A+B Ptot = 1 atm, T = 1000 K,
K = 1.8 × 109 Torr × exp ( - 2 eV / kB T ) = 0.153
Assume PA ≈ PB find PAB

PAPB
Solution: K= = 0.153
PAB
and Ptot = PA + PB + PAB , PA ≈ PB. ∴ 760 Torr = 2PA + PAB

PA2 = 0.153 PAB = 0.153 (760 - 2 PA), quadratic → PA = 10.8 Torr = PB ,

2 so PAB = 738 Torr
PA + 0.306PA " 0.153 # 760 = 0
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 you change T?

Lec. 4 Mon., Feb. 14, 2005 21

Atmospheric Pressure CVD: APCVD

(little used today, but illustrative)
High P, small λ => 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 + 2H2 O T = 240 - 450°C
Done in N2 ambient (low partial pressure of active gas, reduces film growth rate)
add 4 - 12% PH3 to make silica flow, planarize.

ln v Transport ltd APCVD

low T,
reaction rate
limited

1/T
Lec. 4 Mon., Feb. 14, 2005 22

11
 Low Pressure CVD (LPCVD) for dielectrics and semiconductors

" kB T
Equilibrium not achieved at low P where = Kn > 1 "=
L 2# d 2 P
(molecular flow, few collisions).

lower P => higher Dg, hg; this improves transport reduces boundary layer,
extends reaction-controlled regime (which is where you operate)

ks term

hg at 1 Torr
ln v
LPCVD
hg at 760 Torr

Transport
limited Reaction limited

1/T

Lec. 4 Mon., Feb. 14, 2005 23

Low Pressure CVD (LPCVD) for dielectrics and semiconductors

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

Lec. 4 Mon., Feb. 14, 2005 24

12
Low Pressure CVD (LPCVD) for dielectrics and semiconductors
In such non-equilibrium, large λ, reactant-starved cases,
growth rate is controlled by gas kinetics

LPCVD is kinetically throttled; transport-rate controlled

Silane pyrolysis SiH4 (g) → Si(s) + 2H2 (g) T = 575 - 650°C

10 - 100 nm/min
(APCVD is at equilibrium; transport limited)

LPCVD
Requires no carrier gas
Fewer gas-phase reactions, fewer particulates
Eliminates boundary-layer problem
Lower p => larger Dg, extends reaction limited regime
Good conformal growth (unlike sputtering or other PVD methods which
are more directional)

Strong T dependence to reaction growth rate.

Easier to control T with hot-walled furnace.
Lec. 4 Mon., Feb. 14, 2005 25

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

MOS metallization: avoid contact interaction betw. Al & Si, SiO2, T < 450°C

At low T, surface diffusion is slow,

must supply kinetic energy for surface diffusion.
Plasma provides that energy…and 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 oxide
WF6 + 3H2 → W + 6 HF
ΔG ≈ 70 kJ / mole (0.73 eV/atom)
semi
below 400°C
Lec. 4 Mon., Feb. 14, 2005 26

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Lec. 4 Mon., Feb. 14, 2005 27

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