Plasma modelling & reactor design

Alan Howling, Ben Strahm, Christoph Hollenstein

Ecole Polytechnique Fdrale de Lausanne (EPFL), Switzerland
Center for Research in Plasma Physics (CRPP)

1) The "plasma dimension" for plasma deposition of c-Si:H

2) Direct pumping of a plasma reactor
... and one non-intrusive plasma diagnostic for each.

IWTFSSC-2 Berlin April 2009

1) Plasma-Enhanced Chemical Vapour Deposition of c-Si:H

silane

hydrogen

black box
PECVD

SiH

1) PECVD reactor setup

PRF[W]
f [MHz]
2

hydrogen

Plasma Box,
Oerlikon
principle:
Jacques Schmitt

butterfly
valve
process
pumps

silane

vacuum chamber

SiH

RF connection
4

showerhead
RF electrode

gas flow

heating

grounded box

plasma box
side view
glass substrate

1) Hydrogen dilution for plasma deposition of c-Si:H

c
1

0.05
0

silane

hydrogen

plasma box

SiH

low silane concentration c =

is commonly used

SiH4

total

< 5%

1) Reason for hydrogen dilution

Need high ratio of
H to SiHx fluxes

"Add more hydrogen

intuitively

than silane"

to deposit c-Si:H
Selective etching
model

Chemical annealing
model

Surface diffusion
model

1) ...but the optimal plasma control parameters are less clear

c
1

3
0.05
0

silane

hydrogen

f [MHz]
gap

tot
SiH

PRF[W]

area

p[mbar]

plasma black box:

parameter
inter-dependence

1) ...because the plasma is complex.

H
SiH

{molecules}

H2

SiH4

SiH4

polysilanes, dust

PRF[W]

H2

{electron dissn: ne, Te}

f [MHz]

SiHx , H, cations, anions

{sec y reactions}
polysilanes, dust

{transport in the plasma and the sheath}

{surface reactions}

SiHx

H, H2

1) Consider low pressures (< 2 mbar)

H
SiH

{molecules}

H2

SiH4

H2

PRF[W]
f [MHz]

{electron dissn: ne, Te}

SiHx , H, cations, anions

{transport in the plasma and the sheath}

{surface reactions}

SiHx

H, H2

SiH4

1) Consider only the majority species

H
SiH

{molecules}

H2

SiH4

H2

SiH4

All reactive species (SiHx, H, and ions) have

very low density because of their volume
and surface reactions

H2 and SiH4 have the dominant partial

pressures in the plasma reactor

Only H2 and SiH4 leave the plasma reactor

The partial pressure of SiH4 (and H2) is ~the
same in the pumping line as in the plasma

"The plasma
composition
(and deposition)
is determined by
the partial
pressures of
SiH4 and H2
in the plasma"

1) How to measure the silane partial pressure in the plasma?

"inaccessible" plasma reactor

load lock

gate valve

vacuum chamber
plasma box
heated
closed
showerhead

butterfly
valve
pumping line

substrate loading door

process
pumps

1) FTIR in pump line: Non-intrusive diagnostic for SiH4 pressure

IR source

1 m single pass

Fourier transform infrared (FTIR)

absorption spectroscopy
via ZnSe windows.

extended
pumping
line

p IR detector

1) Silane partial pressure measurement

a) Silane Q-branch absorbance; b) Integrate spectrum; c) Read off a calibrated curve

Silane pressure with plasma < silane pressure without plasma,

0
pSiH4 < pSiH
4

due to electron dissociation of silane (irreversible loss ).

Hydrogen partial pressure increases with plasma
(surface recombination, & pump speed adjustment)

1) Silane input concentration (without plasma)

H
SiH

0
0
pSiH
+
p
H2 = p
4

0
0
pSiH
+
p
H2 = p
4

Define
silane input concentration, c =
Note 0 c 1

0
pSiH
4

1) Silane concentration with plasma

H
SiH

pSiH4 + pH2 = p

2
4

pSiH4 + pH2 = p

Define
silane concentration with plasma, cpl =

p
pSiH4
p

1) Silane depletion due to plasma

H
SiH

pSiH4 + pH2 = p

pSiH4 + pH2 = p

Define
silane fractional depletion, D =
Note 0 D 1

0
pSiH4
pSiH
4
0
pSiH
4

1) Silane concentration in plasma

H
SiH

pSiH4 + pH2 = p

pSiH4 + pH2 = p

Therefore

silane concentration in plasma, cpl = c (1 D )

2 parameters, c & D,
define the plasma
composition

the "plasma dimension"

infinitely strong plasma

concentration

pure silane
vanishingly weak plasma

silane input concentration, c

1) The plasma "black box" becomes a {c,D} unit box

infinitely diluted silane

silane depletion fraction, D

silane input concentration, c

1) Contours of constant plasma composition

1

same plasma composition for

cpl = c (1 D ) = const .

silane depletion fraction, D

silane input concentration, c

1) Contours of constant plasma composition

1

c =1
D = 0.95

cpl = c (1 D ) = 0.05

(
0

c = 0.05
D = 0.1

)
IN THE
5% silane
95% hydrogen PLASMA
NO input dilution,
95% depletion

silane depletion fraction, D

5% silane IN THE
95% hydrogen PLASMA
strong input dilution,
weak depletion

1) Same plasma composition = same film properties

Constant plasma
composition, cpl, gives
constant film properties

1) Same plasma composition = same film properties

transition
material

1) Same plasma composition = same film properties

cpl = 0.5%
cpl = 1.2%

Microcrystalline silicon can be deposited even with high silane concentration,

provided that the silane depletion fraction is sufficiently high,
because then the plasma is dominated by hydrogen.

silane input concentration, c

1) Two regimes of operation

1

REGIME 2 "recent" :
Film crystallinity governed by
strong plasma depletion, even
for high silane concentration.

REGIME 1 "conventional" :
Film crystallinity governed by
hydrogen dilution of silane,
'independent' of plasma.

silane depletion fraction, D

1) Simple plasma chemistry model

Based on a reduced set of gas phase reactions
k1
e + SiH 4
SiH 2 + 2H + e

+
e

kH
e + H 2
2H + e

and simplified surface reactions.

SiH 2 Si surf + H 2
S

H + H surf
H 2 + vacancy
H + vacancy
H surf
1
R
H
H2
2

+
+

+
+

1) Simple, analytical plasma chemistry model

IN

Plasma reactions & deposition

SiH4
H2

= kne nSiH4
+ S nSiH2

{radical fluxes}
{surface reaction}

+ ( R 2 ) nH

S nSiH2
deposition

OUT
+ a nSiH4

= kHne nH2

+ a nH2

R nH

H+H
recombination

A zero-dimensional model is appropriate to showerhead reactors

1) Simple, analytical plasma chemistry model

Just one silane dissociation channel here: e + SiH4

SiH2 + 2H + e

More detailed plasma chemistry only changes the numerical constants:

... the general conclusions remain the same.

radical
flux ratio

H
RnH
=
=
SiH2 SnSiH2

kH nH2
2
k nSiH4

kH 1
1 + 2
+ 2 = 2

k
c
pl

Hydrogen and silane are the dominant partial pressures;

so we can expect radical densities to depend on them.

"This shows why the plasma deposition is determined by cpl ,

the silane concentration in the plasma."

1) Depletion accounts for all of the plasma parameters

plasma black box
PRF[W]
f [MHz]
gap

tot

area

p[mbar]

analytical
model

a kne
D = 1+

(1 + c )

6 Tgas total
-1

a s = effective pumping speed = 6.1 10

;
p gap area

kne s-1 = silane dissociation rate = function of ( PRF , f [MHz ]) ;

SiH4
c = silane input concentration,
.
total

D if any of { p, gap, area, c, PRF , f } &/or

{ total, Tgas }

1) The "plasma dimension" for plasma deposition of c-Si:H

2) Direct pumping of a plasma reactor

IWTFSSC-2 Berlin April 2009

2) Plasma chemistry equilibration time to steady-state depletion

Feitknecht et al (2002)

SiH normalized intensity

van den Donker et al (2005)

Almost a minute to
reach the plasma
composition suitable to
grow c-Si:H...

20

40

60

time (s)

c-Si:H

time (s)

... thick amorphous incubation layer

... deteriorates solar cell performance.

2) OES: Non-intrusive, rapid diagnostic for equilibration time

pump
grid

Optical
Emission
Spectrometer
plasma emission

2) Time-resolved optical emission spectrum from plasma ignition

Emission from silane radicals, SiH*, falls as the silane becomes depleted
Emission from excited molecular and atomic hydrogen rises as its partial pressure rises

The plasma chemistry equilibration time is less than one second!

2) Compare open and closed reactors (numerical)

Open laboratory reactor
(axial symmetry)

Closed, directly-pumped plasma box

(lateral view)

Plasma zone (20 cm in diameter)

Dead volume

57 cm

Plasma zone

indirect pumping

t=0-100 s

time to steady-state > 100 s !

direct
pumping

t=0-1 s
time to steady-state < 1 s !

Silane back-diffusion from any intermediate

dead volume increases the equilibration time.

2) Practical consequence of the pumping configuration

Amorphous
incubation
layers with
open door

409 nm

96 nm

plasma box side view

<10 nm
su
bs
tra
te

But the door is normally

closed, the amorphous
incubation layer is then
thinner than 10 nm.

Two Conclusions
1. Plasma composition and deposition depend on the silane concentration in the plasma,
cpl=c(1-D) , and not only on the silane concentration in the input flow, c.
Strong hydrogen dilution in the plasma, and c-Si:H deposition, can be obtained with high input
concentration of silane.
- monitored non-intrusively by FTIR in the pumping line.

2. Rapid equilibration of plasma chemistry requires a closed, directly-pumped showerhead

reactor with a uniform plasma - avoid gas circulation between the plasma and any dead volumes.
- monitored non-intrusively by OES in the pumping line.

Refs. B. Strahm et al, Plasma Sources, Sci. Technol. 16 80 (2007).

A. A. Howling et al, Plasma Sources, Sci. Technol. 16 679 (2007).

Acknowledgements: Swiss Federal Research Grant CTI 6947.1; and

Dr. U. Kroll and colleagues, Oerlikon-Solar Lab SA, Neuchtel, Switzerland.