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Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009


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Chemical Vapour Deposition of Metallic Films:
from Unary Systems to Complex Intermetallics
Constantin Vahlas
Institut Carnot CIRIMAT
Toulouse
constantin.vahlas@ensiacet.fr
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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CVD: one of the most important methods for preparing
metallic and ceramic thin films and coatings
Protection (corrosion, wear)
Optical properties
Electronic properties
Magnetic properties
Decoration
New hybrid- properties
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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CVD coated steel tools
Segmented forming tool
for automobile door
Drawing ring
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Outline
Definitions
Reactors
Precursors
Precursors delivery systems
Surface events
Conformal deposition
Selectivity
Infiltration of preforms
Deposition on powders
Competitive reactions
Towards MOCVD processed metallic alloy coatings: the
Al-Cu-Fe system
Concluding remarks
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Definitions
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Chemical Vapor Deposition: The general frame
Chemical vapor deposition is a process where one
or more volatile precursors are transported via the
vapour phase to the reaction chamber, where they are
decomposed on a heated substrate to produce high-
purity, high-performance solid materials.
Precursor: person or thing that comes before sth.
(Oxford Advanced Dictionary, 1989)
Halide
Molecular compound (MOCVD)
2
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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+
Main gas flow region
Adsorption
Surface reaction Diffusion
Dsorption
Nucleation
Growth
Ligand Metallic centre
Transport
Diffusion
Gas phase reaction
+
Formation of
precursor vapors
Vaporization
Sublimation
Liquid injection
Diagnostics:
- Gas phase
- Surface
Reactor
Configuration
& design
- Growth rate
- -structure
- Composition
- Phases
- Adhesion
Post deposition
Thermal treatments
Properties
Modelling:
- Reactor
- Transport phenomena
- Deposition chemistry
- Surface electronic properties
Substrate
The MOCVD process: a sequence of elemental steps which have to be
understood, controlled and optimized
Selection of
molecular
precursors
Vapor pressure
Stability
Shelf life
Dissociation scheme
Synthesis
Cost
Environment
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Chemistry in Chemical Vapor Deposition
In every CVD process, there is some path involving physical phenomena
AND a reaction that converts the vapors to a solid.
Part of the task of designing the reactor and process is always to force
this reaction to happen only where and when it is desired (typically on
the substrate), and not everywhere else.
Undesired reactions result in particles which can fall onto the
substrates, coating of chamber walls, and clogging of exhaust openings.
The approaches to achieving this selectivity typically rely on five levers:
Precursors chemistry
Temperature
Time
Pressure
Surface specificity.
+
Adsorption
Surface reaction Diffusion
Dsorption
Nucleation
Growth
Transport Transport
Diffusion
Gas phase reaction
+
Substrate
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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No universal processing technique available!
Minimum waste
Access to all metals
High throughput Lower substrate T
Conformal coverage Ease of development
CVD PVD
Advantages
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Reactors
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Reactors
Gas phase introduction
By products & pressure
management
Deposition chamber
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Low pressure UV Hg lamp
Air cooling
LN
2
trap
B
h
Process activation
Thermal
Plasma
Photoactivation
Laser
Jian Mi, PhD thesis, Georgia Tech, 2006 S. Vidal, PhD thesis, Toulouse Natl. Pol. Inst, 2001
(hfa)Cu(COD)
272 nm
3
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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CVD Reactor types 1: Hot wall
Precursor
inlet

higher throughput

large heated
surface area
precursor depletion
Unreacted
precursor
& byproducts
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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CVD Reactor types 2: Cold wall

better control of uniformity

lower throughput
Precursor
inlet
Unreacted
precursor
& byproducts
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Moving the wafers at constant
speed through a heated
reactor chamber
Install CVD processes at
appropriate positions in steel
or glass facilities.
Controlled by temperature,
process gas flow rate, and
belt speed.

High growth rates


High equipment throughput
Good uniformity
Capability to process large-
diameter wafers
CVD reactor types 3: Atmospheric pressure, conveyor belt or
continuous flow reactors

Particulate formation from gas-phase


nucleation
High gas consumption
Requests frequent reactor cleaning
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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CVD reactor types 4: Coating parts in FBCVD reactors
Treating agent: inert oxide (the filler: Al
2
O
3
, SiO
2
, ZrO
2
, TiO
2
) + powder of source metal
(the donor of the element to be coated)
Fluidizing gas: Inert gas + activator (halides, alcali metal halides)
Donor + activator vapor precursors of the coating forming element (3HCl + Al AlCl
3
+ 1.5 H
2
)
Kinkel et al., Steel Res. 1995, 66, 318
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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High T (>1000K), diffusion of the substrate material
Substrate: Ni
Donor: FeAl
Activator: NH
4
Cl
Coating: NiAl
Voudouris & Angelopoulos, High Temp. Mater. Process. 1998, 2, 165
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Different types of reactors, depending on:
The type of activation (thermal, plasma, photon)
The geometry (vertical, horizontal)
The activated parts (hot, cold wall)
The best choice of a films deposition technique depends on targeted
application
In the case CVD is foreseen as the best solution, the optimum choice of
the reactor configuration still depends on the particular specifications
4
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Temperature related growth rate:
the three main regions of the Arrhenius plot
T
-1
/ K
-1
127 C
29
30
31
32
33
34
0.0005 0.0010 0.0015 0.0020 0.0025
L
n
(
g
r
o
w
t
h

r
a
t
e

/

m
o
l
e
c
u
l
e

c
m
-
2

s
-
1
)
227 C 394 C 727 C 1727 C
Flux limited kinetics
Surface
reaction
rate
limited
kinetics
Competing
processes
Taylor et al., J. Am. Chem. Soc., 1999, 121, 5220
+
Adsorption
Surface reaction Diffusion
Dsorption
Nucleation
Growth
Transport Transport
Diffusion
Gas phase reaction
+
Substrate
TiO
2
from Ti(OiPr)
4
E
a
E
a
: the minimum energy necessary for
a specific chemical reaction to occur
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Precursors
+
Ligand Metallic centre
+
Substrate
Selection of
molecular
precursors
Vapor pressure
Stability
Shelf life
Dissociation scheme
Synthesis
Cost
Environment
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Chemical Vapor Deposition: CVD depends on the
availability of a volatile chemical which can be converted by
some reaction into the desired solid film.
What makes the vapors (that is, volatility)
How these vapors can react in the gas phase or on the surfaces to
be converted into the film?
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Evolution: larger possibilities, smaller scales, higher
complexity
Traditionnal CVD: Halogenide precursors (WF
6
, TiCl
4
, SiH
2
Cl
2
)
T > 700 C, limited possibilities
Metal-organic CVD & Organometallic CVD: Molecular compounds
T
amb
< T < 600 C, numerous
possibilities, high complexity
W
C
C C
C
C
C
O
O
O
O
O
O
H
Al
Me
2
EtN
H
H
+
Adsorption
Surface reaction Diffusion
Dsorption
Nucleation
Growth
Transport
Diffusion
Gas phase reaction
+
Substrate
+
Adsorption
Surface reaction Diffusion
Dsorption
Nucleation
Growth
Transport Transport
Diffusion
Gas phase reaction
+
Substrate
B
u
tte
rfly
c
h
e
m
is
try
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Co-deposition: Specific criteria
Compatibility of transport & deposition
conditions (e.g. T)
No gas phase interaction
Compatible surface chemistry
+
Adsorption
Surface reaction Diffusion
Dsorption
Nucleation
Growth
Transport
Diffusion
Gas phase reaction
+
Substrate
+
Adsorption
Surface reaction Diffusion
Dsorption
Nucleation
Growth
Transport Transport
Diffusion
Gas phase reaction
+
Substrate
The difference between a molecular
compound and a metalorganic precursor
Molecular precursors:
Compatibility, Transport properties
CVD
Microstructure
Optimization
material/process
Quantum chemistry,
thermochemistry,
chimique chemical
kinetics
Properties
Diagnostics
Qualification
General criteria
Liquid rather than gas or solid
Convenient volatility
Thermal stability
High purity or easily purified
Long shelf life
Easy & clean decomposition on the substrate
Non toxic
Environmentally compatible
Low cost
i
m
p
o
s
s
i
b
l
e

t
o

m
e
e
t
a
l
l

c
r
i
t
e
r
i
a
M
a
u
r
y
,

J
.

P
h
y
s
.

I
V
,

C
5
,

1
9
9
5
,

4
4
9
C
M
A

N
o
E
,

2
0
0
5

-
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Precursor architecture: a major issue
Molecular Structure and Bonding Controls:
Precursor Volatility
Deposition kinetics
Growth rate
Composition
-structure
H
Al
Me
2
EtN
H
H
H
Al
Me
3
N
H
H
Solid
(AlH
3
-TMA)
ads
(AlH
3
)
ads
+ (TMA)
ads
AlH
3,ads
Al
ads
+ 3H
ads
3H
ads
1.5H
3,ads
1.5H
3,g
Liquid
(AlH
3
-DMEA)
ads
AlH
3,ads
+ (DMEA)
ads
AlH
3,ads
Al
ads
+ 3H
ads
3H
ads
1.5H
3,ads
1.5H
3,g
Dubois et al. Surf. Sci. 1990, 236, 77 Kim et al. Appl. Phys. Lett. 1990, 236, 77
5
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Vahlas & Brissonneau, Annales Chimie, Sci. Mater., 2000, 25, 81
V
a
r
i
o
u
s

s
o
l
u
t
i
o
n
s

f
o
r

v
a
r
i
o
u
s

c
o
n
s
t
r
a
i
n
t
s
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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MOCVD of Re: a processing route beyond the state of the art
Re: interesting material for high T applications in structural systems and
energy
High Tf (3453K), low vapor pressure @Tf (0.1 Pa @ 3073K), mechanical
properties x2 those of W and Mo up to 1473K, excellent corrosion & fretting
resistance @ high T (2
nd
to Os)
Elevated cost
Heterogeneous catalysis, heat exchangers, space and missiles propulsion,
hot gas valves
Sherman, et al., JOM., 1991, 20
Bryskin and Danek, JOM., 1991, 24
Re coatings:
Powder metallurgy: too expensive, too long, no net shape
High T CVD: ReF
6
+ H
2
, ~800 C, handling of fluorides and effluents
ReCl
5
+ H
2
, ~1200 C, non compact -structure
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Transport behavior of Re
2
(CO)
10
Important weight loss @ 503K : complete sublimation
Endothermic peak @ 503K : either decomposition and/or vaporization
Two small endothermic peaks @ 374K and 465K. Either crystallographic
transformation or monomerization (supplier: 443K)

DTA
TGA
F. Juarez-Lopez, PhD thesis,
Toulouse Natl. Pol. Inst, 2005
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Time (min)
0 200 400 600 800 1000
P

(
P
a
)
0
100
200
300
400
500
600
425K (152 C)
381K (108 C)
397K (124 C)
Intense increase of P with t
Stabilized P @ 108 C:
no decomposition
Saturated vapor pressure of Re
2
(CO)
10
Slight increase of P with t
1/T (K)
0,0024 0,0026 0,0028 0,0030 0,0032
lo
g
1
0
P
(
T
o
r
r
)
-2
-1
0
1
152 C
108 C
72 C
54 C 40 C
33 C
124 C
log
10
P (torr) = - 3116,7/T(K) + 7,9689
Juarez et al., Electrochem. Soc. PV 2003-08, 538
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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T=408 C
P=1 atm
50 nm 50 nm
Original, low-T process for Re films


10 m
Lafont, et al., Scripta Mat., 2004, 51(7), 699
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Molecular compounds provide a much wider spectrum of use than
traditional halide compounds
A long list of criteria for the qualification of a compound as a precursor
for a CVD process
Extremely difficult if not impossible to satisfy all criteria: compromise
No universal precursor for all processes involving deposition of a given
metal: one precursor for each application?
6
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Precursor delivery systems
+
Ligand Metallic centre
+
Formation of
precursor vapors
Vaporization
Sublimation
Liquid injection
Substrate
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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N
2
flow rate (sccm)
0 2000 4000 6000 8000 10000 12000
[
A
l
(
a
c
a
c
)
3
]

f
l
o
w

r
a
t
e

(
g
/
h
)
0.00
0.05
0.10
0.15
0.20
0.25
0.30
5 g
10 g
20 g
50 g
100 g
150 g
max
Bubblers
V
V
V
Carrier gas
H
2
N
2
Ar
Mass flow
controller
Bubbler - pure liquid
or solid precursor
F
pr
= (F
cg
P
T
/P
tot
)[1 exp(-Q/F
cg
)]
1
1
0

m
m
40 mm
1
1
0

m
m
40 mm
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Precursor Delivery Systems - Direct Liquid Injection
Precursor mass flow rate
Pumping rate
Precursor concentration
Vapor pressure
Nik Nik loc locne ne
Cobaltoc Cobaltoc ne ne
TIBA TIBA
Ar Ar
H2 H2
evacuation evacuation
Nik Nik loc locne ne
Cobaltoc Cobaltoc ne ne
TIBA TIBA
Ar Ar
H2 H2
evacuation evacuation
: Precision, reproducibility
: Use of solvents (process &
effluents management), incomplete
evaporation, limited solubility, use of
chlorinated ligands)
Carrier gas
H
2
N
2
Ar
Mass flow
controller
Bubbler - precursor
& solvent
Pump Gasification
Carrier gas
H
2
N
2
Ar
Mass flow
controller
Bubbler - precursor
& solvent
Pump Gasification
www.kemstream.com
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Precursor Delivery Systems
Sublimation in a fluidized bed
Vahlas et al., Chem. Vap. Dep., 2007, 13, 123
Rapid & efficient mixing (isothermal
operation)
Continuous operation
Scale up
High mass & heat transfer rates
Under development
Dbit gaz vecteur (sccm)
0 2500 5000 7500 10000 12500
D

b
it

P
r

c
u
r
s
e
u
r

(
g
/
h
)
0,00
0,05
0,10
0,15
0,20
0,25
0,30
0,35
US Pat. 2008 268143(A1)
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
35
The objective: To generate the vapors and transport them to the
deposition zone
Robust, reliable precursor feeding systems are necessary for the scaling
up and the industrial implementation of a CVD process
Stable feeding rate vs deposition time
High feeding rate:
In the diffusion limited regime
To avoid starving regime
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Adsorption
Surface reaction Diffusion
Nucleation
Growth
+
Substrate
Desorption
Definitions
Reactors
Precursors
Precursors delivery systems
Surface events
Conformal deposition
Selectivity
Infiltration of preforms
Deposition on powders
Competitive reactions
Towards MOCVD processed metallic alloy coatings: the
Al-Cu-Fe system
Concluding remarks
7
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
37
Surface events 1: conformal deposition
Fully conformal 10 nm Cu seed-layer
on TiN barrier in a 200 nm structure
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
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Surface events 2: Selectivity
Preparing patterned metal films:
Blanket deposition + selective area
etching
Blanket deposition into substrate
trenches followed by chemical-
mechanical polishing
Selective CVD
deposition of a material onto one surface
(the growth surface) in the presence of
another surface (the non-growth surface)
Cu on Si, not on SiO
2
e
f
f
i
c
i
e
n
t
l
e
s
s
e
f
f
i
c
i
e
n
t
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
39
Mechanisms for selective deposition rely on:
- inhibiting adsorption and reaction of the precursor and nucleation of the
metal on the non growth surface,
- promoting these processes on the growth surface
1. Intrinsic reaction rate of the precursor on the non-growing surface slower than
on the grow surface and on the growing film
2. The growth surface (e.g. Si) acts as a reducing agent and is selectively,
sacrificially consumed by the precursor (e.g. WF
6
)
3. Dissociation of a co-reactant (a reducing agent, e.g. H
2
) occurs on the growth
surface (e.g. a metal) but not on the adjacent non-growth surface (e.g. SiO
2
,
polymer, metal oxide)
4. Rate increase on the growth surface by photo-chemically driven reactions
5. Selective passivation of the non-growth surface prevents adsorption of the
precursor on the non-growth surface while adsorption and reaction occur on the
growth surface
6. A species is present on the non-growth surface that getters (removes) the
nucleating species
7. A free energy barrier for the formation of the metal nuclei inhibits nucleation on
the non-growth surface; smaller barrier on the initial growth surface allowing
for physical nucleation to occur
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
40
Surface events 3: infiltration of preforms; a case study
Potential technological applications & markets for a proprietary material
developed by an SME :
Materials solutions for the air treatment in small volumes (passengers
cabins in cars, space stations)
Catalytic converters made of metallic carriers
Catalytic support
(e.g. -Al
2
O
3
) some 100 nm
Catalyst particles
(e.g. Pt) some nm
some 10 m some 10 m
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
41
i. The substrate
SS, Cu, Ni
= 19 mm
e = 1 mm
Porosity 50 and 70%
Pores size 20 and 100 m
BET = 0.5 2 m
2
/g
SEF = 30 190 m
2
/m
2
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
42
Al
2
O
3
as a catalyst support
Levin & Brandon, J. Am. Ceram. Soc., 1995, 81(8), 1998 -AlOOH -Al
2
O
3
-Al
2
O
3
: convenient catalyst or catalytic support
Liu & Truitt, J. Am. Chem. Soc., 1998, 119, 9856
300 500 C
Impregnation of boehmite in
vacuum
Calcination at 450C/4 h
Alphonse & Courty, Thermochim. Acta, 2005, 425, 75
8
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
43
Al
2
O
3
covers the internal surface
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
44
Pt(acac)
2
@(390 C, 50 Torr) Pt
Pt by F-MOCVI on Al
2
O
3
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
45
Pt concentration higher at the entrance side of the disk and at its central part
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
46
200 nm 200 nm 200 nm
t
deposition
= 60 min
Pt = 4.5 wt %
BET = 5 m
2
/g
High Pt load
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
47
100 nm 100 nm 100 nm
t
deposition
= 10 min
Pt = 0.3 wt %
BET = 15 m
2
/g
Low Pt load
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
48
0
10
20
30
40
50
60
70
80
90
100
140 160 180 200 220 240 260
Temperature (
o
C)
C
O

c
o
n
v
e
r
s
i
o
n

(
%
)
CO to CO
2
conversion
O
2
/CO = 0.33
t
contact
= 0,0053 s
T
50
= 203C, 209C
- O
2
/CO = 0.5
t
contact
= 0.0400 s
T
50
= 199C
Cho et al., Cat. Lett., 2005, 103, 257
- O
2
/CO = 99/1
t
contact
= 0.0480 s
T
50
= 98C
Carberry et al, Cat. Lett., 1990, 4, 43
Similar catalytic activity for both loads
Christoglou et al., Surf. Coat. Tech., 2007, 201, 9195
Compares favorably with state of the art
9
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
49
Surface events 4: Deposition on powders
particle
coatings for
nuclear
applications
thick and continuous
deposits on dense
(non-porous) powders
Large scale
production of new
classes of materials:
supported catalysts,
nanomaterials
Vahlas et al. Mat. Sci. Eng. R 2006, 53, 1
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
50
CVD on powders: major differences from deposition on flat substrates
LARGE available surface:
surface reactions are so extended
that gaseous precursors are very
often totally consumed a few
centimeters after their entrance into
the fluidised-bed reactor in a
laboratory scale contactor
compensated by vigorous mixing:
uniform deposition
High heat transfer rates:
Isothermal conditions
Available growth surface per heated volume (m
2
/m
3
)
1e+1 1e+2 1e+3 1e+4 1e+5 1e+6 1e+7 1e+8
. FBCVD on porous particles
. CVI
. FBCVD on dense particles
. Hot wall multiwafer tubular
. Single wafer
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
51
Chemical engineering findings
The objective:
Each particle will
present its entire
surface to the
gaseous reactants
during the process
FB:
A bed of solid
particles over a gas-
distributing plate
(often called the
grid), is made to
behave like a liquid
by passing gas
through it at a flow
rate above a certain
critical value
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
52
The Geldard diagram
Group A (20150 m, < 2 g/cm
3
) & B
(sand): easy
Group D: large particles
Group C: cohesive
small size
strong electrostatic charges
wet, sticky non spherical materials
No sharp separation
Fluidization and powder classification:
The basic principles
Crossing of the bed by the gas flow
results in a pressure drop (P)
through the bed ( essential
information on the characteristics of
the bed).
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
53
Improve the performance of gas turbines Increase combustion temperature
Increase components temperature
Risk of degradation
Superalloy
MCrAlY
Al
2
O
3
-
YSZ
Hot Gas
Al2O3
Superalloy
MCrAlY MCrAlY
Al
2
O
3
-
YSZ YSZ
Hot Gas
Cooling Air
T
h
e
r
m
a
l

B
a
r
r
i
e
r
Superalloy
MCrAlY MCrAlY
Al
2
O
3
-
YSZ YSZ
Hot Gas
Al2O3
Superalloy
MCrAlY MCrAlY
Al
2
O
3
-
YSZ YSZ
Hot Gas
Cooling Air Cooling Air
T
h
e
r
m
a
l

B
a
r
r
i
e
r
Application of a thermal barrier
Doping of the bond coats
by different metals (Zr, Hf,
Re, Ru) is beneficial to
the mechanical and/or
oxidation resistance of the
barriers (e.g. Czech et al., Surf. Coat.
Techn., 1995, 76-77, 28)
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
54
Praxair, NI-482 powders
50
m
50
m
wt %
Ni 42
Co 23
Cr 20
Al 8
Y 1
Ta 5
High density
Spherical shape
Agglomerates
Large size distribution
Particles belonging to
groups C, A et B
NI-482 particles size (m)
10 100 1000
N
I
-
4
8
2

p
a
r
t
ic
le
s
s
iz
e

d
is
t
r
ib
u
t
io
n

(
%
)
0
1
2
3
4
5
6
7
8
NI-482
density
are off Geldarts classification
10
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
55
a
b
c
d
e
The MOCVD process requires fluidization in a spouted bed
0,00 0,01 0,02 0,03 0,04
0
200
400
600
800
1000
1200
1400
1600
1800
0,00 0,01 0,02 0,03 0,04
P

(
P
a
)
0
200
400
600
800
1000
1200
1400
1600
1800
H/D=1,5
0,00 0,01 0,02 0,03 0,04
0
200
400
600
800
1000
1200
1400
1600
1800
Gas velocity (m/s)
0,00 0,01 0,02 0,03 0,04
P

(
P
a
)
0
200
400
600
800
1000
1200
1400
1600
1800
H/D=1,5
0,00 0,01 0,02 0,03 0,04
0
200
400
600
800
1000
1200
1400
1600
1800
0,00 0,01 0,02 0,03 0,04
P

(
P
a
)
0
200
400
600
800
1000
1200
1400
1600
1800
H/D=1,5
0,00 0,01 0,02 0,03 0,04
0
200
400
600
800
1000
1200
1400
1600
1800
Gas velocity (m/s)
0,00 0,01 0,02 0,03 0,04
P

(
P
a
)
0
200
400
600
800
1000
1200
1400
1600
1800
H/D=1,5
which should be optimized
taking into account the constraints of the powders
Caussat et al., Powder Techn., 2006, 165, 63
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
56
The design of the reactor considers the constraints both
of the fluidization and of deposition
Filters
Grid
(Powder before
spouting)
H
2
/ O
2
N
2
Spouted bed
Frit
Precursors:
Ru(C
5
H
5
)
2
Re
2
(CO)
10
SSteel reactor
Gas panel
Juarez et al., J. Phys. IV., 2001, 11, 1117
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
57
10 m
SEM EDS Ru
Deposition of Ru from RuCp
2
+ H
2
T = 898K
Q
RuCP2
= 0,30 sccm
Q
H2
= 428 sccm
U
gas
> U
ms
Vahlas et al., Chem. Vap. Dep., 2002, 4, 127
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
58
Theta (degrees)
10 20 30 40 50 60
Ru doped
NiCoCrAlY
Ru JCPDS 6-663
1 wt % Ru
Well defined crystallites
50 nm 50 nm 50 nm 50 nm
D1
D2
D3
D4
D5
D1
D2
D3
D4
D5
D (cm) dexp (nm) Plane dJCPDS #6-663
1 0,85 0,235 100 0,2343
2 1,0 0,211 002 0,2142
3 1,28 0,205 101 0,2056
4 1,68 0,157 102 0,1581
5 2,10 0,119 103 0,1219
C contamination: C/Ru=4
Lafont et al., Scripta Mat., 2004, 51(7), 699
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
59
10 m
SEM QSB
EDS Ru
Homogeneous distribution of the deposit
Ru 0,90 wt %
No C contamination
Deposition from RuCp
2
+ O
2
T = 523K
Q
RuCP2
= 0,36 sccm
Q
O2
= 160 sccm
Constantin Vahlas SOPRANO Meeting, Caen, 17 July 2009
60
Continuous film, composed of ~30 nm crystallites
100 nm 100 nm 100 nm 100 nm
50 nm 50 nm 50 nm 50 nm