Chapter 18: Modeling Surface Chemistry
Chapter 18: Modeling Surface Chemistry
18.1. Introduction
In chemically reacting laminar flows, such as those encountered in chemical vapor deposition (CVD)
applications, accurate modeling of time-dependent hydrodynamics, heat and mass transfer, and
chemical reactions (including wall surface reactions ) is important.
In this tutorial, surface reactions are considered. Modeling the reactions taking place at gas-solid interfaces
is complex and involves several elementary physico-chemical processes like adsorption of gas-phase
species on the surface, chemical reactions occurring on the surface, and desorption of gases from the
surface back to the gas phase.
This tutorial demonstrates how to do the following:
Enable physical models and define boundary conditions for a chemically reacting laminar flow involving
wall surface reactions.
18.2. Prerequisites
This tutorial is written with the assumption that you have completed one or more of the introductory
tutorials found in this manual:
Introduction to Using ANSYS FLUENT in ANSYS Workbench: Fluid Flow and Heat Transfer in a Mixing
Elbow (p. 1)
Introduction to Using ANSYS FLUENT: Fluid Flow and Heat Transfer in a Mixing Elbow (p. 131)
and that you are familiar with the ANSYS FLUENT navigation pane and menu structure. Some steps in
the setup and solution procedure will not be shown explicitly.
Before beginning with this tutorial, see "Modeling Species Transport and Finite-Rate Chemistry" in the
User's Guide for more information about species transport, chemically reacting flows, wall surface reaction
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the inlet at the top. These gases flow over the hot, spinning disk depositing thin layers of gallium and
arsenide on it in a uniform, repeatable manner. The disk rotation generates a radially pumping effect,
which forces the gases to flow in a laminar manner down to the growth surface, outward across the
disk, and finally to be discharged from the reactor.
The semiconductor materials Ga(s) and As(s) are deposited on the heated surface governed by the following surface reactions.
+
+
+
+ + +
(181)
(182)
The inlet gas is a mixture of Trimethyl Gallium, which has a mass fraction of 0.15, and Arsine, which has
a mass fraction of 0.4. The mixture velocity at the inlet is 0.02189 m/s. The disk rotates at 80 rad/sec.
The top wall (wall-1) is heated to 473 K and the sidewalls (wall-2) of the reactor are maintained at 343 K.
The susceptor (wall-4) is heated to a uniform temperature of 1023 K and the bottom wall (wall-6) is at
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18.4.1. Preparation
1.
Extract the file surface_chem.zip from the ANSYS_Fluid_Dynamics_Tutorial_Inputs.zip archive which is available from the Customer Portal.
Note
For detailed instructions on how to obtain the ANSYS_Fluid_Dynamics_Tutorial_Inputs.zip file, please refer to Preparation (p. 3) in Introduction to Using ANSYS
FLUENT in ANSYS Workbench: Fluid Flow and Heat Transfer in a Mixing Elbow (p. 1).
2.
3.
4.
Note
The Display Options are enabled by default. Therefore, after you read in the mesh, it will
be displayed in the embedded graphics window.
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2.
a.
Select cm (centimeters) from the Mesh Was Created In drop-down list in the Scaling group box.
b.
Click Scale and verify that the domain extents are as shown in the Scale Mesh dialog box.
The default SI units will be used in this tutorial, hence there is no need to change any units.
c.
3.
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Note
It is a good practice to check the mesh after manipulating it (i.e., scale, convert to
polyhedra, merge, separate, fuse, add zones, or smooth and swap). This will ensure
that the quality of the mesh has not been compromised.
4.
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Extra
You can use the left mouse button to rotate the image and view it from different angles.
Use the right mouse button to check which zone number corresponds to each
boundary. If you click the right mouse button on one of the boundaries in the graphics
window, its name and type will be printed in the ANSYS FLUENT console. This feature
is especially useful when you have several zones of the same type and you want to
distinguish between them quickly. Use the middle mouse button to zoom the image.
5.
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Energy Edit...
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2.
a.
b.
Species Edit...
Although you enable reactions, you still run a non-reacting flow to produce an initial solution. You
will run a reacting flow in step 8.
a.
b.
759
Disable Heat of Surface Reactions in the Wall Surface Reaction Options group box.
d.
Enable Mass Deposition Source in the Wall Surface Reaction Options group box.
Mass Deposition Source is enabled because there is a certain loss of mass due to the surface
deposition reaction, i.e., As(s) and Ga(s) are being deposited out. If you were to do an overall mass
balance without taking this fact into account, you would end up with a slight imbalance.
e.
f.
g.
h.
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, ,
,
), the site species (Ga_s and
air Create/Edit...
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a.
b.
c.
Specify the properties as shown in Table 18.1: Properties of arsine (p. 761).
Value
Density
Cp (Specific Heat)
kinetic-theory
Thermal Conductivity
kinetic-theory
Viscosity
kinetic-theory
Molecular Weight
77.95
130579.1
Reference Temperature
298.15
Tip
Scroll down in the Properties group box to see all the parameters.
d.
761
e.
f.
Select arsine (ash3) from the FLUENT Fluid Materials drop-down list.
The Properties group box will expand to show L-J Characteristic Length, L-J Energy Parameter,
and Degrees of Freedom.
2.
g.
h.
i.
j.
762
air Create/Edit...
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Enter the parameter values for each of the species as shown in Table 18.2: Properties of Species (p. 763)
Ga(CH_3)_3 CH_3
H_2
Ga_s
As_s
Ga
As
Name
tmg
hydrogen
ga_s
as_s
ga
as
Chemical
Formula
ga<ch3>3 ch3
h2
ga_s
as_s
ga
as
Cp
(Specific
Heat)
kinetictheory
kinetictheory
kinetictheory
520.64
520.64
1006.43 1006.43
Thermal
Conductivity
kinetictheory
kinetictheory
kinetictheory
0.0158
0.0158
kinetictheory
kinetictheory
Viscosity
kinetictheory
kinetictheory
kinetictheory
2.125
e05
2.125
e05
kinetictheory
kinetictheory
Molecular
Weight
114.83
15
2.02
69.72
74.92
69.72
74.92
Standard
State
Enthalpy
2.044
e+07
-3117.71 -3117.71 0
Standard
State
Entropy
Reference
Temperature
298.15
298.15
298.15
298.15
298.15
298.15
298.15
L-J
Charac-
5.68
3.758
2.827
ch3g
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Ga(CH_3)_3 CH_3
H_2
Ga_s
As_s
Ga
As
L-J Energy
Parameter
398
148.6
59.7
Degrees
of
Freedom
teristic
Length
b.
c.
Click No in the Question dialog box when asked if you want to overwrite air.
mixture-template Create/Edit...
a.
b.
Click Change/Create.
c.
d.
Set the Selected Species, Selected Site Species, and Selected Solid Species.
i.
764
in the text entry box, use < and > instead of (
Click the Edit... button to the right of the Mixture Species drop-down list to open the Species
dialog box.
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ii.
Set the Selected Species, Selected Site Species, and Selected Solid Species from the
Available Materials selection list as shown in Table 18.3: Selected Species (p. 765)
Selected Site
Species
Selected Solid
Species
ash3
ga_s
ga
as_s
as
ch3
h2
Warning
The species should appear in the same order as shown in Table 18.3: Selected
Species (p. 765). Ensure that h2 is at the bottom in the Selected Species selection list. ANSYS FLUENT will interpret the last species in the list as the bulk
species.
To add/remove the species:
To add a particular species to the list, select the required species from the Available Materials
selection list and click Add in the corresponding species selection list (Selected Species, Selected Site Species, or Selected Solid Species).
To remove an unwanted species from the selection list, select the species from the selection
list (i.e., Selected Species, Selected Site Species, or Selected Solid Species) and click Remove
in the corresponding selection list.
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Click OK to close the Species dialog box after all the species are set under the respective
categories.
Click the Edit... button to the right of the Reaction drop-down list to open the Reactions
dialog box.
ii.
Increase the Total Number of Reactions to 2, and define the following reactions using the
parameters in Table 18.4: Reaction Parameters (p. 767) :
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+ + +
(183)
+ + +
(184)
Reaction Name
gallium-dep
arsenic-dep
Reaction ID
Reaction Type
Wall Surface
Wall Surface
Number of Reactants
Species
ash3, ga_s
ga ch3 3, as_s
Stoich. Coefficient
ash3= 1, ga_s= 1
ga ch3 3= 1, as_s= 1
Rate Exponent
ash3= 1, ga_s= 1
ga ch3 3= 1, as_s= 1
Arrhenius Rate
Number of
Products
Species
ga, as_s, h2
Stoich. Coefficient
Rate Exponent
as_s= 0, h2= 0
ga_s= 0, ch3= 0
Click OK to save the data and close the Reactions dialog box.
Click the Edit... button to the right of the Mechanism drop-down list to open the Reaction
Mechanisms dialog box.
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767
ii.
iii.
iv.
v.
vi.
viii. Click the Define... button to the right of site-1 to open the Site Parameters dialog box.
A.
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ix.
B.
Select ga_s as the first site species and enter 0.7 for Initial Site Coverage.
C.
Select as_s as the second site species and enter 0.3 for Initial Site Coverage.
D.
g.
Retain the default selection of incompressible-ideal-gas from the Density drop-down list.
h.
Retain the default selection of mixing-law from the Cp (Specific Heat) drop-down list.
i.
j.
k.
Retain the default selection of kinetic-theory from the Mass Diffusivity drop-down list.
l.
Retain the default selection of kinetic-theory from the Thermal Diffusion Coefficient drop-down
list.
1.
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2.
770
outlet Edit...
velocity-inlet Edit...
a.
Retain the default selection of Magnitude, Normal to Boundary from the Velocity Specification
Method drop-down list.
b.
Retain the default selection of Absolute from the Reference Frame drop-down list.
c.
e.
i.
f.
3.
Set the Species Mass Fractions for ash3 to 0.4, ga < ch3 > 3 to 0.15, and ch3 to 0.
wall-1 Edit...
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b.
4.
i.
ii.
b.
5.
ii.
772
wall-2 Edit...
wall-4 Edit...
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a.
b.
c.
d.
e.
f.
i.
ii.
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773
g.
6.
i.
Enable Reaction.
ii.
Retain the selection of gaas-ald from the Reaction Mechanisms drop-down list.
b.
c.
d.
e.
7.
i.
ii.
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wall-5 Edit...
wall-6 Edit...
b.
i.
ii.
a.
b.
Enable Gravity.
c.
Enter 9.81
d.
e.
The Operating Conditions dialog box can be accessed from the Cell Zone Conditions task page as well
as the Boundary Conditions task page.
Species Edit...
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775
b.
3.
a.
Select Coupled from the Scheme drop-down list in the Pressure-Velocity Coupling group box.
b.
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4.
5.
Residuals Edit...
Retain the default settings and close the Residual Monitors dialog box.
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6.
a.
Retain the default selection of Hybrid Initialization from the Initialization Methods group
box.
b.
Click Initialize.
7.
a.
778
Species Edit...
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2.
a.
b.
Enable Mass Deposition Source in the Wall Surface Reaction Options group box.
c.
Residuals Edit...
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779
3.
4.
780
a.
Retain the default selection of Mass Flow Rate in the Options group box.
b.
Select outlet, velocity-inlet, and wall-4 from the Boundaries selection list.
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a.
b.
Select Species... and Surface Deposition Rate of ga from the Contours of drop-down lists.
c.
d.
Rotate the display with the mouse to obtain the view as shown in (Figure 18.3 (p. 782)).
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781
6.
782
Residuals Edit...
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7.
a.
b.
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9.
a.
Retain the default selection of Mass Flow Rate in the Options group box.
b.
Retain the selection of outlet and velocity-inlet in the Boundaries selection list.
c.
784
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2.
a.
Select Mesh... and Z-Coordinate from the Surface of Constant drop-down lists.
b.
Click Compute.
c.
d.
e.
Display contours of temperature on the plane surface created. (Figure 18.5 (p. 787)).
Graphics and Animations
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785
786
a.
b.
Select Temperature... and Static Temperature from the Contours of drop-down lists.
c.
d.
e.
Click Display.
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Figure 18.5 (p. 787) shows the temperature distribution across a plane just above the rotating disk. You
can see that the disk has a temperature of 1023 K.
3.
a.
Select Species... and Surface Deposition Rate of ga from the Contours of drop-down lists.
b.
c.
d.
Click Display.
You may need to use the left mouse button to rotate the image so that you can see the contours on
the top side of wall-4 where the deposition takes place.
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787
4.
788
a.
Select Species... and Surface Coverage of ga_s from the Contours of drop-down lists.
b.
c.
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Figure 18.7 (p. 789) shows the rate of surface coverage of the site species ga_s.
5.
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789
a.
Enter the values for x0, x1, y0, y1, z0, and z1 as shown in the Line/Rake Surface dialog box.
You can also select the points by clicking Select Points with Mouse. Then, in the graphic display,
click at the center of wall-4 and at the edge using the right mouse button.
6.
b.
Click Create.
c.
Plot the surface deposition rate of Ga versus radial distance (Figure 18.8 (p. 791)).
Plots
790
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Summary
a.
b.
Select Species... and Surface Deposition Rate of ga from the Y Axis Function drop-down lists.
The source/sink terms due to the surface reaction are deposited in the cell adjacent to the wall
cells, so it is necessary to plot the cell values and not the node values.
c.
d.
The peak surface deposition rate occurs at the center of wall-4 (where the concentration of the mixture
is highest).
Extra
You can also perform all the postprocessing steps to analyze the deposition of As.
7.
18.5. Summary
The main focus of this tutorial is the accurate modeling of macroscopic gas flow, heat and mass transfer,
species diffusion, and chemical reactions (including surface reactions) in a rotating disk CVD reactor. In
this tutorial, you learned how to use the two-step surface reactions involving site species, and computed
simultaneous deposition of gallium and arsenide from a mixture of precursor gases on a rotating susRelease 14.0 - SAS IP, Inc. All rights reserved. - Contains proprietary and confidential information
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791
792
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