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Tut 03 Intro Tut 18 Surface Chemistry PDF
Tut 03 Intro Tut 18 Surface Chemistry PDF
18.1. Introduction
In chemically reacting laminar flows, such as those encountered in chemical vapor deposition (CVD) applic-
ations, 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.
18.2. Prerequisites
This tutorial is written with the assumption that you have completed Introduction to Using ANSYS FLUENT:
Fluid Flow and Heat Transfer in a Mixing Elbow (p. 111), and that you are familiar with the ANSYS FLUENT nav-
igation 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 modeling,
and chemical vapor deposition. In particular, you should be familiar with the Arrhenius rate equation, as this
equation is used for the surface reactions modeled in this tutorial.
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Chapter 18: Modeling Surface Chemistry
The semiconductor materials Ga(s) and As(s) are deposited on the heated surface governed by the following
surface reactions.
+ → + + (18–1)
+ → + + (18–2)
The inlet gas is a mixture of Trimethyl Gallium and Arsine and the mass fraction of Ga is 0.15 and
is 0.4, respectively. 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 303 K.
These CVD reactors are typically known as cold-wall reactors, where only the wafer surface is heated to
higher temperatures, while the remaining reactor walls are maintained at low temperatures.
In this tutorial, simultaneous deposition of Ga and As is simulated and examined. The mixture properties
and the mass diffusivity are determined based on kinetic theory. Detailed surface reactions with multiple
sites and site species, and full multi-component/thermal diffusion effects are also included in the simulation.
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18.4.3. Step 2: General Settings
The purpose of this tutorial is to demonstrate surface reaction capabilities in ANSYS FLUENT. Convective
heat transfer is considered to be the dominant mechanism compared to radiative heat transfer, thus radiation
effects are ignored.
18.4.1. Preparation
1. Download surface_chem.zip from the ANSYS Customer Portal or the User Services Center to your
working folder (as described in Preparation (p. 4) of Introduction to Using ANSYS FLUENT in ANSYS
Workbench: Fluid Flow and Heat Transfer in a Mixing Elbow (p. 1)).
2. Unzip surface_chem.zip.
The file surface.msh can be found in the surface_chem folder created after unzipping the file.
3. Use FLUENT Launcher to start the 3D version of ANSYS FLUENT.
For more information about FLUENT Launcher, see Starting ANSYS FLUENT Using FLUENT Launcher in
the User’s Guide.
4. Enable Double Precision.
Note
The Display Options are enabled by default. Therefore, after you read in the mesh, it will be
displayed in the embedded graphics window.
General
General → Check
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Chapter 18: Modeling Surface Chemistry
ANSYS FLUENT will perform various checks on the mesh and will report the progress in the console. Ensure
that the reported minimum volume is a positive number.
2. Scale the mesh.
General → Scale...
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. Close the Scale Mesh dialog box.
3. Check the mesh.
General → Check
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.
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18.4.3. Step 2: General Settings
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.
General
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Chapter 18: Modeling Surface Chemistry
Models
In this problem, the energy equation and the species conservation equations will be solved, along with the mo-
mentum and continuity equations.
Although you enable reactions, you still run a non-reacting flow to produce an initial solution. You will run
reacting flow in step 8.
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18.4.4. Step 3: Models
The Species Model dialog box will expand to show relevant input options.
b. Enable Volumetric and Wall Surface in the Reactions group box.
c. 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.
d. Enable Inlet Diffusion in the Options group box.
e. Retain the default setting for Diffusion Energy Source.
This includes the effect of enthalpy transport due to species diffusion in the energy equation, which
contributes to the energy balance, especially for the case of Lewis numbers far from unity.
f. Enable Full Multicomponent Diffusion and Thermal Diffusion.
The Full Multicomponent Diffusion activates Stefan-Maxwell’s equations and computes the diffusive
fluxes of all species in the mixture to all concentration gradients. The Thermal Diffusion effects cause
heavy molecules to diffuse less rapidly, and light molecules to diffuse more rapidly, toward heated
surfaces.
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Chapter 18: Modeling Surface Chemistry
ANSYS FLUENT will list the properties in the console, that are required for the models that you have
enabled.
An Information dialog box will open reminding you to confirm the property values that have been
extracted from the database.
Materials
In this step, you will create the gas-phase species ( , , ,
), the site species (Ga_s and
As_s), and solid species (Ga and As).
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18.4.5. Step 4: Materials
Ignore the Density parameter as the density will be set to incompressible-ideal-gas for mixture.
Tip
Scroll down in the Properties group box to see all the parameters.
A Question dialog box will open, asking if you want to overwrite air.
Properties group box will expand to show L-J Characteristic Length, L-J Energy Parameter, and
Degrees of Freedom.
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Chapter 18: Modeling Surface Chemistry
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18.4.5. Step 4: Materials
To enter complex formulae such as Ga( ) in the text entry box, use ‘ <’ and ‘ >’ instead of ‘ (’ and ‘ )’,
respectively.
3. Set the mixture species.
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Chapter 18: Modeling Surface Chemistry
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. 696)
Warning
The species should appear in the same order as shown in Table 18.3: Selected
Species (p. 696). Ensure that h2 is at the bottom in the Selected Species selection
list.
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18.4.5. Step 4: Materials
ii. Increase the Total Number of Reactions to 2, and define the following reactions using the
parameters in Table 18.4: Reaction Parameters (p. 697) :
+ → + + (18–3)
+ → + + (18–4)
further reacts with H ( + → ) on the substrate producing .
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Chapter 18: Modeling Surface Chemistry
Parameter For Equation 18–3 (p. 697) For Equation 18–4 (p. 697)
Reaction Type Wall Surface Wall Surface
Number of Reactants 2 2
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 PEF= 1e+06, AE= 0, TE= 0.5 PEF= 1e+12, AE= 0, TE= 0.5
Number of Products 3 3
Species ga, as_s, h2 as, ga_s, ch3
Stoich. Coefficient ga= 1, as_s= 1, h2= 1.5 as= 1, ga_s= 1, ch3= 3
Rate Exponent as_s= 0, h2= 0 ga_s= 0, ch3= 0
Set the ID to 2 in order to set the parameters for the second reaction.
iii. Click OK to save the data and close the Reactions dialog box.
f. Set the reaction mechanisms for the mixture.
i. Click the Edit... button to the right of the Mechanism drop-down list to open the Reaction
Mechanisms dialog box.
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18.4.6. Step 5: Boundary Conditions
Boundary Conditions
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18.4.6. Step 5: Boundary Conditions
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. Enter 0.02189 m/s for Velocity Magnitude.
d. Click the Thermal tab and enter 293 K for Temperature.
e. Click the Species tab.
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Chapter 18: Modeling Surface Chemistry
i. Set the Species Mass Fractions for ash3 to 0.4, ga < ch3 > 3 to 0.15, and ch3 to 0 respect-
ively.
f. Click OK to close the Velocity Inlet dialog box.
3. Set the boundary conditions for wall-1.
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18.4.6. Step 5: Boundary Conditions
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Chapter 18: Modeling Surface Chemistry
i. Enable Reaction.
ii. Retain the selection of gaas-ald from the Reaction Mechanisms drop-down list.
g. Click OK to close the Wall dialog box.
6. Set the boundary conditions for wall-5.
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18.4.8. Step 7: Non-Reacting Flow Solution
Boundary Conditions
The Operating Conditions dialog box can be accessed from the Cell Zone Conditions task page as well as the
Boundary Conditions task page.
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Chapter 18: Modeling Surface Chemistry
Solution Controls
Solution Initialization
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18.4.8. Step 7: Non-Reacting Flow Solution
Note
For flows in complex topologies, hybrid initialization will provide better initial velocity
and pressure fields than standard initialization. This in general will help in improving
the convergence behavior of the solver.
Run Calculation
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Chapter 18: Modeling Surface Chemistry
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18.4.9. Step 8: Reacting Flow Solution
Run Calculation
a. Retain the default selection of Mass Flow Rate in the Options group box.
b. Select outlet and velocity-inlet from the Boundaries selection list.
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Chapter 18: Modeling Surface Chemistry
Rotate the display with the mouse to obtain the view as shown in (Figure 18.3 (p. 711)).
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18.4.9. Step 8: Reacting Flow Solution
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Chapter 18: Modeling Surface Chemistry
Run Calculation
a. Retain the default selection of MassFlow Rate in the Options group box.
b. Retain the selection of outlet and velocity-inlet in the Boundaries selection list.
c. Click Compute and close the Flux Reports dialog box.
9. Save the case and data files (surface-react1.cas.gz and surface-react1.dat.gz).
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18.4.9. Step 8: Reacting Flow Solution
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Chapter 18: Modeling Surface Chemistry
Surface → Iso-Surface...
a. Select Mesh and Z-Coordinate from the Surface of Constant drop-down lists.
b. Click Compute.
c. Enter 0.075438 m for Iso-Values.
d. Enter z=0.07 for New Surface Name.
e. Click Create and close the Iso-Surface dialog box.
2. Display contours of temperature on the plane surface created. (Figure 18.6 (p. 716)).
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18.4.10. Step 9: Postprocessing
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Chapter 18: Modeling Surface Chemistry
Figure 18.6 (p. 716) 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. Display contours of surface deposition rates of ga (Figure 18.7 (p. 717)).
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.
Figure 18.7 (p. 717)shows the gradient of surface deposition rate of ga. The maximum deposition is seen at
the center of the disk.
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18.4.10. Step 9: Postprocessing
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Chapter 18: Modeling Surface Chemistry
Figure 18.8 (p. 718)shows the rate of surface coverage of the site species ga_s.
5. Create a line surface from the center of wall-4 to the edge.
Surface → Line/Rake...
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18.4.10. Step 9: Postprocessing
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.
b. Click Create.
c. Close the Line/Rake Surface dialog box.
6. Plot the surface deposition rate of Ga v/s radial distance (Figure 18.9 (p. 720)).
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. Select line-9 from the Surfaces selection list.
d. Click Plot and close the Solution XY Plot dialog box.
The peak surface deposition rate occurs at the center of wall-4 (where the concentration of the mixture is
highest).
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Chapter 18: Modeling Surface Chemistry
Extra
You can also perform all the postprocessing steps to analyze the deposition of As.
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 simul-
taneous deposition of gallium and arsenide from a mixture of precursor gases on a rotating susceptor. Note
that the same approach is valid if you are simulating multi-step reactions with multiple sites/site species.
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