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Chemical Etching
Introduction
This example illustrates the principle of wet chemical etching. Wet chemical etching is particularly important for microelectronics industry for patterning of integrated circuit, MEMS devices, optoelectronic and pressure sensors. Wet etching processes use solution based (“wet”) etchants, where the substrate to be etched is immersed in a controlled flow of etchant. Wet etching process is selective isotropic, fast (usually reaction rate limited) and reproducible. Due to its reproducibility the technique is often used for micropatterning of substrates.
A wet etching process involves chemical reaction that consume the original reactant and produce new reactant. The wet etch process can be described by three basic steps:
The purpose of this tutorial is to examine how the copper substrate material is depleted and how the cavity shape evolves during the wet etching process. The rate of the etching reaction depends on the local concentration of a reactant, which is transported to the surface by coupled convection-diffusion. The laminar flow profile of the etchant fluid changes due to the shape evolution of the etched cavity.
Model Definition
The simplified 2D model geometry consists of a masked copper substrate with an exposed surface which is to be wet etched. The geometry is shown in Figure 1. The top rectangular domain has fluid flowing over the exposed copper substrate as marked in the x-direction. The fluid reacts only with the unmasked copper as the etching proceeds.
Figure 1: Schematic diagram of the chemical etching under a laminar flow of the etchant.
transport OF CHEMICAL species
Equation 1 describes mass flux of the etching species as given by diffusion and convection
(1)
where D (SI unit: m2/s) denotes the diffusion coefficient and (SI unit: mol/m3) is the concentration. The modeled species has a diffusion coefficient of 1 · 109 m2/s. At the inlet and top boundary of the flow, concentration is equal to the bulk concentration the etchant solution. At the etching surface (moving boundary) the flux condition is considered as in Equation 2:
(2)
where k (SI unit: m/s) is the etching rate constant for linear kinetics of the etching species and n is the normal vector. k is assumed to be independent of the position on the surface. A No Flux condition is used for all other boundaries except the moving boundary.
LAMINAR FLOW
At the cavity, the flow field can be calculated by Equation 3:
(3)
where ρ is the fluid density (SI unit: kg/m3), p is the pressure (SI unit: Pa), μ is the dynamic viscosity (SI unit: Pa·s), F is the volume force vector (indicated as the boundary stress in the modeling instructions), and u is the fluid velocity (SI unit: m/s). Along with continuity Equation 4
(4)
Along the moving wall, a no slip condition is applied.
deformed geometry
The movement of the boundary is defined by an interfacial condition on the boundary,
(5)
where υ is velocity of the moving mesh in the normal direction, D, M, and ρ are the diffusion coefficient (SI unit: m2/s), molar mass (SI unit: mol/m3), and density (SI unit: kg/m3) of the etching species, respectively.
Results and Discussion
Figure 2 shows the concentration of etchant species CuCl2 at t = 10000 s for an initial cavity radius of 0.5 mm. The etch profile is asymmetric owing to the fluid flow in the x-direction. The etch rate is higher around the area where laminar flow first encounters the boundary layer in fluid direction. Concentration becomes uniform deeper into the cavity as laminar flow can no longer transport reactant to the boundary layer owing to larger aspect ratio. (See also the velocity profile in Figure 3.)
Figure 2: Concentration profile of CuCl2 etchant at t = 10000 s over unmasked copper cavity.
Figure 3 shows the velocity profile for etchant flow at t = 10000 s. The velocity is zero close to the moving boundary. The fluid flow eventually becomes weak deeper as the aspect ratio of cavity increases with time.
Figure 3: Arrow surface plot depicting velocity profile of CuCl2 etchant after t=10000 s over the deformed geometry of copper cavity.
Figure 4: Mesh deformation after t=10000 s over the etching unmasked copper cavity.
Figure 4 shows mesh deformation for deforming geometry at t = 10000 s.
Reference
1. D.J. Economou and others, “Effect of transport and reaction on the shape evolution of cavities during wet chemical etching”, J. Electrochem. Soc., vol. 136, no. 7, pp. 1997–2004, 1989.
Application Library path: COMSOL_Multiphysics/Chemical_Engineering/chemical_etching
Modeling Instructions
From the File menu, choose New.
New
In the New window, click  Model Wizard.
Model Wizard
1
In the Model Wizard window, click  2D.
Add the required physics.
2
In the Select Physics tree, select Chemical Species Transport>Transport of Diluted Species (tds).
3
Click Add.
4
In the Concentration text field, type cCuCl2.
5
In the Select Physics tree, select Mathematics>Deformed Mesh>Deformed Geometry (dg).
6
Click Add.
7
In the Select Physics tree, select Fluid Flow>Single-Phase Flow>Laminar Flow (spf).
8
Click Add.
9
Click  Study.
10
In the Select Study tree, select General Studies>Stationary.
11
Global Definitions
Parameters 1
1
In the Model Builder window, expand the Component 1 (comp1)>Definitions node, then click Global Definitions>Parameters 1.
2
In the Settings window for Parameters, locate the Parameters section.
3
Click  Load from File.
4
Next, define the variable v_surface corresponding to the velocity of the moving boundary.
Definitions
Variables 1
1
In the Model Builder window, under Component 1 (comp1) right-click Definitions and choose Variables.
2
In the Settings window for Variables, locate the Variables section.
3
Geometry 1
Rectangle 1 (r1)
1
In the Model Builder window, expand the Component 1 (comp1)>Geometry 1 node.
2
Right-click Geometry 1 and choose Rectangle.
3
In the Settings window for Rectangle, locate the Size and Shape section.
4
In the Width text field, type d_mask.
5
In the Height text field, type h_mask.
Rectangle 2 (r2)
1
In the Geometry toolbar, click  Rectangle.
2
In the Settings window for Rectangle, locate the Size and Shape section.
3
In the Width text field, type h_boundary_layer.
4
In the Height text field, type h_seed_cavity.
5
Locate the Position section. In the x text field, type -h_seed_cavity.
6
In the y text field, type -h_seed_cavity.
Fillet 1 (fil1)
1
In the Geometry toolbar, click  Fillet.
2
Click the  Zoom Extents button in the Graphics toolbar.
3
On the object r2, select Points 1 and 2 only.
4
In the Settings window for Fillet, locate the Radius section.
5
In the Radius text field, type h_seed_cavity/2.
Rectangle 3 (r3)
1
In the Geometry toolbar, click  Rectangle.
2
In the Settings window for Rectangle, locate the Size and Shape section.
3
In the Width text field, type d_mask*2.
4
In the Height text field, type 3*h_mask.
5
Locate the Position section. In the x text field, type -d_mask/2.
6
In the y text field, type h_mask.
7
Click  Build All Objects.
Definitions
Moving Boundary
1
In the Definitions toolbar, click  Explicit.
2
In the Settings window for Explicit, type Moving Boundary in the Label text field.
3
Locate the Input Entities section. From the Geometric entity level list, choose Boundary.
4
Add Material
1
In the Home toolbar, click  Add Material to open the Add Material window.
2
Go to the Add Material window.
3
In the tree, select Built-in>Water, liquid.
4
Click Add to Component in the window toolbar.
5
In the Home toolbar, click  Add Material to close the Add Material window.
Transport of Diluted Species (tds)
Transport Properties 1
1
In the Model Builder window, expand the Component 1 (comp1)>Transport of Diluted Species (tds)>Transport Properties 1 node, then click Transport Properties 1.
2
In the Settings window for Transport Properties, locate the Convection section.
3
From the u list, choose Velocity field (spf).
4
Locate the Diffusion section. In the DcCuCl2 text field, type D.
Concentration 1
1
In the Model Builder window, expand the Component 1 (comp1)>Transport of Diluted Species (tds)>No Flux 1 node.
2
Right-click Transport of Diluted Species (tds) and choose Concentration.
3
4
In the Settings window for Concentration, locate the Concentration section.
5
Select the Species cCuCl2 check box.
6
In the c0,cCuCl2 text field, type cCuCl2_bulk.
Outflow 1
1
In the Physics toolbar, click  Boundaries and choose Outflow.
2
Flux 1
1
In the Physics toolbar, click  Boundaries and choose Flux.
2
In the Settings window for Flux, locate the Boundary Selection section.
3
From the Selection list, choose Moving Boundary.
4
Locate the Inward Flux section. Select the Species cCuCl2 check box.
5
In the J0,cCuCl2 text field, type r_surface.
Deformed Geometry (dg)
1
In the Model Builder window, under Component 1 (comp1) click Deformed Geometry (dg).
2
In the Settings window for Deformed Geometry, locate the Frame Settings section.
3
From the Geometry shape function list, choose 1.
4
Locate the Free Deformation Settings section. From the Mesh smoothing type list, choose Hyperelastic.
Free Deformation 1
1
In the Physics toolbar, click  Domains and choose Free Deformation.
2
Zero Normal Mesh Displacement 1
1
In the Physics toolbar, click  Boundaries and choose Zero Normal Mesh Displacement.
2
Prescribed Normal Mesh Velocity 1
1
In the Physics toolbar, click  Boundaries and choose Prescribed Normal Mesh Velocity.
2
In the Settings window for Prescribed Normal Mesh Velocity, locate the Boundary Selection section.
3
From the Selection list, choose Moving Boundary.
4
Locate the Normal Mesh Velocity section. In the vn text field, type v_surface.
Laminar Flow (spf)
In the Model Builder window, under Component 1 (comp1) click Laminar Flow (spf).
Wall 2
1
In the Physics toolbar, click  Boundaries and choose Wall.
2
3
In the Settings window for Wall, click to expand the Wall Movement section.
4
From the Translational velocity list, choose Manual.
5
Specify the utr vector as
Boundary Stress 1
1
In the Physics toolbar, click  Boundaries and choose Boundary Stress.
2
Study 1
Step 1: Stationary
1
In the Model Builder window, under Study 1 click Step 1: Stationary.
2
In the Settings window for Stationary, locate the Physics and Variables Selection section.
3
In the table, clear the Solve for check box for Deformed Geometry (dg).
Time Dependent
1
In the Study toolbar, click  Study Steps and choose Time Dependent>Time Dependent.
2
In the Settings window for Time Dependent, locate the Study Settings section.
3
In the Output times text field, type range(0,500,10000).
4
In the Study toolbar, click  Compute.
Results
Concentration (tds)
1
Click the  Zoom Extents button in the Graphics toolbar.
2
In the Concentration (tds) toolbar, click  Plot.
Arrow Surface 1
1
In the Model Builder window, right-click Velocity (spf) and choose Arrow Surface.
2
In the Settings window for Arrow Surface, locate the Coloring and Style section.
3
From the Arrow length list, choose Logarithmic.
4
From the Color list, choose White.
5
In the Velocity (spf) toolbar, click  Plot.
Pressure (spf)
1
Click the  Zoom Extents button in the Graphics toolbar.
2
In the Model Builder window, click Pressure (spf).
3
In the Pressure (spf) toolbar, click  Plot.
Mesh
1
In the Home toolbar, click  Add Plot Group and choose 2D Plot Group.
2
Right-click 2D Plot Group 4 and choose Rename.
3
In the Rename 2D Plot Group dialog box, type Mesh in the New label text field.
4
Mesh 1
1
Right-click Mesh and choose Mesh.
2
In the Mesh toolbar, click  Plot.
Animation 1
1
In the Results toolbar, click  Animation and choose Player.
2
In the Settings window for Animation, click  Show Frame.
3
Locate the Frames section. From the Frame selection list, choose All.
4
In the Frame number text field, type 101.
5
Right-click Animation 1 and choose Play.