IP Library › Granted Patent US 11,124,889
Granted Patent B2
US 11,124,889 · App. 16/434,049 · Granted Sep 21, 2021

Methods for fabricating and etching porous silicon carbide structures

Inventors: Rachel Cannara (Kirkland, WA); Emma Rae Mullen (Seattle, WA); Fred Sharifi (Kirkland, WA)
Assignee: Elwha LLC
C25D11/32C25F3/12
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Quick Facts
Patent No.
US 11,124,889
App. No.
16/434,049
Granted
Sep 21, 2021
Kind
B2
Abstract

The present disclosure relates to methods of fabricating a porous structure, such as a porous silicon carbide structure. The methods can include a step of providing a structure to be rendered porous, and a step of providing an etching solution. The methods can also include a step of electrochemically etching the structure to produce pores through at least a region of the structure, resulting in the formation of a porous structure. The morphology of the porous structure can be controlled by one or more parameters of the electrochemical etching process, such as the strength of the etching solution and/or the applied voltage.

Claims (57)

1. A method of fabricating a porous silicon carbide structure having a selected morphology, comprising:

providing a silicon carbide structure;

providing an etching solution comprising a reducing agent and an oxidizing agent;

electrochemically etching the silicon carbide structure with the etching solution to produce pores through a region of the silicon carbide structure to form a porous silicon carbide structure, wherein electrochemically etching the silicon carbide structure comprises applying a voltage to a surface of the silicon carbide structure to produce a current through the region of the silicon carbide structure;

monitoring a slope of the current versus time; and

controlling an etch propagation rate of the etching solution through the region of the silicon carbide structure to avoid a change in the monitored slope and achieve the selected morphology, wherein the current is proportional to a removal rate of material, and wherein the slope is negative.

2. The method of claim 1 , wherein the silicon carbide structure comprises a 3C, 4H, or 6H polytype of silicon carbide.

3. The method of claim 1 , wherein the silicon carbide structure comprises a silicon carbide semiconductor.

4. The method of claim 1 , wherein the silicon carbide structure comprises a predefined electronic carrier concentration.

5. The method of claim 1 , wherein the silicon carbide structure comprises a predefined crystalline designation.

6. The method of claim 1 , wherein the oxidizing agent comprises water, an alcohol, hydrogen peroxide, or a mixture thereof.

7. The method of claim 1 , wherein the reducing agent comprises hydrofluoric acid.

8. The method of claim 7 , wherein the concentration of the hydrofluoric acid is from about 1% to about 50%, from about 1% to about 20%, from about 1% to about 15%, from about 1% to about 10%, from about 1% to about 5%, or from about 2% to about 5%, by volume.

9. The method of claim 7 , wherein the etch propagation rate is dependent upon the concentration of the hydrofluoric acid.

10. The method of claim 7 , wherein the concentration of hydrofluoric acid is inversely proportional to a porosity of the porous silicon carbide structure.

11. The method of claim 1 , wherein the etching solution further comprises a surfactant.

12. The method of claim 1 , wherein the voltage is from about 20 V to about 40 V, from about 20 V to about 30 V, or from about 20 V to about 26 V.

13. The method of claim 1 , wherein the selected morphology comprises at least one of a selected average pore diameter, a selected pore wall thickness, or a selected porosity.

14. The method of claim 1 , wherein the selected morphology comprises an average pore wall thickness of between about 2 nm and about 200 nm.

15. The method of claim 1 , wherein the selected morphology comprises an average pore diameter of between about 0.1 μm and about 3 μm.

16. The method of claim 1 , wherein the selected morphology comprises an average pore diameter of between about 0.1 μm and about 3 μm, and an average pore wall thickness of between about 2 nm and about 200 nm.

17. The method of claim 1 , wherein the selected morphology comprises a porosity of from about 60% to about 96%.

18. The method of claim 1 , wherein the selected morphology comprises a substantially uniform material density.

19. The method of claim 1 , wherein controlling the etch propagation rate comprises:

selecting a concentration of reducing agent; and

selecting a voltage;

wherein the etch propagation rate is inversely proportional to a porosity of the selected morphology at the selected concentration and selected voltage.

20. The method of claim 19 , wherein the selected concentration is from about 1% to about 50%, from about 1% to about 20%, from about 1% to about 15%, from about 1% to about 10%, from about 1% to about 5%, or from about 2% to about 5%, by volume, and the selected voltage is from about 20 V to about 40 V, from about 20 V to about 30 V, or from about 20 V to about 26 V.

21. The method of claim 1 , wherein the silicon carbide structure is electrochemically etched beginning at an “Si” face.

22. The method of claim 1 , wherein the silicon carbide structure is electrochemically etched beginning at a “C” face.

23. A method of fabricating a porous structure, comprising:

providing a starting structure to be rendered porous, wherein the starting structure comprises silicon carbide;

providing an etching solution comprising a selected reducing agent and an oxidizing agent;

electrochemically etching the starting structure with the etching solution to produce pores through a region of the starting structure to form a porous structure, wherein electrochemically etching the structure comprises applying a voltage to a surface of the structure to produce a current through the region of the structure;

monitoring a slope of the current versus time; and

controlling an etch propagation rate of the etching solution through the region of the structure to avoid a change in the monitored slope and achieve a selected porosity, wherein the current is proportional to a removal rate of material, and wherein the slope is negative.

24. The method of claim 23 , wherein the selected porosity is greater than 90%.

25. The method of claim 23 , wherein the reducing agent comprises hydrofluoric acid.

26. The method of claim 23 , wherein controlling the etch propagation rate comprises:

selecting a concentration of reducing agent; and

selecting a voltage;

wherein the etch propagation rate is inversely proportional to the porosity at the selected concentration and selected voltage.

27. The method of claim 26 , wherein the selected concentration is from about 1% to about 50%, from about 1% to about 20%, from about 1% to about 15%, from about 1% to about 10%, from about 1% to about 5%, or from about 2% to about 5%, and the selected voltage is from about 20 V to about 40 V, from about 20 V to about 30 V, or from about 20 V to about 26 V.

28. The method of claim 23 , wherein the starting structure is electrochemically etched beginning at an “Si” face.

29. The method of claim 23 , wherein the starting structure is electrochemically etched beginning at a “C” face.

30. A method of fabricating a porous semiconductor structure via an electrochemical etch process, comprising:

providing a semiconductor structure comprising silicon carbide;

providing an etching solution comprising a reducing agent and an oxidizing agent;

selecting a concentration of the reducing agent;

electrochemically etching the semiconductor structure with the etching solution to produce pores through a region of the semiconductor structure to form a porous semiconductor structure, wherein electrochemically etching the semiconductor structure comprises selecting a voltage and applying the selected voltage to a surface of the semiconductor structure to produce a current through the region of the semiconductor structure;

monitoring a slope of the current versus time; and

controlling an etch propagation rate of the etching solution through the region of the semiconductor structure to avoid a change in the monitored slope and achieve a selected morphology, wherein the current is proportional to a removal rate of material, and wherein the slope is negative,

wherein the porous semiconductor structure comprises a selected porosity.

31. The method of claim 30 , wherein the selected concentration is from about 1% to about 50%, from about 1% to about 20%, from about 1% to about 15%, from about 1% to about 10%, from about 1% to about 5%, or from about 2% to about 5%, by volume, and the selected voltage is from about 20 V to about 40 V, from about 20 V to about 30 V, or from about 20 V to about 26 V.

32. The method of claim 30 , wherein an etch propagation rate is dependent upon the selected concentration.

33. The method of claim 30 , wherein the porous semiconductor structure comprises a selected average pore diameter.

34. The method of claim 1 , wherein controlling the etch propagation rate comprises changing a concentration of the reducing agent.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 12, 2024
From: ELWHA LLC
To: THE INVENTION SCIENCE FUND II, LLC
Reel/Frame 066732/0618 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 12, 2024
From: THE INVENTION SCIENCE FUND II, LLC
To: CARILLON TECHNOLOGIES LLC
Reel/Frame 066733/0579 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 13, 2020
From: MULLEN, EMMA RAE
To: ELWHA LLC
Reel/Frame 053195/0543 →
Continuity (3)
Continuation PCTUS2017066854 · Dec 15, 2017
Provisional Application 62435605 · Dec 16, 2016
Related Publication 20200006074A1 · Jan 2, 2020