Carbon dioxide gas sensors and method of manufacturing and using same

• US 8,702,962 B1
• Filed: 08/20/2008
• Issued: 04/22/2014
• Est. Priority Date: 05/25/2007
• Status: Active Grant

• Current Assignee: National Aeronautics and Space Administration (Government of the United States of America)
• Original Assignee: United States Administrator of National Aeronautics and Space Administration
• Inventors: Hunter, Gary W., Xu, Jennifer C.
• Primary Examiner(s): Dieterle, Jennifer
• Application Number:
  US12/195,358
• Time in Patent Office: 2,071 Days
• Field of Search: 204/400, 204421-431, 204/410, 204/411, 205/784, 205/781, 2057835-785, 205/787, 427/58, 73/233.1, 73/233.2
• US Class Current: 205/784
• CPC Class Codes: G01N 27/4074 for detection of gases other than oxygen
• CPC Class Codes: G01N 33/004 for CO, CO2

Abstract

A gas sensor comprises a substrate layer; a pair of interdigitated metal electrodes, said electrodes include upper surfaces, the electrodes selected from the group consisting of Pt, Pd, Au, Ir, Ag, Ru, Rh, In, Os, and their alloys. A first layer of solid electrolyte staying in between electrode fingers and partially on said upper surfaces of said electrodes, said first layer selected from NASICON, LISICON, KSICON and β″-Alumina. A second layer of metal carbonate(s) as an auxiliary electrolyte engaging said upper surfaces of the electrodes and the first solid electrolyte. The metal carbonates selected from the group consisting of the following ions Na⁺, K⁺, Li⁺, Ag⁺, H⁺, Pb²⁺, Sr²⁺, Ba²⁺, and any combination thereof. An extra layer of metal oxide selected from the group consisting of SnO₂, In₂O₃, TiO₂, WO₃, ZnO, Fe₂O₃, ITO, CdO, U₃O₈, Ta₂O₅, BaO, MoO₂, MoO₃, V₂O₅, Nb₂O₅, CuO, Cr₂O₃, La₂O₃, RuO₃, RuO₂, ReO₂, ReO₃, Ag₂O, CoO, Cu₂O, SnO, NiO, Pr₂O₃, BaO, PdO₂, HfO₃, HfO₃ or other metal oxide and their mixtures residing above and in engagement with the second electrolyte to improve sensor performance and/or to reduce sensor heating power consumption.

Claims

1. A process for sensing carbon dioxide, including the following steps:

applying a constant direct current voltage across a pair of electrodes, said electrodes being separated by an electrolyte material containing sodium, said electrodes located between a layer of Alumina substrate and a carbonate layer of auxiliary electrolyte, and, an extra layer of metal oxide selected from the group consisting of SnO₂, In₂O₃, TiO₂, WO₃, ZnO, Fe₂O₃, ITO, CdO, U₃O₈, Ta₂O₅, BaO, MoO₂, V₂O₅, Nb₂O₅, CuO, Cr₂O₃, La₂O₃, RuO₃, RuO₂, ReO₂, ReO₃, Ag₂O, CoO, Cu₂O, SnO, NiO, Pr₂O₃, BaO, PdO₂, and HfO₃ and mixtures thereof residing above and in engagement with said auxiliary electrolyte;

reacting carbon dioxide with said electrolyte material containing sodium at a first three-point boundary, said first three point boundary being at the joinder of one of said electrode, said electrolyte material containing sodium, and a barium containing auxiliary electrolyte;

reacting an oxide of sodium at a second three-point boundary, said second three-point boundary being at the joinder of the other of said electrodes, said electrolyte material containing sodium, and a barium containing auxiliary electrolyte;

measuring the resulting current; and

,

correlating change in current to the concentration of carbon dioxide.

2. A process for sensing carbon dioxide as claimed in claim 1 wherein said extra layer of metal oxide selected from the group consisting of SnO₂, In₂O₃, TiO₂, WO₃, ZnO, Fe₂O₃, ITO, CdO, U₃O₈, Ta₂O₅, BaO, MoO₂, MoO₃, V₂O₅, Nb₂O₅, CuO, Cr₂O₃, La₂O₃, RuO₃, RuO₂, ReO₂, ReO₃, Ag₂O, CoO, Cu₂O, SnO, NiO, Pr₂O₃, PdO₂, and HfO₃ is mixed with said auxiliary carbonate to improve sensor performance and/or to reduce sensor heating power consumption.

3. A process for sensing carbon dioxide as claimed in claim 1 wherein said metal oxide layer or metal oxide mixtures layer further comprises a catalytic metal used in combination therewith and selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, W, V, Nb, Ta, Cr, Mo, Cu, Fe, Mn, Co, Ni, Ti, Zn, Cd or an alloy thereof.

4. A gas sensor comprising:

a substrate layer;

a pair of interdigitated metal electrodes each having a plurality of electrode fingers, said electrodes include upper surfaces, said electrodes, selected from the group consisting of Pt, Pd, Au, Ir, Ag, Ru, Rh, In, and Os, and alloys thereof;

a first layer of solid electrolyte staying in between electrode fingers and partially on said upper surfaces of said electrodes, said first layer selected from NASICON, LISICON, KSICON, and β

″

-Alumina;

a second layer of metal carbonate(s) as an auxiliary electrolyte engaging said upper surfaces of said electrodes and said first solid electrolyte;

said metal carbonates comprise an element selected from the group consisting of the following ions Na⁺, K⁺, Li⁺, Ag⁺, H⁺, Pb²⁺, Sr²⁺, Ba²⁺, and any combination thereof;

an extra layer of metal oxide selected from the group consisting of SnO₂, In₂O₃, TiO₂, WO₃, ZnO, Fe₂O₃, ITO, CdO, U₃O₈, Ta₂O₅, BaO, MoO₂, V₂O₅, Nb₂O₅, CuO, Cr₂O₃, La₂O₃, RuO₃, RuO₂, ReO₂, ReO₃, Ag₂O, CoO, Cu₂O, SnO, NiO, Pr₂O₃, BaO, PdO₂, and HfO₃ and mixtures thereof residing above and in engagement with said auxiliary electrolyte to improve sensor performance and/or to reduce sensor heating power consumption.

5. A gas sensor as claimed in claim 4 wherein said extra layer of metal oxide selected from the group consisting of SnO₂, In₂O₃, TiO₂, WO₃, ZnO, Fe₂O₃, ITO, CdO, U₃O₈, Ta₂O₅, BaO, MoO₂, V₂O₅, Nb₂O₅, CuO, Cr₂O₃, La₂O₃, RuO₃, RuO₂, ReO₂, ReO₃, Ag₂O, CoO, Cu₂O, SnO, NiO, Pr₂O₃, BaO, PdO₂, and HfO₃ is mixed with Na₂CO₃/BaCO₃ to improve sensor performance and/or to reduce sensor heating power consumption.

6. A gas sensor as claimed in claim 4 wherein said metal oxide layer or metal oxide mixtures layer further comprises a catalytic metal used in combination therewith and selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, W, V, Nb, Ta, Cr, Mo, Cu, Fe, Mn, Co, Ni, Ti, Zn, Cd or an alloy thereof.

7. A gas sensor comprising:

a substrate layer;

a pair of interdigitated metal electrodes each having a plurality of electrode fingers, said electrodes include upper surfaces, said electrodes, selected from the group consisting of Pt, Pd, Au, Ir, Ag, Ru, Rh, In, and Os, and alloys thereof;

a first layer of solid electrolyte staying in between electrode fingers and partially on said upper surfaces of said electrodes, said first layer selected from NASICON, LISICON, KSICON, and β

″

-Alumina;

a second layer of metal carbonate(s) as an auxiliary electrolyte engaging said upper surfaces of said electrodes and said first solid electrolyte;

said metal carbonates comprise an element selected from the group consisting of the following ions Na⁺, K⁺, Li⁺, Ag⁺, H⁺, Pb²⁺, Sr²⁺, Ba²⁺, and any combination thereof;

an extra layer of metal oxide selected from the group consisting of SnO₂, In₂O₃, TiO₂, WO₃, ZnO, Fe₂O₃, ITO, CdO, U₃O₈, Ta₂O₅, BaO, MoO₂, V₂O₅, Nb₂O₅, CuO, Cr₂O₃, La₂O₃, RuO₃, RuO₂, ReO₂, ReO₃, Ag₂O, CoO, Cu₂O, SnO, NiO, Pr₂O₃, BaO, PdO₂, and HfO₃ and mixtures thereof mixed with Na₂CO₃/BaCO₃ and residing above and in engagement with said auxiliary electrolyte to improve sensor performance and/or to reduce sensor heating power consumption.

8. A gas sensor as claimed in claim 7 wherein said metal oxide layer or metal oxide mixtures layer further comprises a catalytic metal used in combination therewith and selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, W, V, Nb, Ta, Cr, Mo, Cu, Fe, Mn, Co, Ni, Ti, Zn, Cd or an alloy thereof.

9. A process for fabricating a carbon dioxide sensor including the following steps:

depositing platinum interdigitated finger electrodes on a Alumina substrate, said electrodes having an upper surface;

depositing solid electrolyte selected from the group of LISICON, KSICON, NASICON or and β

″

-Alumina between said finger electrodes and on a portion of said upper surface of said interdigitated finger electrodes; and

,

depositing an auxiliary electrolyte material comprising a compound selected from the group consisting of Sodium Carbonate, Barium Carbonate, and mixtures thereof on top of the electrodes; and

,

depositing an extra layer of metal oxide selected from the group consisting of SnO₂, In₂O₃, TiO₂, WO₃, ZnO, Fe₂O₃, ITO, CdO, U₃O₈, Ta₂O₅, BaO, MoO₂, V₂O₅, Nb₂O₅, CuO, Cr₂O₃, La₂O₃, RuO₃, RuO₂, ReO₂, ReO₃, Ag₂O, CoO, Cu₂O, SnO, NiO, Pr₂O₃, BaO, PdO₂, and HfO₃, and mixtures thereof residing above and in engagement with said auxiliary electrolyte to improve sensor performance and/or to reduce sensor heating power consumption.

10. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said metal oxide layer or metal oxide mixtures layer further comprises a catalytic metal used in combination therewith and selected from the group consisting of Ru, Rh, Pd, Os, Ir, Pt, Au, Ag, W, V, Nb, Ta, Cr, Mo, Cu, Fe, Mn, Co, Ni, Ti, Zn, Cd or an alloy thereof.

11. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said metal oxides are applied via sol gel deposition, sputtering, evaporation, or screen printing processes.

12. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said metal oxides are applied by sputtering.

13. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said metal oxides are applied by e-beam evaporation.

14. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said metal oxides are applied by screen printing.

15. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said step of depositing interdigitated finger electrodes includes the following steps:

patterning said alumina substrate with photoresist and an interdigitated finger electrode photomask;

developing and removing imidized photoresist;

depositing a layer of 50 Å

of material selected from the group consisting of Platinum Oxide and Titanium on said Alumina substrate;

depositing a layer of 4000 Å

of Platinum on said Alumina substrate;

patterning said alumina substrates again to cover said upper surface of said interdigitated finger electrodes and said Alumina substrate with photoresist; and

,

developing and removing imidized photoresist.

16. A process for fabricating a carbon dioxide sensor as claimed in claim 15 wherein said step of depositing solid electrolyte NASICON between said finger electrodes and on a portion of said upper surface of said interdigitated finger electrodes includes the following steps:

depositing solid NASICON over said Alumina substrate, said interdigitated finger electrodes and the unimidized photoresist;

removing said unimidized photoresist with acetone to remove NASICON from said upper surface of said interdigitated finger electrodes exposing said upper surfaces of said interdigitated electrodes; and

,

heating said substrate in an oven at a temperature range of 850°

C.

17. A process for fabricating carbon dioxide sensor as claimed in claim 16 wherein the step of the depositing an auxiliary electrolyte material comprising sodium carbonate and barium carbonate on top of the electrodes includes the steps of:

sputtering solid auxiliary electrolyte layer between said interdigitated finger electrodes and on said NASICON using a shadow mask; and

,

heating said substrates in an oven at approximately 686°

C. for 10 minutes and at approximately 710°

C. for 20 minutes.

18. A process for fabricating a carbon dioxide sensor as claimed in claim 16 wherein said step of depositing solid NASICON over said Alumina substrate, said interdigitated finger electrodes and the unimidized photoresist, said NASICON solid electrolyte is deposited by e-beam evaporation.

19. A process for fabricating a carbon dioxide sensor as claimed in claim 16 wherein said step of depositing solid NASICON over said Alumina substrate, said interdigitated finger electrodes and the unimidized photoresist, said NASICON solid electrolyte is deposited by sputtering.

20. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said step of depositing solid electrolyte NASICON between said finger electrodes and on a portion of said upper surface of said interdigitated finger electrodes is performed by e-beam evaporation.

21. A process for fabricating a carbon dioxide sensor as claimed in claim 9 wherein said step of depositing solid electrolyte NASICON between said finger electrodes and on a portion of said upper surface of said interdigitated finger electrodes is performed by sputtering.