Fuel cell planarly integrated on a monocrystalline silicon chip and process of fabrication

• US 7,892,693 B2
• Filed: 12/15/2006
• Issued: 02/22/2011
• Est. Priority Date: 12/16/2005
• Status: Active Grant

• Current Assignee: STMicroelectronics SRL (STMicroelectronics NV)
• Original Assignee: STMicroelectronics SRL (STMicroelectronics NV)
• Inventors: La Magna, Luigi, Leonardi, Salvatore, Siciliano, Simone Angelo
• Primary Examiner(s): Ridley; Basia
• Assistant Examiner(s): Buchanan; Jacob
• Application Number:
  US11/611,521
• Publication Number:
  US 20070148527A1
• Time in Patent Office: 1,530 Days
• Field of Search: 429/400, 429479-497, 429507-508, 429523-526, 429532-535, 502/101
• US Class Current: 429/479
• CPC Class Codes: H01M 2008/1095 Fuel cells with polymeric electrolytes
• CPC Class Codes: H01M 8/0271 Sealing or supporting means around electrodes, matrices or membranes
• CPC Class Codes: H01M 8/04089 of gaseous reactants
• CPC Class Codes: H01M 8/1097 Fuel cells applied on a support, e.g. miniature fuel cells deposited on silica supports
• CPC Class Codes: H01M 8/241 with solid or matrix-supported electrolytes
• CPC Class Codes: H01M 8/2425 High-temperature cells with solid electrolytes
• CPC Class Codes: Y02E 60/50 Fuel cells

Abstract

A fuel cell is entirely fabricated on a single monocrystalline silicon substrate, and substantially overcomes leak proofing and wafer bonding difficulties and criticalities while ensuring an intrinsic sturdiness of the planarly integrated functional structure of the fuel cell. The integrated fuel cell is formed in an oxidized porous silicon region on a monocrystalline silicon substrate that is pervious to fluid flow and is electrically nonconductive with the monocrystalline silicon substrate.

Claims

1. A planarly integrated fuel cell comprising:

a monocrystalline silicon chip including an oxidized porous silicon region preliminarily rendered porous and permeable to fluids and is electrically non-conductive;

at least one pair of parallel channels comprising an anode feed channel and a cathode feed channel extending in the oxidized porous silicon region, said at least one pair of parallel channels defining a central oxidized porous silicon ridge therebetween;

a dielectric cap over said at least one pair of parallel channels and having inlet and outlet holes formed therethrough in correspondence to opposite ends of said at least one pair of parallel channels for separately circulating a fluid fuel in the anode feed channel and air or other oxygen containing mixture in the cathode feed channel;

a pair of parallel metal electrodes extending over said central oxidized porous silicon ridge and extending a length of said at least one pair of parallel channels;

cathodically deposited uninterrupted electrically conductive threads of a catalytic metal, stemming from a bottom surface of each of said metal electrodes and extending to a side face of said central oxidized porous silicon ridge defining a side wall of a respective channel extending alongside of the electrode;

ion permeable resin filling the pores in an innermost central portion of said central oxidized porous silicon ridge to impede fluid flow from one channel to the other, and partly filling the pores in proximity of the sides of said central oxidized porous silicon ridge defining the side walls of the respective channels, and forming uninterrupted ion permeable resin domains extending from the catalytic metal threads stemming from one metal electrode to the catalytic metal threads stemming from the other metal electrode; and

a connector for electrically connecting said pair of parallel metal electrodes to an external load circuit of the integrated fuel cell.

2. The planarly integrated fuel cell according to claim 1, wherein said dielectric cap is a separately fabricated element with respect to said monocrystalline silicon chip.

3. The planarly integrated fuel cell according to claim 1, wherein said dielectric cap comprises a first multilayered dielectric stack and an electrically isolated polysilicon layer forming a hard mask having a plurality of holes for forming by wet etch said at least one pair of parallel channels, and a top dielectric layer plugging the plurality of holes through the underlying polysilicon layer and a dielectric stack of a hard mask, except in correspondence to the inlet and outlet holes.

4. The planarly integrated fuel cell according to claim 1, wherein said central oxidized porous silicon ridge has an innermost central portion, underneath a separation gap between said parallel metal electrodes having pores of smaller average size than pores at and near the side faces thereof defining side walls of the respective channels.

5. The planarly integrated fuel cell according to claim 1, wherein said ion permeable resin comprises a cation exchange resin that fills the pores in said central oxidized porous silicon ridge when in a liquid form, and is then cured after evaporating the solvent.

6. An integrated fuel cell comprising:

a monocrystalline silicon chip comprising an oxidized porous silicon region;

a pair of parallel channels in said oxidized porous silicon region and comprising an anode feed channel and a cathode feed channel, said pair of parallel channels defining a central oxidized porous silicon ridge therebetween;

a dielectric cap over said pair of parallel channels and having inlet and outlet holes formed therethrough in correspondence to opposite ends of said pair of parallel channels for separately circulating a fluid fuel in the anode feed channel and an oxygen containing mixture in the cathode feed channel;

a pair of parallel electrodes extending over said central oxidized porous silicon ridge and extending a length of said pair of parallel channels;

electrically conductive threads stemming from a bottom surface of each of said electrodes and extending to a side face of said central oxidized porous silicon ridge defining a side wall of a respective channel extending alongside the electrode;

ion permeable resin filling the pores in an innermost central portion of said central oxidized porous silicon ridge to impede fluid flow from one channel to the other, and partly filling the pores in proximity of the sides of said central oxidized porous silicon ridge defining the side walls of the respective channels, and forming uninterrupted ion permeable resin domains extending from the electrically conductive threads stemming from one electrode to the electrically conductive threads stemming from the other electrode; and

a connector for electrically connecting said pair of parallel electrodes to an external load circuit.

7. The integrated fuel cell according to claim 6, wherein the electrically conductive threads comprise at least one of platinum, iridium, ruthenium, palladium, rhodium and alloys thereof.

8. The integrated fuel cell according to claim 6, wherein said dielectric cap is a separately fabricated element with respect to said monocrystalline silicon chip.

9. The integrated fuel cell according to claim 6, wherein said dielectric cap comprises a first multilayered dielectric stack and an electrically isolated polysilicon layer forming a hard mask having a plurality of holes for forming said pair of parallel channels, and a top dielectric layer plugging the plurality of holes through the underlying polysilicon layer and a dielectric stack of a hard mask, except in correspondence to the inlet and outlet holes.

10. The integrated fuel cell according to claim 6, wherein said central oxidized porous silicon ridge has an innermost central portion, underneath a separation gap between said pair of parallel electrodes, and has pores of smaller average size than pores at and near the side faces thereof.

11. The integrated fuel cell according to claim 6, wherein said ion permeable resin is initially in a liquid form for filling the pores in the innermost central portion of said central oxidized porous silicon ridge, and is then cured after evaporating the solvent.

12. A process for fabricating a planarly integrated fuel cell comprising:

forming an oxidized porous silicon region in a monocrystalline silicon chip, the oxidized porous silicon region being preliminarily rendered porous and permeable to fluids and being electrically non-conductive;

forming at least one pair of parallel channels comprising an anode feed channel and a cathode feed channel extending in the oxidized porous silicon region, the at least one pair of parallel channels defining a central oxidized porous silicon ridge therebetween;

forming a dielectric cap over the at least one pair of parallel channels and having inlet and outlet holes formed therethrough in correspondence to opposite ends of the at least one pair of parallel channels for separately circulating a fluid fuel in the anode feed channel and air or other oxygen containing mixture in the cathode feed channel;

forming a pair of parallel metal electrodes extending over the central oxidized porous silicon ridge and extending a length of the at least one pair of parallel channels;

cathodically depositing uninterrupted electrically conductive threads of a catalytic metal, stemming from a bottom surface of each of the metal electrodes and extending to a side face of the central oxidized porous silicon ridge defining a side wall of a respective channel extending alongside of the electrode;

filling the pores with ion permeable resin in an innermost central portion of the central oxidized porous silicon ridge to impede fluid flow from one channel to the other, and partly filling the pores in proximity of the sides of the central oxidized porous silicon ridge defining the side walls of the respective channels, and forming uninterrupted ion permeable resin domains extending from the catalytic metal threads stemming from one metal electrode to the catalytic metal threads stemming from the other metal electrode; and

forming a connector for electrically connecting the pair of parallel metal electrodes to an external load circuit of the integrated fuel cell.

13. The process according to claim 12, wherein forming the oxidized porous silicon region in the monocrystalline silicon chip comprises processing a wafer of monocrystalline silicon by electrochemically eroding the crystalline silicon in an aqueous hydrofluoric acid solution forming an elongated region of porous silicon residue;

and oxidizing the elongated region of porous silicon residue rendering it electrically non-conductive.

14. The process according to claim 13, wherein forming the at least one pair of parallel channels comprises:

forming a multilayered dielectric stack for a hard mask over a surface of the monocrystalline silicon; and

forming by a masked anisotropic dry etch of the dielectric hard mask stack the two parallel trenches reaching down to the oxidized porous silicon region.

15. The process according to claim 14, wherein forming the pair of parallel metal electrodes comprises:

forming over a surface of the wafer, after removing the dielectric hard mask, an electrically conductive metallic multilayered stack including a topping flash sputtered metal seed layer; and

growing, by galvanically depositing gold through defined parallel openings of a mask, parallel conductive metal electrodes over the metal seed layer on the oxidized porous silicon region and on adjacent definition edges of the dielectric stack of the hard mask, for forming connectable anode and cathode electrodes of the integrated cell.

16. The process according to claim 15, further comprising:

removing the mask and the metallic multilayered stack from the surface of the wafer;

depositing at least one planarizing layer of a dielectric material; and

after having formed by etching of the oxidized porous silicon region, the parallel spaced channels defining a central ridge portion there between, on a top of which the pair of parallel metal electrodes were formed.

17. The process according to claim 12, wherein the cathodically depositing uninterrupted electrically conductive threads of a catalytic metal comprise:

electroplating the catalytic metal from a solution containing ions of the metal to form electrically conductive uninterrupted threads of catalytic metal stemming from the bottom metallic surface of a cathodically polarized one of the two metal electrodes; and

growing the threads through the open pores of the oxidized porous silicon of the central ridge portion without filling completely the voids, as far as reaching the side surface of definition of the central ridge portion of oxidized porous silicon, while anodically polarizing a counterelectrode immersed in the solution and biasing the other solid metal electrode of the cell to a positive voltage insufficiently lower than the voltage of the counterelectrode to prevent deposition thereon or toward it, and repeating the process step by inverting the metal electrodes, forming respective distinct dispersed active electrode structures of the fuel cell.

18. The process according to claim 12, wherein the dielectric cap is a separately fabricated element with respect to the monocrystalline silicon chip.

19. The process according to claim 12, wherein the dielectric cap comprises a first multilayered dielectric stack and an electrically isolated polysilicon layer forming a hard mask having a plurality of holes for forming by wet etch the at least one pair of parallel channels, and a top dielectric layer plugging the plurality of holes through the underlying polysilicon layer and a dielectric stack of a hard mask, except in correspondence to the inlet and outlet holes.

20. The process according to claim 12, wherein the central oxidized porous silicon ridge has an innermost central portion, underneath a separation gap between the parallel metal electrodes having pores of smaller average size than pores at and near the side faces thereof defining side walls of the respective channels.

21. The process according to claim 12, wherein the ion permeable resin comprises a cation exchange resin that fills the pores in the central oxidized porous silicon ridge when in a liquid form, and is then cured after evaporating the solvent.