Nanotube coatings for implantable electrodes

• US 7,162,308 B2
• Filed: 11/21/2003
• Issued: 01/09/2007
• Est. Priority Date: 11/26/2002
• Status: Active Grant

• Current Assignee: Greatbatch Limited (Greatbatch Incorporated)
• Original Assignee: Wilson Greatbatch Technologies, Inc.
• Inventors: O'Brien, Robert C., Frysz, Christine
• Primary Examiner(s): MANUEL, GEORGE C
• Application Number:
  US10/719,632
• Publication Number:
  US 20050075708A1
• Time in Patent Office: 1,145 Days
• Field of Search: 607/116, 607/121, 607/122, 977/DIG.1
• US Class Current: 607/116
• CPC Class Codes: A61N 1/05 for implantation or insertion into the body, e.g. heart electrode A61N1/06 takes precedence
• CPC Class Codes: A61N 1/0551 Spinal or peripheral nerve electrodes
• CPC Class Codes: A61N 1/056 Transvascular endocardial electrode systems
• CPC Class Codes: A61N 1/36017 with leads or electrodes penetrating the skin
• CPC Class Codes: A61N 1/3605 Implantable neurostimulators for stimulating central or peripheral nerve system
• CPC Class Codes: B21C 37/00 Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites

Abstract

Coatings for implantable electrodes consisting of single- or multi-walled nanotubes, nanotube ropes, carbon whiskers, and a combination of these are described. The nanotubes can be carbon or other conductive nanotube-forming materials such as a carbon-doped boron nitride. The nanotube coatings are grown “in situ” on a catalytic substrate surface from thermal decomposition, or they are bonded to the substrate using a metal or conductive metal oxide thin film binder deposited by means of a metal compound precursor in liquid form. In the latter case, the precursor/nanotube coating is then converted to a pure metal or conductive metal oxide, resulting in the desired surface coating with imbedded nanotubes.

Claims

1. An implantable electrode intended to be imbedded in body tissue, which comprises:

a) a substrate;

b) a biocompatible and electrically conductive catalyzing coating supported on the substrate; and

c) a multiplicity of carbon-containing nanotubes, each comprising a sidewall having a length extending to first and second ends, wherein at least one of the first and second ends is covalently bonded to the coating, the surface portions of the nanotubes that are not covalently bonded exhibiting relatively low polarization with respect to the portions of the nanotubes that are covalently bonded to the coating, wherein with the electrode imbedded in body tissue, electrical energy is transferable through the substrate, the catalyzing coating and then from exposed portions not covalently bonded to the coating of the multiplicity of nanotubes to the body tissue in a low energy loss manner suitable for an implantable electrode.

2. The electrode of claim 1 wherein the substrate is selected from the group consisting of tantalum, titanium, zirconium, iridium, platinum, and niobium.

3. The electrode of claim 1 wherein the substrate is different than the catalyzing coating and the catalyzing coating is selected from the group consisting of tantalum, titanium, zirconium, iridium, platinum, niobium, carbon, and nitrogen-doped carbon.

4. The electrode of claim 3 wherein the nitrogen in the nitrogen-doped carbon is provided at a concentration of about 1 to about 57 atomic percent.

5. The electrode of claim 1 wherein the coating is selected from the group consisting of a nitride, a carbide, a carbonitride, and an oxide of the group of tantalum, titanium, zirconium, iridium, platinum, and niobium.

6. The electrode of claim 1 wherein the nanotubes are in a form selected from the group consisting of single-wall nanotubes, multiwall nanotubes, nanotube ropes, carbon whiskers, and combinations thereof.

7. The electrode of claim 1 wherein the nanotubes are of carbon-doped boron nitride.

8. The electrode of claim 1 wherein the nanotubes are characterized as having been grown from a reaction gas selected from the group consisting of acetylene, methyl acetylene-propadiene, and a gas of the paraffin series.

9. The electrode of claim 8 wherein the reaction gas is characterized as having an ammonium addition.

10. The electrode of claim 1 comprising the nanotubes adhering to tantalum coated on a titanium substrate.

11. A method for providing an implantable electrode, comprising the steps of:

a) providing a substrate;

b) coating a catalytic material selected from the group consisting of carbon, nitrogen-doped carbon, tantalum, titanium, zirconium, iridium, platinum, and niobium or a nitride, a carbide, a carbonitride, and an oxide thereof on the substrate;

c) heating the coated substrate;

d) contacting the heated substrate with a flowing hydrogen-containing gas stream to thereby provide a multiplicity of carbon-containing nanotubes covalently bonded to the coated substrate, the nanotubes comprising a sidewall having a length extending to first and second ends, wherein at least one of the first and second ends is covalently bonded to the coating, the surface portions of the nanotubes that are not covalently bonded exhibiting relatively low polarization with respect to the portions of the nanotubes that are covalently bonded to the coating; and

e) wherein with the electrode imbedded in body tissue in a functional manner, electrical energy is transferable through the substrate, the catalyzing coating and then from exposed portions not covalently bonded to the coating of the multiplicity of nanotubes to the body tissue in a low energy loss manner suitable for an implantable electrode.

12. The method of claim 11 including heating the coated substrate to a temperature of about 350°

C. to about 1,150°

C.

13. The method of claim 11 including cooling the nanotube coated substrate in hydrogen prior to use.

14. A method of providing an implantable electrode, comprising the steps of:

a) providing a substrate;

b) providing nanotubes mixed with a binder precursor selected from chloroiridic acid, chloroplatinic acid, titanium (IV) chloride, zirconium (IV) chloride, niobium (V) chloride, and tantalum (V) chloride in a solvent;

c) contacting the binder precursor to the substrate;

d) converting the binder precursor to a coating on the substrate having a multiplicity of nanotubes covalently bonded thereto, the nanotubes comprising a sidewall having a length extending to first and second ends, wherein at least one of the first and second ends is covalently bonded to the coating, the surface portions of the nanotubes that are not covalently bonded exhibiting relatively low polarization with respect to the portions of the nanotubes that are covalently bonded to the coating; and

d) wherein with the electrode imbedded in body tissue in a functional manner, electrical energy is transferable through the substrate, the catalyzing coating and then from exposed portions not covalently bonded to the coating of the multiplicity of nanotubes to the body tissue in a low energy loss manner suitable for an implantable electrode.

15. The method of claim 14 including heating the binder precursor coated substrate in either an oxidizing or an inert atmosphere.

16. The method of claim 14 including heating the binder precursor coated substrate at a temperature of about 300°

C. to about 500°

C.

17. The method of claim 14 including heating the binder precursor coated substrate for a time ranging from about 30 minutes to about 3 hours.

18. The method of claim 14 including heating the chloroiridic acid binder precursor in an oxidizing atmosphere to provide the nanotubes adhered to an iridium oxide binder coated on the substrate.

19. The method of claim 14 including heating the chloroplatinic acid, titanium (IV) chloride, zirconium (IV) chloride, niobium (V) chloride, and tantalum (V) chloride binder precursors in an inert atmosphere to provide the nanotubes adhered to a binder of platinum, titanium, zirconium, niobium, and tantalum, respectively, coated on the substrate.

20. A method for providing an implantable electrode, comprising the steps of:

a) providing a substrate;

b) coating a carbonaceous catalytic material on the substrate;

c) heating the carbonaceous coated substrate;

d) contacting the heated substrate with a flowing hydrogen-containing gas stream to thereby provide a multiplicity of carbon-containing nanotubes covalently bonded to the carbonaceous coated substrate, the nanotubes comprising a sidewall having a length extending to first and second ends, wherein at least one of the first and second ends is covalently bonded to the coating, the surface portions of the nanotubes that are not covalently bonded exhibiting relatively low polarization with respect to the portions of the nanotubes that are covalently bonded to the coating; and

e) wherein with the electrode imbedded in body tissue in a functional manner, electrical energy is transferable transfers through the substrate, the catalyzing coating and then from exposed portions not covalently bonded to the coating of the multiplicity of nanotubes to the body tissue in a low energy loss manner suitable for an implantable electrode.

21. The method of claim 20 including heating the carbonaceous coated substrate to a temperature of about 350°

C. to about 1,150°

C.

22. The method of claim 20 including sputtering the carbonaceous catalytic material on the substrate.

23. The method of claim 20 including providing the sputtered carbonaceous catalytic material as nitrogen-doped carbon.

24. The method of claim 20 including providing the nitrogen in the nitrogen-doped carbon at a concentration of about 1 to about 57 atomic percent.

25. A method for providing an implantable electrode, comprising the steps of:

a) providing a substrate;

b) coating a catalytic material selected from the group consisting of carbon, nitrogen-doped carbon, tantalum, titanium, zirconium, iridium, platinum, and niobium or a nitride, a carbide, a carbonitride, and an oxide thereof on the substrate;

c) subjecting the coated substrate to a plasma assisted chemical vapor deposition process containing a flowing hydrocarbon-containing gas stream to thereby provide a multiplicity of carbon-containing nanotubes covalently bonded to the coated substrate, the nanotubes comprising a sidewall having a length extending to first and second ends, wherein at least one of the first and second ends is covalently bonded to the coating, the surface portions of the nanotubes that are not covalently bonded exhibiting relatively low polarization with respect to the portions of the nanotubes that are covalently bonded to the coating; and

d) wherein with the electrode imbedded in body tissue in a functional manner, electrical energy is transferable through the substrate, the catalyzing coating and then from exposed portions not covalently bonded to the coating of the multiplicity of nanotubes to the body tissue in a low energy loss manner suitable for an implantable electrode.

26. The method of claim 25 including utilizing microwave excitation in the plasma assisted chemical vapor deposition process.