Method for depositing a hard protective coating

• US 5,846,613 A
• Filed: 08/11/1997
• Issued: 12/08/1998
• Est. Priority Date: 11/07/1994
• Status: Expired due to Fees

• Current Assignee: Plasma Innovations GmbH
• Original Assignee: Stephane Neuville
• Inventors: Neuville, Stephane
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): MEEKS, TIMOTHY HOWARD
• Application Number:
  US08/836,630
• Time in Patent Office: 484 Days
• Field of Search: 427/575, 427/576, 427/577, 427/249, 427/255.2, 204/192.12, 204/192.16
• US Class Current: 427/575
• CPC Class Codes: C23C 14/0036 Reactive sputtering
• CPC Class Codes: C23C 14/0605 Carbon
• CPC Class Codes: C23C 14/0641 Nitrides C23C14/0617 takes precedence
• CPC Class Codes: C23C 14/0658 Carbon nitride
• CPC Class Codes: C23C 16/26 Deposition of carbon only
• CPC Class Codes: C23C 16/347 Carbon nitride
• CPC Class Codes: C23C 16/50 using electric discharges generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34

Abstract

A method for depositing a hard protective coating on at least one part, wherein 10-70% of nitrogen combined with 10-70% of a mixture of helium and argon or 10-70% of neon for strongly exciting and dissociating the nitrogen and hydrogen, is added to a precursor gas, and the energy delivered to each atom of the precursor gas is selected so as to achieve so-called "Lifschitz" conditions which define the energy range in which a maximum number of diamond-like tetrahedral structures are produced instead of graphite structures.

Claims

1. Method of depositing on at least one part a protective coating which is substantially hydrogen-free, has a predominately tetrahedral structure and is based on carbon and nitrogen, on titanium, nitrogen, and carbon, or on boron and nitrogen, using plasma enhanced chemical vapor deposition by introducing a precursor gas containing elements to be deposited into a vacuum chamber containing a metal support connected to a power generator producing direct or alternating current and operating in the radio-frequency or microwave range and on which the part to be coated is placed, and maintaining an electrical discharge inside the chamber so as to increase the temperature of the part to a value of between 150°

and 400°

C., and at power and pressure conditions at which the precursor gas is excited physically and chemically and ionized in the form of plasma so as to cause said protective coating to be deposited on the part by ion bombardment, characterized in that the precursor gas contains nitrogen, a gas providing dissociated hydrogen within the plasma and boron or one of its compounds;

in that added to the precursor gas is between 10 and 70% of a mixture of helium and argon or between 10 and 70% neon of which the role is to excite and dissociate the nitrogen and hydrogen simultaneously; and

in that the energy supplied to each atom of the precursor gas is selected so that the coating possesses a maximum number of tetrahedral structures at the expense of hexagonal structures.

2. Method of depositing a protective coating according to claim 1, characterized in that the precursor gas contains between 10 and 70% nitrogen and one or a plurality of hydrocarbons acting as hydrogen-providing gas;

and in that energy of between 100 and 150 eV is supplied to each carbon atom of said precursor gas.

3. Method of depositing a protective coating according to claim 1, characterized in that the precursor gas contains titanium, between 10 and 70% of hydrogen, and one or a plurality of hydrocarbons.

4. Method according to claim 1, characterized in that added to the precursor gas is between 0.5 and 5% boron acting as a catalyst to separate CH bonds so as to enable the hydrogen to be eliminated by recombining with atomic hydrogen and atomic nitrogen and to facilitate formation of CN bonds.

5. Method of depositing a protective coating according to claim 1, characterized in that the precursor gas contains between 10 and 70% hydrogen and said boron compound is selected from the group consisting of diborane, boron chloride, and trimethylboron.

6. Method according to claim 1, characterized in that the power and pressure conditions prevailing in the vacuum chamber are selected to produce a plasma with a non-collisional sheath.

7. Method according to claim 1, characterized in that said power generator operates in the microwave range.

8. Method according to claim 1, characterized in that pulsation is superimposed on the current supplied by the generator such that the plasma is activated only for a cyclic fraction of the treatment time.

9. Method of depositing on at least one part a protective coating which is substantially hydrogen-free, has a predominately tetrahedral structure and is based on carbon and nitrogen, on titanium, nitrogen and carbon or on boron and nitrogen, using physical vapor deposition which may or may not be enhanced by a magnetic field, by introducing a sputtering gas containing elements to be deposited into a vacuum chamber containing a metal support connected to a power generator producing direct or alternating current and operating in the radio-frequency or microwave range and on which is placed the part to be coated, creating an electrical discharge so as to physically and chemically excite the sputtering gas and ionize it in the form of plasma, providing a target which is made from a material containing elements to be deposited in the vacuum chamber and supplying said target with direct or radio-frequency current so as to cause said protective coating to be deposited on the part, characterized in that the sputtering gas contains nitrogen, a gas providing dissociated hydrogen within the plasma and boron or one of its compounds when boron is not present in the material constituting the target;

in that added to the sputtering gas is between 10 and 70% of a mixture of helium and argon or between 10 and 70% neon of which the role is to excite and dissociate the nitrogen and hydrogen simultaneously; and

in that the current supplying the support bearing the part is selected so as to give rise to radio-frequency polarization of the support, so that the coating possesses a maximum number of tetrahedral structures at the expense of hexagonal structures.

10. Method of depositing a protective coating according to claim 9, characterized in that a graphite target is sputtered;

and in that the gas for sputtering said target contains between 5 and 40% nitrogen and between 5 and 40% hydrogen.

11. Method according to claim 10, characterized in that added to the sputtering gas is between 0.5 and 5% boron acting as a catalyst to separate CH bonds so as to enable hydrogen to be eliminated by recombination with atomic hydrogen and atomic nitrogen and to facilitate the formation of CN bonds.

12. Method of depositing a protective coating according to claim 9, characterized in that a titanium or titanium nitride target is sputtered;

and in that the gas for sputtering said target contains between 10 and 70% of hydrogen, and one or a plurality of hydrocarbons.

13. Method of depositing a protective coating according to claim 9, characterized in that a solid boron nitride target is sputtered;

and in that the gas for sputtering said target contains between 5 and 40% nitrogen and between 5 and 40% hydrogen.