JP2006037230A5 - - Google Patents

Description

Method and apparatus for producing metal nitride film

  The present invention relates to a method and an apparatus for producing a metal nitride thin film. The metal nitride thin film is a surface of a chemical container that requires surface hardening treatment such as a barrier metal film or a tool, decoration of various parts, and corrosion resistance. Used as a treatment film.

  In recent years, metal oxide and metal nitride thin films have been used in various fields. A metal oxide thin film is used for a semiconductor or the like by paying attention to its high relative dielectric constant, for example. On the other hand, metal nitride thin films are used as barrier metal films for the purpose of preventing copper diffusion in copper interconnects such as LSIs, and are used for surface treatment of tools and the like by utilizing their high hardness. In order to impart sufficient characteristics to these thin films, it is necessary to form films with high crystallinity and a stable composition.

JP 2001-284285 A International Publication No. 01/073159 Pamphlet

  However, conventionally used film formation methods are mainly physical vapor deposition methods such as sputtering, and the film formation by sputtering destroys the crystallinity and composition of the thin film during film formation, thereby obtaining desired film characteristics. I couldn't.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method and an apparatus for producing a metal nitride film having high crystallinity and a stable composition.

The metal nitride film manufacturing method according to the first invention for solving the above object is as follows:
The halogen gas supplied into the chamber in which the substrate is accommodated is turned into plasma to generate halogen gas plasma,
A member to be etched formed of a metal capable of generating a high vapor pressure halide is etched with the halogen gas plasma to form a precursor of a metal component and a halogen gas,
When the metal component of the precursor is formed on the substrate by making the temperature of the substrate lower than the temperature of the member to be etched,
Further, the nitrogen gas supplied into the chamber is turned into plasma to generate nitrogen gas plasma, and a metal nitride film is formed on the substrate.

A metal nitride film manufacturing method according to a second invention for solving the above object is as follows:
The halogen gas supplied into the chamber in which the substrate is accommodated is turned into plasma to generate halogen gas plasma,
A member to be etched formed of a metal capable of generating a high vapor pressure halide is etched with the halogen gas plasma to form a precursor of a metal component and a halogen gas,
When the metal component of the precursor is formed on the substrate by making the temperature of the substrate lower than the temperature of the member to be etched,
Further, nitrogen gas is supplied into the chamber, and a metal nitride film is formed on the substrate.

A metal nitride film manufacturing method according to a third invention for solving the above object is the metal nitride film manufacturing method according to the first invention.
The nitrogen gas plasma forms metal nitride on the substrate by performing at least one of the following processes A, B, and C.
Step A: Step of nitriding a metal component already formed on the substrate.
Step B: A step of nitriding the precursor of the metal component and the halogen gas to form a precursor of the metal component and the nitrogen gas.
Step C: A step of forming a precursor of a metal component and nitrogen gas by etching the member to be etched.

A metal nitride film manufacturing method according to a fourth invention for solving the above object is the metal nitride film manufacturing method according to the second invention.
The nitrogen gas forms at least one of the following processes A and B to form a metal nitride film on the substrate.
Step A: Step of nitriding a metal component already formed on the substrate.
Step B: A step of nitriding the precursor of the metal component and the halogen gas to form a precursor of the metal component and the nitrogen gas.

A metal nitride film manufacturing method according to a fifth invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to fourth inventions.
The halogen gas and nitrogen gas are respectively supplied into the chamber from independent supply means.

A metal nitride film manufacturing method according to a sixth invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to fourth inventions.
The halogen gas and nitrogen gas are supplied into the chamber from the same one supply means.

A metal nitride film manufacturing method according to a seventh invention for solving the above object is the metal nitride film manufacturing method according to the fifth or sixth invention,
Nitrogen gas is supplied after the halogen gas is supplied.

A metal nitride film manufacturing method according to an eighth invention for solving the above object is the metal nitride film manufacturing method according to the fifth or sixth invention,
It is characterized in that the sequence of supplying nitrogen gas is alternately repeated after supplying halogen gas.

A metal nitride film manufacturing method according to a ninth invention for solving the above object is the metal nitride film manufacturing method according to the fifth or sixth invention, wherein
A halogen gas and a nitrogen gas are supplied simultaneously.

A metal nitride film manufacturing method according to a tenth aspect of the present invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to ninth aspects of the invention,
At least one of the halogen gas plasma and the nitrogen gas plasma is inductively coupled plasma.

A metal nitride film manufacturing method according to an eleventh invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to ninth inventions.
At least one of the halogen gas plasma and the nitrogen gas plasma is a capacitively coupled plasma.

A metal nitride film manufacturing method according to a twelfth aspect of the present invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to ninth aspects of
At least one of the halogen gas plasma and the nitrogen gas plasma is a hybrid plasma composed of inductively coupled plasma and capacitively coupled plasma.

A metal nitride film manufacturing method according to a thirteenth invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to twelfth inventions.
At least one of the halogen gas plasma and the nitrogen gas plasma is plasma that has been converted into plasma outside the chamber and supplied into the chamber in advance.

A metal nitride film manufacturing method according to a fourteenth aspect of the present invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to thirteenth aspects of the present invention.
The metal is at least one metal selected from the group consisting of tantalum, tungsten, titanium, and silicon.

A metal nitride film manufacturing method according to a fifteenth aspect of the invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to fourteenth aspects of the invention.
The halogen is chlorine.

A metal nitride film manufacturing apparatus according to a sixteenth aspect of the invention for solving the above object is as follows.
A chamber containing a substrate;
A metal member to be etched provided at a position facing the substrate in the chamber;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Plasma generation that generates nitrogen gas plasma by generating plasma inside the chamber and etching the member to be etched with the nitrogen gas plasma to generate a precursor of a metal component and nitrogen gas contained in the member to be etched. Means,
Temperature control means for forming the precursor, which is a metal nitride, on the substrate by making the temperature of the substrate lower than the temperature of the member to be etched.

A metal nitride film manufacturing apparatus according to a seventeenth invention for solving the above-described object is
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Plasma generating means for generating halogen gas plasma and nitrogen gas plasma by plasmaizing the inside of the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

An apparatus for producing a metal nitride film according to an eighteenth aspect of the invention for solving the above object is as follows:
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Plasma generating means for generating halogen gas plasma by converting the inside of the chamber into plasma;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a nineteenth invention for solving the above-described object is
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
The inside of the chamber is turned into plasma to generate halogen gas plasma and nitrogen gas plasma, and the member to be etched is etched with the halogen gas plasma, whereby a first component of the metal component and halogen gas contained in the member to be etched is obtained. A precursor is generated, and a second precursor of a metal component and nitrogen gas contained in the member to be etched is generated by etching the member to be etched with the nitrogen gas plasma, and the metal halide is the metal halide. Plasma generating means for changing the first precursor to the second precursor which is a metal nitride by the nitrogen gas plasma;
By making the temperature of the substrate lower than the temperature of the member to be etched, the metal component of the first precursor and the second precursor are formed on the substrate, and the formed metal component And a temperature control means for changing the metal nitride into a metal nitride by the nitrogen gas plasma,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a twentieth invention for solving the above-mentioned object is
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
The inside of the chamber is turned into plasma to generate halogen gas plasma, and the member to be etched is etched with the halogen gas plasma to generate a precursor of a metal component and a halogen gas contained in the member to be etched. Plasma generating means for nitriding the precursor which is a metal phosphide with the nitrogen gas to convert it into a metal nitride;
By making the temperature of the substrate lower than the temperature of the member to be etched, the metal component of the precursor and the metal nitride are formed on the substrate, and the formed metal component is formed by the nitrogen gas. Temperature control means for changing to metal nitride,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a twenty-first invention for solving the above object is any one of the metal nitride film manufacturing apparatuses according to the seventeenth to twentieth inventions.
The halogen gas supply means and the nitrogen gas supply means are independent supply means.

A metal nitride film manufacturing apparatus according to a twenty-second invention for solving the above object is any one of the metal nitride film manufacturing apparatuses according to the seventeenth to twentieth inventions.
The halogen gas supply unit and the nitrogen gas supply unit are integrated to supply the halogen gas and the nitrogen gas from one supply unit.

A metal nitride film manufacturing apparatus according to a twenty-third invention for solving the above object is the metal nitride film manufacturing apparatus according to the twenty-first or twenty-second invention.
The apparatus further comprises gas supply control means for supplying nitrogen gas by the nitrogen gas supply means for a second predetermined time after the halogen gas is supplied by the halogen gas supply means for a first predetermined time.

A metal nitride film manufacturing apparatus according to a twenty-fourth invention for solving the above object is the metal nitride film manufacturing apparatus according to the twenty-first or twenty-second invention.
The apparatus further comprises gas supply control means for alternately repeating the order of supplying nitrogen gas for a second predetermined time by the nitrogen gas supply means after the halogen gas is supplied by the halogen gas supply means for a first predetermined time. .

A metal nitride film manufacturing apparatus according to a twenty-fifth invention for solving the above object is the metal nitride film manufacturing apparatus according to the twenty-first or twenty-second invention,
Further, the present invention is characterized in that gas supply control means for simultaneously supplying the halogen gas and the nitrogen gas is provided.

A metal nitride film manufacturing apparatus according to a twenty-sixth aspect of the present invention for solving the above-described object is
A chamber containing a substrate;
A metal member to be etched provided at a position facing the substrate in the chamber;
Plasma generating means provided outside the chamber, generating nitrogen gas plasma by converting nitrogen gas into plasma, and supplying the nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a twenty-seventh aspect of the invention for solving the above-described object is
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
First plasma generating means for generating halogen gas plasma by converting the inside of the chamber into plasma;
A second plasma generating means provided outside the chamber for generating nitrogen gas plasma by converting nitrogen gas into plasma, and supplying the nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a twenty-eighth aspect of the present invention for solving the above object is
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
First plasma generating means for generating nitrogen gas plasma by converting the inside of the chamber into plasma;
A second plasma generating means provided outside the chamber and generating halogen gas plasma by converting the halogen gas into plasma, and supplying the halogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a twenty-ninth aspect of the invention for solving the above-described object is
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Plasma generating means provided outside the chamber and generating halogen gas plasma and nitrogen gas plasma by converting the halogen gas and nitrogen gas into plasma, and supplying the halogen gas plasma and nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a thirtieth invention for solving the above object is as follows:
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
A first plasma generating means provided outside the chamber for generating halogen gas plasma by converting the halogen gas into plasma, and supplying the halogen gas plasma into the chamber;
A second plasma generating means provided outside the chamber for generating nitrogen gas plasma by converting nitrogen gas into plasma, and supplying the nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a thirty-first invention for solving the above object is as follows:
A chamber containing a substrate;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Plasma generating means provided outside the chamber, generating halogen gas plasma by converting the halogen gas into plasma, and supplying the halogen gas plasma into the chamber;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
A metal nitride film is formed on the substrate.

A metal nitride film manufacturing apparatus according to a thirty-second invention for solving the above object is any one of the sixteenth to twenty-fifth, twenty-eighth, and thirty-first invention metal nitride film manufacturing apparatuses.
The nitrogen gas supply means includes a gas flow path of a ring-shaped pipe disposed around the substrate and a nozzle provided in the gas flow path for injecting nitrogen gas toward the substrate.

A metal nitride film manufacturing apparatus according to a thirty-third invention for solving the above object is any one of the metal nitride film manufacturing apparatuses according to the sixteenth, seventeenth and nineteenth inventions.
The nitrogen gas supply means includes a gas flow path of a ring-shaped pipe made of a conductor disposed around the substrate, and a nozzle that is provided in the gas flow path and injects the nitrogen gas toward the substrate. In addition, a capacitively coupled nitrogen gas plasma is generated between the substrate and the substrate by feeding.

A metal nitride film manufacturing apparatus according to a thirty-fourth invention for solving the above object is any one of the metal nitride film manufacturing apparatuses according to the sixteenth, seventeenth, or nineteenth invention.
The nitrogen gas supply means includes a gas flow path of a ring-shaped pipe made of a conductor disposed around the substrate, and a nozzle that is provided in the gas flow path and injects the nitrogen gas toward the substrate. In addition, at least one place in the circumferential direction of the ring-shaped pipe is insulated, and inductively coupled nitrogen gas plasma is generated between the substrate and the substrate by feeding.

A metal nitride film manufacturing apparatus according to a thirty-fifth aspect of the present invention for solving the above object is any one of the metal nitride film manufacturing apparatuses according to the sixteenth to thirty-fourth aspects of the present invention.
The metal is at least one metal selected from the group consisting of tantalum, tungsten, titanium, and silicon.

A metal nitride film production apparatus according to a thirty-sixth aspect of the present invention for solving the above object is any one of the metal nitride film production apparatuses according to the seventeenth to thirty-fifth aspects of the invention.
The halogen is chlorine.

A metal nitride film manufacturing method according to a thirty-seventh aspect of the present invention for solving the above object is any one of the metal nitride film manufacturing methods according to the first to fifteenth inventions.
The metal is copper.

A metal nitride film manufacturing apparatus according to a thirty-eighth invention for solving the above object is any one of the metal nitride film manufacturing apparatuses according to the sixteenth to thirty-sixth inventions.
The metal is copper.

In the invention described in [Claim 1], the halogen gas supplied into the chamber in which the substrate is accommodated is turned into plasma to generate halogen gas plasma,
A member to be etched formed of a metal capable of generating a high vapor pressure halide is etched with the halogen gas plasma to form a precursor of a metal component and a halogen gas,
By making the temperature of the substrate lower than the temperature of the member to be etched, when the metal component of the precursor is formed on the substrate, the nitrogen gas supplied into the chamber is further converted into plasma to generate nitrogen gas plasma. Since the metal nitride film is formed on the substrate,
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied.

In the invention described in [Claim 2], the halogen gas supplied into the chamber in which the substrate is accommodated is turned into plasma to generate halogen gas plasma,
A member to be etched formed of a metal capable of generating a high vapor pressure halide is etched with the halogen gas plasma to form a precursor of a metal component and a halogen gas,
When the metal component of the precursor is formed on the substrate by making the temperature of the substrate lower than the temperature of the member to be etched,
Further, nitrogen gas was supplied into the chamber, and metal nitride was formed on the substrate.
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied. Furthermore, since the metal nitride film can be formed without turning nitrogen into plasma, the film formation cost can be reduced.

In the invention described in [Claim 3], in the invention described in [Claim 1],
Since the nitrogen gas plasma performs at least one of the following steps A, B, and C, a metal nitride film is formed on the substrate.
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied.
Step A: Step of nitriding a metal component already formed on the substrate.
Step B: A step of nitriding the precursor of the metal component and the halogen gas to form a precursor of the metal component and the nitrogen gas.
Step C: A step of forming a precursor of a metal component and nitrogen gas by etching the member to be etched.

In the invention described in [Claim 4], in the invention described in [Claim 2],
Since the nitrogen gas forms at least one of the following steps A and B to form a metal nitride film on the substrate,
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied. Furthermore, since the metal nitride film can be formed without turning nitrogen into plasma, the film formation cost can be reduced.
Step A: Step of nitriding a metal component already formed on the substrate.
Step B: A step of nitriding the precursor of the metal component and the halogen gas to form a precursor of the metal component and the nitrogen gas.

In the invention described in [Claim 5], in the invention described in any one of [Claim 1] to [Claim 4],
Since the halogen gas and nitrogen gas are supplied to the inside of the chamber from independent supply means,
The supply of each gas used can be controlled with high accuracy, and the purity of each gas used can be maintained.

In the invention described in [Claim 6], in the invention described in any one of [Claim 1] to [Claim 4],
Since the halogen gas and nitrogen gas are supplied into the chamber from the same one supply means,
Equipment such as gas piping can be made compact, and the degree of freedom around the device can be improved.

In the invention described in [Claim 7], in the invention described in [Claim 5] or [Claim 6],
Since we decided to supply nitrogen gas after supplying halogen gas,
Supply of each use gas can be controlled easily.

In the invention described in [Claim 8], in the invention described in [Claim 5] or [Claim 6],
Since the order of supplying nitrogen gas after supplying halogen gas was repeated alternately,
In addition to the effects of the invention described in [Claim 7], it is possible to cope with the formation of a film having a larger film thickness.

In the invention described in [Claim 9], in the invention described in [Claim 5] or [Claim 6],
Because we decided to supply halogen gas and nitrogen gas at the same time,
The deposition rate can be improved.

In the invention described in [Claim 10], in the invention described in any one of [Claim 1] to [Claim 9],
Since at least one of the halogen gas plasma or the nitrogen gas plasma is inductively coupled plasma,
The present invention can be implemented using the current apparatus configuration.

In the invention described in [Claim 11], in the invention described in any one of [Claim 1] to [Claim 9],
Since at least one of the halogen gas plasma or the nitrogen gas plasma is a capacitively coupled plasma,
The present invention can be implemented using the current apparatus configuration.

In the invention described in [Claim 12], in the invention described in any one of [Claim 1] to [Claim 9],
Since at least one of the halogen gas plasma or the nitrogen gas plasma is a hybrid plasma composed of inductively coupled plasma and capacitively coupled plasma,
The present invention can be implemented using the current apparatus configuration. Furthermore, the plasma can be in the intermediate state between the high electron density and electron temperature of the inductively coupled plasma and the low electron density and electron temperature of the capacitively coupled plasma. Can be membrane.

In the invention described in [Claim 13], in the invention described in any one of [Claim 1] to [Claim 12],
Since at least one of the halogen gas plasma or the nitrogen gas plasma is converted into plasma that has been converted into plasma outside the chamber and supplied into the chamber,
Damage to the thin film due to plasma generated in the chamber can be reduced or prevented.

In the invention described in [Claim 14], in the invention described in any one of [Claim 1] to [Claim 13],
Since the metal is at least one metal selected from the group consisting of tantalum, tungsten, titanium, and silicon,
A desired thin film can be produced and applied to, for example, a barrier metal film.

In the invention described in [Claim 15], in the invention described in any one of [Claim 1] to [Claim 14],
Since the halogen is chlorine,
The deposition rate can be improved and the deposition cost can be reduced.

In the invention described in (Claim 16), a chamber in which the substrate is accommodated,
A metal member to be etched provided at a position facing the substrate in the chamber;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Plasma generation that generates nitrogen gas plasma by generating plasma inside the chamber and etching the member to be etched with the nitrogen gas plasma to generate a precursor of a metal component and nitrogen gas contained in the member to be etched. Means,
Since the temperature of the substrate is made lower than the temperature of the member to be etched, the temperature control means for forming the precursor, which is a metal nitride, on the substrate is provided.
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied.

In the invention described in (Claim 17), a chamber in which the substrate is accommodated;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Plasma generating means for generating halogen gas plasma and nitrogen gas plasma by plasmaizing the inside of the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied.

In the invention described in (Claim 18), a chamber in which the substrate is accommodated;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Plasma generating means for generating halogen gas plasma by converting the inside of the chamber into plasma;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied. Furthermore, since the metal nitride film can be formed without turning nitrogen into plasma, the film formation cost can be reduced.

In the invention described in (Claim 19), a chamber in which the substrate is accommodated,
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
The inside of the chamber is turned into plasma to generate halogen gas plasma and nitrogen gas plasma, and the member to be etched is etched with the halogen gas plasma, whereby a first component of the metal component and halogen gas contained in the member to be etched is obtained. A precursor is generated, and a second precursor of a metal component and nitrogen gas contained in the member to be etched is generated by etching the member to be etched with the nitrogen gas plasma, and the metal halide is the metal halide. Plasma generating means for changing the first precursor to the second precursor which is a metal nitride by the nitrogen gas plasma;
By making the temperature of the substrate lower than the temperature of the member to be etched, the metal component of the first precursor and the second precursor are formed on the substrate, and the formed metal component And a temperature control means for changing the metal nitride into a metal nitride by the nitrogen gas plasma,
Since metal nitride was deposited on the substrate,
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied.

In the invention described in [Claim 20], a chamber in which the substrate is accommodated;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
The inside of the chamber is turned into plasma to generate halogen gas plasma, and the member to be etched is etched with the halogen gas plasma to generate a precursor of a metal component and a halogen gas contained in the member to be etched. Plasma generating means for nitriding the precursor which is a metal phosphide with the nitrogen gas to convert it into a metal nitride;
By making the temperature of the substrate lower than the temperature of the member to be etched, the metal component of the precursor and the metal nitride are formed on the substrate, and the formed metal component is formed by the nitrogen gas. Temperature control means for changing to metal nitride,
Since metal nitride was deposited on the substrate,
A metal nitride film having a uniform film quality with high crystallinity and a stable composition can be formed. In addition, since a metal nitride film having desired film characteristics can be formed, for example, a surface treatment film of a chemical container that requires surface hardening treatment of a barrier metal film, a tool, decoration of various parts, and corrosion resistance Etc. can be applied. Furthermore, since the metal nitride film can be formed without turning nitrogen into plasma, the film formation cost can be reduced.

In the invention described in [Claim 21], in the invention described in any one of [Claim 17] to [Claim 20],
Since the halogen gas supply means and the nitrogen gas supply means are independent supply means,
The supply of each gas used can be controlled with high accuracy, and the purity of each gas used can be maintained.

In the invention described in [Claim 22], in the invention described in any one of [Claim 17] to [Claim 20],
Since the halogen gas supply unit and the nitrogen gas supply unit are integrated to supply the halogen gas and the nitrogen gas from one supply unit,
Equipment such as gas piping can be made compact, and the degree of freedom around the device can be improved.

In the invention described in [Claim 23], in the invention described in [Claim 21] or [Claim 22],
Furthermore, since the halogen gas is supplied by the halogen gas supply means for a first predetermined time, and further provided with a gas supply control means for supplying the nitrogen gas by the nitrogen gas supply means for a second predetermined time,
Supply of each use gas can be controlled easily.

In the invention described in [Claim 24], in the invention described in [Claim 21] or [Claim 22],
Furthermore, since the halogen gas is supplied by the halogen gas supply means for a first predetermined time, the gas supply control means repeats the order of supplying the nitrogen gas by the nitrogen gas supply means for a second predetermined time.
In addition to the effects of the invention described in [Claim 23], it is possible to cope with the formation of a film having a larger film thickness.

In the invention described in [Claim 25], in the invention described in [Claim 21] or [Claim 22],
Furthermore, since the gas supply control means for supplying the halogen gas and the nitrogen gas simultaneously is provided,
The deposition rate can be improved.

In the invention described in (Claim 26), a chamber in which the substrate is accommodated;
A metal member to be etched provided at a position facing the substrate in the chamber;
Plasma generating means provided outside the chamber, generating nitrogen gas plasma by converting nitrogen gas into plasma, and supplying the nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
Damage to the thin film due to plasma can be reduced or prevented.

In the invention described in (Claim 27), a chamber in which the substrate is accommodated;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Halogen gas supply means for supplying a halogen gas between the substrate and the member to be etched;
First plasma generating means for generating halogen gas plasma by converting the inside of the chamber into plasma;
A second plasma generating means provided outside the chamber for generating nitrogen gas plasma by converting nitrogen gas into plasma, and supplying the nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
Damage to the thin film due to plasma generated in the chamber can be reduced or prevented.

In the invention described in (Claim 28), a chamber in which the substrate is accommodated,
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
First plasma generating means for generating nitrogen gas plasma by converting the inside of the chamber into plasma;
A second plasma generating means provided outside the chamber and generating halogen gas plasma by converting the halogen gas into plasma, and supplying the halogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
Damage to the thin film due to plasma generated in the chamber can be reduced or prevented.

In the invention described in (Claim 29), a chamber in which the substrate is accommodated;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Plasma generating means provided outside the chamber and generating halogen gas plasma and nitrogen gas plasma by converting the halogen gas and nitrogen gas into plasma, and supplying the halogen gas plasma and nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
Damage to the thin film due to plasma can be reduced or prevented.

In the invention described in (Claim 30), a chamber in which the substrate is accommodated;
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
A first plasma generating means provided outside the chamber for generating halogen gas plasma by converting the halogen gas into plasma, and supplying the halogen gas plasma into the chamber;
A second plasma generating means provided outside the chamber for generating nitrogen gas plasma by converting nitrogen gas into plasma, and supplying the nitrogen gas plasma into the chamber;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
Damage to the thin film due to plasma can be reduced or prevented. Furthermore, the plasma of each gas used can be controlled independently.

In the invention described in (Claim 31), a chamber in which the substrate is accommodated,
A member to be etched, formed of a metal capable of generating a high vapor pressure halide, and provided in a position facing the substrate in the chamber;
Plasma generating means provided outside the chamber, generating halogen gas plasma by converting the halogen gas into plasma, and supplying the halogen gas plasma into the chamber;
Nitrogen gas supply means for supplying nitrogen gas between the substrate and the member to be etched;
Temperature control means for lowering the temperature of the substrate lower than the temperature of the member to be etched,
Since metal nitride was deposited on the substrate,
Damage to the thin film due to plasma can be reduced or prevented.

In the invention described in [Claim 32], in the invention described in any one of [Claim 16] to [Claim 25], [Claim 28], [Claim 31],
Since the nitrogen gas supply means comprises a gas flow path of a ring-shaped pipe disposed around the substrate, and a nozzle that is provided in the gas flow path and injects nitrogen gas toward the substrate,
The thin film formed on the substrate can efficiently be nitrided, and the purity of the metal nitride film formed can be improved.

In the invention described in [Claim 33], in the invention described in any one of [Claim 16], [Claim 17] or [Claim 19],
The nitrogen gas supply means includes a gas flow path of a ring-shaped pipe made of a conductor disposed around the substrate, and a nozzle that is provided in the gas flow path and injects the nitrogen gas toward the substrate. Since the capacitively coupled nitrogen gas plasma is generated between the substrate and the power supply,
In addition to the effect of the invention described in [Claim 32], nitrogen gas plasma can be directly applied to the thin film, so that the purity of the metal nitride film to be formed can be further improved.

In the invention described in [Claim 34], in the invention described in any one of [Claim 16], [Claim 17] or [Claim 19],
The nitrogen gas supply means includes a gas flow path of a ring-shaped pipe made of a conductor disposed around the substrate, and a nozzle that is provided in the gas flow path and injects the nitrogen gas toward the substrate. Since at least one place in the circumferential direction of the ring-shaped pipe is insulated and inductively coupled nitrogen gas plasma is generated between the substrate and the power supply,
In addition to the effect of the invention described in [Claim 32], nitrogen gas plasma can be directly applied to the thin film, so that the purity of the metal nitride film to be formed can be further improved.

In the invention described in [Claim 35], in the invention described in any one of [Claim 16] to [Claim 34],
Since the metal is at least one metal selected from the group consisting of tantalum, tungsten, titanium, and silicon,
A desired thin film can be produced and applied to, for example, a barrier metal film.

In the invention described in [Claim 36], in the invention described in any one of [Claim 17] to [Claim 35],
Since the halogen is chlorine,
The deposition rate can be improved and the deposition cost can be reduced.

In the invention described in [Claim 37], in the invention described in any one of [Claim 1] to [Claim 15],
Since the metal is copper, a desired thin film can be formed.

In the invention described in [Claim 38], in the invention described in any one of [Claim 16] to [Claim 36],
Since the metal is copper, a desired thin film can be formed.

Hereinafter, a metal nitride film manufacturing method and a metal nitride film manufacturing apparatus according to an embodiment of the present invention will be described with reference to the drawings. The metal nitride film manufacturing method and metal nitride film manufacturing apparatus according to the present invention are further improved by using nitrogen gas plasma or nitrogen gas as compared with the method and apparatus for forming a metal film using halogen gas plasma previously proposed by the present inventors. In addition, by using only nitrogen gas plasma, a metal nitride thin film applied to, for example, a barrier metal film or the like is formed on a substrate.

< First Embodiment >
A metal nitride film manufacturing method and a metal nitride film manufacturing apparatus according to the first embodiment will be described with reference to FIG. FIG. 1 shows a schematic side view of a metal nitride film production apparatus for performing a metal nitride film production method according to the first embodiment of the present invention.

As shown in FIG. 1 , a support base 2 is provided in the vicinity of the bottom of a chamber 1 made of, for example, ceramics (made of an insulating material), and a substrate 3 is placed on the support base 2. . The support base 2 is provided with a temperature control means 6 including a heater 4 and a refrigerant flow means 5, and the support base 2 is heated to a predetermined temperature (for example, a temperature at which the substrate 3 is maintained at 100 ° C. to 200 ° C.). ) Is controlled.

  The upper surface of the chamber 1 is an opening, and the opening is closed by a member to be etched 7 formed of a metal capable of forming a high vapor pressure halide. The inside of the chamber 1 closed by the member 7 to be etched is maintained at a predetermined pressure by the vacuum device 8. In this embodiment, titanium (Ti) is used as the material of the member 7 to be etched. However, the material is not limited to this, and tantalum (Ta), tungsten (W), silicon (Si), or copper (depending on the nitride film to be formed) Cu) or the like may be used.

  A coiled plasma antenna 9 is provided around the cylindrical portion of the chamber 1, and a matching unit 10 and a power source 11 are connected to the plasma antenna 9 to supply a high-frequency current. Plasma generating means is constituted by the plasma antenna 9, the matching unit 10 and the power source 11.

  In the cylindrical portion of the chamber 1 at a position slightly higher than the support base 2, a source gas containing chlorine gas as a halogen gas inside the chamber 1 (He, Ar, etc., the chlorine concentration is ≦ 50%, preferably about 10%) A nozzle 12 having a function (halogen gas supply means) for supplying (diluted chlorine gas) is connected. The nozzle 12 opens toward the member 7 to be etched, and the raw material gas is sent to the nozzle 12 via the flow rate controller 13. The source gas is sent from the substrate 3 side to the etched member 7 side along the wall surface in the chamber 1 during film formation. Gases that are not involved in film formation are exhausted from the exhaust port 17.

  A slit-shaped opening 31 is formed around the cylindrical portion of the chamber 1 at substantially the same height as the substrate 3, and one end of the cylindrical passage 32 is fixed to the opening 31. A cylindrical excitation chamber 33 made of an insulator is provided in the middle of the passage 32, and a coiled plasma antenna 34 is provided around the excitation chamber 33. The plasma antenna 34 is connected to the matching unit 10 and the power source 11. Then, a high frequency current is supplied. A flow rate controller 13 ′ is connected to the other end side of the passage 32, and nitrogen gas is supplied into the passage 32 via the flow rate controller 13 ′. Hereinafter, a part constituted by the opening 31, the passage 32, the excitation chamber 33, the plasma antenna 34, the matching unit 10, the power source 11, and the flow rate controller 13 ′ is referred to as “outside chamber plasma generation chamber”.

Note that fluorine (F ₂ ), bromine (Br ₂ ), iodine (I ₂ ), or the like can be used as the halogen contained in the source gas. Further, the flow rate controllers 13 and 13 ′ have a function as a gas supply control unit, and by interlocking, the function of supplying the nitrogen gas for the second predetermined time after supplying the source gas for the first predetermined time, A function of supplying each gas alternately in an order of supplying nitrogen gas for a second predetermined time after supplying for a first predetermined time and a function for supplying raw materials and nitrogen gas simultaneously.

  In the metal nitride film production apparatus described above, the TiN (titanium nitride) thin film 16 is formed by the method described in detail below.

First, the source gas and the nitrogen gas are simultaneously supplied from the nozzle 12 into the chamber 1 and the excitation chamber 33. Next, an electromagnetic wave is incident on the inside of the chamber 1 from the plasma antenna 9 and an electromagnetic wave is incident on the inside of the excitation chamber 33 from the plasma antenna 34, thereby ionizing chlorine gas and nitrogen gas in the raw material gas to generate chlorine gas. Plasma and nitrogen gas plasma are generated. The chlorine gas plasma is generated in the region shown by the gas plasma 14, and the nitrogen gas plasma is generated in the excitation chamber 33. The reaction at this time can be expressed by the following formula.
Cl ₂ → 2Cl ^* (21)
N ₂ → 2N ^* (22)
Here, Cl ^* represents a chlorine gas radical and an N ^* nitrogen gas radical.

  Since the nitrogen gas plasma has a predetermined differential pressure set between the pressure in the chamber 1 and the pressure in the excitation chamber 33 by the vacuum device 8, the nitrogen gas plasma passes through the opening 31 from the excitation chamber 33, particularly in the substrate 3. Sent to the surrounding area.

The chlorine gas plasma and nitrogen gas plasma heat the member 7 to be etched and cause an etching reaction in the member 7 to be etched. The reaction at this time is represented by the following formula.
Ti (s) + 4Cl ^* → TiCl ₄ (g) (23)
Ti (s) + N ^* → TiN (g) (24)
Here, s represents a solid state and g represents a gas state. Expression (23) represents a gasified state in which the Ti component of the member to be etched 7 is etched by chlorine gas plasma. Expression (24) represents a gasified state in which the Ti component of the member to be etched 7 is etched by nitrogen gas plasma. The precursor 15 is these gasified TiCl ₄ and TiN and substances (Ti _X1 Cl _Y1 and Ti _X2 N _Y2 ) having a composition ratio different from those. In the present embodiment, since nitrogen gas plasma is sent to the peripheral region of the substrate 3 in particular, it is considered that the reaction of the above equation (24) does not occur much compared to the above equation (23).

When the gas plasma 14 is generated, the member 7 to be etched is heated, and the substrate 3 is cooled by the temperature control means, so that the temperature of the substrate 3 becomes lower than the temperature of the member 7 to be etched. As a result, the precursor 15 is adsorbed on the substrate 3. The reaction at this time is represented by the following formula.
TiCl ₄ (g) → TiCl ₄ (ad) (25)
TiN (g) → TiN (ad) (26)
Here, ad represents an adsorption state.

TiN (titanium nitride) adsorbed on the substrate 3 becomes a part of the TiN thin film 16 as it is as shown in the following equation.
TiN (ad) → TiN (s) (27)

On the other hand, TiCl ₄ (titanium chloride) adsorbed on the substrate 3 becomes TiN (titanium nitride) through the following two forms of reaction, and becomes a part of forming the TiN thin film 16. The first reaction is directly nitrided by nitrogen gas radicals to become TiN (titanium nitride). The reaction at this time is represented by the following formula.
TiCl ₄ (ad) + N ^* → TiN (s) + 2Cl ₂ ↑ (28)
The second reaction is reduced by chlorine gas radicals to become Ti components, and then nitrided by nitrogen gas radicals to become TiN (titanium nitride). The reaction at this time is represented by the following formula.
TiCl ₄ (ad) + 4Cl ^* → Ti (s) + 4Cl ₂ ↑ (29)
Ti (s) + N ^* → TiN (s) (30)
In this embodiment, since nitrogen gas plasma is sent to the peripheral region of the substrate 3 in particular, it is considered that TiN (titanium nitride) generation by these two forms frequently occurs.

Further, a part of the gasified TiCl ₄ (titanium chloride) generated in the above equation (23) is nitrided by a nitrogen gas radical and adsorbed to the substrate 3 as shown in the above equation (25). TiN (titanium nitride). The reaction at this time is represented by the following formula.
TiCl ₄ (g) + N ^* → TiN (g) + 2Cl ₂ ↑ (31)
Thereafter, TiN (titanium nitride) in a gas state is formed on the substrate 3 by the reactions of the above formulas (26) and (27) and becomes a part of forming the TiN thin film 16.

  The obtained TiN thin film had a stable elemental composition, and as a result of X-ray analysis, it was found that the thin film had high crystallinity. That is, according to the present embodiment, it is possible to form the TiN thin film 16 having a uniform film quality and capable of obtaining desired film characteristics.

  In the metal nitride film manufacturing apparatus according to the present embodiment, as means for generating nitrogen gas plasma in the excitation chamber 33, means using an induction coil is used, but the invention is not limited to this. For example, microwaves, lasers, electron beams, radiated light, etc. It is also possible to use.

  In the present embodiment, the example in which the source gas (containing chlorine gas) and the nitrogen gas are simultaneously supplied by the gas supply control unit has been described, but the present invention is not limited thereto.

That is, even when the source gas is supplied for the first predetermined time and then the nitrogen gas is supplied for the second predetermined time, the TiN thin film 16 having a uniform film quality can be similarly formed. In this case, basically, a TiN thin film (formula (30)) formed by nitriding with nitrogen gas plasma after forming a Ti thin film and etching of the member to be etched by nitrogen gas plasma are used. A TiN thin film 16 composed of the TiN thin film to be formed (reactions represented by the above formulas (24), (26), and (27)) is formed. Therefore, it is considered that there is no reaction in which TiCl _{4 in the} gas state represented by the formula (31) is nitrided by nitrogen gas radicals to form a film. However, when the nitrogen gas is supplied for the second predetermined time after the source gas is supplied for the first predetermined time, it is necessary to make the first predetermined time relatively short and the second predetermined time relatively long. This is because, in the case of a thick Ti thin film formed by extending the first predetermined time, the nitriding reaction of the Ti thin film by the nitrogen gas plasma represented by the above formula (30) does not reach the inside of the thin film, This is because the Ti simple metal remains in the thin film.

  Further, even when the respective gases are alternately supplied in the order in which the nitrogen gas is supplied for the second predetermined time after the source gas is supplied for the first predetermined time, the TiN thin film 16 having a uniform film quality can be similarly formed. . When nitrogen gas is supplied for the second predetermined time after supplying the above-mentioned source gas for the first predetermined time, it is not possible to cope with the film formation with a thick film. The TiN thin film 16 having a thick film can be obtained as a result by repeating the process many times.

  In the present embodiment, an example is shown in which chlorine gas plasma and nitrogen gas plasma are generated to form a film, but the present invention is not limited to this.

  That is, the TiN thin film 16 having a uniform film quality can be similarly formed even if nitrogen gas is allowed to contribute to film formation in a nitrogen gas state without being converted into plasma. In this case, power supply to the plasma antenna 34 is stopped, and the inside of the excitation chamber 33 is allowed to pass through the nitrogen gas as it is to participate in the film formation reaction. By using nitrogen gas directly in the film formation reaction, it is considered that the TiN thin film 16 is formed based on the following reaction.

That is, a part of the precursor TiCl ₄ (formula (23)) generated by etching the member 7 to be etched by chlorine gas radicals is adsorbed on the substrate 3, and the other part is nitrided by nitrogen gas and TiN. To form a film. The reaction at this time is represented by the following formula.
2TiCl ₄ (g) + N ₂ → 2TiN (g) + 4Cl ₂ ↑ (32)
TiN (g) → TiN (ad) → TiN (s) (33)
On the other hand, part of TiCl ₄ adsorbed on the substrate is directly nitrided with nitrogen gas to become TiN. The reaction at this time is represented by the following formula.
2TiCl ₄ (ad) + N ₂ → 2TiN (s) + 4Cl ₂ ↑ (34)
The other part is reduced by chlorine gas radicals, and then is nitrided by nitrogen gas to form TiN. The reaction at this time is represented by the following formula.
TiCl ₄ (ad) + 4Cl ^* → Ti (s) + 4Cl ₂ ↑ (35)
2Ti (s) + N ₂ → 2TiN (s) (36)

  As a result, the TiN thin film 16 having a uniform film quality can be similarly formed even if nitrogen gas is converted into nitrogen gas and contributed to the film formation reaction. However, since nitrogen gas is less reactive than nitrogen gas plasma, for example, the temperature of the substrate 3 is relatively higher than the method described in the tenth embodiment within a range not to be higher than the member 7 to be etched. The reactivity can be improved by setting to.

  Further, the TiN thin film 16 having a uniform film quality can be formed by using only nitrogen gas plasma without generating chlorine gas plasma (without supplying raw material gas) as in the tenth embodiment. In this case, for example, the supply of the source gas from the nozzle 12 is stopped and the nitrogen gas plasma ejected from the “outside chamber plasma generation chamber” is directed toward the member to be etched 7, and the etching is performed only with the nitrogen gas plasma. The member 7 is etched and the film is formed on the substrate 3. The reaction at this time is represented by the above formulas (22), (24), (26), and (27). In this case, since the chlorine gas plasma does not participate in the film formation reaction, the member to be etched 7 does not need to be a metal that can generate a high vapor pressure halide, and any metal that can be nitrided can be used. Metal may be used.

In addition, although chlorine gas diluted with He, Ar etc. was mentioned as an example and demonstrated as source gas, it is also possible to use chlorine gas independently or to apply HCl gas. When applying the HCl gas, the raw material gas plasma is HCl gas plasma is generated, the precursor produced by etching of the etched member 7 is Ti _x Cl _y. Therefore, the source gas may be any gas containing chlorine, and a mixed gas of HCl gas and chlorine gas can also be used. Of course, when diluting chlorine gas, it may be diluted by mixing with nitrogen gas.

Next, based on FIGS. 2 to 4, illustrating the second to fourth embodiments the metal nitride film production method and metal nitride film production apparatus according to the embodiment of the present invention. Also in the metal nitride film manufacturing method and metal nitride film manufacturing apparatus shown below, chlorine gas and nitrogen gas are simultaneously supplied into plasma to generate plasma (where plasma generation is different). Then, the member to be etched is etched to form a metal nitride thin film on the substrate. Thereby, a thin film of metal nitride having a uniform film quality such as high crystallinity can be formed.

FIG. 2 to FIG. 4 show a schematic configuration of a metal nitride film manufacturing apparatus for performing the metal nitride film manufacturing method according to the second to fourth embodiments of the present invention. The same members as those in the metal nitride film manufacturing apparatus shown in FIG. 1 are denoted by the same reference numerals, and redundant description is omitted.

< Second Embodiment >
In the metal nitride film manufacturing apparatus according to the second embodiment shown in FIG. 2 , the upper surface of the chamber 1 is an opening, and the opening is closed by a plate-like ceiling plate 25 made of an insulating material (for example, ceramic). It is peeling off. A plasma antenna 27 for converting the inside of the chamber 1 into plasma is provided above the ceiling plate 25, and the plasma antenna 27 is formed in a planar ring shape parallel to the surface of the ceiling plate 25. The plasma antenna 27 is connected to the matching unit 10 and the power source 11 and supplied with a high frequency current.

  A member to be etched 26 made of a metal capable of forming a high vapor pressure halide is sandwiched between the opening on the upper surface of the chamber 1 and the ceiling plate 25. In this embodiment, titanium (Ti) is used as the material of the member 26 to be etched. However, the material is not limited to this, and tantalum (Ta), tungsten (W), silicon (Si), or copper (depending on the nitride film to be formed). Cu) or the like may be used.

  The member to be etched 26 is composed of a plurality of protrusions that are provided in the circumferential direction from the inner wall of the chamber 1 and have a notch (space) between the protrusions. For this reason, it arrange | positions between the board | substrate 3 and the ceiling board 25 so that it may become a discontinuous state with respect to the flow direction of the electric current which flows into the plasma antenna 27. FIG.

In the metal nitride film manufacturing apparatus according to the present embodiment, a raw material gas containing chlorine gas as a halogen gas is supplied from the nozzle 12 to the inside of the chamber 1, and electromagnetic waves are incident on the inside of the chamber 1 from the plasma antenna 27. Chlorine gas is ionized to generate chlorine gas plasma. The chlorine gas plasma is generated in a region shown by the gas plasma 14. Nitrogen gas plasma is generated in the excitation chamber 33 by the same mechanism as described in the first embodiment, and is sent to the chamber 1, particularly to the peripheral region of the substrate 3. These plasmas cause an etching reaction in the member 26 to be etched, and the TiN thin film 16 is formed by the same action as in the first embodiment.

  A member to be etched 26, which is a conductor, exists below the plasma antenna 27, but the member to be etched 26 is disposed in a discontinuous state with respect to the flow direction of the current flowing through the plasma antenna 27. The gas plasma 14 is stably generated between the member to be etched 26 and the substrate 3, that is, below the member to be etched 26.

< Third Embodiment >
In the metal nitride film manufacturing apparatus according to the third embodiment shown in FIG. 3 , a plasma antenna 9 is provided around the cylindrical portion of the chamber 1 as compared with the metal nitride film manufacturing apparatus shown in FIG. The matching unit 10 and the power source 11 are connected to the member 7 to be etched, and a high frequency current is supplied to the member 7 to be etched. Further, the support base 2 (substrate 3) is grounded.

In the metal nitride film manufacturing apparatus according to this embodiment, a raw material gas containing chlorine gas as a halogen gas is supplied from the nozzle 12 to the inside of the chamber 1, and an electrostatic field is applied to the inside of the chamber 1 from the member to be etched 7. As a result, chlorine gas is ionized to generate chlorine gas plasma. The chlorine gas plasma is generated in a region shown by the gas plasma 14. Nitrogen gas plasma is generated in the excitation chamber 33 by the same mechanism as described in the first embodiment, and is sent to the chamber 1, particularly to the peripheral region of the substrate 3. These plasmas cause an etching reaction in the member 7 to be etched, and the TiN thin film 16 is formed by the same action as in the first embodiment.

In the metal nitride film manufacturing apparatus according to the present embodiment, the member to be etched 7 itself is applied as an electrode for plasma generation, so that the plasma antenna 9 (see FIG. 1 ) is not required around the cylindrical portion of the chamber 1, The degree of freedom of surrounding configuration can be increased.

< Fourth Embodiment >
In the metal nitride film manufacturing apparatus according to the fourth embodiment shown in FIG. 4 , the upper surface of the chamber 1 is an opening, and the opening is closed by, for example, a ceramic (made of an insulating material) ceiling plate 29. ing. On the lower surface of the ceiling plate 29, an etching target member 30 made of a metal capable of forming a high vapor pressure halide is provided, and the etching target member 30 has a quadrangular pyramid shape.

Further, in the metal nitride film manufacturing apparatus according to the present embodiment, the plasma antenna 9 is not provided around the cylindrical portion of the chamber 1 as compared with the metal nitride film manufacturing apparatus shown in FIG. In addition to a dedicated “outside chamber plasma generation chamber”, a “outside chamber plasma generation chamber” dedicated to the source gas is provided. Thus, the nitrogen gas and the source gas are separately converted into plasma, and nitrogen gas plasma is supplied so as to cover the substrate 3, and the source gas plasma is supplied toward the member to be etched 30.

As described above, the second to fourth embodiments have been described in detail. In the second to fourth embodiments as well, the obtained TiN thin film has a stable elemental composition as in the first embodiment. As a result of X-ray analysis, it was found that the thin film has high crystallinity. That is, according to the second to fourth embodiments , it is possible to form the TiN thin film 16 having uniform film quality and capable of obtaining desired film characteristics.

Also in the second to fourth embodiments , as in the first embodiment , the example in which the source gas (containing chlorine gas) and the nitrogen gas are simultaneously supplied by the gas supply control means has been shown. It is not something that can be done. That is, when the source gas is supplied for the first predetermined time and then the nitrogen gas is supplied for the second predetermined time, or after the source gas is supplied for the first predetermined time and then the nitrogen gas is supplied for the second predetermined time, the respective gases are alternately supplied. Even when supplied, the TiN thin film 16 having a uniform film quality can be similarly formed. The mechanism for forming the TiN thin film 16 in this case is as described in the first embodiment.

Also, in the second to fourth embodiments , as in the first embodiment , an example was shown in which film formation was performed by generating chlorine gas plasma and nitrogen gas plasma. However, the present invention is not limited to this. . That is, the TiN thin film 16 having a uniform film quality can be formed as in the first embodiment even if nitrogen gas is not converted into plasma and contributes to film formation in the state of nitrogen gas. If power supply to the plasma antenna is stopped, the nitrogen gas can be contributed to the film formation reaction.

Also in the second to fourth embodiments , as in the first embodiment , the chlorine gas plasma is not generated (the source gas is not supplied), and only the nitrogen gas plasma is used in the first embodiment. Similarly, a TiN thin film 16 having a uniform film quality can be formed.

In the second to fourth embodiments, as in the first embodiment, the chlorine gas diluted with He, Ar or the like has been described as an example of the source gas, but the chlorine gas is used alone. It is also possible to use or apply HCl gas. The source gas may be any gas containing chlorine, and a mixed gas of HCl gas and chlorine gas can also be used. Of course, when diluting chlorine gas, it may be diluted by mixing with nitrogen gas.

In the film forming mechanism of the TiN thin film 16 in the first to fourth embodiments described above, nitrogen gas is supplied from the “outside chamber plasma generation chamber” so as to cover the substrate 3 as nitrogen gas plasma, It is considered that etching of the members 7, 26 and 30 to be etched by nitrogen gas radicals (formula (24)) and subsequent film formation reactions (formulas (26) and (27)) are unlikely to occur. On the other hand, the nitriding reaction of the precursor TiCl ₄ (the above formula (31)), in particular, the nitriding reaction of the precursor TiCl ₄ adsorbed on the substrate 3 generated near the substrate 3 (the above formula (28)) and the nitriding reaction of Ti alone ( The above equation (30)) is considered to increase the probability of occurrence.

In the first to fourth embodiments , the nitrogen gas is converted into plasma in the “outside chamber plasma generation chamber” and then supplied into the chamber, but the present invention is not limited to this. For example, the plasma generating means for plasma within Ji Yanba, it is possible to form a similar metal nitride film be plasma in the chamber. In the first to fourth embodiments , an example in which the halogen gas supply unit and the nitrogen gas supply unit are provided independently has been described. However, by providing the halogen gas and nitrogen gas supply unit integrally. The gas piping can also be made compact, and in this case as well, a metal nitride film can be similarly formed.

In the first to fourth embodiments, the shape of the halogen gas supply unit indicated by the nozzle 12 has been described as an example, and the nitrogen gas supply unit has been described as the “outside chamber plasma generation chamber” type. However, the present invention is not limited to this. Absent. For example, even the hard Rogengasu supply means or the nitrogen gas supply means as a ring-shaped pipe that is disposed around the substrate, it is possible to deposit the same metal nitride film. Furthermore, an electrostatic field may be generated between the gas ring of the ring-shaped pipe and the substrate, and halogen gas or nitrogen gas may be converted into plasma (capacitively coupled plasma) and used for the film formation reaction. Alternatively, an induction electric field may be generated between the gas ring of the ring-shaped pipe and the substrate, and halogen gas or nitrogen gas may be converted into plasma (inductively coupled plasma) and used for the film formation reaction. In these cases, a metal nitride film can be similarly formed.

1 is a schematic side view of a metal nitride film manufacturing apparatus for performing a metal nitride film manufacturing method according to a first embodiment of the present invention. It is a schematic side view of the metal nitride film production apparatus which enforces the metal nitride film production method concerning the 2nd Embodiment of this invention. It is a schematic side view of the metal nitride film production apparatus which enforces the metal nitride film production method concerning the 3rd Embodiment of this invention. It is a schematic side view of the metal nitride film production apparatus which enforces the metal nitride film production method concerning the 4th Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Chamber 2 Support stand 3 Substrate 4 Heater 5 Refrigerant distribution means 6 Temperature control means 7, 26, 30 Member to be etched 8 Vacuum apparatus 9, 27, 34 Plasma antenna 10 Matching device 11 Power supply 12 Nozzle 13, 20 Flow rate controller 14, 35 Gas plasma 15 Precursor 17 Exhaust port 25, 29 Ceiling plate 31 Opening 32 Passage 33 Excitation chamber

Images