JP2006037230A - Method and apparatus for producing metal nitride film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing a metal nitride film having high crystallinity and stable composition. <P>SOLUTION: Chlorine gas plasma and nitrogen gas plasma are generated in a chamber 1 by supplying raw gas containing chlorine gas and nitrogen gas from a nozzle 12 and applying electromagnetic wave from a plasma antenna 9. A member 7 to be etched is etched by these gas plasma to form a first precursor consisting of Ti (titanium) element and chlorine gas and a second precursor consisting of Ti element and nitrogen gas. By providing the temperature difference between the member 7 and a substrate 3, TiN as the second precursor is deposited, and a TiN thin film 16 is deposited on the substrate 3 by performing the film deposition after TiCl<SB>4</SB>as the first precursor is nitrided to be TiN by nitrogen gas plasma, by performing nitriding to be TiN after TiCl<SB>4</SB>as the first precursor is adsorbed by the substrate 3, or performing nitriding to be TiN after the Ti element of the first precursor is deposited. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  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 oxide film manufacturing method and a metal oxide film manufacturing apparatus according to an embodiment of the present invention will be described with reference to the drawings. The metal oxide film manufacturing method and the metal oxide film manufacturing apparatus according to the present invention further include oxygen gas plasma or oxygen gas in addition to the method and apparatus for forming a metal film using halogen gas plasma previously proposed by the present inventors. Further, by using only oxygen gas plasma, a thin film of metal oxide such as hafnium oxide, iridium oxide, titanium oxide, zirconium oxide, tantalum oxide having a high relative dielectric constant (for example, 10 to 100) is formed on the substrate. A film is formed on the substrate.

<First Embodiment>
A metal oxide film manufacturing method and a metal oxide 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 oxide film production apparatus for performing a metal oxide 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 set to a predetermined temperature (for example, a temperature at which the substrate 3 is maintained at 100 ° C. to 200 ° C.) by the temperature control means 6. ) 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, hafnium (Hf) is used as the material of the member 7 to be etched. However, the material is not limited to this, and iridium (Ir), titanium (Ti), zirconium (Zr), tantalum (depending on the oxide film to be formed) It may be formed of Ta) or copper (Cu).

  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 almost the same height as the support 2, a source gas containing chlorine gas as a halogen gas inside the chamber 1 (He, Ar, etc., the chlorine concentration is ≦ 50%, preferably 10%) A nozzle 12 having a function (halogen gas supply means) for supplying (chlorine gas diluted to an extent) and a function (oxygen gas supply means) for supplying oxygen gas are connected. The nozzle 12 opens toward the member 7 to be etched, and a raw material gas and an oxygen gas are sent to the nozzle 12 via a flow rate controller 13. The source gas and oxygen gas are sent from the substrate 3 side to the member to be etched 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.

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 controller 13 has a function as a gas supply control means, a function of supplying an oxygen gas for a second predetermined time after supplying the raw material gas for a first predetermined time, and an oxygen after supplying the raw material gas for a first predetermined time. It has a function of supplying each gas alternately in the order of supplying the gas for the second predetermined time and a function of supplying raw materials and oxygen gas simultaneously.

In the metal oxide film manufacturing apparatus described above, the HfO ₂ (hafnium oxide) thin film 16 is formed by the method described in detail below.

First, source gas and oxygen gas are simultaneously supplied into the chamber 1 from the nozzle 12 and electromagnetic waves are incident on the chamber 1 from the plasma antenna 9 to ionize chlorine gas and oxygen gas in the source gas. Chlorine gas plasma and oxygen gas plasma are generated. These plasmas are generated in the region shown by the gas plasma 14. The reaction at this time can be expressed by the following formula.
Cl ₂ → 2Cl ^* (1)
O ₂ → 2O ^* (2)
Here, Cl ^* represents a chlorine gas radical and an O ^* oxygen gas radical.

The chlorine gas plasma and oxygen 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.
Hf (s) + 2Cl ^* → HfCl ₂ (g) (3)
Hf (s) + 2O ^* → HfO ₂ (g) (4)
Here, s represents a solid state and g represents a gas state. Expression (3) represents a gasified state in which the Hf component of the member to be etched 7 is etched by chlorine gas plasma. Expression (4) represents a gasified state in which the Hf component of the member to be etched 7 is etched by oxygen gas plasma. The precursor 15 is these gasified HfCl ₂ and HfO ₂ and substances (Hf _X1 Cl _Y1 and Hf _X2 O _Y2 ) having a composition ratio different from those.

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.
HfCl ₂ (g) → HfCl ₂ (ad) (5)
HfO ₂ (g) → HfO ₂ (ad) (6)
Here, ad represents an adsorption state.

HfO ₂ (hafnium oxide) adsorbed on the substrate 3 becomes a part of the HfO ₂ thin film 16 as it is, as shown in the following equation.
HfO ₂ (ad) → HfO ₂ (s) (7)

On the other hand, HfCl ₂ (hafnium chloride) adsorbed on the substrate 3 becomes HfO ₂ (hafnium oxide) through the following two reactions, and becomes a part of forming the HfO ₂ thin film 16. The first reaction is directly oxidized by oxygen gas radicals to become HfO ₂ (hafnium oxide). The reaction at this time is represented by the following formula.
HfCl ₂ (ad) + 2O ^* → HfO ₂ (s) + Cl ₂ ↑ (8)
The second reaction is reduced by chlorine gas radicals to become Hf components and then oxidized by oxygen gas radicals to become HfO ₂ (hafnium oxide). The reaction at this time is represented by the following formula.
HfCl ₂ (ad) + 2Cl ^* → Hf (s) + Cl ₂ ↑ (9)
Hf (s) + 2O ^* → HfO ₂ (s) (10)

Further, a part of the gasified HfCl ₂ (hafnium chloride) generated in the above equation (3) is oxidized by the oxygen gas radicals before being adsorbed to the substrate 3 as shown in the above equation (5), so that the gas state HfO ₂ (hafnium oxide). The reaction at this time is represented by the following formula.
HfCl ₂ (g) + 2O ^* → HfO ₂ (g) + Cl ₂ ↑ (11)
Thereafter, gaseous HfO ₂ (hafnium oxide) is formed on the substrate 3 by the reactions of the above formulas (6) and (7), and becomes a part of forming the HfO ₂ thin film 16.

The obtained HfO ₂ 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 this embodiment, it is possible to form the HfO ₂ thin film 16 having a uniform film quality and capable of obtaining desired film characteristics.

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

That is, even when the source gas is supplied for the first predetermined time and then the oxygen gas is supplied for the second predetermined time, the HfO ₂ thin film 16 having a uniform film quality can be similarly formed. In this case, basically, an HfO ₂ thin film (formula (10)) formed by oxidation with oxygen gas plasma after the Hf thin film is formed and etching of the member to be etched by oxygen gas plasma are performed. HfO ₂ thin film formed is HfO ₂ thin film 16 consisting a (the above equation (4), (6), the reactions shown in (7)) is formed. Therefore, it is considered that the reaction of forming a film by oxidizing HfCl _{2 in the} gas state represented by the formula (11) by the oxygen gas radical does not occur. However, when the oxygen 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 Hf thin film formed by extending the first predetermined time, the oxidation reaction of the Hf thin film by the oxygen gas plasma represented by the above formula (10) does not reach the inside of the thin film. This is because the Hf single metal remains inside the thin film.

Further, even when the respective gases are alternately supplied in the order in which the oxygen gas is supplied for the second predetermined time after the source gas is supplied for the first predetermined time, the HfO ₂ thin film 16 having a uniform film quality can be similarly formed. it can. If the oxygen gas is supplied for the second predetermined time after the source gas is supplied for the first predetermined time, it is not possible to cope with the film formation with a thick film. By repeating the process many times, a thick HfO ₂ thin film 16 can be obtained.

  Moreover, although the said embodiment showed the example which formed the film | membrane by generating chlorine gas plasma and oxygen gas plasma, it is not restricted to this.

That is, the HfO ₂ thin film 16 having a uniform film quality can be formed as in the first embodiment even if oxygen gas is not converted into plasma and contributes to film formation in the state of oxygen gas. In this case, for example, the supply direction of the oxygen gas is not directed toward the member 7 to be etched but toward the substrate 3. In this way, oxygen gas is supplied to a region where the electromagnetic wave from the plasma antenna 9 hardly reaches, and the oxygen gas remains in the film forming reaction. By using oxygen gas directly in the film formation reaction, it is considered that the HfO ₂ thin film 16 is formed based on the following reaction.

That is, a part of the precursor HfCl ₂ (formula (3)) generated by etching the member 7 to be etched by chlorine gas radicals is adsorbed on the substrate 3 and the other part is oxidized by oxygen gas to be HfO. ₂ is formed. The reaction at this time is represented by the following formula.
HfCl ₂ (g) + O ₂ → HfO ₂ (g) + Cl ₂ ↑ (12)
HfO ₂ (g) → HfO ₂ (ad) → HfO ₂ (s) (13)
On the other hand, a part of HfCl ₂ adsorbed on the substrate is directly oxidized by oxygen gas to become HfO ₂ . The reaction at this time is represented by the following formula.
HfCl ₂ (ad) + O ₂ → HfO ₂ (s) + Cl ₂ ↑ (14)
The other part is reduced by chlorine gas radicals and then oxidized by oxygen gas to become HfO _{2 to} form a film. The reaction at this time is represented by the following formula.
HfCl ₂ (ad) + 2Cl ^* → Hf (s) + Cl ₂ ↑ (15)
Hf (s) + O ₂ → HfO ₂ (s) (16)

As a result, the HfO ₂ thin film 16 having a uniform film quality can be similarly formed even if oxygen gas is converted into oxygen gas without being converted into plasma and contributed to the film formation reaction. However, since oxygen gas is less reactive than oxygen gas plasma, for example, the temperature of the substrate 3 is relatively higher than the method described in the first embodiment within a range that does not become higher than the member 7 to be etched. The reactivity can be improved by setting to.

Further, the HfO ₂ thin film 16 having a uniform film quality can be formed by using only oxygen gas plasma without generating chlorine gas plasma (without supplying raw material gas) as in the first embodiment. In this case, for example, only the oxygen gas is supplied from the nozzle 12 to be converted into plasma by the plasma antenna 9, and the member 7 to be etched and the film formation on the substrate 3 are performed only by the oxygen gas plasma. The reaction at this time is represented by the above formulas (2), (4), (6), and (7). 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 oxidized 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 HCl gas is applied, HCl gas plasma is generated as the source gas plasma, but the precursor generated by etching the member 7 to be etched is Hf _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 oxygen gas.

  Next, based on FIG. 2 thru | or FIG. 9, the metal oxide film preparation method and metal oxide film preparation apparatus concerning the 2nd thru | or 9th embodiment of this invention are demonstrated. In the metal oxide film manufacturing method and metal oxide film manufacturing apparatus shown below, the member to be etched is etched by chlorine gas plasma and oxygen gas plasma generated by simultaneously supplying chlorine gas and oxygen gas into plasma. A metal oxide thin film is formed on a substrate. As a result, a metal oxide thin film having a uniform film quality such as high crystallinity can be formed.

  FIG. 2 to FIG. 9 show a schematic configuration of a metal oxide film manufacturing apparatus for performing the metal oxide film manufacturing method according to the second to ninth embodiments of the present invention. In addition, the same code | symbol is attached | subjected to the same kind member as the metal oxide film production apparatus shown in FIG. 1, and the overlapping description is abbreviate | omitted.

<Second Embodiment>
In the metal oxide 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, hafnium (Hf) is used as the material of the member 26 to be etched. However, the material is not limited to this, and iridium (Ir), titanium (Ti), zirconium (Zr), tantalum (depending on the oxide film to be formed) It may be formed of Ta) or copper (Cu).

  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 oxide film manufacturing apparatus according to this embodiment, a source gas containing oxygen gas and a chlorine gas as a halogen gas is supplied into the chamber 1 from the nozzle 12, and an electromagnetic wave is incident from the plasma antenna 27 into the chamber 1. Thus, chlorine gas and oxygen gas are ionized to generate chlorine gas plasma or oxygen gas plasma. These plasmas are generated in the region shown by the gas plasma 14. Each plasma causes an etching reaction in the member 26 to be etched, and the HfO ₂ 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. Each 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 oxide 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 oxide 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 oxide film manufacturing apparatus according to this embodiment, a source gas containing oxygen gas and a chlorine gas as a halogen gas is supplied into the chamber 1 from the nozzle 12, and an electrostatic field is supplied from the member 7 to be etched into the chamber 1. As a result, chlorine gas and oxygen gas are ionized to generate chlorine gas plasma or oxygen gas plasma. These plasmas are generated in the region shown by the gas plasma 14. Each plasma causes an etching reaction in the member 7 to be etched, and the HfO ₂ thin film 16 is formed by the same action as in the first embodiment.

  In the metal oxide film manufacturing apparatus according to the present embodiment, since the member to be etched 7 itself is applied as an electrode for plasma generation, 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 oxide 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 a ceiling plate 29 made of ceramics (made of an insulating material), for example. 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.

  In this embodiment, hafnium (Hf) is used as the material of the member 30 to be etched. However, the material is not limited to this, and iridium (Ir), titanium (Ti), zirconium (Zr), tantalum (depending on the oxide film to be formed) It may be formed of Ta) or copper (Cu).

  A slit-shaped opening 31 is formed around the cylindrical portion of the chamber 1 at substantially the same height as the member to be etched 30, 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. Flow rate controllers 20 and 13 are connected to the other end side of the passage 32, oxygen gas enters the passage 32 through the flow rate controller 20, and chlorine gas as halogen gas enters the passage 32 through the flow rate controller 13. A source gas containing is supplied. Hereinafter, a part composed of 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 is referred to as an “outside chamber plasma generation chamber”.

Hereinafter, the mechanism that acts on the member to be etched 30 will be described using the raw material gas as an example. The source gas supplied into the passage 32 via the flow rate controller 13 is sent into the excitation chamber 33. Next, electromagnetic waves are incident on the inside of the excitation chamber 33 from the plasma antenna 34 to ionize the chlorine gas and generate a chlorine gas plasma (raw material gas plasma) 35. Since a predetermined differential pressure is set between the pressure in the chamber 1 and the pressure in the excitation chamber 33 by the vacuum device 8, chlorine radicals in the chlorine gas plasma 35 in the excitation chamber 33 are etched from the opening 31 in the chamber 1. Sent to member 30. This chlorine radical causes an etching reaction in the member 30 to be etched. On the other hand, oxygen gas plasma is also generated in a region shown by gas plasma 35 in the same manner, and is sent into the chamber 1 to etch the member 30 to be etched. Thereafter, the HfO ₂ thin film 16 is formed on the substrate 3 by the same reaction as in the first embodiment.

  In the metal oxide film manufacturing apparatus according to the present embodiment, each gas plasma is generated in the excitation chamber 33 isolated from the chamber 1 (provided outside the chamber 1), so that the substrate 3 is exposed to the plasma. The substrate 3 is not damaged by the plasma. For example, when further film formation is performed on the substrate 3 on which a film of another material is formed in the previous process, the next film formation can be performed without damaging the film of the material formed in the previous process. . As a means for generating each gas plasma in the excitation chamber 33, it is also possible to use a microwave, a laser, an electron beam, emitted light, or the like.

  In the first to fourth embodiments, the halogen gas supply means for supplying the source gas (containing halogen gas) and the oxygen gas supply means for supplying oxygen gas are integrated into one supply means (for example, FIG. 1). Shows an example in which both gases are supplied from the nozzle 12. However, the present invention is not limited to this. For example, a nozzle that supplies a source gas and a nozzle that supplies an oxygen gas may be installed separately. In this case, in the apparatus according to the fourth embodiment, as will be described in detail later (the eighth embodiment according to FIG. 8), an excitation chamber dedicated to source gas and an excitation chamber dedicated to oxygen gas are provided. By separately providing both gas supply means, the supply control of both gases can be performed with high accuracy.

<Fifth Embodiment>
The metal oxide film manufacturing apparatus according to the fifth embodiment shown in FIG. 5 is an example to which the first embodiment shown in FIG. 1 is applied. Compared with the metal oxide film manufacturing apparatus shown in FIG. An oxygen gas supply means for supplying oxygen gas and a halogen gas supply means for supplying source gas (containing halogen gas) are installed independently, and when oxygen gas is supplied, it is converted into plasma and supplied into the chamber in advance. It is different in that it can be done.

  In this embodiment, the “outside-chamber plasma generation chamber” described in the fourth embodiment is installed exclusively for oxygen gas, and is converted into plasma before oxygen gas is supplied into the chamber 1 to generate oxygen gas plasma. It is supplied so as to cover the substrate 3. The source gas is supplied from the nozzle 12 into the chamber 1 separately from the oxygen gas plasma, and is converted into plasma by the action of electromagnetic waves incident from the plasma antenna 9.

<Sixth Embodiment>
The metal oxide film manufacturing apparatus according to the sixth embodiment shown in FIG. 6 is an example to which the second embodiment shown in FIG. 2 is applied. Compared with the metal oxide film manufacturing apparatus shown in FIG. An oxygen gas supply means for supplying oxygen gas and a halogen gas supply means for supplying source gas (containing halogen gas) are installed independently, and when oxygen gas is supplied, it is converted into plasma and supplied into the chamber in advance. It is different in that it can be done.

  In this embodiment, the “outside-chamber plasma generation chamber” described in the fourth embodiment is installed exclusively for oxygen gas, and is converted into plasma before oxygen gas is supplied into the chamber 1 to generate oxygen gas plasma. It is supplied so as to cover the substrate 3. The source gas is supplied from the nozzle 12 into the chamber 1 separately from the oxygen gas plasma, and is converted into plasma by the action of electromagnetic waves incident from the plasma antenna 27.

<Seventh Embodiment>
The metal oxide film manufacturing apparatus according to the seventh embodiment shown in FIG. 7 is an example to which the third embodiment shown in FIG. 3 is applied. Compared with the metal oxide film manufacturing apparatus shown in FIG. An oxygen gas supply means for supplying oxygen gas and a halogen gas supply means for supplying source gas (containing halogen gas) are installed independently, and when oxygen gas is supplied, it is converted into plasma and supplied into the chamber in advance. It is different in that it can be done.

  In this embodiment, the “outside-chamber plasma generation chamber” described in the fourth embodiment is installed exclusively for oxygen gas, and is converted into plasma before oxygen gas is supplied into the chamber 1 to generate oxygen gas plasma. It is supplied so as to cover the substrate 3. The source gas is supplied from the nozzle 12 into the chamber 1 separately from the oxygen gas plasma, and is converted into plasma by the action of an electrostatic field incident from the member 7 to be etched.

<Eighth Embodiment>
The metal oxide film manufacturing apparatus according to the eighth embodiment shown in FIG. 8 is an example to which the fourth embodiment shown in FIG. 4 is applied. Compared with the metal oxide film manufacturing apparatus shown in FIG. The difference is that the oxygen gas supply means for supplying oxygen gas and the halogen gas supply means for supplying raw material gas (containing halogen gas) are installed independently.

  In this embodiment, an “outside chamber plasma generation chamber” dedicated to oxygen gas and an “outside chamber plasma generation chamber” dedicated to source gas are installed, and oxygen gas is converted into plasma separately from source gas, and substrate 3 is Oxygen gas plasma is supplied so as to cover it. The source gas is turned into plasma in the excitation chamber 33 and supplied to the member to be etched 30.

The film forming mechanism of the HfO ₂ thin film 16 in the fifth to eighth embodiments is basically the same as the film forming mechanism described in the first to fourth embodiments. However, when oxygen gas is supplied from the “outside chamber plasma generation chamber” so as to cover the substrate 3 as oxygen gas plasma, etching of the members 7 and 26 to be etched by oxygen gas radicals (formula (4)) and Subsequent film formation reactions (formulas (6) and (7)) are unlikely to occur. On the other hand, the oxidation reaction of the precursor HfCl ₂ (the above formula (11)), particularly the oxidation reaction of the precursor HfCl ₂ adsorbed on the substrate 3 generated near the substrate 3 (the above formula (8)) and the oxidation reaction of Hf alone ( The above equation (10)) is considered to increase the probability of occurrence.

  In the fifth to eighth embodiments, the supply means for the chlorine gas and the oxygen gas is separately provided, so that the supply control of both gases can be performed with high accuracy. Furthermore, since oxygen gas is converted into plasma in advance and sprayed directly onto the substrate 3, a thin film of metal oxide can be efficiently formed. If power supply to the plasma antenna 34 ′ is stopped, oxygen gas can be contributed to the film forming reaction.

<Ninth Embodiment>
The metal oxide film manufacturing apparatus according to the ninth embodiment shown in FIG. 9 is an example to which the second embodiment shown in FIG. 2 is applied. Compared with the metal oxide film manufacturing apparatus shown in FIG. An oxygen gas supply means (gas ring 40, etc.) for supplying oxygen gas and a halogen gas supply means (nozzle 12, etc.) for supplying source gas (containing halogen gas) are installed independently, and the oxygen gas supply means is a substrate. It differs in that it is a ring-shaped pipe arranged around the.

  A gas ring 40 of a ring-shaped pipe is provided around the support base 2 inside the chamber 1 to form a gas flow path, and oxygen gas is sent to the gas ring 40 from the outside of the apparatus. In addition, the gas ring 40 shown in FIG. 9 is a sectional side view, and the pipe which becomes a gas flow path is shown in a circular shape. The gas ring 40 is provided with a large number of ejection holes as gas nozzles in the circumferential direction on the inner diameter side of the ring, and oxygen gas is sent to the gas ring 40 so that oxygen gas is ejected from the ejection holes toward the substrate 3. ing.

  Further, the gas ring 40 is made of a conductor, and a high frequency current is supplied from the power source 11 via the matching unit 10. On the other hand, the substrate 3 is grounded, and an electrostatic field is generated between the gas ring 40 and the substrate 3 by supplying power to the gas ring 40.

In the present embodiment, the source gas supplied from the nozzle 12 toward the member to be etched 26 contributes to the formation of the HfO ₂ thin film 16 by the same action as the source gas in the second embodiment. On the other hand, oxygen gas is supplied from the gas ring 40 toward the substrate 3 and is converted into plasma by the action of an electrostatic field generated by power supply to the gas ring 40. As a result, oxygen gas plasma (capacitive coupling) is formed around the substrate 3. Type plasma). Thereby, the HfO ₂ thin film 16 can be efficiently formed.

The film forming mechanism of the HfO ₂ thin film 16 in this embodiment is basically the same as that in the second embodiment. However, since oxygen gas plasma is generated around the substrate 3, the etching of the member 26 to be etched by oxygen gas radicals (formula (4)) and subsequent film formation reactions (formulas (6) and (7)) are performed. Is unlikely to occur. On the other hand, an oxidation reaction of the precursor HfCl ₂ generated by the chlorine gas radical (the above formula (11)), particularly an oxidation reaction of the precursor HfCl ₂ adsorbed on the substrate 3 generated in the vicinity of the substrate 3 (the above formula (8)) and It is considered that the oxidation reaction of Hf alone (the above formula (10)) is likely to occur.

In the case where oxygen gas is supplied without supplying power to the gas ring 40, the oxygen gas is not converted into plasma and is involved in the film forming reaction as oxygen gas. Also in this case, the HfO ₂ thin film 16 having a uniform film quality can be formed as in the first embodiment.

  Further, the oxygen gas can be converted into plasma even if one place in the circumferential direction of the gas ring 40 is insulated and one side is connected to the power supply 11 side with the insulating portion interposed therebetween and the other side is grounded. In this case, inductively coupled oxygen gas plasma can be generated between the gas ring 40 and the substrate 3.

  Furthermore, the halogen gas (chlorine gas) may be supplied into the chamber by making the shape of the nozzle 12 as the halogen gas supply means like the gas ring 40. In this case, the direction of the ejection holes provided in the circumferential direction on the inner diameter side of the ring is preferably directed toward the member to be etched so that the chlorine gas plasma generated from the source gas can etch the member 26 to be etched. .

Although the second to ninth embodiments have been described in detail above, the obtained HfO ₂ thin film has a stable elemental composition in the _second to ninth embodiments 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 ninth embodiments, it is possible to form the HfO ₂ thin film 16 having a uniform film quality and obtaining desired film characteristics.

Also, in the second to ninth embodiments, as in the first embodiment, the example in which the source gas (containing chlorine gas) and the oxygen gas are simultaneously supplied by the gas supply control means has been described. It is not something that can be done. That is, when the source gas is supplied for the first predetermined time and then the oxygen gas is supplied for the second predetermined time, or after the source gas is supplied for the first predetermined time, the oxygen gas is supplied alternately for the second predetermined time. Even when supplied, the HfO ₂ thin film 16 having a uniform film quality can be similarly formed. The mechanism for forming the HfO ₂ thin film 16 in this case is as described in the first embodiment.

Also, in the second to ninth embodiments (excluding the fourth embodiment), as in the first embodiment, an example was shown in which film formation was performed by generating chlorine gas plasma and oxygen gas plasma. However, it is not limited to this. That is, the HfO ₂ thin film 16 having a uniform film quality can be formed as in the first embodiment even if oxygen gas is not converted into plasma and contributes to film formation in the state of oxygen gas. In the fourth embodiment, due to the nature of the apparatus, oxygen gas cannot be converted into plasma, and chlorine gas cannot be converted into plasma and these cannot be supplied simultaneously. However, in the apparatus according to the fourth embodiment, when the timing for supplying oxygen gas and chlorine gas plasma is changed, it is possible to use oxygen gas that is not converted to plasma and is uniform as in the first embodiment. The HfO ₂ thin film 16 having a film quality can be formed.

Also in the second to ninth embodiments, as in the first embodiment, the chlorine gas plasma is not generated (the source gas is not supplied), and only the oxygen gas plasma is used in the first embodiment. Similarly, the HfO ₂ thin film 16 having a uniform film quality can be formed.

  Also, in the second to ninth embodiments, as in the first embodiment, the chlorine gas diluted with He, Ar, etc. is 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 oxygen gas.

  Next, a metal nitride film manufacturing method and a metal nitride film manufacturing apparatus according to an embodiment of the present invention will be described based on 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.

<Tenth Embodiment>
A metal nitride film manufacturing method and a metal nitride film manufacturing apparatus according to the tenth embodiment will be described with reference to FIG. FIG. 10 shows a schematic side view of a metal nitride film production apparatus for performing the metal nitride film production method according to the tenth embodiment of the present invention.

  As shown in FIG. 10, 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 set to a predetermined temperature (for example, a temperature at which the substrate 3 is maintained at 100 ° C. to 200 ° C.) by the temperature control means 6. ) 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, a metal nitride film manufacturing method and a metal nitride film manufacturing apparatus according to the eleventh to thirteenth embodiments of the present invention will be described with reference to FIGS. 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. 11 to FIG. 13 show a schematic configuration of a metal nitride film manufacturing apparatus for performing the metal nitride film manufacturing method according to the eleventh to thirteenth embodiments of the present invention. In addition, the same code | symbol is attached | subjected to the same kind member as the metal nitride film production apparatus shown in FIG. 10, and the overlapping description is abbreviate | omitted.

<Eleventh embodiment>
In the metal nitride film manufacturing apparatus according to the eleventh embodiment shown in FIG. 11, 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 tenth 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 to be etched 26, and the TiN thin film 16 is formed by the same action as in the tenth 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.

<Twelfth Embodiment>
In the metal nitride film manufacturing apparatus according to the twelfth embodiment shown in FIG. 12, 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 tenth 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 tenth 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. 10) is not required around the cylindrical portion of the chamber 1, The degree of freedom of surrounding configuration can be increased.

<13th Embodiment>
In the metal nitride film manufacturing apparatus according to the thirteenth embodiment shown in FIG. 13, the upper surface of the chamber 1 is an opening, and the opening is closed by a ceiling plate 29 made of, for example, ceramics (made of an insulating material). 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.

  Although the eleventh to thirteenth embodiments have been described in detail above, in the eleventh to thirteenth embodiments as well, the obtained TiN thin film has a stable elemental composition as in the tenth embodiment. As a result of X-ray analysis, it was found that the thin film has high crystallinity. That is, according to the eleventh to thirteenth embodiments, the TiN thin film 16 having a uniform film quality and capable of obtaining desired film characteristics can be formed.

  Also, in the eleventh to thirteenth embodiments, as in the tenth 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 described. Is not something 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 tenth embodiment.

  Also, in the eleventh to thirteenth embodiments, as in the tenth embodiment, an example of forming a film by generating chlorine gas plasma and nitrogen gas plasma has been shown, but 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 tenth 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 eleventh to thirteenth embodiments, as in the tenth embodiment, the tenth embodiment is performed using only nitrogen gas plasma without generating chlorine gas plasma (without supplying raw material gas). Similarly, a TiN thin film 16 having a uniform film quality can be formed.

  In the eleventh to thirteenth embodiments, as in the tenth embodiment, the chlorine gas diluted with He, Ar, or the like is 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 tenth to thirteenth 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 tenth to thirteenth embodiments, 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, as will be described in the first to third embodiments, a metal nitride film can be formed in the same manner even if plasma is generated in the chamber by plasma generating means for converting the chamber into plasma. In the tenth to thirteenth embodiments, an example in which the halogen gas supply means and the nitrogen gas supply means are provided independently has been described. However, by providing the halogen gas and nitrogen gas supply means 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 tenth to thirteenth embodiments, the shape of the halogen gas supply means indicated by the nozzle 12 has been described as an example, and the nitrogen gas supply means has been described as the “outside chamber plasma generation chamber” type, but this is not a limitation. Absent. For example, as shown in the ninth embodiment, a metal nitride film can be similarly formed even when a halogen gas supply unit or a nitrogen gas supply unit is formed as a ring-shaped pipe disposed around a substrate. 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.

It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 1st Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 2nd Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 3rd Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 4th Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 5th Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 6th Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 7th Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which implements the metal oxide film preparation method concerning the 8th Embodiment of this invention. It is a schematic side view of the metal oxide film preparation apparatus which enforces the metal oxide film preparation method concerning the 9th Embodiment of this invention. It is a schematic side view of the metal nitride film preparation apparatus which enforces the metal nitride film preparation method concerning the 10th Embodiment of this invention. It is a schematic side view of the metal nitride film preparation apparatus which enforces the metal nitride film preparation method concerning the 11th Embodiment of this invention. It is a schematic side view of the metal nitride film preparation apparatus which enforces the metal nitride film preparation method concerning the 12th Embodiment of this invention. It is a schematic side view of the metal nitride film preparation apparatus which enforces the metal nitride film preparation method concerning the 13th 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, 34 'Plasma antenna 10, 10' Matching device 11, 11 'Power supply 12 Nozzles 13, 20 Flow controllers 14, 35 Gas plasma 15 Precursor 16 HfO ₂ thin film 17 Exhaust port 25, 29 Ceiling plate 31, 31 ′ Opening 32, 32 ′ Passage 33, 33 ′ Excitation chamber 40 Gas ring

Claims (38)

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, a nitrogen nitride film supplied to the chamber is converted into plasma to generate nitrogen gas plasma, and a metal nitride film is formed on the substrate. 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,
Furthermore, nitrogen gas is supplied into the chamber, and a metal nitride film is formed on the substrate. In the method for producing a metal nitride film according to claim 1,
A method for producing a metal nitride film, wherein the nitrogen gas plasma forms at least one of the following steps A, B, and C to form a metal nitride 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.
Step C: A step of forming a precursor of a metal component and nitrogen gas by etching the member to be etched. In the method for producing a metal nitride film according to claim 2,
A method for producing a metal nitride film, wherein the nitrogen gas forms at least one of the following steps A and B to form a metal nitride 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. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 4],
A metal nitride film manufacturing method, wherein the halogen gas and the nitrogen gas are respectively supplied into the chamber from independent supply means. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 4],
A metal nitride film manufacturing method, characterized in that the halogen gas and nitrogen gas are supplied into the chamber from the same one supply means. In the metal nitride film manufacturing method according to [Claim 5] or [Claim 6],
A metal nitride film manufacturing method, wherein nitrogen gas is supplied after supplying halogen gas. In the metal nitride film manufacturing method according to [Claim 5] or [Claim 6],
A method for producing a metal nitride film, comprising alternately repeating the order of supplying nitrogen gas after supplying halogen gas. In the metal nitride film manufacturing method according to [Claim 5] or [Claim 6],
A method for producing a metal nitride film, wherein a halogen gas and a nitrogen gas are supplied simultaneously. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 9],
At least one of the halogen gas plasma and the nitrogen gas plasma is inductively coupled plasma. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 9],
At least one of the halogen gas plasma and the nitrogen gas plasma is a capacitively coupled plasma. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 9],
A method for producing a metal nitride film, wherein at least one of the halogen gas plasma and the nitrogen gas plasma is a hybrid plasma comprising inductively coupled plasma and capacitively coupled plasma. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 12],
At least one of the halogen gas plasma and the nitrogen gas plasma is a plasma that has been converted into plasma outside the chamber and supplied into the chamber in advance. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 13],
The metal nitride film manufacturing method, wherein the metal is at least one metal selected from the group consisting of tantalum, tungsten, titanium, and silicon. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 14],
A method for producing a metal nitride film, wherein the halogen is chlorine. 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,
An apparatus for producing a metal nitride film, comprising: 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 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. In the metal nitride film manufacturing apparatus according to any one of [Claim 17] to [Claim 20],
The metal nitride film manufacturing apparatus, wherein the halogen gas supply means and the nitrogen gas supply means are independent supply means. In the metal nitride film manufacturing apparatus according to any one of [Claim 17] to [Claim 20],
An apparatus for producing a metal nitride film, wherein 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. In the metal nitride film manufacturing apparatus according to [Claim 21] or [Claim 22],
The metal nitride film manufacturing method further comprises gas supply control means for supplying the 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. apparatus. In the metal nitride film manufacturing apparatus according to [Claim 21] or [Claim 22],
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. Metal nitride film production equipment. In the metal nitride film manufacturing apparatus according to [Claim 21] or [Claim 22],
Furthermore, a metal nitride film manufacturing apparatus comprising gas supply control means for simultaneously supplying the halogen gas and the nitrogen gas. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. 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,
An apparatus for producing a metal nitride film, comprising depositing a metal nitride on the substrate. [Claim 16] to [Claim 25], [Claim 28], [Claim 31]
The nitrogen gas supply means includes 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. Metal film production equipment. In the metal nitride film production apparatus according to 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. An apparatus for producing a metal nitride film, wherein capacitively coupled nitrogen gas plasma is generated between the substrate and the substrate by feeding. In the metal nitride film production apparatus according to 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. An apparatus for producing a metal nitride film, wherein at least one portion 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 power feeding. [Claim 16] In the metal nitride film manufacturing apparatus according to any one of [Claim 34],
The metal nitride film manufacturing apparatus, wherein the metal is at least one metal selected from the group consisting of tantalum, tungsten, titanium, and silicon. In the metal nitride film manufacturing apparatus according to any one of [Claim 17] to [Claim 35],
The metal nitride film manufacturing apparatus, wherein the halogen is chlorine. In the method for producing a metal nitride film according to any one of [Claim 1] to [Claim 15],
A metal nitride film manufacturing method, wherein the metal is copper. [Claim 16] In the metal nitride film manufacturing apparatus according to any one of [Claim 36],
The metal nitride film manufacturing apparatus, wherein the metal is copper.

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