Barrier metal film production apparatus, barrier metal film production method, metal film production method, and metal film production apparatus

Abstract

A Cl 2 gas plasma is generated at a site within a chamber between a substrate and a metal member. The metal member is etched with the Cl 2 gas plasma to form a precursor. A nitrogen gas is excited in a manner isolated from the chamber accommodating the substrate. A metal nitride is formed upon reaction between excited nitrogen and the precursor, and formed as a film on the substrate. After film formation of the metal nitride, a metal component of the precursor is formed as a film on the metal nitride on the substrate. In this manner, a barrier metal film with excellent burial properties and a very small thickness is produced at a high speed, with diffusion of metal being suppressed and adhesion to the metal being improved.

1 . A metal film production method involving treatment of a surface of a substrate having a barrier metal film of a metal nitride formed thereon, comprising: 
 performing a surface treatment which removes nitrogen atoms in a superficial layer of the barrier metal film to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film, thereby substantially forming a metal layer on the superficial layer.    
   
   
       2 . A metal film production method involving treatment of a surface of a substrate having a barrier metal film of a metal nitride formed thereon, comprising: 
 performing a surface treatment which removes nitrogen atoms in a superficial layer of the barrier metal film with a rare gas plasma to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film, thereby substantially forming a metal layer on the superficial layer.    
   
   
       3 . A metal film production method involving treatment of a surface of a substrate having a barrier metal film of a metal nitride formed thereon, comprising: 
 performing a surface treatment which etches the surface of the barrier metal film with a rare gas plasma to flatten the barrier metal film;    forming a metal film on the flattened barrier metal.    
   
   
       4 . A metal film production method involving treatment of a surface of a substrate having a barrier metal film of a metal nitride formed thereon, comprising: 
 performing a surface treatment which etches the surface of the barrier metal film with a rare gas plasma to flatten the barrier metal film, and removes nitrogen atoms in a superficial layer of the barrier metal film by the rare gas plasma to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film, thereby substantially forming a metal layer on the superficial layer.    
   
   
       5 . A metal film production method comprising: 
 supplying a source gas containing a halogen to an interior of a chamber between a substrate and a metallic etched member;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas, and also exciting a gas containing nitrogen in a manner isolated from the chamber accommodating the substrate;    forming a metal nitride upon reaction between excited nitrogen and the precursor;    making a temperature of the substrate lower than a temperature of means for formation of the metal nitride to form the metal nitride as a film on the substrate for use as a barrier metal film; and    performing a surface treatment which etches the barrier metal film with a rare gas plasma to flatten the barrier metal film.    
   
   
       6 . A metal film production method comprising: 
 supplying a source gas containing a halogen to an interior of a chamber between a substrate and a metallic etched member;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas, and also exciting a gas containing nitrogen in a manner isolated from the chamber accommodating the substrate;    forming a metal nitride upon reaction between excited nitrogen and the precursor;    making a temperature of the substrate lower than a temperature of means for formation of the metal nitride to form the metal nitride as a film on the substrate for use as a barrier metal film; and    performing a surface treatment which removes nitrogen atoms in a superficial layer of the barrier metal film with a rare gas plasma to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film, thereby substantially forming a metal layer on the superficial layer.    
   
   
       7 . A metal film production method comprising: 
 supplying a source gas containing a halogen to an interior of a chamber between a substrate and a metallic etched member;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas, and also exciting a gas containing nitrogen in a manner isolated from the chamber accommodating the substrate;    forming a metal nitride upon reaction between excited nitrogen and the precursor;    making a temperature of the substrate lower than a temperature of means for formation of the metal nitride to form the metal nitride as a film on the substrate for use as a barrier metal film; and    performing a surface treatment which etches the barrier metal film on a surface of the substrate with a rare gas plasma to flatten the barrier metal film, and removes nitrogen atoms in a superficial layer of the barrier metal film by the rare gas plasma to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film.    
   
   
       8 . A metal film production method comprising: 
 performing a surface treatment which generates a rare gas plasma within a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon, to etch the barrier metal film on a surface of the substrate with the rare gas plasma, thereby flattening the barrier metal film;    then supplying a source gas containing a halogen into the chamber;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that an etched member made of a metal is etched with the source gas plasma to form a precursor within the chamber from a metal component contained in the etched member and the source gas; and    making a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the substrate having the barrier metal film flattened.    
   
   
       9 . A metal film production method comprising: 
 performing a surface treatment which generates a rare gas plasma within a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon, to etch the barrier metal film on a surface of the substrate with the rare gas plasma, thereby flattening the barrier metal film, and removes nitrogen atoms in a superficial layer of the barrier metal film by the rare gas plasma to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film;    then supplying a source gas containing a halogen into the chamber;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that an etched member made of a metal is etched with the source gas plasma to form a precursor within the chamber from a metal component contained in the etched member and the source gas; and    making a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the substrate having the barrier metal film flattened and having the nitrogen content of the superficial layer relatively decreased.    
   
   
       10 . The metal film production method of any one of  claims 1  to  9 , further comprising: 
 applying a densification treatment for densifying metal atoms in a superficial layer of the barrier metal film by heating after flattening the barrier metal film, or relatively decreasing the nitrogen content of the superficial layer, or flattening the barrier metal film and also relatively decreasing the nitrogen content of the superficial layer.    
   
   
       11 . The metal film production method of  claim 2 , wherein the rare gas plasma is an argon gas plasma.  
   
   
       12 . The metal film production method of  claim 1 , wherein the metal nitride is tantalum nitride, tungsten nitride or titanium nitride.  
   
   
       13 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate;    a metallic etched member provided in the chamber at a position opposed to the substrate;    halogen gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    barrier plasma generation means which converts an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas;    excitation means for exciting a gas containing nitrogen in a manner isolated from the chamber;    formation means for forming a metal nitride upon reaction between nitrogen excited by the excitation means and the precursor;    control means which makes a temperature of the substrate lower than a temperature of the formation means to form the metal nitride as a film on the substrate for use as a barrier metal film;    rare gas supply means for supplying a rare gas to a site above a surface of the substrate; and    surface treatment plasma generation means which converts the atmosphere within the chamber into a plasma to generate a rare gas plasma so that the barrier metal film on the surface of the substrate is etched with the rare gas plasma to flatten the barrier metal film.    
   
   
       14 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate;    a metallic etched member provided in the chamber at a position opposed to the substrate;    halogen gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    barrier plasma generation means which converts an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas;    excitation means for exciting a gas containing nitrogen in a manner isolated from the chamber;    formation means for forming a metal nitride upon reaction between nitrogen excited by the excitation means and the precursor;    control means which makes a temperature of the substrate lower than a temperature of the formation means to form the metal nitride as a film on the substrate for use as a barrier metal film;    rare gas supply means for supplying a rare gas to a site above a surface of the substrate; and    surface treatment plasma generation means for performing a surface treatment which converts the atmosphere within the chamber into a plasma to generate a rare gas plasma so that the barrier metal film on the surface of the substrate is etched with the rare gas plasma to flatten the barrier metal film, and removes nitrogen atoms in a superficial layer of the barrier metal film to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film.    
   
   
       15 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon;    rare gas supply means for supplying a rare gas to an interior of the chamber above a surface of the substrate;    surface treatment plasma generation means which converts an atmosphere within the chamber into a plasma to generate a rare gas plasma so that the barrier metal film on the surface of the substrate is etched with the rare gas plasma to flatten the barrier metal film;    a metallic etched member provided in the chamber;    source gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    plasma generation means which converts the source gas containing the halogen into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas; and    control means which makes a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the flattened barrier metal film.    
   
   
       16 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon;    rare gas supply means for supplying a rare gas to an interior of the chamber above a surface of the substrate;    surface treatment plasma generation means which converts an atmosphere within the chamber into a plasma to generate a rare gas plasma so that the barrier metal film on the surface of the substrate is etched with the rare gas plasma to flatten the barrier metal film, and also removes nitrogen atoms in a superficial layer of the barrier metal film by the rare gas plasma to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film;    a metallic etched member provided in the chamber;    source gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    plasma generation means which converts the source gas containing the halogen into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas; and    control means which makes a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the barrier metal film flattened and having the nitrogen content of the superficial layer relatively decreased.    
   
   
       17 . The metal film production apparatus of any one of  claims 13  to  16 , further comprising: 
 densification treatment means for densifying metal atoms in the superficial layer by heating after flattening the barrier metal film, or relatively decreasing the nitrogen content of the superficial layer, or flattening the barrier metal film and also relatively decreasing the nitrogen content of the superficial layer.    
   
   
       18 . The metal film production apparatus of  claim 13 , wherein the rare gas plasma is an argon gas plasma.  
   
   
       19 . The metal film production apparatus of  claim 13 , wherein the metal nitride is tantalum nitride, tungsten nitride or titanium nitride.  
   
   
       20 . A metal film production method involving treatment of a surface of a substrate having a barrier metal film of a metal nitride formed thereon, comprising: 
 performing a surface treatment which reacts the barrier metal film on the surface of the substrate in a reducing gas atmosphere to remove nitrogen atoms in a superficial layer of the barrier metal film so as to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film, thereby substantially forming a metal layer on the superficial layer.    
   
   
       21 . A metal film production method comprising: 
 supplying a source gas containing a halogen to an interior of a chamber between a substrate and a metallic etched member;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas, and also exciting a gas containing nitrogen in a manner isolated from the chamber accommodating the substrate;    forming a metal nitride upon reaction between excited nitrogen and the precursor;    making a temperature of the substrate lower than a temperature of means for formation of the metal nitride to form the metal nitride as a film on the substrate for use as a barrier metal film; and    performing a surface treatment which reacts the barrier metal film on a surface of the substrate in a reducing gas atmosphere to remove nitrogen atoms in a superficial layer of the barrier metal film, thereby decreasing a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film.    
   
   
       22 . A metal film production method comprising: 
 performing a surface treatment in a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon, said surface treatment comprising reacting the barrier metal film on a surface of the substrate in a reducing gas atmosphere to remove nitrogen atoms in a superficial layer of the barrier metal film, thereby decreasing a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film;    then supplying a source gas containing a halogen into the chamber;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that a metallic etched member is etched with the source gas plasma to form a precursor within the chamber from a metal component contained in the etched member and the source gas; and    making a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the substrate having the barrier metal film relatively decreased the nitrogen content of the superficial layer.    
   
   
       23 . The metal film production method of any one of  claims 20  to  22 , wherein the reducing gas atmosphere is a hydrogen gas plasma.  
   
   
       24 . The metal film production method of  claim 20 , wherein the metal nitride is tantalum nitride, tungsten nitride, or titanium nitride.  
   
   
       25 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate;    a metallic etched member provided in the chamber at a position opposed to the substrate;    halogen gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    barrier plasma generation means which converts an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas;    excitation means for exciting a gas containing nitrogen in a manner isolated from the chamber;    formation means for forming a metal nitride upon reaction between nitrogen excited by the excitation means and the precursor;    control means which makes a temperature of the substrate lower than a temperature of the formation means to form the metal nitride as a film on the substrate for use as a barrier metal film;    reducing gas supply means for supplying a reducing gas to a site above a surface of the substrate; and    surface treatment means which reacts the barrier metal film on the surface of the substrate in a reducing gas atmosphere to remove nitrogen atoms in a superficial layer of the barrier metal film, thereby decreasing a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film.    
   
   
       26 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon;    reducing gas supply means for supplying a reducing gas to a site above a surface of the substrate;    surface treatment means which reacts the barrier metal film on the surface of the substrate in a reducing gas atmosphere to remove nitrogen atoms in a superficial layer of the barrier metal film, thereby decreasing a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film;    a metallic etched member provided in the chamber;    source gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    plasma generation means which converts the source gas containing the halogen into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas; and    control means which makes a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the barrier metal film having the nitrogen content of the superficial layer relatively decreased.    
   
   
       27 . The metal film production apparatus of  claim 25  or  26 , wherein the reducing gas supply means is means for supplying a gas containing hydrogen, and the surface treatment means is hydrogen gas plasma generation means for generating a hydrogen gas plasma.  
   
   
       28 . The metal film production apparatus  claim 25 , wherein the metal nitride is tantalum nitride, tungsten nitride, or titanium nitride.  
   
   
       29 . A metal film production method comprising: 
 supplying a source gas containing a halogen to an interior of a chamber between a substrate and a metallic etched member;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas, and also exciting a gas containing nitrogen in a manner isolated from the chamber accommodating the substrate;    forming a metal nitride upon reaction between excited nitrogen and the precursor;    making a temperature of the substrate lower than a temperature of means for formation of the metal nitride to form the metal nitride as a film on the substrate for use as a barrier metal film; and    performing a surface treatment which forms nuclei of silicon atoms on a surface of the barrier metal film on a surface of the substrate by a gas plasma containing silicon;    forming a metal film on the barrier metal film having the nuclei of silicon atoms formed on the surface.    
   
   
       30 . A metal film production method comprising: 
 performing a surface treatment in a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon, said surface treatment comprising forming nuclei of silicon atoms on a surface of the barrier metal film on a surface of the substrate by a gas plasma containing silicon;    then supplying a source gas containing a halogen into the chamber;    converting an atmosphere within the chamber into a plasma to generate a source gas plasma so that a metallic etched member is etched with the source gas plasma to form a precursor within the chamber from a metal component contained in the etched member and the source gas; and    making a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the substrate having the nuclei of silicon atoms formed on the surface of the barrier metal film.    
   
   
       31 . The metal film production method of  claim 29  or  30 , wherein the gas containing silicon is a silane.  
   
   
       32 . The metal film production method of  claim 29 , wherein the metal nitride is tantalum nitride, tungsten nitride, or titanium nitride.  
   
   
       33 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate;    a metallic etched member provided in the chamber at a position opposed to the substrate;    halogen gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    barrier plasma generation means which converts an atmosphere within the chamber into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas;    excitation means for exciting a gas containing nitrogen in a manner isolated from the chamber;    formation means for forming a metal nitride upon reaction between nitrogen excited by the excitation means and the precursor;    control means which makes a temperature of the substrate lower than a temperature of the formation means to form the metal nitride as a film on the substrate for use as a barrier metal film;    silicon-containing gas supply means for supplying a gas containing silicon to a site above a surface of the substrate; and    surface treatment plasma generation means which generates a gas plasma containing silicon to form nuclei of silicon atoms on a surface of the barrier metal film on the surface of the substrate before forming a metal film thereon.    
   
   
       34 . A metal film production apparatus, comprising: 
 a chamber accommodating a substrate having a barrier metal film of a metal nitride formed thereon;    silicon-containing gas supply means for supplying a gas containing silicon to a site above a surface of the substrate;    surface treatment plasma generation means which generates a gas plasma containing silicon to form nuclei of silicon atoms on a surface of the barrier metal film on the surface of the substrate;    a metallic etched member provided in the chamber;    source gas supply means for supplying a source gas containing a halogen to an interior of the chamber between the substrate and the etched member;    plasma generation means which converts the source gas containing the halogen into a plasma to generate a source gas plasma so that the etched member is etched with the source gas plasma to form a precursor from a metal component contained in the etched member and the source gas; and    control means which makes a temperature of the substrate lower than a temperature of the etched member to form the metal component of the precursor as a film on the barrier metal film having the nuclei of silicon atoms formed on the surface thereof.    
   
   
       35 . The metal film production apparatus of  claim 33  or  34 , wherein the gas containing silicon is a silane.  
   
   
       36 . The metal film production apparatus of  claim 33 , wherein the metal nitride is tantalum nitride, tungsten nitride, or titanium nitride.  
   
   
       37 . A metal film comprising a metal layer substantially formed on a superficial layer of a barrier metal film of a metal nitride formed on a surface of a substrate with keeping an entire thickness of the barrier metal film, said metal layer being formed by performing a surface treatment which removes nitrogen atoms in the superficial layer of the barrier metal film to decrease a nitrogen content of the superficial layer relative to an interior of a matrix of the barrier metal film.  
   
   
       38 . The metal film of  claim 37 , further comprising irregularities created on the metal layer of the superficial layer by removing nitrogen atoms.