Method and composition for fine copper slurry for low dishing in ECMP

Abstract

A method of processing a substrate having a conductive material layer disposed thereon is provided which includes positioning the substrate in a process apparatus and supplying a first polishing composition between to the substrate. The polishing composition comprises phosphoric acid, at least one chelating agent, a corrosion inhibitor, a salt, an oxidizer, abrasive particulates, at least one pH adjusting agent to provide a pH from about 4 to about 7 and a solvent. The method further includes forming a passivation layer on the conductive material layer, abrading the passivation layer to expose a portion of the conductive material layer, applying a first bias to the substrate, and removing at least about 50% of the conductive material layer. The method further includes separating the substrate from the first polishing composition, exposing the substrate to a second polishing composition and a second bias, and continuing to remove the conductive material layer.

1 . A method of processing a substrate having a conductive material layer disposed thereon, comprising: 
 positioning the substrate in a process apparatus;    exposing the substrate to a first polishing composition;    applying a first bias to the substrate;    removing at least 50% of the conductive material layer;    exposing the substrate to a second polishing composition and a second bias; and    continuing to remove the conductive material layer.    
     
     
         2 . The method of  claim 1 , wherein the first polishing composition comprises phosphoric acid, at least one chelating agent, a corrosion inhibitor, a salt, an oxidizer, and abrasive particulates.  
     
     
         3 . The method of  claim 1 , wherein the conductive material layer comprises copper or a copper alloy.  
     
     
         4 . The method of  claim 3 , wherein applying the first bias removes at least about 80% of the conductive material layer.  
     
     
         5 . The method of  claim 3 , wherein the second polishing composition comprises: 
 from about 0.1 wt % to about 5 wt % of phosphoric acid;    from about 0.1 wt % to about 5 wt % of at least one chelating agent; and    from about 0.01 wt % to about 1 wt % of the corrosion inhibitor.    
     
     
         6 . The method of  claim 5 , wherein the at least one chelating agent of the second polishing composition is selected from the group consisting of glycine, ethylenediamine, ethylenediamine tetraacetate, citric acid, ammonium citrate, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         7 . The method of  claim 6 , wherein the corrosion inhibitor of the second polishing composition is selected from the group consisting of benzotriazole, 5-methyl-1-benzotriazole, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         8 . The method of  claim 7 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is glycine.  
     
     
         9 . The method of  claim 7 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is ethylenediamine and ammonium citrate.  
     
     
         10 . The method of  claim 9 , wherein the second polishing composition further comprises polyethylene glycol.  
     
     
         11 . The method of  claim 7 , wherein the second polishing composition further comprises at least one member selected from the group consisting of abrasive particulates, hydrogen peroxide, derivatives thereof, and combinations thereof.  
     
     
         12 . The method of  claim 11 , wherein the second polishing composition comprises at least one pH adjusting agent to provide a pH from about 4 to about 7 and a solvent.  
     
     
         13 . The method of  claim 2 , wherein the first polishing composition has a conductivity in a range from about 30 mS to about 60 mS.  
     
     
         14 . The method of  claim 13 , wherein the second polishing composition has a conductivity in a range from about 15 mS to about 40 mS.  
     
     
         15 . The method of  claim 14 , wherein the first polishing composition comprises: 
 from about 1 wt % to about 10 wt % of phosphoric acid;    from about 0.1 wt % to about 6 wt % of the at least one chelating agent;    from about 0.01 wt % to about 1 wt % of the corrosion inhibitor;    from about 0.5 wt % to about 10 wt % of the salt;    from about 0.2 wt % to about 5 wt % of the oxidizer; and    from about 0.05 wt % to about 1 wt % of the abrasive particulates.    
     
     
         16 . A method of processing a substrate having a conductive material layer disposed thereon, comprising: 
 positioning the substrate in a process apparatus;    exposing the substrate to a first polishing composition comprising phosphoric acid, at least one chelating agent, a corrosion inhibitor, a salt, an oxidizer, and abrasive particulates;    applying a first bias to the substrate;    removing at least 50% of the conductive material layer;    exposing the substrate to a second polishing composition and a second bias; and    continuing to remove the conductive material layer.    
     
     
         17 . The method of  claim 16 , wherein the conductive material layer comprises copper or a copper alloy.  
     
     
         18 . The method of  claim 16 , wherein applying the first bias removes at least about 80% of the conductive material layer.  
     
     
         19 . The method of  claim 17 , wherein the second polishing composition comprises: 
 from about 0.1 wt % to about 5 wt % of phosphoric acid;    from about 0.1 wt % to about 5 wt % of at least one chelating agent; and    from about 0.01 wt % to about 1 wt % of the corrosion inhibitor.    
     
     
         20 . The method of  claim 19 , wherein the at least one chelating agent of the second polishing composition is selected from the group consisting of glycine, ethylenediamine, ethylenediamine tetraacetate, citric acid, ammonium citrate, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         21 . The method of  claim 20 , wherein the corrosion inhibitor of the second polishing composition is selected from the group consisting of benzotriazole, 5-methyl-1-benzotriazole, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         22 . The method of  claim 21 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is glycine.  
     
     
         23 . The method of  claim 21 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is ethylenediamine and ammonium citrate.  
     
     
         24 . The method of  claim 23 , wherein the second polishing composition further comprises polyethylene glycol.  
     
     
         25 . The method of  claim 21 , wherein the second polishing composition further comprises at least one member selected from the group consisting of abrasive particulates, hydrogen peroxide, derivatives thereof, and combinations thereof.  
     
     
         26 . The method of  claim 25 , wherein the second polishing composition comprises at least one pH adjusting agent to provide a pH from about 4 to about 7 and a solvent.  
     
     
         27 . The method of  claim 17 , wherein the first polishing composition has a conductivity in a range from about 30 mS to about 60 mS.  
     
     
         28 . The method of  claim 19 , wherein the second polishing composition has a conductivity in a range from about 15 mS to about 40 mS.  
     
     
         29 . The method of  claim 27 , wherein the first polishing composition comprises: 
 from about 1 wt % to about 10 wt % of phosphoric acid;    from about 0.1 wt % to about 6 wt % of the at least one chelating agent;    from about 0.01 wt % to about 1 wt % of the corrosion inhibitor;    from about 0.5 wt % to about 10 wt % of the salt;    from about 0.2 wt % to about 5 wt % of the oxidizer; and    from about 0.05 wt % to about 1 wt % of the abrasive particulates.    
     
     
         30 . A method of processing a substrate having a conductive material layer disposed thereon, comprising: 
 positioning the substrate in a process apparatus comprising a first electrode and a second electrode;    supplying a first polishing composition between the first electrode and the substrate, wherein the polishing composition comprises phosphoric acid, at least one chelating agent, a corrosion inhibitor, a salt, an oxidizer, abrasive particulates, at least one pH adjusting agent to provide a pH from about 4 to about 7, and a solvent;    forming a passivation layer on the conductive material layer;    abrading the passivation layer to expose a portion of the conductive material layer;    applying a first bias between the first electrode and the second electrode;    removing at least about 50% of the conductive material layer;    separating the substrate from the first polishing composition;    exposing the substrate to a second polishing composition and a second bias; and    continuing to remove the conductive material layer.    
     
     
         31 . The method of  claim 30 , wherein the conductive material layer comprises copper or a copper alloy.  
     
     
         32 . The method of  claim 31 , wherein applying the first bias removes at least about 80% of the conductive material layer.  
     
     
         33 . The method of  claim 31 , wherein the second polishing composition comprises: 
 from about 0.1 wt % to about 5 wt % of phosphoric acid;    from about 0.1 wt % to about 5 wt % of at least one chelating agent; and    from about 0.01 wt % to about 1 wt % of the corrosion inhibitor.    
     
     
         34 . The method of  claim 33 , wherein the at least one chelating agent of the second polishing composition is selected from the group consisting of glycine, ethylenediamine, ethylenediamine tetraacetate, citric acid, ammonium citrate, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         35 . The method of  claim 34 , wherein the corrosion inhibitor of the second polishing composition is selected from the group consisting of benzotriazole, 5-methyl-1-benzotriazole, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         36 . The method of  claim 35 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is glycine.  
     
     
         37 . The method of  claim 35 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is ethylenediamine and ammonium citrate.  
     
     
         38 . The method of  claim 37 , wherein the second polishing composition further comprises polyethylene glycol.  
     
     
         39 . The method of  claim 35 , wherein the second polishing composition further comprises at least one member selected from the group consisting of abrasive particulates, hydrogen peroxide, derivatives thereof and combinations thereof.  
     
     
         40 . The method of  claim 39 , wherein the second polishing composition comprises at least one pH adjusting agent to provide a pH from about 4 to about 7 and a solvent.  
     
     
         41 . The method of  claim 31 , wherein the first polishing composition has a conductivity in a range from about 30 mS to about 60 mS.  
     
     
         42 . The method of  claim 33 , wherein the second polishing composition has a conductivity in a range from about 15 mS to about 40 mS.  
     
     
         43 . The method of  claim 41 , wherein the first polishing composition comprises: 
 from about 1 wt % to about 10 wt % of phosphoric acid;    from about 0.1 wt % to about 6 wt % of the at least one chelating agent;    from about 0.01 wt % to about 1 wt % of the corrosion inhibitor;    from about 0.5 wt % to about 10 wt % of the salt;    from about 0.2 wt % to about 5 wt % of the oxidizer; and    from about 0.05 wt % to about 1 wt % of the abrasive particulates.    
     
     
         44 . A method of processing a substrate having a conductive material layer disposed thereon, comprising: 
 providing the substrate to a process apparatus;    exposing the substrate to a first polishing composition, wherein the first polishing composition comprises: 
 from about 1 wt % to about 10 wt % of phosphoric acid;  
 from about 0.1 wt % to about 6 wt % of at least one chelating agent;  
 from about 0.01 wt % to about 1 wt % of a corrosion inhibitor;  
 from about 0.5 wt % to about 10 wt % of a salt;  
 from about 0.2 wt % to about 5 wt % of an oxidizer;  
 from about 0.05 wt % to about 1 wt % of an abrasive particulates;  
 at least one pH adjusting agent to provide a pH from about 4 to about 7; and  
 a solvent;  
   applying a first bias to the substrate;    removing at least 50% of the conductive material layer; and    exposing the substrate to a second polishing composition and a second bias to continue removing the conductive layer, wherein the second polishing composition comprises: 
 about 0.1 wt % to about 5 wt % of phosphoric acid;  
 from about 0.1 wt % to about 5 wt % of at least one chelating agent; and  
 from about 0.01 wt % to about 1 wt % of the corrosion inhibitor.  
   
     
     
         45 . The method of  claim 44 , wherein the conductive material layer comprises copper or a copper alloy.  
     
     
         46 . The method of  claim 45 , wherein applying the first bias removes at least about 80% of the conductive material layer.  
     
     
         47 . The method of  claim 44 , wherein the at least one chelating agent of the second polishing composition is selected from the group consisting of glycine, ethylenediamine, ethylenediamine tetraacetate, citric acid, ammonium citrate, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         48 . The method of  claim 47 , wherein the corrosion inhibitor of the second polishing composition is selected from the group consisting of benzotriazole, 5-methyl-1-benzotriazole, salts thereof, derivatives thereof, and combinations thereof.  
     
     
         49 . The method of  claim 48 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is ethylenediamine and ammonium citrate.  
     
     
         50 . The method of  claim 48 , wherein the corrosion inhibitor of the second polishing composition is benzotriazole and the at least one chelating agent of the second polishing composition is glycine.  
     
     
         51 . The method of  claim 50 , wherein the second polishing composition further comprises polyethylene glycol.  
     
     
         52 . The method of  claim 48 , wherein the second polishing composition further comprises at least one member selected from the group consisting of abrasive particulates, hydrogen peroxide, derivatives thereof, and combinations thereof.  
     
     
         53 . The method of  claim 52 , wherein the second polishing composition comprises at least one pH adjusting agent to provide a pH from about 4 to about 7 and a solvent  
     
     
         54 . The method of  claim 45 , wherein the first polishing composition has a conductivity in a range from about 30 mS to about 60 mS.  
     
     
         55 . The method of  claim 47 , wherein the second polishing composition has a conductivity in a range from about 15 mS to about 40 mS.  
     
     
         56 . A method of processing a substrate having a conductive material layer disposed thereon, comprising: 
 positioning the substrate in a process apparatus;    exposing the substrate to a first polishing composition with a first conductivity in a range from about 30 mS to about 60 mS and comprising an oxidizer and abrasive particulates;    applying a first bias to the substrate;    exposing the substrate to a second polishing composition with a second conductivity in a range from about 15 mS to about 40 mS;    applying a second bias to the substrate; and    continuing to remove the conductive layer.    
     
     
         57 . A method of processing a substrate having a conductive material layer disposed thereon, comprising: 
 positioning the substrate in a process apparatus;    exposing the substrate to a first polishing composition comprising phosphoric acid, at least one chelating agent, a corrosion inhibitor, a salt, an oxidizer, abrasive particulates, at least one pH adjusting agent to provide a pH from about 4 to about 7, and a solvent;    applying a first bias to the substrate;    exposing the substrate to a second polishing composition comprising phosphoric acid, at least one chelating agent, a corrosion inhibitor, abrasive particulates, at least one pH adjusting agent to provide a pH from about 4 to about 7, and a solvent;    applying a second bias to the substrate; and    continuing to remove the conductive layer.