Systems and methods for the electrolytic removal of metals from substrates

Abstract

The present invention provides methods and systems for the electrolytic removal of platinum and/or other of the Group 8-11 metals from substrates.

1 - 40 . (cancelled)  
     
     
         41 . A method for electrochemically removing a metal from a substrate surface with an electrolyte, the method comprising: 
 positioning a substrate comprising a metal-containing surface to interface with an electrolyte, wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 8-11 metal and a combination thereof; and    applying an alternating or bipolar pulsed electrical current between the substrate and the electrolyte.    
     
     
         42 . The method of  claim 41  wherein the substrate is a semiconductor substrate or substrate assembly.  
     
     
         43 . The method of  claim 42  wherein the substrate is a silicon wafer.  
     
     
         44 . The method of  claim 41  wherein the metal-containing surface of the substrate comprises a metal selected from the group consisting of a Group 8-11 metal, and a combination thereof, which is in elemental form or an alloy thereof.  
     
     
         45 . The method of  claim 41  wherein the metal-containing surface of the substrate comprises a metal selected from the group consisting of a Group 8-11 second row metal, a Group 8-11 third row metal, and a combination thereof.  
     
     
         46 . The method of  claim 41  wherein the metal-containing surface of the substrate comprises a metal selected from the group consisting of Co, Rh, Ir, Ni, Pd, Pt, Ru, Os, Au, and Ag.  
     
     
         47 . The method of  claim 46  wherein the metal-containing surface comprises elemental platinum.  
     
     
         48 . The method of  claim 41  wherein the metal is present in an amount of about 50 atomic percent or more.  
     
     
         49 . The method of  claim 41  wherein the metal-containing surface comprises a conductive oxide, silicide, or combination thereof.  
     
     
         50 . The method of  claim 41  wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 8-10 metal and a combination thereof.  
     
     
         51 . The method of  claim 41  wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 11 metal and a combination thereof.  
     
     
         52 . The method of  claim 41  wherein the electrolyte comprises an aqueous solution selected from the group consisting of hydrochloric acid, ammonium hydroxide, acetic acid, sulfuric acid, and phosphoric acid.  
     
     
         53 . The method of  claim 41  wherein the electrolyte has a concentration within a range of about 0.01 Molar to about 12 Molar.  
     
     
         54 . The method of  claim 41  wherein the alternating current has a voltage in a range of about 1 to about 100 volts.  
     
     
         55 . The method of  claim 41  wherein the alternating current has a current in a range of about 0.001 to about 40 Amperes.  
     
     
         56 . A method for electrochemically removing a metal from a substrate surface with an electrolyte, the method comprising: 
 positioning a semiconductor substrate or substrate assembly comprising a metal-containing surface to interface with an electrolyte, wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 8-11 metal and a combination thereof; and    applying an alternating electrical current between the semiconductor substrate or substrate assembly and the electrolyte.    
     
     
         57 . The method of  claim 56  wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 8-10 metal and a combination thereof.  
     
     
         58 . The method of  claim 56  wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 11 metal and a combination thereof.  
     
     
         59 . The method of  claim 56  wherein the electrolyte comprises an aqueous solution selected from the group consisting of hydrochloric acid, ammonium hydroxide, acetic acid, sulfuric acid, and phosphoric acid.  
     
     
         60 . The method of  claim 56  wherein the electrolyte has a concentration within a range of about 0.01 Molar to about 12 Molar.  
     
     
         61 . The method of  claim 56  wherein the alternating current has a voltage in a range of about 1 to about 100 volts.  
     
     
         62 . The method of  claim 56  wherein the alternating current has a current in a range of about 0.001 to about 40 Amperes.  
     
     
         63 . A method for electrochemically removing a metal from a substrate surface with an electrolyte, the method comprising: 
 positioning a semiconductor substrate or substrate assembly comprising a metal-containing surface to interface with an electrolyte, wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 8-11 second row metal, a Group 8-11 third row metal, and a combination thereof; and    applying an alternating or bipolar pulsed electrical current between the semiconductor substrate or substrate assembly and the electrolyte.    
     
     
         64 . The method of  claim 63  wherein the metal is in elemental form or an alloy thereof.  
     
     
         65 . The method of  claim 63  wherein the metal-containing surface comprises elemental platinum.  
     
     
         66 . The method of  claim 63  wherein the metal is present in an amount of about 50 atomic percent or more.  
     
     
         67 . The method of  claim 63  wherein the metal-containing surface comprises a conductive oxide, silicide, or combination thereof.  
     
     
         68 . The method of  claim 63  wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 8-10 metal and a combination thereof.  
     
     
         69 . The method of  claim 63  wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 11 metal and a combination thereof.  
     
     
         70 . The method of  claim 63  wherein the electrolyte comprises an aqueous solution selected from the group consisting of hydrochloric acid, ammonium hydroxide, acetic acid, sulfuric acid, and phosphoric acid.  
     
     
         71 . The method of  claim 63  wherein the electrolyte has a concentration within a range of about 0.01 Molar to about 12 Molar.  
     
     
         72 . The method of  claim 63  wherein the alternating current has a voltage in a range of about 1 to about 100 volts.  
     
     
         73 . The method of  claim 63  wherein the alternating current has a current in a range of about 0.001 to about 40 Amperes.  
     
     
         74 . A method for electrochemically removing a metal from a substrate surface with an electrolyte, the method comprising: 
 positioning a substrate comprising a metal-containing surface to interface with an electrolyte, wherein the metal-containing surface comprises a metal selected from the group consisting of a Group 8-10 second row metal, a Group 8-10 third row metal, and a combination thereof; and    applying an alternating electrical current between the substrate and the electrolyte.    
     
     
         75 . The method of  claim 74  wherein the electrolyte comprises an aqueous solution selected from the group consisting of hydrochloric acid, ammonium hydroxide, acetic acid, sulfuric acid, and phosphoric acid.  
     
     
         76 . The method of  claim 74  wherein the electrolyte has a concentration within a range of about 0.01 Molar to about 12 Molar.  
     
     
         77 . The method of  claim 74  wherein the alternating current has a voltage in a range of about 1 to about 100 volts.  
     
     
         78 . The method of  claim 74  wherein the alternating current has a current in a range of about 0.001 to about 40 Amperes.