Anodes for electroplating operations, and methods of forming materials over semiconductor substrates

Abstract

The invention includes anodes for electroplating, baths. The anodes have a purity of at least 99.9%, and comprise one or more of silver, gold, nickel, chromium, copper or various solder compositions. The anodes can, for example, comprise at least 99.995% copper/phosphorus alloy, by weight; or at least 99.995% nickel and sulfur, by weight. The invention also includes methods of electroplating, materials over semiconductor substrates.

1 . An anode for an electroplating bath comprising a total number of grains therein, and wherein at least 25% of the total number of grains have a common crystallographic texture as one another, and wherein the common crystallographic texture is (001).  
     
     
         2 . The anode of  claim 1  wherein at least 50% of the total number of grains have the common crystallographic texture as one another.  
     
     
         3 . The anode of  claim 1  wherein at least 75% of the total number of grains have the common crystallographic texture as one another.  
     
     
         4 . The anode of  claim 1  wherein at least 90% of the total number of grains have the common crystallographic texture as one another.  
     
     
         5 . The anode of  claim 1  comprising an HCP metal.  
     
     
         6 . The anode of  claim 1  comprising cobalt.  
     
     
         7 . An anode for an electroplating bath comprising an average grain size of less than 100 micrometers.  
     
     
         8 . The anode of  claim 7  comprising an average grain size of less than 50 micrometers.  
     
     
         9 . The anode of  claim 7  comprising an average grain size of less than 10 micrometers.  
     
     
         10 . The anode of  claim 7  comprising an average grain size of less than 1 micrometer.  
     
     
         11 . The anode of  claim 7  comprising predominantly one or more of silver, gold, nickel, cobalt and chromium by weight.  
     
     
         12 . An anode for an electroplating bath and having an alpha particle emission rate of less than 0.1 counts/(cm 2  hr).  
     
     
         13 . The anode of  claim 12  having an alpha particle emission rate of less than 0.02 counts/(cm 2  hr).  
     
     
         14 . The anode of  claim 12  having an alpha particle emission rate of less than 0.002 counts/(cm 2  hr).  
     
     
         15 . The anode of  claim 12  comprising less than 3 ppb total of thorium and uranium.  
     
     
         16 . The anode of  claim 12  comprising less than 1 ppb total of thorium and uranium.  
     
     
         17 . The anode of  claim 12  comprising less than 0.5 ppb total of thorium and uranium.  
     
     
         18 . The anode of  claim 12  comprising one or more of bismuth, silver, tin, lead, copper, nickel, chromium, and cobalt.  
     
     
         19 . An anode for an electroplating bath, the anode comprising at least 99.99% of silver, gold, nickel, chromium or cobalt, by weight.  
     
     
         20 . The anode of  claim 19  comprising at least 99.99% silver.  
     
     
         21 . The anode of  claim 19  comprising at least 99.99% gold.  
     
     
         22 . The anode of  claim 19  comprising at least 99.99% chromium.  
     
     
         23 . The anode of  claim 19  comprising at least 99.99% cobalt.  
     
     
         24 . The anode of  claim 19  comprising at least 99.99% nickel.  
     
     
         25 . The anode of  claim 19  comprising less than 3 parts per billion of uranium, and further comprising less than 3 parts per billion of thorium.  
     
     
         26 . The anode of  claim 19  comprising an average grain size of less than 100 micrometers.  
     
     
         27 . The anode of  claim 19  comprising an average grain size of less than 50 micrometers.  
     
     
         28 . The anode of  claim 19  comprising an average grain size of less than 10 micrometers.  
     
     
         29 . The anode of  claim 19  comprising an average grain size of less than 1 micrometer.  
     
     
         30 . The anode of  claim 19  comprising at least 99.995% nickel, by weight.  
     
     
         31 . The anode of  claim 30  comprising an average grain size of less than 100 micrometers.  
     
     
         32 . The anode of  claim 30  comprising an average grain size of less than 50 micrometers.  
     
     
         33 . The anode of  claim 30  comprising an average grain size of less than 10 micrometers.  
     
     
         34 . The anode of  claim 30  comprising an average grain size of less than 1 micrometer.  
     
     
         35 . The anode of  claim 30  comprising at least 99.9995% nickel.  
     
     
         36 . An anode for an electroplating bath comprising at least 99.999% copper, by weight.  
     
     
         37 . The anode of  claim 36  comprising at least 99.9995% copper.  
     
     
         38 . The anode of  claim 36  comprising an average grain size of less than 100 micrometers.  
     
     
         39 . The anode of  claim 36  comprising an average grain size of less than 50 micrometers.  
     
     
         40 . The anode of  claim 36  comprising an average grain size of less than 10 micrometers.  
     
     
         41 . The anode of  claim 36  comprising an average grain size of less than 1 micrometer.  
     
     
         42 . The anode of  claim 36  comprising less than 3 parts per billion of uranium, and further comprising less than 3 parts per billion of thorium.  
     
     
         43 . An anode comprising at least 99.995%, by weight, copper/phosphorous alloy, and comprising an average grain size of less than 100 micrometers.  
     
     
         44 . The anode of  claim 43  wherein the phosphorus concentration is from about 200 ppm to about 1000 ppm, by weight.  
     
     
         45 . The anode of  claim 43  comprising an average grain size of less than 50 micrometers.  
     
     
         46 . The anode of  claim 43  comprising an average grain size of less than 10 micrometers.  
     
     
         47 . The anode of  claim 43  comprising an average grain size of less than 1 micrometer.  
     
     
         48 . An anode for an electroplating bath comprising at least 99.995% nickel and sulfur, by weight.  
     
     
         49 . The anode of  claim 48  comprising from about 0.01% sulfur to about 5% sulfur, by weight.  
     
     
         50 . The anode of  claim 48  comprising an average grain size of less than 100 micrometers.  
     
     
         51 . The anode of  claim 48  comprising an average grain size of less than 50 micrometers.  
     
     
         52 . The anode of  claim 48  comprising an average grain size of less than 10 micrometers.  
     
     
         53 . The anode of  claim 48  comprising an average grain size of less than 1 micrometer.  
     
     
         54 . An anode for an electroplating bath comprising a solder composition having a purity of at least 99.999%, by weight; said solder composition comprising one or more elements selected from the group consisting of tin, antimony, lead, silver, copper and bismuth.  
     
     
         55 . The anode of  claim 54  comprising an average grain size of less than 30 micrometers.  
     
     
         56 . The anode of  claim 54  comprising an average grain size of less than 10 micrometers.  
     
     
         57 . The anode of  claim 54  comprising an average grain size of less than 5 micrometers.  
     
     
         58 . The anode of  claim 54  comprising an average grain size of less than 1 micrometer.  
     
     
         59 . The anode of  claim 54  comprising at least 99.9995% solder.  
     
     
         60 . The anode of  claim 54  comprising less than 3 parts per billion of uranium, and further comprising less than 3 parts per billion of thorium.  
     
     
         61 . The anode of  claim 54  comprising at least 99.999% tin.  
     
     
         62 . The anode of  claim 54  wherein the solder composition comprises tin and antimony.  
     
     
         63 . The anode of  claim 54  wherein the solder composition comprises tin and lead.  
     
     
         64 . The anode of  claim 54  wherein the solder composition comprises tin and silver.  
     
     
         65 . The anode of  claim 54  wherein the solder composition comprises tin, silver and copper.  
     
     
         66 . The anode of  claim 54  wherein the solder composition comprises silver and bismuth.  
     
     
         67 . The anode of  claim 54  wherein the solder composition comprises tin and copper.  
     
     
         68 . A method of forming materials over a semiconductor substrate, comprising: 
 providing a semiconductor substrate having a wiring layer thereon;    electrolytically depositing at least one of silver and nickel over the wiring layer; any silver being deposited from an anode that is at least 99.995% pure in silver; and any nickel being deposited from an anode that is either at least 99.995% pure in nickel, or at least 99.995% pure in nickel and sulfur, with the sulfur being present to a concentration of from about 0.01% to about 5%, by weight; and    forming a solder over the at least one of silver and nickel.    
     
     
         69 . The method of  claim 68  wherein the wiring layer comprises copper, and is formed by electrolytic deposition utilizing an anode that is either at least 99.999% copper, by weight, or at least 99.995% copper/phosphorous alloy, with the phosphorus concentration being from about 200 ppm to about 1000 ppm, by weight.  
     
     
         70 . The method of  claim 68  wherein the solder is formed by electrolytic deposition utilizing an anode that comprises a solder composition having a purity of at least 99.999%, by weight; said solder composition comprising one or more elements selected from the group consisting of tin, antimony, lead, silver, copper and bismuth.  
     
     
         71 . The method of  claim 68  wherein the electrolytic deposition forms nickel over the wiring layer; the electrolytic deposition occurs in a bath, and the bath is initially charged with metallic materials that are either at least 99.995% pure in nickel, or at least 99.995% pure in nickel and sulfur, with the sulfur being present to a concentration of from about 0.01% to about 5%, by weight.  
     
     
         72 . The method of  claim 68  wherein the electrolytic deposition forms silver over the wiring layer; the electrolytic deposition occurs in a bath, and the bath is initially charged with particulates that are at least 99.995% pure in silver.