Barrier chemical mechanical planarization composition and method thereof

Abstract

A barrier chemical mechanical planarization polishing composition is provided that includes the suitable chemical additives. The suitable chemical additives are organic polymer molecules containing ethylene oxide repeating units having the general molecular structure of where n refers to the total numbers of the repeating unit ranging from 6,818 to 181,817; and the molecular weights of polyethylene oxide ranged from 100,000 to 8,000,000. There is also provided a chemical mechanical polishing method using the barrier chemical mechanical planarization polishing composition.

1 . A polishing method for chemical mechanical planarization of a semiconductor substrate having at least one surface having conductive metal lines, vias or trenches, a metal-containing barrier layer and a dielectric layer or low-k on thereof, comprising the steps of:
 c) contacting the at least one surface with a polishing pad;   d) delivering a polishing slurry to the at least one surface, the polishing composition comprising:
 abrasive; 
 organic polymer containing ethylene oxide repeating units having the general molecular structure of 
   
       
         
           
           
               
               
           
         
         
           
             wherein n refers to the total numbers of the repeating unit ranging from 6,818 to 181,817; the organic polymer containing ethylene oxide repeating units having molecular weights ranging from 100,000 to 8,000,000 and concentration ranging from about 5 ppm to about 5,000 ppm; 
           
           oxidizing agent; 
           corrosion inhibitor; and 
           chelator; 
         
         and 
         C) polishing the substrate with the polishing slurry. 
       
     
     
         2 . The method of  claim 1  wherein the organic polymer containing ethylene oxide repeating units having molecular weights ranging from 400,000 to 1,000,000; and concentration ranging from about 25 ppm to about 2,000 ppm. 
     
     
         3 . The method of  claim 1  wherein the abrasive is selected from the group consisting of colloidal silica, alumina, ceria, germania, silica, titania, zirconia, alumina dopes colloidal silica in lattices, organic polymer particles, composite particles comprising organic and inorganic particles, surface modified organic or inorganic particles, and combinations thereof; and is present in an amount ranging from about 0.1% to about 15 wt %. 
     
     
         4 . The method of  claim 1  wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, ammonia, amine compounds, and combinations thereof; and is present in an amount ranging from about 0.01 wt % to about 10 wt %. 
     
     
         5 . The method of  claim 1  wherein the corrosion inhibitor is selected from the group consisting of benzotriazole or benzotriazole derivatives, 3-amino-1,2,4-triazole, 3,5-diamine-1,2,4-triazole, and combinations thereof; and is present in an amount ranging from about 0.001 wt % to about 1.0 wt %. 
     
     
         6 . The method of  claim 1  wherein the chelator is selected from the group consisting of benzosulfonic acid, 4-tolyl sulfonic acid, 2,4-diamino-benzosulfonic acid, itaconic acid, malic acid, malonic acid, tartaric acid, citric acid, oxalic acid, gluconic acid, lactic acid, mandelic acid, and combinations thereof; and is present in an amount ranging from about 0.01 wt % to about 3.0 wt %. 
     
     
         7 . The method of  claim 1  wherein the polishing slurry further comprising a pH adjustor selected from the group consisting of (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, fatty acid, polycarboxylic acid and combinations thereof to lower pH of the polishing slurry; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and combinations thereof to raise pH of the polishing composition; and is present in an amount ranging from about 0.0001 wt % to 2 wt %; and the polishing slurry has a pH from about 2 to about 12. 
     
     
         8 . The method of  claim 1  wherein the polishing composition further comprising a surfactant selected from the group consisting of nonionic, anionic, cationic or amphoteric surfactants, and combinations thereof; and is present in an amount ranging from about 0.0001 wt % to about 1.0 wt % 
     
     
         9 . The method of  claim 1  wherein the conductive metal is copper; the metal-containing barrier layer is a tantalum-containing barrier layer; the dielectric layer is selected from the group consisting of TEOS, and low-k material. 
     
     
         10 . The method of  claim 9  wherein the abrasive is colloidal silica and is present in an amount ranging from about 1 wt % to about 3 wt %; the oxidizing agent is hydrogen peroxide and is present in an amount ranging from about 0.5 wt % to about 2 wt %; the corrosion inhibitor is benzotriazole or benzotriazole derivatives and is present in an amount ranging from about 0.01 wt % to about 0.1 wt %; the chelator is benzosulfonic acid and is present in an amount ranging from about 0.4 wt % to about 1.5 wt %; the organic polymer containing ethylene oxide repeating units having molecular weights ranging from 300,000 to 1,000,000, and concentration ranging from about 50 ppm to about 1,000 ppm; the surfactant is tricosaethylene glycol dodecyl ether and is present in an amount ranging from about 0.010% to about 0.1%; and the slurry has a pH from about 9 to about 11.5. 
     
     
         11 . The method of  claim 10  wherein the polishing composition providing a TaN to TEOS selectivity about 1.5 to about 0.84. 
     
     
         12 . A polishing slurry comprising:
 abrasive;   organic polymer containing ethylene oxide repeating units having the general molecular structure of   
       
         
           
           
               
               
           
         
         
           wherein n refers to the total numbers of the repeating unit ranging from 6,818 to 181,817; and the organic polymer having molecular weights ranging from 100,000 to 8,000,000 and concentration ranging from about 5 ppm to about 5,000 ppm; 
         
         oxidizing agent; 
         corrosion inhibitor; and 
         chelator; 
         wherein the polishing slurry is a barrier chemical mechanical planarization polishing slurry. 
       
     
     
         13 . The slurry of  claim 12  wherein the organic polymer containing ethylene oxide repeating units having molecular weights ranging from 400,000 to 1,000,000; and concentration ranging from about 25 ppm to about 2,000 ppm. 
     
     
         14 . The slurry of  claim 12  wherein the abrasive is selected from the group consisting of colloidal silica, alumina, ceria, germania, silica, titania, zirconia, alumina dopes colloidal silica in lattices, organic polymer particles, composite particles comprising organic and inorganic particles, surface modified organic or inorganic particles, and combinations thereof; and is present in an amount ranging from about 0.1 wt % to about 15 wt %. 
     
     
         15 . The slurry of  claim 12  wherein the oxidizing agent is selected from the group consisting of hydrogen peroxide, periodic acid, potassium iodate, potassium permanganate, ammonium persulfate, ammonium molybdate, ferric nitrate, nitric acid, potassium nitrate, ammonia, amine compounds, and combinations thereof; and is present in an amount ranging from about 0.01 wt % to about 10 wt %. 
     
     
         16 . The slurry of  claim 12  wherein the corrosion inhibitor is selected from the group consisting of benzotriazole or benzotriazole derivatives, 3-amino-1,2,4-triazole, 3,5-diamine-1,2,4-triazole, and combinations thereof; and is present in an amount ranging from about 0.001 wt % to about 1.0 wt %. 
     
     
         17 . The slurry of  claim 12  wherein the chelator is selected from the group consisting of benzosulfonic acid, 4-tolyl sulfonic acid, 2,4-diamino-benzosulfonic acid, itaconic acid, malic acid, malonic acid, tartaric acid, citric acid, oxalic acid, gluconic acid, lactic acid, mandelic acid, and combinations thereof; and is present in an amount ranging from about 0.01 wt % to about 3.0 wt %. 
     
     
         18 . The slurry of  claim 12  wherein the polishing slurry further comprising a pH adjustor selected from the group consisting of (a) nitric acid, sulfuric acid, tartaric acid, succinic acid, citric acid, malic acid, malonic acid, various fatty acids, various polycarboxylic acids and combinations thereof to lower pH of the polishing slurry; and (b) potassium hydroxide, sodium hydroxide, ammonia, tetraethylammonium hydroxide, ethylenediamine, piperazine, polyethyleneimine, modified polyethyleneimine, and combinations thereof to raise pH of the polishing composition; and is present in an amount ranging from about 0.0001 wt % to about 2 wt %; and the polishing slurry has a pH from about 2 to about 12. 
     
     
         19 . The slurry of  claim 12  wherein the polishing slurry further comprising a surfactant selected from the group consisting of nonionic, anionic, cationic or amphoteric surfactants, and combinations thereof;
 and is present in an amount ranging from about 0.0001 wt % to about 1.0 wt %. 
 
     
     
         20 . The slurry of  claim 12  wherein the abrasive is colloidal silica and is present in an amount ranging from about 1 wt % to about 3 wt %; the oxidizing agent is hydrogen peroxide and is present in an amount ranging from about 0.5 wt % to about 2 wt %; the corrosion inhibitor is benzotriazole or benzotriazole derivatives and is present in an amount ranging from about 0.01 wt % to about 0.1 wt %; the chelator is benzosulfonic acid and is present in an amount ranging from about 0.4 wt % to about 1.5 wt %; and the organic polymer containing ethylene oxide repeating units having molecular weights ranging from 400,000 to 1,000,000, and concentration ranging from about 50 ppm to about 1,000 ppm; the surfactant is tricosaethylene glycol dodecyl ether and is present in an amount ranging from about 0.010% to about 0.1%; and the slurry has a pH from about 9 to about 11.5.