Free Radical-Forming Activator Attached to Solid and Used to Enhance CMP Formulations

Abstract

A chemical mechanical polishing composition having: a fluid comprising water and at least one oxidizing compound that produces free radicals when contacted with an activator; and a plurality of particles having a surface and comprising at least one activator selected from ions or compounds of Cu, Fe, Mn, Ti, or mixtures thereof disposed on said surface, wherein at least a portion of said surface comprises a stabilizer. Preferred activators are selected from inorganic oxygen-containing compounds of B, W, Al, and P, for example borate, tungstate, aluminate, and phosphate. The activators are preferably ions of Cu or Fe. Advantageously, certain organic acids, and especially dihydroxy enolic acids, are included in an amount less than about 4000 ppm. Advantageously, activator is coated onto abrasive particles after the particles have been coated with stabilizer.

1 . A slurry composition for chemical-mechanical polishing a substrate, said slurry composition comprising:
 a fluid comprising water and at least one oxidizing compound that produces free radicals when contacted with an activator, and wherein the fluid pH is between about 2 to about 8; and   a plurality of particles having a surface and comprising at least one activator selected from ions or compounds of Cu, Fe, Mn, Ti, or mixtures thereof disposed on said surface, wherein at least a portion of said surface comprises a stabilizer selected from inorganic compounds of B, W, and Al, and   wherein if the particle body is alumina, then the stabilizer comprises B, W, or mixture thereof.   
   
   
       2 . The slurry of  claim 1  further comprising an α,β-dihydroxy enolic compound. 
   
   
       3 . The slurry of  claim 2  wherein the α,β-dihydroxy enolic compound is ascorbic acid, erythorbic acid, or derivatives and/or mixtures thereof. 
   
   
       4 . The slurry of  claim 3 , wherein the pH of the fluid is between about 6 and about 7. 
   
   
       5 . The slurry of  claim 1  wherein:
 said particles comprise silica, alumina, ceria, spinel, or combination thereof;   said stabilizer comprises B; and   said activator is selected from the group consisting of Cu, Fe, Mn, and mixture thereof said activator being associated with the surface of the abrasive particle ad being present in an amount sufficient to provide at least a 20% higher substrate removal rate during chemical mechanical polishing of said substrate, compared to the substrate removal rate during polishing the substrate under the same conditions but wherein the abrasive particle does not comprise activator.   
   
   
       6 . The slurry of  claim 5 , wherein said stabilizer is associated with the surface of the particle, said stabilizer forming a layer between at least a portion of said activator and said particle surface. 
   
   
       7 . The slurry of  claim 1 , wherein said activator is present in an amount between about 0.2 ppm and 12 ppm as metal, based on the weight of the slurry. 
   
   
       8 . The slurry composition of  claim 7 , wherein the activator is present in an amount between about 3 ppm and 8 ppm as metal, based on the weight of the slurry. 
   
   
       9 . The slurry composition of  claim 7  further comprising between 0.01% and 0.5% by weight total of ascorbic acid, alkyne diols, citric acid, lactic acid, glycolic acid, and/or salicylic acid, or combinations thereof. 
   
   
       10 . An abrasive particle for use in chemical mechanical polishing, said abrasive particle comprising:
 a body comprising silica, alumina, ceria, spine, or combination thereof;   a stabilizing coating disposed on the exterior of the particle body, said stabilizing coating comprising an inorganic compound comprising B, W, Al, or mixtures thereof, wherein if the particle body is alumina then the stabilizer comprises B, W, or mixture thereof; and   an activator selected from the group consisting of Cu, Fe, Mn, Ti, or mixture thereof, said activator being associated with the surface of the abrasive particle and being present in an amount sufficient to provide at least a 20% higher substrate removal rate during chemical mechanical polishing of said substrate when used with a liquid comprising a per-type oxidizer capable of producing free radicals, compared to polishing the substrate with the same liquid and under the same conditions but wherein the abrasive panicle does not comprise activator   
   
   
       11 . The abrasive particle of  claim 10 , wherein the surface of the particle body is modified by the stabilizer prior to the activator becoming associated with the surface of the particle. 
   
   
       12 . The abrasive particle of  claim 11 , wherein at least 80% of the surface sites of the particle are coated with said stabilizer. 
   
   
       13 . The abrasive particle of  claim 11 , wherein said stabilizer is associated with the surface of the particle, said stabilizer forming a layer between at least a portion of said activator and said particle surface. 
   
   
       14 . The abrasive particle of  claim 11 , wherein the particle body comprises silica, the stabilizer comprises B, and the activator is present in an amount between 0.01% to 3% by weight of the weight of the particles. 
   
   
       15 . The abrasive particle of  claim 14 , wherein said stabilizer is associated with the surface of the particle, said stabilizer forming a layer between said activator and said particle surface. 
   
   
       16 . The abrasive particle of  claim 10 , wherein at least 80% of the surface sites of the particle are coated with said stabilizer. 
   
   
       17 . The abrasive particle of  claim 16 , wherein the stabilizer comprises B, and the activator is present in an amount between 0.01% to 3% by weight of the weight of the particles. 
   
   
       18 . The abrasive particle of  claim 17 , wherein the activator comprises iron. 
   
   
       19 . The abrasive particle of  claim 10 , wherein the abrasive particle is disposed on the surface of a polishing pad. 
   
   
       20 . (canceled) 
   
   
       21 . (canceled) 
   
   
       22 . (canceled) 
   
   
       23 . (canceled) 
   
   
       24 . (canceled) 
   
   
       25 . (canceled) 
   
   
       26 . (canceled)