Composition for chemical mechanical planarization of copper, tantalum and tantalum nitride

Abstract

Chemical mechanical planarization or spin etch planarization of surfaces of copper, tantalum and tantalum nitride is accomplished by means of the chemical formulations of the present invention. The chemical formulations may optionally include abrasive particles and which may be chemically reactive or inert. Contact or non-contact CMP may be performed with the present chemical formulations. Substantially 1:1 removal rate selectivity for Cu and Ta/TaN is achieved.

We claim:  
     
         1 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising: 
 a) an oxidizing reactant selected from the group consisting of H 2 O 2 , HNO 3  and mixtures thereof; and,    b) a co-reactant is selected from the group consisting of H 3 PO 4 , H 2 SO 4 , HNO 3 , oxalic acid, acetic acid, organic acids and mixtures thereof; and,    c) other additives selected from the group consisting of selected from the group consisting of HCl, aliphatic alcohols, butylated hydroxytoluene, Agidol-2, 2,6-di-tert-butyl-4[(dimethylamino)methyl]phenol, 2,6-di-tert-4N,N-dimethylaminomethylphenol, borax, ethylene glycol, ZnSO 4 , methanol, propanol, poly(oxyethylene)lauryl ether, malic acid, HOOC(CX 2 ) n COOH wherein X═OH, amine, H and n=1-4), 3% tartaric acid, 1% ethylene glycol, 1,2,4-triazole, 1,2,3-triazole, tetrazole, nonionic surfactant, ethanol, triflouroethanol, SiF 6 , organic salt surfactant, polyvinyl alcohol, diphenylsulfamic acid, sodium oxalate, benzotriazole, sodium lignosulfonate, glycol, gelatin carboxymethylcellulose, amines, heavy metal salts, salts of Cu and Ta, KCl, CuCl 2 , SnCl 2 , propylene glycol, 2-ethyl-hexylamine, copper carbonate, low molecular weight alcohols, glycols, phenols, aliphatic alcohols, polyvinylalcohols, anionic surfactants, cationic surfactants, fluorocarbon-based surfactants, nonionic surfactants having the properties of preferentially adhering to certain materials, modifying thereby the chemical reactivity where so adhered, polyvinyl alcohol solution stabalizers and species inhibiting spontaneous decomposition of oxidizing agents, wetting agents and mixtures thereof.    
     
     
         2 ) An etching solution as in  claim 1  further comprising a species selected from the group consisting of CuCl, FeCl, FeCl 3 , and mixtures thereof.  
     
     
         3 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising species selected from the group consisting of NaClO 3 , FeNO 3 , (NH 4 ) 2 S 2 O 8 , CuNH 4 Cl 3 , Na 2 S 2 O 8 , K 2 S 2 O 5 , NH 4 F, CuSO 4 , NH 4 OH, sodium EDTA salt of wetting agent and mixtures thereof.  
     
     
         4 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising species selected from the group consisting of, (NH 4 ) 2 S 2 O 8 , KOH, NH 4 OH, H 2 O 2 , Cu(NO 3 ) 2  and mixtures thereof.  
     
     
         5 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising species selected from the group consisting of HF, HNO 3 , H 2 O 2 , H 2 SO 4 , lactic acid and mixtures thereof.  
     
     
         6 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising species selected from the group consisting of, NaOH, KOH, NH 4 OH, H 2 O 2 , and mixtures thereof.  
     
     
         7 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising: EDTA, NH 4 OH, H 2 O 2 , in aqueous solution.  
     
     
         8 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising: citric acid, erythorbic acid, triethanolamine, in aqueous solution.  
     
     
         9 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising: trisodium citrate, triethanolamine, sodium nitrate, in aqueous solution.  
     
     
         10 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising: H 2 SO 4 , H 2 O 2 , sodium molybdate, phenolsulfonic acid, in aqueous solution.  
     
     
         11 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising: mineral acid, molybdenum salt.  
     
     
         12 ) An etching solution for the planarization of a Cu/Ta/TaN surface as in  claim 1  further comprising abrasive particles selected from the group consisting SiO 2 , Al 2 O 3  metallic and solid elemental particles, polymer particles, oxides, carbides, fluorides, carbonates, borides, nitrides, hydroxides of Al, Ag, Au, Ca, Ce, Cr, Cu, Fe, Gd, Ge, La, In, Hf, Mn, Mg, Ni, Nd, Pb, Pt, P, Sb, Sc, Sn, Tb, Ti, Ta, Th, Y, W, Zn, Zr, and mixtures thereof.  
     
     
         13 ) An etching solution as in  claim 12  wherein said abrasive particles are coated.  
     
     
         14 ) An etching solution as in  claim 13  wherein said coating is a chemically active species.  
     
     
         15 ) An etching solution as in  claim 12  wherein said coating is CeO 2 .  
     
     
         16 ) An etching solution as in  claim 12  wherein said particles are produced by the sol method.  
     
     
         17 ) An etching solution as in  claim 12  wherein said particles have a range of sizes from approximately 4 nanometers to approximately 5 micrometers.  
     
     
         18 ) An etching solution as in  claim 12  wherein said particles have a size less than approximately 5 micrometers.  
     
     
         19 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising 
 a) from approximately 50 parts by volume to approximately 70 parts by volume of concentrated aqueous H 3 PO 4 ; and    b) from approximately 24 parts by volume to approximately 40 parts by volume of concentrated aqueous acetic acid; and,    c) from approximately 3 parts by volume to approximately 10 parts by volume of concentrated aqueous HNO 3 .    
     
     
         20 ) An etching solution as in  claim 19  further comprising from approximately 1 part by volume to approximately 15 parts by volume of concentrated aqueous HF.  
     
     
         21 ) An etching solution for the planarization of a Cu/Ta/TaN surface comprising an aqueous solution of approximately 42% by volume of sulfuric acid, approximately 8% by volume nitric acid and approximately 0.5% by volume hydrochloric acid.