Aqueous cleaning composition containing copper-specific corrosion inhibitor for cleaning inorganic residues on semiconductor substrate

Abstract

A semiconductor wafer cleaning formulation, including 1-35% wt. fluoride source, 20-60% wt. organic amine(s), 0.1-40% wt. nitrogenous component, e.g., a nitrogen-containing carboxylic acid or an imine, 20-50% wt. water, and 0-21% wt. metal chelating agent(s). The formulations are useful to remove residue from wafers following a resist plasma ashing step, such as inorganic residue from semiconductor wafers containing delicate copper interconnecting structures.

1 .- 56 . (canceled) 
     
     
         57 . A method of removing metal halide residue, metal oxide residue, or both from a semiconductor wafer, said method comprising cleaning the wafer by contacting same with a cleaning formulation, wherein said cleaning formulation comprises (i) a fluoride source, (ii) at least one organic amine, (iii) a nitrogen-containing carboxylic acid or an imine, (iv) water, and optionally at least one metal chelating agent. 
     
     
         58 . The method of  claim 57 , wherein the nitrogen-containing carboxylic acid or imine is selected from the group consisting of:
 iminodiacetic acid (IDA),   glycine,   1,1,3,3-tetramethylguanidine (TMG),   CH 3 C(═NCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,   CH 3 C(═NCH 2 CH 2 OCH 2 CH 2 OH)CH 2 C(O)N(CH 3 ) 2 ,   CH 3 C(═NH)CH 2 C(O)CH 3 ,   (CH 3 CH 2 ) 2 NC(═NH)N(CH 3 CH 2 ) 2 ,   HOOCCH 2 N(CH 3 ) 2 , and   HOOCCH 2 N(CH 3 )CH 2 COOH.   
     
     
         59 . The method of  claim 57 , wherein the wafer cleaning composition has a pH greater than 7. 
     
     
         60 . The method of  claim 57 , wherein the amount of nitrogen-containing carboxylic acid or imine is 0.1-40 weight percent, based on the total weight of the composition. 
     
     
         61 . The method of  claim 57 , wherein the fluoride source comprises a fluoride species selected from the group consisting of:
 any combination of ammonia gas or ammonium hydroxide and hydrogen fluoride gas or hydrofluoric acid,   ammonium bifluoride,   ammonium fluoride,   triethanolammonium fluoride (TEAF),   diglycolammonium fluoride (DGAF),   tetramethylammonium fluoride (TMAF),   methyldiethanolammonium fluoride (MDEAF), and   triethylamine tris(hydrogen fluoride) (TREAT-HF).   
     
     
         62 . The method of  claim 57 , wherein the amount of fluoride source is 1-35% weight percent, based on the total weight of the composition. 
     
     
         63 . The method of  claim 57 , wherein the organic amine(s) comprise an amine(s) selected from the group consisting of:
 diglycolamine (DGA),   methyldiethanolamine (MDEA),   pentamethyldiethylenetriamine (PMDETA),   triethanolamine (TEA),   triethylenediamine (TEDA),   hexamethylenetetramine,   3,3-iminobis(N,N-dimethylpropylamine),   monoethanolamine,   2-(methylamino)ethanol,   4-(2-hydroxyethyl)morpholine,   4-(3-aminopropyl)morpholine, and   N,N-dimethyl-2-(2-aminoethoxyl)ethanol.   
     
     
         64 . The method of  claim 57 , wherein the amount of organic amine(s) is 20-60% weight percent, based on the total weight of the composition. 
     
     
         65 . The method of  claim 57 , wherein the amount of water is 20-50% weight percent, based on the total weight of the composition. 
     
     
         66 . The method of  claim 57 , wherein the wafer cleaning formulation further comprises at least one metal chelating agent selected from the group consisting of:
 acetoacetamide,   ammonium carbamate,   ammonium pyrrolidinedithiocarbamate (APDC),   dimethyl malonate,   methyl acetoacetate,   N-methyl acetoacetamide,   2,4-pentanedione,   1,1,1,5,5,5-hexafluoro-2,4-pentanedione H(hfac),   2,2,6,6-tetrammethyl-3,5-heptanedione H(thd),   tetramethylammonium thiobenzoate,   tetramethylammonium trifluoroacetate,   tetramethylthiuram disulfide (TMTDS),   trifluoracetic acid,   lactic acid,   ammonium lactate,   malonic acid,   formic acid,   acetic acid,   propionic acid,   gamma-butyrolactone,   iminodiacetic acid,   methyldiethanolammonium trifluoroacetate, and   trifluoroacetic acid.   
     
     
         67 . The method of  claim 66 , wherein the amount of at least one metal chelating agent is 0-21% weight percent, based on the total weight of the composition. 
     
     
         68 . The method of  claim 57 , wherein said fluoride source comprises a compound having the general formula R 1 R 2 R 3 R 4 NF in which each of the R groups is independently selected from hydrogen atoms, C 1 -C 8  alkyl, aryl and alkenyl groups, and wherein said formulation includes a metal chelating agent of the formula:
   X—CHR—Y
   in which R is either hydrogen, C 1 -C 8  alkyl, aryl or alkenyl group and X and Y are functional groups containing multiply bonded moieties having electron-withdrawing properties.   
     
     
         69 . The method of  claim 67 , wherein each of X and Y is independently selected from CONH 2 , CONHR′, CN, NO 2 , SOR′, and SO 2 Z in which R′ is C 1 -C 8  alkyl and Z is hydrogen, halo, or C 1 -C 8  alkyl. 
     
     
         70 . The method of  claim 57 , wherein the nitrogen-containing carboxylic or imine comprises iminodiacetic acid.