Use of non-oxidizing strong acids for the removal of ion-implanted resist

Abstract

A method and composition for removing bulk and/or ion-implanted resist material from microelectronic devices have been developed. The compositions effectively remove the ion-implanted resist material while not damaging the silicon-containing or germanium-containing materials.

1 . A method of removing resist from a microelectronic device surface having same thereon, said method comprising contacting a composition to the microelectronic device surface at conditions necessary to substantially remove the resist from the microelectronic device surface, wherein the composition comprises (a) at least one non-oxidizing acid and at least one fluoride and/or bromide compound, with the proviso that the composition is substantially devoid of oxidizers, or (b) a sulfur-containing acid, HCl, and optionally at least one fluoride and/or bromide compound, wherein the HCl is generated using either HCl (hydrogen chloride) added as a dissolved gas or an HCl-generating compound. 
     
     
         2 . The method of  claim 1 , wherein the resist comprises bulk resist, ion-implanted resist, or both bulk and ion-implanted resist. 
     
     
         3 . The method of  claim 1 , wherein conditions comprise time in a range from about 10 sec to about 60 minutes, at temperature in a range from about 20° C. to about 200° C. 
     
     
         4 . The method of  claim 1 , further comprising rinsing the surface with at least one solvent selected from the group consisting of water, dimethyl sulfoxide (DMSO), isopropanol, N-methylpyrrolidone (NMP), dimethylacetamide, sulfolane and other sulfones, methanol, a surfactant and gamma-butyrolactone. 
     
     
         5 .- 8 . (canceled) 
     
     
         9 . The method of  claim 1 , wherein the at least one non-oxidizing acid comprises a species selected from the group consisting of methanesulfonic acid, oxalic acid, citric acid, tartaric acid, picolinic acid, succinic acid, acetic acid, lactic acid, sulfosuccinic acid, benzoic acid, propionic acid, formic acid, pyruvic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, malic acid, ascorbic acid, mandelic acid, heptanoic acid, butyric acid, valeric acid, glutaric acid, phthalic acid, hypophosphorous acid, salicylic acid, 5-sulfosalicylic acid, ethanesulfone acid, butanesulfonic acid, p-toluenesulfonic acid, dichloroacetic acid, difluoroacetic acid, monochloroacetic acid, monofluoroacetic acid, hydrochloric acid, trichloroacetic acid, trifluoroacetic acid, hydrobromic acid (62 wt %), sulfuric acid, and combinations thereof. 
     
     
         10 . The method of  claim 1 , comprising at least one fluoride compound, wherein the at least one fluoride compound comprises a species selected from the group consisting of hydrofluoric acid, tetrafluoroboric acid, hexafluorotitanic acid, hexafluorosilicic acid, hexafluorozirconic acid, tetrafluoboric acid, tetrabutylammonium trifluoromethanesulfonate, tetraalkylammonium tetrafluoroborates (NR 1 R 2 R 3 R 4 BF 4 ) tetraalkylammonium hexafluorophosphates (NR 1 R 2 R 3 R 4 PF 6 ), tetraalkylammonium fluorides (NR 1 R 2 R 3 R 4 F), ammonium bifluoride, ammonium fluoride, and combinations thereof, where R 1 , R 2 , R 3 , R 4  may be the same as or different from one another and is selected from the group consisting of hydrogen, straight-chained or branched C 1 -C 6  alkyl groups, C 1 -C 6  alkoxy groups, and substituted or unsubstitued aryl groups, and combinations thereof. 
     
     
         11 . The method of  claim 1 , comprising at least one bromide compound, wherein the at least one bromide compound comprises hydrobromic acid. 
     
     
         12 . The method of  claim 1 , wherein the composition (a) further comprises at least one acid-resistant surfactant, and/or at least one compound that lowers the melting point of the composition, wherein the at least one compound comprises at least one dialkyl sulfone, sulfuric acid, or sulfolane. 
     
     
         13 . (canceled) 
     
     
         14 . The method of  claim 12 , wherein the at least one dialkyl sulfone comprises a species selected from the group consisting of dimethylsulfone, ethyl methyl sulfone, dipropyl sulfone, ethyl propyl sulfone, diethyl sulfone, dibutyl sulfone, and combinations thereof. 
     
     
         15 . (canceled) 
     
     
         16 . (canceled) 
     
     
         17 . The method of  claim 1 , wherein the sulfur-containing acid comprises a species selected from the group consisting of concentrated sulfuric acid, 100% sulfuric acid, “fuming” sulfuric acid (containing excess SO 3 ), chlorosulfonic acid (ClSO 3 H), mixtures of chlorosulfonic acid and sulfuric acid, trifluoromethanesulfonic acid (CF 3 SO 3 H) and fluorosulfonic acid (FSO 3 H). 
     
     
         18 . The method of  claim 1 , wherein the HCl-generating compound comprises a species selected from the group consisting of thionyl chloride (SOCl 2 ), phosphoryl trichloride (POCl 3 ), sulfuryl chloride (SO 2 Cl 2 ), boron trichloride (BCl 3 ), germanium tetrachloride (GeCl 4 ), chlorosulfonic acid, (ClSO 3 H), and combinations thereof. 
     
     
         19 .- 21 . (canceled) 
     
     
         22 . The method of  claim 1 , wherein the composition (b) is substantially devoid of oxidizers. 
     
     
         23 . A composition for stripping resist from a microelectronic device comprising same, said composition comprising (a) at least one non-oxidizing acid, at least one of a fluoride species and/or a bromide compound, and at least one compound that lowers the melting point of the composition, with the proviso that the composition is substantially devoid of oxidizers, or (b) a sulfur-containing acid, HCl, and optionally at least one fluoride and/or at least one bromide compound. 
     
     
         24 . (canceled) 
     
     
         25 . The composition of  claim 23 , wherein the at least one non-oxidizing acid comprises a species selected from the group consisting of methanesulfonic acid, oxalic acid, citric acid, tartaric acid, picolinic acid, succinic acid, acetic acid, lactic acid, sulfosuccinic acid, benzoic acid, propionic acid, formic acid, pyruvic acid, oxalic acid, maleic acid, malonic acid, fumaric acid, malic acid, ascorbic acid, mandelic acid, heptanoic acid, butyric acid, valeric acid, glutaric acid, phthalic acid, hypophosphorous acid, salicylic acid, 5-sulfosalicylic acid, ethanesulfone acid, butanesulfonic acid, p-toluenesulfonic acid, dichloroacetic acid, difluoroacetic acid, monochloroacetic acid, monofluoroacetic acid, hydrochloric acid, trichloroacetic acid, trifluoroacetic acid, hydrobromic acid (62 wt %), sulfuric acid, and combinations thereof. 
     
     
         26 . The composition of  claim 23 , comprising at least one fluoride compound, wherein the at least one fluoride species comprises a species selected from the group consisting of hydrofluoric acid, tetrafluoroboric acid, hexafluorotitanic acid, hexafluorosilicic acid, hexafluorozirconic acid, tetrafluoboric acid, tetrabutylammonium trifluoromethanesulfonate, tetraalkylammonium tetrafluoroborates (NR 1 R 2 R 3 R 4 BF 4 ) tetraalkylammonium hexafluorophosphates (NR 1 R 2 R 3 R 4 PF 6 ), tetraalkylammonium fluorides (NR 1 R 2 R 3 R 4 F), ammonium bifluoride, ammonium fluoride, and combinations thereof, where R 1 , R 2 , R 3 , R 4  may be the same as or different from one another and is selected from the group consisting of hydrogen, straight-chained or branched C 1 -C 6  alkyl groups, C 1 -C 6  alkoxy groups, and substituted or unsubstitued aryl groups, and combinations thereof. 
     
     
         27 . The composition of  claim 23 , comprising at least one bromide species, wherein the at least one bromide species comprises hydrobromic acid. 
     
     
         28 . The composition of  claim 23 , wherein the at least one compound that lowers the melting point of the composition comprises at least one dialkyl sulfone, sulfuric acid, or sulfolane. 
     
     
         29 . The composition of  claim 28 , wherein the at least one dialkyl sulfone comprises a species selected from the group consisting of dimethylsulfone, ethyl methyl sulfone, dipropyl sulfone, ethyl propyl sulfone, diethyl sulfone, dibutyl sulfone, and combinations thereof. 
     
     
         30 . (canceled) 
     
     
         31 . The composition of  claim 23 , wherein the sulfur-containing acid comprises a species selected from the group consisting of concentrated sulfuric acid, 100% sulfuric acid, “fuming” sulfuric acid (containing excess SO 3 ), chlorosulfonic acid (ClSO 3 H), mixtures of chlorosulfonic acid and sulfuric acid, trifluoromethanesulfonic acid (CF 3 SO 3 H) and fluorosulfonic acid (FSO 3 H). 
     
     
         32 . (canceled) 
     
     
         33 . The composition of  claim 23 , wherein the composition (b) is substantially devoid of oxidizers.