Compositions and methods for high-efficiency cleaning of semiconductor wafers

Abstract

A composition including supercritical fluid and at least one additive selected from fluoro species, and primary and/or secondary amines, optionally with co-solvent, low k material attack-inhibitor(s) and/or surfactant(s). The composition has particular utility for cleaning of semiconductor wafers to remove post-ashing residues therefrom.

1 .- 96 . (canceled)  
     
     
         97 . A method of cleaning a semiconductor wafer having residue thereon, said method comprising contacting the semiconductor wafer with a cleaning composition for sufficient time to remove residue from the semiconductor wafer having same thereon, wherein said cleaning composition comprises at least one cleaning concentrate and at least one supercritical fluid and said cleaning concentrate comprises at least one fluoro species and boric acid.  
     
     
         98 . The method of  claim 97 , further comprising forming said cleaning composition by: 
 (a) subjecting at least one source fluid to pressure and temperature conditions wherein the source fluid becomes said supercritical fluid; and    (b) adding said cleaning concentrate to the supercritical fluid to produce said cleaning composition.    
     
     
         99 . The method of  claim 97 , wherein the at least one source fluid comprises a species selected from the group consisting of carbon dioxide, oxygen, argon, krypton, xenon, ammonia, methane, methanol, dimethyl ketone, hydrogen, forming gas, and sulfur hexafluoride.  
     
     
         100 . The method of  claim 97 , wherein the at least one source fluid comprises carbon dioxide.  
     
     
         101 . The method of  claim 97 , wherein the at least one fluoro species comprises a fluorine-containing compound selected from the group consisting of hydrogen fluoride (HF), ammonium fluoride (NH 4 F), alkyl hydrogen fluoride (NRH 3 F), dialkylammonium hydrogen fluoride (NR 2 H 2 F), trialkylammonium hydrogen fluoride (NR 3 HF), trialkylammonium trihydrogen fluoride (NR 3 (3HF)), tetraalkylammonium fluoride (NR 4 F), and xenon difluoride (XeF 2 ), wherein each R is independently selected from C 1 -C 8  alkyl and C 6 -C 10  aryl.  
     
     
         102 . The method of  claim 97 , wherein the at least one fluoro species comprises triethylamine trihydrogen fluoride.  
     
     
         103 . The method of  claim 97 , wherein the cleaning concentrate further comprises at least one co-solvent.  
     
     
         104 . The method of  claim 103 , wherein the at least one co-solvent comprises an organic species selected from the group consisting of methanol, ethanol, isopropyl alcohol, N-alkylpyrrolidones, N-arylpyrrolidones, dimethylsulfoxide, sulfolane, catechol, ethyl lactate, acetone, butyl carbitol, monoethanolamine, butyrol lactone, diglycol amine, γ-butyrolactone, butylene carbonate, ethylene carbonate, and propylene carbonate, wherein alkyl is C 1 -C 8  alkyl and aryl is C 6 -C 10  aryl.  
     
     
         105 . The method of  claim 103 , wherein the at least one co-solvent comprises an organic species selected from the group consisting of methanol, ethanol, and isopropyl alcohol.  
     
     
         106 . The method of  claim 97 , wherein the supercritical fluid is present in an amount of from about 80% by weight to about 99.01% by weight, based on the total weight of the composition.  
     
     
         107 . The method of  claim 97 , wherein the at least one fluoro species is present in an amount of from about 0.01% by weight to about 5% by weight, based on the total weight of the composition.  
     
     
         108 . The method of  claim 97 , wherein the boric acid is present in an amount of up to about 5% by weight, based on the total weight of the composition.  
     
     
         109 . The method of  claim 103 , wherein the at least one co-solvent is present in an amount of from about 1% to about 20% by weight, based on the total weight of the composition.  
     
     
         110 . The method of  claim 97 , wherein the contacting is carried out at pressure in a range of from about 800 to about 10,000 psi.  
     
     
         111 . The method of  claim 97 , wherein the contacting is carried out at temperature in a range of from about 20 to about 150° C.  
     
     
         112 . The method of  claim 97 , wherein the residue comprises material selected from the group consisting of post-etch photoresist residue and post-ash residue.  
     
     
         113 . The method of  claim 97 , further comprising washing the semiconductor wafer, at a region at which residue has been removed, with a SCF-containing solution to remove post-removal residue and fluoro species from said semiconductor wafer.  
     
     
         114 . The method of  claim 103 , wherein the cleaning concentrate comprises triethylamine trihydrogen fluoride, boric acid, and at least one co-solvent, wherein the at least one co-solvent comprises an alcohol selected from the group consisting of methanol, ethanol, and isopropyl alcohol.  
     
     
         115 . A kit comprising, in one or more containers, two or more of the following reagents for forming a cleaning concentrate: at least one fluoro species, boric acid, and optionally at least one co-solvent, wherein the kit is adapted to form a cleaning concentrate which is suitable for combination with at least supercritical fluid.  
     
     
         116 . A composition for cleaning semiconductor wafers, wherein the composition comprises a supercritical fluid, at least one fluoro species, boric acid, and at least one co-solvent.  
     
     
         117 . The composition of  claim 116 , further comprising residue material.  
     
     
         118 . The composition of  claim 117 , wherein the residue comprises material selected from the group consisting of post-etch photoresist residue and post-ash residue.