Removal of high-dose ion-implanted photoresist using self-assembled monolayers in solvent systems

Abstract

A method and self assembled monolayer (SAM)-containing compositions for removing bulk and hardened photoresist material from microelectronic devices have been developed. The SAM-containing composition includes at least one solvent, at least one catalyst, at least one SAM component, and optionally a surfactant. The SAM-containing compositions effectively remove the hardened photoresist material while simultaneously passivating the underlying silicon-containing layer(s) in a one step process.

1 . (canceled)  
     
     
         2 . A method of removing bulk and hardened photoresist material from a microelectronic device having said photoresist material thereon, said method comprising contacting the microelectronic device with a SAM-containing composition for sufficient time and under sufficient contacting conditions to at least partially remove said photoresist material from the microelectronic device, wherein the SAM-containing composition includes at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one surfactant.  
     
     
         3 . The method of  claim 2 , wherein said contacting is carried out at conditions selected from the group consisting of: time of from about 1 minute to about 60 minutes; temperature in a range of from about 30° C. to about 80° C., and combinations thereof.  
     
     
         4 . (canceled)  
     
     
         5 . The method of  claim 2 , wherein the solvent comprises at least one solvent selected from the group consisting of toluene, decane, octane, dodecane, pentane, hexane, tetrahydrofuran (THF), carbon dioxide, methanol, ethanol, isopropanol, N-methylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, dimethylsulfoxide (DMSO), sulfolane, ethyl lactate, ethyl acetate, toluene, acetone, butyl carbitol, monoethanolamine, butyrol lactone, diglycol amine, alkyl ammonium fluoride, γ-butyrolactone, butylene carbonate, ethylene carbonate, propylene carbonate, and mixtures thereof;  
       wherein the catalyst comprises an amine selected from the group consisting of trimethylamine, triethylamine, butylamine, pyridine, and combinations thereof; and  
       wherein the SAM component comprises a silane selected from the group consisting of: (RO) 3 SiX, (RO) 2 SiX 2 , (RO)SiX 3 , (R) 3 SiX, (R) 2 SiX 2 , and (R)SiX 3 , where X=F, Cl, Br and I, and R=methyl, ethyl, propyl, butyl, octyl, decyl, and dodecyl; fluorinated derivatives thereof; and combinations thereof.  
     
     
         6 . The method of  claim 2 , wherein the mole ratio of SAM(s) relative to catalyst(s) in a liquid SAM-containing composition is in a range from about 1:10 to about 5:1 and the mole ratio of SAM(s) relative to solvent(s) is in a range from about 1:200 to about 1:50.  
     
     
         7 . The method of  claim 2 , wherein the microelectronic device comprises an article selected from the group consisting of semiconductor substrates, flat panel displays, and microelectromechanical systems (MEMS).  
     
     
         8 . The method of  claim 2 , wherein the bulk and hardened photoresist materials comprise dopant ions selected from the group consisting of arsenic ions, boron ions, phosphorous ions, indium ions, and antimony ions.  
     
     
         9 . The method of  claim 2 , wherein the contacting comprises a process selected from the group consisting of: spraying the SAM-containing composition on a surface of the microelectronic device; dipping the microelectronic device in a sufficient volume of SAM-containing composition; 
 contacting a surface of the microelectronic device with another material that is saturated with the SAM-containing composition; contacting the microelectronic device with a circulating SAM-containing composition; contacting the microelectronic device with a continuous flow of the SAM-containing composition; and contacting the microelectronic device surface with a static volume of the SAM-containing composition for a continued period of time.    
     
     
         10 . The method of  claim 2 , further comprising rinsing the microelectronic device following contact with the SAM-containing composition.  
     
     
         11 . The method of  claim 2 , wherein the at least one SAM component and the at least one catalyst are present in amounts effective to simultaneously passivate a silicon-containing layer on said microelectronic device and remove bulk and hardened photoresist material from the microelectronic device having said material thereon.  
     
     
         12 . The method of  claim 11 , wherein the silicon-containing layer comprises a silicon-containing compound selected from the group consisting of silicon; silicon dioxide; TEOS; silicon nitride; 
 silicon-containing organic polymers; silicon-containing hybrid organic/inorganic materials; organosilicate glass (OSG); fluorinated silicate glass (FSG); carbon-doped oxide (CDO) glass; and combinations thereof.    
     
     
         13 . The method of  claim 11 , wherein the underlying silicon-containing layer has a contact angle in a range from about 60 degrees to about 120 degrees following formation of the SAM-passivating layer.  
     
     
         14 . The method of  claim 2 , further comprising removing a SAM-passivating layer from the microelectronic device with a depassivating composition following at least partial removal of said photoresist material from the microelectronic device.  
     
     
         15 . The method of  claim 14 , wherein the depassivating composition comprises compounds selected from the group consisting of pyridine/HF complexes, pyridine/HCl complexes, pyridine/HBr complexes, triethylamine/HF complexes, fluorosilicic acid, hydrofluoric acid, tetrafluoroboric acid, triethylamine/HCl complexes, triethylamine/formic acid complexes, peroxide derivatives thereof, concentrated HCl, ammonium hydroxide, and combinations thereof.  
     
     
         16 . The method of  claim 2 , wherein the solvent comprises dense carbon dioxide.  
     
     
         17 . The method of  claim 16 , wherein said contacting comprises conditions selected from the group consisting of: pressure in a range of from about 1500 to about 4500 psi; time in a range of from about 5 to about 30 minutes; temperature in a range of from about 40° C. to about 75° C.; and combinations thereof.  
     
     
         18 . (canceled)  
     
     
         19 . (canceled)  
     
     
         20 . (canceled)  
     
     
         21 . A method of removing a self assembled monolayer (SAM) passivating layer from a microelectronic device with a depassivating composition, wherein the depassivating composition comprises compounds selected from the group consisting of pyridine/HF complexes, pyridine/HCl complexes, pyridine/HBr complexes, triethylamine/HF complexes, fluorosilicic acid, hydrofluoric acid, tetrafluoroboric acid, triethylamine/HCl complexes, triethylamine/formic acid complexes, peroxide derivatives thereof, concentrated HCl, ammonium hydroxide, and combinations thereof.  
     
     
         22 . A self assembled monolayer (SAM)-containing composition, comprising at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one surfactant, wherein said SAM-containing composition is suitable for removing bulk and hardened photoresist material from a microelectronic device having said photoresist material thereon.  
     
     
         23 . The SAM-containing composition of  claim 22 , wherein the mole ratio of SAM(s) relative to catalyst(s) in a liquid SAM-containing composition is in a range from about 1:10 to about 5:1, and the mole ratio of SAM(s) relative to solvent(s) is in a range from about 1:200 to about 1:50.  
     
     
         24 . The SAM-containing composition of  claim 22 , wherein the solvent comprises at least one non-polar solvent selected from the group consisting of toluene, decane, dodecane, octane, pentane, hexane, tetrahydrofuran (THF), carbon dioxide, and mixtures thereof.  
     
     
         25 . The SAM-containing composition of  claim 24 , further comprising an additional solvent selected from the group consisting of methanol, ethanol, isopropanol, N-methylpyrrolidinone, N-octylpyrrolidinone, N-phenylpyrrolidinone, dimethylsulfoxide (DMSO), sulfolane, ethyl lactate, ethyl acetate, toluene, acetone, butyl carbitol, monoethanolamine, butyrol lactone, diglycol amine, alkyl ammonium fluoride, γ-butyrolactone, butylene carbonate, ethylene carbonate, propylene carbonate, and mixtures thereof.  
     
     
         26 . The SAM-containing composition of  claim 22 , wherein the solvent comprises toluene.  
     
     
         27 . The SAM-containing composition of  claim 22 , wherein the solvent comprises dense carbon dioxide.  
     
     
         28 . The SAM-containing composition of  claim 22 , wherein the SAM component comprises a silane selected from the group consisting of: (RO) 3 SiX, (RO) 2 SiX 2 , (RO)SiX 3 , (R) 3 SiX, (R) 2 SiX 2 , and (R)SiX 3 , where X=F, Cl, Br and I, and R=methyl, ethyl, propyl, butyl, octyl, decyl, and dodecyl; fluorinated derivatives thereof; and combinations thereof.  
     
     
         29 . The SAM-containing composition of  claim 22 , wherein the SAM component comprises an alkylchlorosilane selected from the group consisting of Cl 3 SiMe, Cl 2 SiMe 2 , and ClSiMe 3 .  
     
     
         30 . The SAM-containing composition of  claim 22 , wherein the catalyst comprises an amine selected from the group consisting of trimethylamine, triethylamine, butylamine, pyridine, and combinations thereof.  
     
     
         31 . The SAM-containing composition of  claim 22 , comprising at least one surfactant.  
     
     
         32 . The SAM-containing composition of  claim 22 , wherein the surfactant comprises a surfactant species selected from the group consisting of fluoroalkyl surfactants, polyethylene glycols, polypropylene glycols, polyethylene glycol ethers, polypropylene glycol ethers, carboxylic acid salts, dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid salts, polyacrylate polymers, dinonylphenyl polyoxyethylene, silicone polymers, modified silicone polymers, acetylenic diols, modified acetylenic diols, alkylammonium salts, modified alkylammonium salts, and combinations thereof.  
     
     
         33 . The SAM-containing composition of  claim 22 , wherein the composition comprises toluene, Cl 3 SiMe and triethylamine.  
     
     
         34 . The SAM-containing composition of  claim 22 , wherein the microelectronic device comprises an article selected from the group consisting of semiconductor substrates, flat panel displays, and microelectromechanical systems (MEMS).  
     
     
         35 . The SAM-containing composition of  claim 22 , wherein the bulk and hardened photoresist materials comprise dopant ions selected from the group consisting of arsenic ions, boron ions, phosphorous ions, indium ions and antimony ions.  
     
     
         36 . The SAM-containing composition of  claim 22 , wherein the at least one SAM component and the at least one catalyst are present in amounts effective to simultaneously passivate a silicon-containing layer on said microelectronic device and remove bulk and hardened photoresist material from the microelectronic device having said material thereon.  
     
     
         37 . The SAM-containing composition of  claim 36 , wherein the silicon-containing layer comprises a silicon-containing compound selected from the group consisting of silicon; silicon dioxide; TEOS; silicon nitride; silicon-containing organic polymers; silicon-containing hybrid organic/inorganic materials; organosilicate glass (OSG); fluorinated silicate glass (FSG); carbon-doped oxide (CDO) glass; and combinations thereof.  
     
     
         38 . The SAM-containing composition of  claim 27 , wherein the carbon dioxide is supercritical.  
     
     
         39 . The SAM-containing composition of  claim 22 , further comprising photoresist residue material, wherein the photoresist comprises bulk photoresist, hardened photoresist, or combinations thereof.  
     
     
         40 . The SAM-containing composition of  claim 39 , wherein the photoresist comprises an ion selected from the group consisting of boron ions, arsenic ions, phosphorus ions, indium ions, antimony ions, and combinations thereof.  
     
     
         41 . A kit comprising, in one or more containers, SAM-containing composition reagents, wherein the SAM-containing composition comprises at least one solvent, at least one catalyst, at least one SAM component, and optionally at least one surfactant, and wherein the kit is adapted to form a SAM-containing composition suitable for removing bulk and hardened photoresist material from a microelectronic device having said photoresist material thereon.  
     
     
         42 . A method of manufacturing a microelectronic device, said method comprising contacting the microelectronic device with the SAM-containing composition of  claim 22  for sufficient time to at least partially remove bulk and hardened photoresist material from the microelectronic device having said material thereon.