Spin-coatable metal doped silicon-containing film-forming compositions and processes of using them for deposition

Abstract

A metal doped silicon-containing film-forming composition for forming a metal doped silicon-containing film comprises: 1) at least one silicon-containing precursor, 2) a metal precursor, and 3) a solvent, wherein the metal precursor is selected from an alkyl metal, alkyl metalloxane or polymetalloxane, wherein the metal doped silicon-containing film-forming composition is capable of forming the metal doped silicon-containing film.

1 . A metal doped silicon-containing film-forming composition for forming a metal doped silicon-containing film, the composition comprising:
 i) at least one silicon-containing precursor;   ii) a metal precursor; and   iii) a solvent,   wherein the metal precursor is selected from an alkyl metal, alkyl metalloxane or polymetalloxane;   wherein the metal doped silicon-containing film-forming composition is capable of forming the metal doped silicon-containing film.   
     
     
         2 . The composition of  claim 1 , wherein the at least one silicon precursor is
 a compound comprising an aminosilane having the formula:
   [(R 1 ) 2-m NH m ] n Si(R 2 ) 4-n , 
   wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=1-4, m=0 or 1;   a compound comprising an aminopolysilane with a repeating unit having the formula:
 —[(R 1   2-m NH m ) n Si p (R 2 ) q ]—, where each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-2, m=0 or 1, p≥2, q=0-2; and 
 a terminal group having the formula: [(R 1   2-m NH m ) n (R 2 ) 3-n Si]—, wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-3, m=0 or 1; 
   a compound comprising an alkoxysilane having the formula: [R 1 O] n Si(R 2 ) 4-n , wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=1-4;   a compound comprising an alkoxypolysilane with a repeating unit having the formula:
 —[(R 1 O) n Si p (R 2 ) q ]—, wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-2, p≥2, q=0-2; and 
 a terminal group having the formula: [(R 1 O) n (R 2 ) 3-n Si]—, wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-3; 
   a compound comprising NH— and silicon-containing molecules, including polysilazane, with a repeating unit selected from the general formulae (1a), (1b), (1c), and a terminal group of the formula —NH 2  or —SiH 3 .   
       
         
           
           
               
               
           
         
         a compound comprising a polysilane with a repeating unit having the formula:
 —[SiR 1   n ]—, wherein each R 1  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-2; and 
 a terminal group of —SiH 3 . 
 
         a compound comprising a polysilazane with a repeating unit selected from the general formulae (2a), (2b), (2c), (2d), (2e), and (2f) and a terminal group of —SiH 3 : 
       
       
         
           
           
               
               
           
         
         a compound having a polysiloxane with a repeating unit of the formula:
 —[O—(R 1 O) n Si(R 2 ) 2-n ]—, where each R 1  is selected from the group consisting of hydrogen or alkyl groups of C 1  to C 6 ; each R 2  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0, 1 or 2, and 
 a terminal group of the formula: [(R 1 O) n (R 2 ) 3-n Si]—, where each R 1  is independently selected from the group consisting of hydrogen or alkyl groups of Cito C 6 ; each R 2  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0, 1, 2 or 3. 
 
       
     
     
         3 . The composition of  claim 1 , wherein the at least one silicon precursor contains nitrogen, oxygen, or a combination of nitrogen and oxygen. 
     
     
         4 . The composition of  claim 1 , wherein the at least one silicon precursor are selected from the group consisting of polysilanes, polysilazanes, aminosilanes, aminopolysilanes, alkoxysilanes, and alkoxypolysilanes. 
     
     
         5 . The composition of  claim 1 , wherein the at least one silicon precursor are selected from tetrakis(dimethylamino) silane, tris(dimethylamino) silane, poly(1,1-dimethylsilazane), polyvinylsilazane, trimethoxysilane, triisopropylsilane, ethoxy-nonamethyltetrasilane, methoxy octamethyltetrasilane, perhydropolysilazane, polymethylsilane, poly(methylphenyl) silane, polymethylhydroxosiloxane, polydimethylsiloxane, poly(ethyl methyl) siloxane, or polymethylhydrosiloxane. 
     
     
         6 . The composition of  claim 1 , wherein the amount of the metal precursor ranges between approximately 0.5% w/w and approximately 99.5% w/w. 
     
     
         7 . The composition of  claim 1 , wherein the amount of the at least one silicon-containing precursor ranges from about 0.005 to 60 mol % based on the mole of the metal precursor present. 
     
     
         8 . The composition of  claim 1 , wherein a metal in the metal precursor is selected from Al, Ti, Zr, Sn, Ni, W, Hf, Ta, B, Ga, Cr, Ge, or In. 
     
     
         9 . The compositions of claim  10 , wherein the amount of the metal in the metal precursor ranges from about 0.01% wt/wt to 80% wt/wt. 
     
     
         10 . The composition of  claim 1 , wherein the metal precursor is an aluminium precursor selected from an alkyl aluminium selected from trimethylaluminum, triethylaluminum, trioctylaluminum, or tri(Isobutyl)aluminium, or an alkyl aluminiumloxanes or polyalkyl aluminiumloxanes selected from polymethylaluminoxane, methylaluminoxane, modified methylaluminoxane, Isobutylaluminoxane, or tetraisobutyldialuminoxane. 
     
     
         11 . The composition of  claim 1 , wherein the solvent is a solvent mixture, each solvent has different boiling points in order to adjust the composition viscosity or deposited film thickness. 
     
     
         12 . The composition of  claim 1 , further comprising a crosslinking catalyst, wherein the crosslinking catalyst is present in an amount of 0.01 to 10 parts by weight, based on 100 parts by weight of the metal precursor. 
     
     
         13 . A process for forming a metal doped silicon-containing film, the process comprising:
 treating the surface of a substrate to reduce the surface energy of the substrate;   applying a metal doped silicon-containing film-forming composition onto the substrate to form a deposited film thereon through a deposition method; and   heating the substrate with the deposited film in an oxygen- or nitrogen-containing atmosphere at temperatures characterized as sufficient to remove an organic part of the deposited film to form the metal doped silicon-containing film,   wherein the metal doped silicon-containing film-forming composition comprising:
 i) at least one silicon-containing precursor; 
 ii) a metal precursor; and 
 iii) a solvent, 
   wherein the metal precursor is selected from an alkyl metal, alkyl metalloxane or polymetalloxane;   wherein the metal doped silicon-containing film-forming composition is capable of forming the metal doped silicon-containing film.   
     
     
         14 . The process of  claim 13 , wherein the temperatures range from approximately 40° C. to approximately 1500° C. 
     
     
         15 . The process of  claim 13 , wherein the deposition method includes a spin coating, spray coating, dip coating, or slit coating technique. 
     
     
         16 . The process of  claim 13 , further comprising the steps of
 pre-baking the deposited film under N 2  atmosphere at a temperature ranging from approximately 40° C. to 400° C.; and   subsequently hardbaking the deposited by a heat-induced radical reaction or a UV-Vis photo induced radical reaction in an atmosphere of O 2 , O 3 , H 2 O, H 2 O 2 , N 2 O, or NO, air, compressed air, or combinations thereof at a temperature range of 200-1500° C. to convert the deposited film to the metal doped silicon-containing film.   
     
     
         17 . The process of  claim 13 , wherein the metal doped silicon-containing film is a SiMO x , SiMO x N y , SiMO x C y , SiMN x , or SiMO x C y N z  film, wherein M is selected from Al, Ti, Zr, Sn, Ni, W, Hf, Ta, B, Ga, Cr, Ge, or In, and x, y and z are integers. 
     
     
         18 . The process of  claim 13 , further comprising the step of adding a reactive gas to the composition, wherein the reactive gas is selected from a reduced agent H 2 , an N-source selected from NH 3  or hydrazines, or an oxidizing agent selected from O 2 , O 3 , ambient air, compressed dry air, humid air, H 2 O, H 2 O 2 , organic peroxides, NO, N 2 O, NO 2 , CO, CO 2 , SO 2  or combinations thereof. 
     
     
         19 . A metal doped silicon-containing film comprising
 an etch rate selectivity to a silicon oxide film or silicon nitride film greater than 5; and   a film shrinkage ranging from approximately 0% to approximately 40%.   
     
     
         20 . The metal doped silicon-containing film of  claim 19  being a metal doped silicon-containing filing gap, wherein a gap to be filled has an aspect ratio ranging from approximately 1:1 to approximately 200:1, and a critical dimension ranging from approximately 1 nanometer to approximately 10 micrometers. 
     
     
         21 . The composition of  claim 13 , wherein the at least one silicon precursor is
 a compound comprising an aminosilane having the formula:
   [(R 1 ) 2-m NH m ] n Si(R 2 ) 4-n , 
   wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=1-4, m=0 or 1;   a compound comprising an aminopolysilane with a repeating unit having the formula:
 —[(R 1   2-m NH m ) n Si p (R 2 ) q ]—, where each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-2, m=0 or 1, p≥2, q=0-2; and 
 a terminal group having the formula: [(R 1   2-m NH m ) n (R 2 ) 3-n Si]—, wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-3, m=0 or 1; 
   a compound comprising an alkoxysilane having the formula: [R 1 O] n Si(R 2 ) 4-n , wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=1-4;   a compound comprising an alkoxypolysilane with a repeating unit having the formula:
 —[(R 1 O) n Si p (R 2 ) q ]—, wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-2, p≥2, q=0-2; and 
 a terminal group having the formula: [(R 1 O) n (R 2 ) 3-n  Si]—, wherein each R 1  is independently selected from alkyl groups of C 1  to C 6 ; each R 2  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-3; 
   a compound comprising NH— and silicon-containing molecules, including polysilazane, with a repeating unit selected from the general formulae (1a), (1b), (1c), and a terminal group of the formula —NH 2  or —SiH 3 .   
       
         
           
           
               
               
           
         
         a compound comprising a polysilane with a repeating unit having the formula:
 —[SiR 1   n ]—, wherein each R 1  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0-2; and 
 a terminal group of —SiH 3 . 
 
         a compound comprising a polysilazane with a repeating unit selected from the general formulae (2a), (2b), (2c), (2d), (2e), and (2f) and a terminal group of —SiH 3 : 
       
       
         
           
           
               
               
           
         
         a compound having a polysiloxane with a repeating unit of the formula:
 —[O—(R 1 O) n Si(R 2 ) 2-n ]—, where each R 1  is selected from the group consisting of hydrogen or alkyl groups of C 1  to C 6 ; each R 2  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0, 1 or 2, and 
 a terminal group of the formula: [(R 1 O) n (R 2 ) 3-n  Si]—, where each R 1  is independently selected from the group consisting of hydrogen or alkyl groups of Cito C 6 ; each R 2  is independently selected from the group consisting of hydrogen, alkyl, vinyl, allyl, and phenyl; and n=0, 1, 2 or 3. 
 
       
     
     
         22 . The composition of  claim 13 , wherein the at least one silicon precursor contains nitrogen, oxygen, or a combination of nitrogen and oxygen. 
     
     
         23 . The composition of  claim 13 , wherein the at least one silicon precursor are selected from the group consisting of polysilanes, polysilazanes, aminosilanes, aminopolysilanes, alkoxysilanes, and alkoxypolysilanes. 
     
     
         24 . The composition of  claim 13 , wherein the at least one silicon precursor are selected from tetrakis(dimethylamino) silane, tris(dimethylamino) silane, poly(1,1-dimethylsilazane), polyvinylsilazane, trimethoxysilane, triisopropylsilane, ethoxy-nonamethyltetrasilane, methoxy octamethyltetrasilane, perhydropolysilazane, polymethylsilane, poly(methylphenyl) silane, polymethylhydroxosiloxane, polydimethylsiloxane, poly(ethyl methyl) siloxane, or polymethylhydrosiloxane. 
     
     
         25 . The composition of  claim 13 , wherein a metal in the metal precursor is selected from Al, Ti, Zr, Sn, Ni, W, Hf, Ta, B, Ga, Cr, Ge, or In. 
     
     
         26 . The compositions of  claim 13 , wherein the amount of the metal in the metal precursor ranges from about 0.01% wt/wt to 80% wt/wt. 
     
     
         27 . The composition of  claim 13 , wherein the metal precursor is an aluminium precursor selected from an alkyl aluminium selected from trimethylaluminum, triethylaluminum, trioctylaluminum, or tri(Isobutyl)aluminium, or an alkyl aluminiumloxanes or polyalkyl aluminiumloxanes selected from polymethylaluminoxane, methylaluminoxane, modified methylaluminoxane, Isobutylaluminoxane, or tetraisobutyldialuminoxane. 
     
     
         28 . The composition of  claim 13 , wherein the amount of the metal precursor ranges between approximately 0.5% w/w and approximately 99.5% w/w. 
     
     
         29 . The composition of  claim 13 , wherein the amount of the at least one silicon-containing precursor ranges from about 0.005 to 60 mol % based on the mole of the metal precursor present.