Metal Precursor Solutions For Chemical Vapor Deposition

Abstract

Metal source containing precursor liquid solutions for chemical vapor deposition processes, including atomic layer deposition, for fabricating conformal metal-containing films on substrates are described. More specifically, the metal source precursor liquid solutions are comprised of (i) at least one metal complex selected from β-diketonates, β-ketoiminates, β-diiminates, alkyl metal, metal carbonyl, alkyl metal carbonyl, aryl metal, aryl metal carbonyl, cyclopentadienyl metal, cyclopentadienyl metal isonitrile, cyclopentadienyl metal nitrile, cyclopentadienyl metal carbonyl, metal alkoxide, metal ether alkoxide, and metal amides wherein the ligand can be monodentate, bidentate and multidentate coordinating to the metal atom and the metal is selected from group 2 to 14 elements, and (ii) a solvent selected from organic amides including linear amides and cyclic amides for such metal source containing precursors.

1 . A metal source precursor solution having utility for chemical vapor deposition or atomic layer deposition in the manufacture of semiconductor device structures, said metal source precursor solution consisting essentially of:
 (i) at least one metal coordination complex comprising a metal coordinatively bound to at least one ligand in a stable complex; and,   (ii) an organic amide solvent for said metal coordination complex.   
     
     
         2 . The metal source precursor solution of  claim 1  wherein the metal coordination complex is selected from the group consisting of:
 (a) Metal β-diketonates having the formula:   
       
         
           
           
               
               
           
         
         wherein M is a metal selected from Group 2 to 14 and wherein R 1-3  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 3-10  alkylsilyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, and fluorinated C 1-10  alkyl; wherein x is an integer 2, 3, or 4 depending on the valence of M; 
         (b) Metal β-ketoiminates having the formula: 
       
       
         
           
           
               
               
           
         
         wherein M is a metal selected from Group 2 to 14 and wherein R 1-3  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 3-10  alkylsilyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, and fluorinated C 1-10  alkyl; R 4  is linear or branched selected from the group consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl, and fluorinated C 1-10  alkyl; x is an integer 2, 3, or 4 depending on the valence of M; 
         (c) Metal β-diiminates having the formula: 
       
       
         
           
           
               
               
           
         
         wherein M is selected from Group 2 to 13, and wherein R 1-3  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, linear C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl, and fluorinated C 1-10  alkyl; wherein x is the integer 2, 3, or 4; R 4-5  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl; and x is an integer 2, 3, or 4 depending on the valence of M; 
         (d) Metal Alkoxy β-diketonates having the formula: 
       
       
         
           
           
               
               
           
         
         wherein M is a metal ion selected from Group 4 and 5 metals and wherein R 1-3  are linear, branched or cyclic independently selected from the groups consisting of C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl; R 4  is linear or branched independently selected from the group consisting of C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl; and m and n are at least 1 and the sum of m plus n is equal to the valence of the metal M; 
         (e) Alkyl Metal β-diketonates having the formula: 
       
       
         
           
           
               
               
           
         
         wherein M is a metal ion selected from Group 8, 9, and 10 metals including iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum; wherein R 1-3  are linear, branched or cyclic selected from the groups consisting of C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl; wherein R 4  is linear, branched or cyclic selected from the groups consisting of C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-10  cycloalkene, C 6-12  cycloalkyne, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl; m and n are each at least 1 and the sum of m plus n is equal to the valence of the metal M and n is equal to the valence of the metal M if R 4  is a neutral ligand; 
         (f) Metal Alkoxy β-ketoiminates having the formula: 
       
       
         
           
           
               
               
           
         
         wherein M is a metal ion selected from Group 4 and 5 metals; R 1-5  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl; and m and n are at least 1 and the sum of m plus n is equal to the valence of the metal M; 
         (g) Metal β-ketoiminates with the formula: 
       
       
         
           
           
               
               
           
         
         wherein M is a metal ion selected from Group 11 metals; wherein R 12  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl or halogen; R 34  are linear or branched independently selected from the group consisting of C 1-4  linear or branched alkyl, C 1-4  linear or branched alkenyl, C 1-4  linear or branched alkynyl and fluorinated C 1-4  alkyl, preferably R 4  is a 2 to 3 carbon atom linkage, thus making a five- or six-member coordinating ring to the metal center; R 5-6  are linear, branched or cyclic independently selected from the group consisting of C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, fluorinated C 1-10  alkyl or connected to form a ring containing carbon, oxygen, or nitrogen atoms; and Y is either an oxygen, or a nitrogen substituted with a hydrogen, C 1-6  alkyl or C 6-10  aryl group 
         (h) Metal alkyl having the formula:
   MR 1   x R 2   y    
 
         wherein M is a metal selected from Group 2 to 14 wherein R 1  and R 2  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl, fluorinated C 1-10  alkyl, cyclopendienyl (Cp) and alkylcyclopendienyl; x is an integer 0, 1, 2, 3, or 4; y is an integer 0, 1, 2, 3, or 4 and x+y=the valence of M; 
         (i) Alkyl metal carbonyl having the formula:
   (CO) y MR x    
 
         wherein M is a metal selected from Group 2 to 14; R is linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl, fluorinated C 1-10  alkyl, cyclopendienyl (Cp) and alkylcyclopendienyl and mixtures thereof; x is the integer 2, 3, or 4; y is the integer 1, 2, 3, or 4 and x=the valence of M; 
         (j) Metal carbonyl with the formula:
   M x (CO) y    
 
         wherein M is a metal selected from Group 8 to 10, x is the integer 1, 2, or 3 and y is in an integer from 4 to 12, where x times the valence of the metal=2y; 
         (k) Metal alkoxide with the formula:
   M(OR) n    
 
         wherein M is a metal selected from Group 2 to 14; R is linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl, and mixtures thereof; and n is the integer 2, 3, 4, or 5 equal to the valence of M;
   and 
 
         (l) Metal amides with the formula:
   M(NR 1 R 2 ) n    
 
         wherein M is a metal selected from Group 2 to 14; wherein R 1-2  are linear, branched or cyclic independently selected from the groups consisting of hydrogen, C 1-10  alkyl, C 1-10  alkenyl, C 1-10  alkynyl, C 5 -C 10  cycloaliphatic, C 6-12  aryl, C 3-10  alkylsilyl and fluorinated C 1-10  alkyl; and n is the integer 2, 3, 4, or 5 equal to the valence of M; 
       
     
     
         3 . The metal source precursor solution of  claim 2  and wherein the ligand of the metal coordination complexes is either (a) identical to result in degenerative ligand exchange, or (b) resistant to non-degenerative ligand exchange in relation to one another. 
     
     
         4 . The metal source precursor solution of  claim 2  wherein the solvent comprises an amide represented by the formula:
   RCONR′R″   wherein R and R′ are linear or branched alkyl having from 1-10 carbon atoms or connected to form a cyclic group (CH 2 ) n , n is from 4-6, and R″ is alkyl having from 1 to 4 carbon atoms and cycloalkyl.   
     
     
         5 . The metal source precursor solution of  claim 4  wherein the solvent is selected from the group consisting of N-methyl-2-pyrrolidinone, N-ethyl 2-pyrrolidinone and N-cyclohexyl 2-pyrrolidinone. 
     
     
         6 . The metal source precursor solution of  claim 4  wherein the metal of the metal coordination complex is selected from the group consisting of formulas (a), (b), and (c), and the metal is selected from the group consisting of Mg, Ca, Sr, Ba, Y, La, Ce, Sm, Tb, Er, Yb, Lu, Ti, Zr, Hf, Fe, Co, Ni, Ru, Ir, Rh, Cu, Al, Sn, and Pb. 
     
     
         7 . The metal source precursor solution of  claim 6  wherein the ligand is selected from the group consisting of acetylacetonate (acac), hexafluoroacetylacetonate (hfacac); trifluoroacetylacetonate (tfacac); tetramethylheptanedionate (thd); fluorodimethyloctanedionate (fod); and heptafluoro-dimethyloctanedionate. 
     
     
         8 . The metal source precursor solution of  claim 7  wherein the metal coordination complex is selected from the group consisting of Sr(thd) 2 , Ba(thd) 2 , Co(acac) 2 , Ni(acac) 2 , Cu(acac) 2 , Ru(thd) 3 , La(thd) 3 , Y(thd) 3 , Ti(thd) 4 , Hf(thd) 4 , and Zr(thd) 4 . 
     
     
         9 . The metal source precursor solution of  claim 2  wherein the metal coordination complex is selected from the group consisting of the formulas (d) and (e) and the metal is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, and tantalum. 
     
     
         10 . The metal source precursor solution of  claim 2  wherein the metal coordination complex is represented by the formula (k) and is selected from the group consisting of Ti( i PrO) 4 , Hf(OBu t ) 4 , Zr(OBu t ) 4 , and Ta 2 (OEt) 10 . 
     
     
         11 . The metal source precursor solution of  claim 2  wherein metal coordination complex is represented by the formula (l) and is selected from the group consisting of Cp 2 Ru(CO) 2 , (1,3-cyclohexdiene)Ru(CO) 3 , CpCo(CO) 2 , CpRe(CO) 3 , and  i PrCpRe(CO) 3 . 
     
     
         12 . The metal source precursor solution of  claim 2  where metal coordination complex is represented by the formula (j) and is selected from the group consisting of Ru 3 (CO) 12 , W(CO) 6 , Mo(CO) 6 , CO 2 (CO) 8 , and Ni(CO) 4 . 
     
     
         13 . The metal source precursor solution of  claim 2  wherein the metal coordination complex is bis(2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclo-octadiene)ruthenium(II). 
     
     
         14 . The metal source precursor solution of  claim 2  wherein the metal coordination complex is represented by the formula (h) and is selected from the group consisting of CoCp 2 , SrCp 2 , Sr( i PrCp) 2 , Sr( i Pr 3  Cp) 2 , BaCp 2 , Ba( i PrCp) 2 , Ba( i Pr 3  Cp) 2 , RuCp 2 , Ru(MeCp)(EtCp), Ru(EtCp) 2 , NiCp 2 , Cp 2 HfMe 2 , and Cp 2 ZrMe 2 . 
     
     
         15 . The metal source precursor solution of  claim 2  wherein the metal coordination complex is represented by the formula (l) and is selected from the group consisting of tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethyl)titanium (TEMAT), tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethyl)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), tetrakis(ethylmethyl)hafnium (TEMAH), tert-butylimino tri(diethylamino)tantalum (TBTDET), tert-butylimino tri(dimethylamino)tantalum (TBTDMT), tert-butylimino tri(ethylmethylamino)tantalum (TBTEMT), ethyllimino tri(diethylamino)tantalum (EITDET), ethyllimino tri(dimethylamino)tantalum (EITDMT), ethyllimino tri(ethylmethylamino)tantalum (EITEMT), tert-amylimino tri(dimethylamino)tantalum (TAIMAT), tert-amylimino tri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, and bis(tert-butylimino)bis(ethylmethylamino)tungsten. 
     
     
         16 . The metal source precursor solution of  claim 1  wherein the metal coordination complex is selected from the group consisting of Cu(CF 3 C(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )CF 3 ), Cu(CF 3 C(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH 2 CH(Me)OSiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH 2 CH 2 OSiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH 2 CH 2 N(Me)SiMe 2 C 2 H 3 )Me), Cu(MeC(O)CHC(NCH(Et)CH 2 OSiMe 2 C 2 H 3 )Me). 
     
     
         17 . A process for the vapor deposition employing a metal-containing precursor solution for forming a conformal metal-containing film wherein said metal-containing precursor solution is vaporized in a chamber and the metal deposited onto a substrate, which comprises using the metal source precursor solution of  claim 1  as said metal-containing precursor solution.