Metal-Enolate Precursors For Depositing Metal-Containing Films

Abstract

Organometallic compounds suitable for use as vapor phase deposition precursors for metal-containing films are provided. Methods of depositing metal-containing films using certain organometallic precursors are also provided. Such metal-containing films are particularly useful in the manufacture of electronic devices.

1 . A metal-containing precursor comprising an enolate ligand represented by the following Formula 1: 
       
         
           
           
               
               
           
         
       
       wherein, M is a metal with an oxidation state of (n), from +2 to +6, selected from the Lanthanides or Group 3 to Group 16, of the Periodic Table; R 1 , R 2  and R 3  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl tert-amyl, and valeraldyl; (L) is an anionic ligand or a mixture of anionic ligands selected from the group consisting of: alkyl substituted enolate, alkoxy, alkyl amino, dialkylamino, diketonate, ketoiminate, diiminate, guanidinate, amidinate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxy substituted cyclopentadienyl, amino substituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxy substituted pyrrolyl, amino substituted pyrrolyl; imidazolate, alkyl substituted imidazolate, alkoxy substituted imidazolate, amino substituted imidazoolate, alkoxy substituted imidazolate, pyrazole, alkyl substituted pyrazole, alkoxy substituted pyrazolate, and alkoxy substituted pyrazolate; (L) can also be a dienolate dianion; (Z) is a neutral coordinating ligand selected from the group consisting of an alkylamine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (y)=1 to 4; (x)=1 to 6; and R 2  can form a cyclic structure with M. 
     
     
         2 . The precursor of  claim 1  comprising bis(2,2,5,5-tetramethylhex-3-en-3-olato)hexa(ethoxy)di-titanium. 
     
     
         3 . The precursor of  claim 1  comprising bis(2,2,5,5-tetramethylhex-3-en-3-olato)(bis(iso-propoxy)titanium. 
     
     
         4 . The precursor of  claim 1  comprising tris(2,2,5,5-tetramethylhex-3-en-3-olato)(dimethylamido)titanium. 
     
     
         5 . The precursor of  claim 1  comprising a compound from Formula 1, wherein (L) is a C 1 -C 10  alkoxy group, as represented by structure A1. 
       
         
           
           
               
               
           
         
       
       wherein, M is a metal with an oxidation state of (n) ranging from +2 to +6, selected from the Lanthanides or Group 3 to Group 16, of the Periodic Table; R 1 , R 2 , and R 3  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; R 4  is selected from the group methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl tert-amyl, and valeraldyl; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (y)=1-4; (x)=1 to 6. 
     
     
         6 . The precursor of  claim 1  comprising a compound from Formula 1, wherein (L) is an alkoxy anion, as represented by Structure A2: 
       
         
           
           
               
               
           
         
       
       wherein, M is a metal with an oxidation state of (n) ranging from +2 to +6, selected from the Lanthanides or Group 3 to Group 16, of the Periodic Table; R 1 , R 2  and R 3  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl and tert-amyl, and valeraldyl; R 4  is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (y)=1-4; (x)=1 to 6. 
     
     
         7 . The precursor of  claim 1  comprising a compound from Formula 1, wherein (L) is a cyclopentadienyl anion, as represented by Structure B 
       
         
           
           
               
               
           
         
       
       wherein, M is a metal with an oxidation state of (n) ranging from +2 to +6, selected from the Lanthanides or Group 3 to Group 16, of the Periodic Table; R 1 , R 2 , R 3  and R 5  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (y)=1-4; (x)=1 to 6; (m)=1 to 5. 
     
     
         8 . The precursor of  claim 1  comprising a compound from Formula 1, wherein (L) is a pyrrolyl anion, as represented by Structure C: 
       
         
           
           
               
               
           
         
       
       wherein, M is a metal with an oxidation state of (n) ranging from +2 to +6, selected from the Lanthanides or Group 3 to Group 16, of the Periodic Table; R 1 , R 2 , R 3  and R 6  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (y)=1 to 4; (x)=1 to 6; (p)=1 to 4. 
     
     
         9 . The precursor of  claim 1  comprising a compound from Formula 1, wherein (L) is an imidazolate anion, as represented by Structure D: 
       
         
           
           
               
               
           
         
       
       wherein, M is a metal with an oxidation state of (n) ranging from +2 to +6, selected from the Lanthanides or Group 3 to Group 16, of the Periodic Table; R 1 , R 2 , R 3  and Ware independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (y)=1 to 4; (x)=1 to 6; (q)=1, 2 or 3. 
     
     
         10 . The precursor of  claim 1  comprising a compound from Formula 1, wherein (L) is a pyrazolate anion, as represented by Structure E: 
       
         
           
           
               
               
           
         
       
       wherein M is a metal with an oxidation state of (n) ranging from +2 to +6 selected from the Lanthanides or Group 3 to Group 16 of the Periodic Table; (n) ranges from +2 to +6; R 1 , R 2 , R 3  and R 8  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl tert-amyl, valeraldyl and tert-amyl; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (x)=1 to 4; r=1, 2 or 3; (y)=1 to 4. 
     
     
         11 . The precursor of  claim 1  comprising a compound represented by Formula 2: 
       
         
           
           
               
               
           
         
       
       wherein M is a metal with an oxidation state of (n) ranging from +2 to +6 selected from the Lanthanides or Group 3 to Group 16 of the Periodic Table; R 9 , R 10 , R 11  and R 12  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, valeraldyl; (L) represents an anion or anions selected from the group consisting of: alkyl substituted enolate anion, alkoxy, guanidinate, amidinate, dialkylamide, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, aminosubsitituted pyrrolyl, alkyl substituted imidazolate, and alkoxysubstituted imidazolate; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (x)=1 to 3; (y)=1 to 4. 
     
     
         12 . The precursor of  claim 11  comprising bis(2,2,7,7-tetramethylocta-3,5-dien-3,6-diolato)bis(dimethylamino)titanium. 
     
     
         13 . The precursor of  claim 1  comprising is a compound represented by Formula 3: 
       
         
           
           
               
               
           
         
       
       wherein M is a metal with an oxidation state of (n) ranging from +2 to +6 selected from the Lanthanides or Group 3 to Group 16 of the Periodic Table; R 13 , R 14  and R 15  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; (L) represents an anion or anions selected from the group consisting of: alkyl substituted enolate anion, alkoxy, guanidinate, amidinate, dialkylamide, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, aminosubsitituted pyrrolyl; alkyl substituted imidazolate, and alkoxysubstituted imidazolate; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (x)=1 to 3; (y)=1 to 4. 
     
     
         14 . The precursor of  claim 1  comprising a compound represented by Structure 4: 
       
         
           
           
               
               
           
         
       
       wherein M is a metal with an oxidation state of (n) ranging from +2 to +6 selected from the Lanthanides or Group 3 to Group 16 of the Periodic Table; R 16 , R 17  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; (L) represents an anion or anions selected from the group consisting of: alkyl substituted enolate anion, alkoxy, guanidinate, amidinate, dialkylamide, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, aminosubsitituted pyrrolyl; alkyl substituted imidazolate, and alkoxysubstituted imidazolate; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (x)=1 to 3; (y)=1 to 4. 
     
     
         15 . The precursor of  claim 1  comprising a compound represented by Formula 4: 
       
         
           
           
               
               
           
         
       
       wherein M is a metal with an oxidation state of (n) ranging from +2 to +6 selected from the Lanthanides or Group 3 to Group 16 of the Periodic Table; R 18 , R 19  R 20  and R 21  are independently H or C 1 -C 6  selected from the group consisting of: methyl, ethyl, propyl, iso-propyl, butyl, isobutyl, sec-butyl, pentyl, isopentyl, sec pentyl, hexyl, sec-hexyl, tert-butyl, tert-amyl, and valeraldyl; (L) represents an anion or anions selected from the group consisting of: alkyl substituted enolate anion, alkoxy, guanidinate, amidinate, dialkylamide, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, aminosubsitituted pyrrolyl; alkyl substituted imidazolate, and alkoxysubstituted imidazolate; (Z) is a neutral coordinating ligand selected from the group consisting of an alkyl amine, polyalkylamine, ether, polyether, imidazole, pyridine, alkyl substituted pyridine, pyrimidine, alkyl substituted pyrimidine, and oxazole; (x)=1 to 3; (y)=1 to 4. 
     
     
         16 . The compound of  claim 1  selected from the group consisting of:
 methylcyclopentadienyltri(4,4-dimethylpent-2-en-3-olato)titanium, 
 methylcyclopentadienyltri(4,4-dimethylpent-2-en-3-olato)zirconium, 
 methylcyclopentadienyltri(4,4-dimethylpent-2-en-3-olato)hafnium, 
 ethylcyclopentadienyltri(4,4-dimethylpent-2-en-3-olato)titanium, 
 ethylcyclopentadienyltri(4,4-dimethylpent-2-en-3-olato)zirconium, 
 ethylcyclopentadienyltri(4,4-dimethylpent-2-en-3-olato)hafnium, 
 methylcyclopentadienyltri(4,4-dimethylpent-2-en-3-olato)titanium, 
 methylcyclopentadienyltri(2,2,5-trimethylhex-3-en-3-olato)zirconium, 
 methylcyclopentadienyltri(2,2,5-trimethylhex-3-en-3-olato)hafnium, 
 ethylcyclopentadienyltri(2,2,5-trimethylhex-3-en-3-olato)titanium, 
 ethylcyclopentadienyltri(2,2,5-trimethylhex-3-en-3-olato)zirconium, 
 ethylcyclopentadienyltri(2,2,5-trimethylhex-3-en-3-olato)hafnium, 
 methylcyclopentadienyltri(2,2,5,5-tetramethylhex-3-en-3-olato)titanium, 
 methylcyclopentadienyltri(2,2,5,5-tetramethylhex-3-en-3-olato)zirconium, 
 methylcyclopentadienyltri(2,2,5,5-tetramethylhex-3-en-3-olato)hafnium, 
 ethylcyclopentadienyltri(2,2,5,5-tetramethylhex-3-en-3-olato)titanium, 
 ethylcyclopentadienyltri(2,2,5,5-tetramethylhex-3-en-3-olato)zirconium, and 
 ethylcyclopentadienyltri(2,2,5,5-tetramethylhex-3-en-3-olato)hafnium. 
 
     
     
         17 . A method for forming a metal-containing film by a vapor deposition, the method comprises the steps of:
 a. introducing a metal-containing precursor of  claim 1  in a vapor state into a reaction chamber and chemisorbing the metal-containing precursor onto a substrate which is heated;   b. purging away the unreacted metal-containing precursor;   c. introducing an oxygen source onto the heated substrate to react with the sorbed metal-containing precursor; and   d. purging away the unreacted oxygen source.   
     
     
         18 . A method for forming a metal-containing films using the precursors of  claim 1 . 
     
     
         19 . A method for forming a metal containing film using the precursors of  claim 1  in a CVD technique. 
     
     
         20 . A method for forming a metal containing film using the precursors of  claim 1  in a PECVD technique. 
     
     
         21 . A method for forming a metal containing film using the precursors of  claim 1  in an AVD technique. 
     
     
         22 . A method for forming a metal-containing film by an ALD method, the method comprises the steps of:
 a. introducing a metal-containing precursor of  claim 1  in a vapor state into a reaction chamber and chemisorbing the metal-containing precursor onto a heated substrate;   b. purging away the unreacted metal-containing precursor;   c. introducing an oxidizing source selected from the group consisting of oxygen, ozone, nitrous oxide or water onto the heated substrate to react with the adsorbed metal-containing precursor; and,   d. purging away the unreacted oxidizing source; and,   this sequence of cycles is then repeated to build up the metal oxide film to a desired thickness.