Volatile Dihydropyrazinly and Dihydropyrazine Metal Complexes

Abstract

A composition comprising dihydropyrazinyl anions that can be coordinated as 6 electron ligands to a broad range of different metals to yield volatile metal complexes for ALD and CVD depositions are described herein. Also described herein are undeprotonated dihydropyrazines that can coordinate to metals as stabilizing neutral ligands. In one embodiment, the composition is used for the direct liquid injection delivery of the metal dihydropyrazinyl complex precursor to the chamber of an ALD or CVD chamber for the deposition of metal-containing thin films such as, for example, ruthenium or cobalt metal films.

1 . A composition comprising a compound having Formula 3D comprising: 
       
         
           
           
               
               
           
         
         where R 1 , R 2 , R 3 , R 4  are each independently selected from a C 1 -C 6  linear, branched, or cyclic alkyl group; R 5  is independently selected from a H atom and a C 1 -C 6  linear, branched, or cyclic alkyl group; (L) is an anion selected from cyclopentadienyl, pentaalkylcyclopentadienyl, pentamethylpentadienyl, dimethylpentadienyl, trimethylpentadienyl, methylcyclopentadienyl, ethylcyclopentdienyl, imidazolyl, trialkylimidazolyl, pyrrolyl, and alkyl pyrrolyl; M is a monovalent metal; x=1; y=1 or 2; and Z is independently selected from a H atom; a C 1 -C 6  linear, branched, or cyclic alkyl group, and SiR 6  where R 6  is independently selected from a C 1 -C 6  linear or branched C 1 -C 3  alkyl group. 
       
     
     
         2 . A composition comprising a compound having the following Formula 3E comprising: 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , R 3 , R 4  are each independently selected from a C 1 -C 6  linear, branched, or cyclic alkyl group; R 5  is selected from a H atom and a C 1 -C 6  linear, branched, or cyclic alkyl group; (Q) is selected from benzene and an alkylated benzene; M is a metal; x is 1 or 2; y=1; and Z is independently selected from a H atom and a C 1 -C 6  linear, branched, or cyclic C 1 -C 6  group, and SiR 6  where R 6  is a C 1 -C 3  linear or branched, alkyl group. 
       
     
     
         3 . A method for forming a metal oxide film on a substrate wherein the film comprises a thickness, the method comprising:
 a. introducing a metal dihydopyrazinyl complex comprising at least one selected from a Formula, 3D, 3E compound or combinations thereof;   b. chemisorbing the metal dihydopyrazinyl complex onto the substrate;   c. purging away the a metal dihydopyrazinyl complex using a purge gas;   d. providing an oxygen source to the metal dihydopyrazinyl complex onto the heated substrate to react with the sorbed metal dihydopyrazinyl complex containing composition; and   e. optionally purging away any unreacted oxygen source.   
     
     
         4 . The method of  claim 4  wherein steps a. through d. and optional step e. are repeated until the thickness of film is established. 
     
     
         5 . The method of  claim 4  wherein the method is an atomic layer deposition process. 
     
     
         6 . The method of  claim 4  wherein the metal dihydopyrazinyl complex comprises at least one selected from cobalt(pentamethylcyclopentadienyl)(2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine), ruthenium (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine)(benzene), and combinations thereof. 
     
     
         7 . A method for forming a metal film on a substrate wherein the film comprises a thickness, the method comprising:
 a. introducing a metal dihydopyrazinyl complex comprising at least one selected from a Formula 3D, 3E compound or combinations thereof;   b. chemisorbing the metal dihydopyrazinyl complex onto the substrate;   c. purging away the a metal dihydopyrazinyl complex using a purge gas;   d. providing a reducing agent to the metal dihydopyrazinyl complex onto the heated substrate to react with the sorbed metal dihydopyrazinyl complex; and   e. optionally purging away any unreacted reducing agent.   
     
     
         8 . The method of  claim 8  wherein steps a. through d. and optional step e. are repeated until the thickness of film is established. 
     
     
         9 . The method of  claim 8  wherein the method is an atomic layer deposition process. 
     
     
         10 . The method of  claim 8  wherein the metal dihydopyrazinyl complex comprises at least one compound selected from cobalt(pentamethylcyclopentadienyl)(2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine), ruthenium (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine)(benzene) and combinations thereof. 
     
     
         11 . The method of  claim 8  wherein the reducing agent is selected from hydrogen, hydrogen plasma, ammonia, ammonia plasma, hydrogen/nitrogen plasma, alkylsilane and mixture thereof.