Germanium compound delivery device

Abstract

Germanium compounds suitable for use as vapor phase deposition precursors for germanium films are provided. Methods of depositing films containing germanium using such compounds are also provided. Such germanium films are particularly useful in the manufacture of electronic devices.

1 . A vapor delivery device comprising a vessel having an elongated cylindrical shaped portion having an inner surface having a cross-section, a top closure portion and a bottom closure portion, the top closure portion having an inlet opening for the introduction of a carrier gas and an outlet opening, the elongated cylindrical shaped portion having a chamber containing two or more germanium compounds; the inlet opening being in fluid communication with the chamber and the chamber being in fluid communication with the outlet opening; wherein a first germanium compound is a halogermanium compound of the formula X 1   4-a GeR a , wherein a=0-3, each X 1  is independently a halogen, and each R is independently chosen from H, alkyl, alkenyl, alkynyl, aryl, and NR 4 R 6 , wherein each R 4  and R 6  are independently chosen from H, alkyl, alkenyl, alkynyl and aryl, and wherein a second germanium compound has the formula  
     
       
         
         
             
             
         
       
     
     wherein each R 1  and R 2  are independently chosen from H, alkyl, alkenyl, alkynyl and aryl; each R 3  is independently chosen from alkyl, alkenyl, alkynyl and aryl; X is halogen; a′=0-4; b′=0-4; c′=0-3; d′=0-4 and a′+b′+c′+d′=4; provided that a′+b′≦3 when X 1 =Cl, R=H, and X=Cl.  
   
   
       2 . The delivery device of  claim 1  wherein c′=1-3.  
   
   
       3 . The delivery device of  claim 1  wherein a′=c′=0, b′=1-2 and d′=2-3.  
   
   
       4 . An apparatus for vapor deposition of metal films comprising the vapor delivery device of  claim 1 .  
   
   
       5 . An apparatus comprising a first vapor delivery device comprising a first germanium compound and a second vapor delivery device comprising a second germanium compound, the first and second vapor delivery devices capable of providing the first and second germanium compounds in the vapor phase to a deposition chamber, wherein the first germanium compound is a halogermanium compound of the formula X 1   4-a GeR a , wherein a=0-3, each X 1  is independently a halogen, and each R is independently chosen from H, alkyl, alkenyl, alkynyl, aryl, and NR 4 R 6 , wherein each R 4  and R 6  are independently chosen from H, alkyl, alkenyl, alkynyl and aryl, and wherein the second germanium compound has the formula  
     
       
         
         
             
             
         
       
     
     wherein each R 1  and R 2  are independently chosen from H, alkyl, alkenyl, alkynyl and aryl; each R 3  is independently chosen from alkyl, alkenyl, alkynyl and aryl; X is halogen; a′=0-4; b′=0-4; c′=0-3; d′=0-4 and a′+b′+c′+d′=4; wherein at least one of a′, c′and d′ is not 0; provided that a′+b′≦3 when X 1 =Cl, R=H, and X=Cl.