Methods for forming ruthenium films with beta-diketone containing ruthenium complexes and method for manufacturing metal-insulator-metal capacitor using the same

Abstract

Provided are 1) a method for forming a ruthenium film under a single process condition, whereby high adhesion of the ruthenium film to a lower layer is maintained, and 2) a method for manufacturing an metal-insulator-metal (MIM) capacitor using the ruthenium film forming method. The method for forming a ruthenium film includes supplying bis(isoheptane-2,4-dionato)norbornadiene ruthenium at a flow rate of 0.2-1 ccm and oxygen at a flow rate of 20-60 sccm, and depositing the ruthenium film at a temperature of 330-430° C. under a pressure of 0.5-5 Torr using chemical vapor deposition (CVD).

1 . A method for manufacturing a metal-insulator-metal (MIM) capacitor, comprising: 
 (a) forming a first ruthenium film for a lower electrode on a semiconductor substrate;    (b) forming a dielectric layer on the lower electrode; and    (c) forming a second ruthenium film for an upper electrode on the dielectric layer, step (a) comprising supplying a two β-diketones-coordinated ruthenium complex as a ruthenium source at a flow rate of 0.2-1 ccm and oxygen at a flow rate of 20-60 sccm onto the substrate and depositing the first ruthenium film using CVD, and step (c) comprising supplying a two β-diketones-coordinated ruthenium complex as a ruthenium source at a flow rate of 0.2-1 ccm and oxygen at a flow rate of 20-60 sccm onto the substrate and depositing the second ruthenium film using CVD.    
   
   
       2 . The method according to  claim 1 , wherein the ruthenium source is a two β-diketones and one diene-coordinated ruthenium complex as represented by the formula 1:  
     
       
         
         
             
             
         
       
       wherein R 1  and R 2  are alkyl groups; the total carbon number of R 1  and R 2  is 3 to 5; and R 3 , R 4  and R 5  are interconnected to each other to form a chain.  
     
   
   
       3 . The method according to  claim 2 , wherein the diene is 1,4-cyclohexadiene, norbornadiene, or 1,5-cyclooctadiene.  
   
   
       4 . The method according to  claim 2 , wherein R 1  and R 2  are asymmetric.  
   
   
       5 . The method according to  claim 1 , wherein the ruthenium source is a two β-diketones and one diamine-coordinated ruthenium complex as represented by the formula 2:  
     
       
         
         
             
             
         
       
       wherein R 1  and R 2  are alkyl groups; the total carbon number of R 1  and R 2  is 2 to 5; R 6 , R 7 , R 8 , R 9 , R 10  and R 11  are independently hydrogen or alkyl groups; and the total carbon number of R 6 , R 7 , R 8 , R 9 , R 10  and R 11  is  2  to  8 .  
     
   
   
       6 . The method according to  claim 5 , wherein the diamine is N,N,N′,N′-tetramethylethylenediamine.  
   
   
       7 . The method according to  claim 5 , wherein R 1  and R 2  are asymmetric.  
   
   
       8 . The method according to  claim 1 , wherein the ruthenium source is a two β-diketones and two organic ligands-coordinated ruthenium complex as represented by the formula 3:  
     
       
         
         
             
             
         
       
       wherein, R 1  and R 2  are alkyl groups; the total carbon number of R 1  and R 2  is 2 to 5;  
       and two R 12  are olefin, amine, nitrile or carbonyl.  
     
   
   
       9 . The method according to  claim 8 , wherein the olefin is ethylene, propylene, 2-methylpropylene, butyl, or 1,3-butadiene.  
   
   
       10 . The method according to  claim 9 , wherein the amine is trimethylamine or triethylamine.  
   
   
       11 . The method according to  claim 10 , wherein the nitirile is acetonitrile or acrylonitrile.  
   
   
       12 . The method according to  claim 9 , wherein the two β-diketones are 2,4-hexanedione, 5-methyl-2,4-hexanedione, 2,4-heptanedione, 5-methyl-2,4-heptanedione, 6-methyl-2,4-heptanedione, or 2,4-octanedione.  
   
   
       13 . The method according to  claim 1 , wherein the ruthenium source is bis(isoheptane-2,4-dionato)norbornadiene ruthenium.  
   
   
       14 . The method according to  claim 1 , wherein the ruthenium film is deposited at a temperature of 330-430° C.  
   
   
       15 . The method according to  claim 1 , wherein the ruthenium film is deposited under a pressure of 0.5-5 Torr.  
   
   
       16 . The method according to  claim 1 , wherein the depositing of the ruthenium film includes supplying an inert gas, including nitrogen and argon, onto the substrate.