Group 11 mono-metallic precursor compounds and use thereof in metal deposition

Abstract

The present application provides precursor compounds useful for deposition of a group 11 metal on a substrate, for example, a microelectronic device substrate, as well as methods of synthesizing such precursor compounds. The precursor compounds provided are mono-metallic compounds comprising a diaminocarbene (DAC) having the general formula: “DAC-M-X”, where the diaminocarbene is an optionally substituted, saturated N-heterocyclic diaminocarbene (sNHC) or an optionally substituted acyclic diaminocarbene, M is a group 11 metal, such as copper, silver or gold; and X is an anionic ligand. Also provided are methods of synthesizing the precursor compounds, metal deposition methods utilizing such precursor compounds, and to composite materials, such as, e.g., microelectronic device structures, and products formed by use of such precursors and deposition methods.

1 . A compound of Formula I:
   DAC-M-X  I
   wherein
 DAC is a diaminocarbene that is an optionally substituted, saturated N-heterocyclic diaminocarbene (sNHC) or an optionally substituted acyclic diaminocarbene; 
 M is a transition metal bound to the DAC component at the carbenic atom; and 
 X is an anionic ligand, 
 wherein the compound does not comprise an aryl or heteroaryl group, and M is bound to a non-halogenic atom of X, 
 and wherein the compound will achieve a vapour pressure of at least about 1 torr at 160° C. or less and will remain stable for at least one day at a temperature of at least about 100° C. 
   
     
     
         2 . The compound of  claim 1 , wherein M is a group 11 metal. 
     
     
         3 . The compound of  claim 1 , which is a compound of Formula Ia:
     s NHC-M-X  Ia.
   
     
     
         4 . The compound of  claim 3 , which is a compound of Formula IIa: 
       
         
           
           
               
               
           
         
         wherein
 Y is CR 5 R 6 , (CR 5 R 6 ) 2 , or NR 9 ; 
 R 1  and R 2  are each independently H, or an optionally substituted, branched, straight or cyclic aliphatic group, wherein R 1  and R 2  do not comprise a halo substituent; 
 R 3 , R 4 , R 5  and R 6  are each independently H, or an optionally substituted, branched, straight or cyclic aliphatic group; and 
 R 9  is H, or an optionally substituted, branched, straight or cyclic aliphatic group. 
 
       
     
     
         5 . The compound of  claim 1 , which is a compound of Formula IIb 
       
         
           
           
               
               
           
         
         wherein
 each R 1  and R 2  is independently H, or an optionally substituted, branched, straight or cyclic aliphatic group, wherein R 1  and R 2  do not comprise a halo substituent. 
 
       
     
     
         6 . The compound of  claim 1 , wherein X is not bound to M via an oxygen-metal bond. 
     
     
         7 . The compound of  claim 1 , wherein X is heterocycle, piperidinyl, pyrrolidinyl, alkoxide, alkyl, hydride, hydroxide, diketonate, diketiminate, amidinate or guanidinate or is an amide having the following structure: 
       
         
           
           
               
               
           
         
         where R 7  and R 8  are each independently an optionally substituted branched, straight or cyclic aliphatic group, an optionally substituted branched or straight C 1  to C 12  alkylsilyl, or R 7  and R 8  together with the amide nitrogen form an optionally substituted heterocycle. 
       
     
     
         8 . The compound of  claim 7 , wherein R 7  and R 8  are each independently H, a C 1  to C 12  alkyl or heteroalkyl, or a C 3  to C 12  cycloalkyl or cyclic heteroalkyl. 
     
     
         9 . The compound of  claim 8 , wherein X is —N(SiMe 3 ) 2 . 
     
     
         10 . The compound of  claim 4 , wherein R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are each independently H, a C 1  to C 12  alkyl, or heteroalkyl or a C 3  to C 12  cycloalkyl or cyclic heteroalkyl. 
     
     
         11 . The compound of  claim 4 , wherein R 1 , R 2 , R 3 , R 4 , R 5  and R 6  are each independently H, a C 1  to C 6  alkyl or heteroalkyl, or a C 3  to C 8  cycloalkyl or cyclic heteroalkyl. 
     
     
         12 . The compound of  claim 11 , wherein R 1  and R 2  are each independently methyl, ethyl, propyl, isopropyl, butyl, 1-methylpropyl, or t-butyl. 
     
     
         13 . The compound of  claim 1 , wherein M is copper, silver, or gold. 
     
     
         14 . The compound of  claim 1 , which is: 
       
         
           
           
               
               
           
         
         
           
           
               
               
           
         
         
           
           
               
               
           
         
       
     
     
         15 . The compound of  claim 4 , which is 1,3-diisopropyl-imidazolin-2-ylidene copper hexamethyldisilazide. 
     
     
         16 . (canceled) 
     
     
         17 . The compound of  claim 1 , wherein the compound remains stable at a temperature of at least about 150° C. for an extended period. 
     
     
         18 . The compound of  claim 1 , which is at least 95% pure. 
     
     
         19 . The compound of  claim 1 , which is at least 98% pure. 
     
     
         20 . A process for depositing a metal film on a substrate, comprising chemical vapour deposition (CVD), atomic layer deposition (ALD), plasma enhanced chemical vapour deposition (PE-CVD) or plasma enhanced atomic layer deposition (PE-ALD) using a compound of  claim 1 , wherein M is a group 11 metal, as a precursor compound. 
     
     
         21 . A process for forming a thin film comprising a metal, said process comprising the following step:
 (a) exposing a substrate to vapour comprising a precursor compound of Formula I:
   DAC-M-X  I
 
   wherein
 DAC is a diaminocarbene that is an optionally substituted, saturated N-heterocyclic diaminocarbene (sNHC) or an optionally substituted acyclic diaminocarbene; 
 M is a group 11 metal bound to the sNHC component at the carbenic atom; and 
 X is an anionic ligand, 
   and wherein the precursor compound does not comprise an aryl or heteroaryl group, and M is bound to a non-halogenic atom of X.   
     
     
         22 . (canceled) 
     
     
         23 . (canceled) 
     
     
         24 . The process of  claim 21 , wherein in the step of exposing a substrate to vapour comprising a precursor compound, the substrate is exposed to a vapour comprising the precursor compound and a reactive gas to form a metal film on the surface of the substrate. 
     
     
         25 . The process of  claim 21  additionally comprising:
 volatilizing the precursor compound to form a precursor vapour prior to exposing the substrate to the precursor vapour. 
 
     
     
         26 . The process of  claim 21 , wherein the precursor compound is:
 a compound of Formula Ia:
     s NHC-M-X  Ia;
 
   or
 a compound of Formula IIa: 
   
       
         
           
           
               
               
           
         
         wherein
 Y is CR5R6, (CR5R6)2, or NR9; 
 R 1  and R 2  are each independently H, or an optionally substituted, branched, straight or cyclic aliphatic group, wherein R 1  and R 2  do not comprise a halo substituent; 
 R 3 , R 4 , R 5  and R 6  are each independently H, or an optionally substituted, branched, straight or cyclic aliphatic group; and 
 R 9  is H, or an optionally substituted, branched, straight or cyclic aliphatic group; or 
 a compound of Formula IIb: 
 
       
       
         
           
           
               
               
           
         
         wherein
 each R 1  and R 2  is independently H, or an optionally substituted, branched, straight or cyclic aliphatic group, wherein R 1  and R 2  do not comprise a halo substituent 
 
       
     
     
         27 .- 29 . (canceled) 
     
     
         30 . The process of  claim 21 , wherein the temperature of vaporization of the compound is above 50° C. 
     
     
         31 . The process of  claim 21 , further comprising heating the substrate. 
     
     
         32 . The process of  claim 21 , wherein the substrate comprises: glass; TaN; TiN; sapphire; indium tin oxide (ITO); SiO 2 ; silicon; silicon nitride; silicon oxy nitride; silicon oxycarbide; fused silica; polymeric material; tungsten; tantalum; ruthenium; organic materials; another metal or alloy used as a barrier layer in semiconductor manufacturing; or any combination thereof. 
     
     
         33 . The process of  claim 21 , wherein M is Cu, Ag, or Au. 
     
     
         34 . A system for use in metal deposition to form a thin film on a substrate, comprising a precursor compound according to  claim 1 , wherein M is a group 11 metal. 
     
     
         35 . The system of  claim 34 , wherein said precursor compound is in an air-tight container. 
     
     
         36 . The system of  claim 35 , wherein said air-tight container is a bubbler configured for use with an ALD tool, a flame sealed ampule, or a vial or tube having a cap that is removably attached to said vial or tube to produce an air-tight seal. 
     
     
         37 . (canceled) 
     
     
         38 . The system  claim 34 , wherein the precursor compound is packaged under an inert atmosphere. 
     
     
         39 . (canceled) 
     
     
         40 . The system of  claim 34 , additionally comprising a desiccant, an anti-oxidant or an additive for inhibiting spontaneous decomposition of said precursor compound. 
     
     
         41 . The system of  claim 34 , additionally comprising means for volatilizing said precursor compound. 
     
     
         42 . The system of  claim 41 , wherein said means for volatilizing said precursor compound is comprised within an atomic layer deposition (ALD) or chemical vapour deposition (CVD) tool. 
     
     
         43 . An atomic layer deposition (ALD) precursor formulation comprising a mono-metallic precursor compound of  claim 1 , wherein M is a group 11 metal. 
     
     
         44 . The ALD precursor formulation of  claim 43 , packaged in an air-tight container under an inert atmosphere. 
     
     
         45 . (canceled) 
     
     
         46 . A method of synthesizing a metal precursor compound of Formula Ia
   DAC-M-X  Ia
   wherein
 DAC is a diaminocarbene that is an optionally substituted, saturated N-heterocyclic diaminocarbene (sNHC) or an optionally substituted acyclic diaminocarbene; 
 M is a metal bound to the sNHC component at the carbenic atom; and 
 X is an anionic ligand, 
 and wherein DAC and X do not comprise an aryl or heteroaryl group, 
   said method comprising:
 reacting an DAC metal halide with a salt of the anionic ligand such that a bond is formed between M and a non-halogenic atom of X. 
   
     
     
         47 . The method of  claim 46 , wherein M is a group 11 metal. 
     
     
         48 . The method of  claim 46 , comprising reacting a metal halide of Formula IV: 
       
         
           
           
               
               
           
         
         wherein B is a halide;
 Y is CR 5 R 6 , (CR 5 R 6 ) 2 , or NR 5 ; 
 R 1  and R 2  are each independently H, or an optionally substituted branched, straight or cyclic aliphatic group, wherein R 1  and R 2  do not comprise any halide atoms; and 
 R 3 , R 4 , R 5  and R 6  are each independently H, or an optionally substituted, branched, straight or cyclic aliphatic group; 
 
         with a salt of the anionic ligand X to produce a compound of Formula IIa: 
       
       
         
           
           
               
               
           
         
         wherein the precursor compound does not comprise an aryl or heteroaryl group, and M is bound to a non-halogenic atom of X. 
       
     
     
         49 . The method of  claim 46 , comprising reacting a metal halide of Formula IVb: 
       
         
           
           
               
               
           
         
         wherein B is a halide;
 Y is CR 5 R 6 , (CR 5 R 6 ) 2 , or NR 5 ; 
 R 1  and R 2  are each independently H, or an optionally substituted branched, straight or cyclic aliphatic group, wherein R 1  and R 2  do not comprise any halide atoms; and 
 R 3 , R 4 , R 5  and R 6  are each independently H, or an optionally substituted, branched, straight or cyclic aliphatic group; 
 
         with a salt of the anionic ligand X to produce a compound of Formula IIb: 
       
       
         
           
           
               
               
           
         
         wherein the precursor compound does not comprise an aryl or heteroaryl group, and M is bound to a non-halogenic atom of X. 
       
     
     
         53 . The process of  claim 21 , wherein the process is carried out under conditions that permit adsorption of the precursor compound to form a monolayer on the substrate and the process additionally comprises:
 (b) purging excess precursor compound;   (c) exposing the adsorbed precursor monolayer formed in step (a) to a reactant precursor compound to reduce the precursor monolayer to form a metal layer; and   (d) repeating steps (a)-(c) until the thin film reaches a desired thickness.   
     
     
         54 . The process of  claim 53 , wherein the reactant precursor is:
 plasma;   an oxidizing gas, such as oxygen, ozone, water, hydrogen peroxide, nitric oxide, nitrogen dioxide, a radical species thereof, or a mixture of any two or more of the oxidizing gases; or   a reducing agent such as one of hydrogen, a forming gas (i.e., ˜5% hydrogen, ˜95% nitrogen mixture), ammonia, a silane, a borane, an amino borane, an alane, formic acid, a hydrazine (e.g., dimethylhydrazine), a radical species thereof, or a mixture of any two or more of the reducing agents.   
     
     
         55 . The compound of  claim 1 , wherein M is a metal selected from the group consisting of Groups 4, 5, 6, 7, and 11 of the periodic table.