Oxygen free deposition of platinum group metal films
Methods of depositing platinum group metal films of high purity, low resistivity, and good conformality are described. A platinum group metal film is formed in the absence of an oxidant. The platinum group metal film is selectively deposited on a conductive substrate at a temperature less than 200° C. by using an organic platinum group metal precursor.
1. A method of depositing a film, the method comprising:
flowing an organic platinum group metal precursor into a deposition chamber in the presence of a reducing agent, wherein the deposition chamber is substantially free of an oxidant, the organic platinum group metal precursor has a structure of general formula I
wherein R 1 and R 2 are independently selected from C 1-4 alkyl, hydrogen, halogen, CO, and cyclopentadienyl; M is a platinum group metal; and L is a ligand comprising at least one carbon-carbon double bond, a (CH 2 ) x where x is 1 to 8, and a NR 3 R 4 where R 3 and R 4 are independently selected from C 1-4 alkyl, hydrogen, or halogen; and
selectively depositing a platinum group metal film on a conductive substrate versus deposition on a nonconductive substrate in a ratio greater than or equal to 5:1 at a temperature less than 200° C., the platinum group metal film having a resistivity of less than 100 μΩ-cm and an impurity of less than 5 atomic %.
2. The method of claim 1 , wherein the platinum group metal is selected from the group consisting of platinum (Pt), palladium (Pd), iridium (Ir), osmium (Os), ruthenium (Ru), rhodium (Rh), and mixtures thereof.
3. The method of claim 2 , wherein the platinum group metal consists essentially of platinum (Pt).
4. The method of claim 1 , wherein the reducing agent is selected from one or more of hydrogen (H 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), silane (SiH 4 ), or disilane (Si 2 H 6 ).
5. The method of claim 1 , wherein the platinum group metal film is one or more of a platinum group metal metallic film, a platinum group metal carbide film, a platinum group metal nitride film, or a platinum group metal silicide film.
6. The method of claim 1 , wherein the conductive substrate comprises a metal selected from one or more of cobalt (Co), copper (Cu), nickel (Ni), ruthenium (Ru), manganese (Mn), silver (Ag), gold (Au), platinum (Pt), iron (Fe), molybdenum (Mo), rhodium (Rh), titanium (Ti), tantalum (Ta), silicon (Si), or tungsten (W).
7. The method of claim 6 , wherein the conductive substrate is one or more of a metal, a metal carbide, a metal nitride, or a metal silicide.
8. A method of depositing a film, the method comprising:
positioning a conductive substrate in a processing chamber;
exposing the conductive substrate to an organic platinum group metal precursor to selectively deposit a platinum group metal film on the conductive substrate versus deposition on a nonconductive substrate in a ratio of greater than or equal to 5:1 at a temperature less than 200° C., the organic platinum group metal precursor having a structure of general formula I
wherein R 1 and R 2 are independently selected from C 1-4 alkyl, hydrogen, halogen, CO, and cyclopentadienyl; M is a platinum group metal; and L is a ligand comprising at least one carbon-carbon double bond, a (CH 2 ) x where x is 1 to 8, and a NR 3 R 4 where R 3 and R 4 are independently selected from C 1-4 alkyl, hydrogen, or halogen;
purging the processing chamber of the organic platinum group metal precursor;
exposing the conductive substrate to a reducing agent, the processing chamber substantially free of an oxidant; and
purging the processing chamber of the reducing agent,
wherein the platinum group metal film has a resistivity of less than 100 μΩ-cm and an impurity of less than 5 atomic %.
9. The method of claim 8 , wherein the platinum group metal is selected from the group consisting of platinum (Pt), palladium (Pd), iridium (Ir), osmium (Os), ruthenium (Ru), and rhodium (Rh).
10. The method of claim 8 , wherein the reducing agent is selected from one or more of hydrogen (H 2 ), ammonia (NH 3 ), hydrazine (N 2 H 4 ), silane (SiH 4 ), or disilane (Si 2 H 6 ).
11. The method of claim 8 , wherein the platinum group metal film is one or more of a platinum group metal metallic film, a platinum group metal carbide film, a platinum group metal nitride film, or a platinum group metal silicide film.
12. The method of claim 8 , wherein the conductive substrate comprises a metal selected from one or more of cobalt (Co), copper (Cu), nickel (Ni), ruthenium (Ru), manganese (Mn), silver (Ag), gold (Au), platinum (Pt), iron (Fe), molybdenum (Mo), rhodium (Rh), titanium (Ti), tantalum (Ta), silicon (Si), or tungsten (W).
13. The method of claim 8 , wherein purging the processing chamber comprises flowing a purge gas over the conductive substrate.
14. The method of claim 8 , wherein the purge gas is selected from one or more of argon (Ar), nitrogen (N 2 ), or helium (He).