Method for nucleation of conductive nitride films
Provided is improved methodology for the nucleation of certain metal nitride substrate surfaces utilizing certain silicon-containing halides, silicon-containing amides, and certain metal precursors, in conjunction with nitrogen-containing reducing gases. While utilizing a pretreatment step, the methodology shows greatly improved nucleation wherein a microelectronic device substrate having such a metal nitride film deposited thereon has a thickness of about 10 Å to about 15 Å and less than about 1% of void area. Once such nucleation has been achieved, traditional layer-upon-layer deposition can rapidly take place.
1. A pretreatment process for metal nitride nucleation on the surface of a microelectronic device substrate in a reaction zone, which comprises:
I. introducing compounds chosen from A, B, and C into a reaction zone under pulsed vapor deposition conditions, wherein said pulsed vapor deposition conditions comprise a plurality of pulse sequences, wherein at least two of compounds, A, B, and C are introduced into said reaction zone, one of which is A, sequentially and in any order, each optionally followed by a purge step with an inert gas, to define a cycle of pulse sequences, wherein said plurality comprises at least three cycles, wherein A, B, and C are defined as:
A. a precursor chosen from silicon-containing halides and silicon-containing amides, wherein A is bis-t-amyl ethylene silylene;
B. a metal precursor, wherein said metal is chosen from titanium, tantalum, molybdenum, tungsten, and niobium; and
C. a nitrogen-containing reducing gas, wherein said nitrogen-containing reducing gas is introduced into said reaction zone once or twice per cycle of each pulse sequence.
2. The process of claim 1 , wherein the cycle of pulse sequences is repeated about 3 to about 15 times.
3. The process of claim 1 , wherein B is TiCl 4 .
4. The process of claim 1 , wherein the pulse sequence is bis-t-amyl ethylene silylene; NH 3 ; TiCl 4 ; and NH 3 .
5. A process for metal nitride nucleation on the surface of a microelectronic device substrate in a reaction zone, the process comprising the process of claim 1 , further comprising:
introducing into said reaction zone a second cycle of pulse sequences comprising introducing compounds D and E into said reaction zone, in either order, each optionally followed by purging with an inert gas:
D. a metal precursor, wherein said metal is chosen from titanium, tantalum, molybdenum, tungsten, and niobium; and
E. a nitrogen-containing reducing gas; and
repeating said second cycle of pulse sequences for a sufficient number of iterations to establish a metal nitride nucleation on a substrate to afford a coverage representing less than about 1% of void areas in a film having a thickness of about 10 Å to about 15 Å.
6. The process of claim 5 , wherein the metal precursor is chosen from TiCl 4 ; TiI 4 ; Ti(NCH 2 CH 3 )Cl; tetrakis(dimethylamido)titanium; TaCl 5 ; MoCl 3 ; WCl 5 ; and NbCl 5 .
7. The process of claim 5 , wherein the metal nitride is chosen from titanium nitride, tantalum nitride, molybdenum nitride, tungsten nitride, and niobium nitride.
8. The process of claim 5 , wherein the nitrogen containing reducing gas is chosen from ammonia, hydrazine, methyl hydrazine, t-butyl hydrazine, 1,1-dimethylhydrazine, and 1,2-dimethylhydrazine.
9. The process of claim 5 , wherein the first cycle of pulse sequences is repeated about 3 to about 15 times.
10. The process of claim 5 , wherein the metal precursor is chosen from TiCl 4 , TiI 4 , Ti(NCH 2 CH 3 )Cl, and TaCl 5 .
11. A pretreatment process for metal nitride nucleation on the surface of a microelectronic device substrate in a reaction zone, which comprises:
I. introducing compounds chosen from A, B, and C into a reaction zone under pulsed vapor deposition conditions, wherein said pulsed vapor deposition conditions comprise a plurality of pulse sequences, wherein at least two of compounds, A, B, and C are introduced into said reaction zone, one of which is A, sequentially and in any order, each optionally followed by a purge step with an inert gas, to define a cycle of pulse sequences, wherein said plurality comprises at least three cycles, wherein A, B, and C are defined as:
A. a precursor chosen from silicon-containing halides and silicon-containing amides, wherein A is a compound of the formula
B. a metal precursor, wherein said metal is chosen from titanium, tantalum, molybdenum, tungsten, and niobium; and
C. a nitrogen-containing reducing gas, wherein said nitrogen-containing reducing gas is introduced into said reaction zone once or twice per cycle of each pulse sequence.
12. The process of claim 11 , wherein the metal precursor is chosen from TiCl 4 ; TiI 4 ; Ti(NCH 2 CH 3 )Cl; tetrakis(dimethylamido)titanium; TaCl 5 ; MoCl 3 ; WCl 5 ; and NbCl 5 .
13. The process of claim 11 , wherein the metal nitride is chosen from titanium nitride, tantalum nitride, molybdenum nitride, tungsten nitride, and niobium nitride.
14. The process of claim 11 , wherein the nitrogen containing reducing gas is chosen from ammonia, hydrazine, methyl hydrazine, t-butyl hydrazine, 1,1-dimethylhydrazine, and 1,2-dimethylhydrazine.
15. A pretreatment process for metal nitride nucleation on the surface of a microelectronic device substrate in a reaction zone, which comprises:
I. introducing compounds chosen from A, B, and C into a reaction zone under pulsed vapor deposition conditions, wherein said pulsed vapor deposition conditions comprise a plurality of pulse sequences, wherein at least two of compounds, A, B, and C are introduced into said reaction zone, one of which is A, sequentially and in any order, each optionally followed by a purge step with an inert gas, to define a cycle of pulse sequences, wherein said plurality comprises at least three cycles, wherein A, B, and C are defined as:
A. a precursor chosen from silicon-containing halides and silicon-containing amides, wherein A is a compound of the formula
B. a metal precursor, wherein said metal is chosen from titanium, tantalum, molybdenum, tungsten, and niobium; and
C. a nitrogen-containing reducing gas, wherein said nitrogen-containing reducing gas is introduced into said reaction zone once or twice per cycle of each pulse sequence.
16. The process of claim 15 , wherein the metal precursor is chosen from TiCl 4 ; TiI 4 ; Ti(NCH 2 CH 3 )Cl; tetrakis(dimethylamido)titanium; TaCl 5 ; MoCl 3 ; WCl 5 ; and NbCl 5 .
17. The process of claim 15 , wherein the metal nitride is chosen from titanium nitride, tantalum nitride, molybdenum nitride, tungsten nitride, and niobium nitride.
18. The process of claim 15 , wherein the nitrogen containing reducing gas is chosen from ammonia, hydrazine, methyl hydrazine, t-butyl hydrazine, 1,1-dimethylhydrazine, and 1,2-dimethylhydrazine.