Amidate precursors for depositing metal containing films
View Patent ↗Volatile metal amidate metal complexes are exemplified by bis(N-(tert-butyl)ethylamidate)bis(ethylmethylamido) titanium; (N-(tert-butyl)(tert-butyl)amidate)tris(ethylmethylamido) titanium; bis(N-(tert-butyl)(tert-butyl)amidate)bis(dimethylamido) titanium and (N-(tert-butyl)(tert-butyl)amidate)tris(dimethylamido) titanium. The term “volatile” refers to any precursor of this invention having vapor pressure above 0.5 torr at temperature less than 200° C. Metal-containing film depositions using these metal amidate ligands are also described.
1. A volatile amidate metal complex represented by the following Formula I:
where M is selected from the Group 2 to Group 15 metals; R 1 is selected from the group consisting of linear or branched alkyl group containing 1 to 5 carbon atom, linear or branched alkoxyalkyl, and linear or branched aminoalkyl; E is R 2 or NR 3 R 4 , where R 2 , R 3 , R 4 are independently selected from the group consisting of linear or branched alkyl group containing 1-6 carbon atoms, cyclic alkyl group containing 4-6 carbon atoms, and an aromatic group containing 6-12 carbon atoms; L is an anionic ligand independently selected from the group consisting of alkoxy, amino, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, and aminosubsitituted pyrrolyl; n is the oxidation state of M; and x is 1 to n−1.
2. The amidate metal complex of claim 1 having vapor pressure above 0.5 torr at a temperature less than 200° C.
3. The amidate metal complex of claim 1 wherein M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, lanthanide metals, calcium, strontium, barium, manganese, cobalt, nickel, iron and combination thereof.
4. The amidate metal complex of claim 1 represented by the Formula II
5. The amidate metal complex of claim 1 represented by the Formula III:
wherein M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, lanthanide metals, calcium, strontium, barium, manganese, cobalt, nickel, iron and combination thereof; where R 2 , R 6 and R 7 are independently selected from the group consisting of linear or branched alkyl group containing 1-6 carbon atoms, cyclic alkyl groups of 4-6 carbon atoms and aromatic groups of 6-12 carbon atoms; R 5 is C 2-3 linear or branched alkylene bridge; L is an anionic ligand independently selected from the group consisting of alkoxy, amino, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, and aminosubsitituted pyrrolyl; n is the oxidation state of M; and x is 0 to n−1.
6. The metal complex of claim 1 represented by the Formula IV:
wherein M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, lanthanide metals, calcium, strontium, barium, manganese, cobalt, nickel, iron and combination thereof; where R 2 and R 9 are independently selected from the group consisting of linear or branched alkyl group containing 1-6 carbon atoms, cyclic alkyl groups of 4-6 carbon atoms and aromatic groups of 6-12 carbon atoms; R 8 is C 2-3 linear or branched alkylene bridge; L is an anionic ligand independently selected from the group consisting of alkoxy, amino, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, and aminosubsitituted pyrrolyl; n is the oxidation state of M; and x is 0 to n−1.
7. The metal complex of claim 1 represented by the Formula V:
where M is selected from the group consisting of Ti, Zr, and Hf; R 1 and R 2 are independently selected from the group consisting of linear or branched alkyl group containing 1 to 6 carbon atom, linear or branched alkoxyalkyl, linear or branched aminoalkyl; R 12 , R 13 are independently selected from the group consisting of linear, cyclic or branched alkyl group containing 1-6 carbon atoms; x is 0, 1, 2 or 3.
8. The metal complex of claim 7 having the following structure where Me is methyl and Bu t is tert-butyl;
9. The metal complex of claim 7 having the following structure where Et is ethyl, Pr i is iso-propyl and Bu t is tert-butyl;
10. The metal complex of claim 7 having the following structure where Me is methyl and Bu t is tert-butyl;
11. The metal complex of claim 7 having the following structure where Me is methyl, Et is ethyl and Bu t is tert-butyl;
12. The metal complex of claim 7 having the following structure where Me is methyl, Et is ethyl and Bu t is tert-butyl;
13. The metal complex of claim 7 having the following structure where Me is methyl and Bu t is tert-butyl;
14. The metal complex of claim 1 represented by the Formula VI:
where M is selected from the group consisting of Ti, Zr, and Hf; R 2 and R 10 are independently selected from the group consisting of linear or branched alkyl group containing 1 to 6 carbon atom; R 1 is selected from the group consisting of linear or branched alkyl group containing 1 to 5 carbon atom; x is 0, 1, 2 or 3; p=1 or 2.
15. The metal complex of claim 12 wherein R 1-2 and R 10 are independently selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and tert-butyl; x is 1 or 2; p=1 or 2.
16. The metal complex of claim 1 represented by Formula VII:
where M is selected from the group consisting of scandium, yttrium, lanthanide metals and mixtures thereof; R 1 and R 2 are independently selected from the group consisting of linear or branched alkyl group containing 1 to 6 carbon atom; L is an anionic ligand independently selected from alkoxy, amido, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, and aminosubsitituted pyrrolyl; x is 0, 1 or 2.
17. The metal complex of claim 1 represented by Formula VIII
where M is selected from the group consisting of calcium, strontium and barium; where R 2 , R 6 and R 7 are independently selected from the group consisting of linear or branched alkyl group containing 1-6 carbon atoms, cyclic alkyl groups of 4-6 carbon atoms, aromatic groups of 6-12 carbon atoms; and R 5 is a linear or branched alkylene bridge, preferably ethylene or propylene group.
18. The metal complex of claim 1 represented by Formula IX:
where M is selected from the group consisting of calcium, strontium and barium; where R 2 and R 9 are independently selected from the group consisting of linear or branched alkyl group containing 1-6 carbon atoms, cyclicalkyl groups of 4-6 carbon atoms and aromatic groups of 6-12 carbon atoms; and R 8 is a linear or branched alkylene bridge, preferably ethylene or propylene group.
19. The metal complex of claim 1 represented by Formula X:
where M is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, lanthanide metals, calcium, strontium, barium, manganese, cobalt, nickel, iron and combination thereof; R 1, 2 & 11 are independently selected from the group consisting of linear or branched alkyl group containing 1 to 6 carbon atom, linear or branched alkoxyalkyl, and linear or branched aminoalkyl; m=0, 1, 2, 3, 4, 5; and n is the oxidation state of M.
20. The metal complex of claim 19 wherein M=Zr; R 1-2 and R 11 are independently selected from the group consisting of methyl (Me), ethyl (Et), n-propyl, iso-propyl (Pr i ) n-butyl, iso-butyl, sec-butyl, and tert-butyl (Bu t ).
21. A method for depositing a metal-containing film on a substrate comprising;
(a) providing a amidate metal complex represented by the following Formula I:
where M is selected from the Group 2 to Group 15 metal; R 1 is selected from the group consisting of linear or branched alkyl group containing 1 to 5 carbon atom, linear or branched alkoxyalkyl, linear or branched aminoalkyl; E is R 2 or NR 3 R 4 , where R 2 , R 3 , R 4 are independently selected from the group consisting of linear, cyclic or branched alkyl group containing 1-6 carbon atoms, or an aromatic group; L is an anionic ligand independently selected from alkoxy, amino, diketonate, ketoiminate, diiminate, cyclopentadienyl, alkyl substituted cyclopentadienyl, alkoxysubstituted cyclopentadienyl, aminosubsitituted cyclopentadienyl, pyrrolyl, alkyl substituted pyrrolyl, alkoxysubstituted pyrrolyl, and aminosubsitituted pyrrolyl; n is the oxidation state of M; and x is 1 to n−1;
(b) providing a substrate; and,
(c) depositing a metal containing film from the amidate metal complex using a process selected from the group consisting of cyclic CVD (CCVD), MOCVD (Metal Organic CVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition (“PECVD”), high density PECVD, photon assisted CVD, plasma-photon assisted (“PPECVD”), cryogenic chemical vapor deposition, chemical assisted vapor deposition, hot-filament chemical vapor deposition, CVD of a liquid polymer precursor, deposition from supercritical fluids, low energy CVD (LECVD), plasma enhanced ALD (PEALD), and plasma enhanced cyclic CVD (PECCVD).
22. The method of claim 21 where the temperature is in the range of 200 to 500° C.
23. The method of claim 21 including co-deposition of metal from a metal complex selected from the group consisting of tetrakis(dimethylamino)zirconium (TDMAZ), tetrakis(diethylamino)zirconium (TDEAZ), tetrakis(ethylmethylamino)zirconium (TEMAZ), tetrakis(dimethylamino)hafnium (TDMAH), tetrakis(diethylamino)hafnium (TDEAH), and tetrakis(ethylmethylamino)hafnium (TEMAH), tetrakis(dimethylamino)titanium (TDMAT), tetrakis(diethylamino)titanium (TDEAT), tetrakis(ethylmethylamino)titanium (TEMAT), tert-butylimino tri(diethylamino)tantalum (TBTDET), tert-butylimino tri(dimethylamino)tantalum (TBTDMT), tert-butylimino tri(ethylmethylamino)tantalum (TBTEMT), ethylimino tri(diethylamino)tantalum (EITDET), ethylimino tri(dimethylamino)tantalum (EITDMT), ethylimino tri(ethylmethylamino)tantalum (EITEMT), tert-amylimino tri(dimethylamino)tantalum (TAIMAT), tert-amylimino tri(diethylamino)tantalum, pentakis(dimethylamino)tantalum, tert-amylimino tri(ethylmethylamino)tantalum, bis(tert-butylimino)bis(dimethylamino)tungsten (BTBMW), bis(tert-butylimino)bis(diethylamino)tungsten, bis(tert-butylimino)bis(ethylmethylamino)tungsten, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)strontium, bis(2,2,6,6-tetramethyl-3,5-heptanedionato)barium, M(R n C 5 H 5−n ) 2 , wherein n=1-5, R is selected from linear or branched C 1-6 alkyls; M(R n C 4 H 4−n ) 2 , wherein n=2-4, R is selected from linear or branched C 1-6 alkyls; M(R n N 2 H 3−n ) 2 , where n=2-3, R is selected from linear or branched C 1-6 alkyls, and combinations thereof.
24. The method of claim 21 including providing an oxygen source selected from the group consisting of water (H 2 O) (e.g., deionized water, purifier water, distilled water), water plasma, oxygen (O 2 ), oxygen plasma, ozone (O 3 ), NO, NO 2 , carbon monoxide (CO), carbon dioxide (CO 2 ) and combinations thereof.
25. The method of claim 21 including providing a nitrogen source selected from the group consisting of NO, NO 2 , ammonia, hydrazine, monoalkylhydrazine, dialkylhydrazine, and combinations thereof.
26. The method of claim 21 including providing an energy source selected from the group consisting of thermal, plasma, pulsed plasma, helicon plasma, high density plasma, inductively coupled plasma, X-ray, e-beam, photon, remote plasma, secondary RF frequency and combinations thereof.
27. The method of claim 21 including the steps comprising;
a. introducing a metal-containing precursor in a vapor state into a reaction chamber and chemisorbing the metal-containing precursor onto a substrate which is heated;
b. purging away the unreacted metal-containing precursor;
c. introducing an oxygen source onto the heated substrate to react with the sorbed metal-containing precursor;
d. purging away the unreacted oxygen source; and
e. the steps are repeated until a desire thickness of metal-containing film is achieved.