Copper CVD precursors with enhanced adhesion properties
View Patent ↗This invention relates to copper(+1)(β-diketonate)(L) and related copper complexes such as copper (+1)(β-ketoiminate)(L) represented by the formula: wherein X represents O or NR 9 , R 1 and R 3 are each independently comprised of the group C 1-8 alkyl, C 1-8 fluoroalkyl, aryl, C 1-8 alkoxy, and C 1-8 alkyl ethers and R 2 is H, C 1-8 alkyl, C 1-8 alkoxy, and halogen, R 9 is C 1-8 alkyl, C 1-8 fluoroalkyl, phenyl, alkylphenyl, trialkylsilyl, and L represents a ligand having the structure: (R 4 )(R 5 )C═(R 6 )(R 7 ) or R 4 —C≡C—R 7 wherein R 4 , is comprised of the group C 1-8 alkanol, C 1-8 alkoxyalkanol, C 1-8 unsaturated alkoxyalkanol, trialkylsilanol, C 1-8 aalkylamine, phenylamine; R 5 , R 6 , and R 7 are comprised of the group H, C 1-8 alkyl, triakylsilyl, alkoxy or phenyl.
1. A monovalent copper(+1)(β-diketonate)(L) or monovalent copper(+1)(β-ketoiminate)(L) complex represented by the formula:
wherein X represents O or NR 9 wherein R 1 and R 3 are each independently, selected from the group consisting of C 1-8 alkyl, C 1-8 fluoroalkyl, aryl, C 1-8 alkoxy, and C 1-8 alkyl ethers and R 2 is H, C 1-8 alkyl, C 1-8 alkoxy, and halogen, R 9 is C 1-8 alkyl, C 1-8 fluoroalkyl, phenyl, alkylpheny, trialkylsilyl, and L represents a ligand having the structure:
(R 4 )(R 5 )C═(R 6 )(R 7 ) or R 4 —C≡C—R 7
wherein R 4 is selected from the group consisting of C 1-8 alkanol, C 1-8 alkoxyalkanol, C 1-8 unsaturated alkoxyalkanol, trialkylsilanol, C 1-8 alkylamine, phenylamine; R 5 , R 6 , and R 7 are selected from the group consisting of H, C 1-8 alkyl, triakylsilyl, alkoxy or phenyl.
2. The complex of claim 1 wherein X is O.
3. The complex of claim 2 wherein R 1 and R 3 are selected from the group consisting of C 1-3 alkyl and C 1-3 fluoroalkyl.
4. The complex of claim 3 wherein R 2 is H.
5. The complex of claim 4 wherein L is represented by the formula:
(R 4 )(R 5 )C═(R 6 )(R 7 ).
6. The complex of claim 5 wherein R 4 is (CH 3 ) 2 COH.
7. The complex of claim 6 wherein R 5 , R 6 , and R 7 are H.
8. The complex of claim 7 wherein R 1 and R 3 are CF 3 .
9. The complex of claim 2 wherein β-diketonate portion of the compound is derived from a β-diketone selected from the group consisting of 1,1,1,5,5,5-hexafluoro-2,4-pentanedione; 4-(2,2,2-trifluoroethyl)imino-1,1,1,5,5,5-hexafluoro-2-pentanone; 5-(2,2,2-trifluoroethyl)imino-1,1,1,2,2,6,6,6-octafluoro-3-hexanone, and 6-(2,2,2-trifluoroethyl)imino-1,1,1,2,2,3,3,7,7,7,-decafluoro-4-heptanone.
10. The complex of claim 4 wherein L is represented by the formula:
R 4 —C≡C—R 7 .
11. The complex of claim 10 wherein R 4 is CH 2 OH.
12. The complex of claim 11 wherein R 7 is H.
13. The complex of claim 12 wherein R 1 and R 3 are CF 3 .
14. The complex of claim 9 wherein the β-diketonate portion is derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione and the ligand L is derived from 2-methyl 3-buten-2-ol.
15. The complex of claim 1 wherein X is NR 9 .
16. The complex of claim 15 wherein R 1 and R 3 are selected from the group consisting of C 1-3 alkyl and C 1-3 fluoroalkyl and R 2 is H.
17. The complex of claim 16 wherein R 9 is C 1-3 fluoroalkyl.
18. The complex of claim 17 wherein L is represented by the formula:
(R 4 )(R 5 )C═(R 6 )(R 7 ).
19. The complex of claim 18 wherein R 4 is (CH 3 ) 2 COH and R 5 , R 6 , and R 7 are H.
20. In a process for the chemical vapor deposition of copper metal on metallic substrates or electrically conducting portions of a substrate using organometallic copper compounds, the improvement which comprises using the monovalent copper complex of claim 1 as the organometallic copper compound.