Methodology for in-situ doping of aluminum coatings

• US 6,534,133 B1
• Filed: 06/30/2000
• Issued: 03/18/2003
• Est. Priority Date: 06/14/1996
• Status: Expired due to Term

• Current Assignee: The Research Foundation for The State University of New York (State University of New York)
• Original Assignee: The Research Foundation for The State University of New York (State University of New York)
• Inventors: Kaloyeros, Alain E., Knorr, Andres, Faltermeier, Jonathan
• Primary Examiner(s): MEEKS, TIMOTHY HOWARD
• Application Number:
  US09/607,900
• Time in Patent Office: 991 Days
• Field of Search: 427/250, 427/252, 427/255.7, 427/576, 438/680, 438/681, 438/687, 438/688
• US Class Current: 427/576
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/4412 Details relating to the exhausts, e.g. pumps, filters, scrubbers, particle traps
• CPC Class Codes: C23C 16/5096 Flat-bed apparatus
• CPC Class Codes: H01L 21/32051 Deposition of metallic or metal-silicide layers
• CPC Class Codes: H01L 21/76877 Filling of holes, grooves or trenches, e.g. vias, with conductive material

Abstract

A chemical vapor deposition process for the in-situ preparation of conformal copper-doped aluminum coatings on a substrate comprises the steps of generating a first flow of a first reactant vapor directed to the substrate in the reactor, the first reactant vapor including a copper source precursor; heating the substrate to a temperature sufficient to decompose the first reactant vapor and form an ultrathin copper seed layer; generating a second flow of a second reactant vapor directed to the substrate in the reactor, the second reactant vapor including an aluminum source precursor; and heating the substrate to a temperature higher than 185° C. to decompose the second reactant vapor and form a copper-doped aluminum film.

Claims

1. A chemical vapor deposition process for the in-situ preparation of conformal copper-doped aluminum coatings on a substrate in a chemical vapor deposition (CVD) reactor comprising:

a. generating a first flow of a first reactant vapor directed to said substrate in said reactor, said first reactant vapor comprising a copper source precursor;

b. heating said substrate to a temperature sufficient to decompose said first reactant vapor and form, directly on a surface of the substrate, a copper layer having a thickness of less than 10 nm;

c. generating a second flow of a second reactant vapor directed to said substrate in said reactor, said second reactant vapor consisting of an aluminum source precursor, and optionally, a carrier gas;

d. heating said substrate to a temperature higher than 185°

C. to decompose said second reactant vapor and form a copper-doped aluminum film.

2. The method of claim 1 wherein said first flow of reactant vapor is generated by vaporizing a mixture of copper source precursor and a precursor diluting agent.

3. The method of claim 2 wherein said precursor diluting agent comprises a liquid medium selected from the group consisting of alcohols, ethanol, methanol, 2-propanol, acetone, hexane, toluene, water, amines, and halides.

4. The method of claim 2 wherein said precursor diluting agent comprises a gaseous medium selected from the group consisting of inert gases, hydrogen, amines, ammonia, water vapor, carbon monoxide, carbon dioxide, and nitrous oxide.

5. The method of claim 2 wherein the concentration of said copper source precursor in said first flow of reactant vapor ranges from 0.001 wt % to 50 wt %.

6. The method of claim 1 wherein said first reactant vapor additionally comprises a gas selected from the group consisting of hydrogen, water vapor, alcohols, helium, argon, xenon, and nitrogen.

7. The method of claim 1 further comprising applying an electrical bias to the substrate.

8. The method of claim 7 wherein the electrical bias on the substrate is selected from the group consisting of direct current (dc), radio frequency of less than 500 kHz, radio frequency from 500 kHz to 10⁶ kHz, and microwave frequency.

9. The method of claim 8 wherein said radio frequency or microwave electrical bias is with electrical power in the range 0.005 Watts/cm² to 100 Watts/cm².

10. The method of claim 7 further comprising the steps of generating a plasma in the reactor.

11. The method of claim 1 comprising the further step of generating a plasma of at least one of said first reactant gas and said second reactant gas in the region above the substrate.

12. The method of claim 11 wherein said plasma is selected from the group consisting of direct current plasma, radio frequency plasma, electron cyclotron plasma, inductively coupled plasma, and microwave plasma.

13. The method of claim 1 wherein said aluminum source precursor has a formula R¹ R² R³ Al, wherein R¹, R² and R³ are independently H or lower alkyl.

14. The method of claim 13 wherein said lower alkyl is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

15. The method of claim 13 wherein said aluminum source precursor is selected from the group consisting of tri-isobutylaluminum, disobutylaluminun hydride, trimethylaluminum, dimethylaluminum hydride, triethylaluminum, and diethylaluminun hydride.

16. The method of claim 1 wherein said aluminum source precursor is an aluminum halide.

17. The method of claim 16 wherein the aluminum halide is aluminum trichloride or aluminum tribromide.

18. The method of claim 1 wherein said aluminum source precursor is an aluminum tris(β

-diketonate).

19. The method of claim 1 wherein said aluminum source precursor is an alkyl amide aluminum.

20. The method of claim 1 wherein said aluminum source precursor is a trialkylamine alane.

21. The method of claim 20 wherein the trialkylamine alane is dimethylethylamine alane, trimethylamine alane, and triethylamine alane.

22. The method of claim 1 wherein said copper is deposited from a precursor selected from the group consisting of copper(I)-tert-butoxide-tetramers, cyclopentadienyl-copper(I)-phosphine compounds, ligand stabilized copper(I) b-diketonates, and copper(II) β

-diketonates.

23. The method of claim 1 comprising the further step of annealing said substrate.

24. The method of claim 1 wherein said second reactant vapor consists or an aluminum source precursor and a carrier gas selected from the group consisting of hydrogen, water vapor, alcohols, helium, argon, xenon, and nitrogen.

25. A chemical vapor deposition process for the in-situ preparation of conformal, copper-doped aluminum coatings on a substrate in a chemical vapor deposition (CVD) reactor comprising the steps of:

a. heating said substrate to a temperature of 225-300°

C.;

b. generating a flow of first reactant vapor directed to said substrate in said reactor, said first reactant vapor including a copper source precursor chosen from copper N,N′

-dimethylketenimidate, copper (II) hexafluoroacetylacetonate, or copper (I) trimethylvinylsilane;

c. decomposing said first reactant vapor and depositing, directly on a surface of the substrate, a conformal copper layer with thickness of less than 10 nanometers;

d. generating a flow of second reactant vapor directed to said substrate in said reactor, said second reactant vapor consisting of an aluminum source precursor chosen from dimethylethylaluminum alane and dimethylaluminum hydride, and optionally, a carrier gas; and

e. decomposing said second reactant vapor and depositing a conformal copper-containing aluminum film over said copper layer.

26. The process of claim 25, wherein said first reactant vapor is generated by vaporizing a mixture of copper source precursor and isopropanol, wherein the concentration of said copper source precursor in isopropanol is 0.1-10 wt %.