Deposition of complex nitride films

• US 7,691,757 B2
• Filed: 06/21/2007
• Issued: 04/06/2010
• Est. Priority Date: 06/22/2006
• Status: Active Grant

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Zagwijn, Peter, Claasen, Tanja, Haukka, Suvi P.
• Primary Examiner(s): Wilczewski; M.
• Assistant Examiner(s): Thomas; Toniae M
• Application Number:
  US11/766,718
• Publication Number:
  US 20080003838A1
• Time in Patent Office: 1,020 Days
• Field of Search: 427/255.28, 427/255.39, 427255393-255394, 438/785
• US Class Current: 438/785
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45546 specially adapted for a substrate stack in the ALD reactor
• CPC Class Codes: H01L 21/32051 Deposition of metallic or metal-silicide layers
• CPC Class Codes: H01L 21/32053 of metal-silicide layers

Abstract

Methods are provided for pulsed chemical vapor deposition (CVD) of complex nitrides, such as ternary metal nitrides. Pulses of metal halide precursors are separated from one another and nitrogen-containing precursor is provided during the metal halide precursor pulses as well as between the metal halide precursor pulses. Two different metal halide precursors can be provided in simultaneous pulses, alternatingly, or in a variety of sequences. The nitrogen-containing precursor, such as ammonia, can be provided in pulses simultaneously with the metal halide precursors and between the metal halide precursors, or continuously throughout the deposition. Temperatures can be kept between about 300° C. and about 700° C.

Claims

1. A method for depositing a nitride-containing film onto a substrate, comprising:

providing a substrate in a reaction chamber;

heating the substrate in the reaction chamber;

flowing a first metal halide precursor into the reaction chamber in temporally separated pulses;

flowing a second metal halide precursor into the reaction chamber in temporally separated pulses; and

flowing a nitrogen containing precursor into the reaction chamber, wherein flowing the nitrogen-containing precursor comprises;

flowing the nitrogen-containing precursor during the pulses of the first and second metal halide precursors to induce a thermally activated reaction between at least one of the metal halide precursors and the nitrogen-containing precursor, and

flowing the nitrogen containing precursor between the pulses of the first and the second metal halide precursors.

2. The method of claim 1, wherein flowing the nitrogen-containing precursor comprises flowing NH₃.

3. The method of claim 1, wherein flowing the nitrogen-containing precursor comprises continuously flowing the nitrogen-containing precursor.

4. The method of claim 3, wherein flowing the nitrogen-containing precursor comprises flowing the nitrogen-containing precursor in the reaction chamber at a constant rate.

5. The method of claim 1, wherein flowing the nitrogen-containing precursor comprises flowing the nitrogen-containing precursor in temporally separated pulses.

6. The method of claim 1, wherein the first metal halide precursor comprises a metal selected from the group consisting of Ti, Zr, Hf V, Nb, Ta, Cr, Mo, W, and Al.

7. The method of claim 6, wherein the second metal halide precursor comprises a metal selected from the group consisting of Si, Ge, B, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, and Al and is different from the first metal.

8. The method of claim 1, wherein the temporally separated pulses of the first metal halide precursor and the second metal halide precursor comprise at least a period of alternation of the first metal halide precursor pulses with the second metal halide precursor pulses.

9. The method of claim 1, wherein flowing the first and second metal halide precursors comprises simultaneously flowing pulses of the first metal halide precursor and pulses of the second metal halide precursor into the reaction chamber.

10. The method of claim 1, wherein providing the substrate comprises providing a plurality of substrates in the reaction chamber.

11. The method of claim 1, wherein the reaction chamber is provided in a vertical furnace.

12. The method of claim 1, wherein the first and second metal halide precursors comprise halogens selected from the group consisting of F, Cl, I, Br and combinations thereof.

13. The method of claim 1, wherein the deposited nitride is selected from the group consisting of TiSiN, TaSiN, TiAlN and TiHfN.

14. The method of claim 1, wherein the deposited nitride is selected from the group consisting of TiSiN, TaSiN, HfSiN, ZrSiN, TiAIN, TaAlN, HfAlN, ZrAlN, TiHfN, TiZrN and HfZrN.

15. The method of claim 1, wherein heating the substrate comprises heating the substrate to a temperature between about 300°

C. and 700°

C.

16. The method of claim 15, wherein heating the substrate comprises heating the substrate to a temperature between about 450°

C. and 550°

C.