Method of forming a transition metal containing film on a substrate by a cyclical deposition process, a method for supplying a transition metal halide compound to a reaction chamber, and related vapor deposition apparatus

• US 10,731,249 B2
• Filed: 02/15/2018
• Issued: 08/04/2020
• Est. Priority Date: 02/15/2018
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Hatanpaa, Timo, Vayrynen, Katja, Ritala, Mikko, Leskela, Markku
• Primary Examiner(s): Louie, Mandy C
• Application Number:
  US15/897,578
• Publication Number:
  US 20190249300A1
• Time in Patent Office: 901 Days
• Field of Search: None
• CPC Class Codes: C23C 16/406 of iron group metals
• CPC Class Codes: C23C 16/45523 Pulsed gas flow or change of composition over time
• CPC Class Codes: C23C 16/45527 characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/28568 the conductive layers comprising transition metals H01L21/28518 takes precedence
• CPC Class Codes: H01L 21/768 Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76879 by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating plating on semiconductors in general H01L21/288
• CPC Class Codes: H01L 23/53209 based on metals, e.g. alloys, metal silicides H01L23/53285 takes precedence
• CPC Class Codes: H01L 23/53238 Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers

Abstract

A method of forming a transition metal containing films on a substrate by a cyclical deposition process is disclosed. The method may include: contacting the substrate with a first vapor phase reactant comprising a transition metal halide compound comprising a bidentate nitrogen containing adduct ligand; and contacting the substrate with a second vapor phase reactant. A method for supplying a transition metal halide compound comprising a bidentate nitrogen containing ligand to a reaction chamber is disclosed, along with related vapor deposition apparatus.

Claims

1. A method of forming a transition metal containing film on a substrate by a cyclical deposition process, the method comprising:

contacting the substrate with a first vapor phase reactant comprising a transition metal halide compound comprising a bidentate nitrogen containing adduct ligand, wherein the a bidentate nitrogen containing adduct ligand coordinates to a transition metal atom of the transition metal halide compound, and wherein a halogen atom is bonded to the metal atom; and

contacting the substrate with a second vapor phase reactant.

2. The method of claim 1, wherein the adduct ligand comprises two nitrogen atoms, each of nitrogen atoms bonded to at least one carbon atom.

3. The method of claim 1, wherein the transition metal halide compound comprise a transition metal chloride.

4. The method of claim 3, wherein the transition metal chloride compound comprises at least one of a cobalt chloride, a nickel chloride, or a copper chloride.

5. The method of claim 4, wherein the transition metal chloride compound comprises at least one of cobalt chloride (TMEDA), or nickel chloride (TMPDA).

6. The method of claim 1, wherein the second vapor phase reactant comprises an oxygen precursor selected from the group consisting of ozone (O₃), molecular oxygen (O₂), oxygen atoms (O), an oxygen plasma, oxygen radicals, oxygen excited species, water (H₂O), and hydrogen peroxide (H₂O₂).

7. The method of claim 6, wherein the transition metal containing film comprises a transition metal oxide.

8. The method of claim 7, wherein the transition metal oxide substantially comprises cobalt (II) oxide (CoO).

9. The method of claim 7, further comprising contacting the transition metal oxide with a reducing agent precursor thereby forming an elemental transition metal.

10. The method of claim 9, wherein the reducing agent precursor comprises at least one of forming gas (H₂+N₂), ammonia (NH₃), hydrazine (N₂H₄), molecular hydrogen (H₂), hydrogen atoms (H), a hydrogen plasma, hydrogen radicals, hydrogen excited species, alcohols, aldehydes, carboxylic acids, boranes, or amines.

11. The method of claim 1, further comprising contacting the substrate with a third vapor phase reactant comprising a reducing agent precursor selected from the group consisting of tertiary butyl hydrazine (C₄H₁₂N₂), hydrogen (H₂), a hydrogen (H₂) plasma, ammonia (NH₃), an ammonia (NH₃) plasma, hydrazine (N₂H₄), silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), germane (GeH₄), digermane (Ge₂H₆), borane (BH₃), and diborane (B₂H₆).

12. The method of claim 1, wherein the transition metal containing film comprises at least one of elemental cobalt, elemental nickel, or elemental copper.

13. The method of claim 1, wherein the cyclical deposition process comprises an atomic layer deposition process.

14. The method of claim 1, wherein the cyclical deposition process comprises a cyclical chemical vapor deposition process.

15. The method of claim 1, wherein the transition metal containing film comprises at least one of an elemental transition metal, a transition metal nitride, a transition metal silicide, a transition metal sulfide, a transition metal selenide, a transition metal phosphide, or a transition metal boride.

16. A method of forming a transition metal containing film on a substrate by a cyclical deposition process, the method comprising:

contacting the substrate with a first vapor phase reactant comprising a transition metal compound comprising an adduct forming ligand that coordinates to a transition metal of the transition metal compound and a halide bonded to the transition metal; and

contacting the substrate with a second vapor phase reactant;

wherein the transition metal is selected group consisting of copper (Cu), nickel (Ni), and cobalt (Co).

17. The method of claim 16, wherein the adduct forming ligand comprises at least one of nitrogen, phosphorous, oxygen, or sulfur.

18. The method of claim 16, wherein the transition metal compound comprises a transition metal halide compound, selected from the group consisting of a transition metal chloride, a transition metal iodide, a transition metal fluoride, or a transition metal bromide.

19. The method of claim 18, wherein the transition metal halide compound comprises a bidentate nitrogen adduct forming ligand.

20. The method of claim 16, wherein the transition metal compound comprises at least one of cobalt chloride (TMEDA), cobalt bromide (TMEDA), cobalt iodide (TMEDA), cobalt chloride (TMPDA), or nickel chloride (TMPDA).

21. The method of claim 16, wherein the transition metal compound comprising an adduct forming ligand is synthesized utilizing a one-step synthesis process comprising, combining a transition metal halide compound and an adduct forming ligand at a temperature of less than 50°

C.

22. The method of claim 16, wherein the second vapor phase reactant comprises at least one of a oxygen precursor, a nitrogen precursor, a silicon precursor, a sulfur precursor, a selenium precursor, a phosphorous precursor, a boron precursor, or a reducing agent.

23. A method for supplying a transition metal halide compound comprising a bidentate nitrogen containing adduct ligand to a reaction chamber, the method comprising:

providing a precursor source vessel configured for containing the transition metal halide compound, wherein the transition metal halide compound comprises a halide atom bonded to a transition metal atom;

fluidly connecting the precursor source vessel to the reaction chamber;

heating the transition metal halide compound contained in the precursor source vessel to a temperature greater than 50°

C.;

generating a vapor pressure of the transition metal halide compound of least at least 0.001 mbar; and

supplying the transition metal halide compound to the reaction chamber.

24. The method of claim 23, wherein the transition metal halide compound comprises at least one of cobalt chloride (TMEDA), nickel chloride (TMPDA).