Methods for forming a metallic film on a substrate by cyclical deposition and related semiconductor device structures

• US 10,468,261 B2
• Filed: 02/15/2017
• Issued: 11/05/2019
• Est. Priority Date: 02/15/2017
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Vayrynen, Katja, Ritala, Mikko, Leskela, Markku
• Primary Examiner(s): Ahmed, Selim U
• Assistant Examiner(s): Clinton, Evan G
• Application Number:
  US15/434,051
• Publication Number:
  US 20180233372A1
• Time in Patent Office: 993 Days
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• 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 21/28556 by chemical means, e.g. CVD, LPCVD, PECVD, laser CVD H01L21/28518 - H01L21/28537 and H01L21/28568 take precedence
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/28568 the conductive layers comprising transition metals H01L21/28518 takes precedence
• CPC Class Codes: H01L 21/76873 for electroplating
• 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

Abstract

Methods for forming a metallic film on a substrate by cyclical deposition are provided. In some embodiments methods may include contacting the substrate with a first reactant comprising a non-halogen containing metal precursor comprising at least one of copper, nickel or cobalt and contacting the substrate with a second reactant comprising a hydrocarbon substituted hydrazine. In some embodiments related semiconductor device structures may include at least a portion of a metallic interconnect formed by cyclical deposition processes.

Claims

1. A method for forming a metallic film on a substrate by cyclical deposition, the method comprising:

contacting the substrate with a first reactant comprising a non-halogen containing metal precursor comprising at least one bidentate ligand and at least one of copper, nickel or cobalt to form metal-containing molecules on a surface of the substrate, wherein the non-halogen containing metal precursor comprises at least one ligand bonded to a metal atom through at least one oxygen atom and at least one nitrogen atom; and

contacting the substrate with a second reactant comprising a hydrocarbon substituted hydrazine precursor to thereby form the metallic film,

wherein the step of contacting the substrate with a second reactant immediately follows the step of contacting the substrate with a first reactant or immediately follows an intervening purge following the step of contacting the substrate with the first reactant, and

wherein the hydrocarbon substituted hydrazine precursor comprises a branch-chained allyl group or sec- or tert-isomer of alkyl group of at least four carbon atoms.

2. The method of claim 1, wherein the cyclical deposition comprises atomic layer deposition.

3. The method of claim 1, wherein the cyclical deposition comprises cyclical chemical vapor deposition.

4. The method of claim 1, further comprising selecting the substituted hydrocarbon hydrazine precursor to comprise a C4-C8 hydrocarbon group.

5. The method of claim 1, further comprising selecting the substituted hydrocarbon hydrazine precursor to comprise an aromatic hydrocarbon group.

6. The method of claim 1, further comprising selecting the substituted hydrocarbon hydrazine precursor to comprise a tertbutyl alkyl group.

7. The method of claim 6, further comprising selecting the alkyl group to comprise at least one of a methyl, an ethyl or a tertbutyl alkyl group.

8. The method of claim 1, wherein the non-halogen containing metal precursor comprises at least one additional ligand which is bonded to the metal atom through at least one nitrogen atom.

9. The method of claim 1, further comprising selecting the non-halogen containing metal precursor to comprise at least two non-halogen containing ligands.

10. The method of claim 1, wherein the method comprises at least one deposition cycle in which the substrate is alternately and sequentially contacted with the first reactant and the second reactant.

11. The method of claim 7, wherein the deposition cycle is repeated two or more times.

12. The method of claim 1, further comprising forming the metallic film to have an electrical resistivity of less than 10 μ

Ω

-cm.

13. The method of claim 1, further comprising forming the metallic film to have an electrical resistivity of less than 10 μ

Ω

-cm at a film thickness of less than 50 nm.

14. The method of claim 1, further comprising heating the substrate to a temperature of less than about 500°

C.

15. The method of claim 8, further comprising heating the substrate to a temperature of more than about 50°

C.

16. The method of claim 1, further comprising selecting the first reactant and the second reactant to comprise non-plasma reactants.

17. The method of claim 1, further comprising selecting the metallic film to comprise at least one of copper, cobalt or nickel.

18. A reaction system configured to perform the method of claim 1.

19. A semiconductor device structure comprising at least a portion of a metallic interconnect formed by the method of claim 1.

20. A method for forming a metallic film on a substrate by cyclical deposition, the method comprising:

contacting the substrate with a first reactant comprising a non-halogen containing metal precursor comprising at least one of Cu(dmap)₂, Ni(dmap)₂ or Co(dmap)₂; and

contacting the substrate with a second reactant comprising a hydrocarbon substituted hydrazine precursor to thereby form the metallic film,

wherein the step of contacting the substrate with a second reactant immediately follows the step of contacting the substrate with a first reactant or immediately follows an intervening purge following the step of contacting the substrate with the first reactant, and

wherein the hydrocarbon substituted hydrazine precursor comprises a branch-chained allyl group or sec- or tert-isomer of alkyl group of at least four carbon atoms.