Methods for depositing nickel films and for making nickel silicide and nickel germanide

• US 10,553,440 B2
• Filed: 06/20/2016
• Issued: 02/04/2020
• Est. Priority Date: 12/19/2008
• Status: Active Grant

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Pore, Viljami J., Haukka, Suvi P., Blomberg, Tom E., Tois, Eva E.
• Primary Examiner(s): Parker, Allen L
• Assistant Examiner(s): Ausar-El, Charles N
• Application Number:
  US15/186,950
• Publication Number:
  US 20170018433A1
• Time in Patent Office: 1,324 Days
• Field of Search: 438664
• CPC Class Codes: H01L 21/28052 the conductor comprising a silicide layer formed by the silicidation reaction of silicon with a metal layer formed by metal ion implantation H01L21/28044
• CPC Class Codes: H01L 21/28518 the conductive layers comprising silicides H01L21/28537 takes precedence
• CPC Class Codes: H01L 21/28568 the conductive layers comprising transition metals H01L21/28518 takes precedence
• CPC Class Codes: H01L 21/321 After treatment
• CPC Class Codes: H01L 21/32133 by chemical means only
• CPC Class Codes: H01L 21/3215 Doping the layers
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76855 After-treatment introducing at least one additional element into the layer
• CPC Class Codes: H01L 21/76886 Modifying permanently or temporarily the pattern or the conductivity of conductive members, e.g. formation of alloys, reduction of contact resistances
• CPC Class Codes: H01L 29/456 on silicon
• CPC Class Codes: H01L 29/665 using self aligned silicidation, i.e. salicide formation of conductive layers comprising silicides H01L21/28518
• CPC Class Codes: H01L 29/78 with field effect produced by an insulated gate H01L29/7725, H01L29/775, H01L29/778 take precedence

Abstract

In one aspect, methods of silicidation and germanidation are provided. In some embodiments, methods for forming metal silicide can include forming a non-oxide interface, such as germanium or solid antimony, over exposed silicon regions of a substrate. Metal oxide is formed over the interface layer. Annealing and reducing causes metal from the metal oxide to react with the underlying silicon and form metal silicide. Additionally, metal germanide can be formed by reduction of metal oxide over germanium, whether or not any underlying silicon is also silicided. In other embodiments, nickel is deposited directly and an interface layer is not used. In another aspect, methods of depositing nickel thin films by vapor phase deposition processes are provided. In some embodiments, nickel thin films are deposited by ALD. Nickel thin films can be used directly in silicidation and germanidation processes.

Claims

1. A method for forming a doped nickel silicide layer on a substrate, comprising:

providing a substrate having at least one exposed silicon region;

depositing a nickel film over the silicon region, wherein depositing the nickel film comprises multiple cycles of a primary nickel deposition process in which the substrate is alternately and sequentially contacted with vapor phase pulses of a nickel precursor and a second reactant comprising an organic reducing agent;

depositing a dopant film comprising a second metal over the silicon region, wherein depositing the dopant film comprises one or more cycles of a dopant deposition process; and

annealing the substrate to form a nickel silicide that is doped with the second metal, wherein the cycles of the primary nickel deposition process and the cycles of the dopant deposition process are carried out at a specific ratio to achieve a desired dopant concentration in the doped metal silicide layer.

2. The method of claim 1 wherein the second metal is platinum.

3. The method of claim 1, wherein depositing the dopant film comprises depositing a dopant oxide by the one or more cycles of the dopant deposition process and subsequently reducing the dopant oxide to form the dopant film.

4. The method of claim 1, wherein the dopant deposition process is carried out after the primary nickel deposition process.

5. The method of claim 1, wherein in each cycle of the primary nickel deposition process no more than about one monolayer of nickel precursor is formed on the substrate surface and the second reactant reacts with the nickel precursor to form the nickel film.

6. The method of claim 1, wherein annealing comprises heating the substrate to a temperature greater than about 350°

C.

7. The method of claim 1, wherein the primary nickel deposition process is an atomic layer deposition-type process.

8. The method of claim 1, wherein the nickel precursor is selected from the group consisting of nickel betadiketonate compounds, nickel betadiketiminato compounds, nickel aminoalkoxide compounds, nickel amidinate compounds, nickel cyclopentadienyl compounds, nickel carbonyl compounds and combinations thereof.

9. The method of claim 1, wherein the nickel precursor has the formula X(acac)_y or X(thd)_y, where X is a metal, y is from about 2 to about 3 and thd is 2,2,6,6-tetramethyl-3,5-heptanediol.

10. The method of claim 1, wherein the nickel precursor is bis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II).

11. The method of claim 1, wherein the dopant deposition process is an atomic layer deposition-type process.