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

• US 9,379,011 B2
• Filed: 08/22/2012
• Issued: 06/28/2016
• 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): Stark, Jarrett
• Assistant Examiner(s): Ausar-El, Charles N
• Application Number:
  US13/592,025
• Publication Number:
  US 20130115768A1
• Time in Patent Office: 1,406 Days
• Field of Search: 438/664
• US Class Current: 1/1
• 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 of depositing a conformal nickel thin film on a substrate by multiple cycles of a vapor deposition process, each cycle comprising alternately and sequentially contacting a substrate in a reaction space with a vapor phase nickel precursor, a second precursor and a third precursor to form a conformal elemental nickel thin film, wherein the second precursor is an organic reducing agent comprising at least one functional group selected from the group consisting of alcohol (—

OH), aldehyde (—

CHO), or carboxylic acid (—

COOH), and wherein the third precursor is selected from hydrogen and forming gas.

2. The method of claim 1, wherein no more than about one monolayer of the nickel precursor is formed on the substrate surface in each cycle.

3. 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.

13. The method of claim 1, wherein the conformal nickel thin film has a thickness non-uniformity between 5% and 40%.

4. An atomic layer deposition-type process for forming a conformal elemental Ni thin film on a substrate in a reaction chamber comprising multiple Ni deposition cycles, each deposition cycle comprising:

providing a first vapor phase reactant pulse comprising a first Ni precursor into the reaction chamber to form a layer of the Ni precursor on the substrate;

removing excess first reactant from the reaction chamber;

providing a second vapor phase reactant pulse to the reaction chamber such that the second reactant reacts with the first Ni precursor on the substrate in a self-limiting manner to form elemental Ni;

removing excess second reactant and reaction byproducts, if any, from the reaction chamber; and

contacting the substrate with a third reactant,

wherein the second vapor phase reactant is an organic reducing agent comprising at least one functional group selected from the group consisting of alcohol (—

OH), aldehyde (—

CHO), or carboxylic acid (—

COOH), and wherein the third reactant is selected from hydrogen and forming gas.

5. The method of claim 4, wherein the first Ni 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.

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

14. The process of claim 4, wherein the conformal elemental Ni thin film has a thickness non-uniformity between 5% and 40%.

7. An ALD-type process for depositing conformal Ni thin films on a substrate in a reaction space comprising multiple Ni deposition cycles, each deposition cycle comprising:

providing a first vapor phase reactant pulse comprising a first Ni precursor into the reaction space to form a layer of the Ni precursor on the substrate;

removing excess first reactant from the reaction space;

providing a second vapor phase reactant pulse to the reaction space, wherein the second reactant is an organic reducing agent;

removing excess second reactant and reaction byproducts, if any, from the reaction space; and

providing a third vapor phase reactant pulse to the reaction space, wherein the third reactant is hydrogen or forming gas; and

removing excess third reactant and reaction byproducts, if any, from the reaction space,

wherein the deposition cycle forms elemental nickel and the process forms a conformal Ni thin film.

8. The method of claim 7, wherein the first Ni 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 8, wherein the first Ni 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-heptanedionato.

10. The method of claim 7 wherein the first nickel precursor is bis(4-N-ethylamino-3-penten-2-N-ethyliminato)nickel (II).

11. The method of claim 7, wherein the organic reducing agent is provided after the Ni precursor but before the hydrogen or forming gas.

12. The method of claim 7, wherein the organic reducing agent is provide after the Ni precursor and after the hydrogen or forming gas.

15. The process of claim 7, wherein the conformal Ni thin films have a thickness non-uniformity between 5% and 40%.