Selective deposition of noble metal thin films

• US 9,469,899 B2
• Filed: 12/02/2014
• Issued: 10/18/2016
• Est. Priority Date: 03/15/2005
• Status: Active Grant

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Huotari, Hannu, Tuominen, Marko, Leinikka, Miika
• Primary Examiner(s): Kebede, Brook
• Application Number:
  US14/557,874
• Publication Number:
  US 20150315703A1
• Time in Patent Office: 686 Days
• Field of Search: 438/585, 438/758
• US Class Current: 1/1
• CPC Class Codes: C23C 16/32 Carbides
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/38 Borides
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: H01L 21/28079 the final conductor layer next to the insulator being a single metal, e.g. Ta, W, Mo, Al
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence
• CPC Class Codes: H01L 29/66583 with initial gate mask or masking layer complementary to the prospective gate location, e.g. with dummy source and drain contacts

Abstract

Processes are provided for selectively depositing thin films comprising one or more noble metals on a substrate by vapor deposition processes. In some embodiments, atomic layer deposition (ALD) processes are used to deposit a noble metal containing thin film on a high-k material, metal, metal nitride or other conductive metal compound while avoiding deposition on a lower k insulator such as silicon oxide. The ability to deposit on a first surface, such as a high-k material, while avoiding deposition on a second surface, such as a silicon oxide or silicon nitride surface, may be utilized, for example, in the formation of a gate electrode.

Claims

1. A method for selectively depositing a thin film comprising one or more noble metals on a substrate comprising a first surface and a second surface in a reaction space, the method comprising:

contacting the first and second surface of the substrate with a gaseous noble metal precursor;

contacting the first and second surface of the substrate with a second gaseous reactant; and

repeating until a thin film of a desired thickness is obtained selectively on the first surface relative to the second surface,

wherein the first surface comprises a material selected from the group consisting of high-k materials, metals, metal nitrides, metal carbides, metal borides, conductive oxides and mixtures thereof; and

wherein the second surface comprises a material selected from the group consisting of silicon oxides, silicon nitrides, silicon oxynitrides, fluorinated silica glass (FSG), carbon doped silicon oxide (SiOC) and materials containing more than about 50% silicon oxide and wherein the temperature is below about 400°

C.

2. The method of claim 1, additionally comprising removing excess gaseous noble metal precursor from the reaction chamber after contacting the substrate with the noble metal precursor and prior to contacting the substrate with the second gaseous reactant.

3. The method of claim 1, wherein the thin film is not formed on the second surface.

4. The method of claim 1, wherein the thin film that is deposited is thicker on the first surface than on the second surface.

5. The method of claim 1, wherein the second surface is SiO₂.

6. The method of claim 1, wherein the second surface is silicon oxynitride.

7. The method of claim 1, wherein the noble metal precursor comprises ruthenium.

8. The method of claim 7, wherein the noble metal precursor is Ru(EtCp)₂.

9. The method of claim 7, wherein a ruthenium layer is deposited on the first surface of the substrate relative to the second surface.

10. The method of claim 9, wherein a conductive layer is subsequently deposited on the ruthenium layer.

11. The method of claim 1, wherein the first surface comprises a material selected from the group consisting of Ta, TaN, TaC_x, TaB_x, Ti, TiN, TiC_x, TiB_x, Nb, NbN, NbC_x, NbB_x Mo, MoN, MoC_x, MoB_x, W, WN, WC_x, WB_x, V, Cr, Fe, Cu, Co, Ni, Cd, Zn, Al, Ag, Au, Ru, RuO_x, Rh, Pt, Pd, Ir, IrO_x and Os.

12. The method of claim 1, wherein the second gaseous reactant comprises oxygen.

13. The method of claim 1, wherein the second gaseous reactant comprises ammonia.

14. The method of claim 1, wherein the second reactant comprises ammonia plasma.

15. The method of claim 1, wherein the substrate is alternately and sequentially contacted with the first and second gaseous reactants.

16. The method of claim 1, wherein the method is an atomic layer deposition process.

17. The method of claim 1, wherein the temperature is below about 350°

C.