Method for selectively depositing a metallic film on a substrate

• US 10,403,504 B2
• Filed: 10/05/2017
• Issued: 09/03/2019
• Est. Priority Date: 10/05/2017
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Longrie, Delphine, de Roest, David Kurt
• Primary Examiner(s): Jang, Bo B
• Application Number:
  US15/726,222
• Publication Number:
  US 20190109009A1
• Time in Patent Office: 698 Days
• Field of Search: None
• CPC Class Codes: C23C 16/0209 by heating
• CPC Class Codes: C23C 16/04 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 16/047 using irradiation by energy or particles
• CPC Class Codes: C23C 16/06 characterised by the deposition of metallic material
• CPC Class Codes: C23C 16/08 from metal halides
• 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: H01L 21/28229 by deposition of a layer, e.g. metal, metal compound or poysilicon, followed by transformation thereof into an insulating layer
• CPC Class Codes: H01L 21/28562 Selective deposition
• CPC Class Codes: H01L 21/30655 comprising alternated and repeated etching and passivation steps, e.g. Bosch process
• CPC Class Codes: H01L 21/32051 Deposition of metallic or metal-silicide layers
• CPC Class Codes: H01L 21/321 After treatment
• CPC Class Codes: H01L 21/4846 Leads on or in insulating or insulated substrates, e.g. metallisation H01L21/4821 takes precedence; metallisation of ceramics in general C04B41/51; printed circuits H05K3/00
• CPC Class Codes: H01L 21/76814 post-treatment or after-treatment, e.g. cleaning or removal of oxides on underlying conductors
• CPC Class Codes: H01L 21/76826 by contacting the layer with gases, liquids or plasmas
• CPC Class Codes: H01L 21/76828 thermal treatment
• 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

A method for selectively depositing a metallic film on a substrate comprising a first dielectric surface and a second metallic surface is disclosed. The method may include, exposing the substrate to a passivating agent, performing a surface treatment on the second metallic surface, and selectively depositing the metallic film on the first dielectric surface relative to the second metallic surface. Semiconductor device structures including a metallic film selectively deposited by the methods of the disclosure are also disclosed.

Claims

1. A method for selectively depositing a metallic film on a substrate comprising a first dielectric surface and a second metallic surface, the method comprising;

exposing the substrate to a passivating agent;

performing a surface treatment on the second metallic surface; and

after performing a surface treatment on the second metallic surface, selectively depositing the metallic film on the first dielectric surface relative to the second metallic surface,

wherein performing a surface treatment on the second metallic surface further comprises removing a passivating layer from the second metallic surface, and

wherein removing the passivating layer from the second metallic surface comprises exposing the passivating layer to formic acid.

2. The method of claim 1, wherein exposing the substrate to a passivating agent and performing a surface treatment on the second metallic surface are performed at a substrate temperature of greater than approximately 250°

C.

3. The method of claim 1, further comprising out-gassing the substrate prior to exposing the substrate to the passivating agent.

4. The method of claim 3, wherein out-gassing the substrate further comprises out-gassing the substrate at a temperature greater than approximately 250°

C. for a time period greater than approximately 15 seconds.

5. The method of claim 1, wherein the passivating agent comprises an alkylhalosilane.

6. The method of claim 1, wherein the passivating agent comprises trimethyl(dimethylamino)silane.

7. The method of claim 1, wherein exposing the substrate to a passivating agent further comprises exposing the substrate to a passivating agent for a time period of greater than 15 seconds.

8. The method of claim 1, wherein the passivating layer comprises benzotriazole or a benzotriazole derivative.

9. The method of claim 1, wherein the second metallic surface comprises a copper oxide and exposing the passivating layer to formic acid reduces the copper oxide to copper.

10. The method of claim 1, wherein exposing the substrate to a passivating agent and performing a surface treatment on the second metallic surface are performed in a first reaction chamber and selectively depositing the metallic film is performed in a second reaction chamber.

11. The method of claim 1, wherein selectively depositing the metallic film comprises performing one or more sequential deposition cycles, each deposition cycle comprising alternating contacting the substrate with a metal containing precursor and contacting the substrate with a reducing agent precursor-.

12. The method of claim 11, wherein the metal containing precursor comprises at least one of tungsten hexafluoride (WF₆), tantalum pentafluoride (TaF₅), niobium pentafluoride (NbF₅), titanium tetrafluoride (TiF₄), a molybdenum fluoride (MoF_x) or a vanadium fluoride (VF_x).

13. The method of claim 11, wherein the reducing agent precursor comprises at least one of hydrogen (H₂), a hydrogen (H₂) plasma, an ammonia (NH₃) plasma, ammonia (NH₃), silane (SiH₄), disilane (Si₂H₆), trisilane (Si₃H₈), germane (GeH₄), digermane (Ge₂H₆), or diborane (B₂H₆).

14. The method of claim 1, wherein selectively depositing the metallic film further comprises heating the substrate to a temperature of greater than approximately 50°

C.

15. The method of claim 1, wherein the metallic film comprises tungsten (W).

16. The method of claim 1, wherein the selectivity is greater than about 90%.

17. A semiconductor device structure comprising the metallic film deposited by the method of claim 1.

18. The semiconductor device structure of claim 17 wherein the metallic film comprises a tungsten film disposed over the first dielectric surface.

19. A method for selectively depositing a metallic film on a substrate comprising a first dielectric surface and a second metallic surface, the method comprising;

exposing the substrate to a passivating agent;

performing a surface treatment on the second metallic surface; and

after performing a surface treatment on the second metallic surface, selectively depositing the metallic film on the first dielectric surface relative to the second metallic surface,

wherein performing a surface treatment on the second metallic surface further comprises removing a passivating layer, comprising benzotriazole or a benzotriazole derivative, from the second metallic surface.

20. The method of claim 19, further comprising out-gassing the substrate prior to exposing the substrate to the passivating agent.