Low resistivity films containing molybdenum

• US 10,510,590 B2
• Filed: 04/09/2018
• Issued: 12/17/2019
• Est. Priority Date: 04/10/2017
• Status: Active Grant

• Current Assignee: Lam Research Corporation
• Original Assignee: Lam Research Corporation
• Inventors: Thombare, Shruti Vivek, Humayun, Raashina, Danek, Michal, Lai, Chiukin Steven, Collins, Joshua, Bamnolker, Hanna, Kennedy, Griffin John, Butail, Gorun, van Cleemput, Patrick A.
• Primary Examiner(s): Blum, David S
• Application Number:
  US15/948,143
• Publication Number:
  US 20180294187A1
• Time in Patent Office: 617 Days
• Field of Search: 438653
• CPC Class Codes: C23C 16/06 characterised by the deposition of metallic material
• CPC Class Codes: C23C 18/08 characterised by the deposition of metallic material
• 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 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76864 Thermal treatment
• CPC Class Codes: H01L 21/76876 for deposition from the gas phase, e.g. CVD
• CPC Class Codes: H01L 21/76877 Filling of holes, grooves or trenches, e.g. vias, with conductive material
• 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
• CPC Class Codes: H01L 23/5226 Via connections in a multilevel interconnection structure
• CPC Class Codes: H01L 23/53266 Additional layers associated with refractory-metal layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H10B 12/488 Word lines
• CPC Class Codes: H10B 41/27 the channels comprising vertical portions, e.g. U-shaped channels
• CPC Class Codes: H10B 43/27 the channels comprising vertical portions, e.g. U-shaped channels

Abstract

Provided herein are low resistance metallization stack structures for logic and memory applications and related methods of fabrication. In some implementations, the methods involve providing a tungsten (W)-containing layer on a substrate; and depositing a molybdenum (Mo)-containing layer on the W-containing layer. In some implementations, the methods involve depositing a Mo-containing layer directly on a dielectric or titanium nitride (TiN) substrate without an intervening W-containing layer.

Claims

1. A method comprising:

depositing a tungsten (W)-containing layer on a substrate by reacting a W-containing precursor with a reducing agent, wherein the reducing agent is a silicon (Si)-containing compound or a boron (B)-containing compound; and

depositing a molybdenum (Mo)-containing layer on the W-containing layer, wherein the Mo-containing layer is deposited by exposing the W-containing layer to a reducing agent and a Mo-containing precursor and wherein the substrate is exposed to the reducing agent at first substrate temperature and is exposed to the Mo-containing precursor at a second substrate temperature, wherein the first substrate temperature is less than the second substrate temperature.

2. The method of claim 1, wherein the W-containing layer is a WCN layer or a W nucleation layer.

3. The method of claim 1, wherein the W-containing precursor is a tungsten chloride precursor.

4. The method of claim 1, wherein the Mo-containing layer is a Mo layer having less than 1 (atomic) % impurities.

5. The method of claim 1, further comprising thermally annealing the Mo-containing layer.

6. The method of claim 1, wherein the Mo-containing precursor selected from:

molybdenum hexafluoride (MoF₆), molybdenum pentachloride (MoCl₅), molybdenum dichloride dioxide (MoO₂Cl₂), molybdenum tetrachloride oxide (MoOCl₄), and molybdenum hexacarbonyl (Mo(CO)₆).

7. The method of claim 1, wherein a substrate temperature during exposure to the Mo-containing precursor is less than 550°

C.

8. The method of claim 1, wherein the reducing agent is a mixture of a boron-containing reducing agent and a silicon-containing reducing agent.

9. A method comprising:

flowing a reducing agent gas to a process chamber housing a substrate at a first substrate temperature to form a conformal reducing agent layer on the substrate; and

exposing the conformal reducing agent layer to a molybdenum-containing precursor at a second substrate temperature to convert the conformal reducing agent layer to molybdenum.

10. The method of claim 9, wherein the reducing agent gas comprises one or more of a silicon-containing compound and a boron-containing compound.

11. The method of claim 10, wherein the first substrate temperature is less than the second substrate temperature.

12. The method of claim 10, wherein the reducing agent gas is a mixture of a boron-containing reducing agent and a silicon-containing reducing agent.

13. The method of claim 10, wherein the first substrate temperature is no more than 400°

C. and the second substrate temperature is at least 500°

C.

14. The method of claim 10, further comprising annealing the molybdenum.

17. The method of claim 10, wherein the conformal reducing agent layer is formed on a tungsten (W)-containing layer.

18. The method of claim 17, wherein the W-containing layer is a WCN layer or a W nucleation layer.

19. The method of claim 11, wherein the reducing agent gas comprises one or more of a boron-containing reducing agent and a silicon-containing reducing agent.

20. The method of claim 10, wherein the molybdenum-containing precursor is selected from:

molybdenum hexafluoride (MoF₆), molybdenum pentachloride (MoCl₅), molybdenum dichloride dioxide (MoO₂Cl₂), molybdenum tetrachloride oxide (MoOCl₄), and molybdenum hexacarbonyl (Mo(CO)₆).

15. A method comprising:

pulsing a reducing agent, wherein the reducing agent is boron (B)-containing, silicon (Si)-containing or germanium (Ge)-containing; and

pulsing a Mo-containing precursor,

wherein the Mo-containing precursor is reduced by the reducing agent or a product thereof to form a multi-component molybdenum-containing film containing one or more of B, Si, and Ge on a substrate.

16. The method of claim 15, wherein the multi-component molybdenum-containing film contains between 5% and 60% (atomic) B, Si, or Ge, and wherein the between 5% and 60% (atomic) B, Si, or Ge is provided by the reducing agent.