Metal nitride carbide deposition by ALD

• US 7,410,666 B2
• Filed: 11/22/2005
• Issued: 08/12/2008
• Est. Priority Date: 09/14/2001
• Status: Expired due to Term

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Li, Wei-Min, Elers, Kai
• Primary Examiner(s): Talbot; Brian K
• Application Number:
  US11/286,203
• Publication Number:
  US 20060078679A1
• Time in Patent Office: 994 Days
• Field of Search: 427/96.8, 427/97.7, 427/98.1, 427/255.28, 427/255.394, 438/643, 438/653, 438/678, 438/687
• US Class Current: 427/97.7
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/36 Carbonitrides
• CPC Class Codes: C23C 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient compositions
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45534 Use of auxiliary reactants other than used for contributing to the composition of the main film, e.g. catalysts, activators or scavengers
• 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 21/76807 for dual damascene structures
• CPC Class Codes: H01L 21/76838 characterised by the formation and the after-treatment of the conductors etching for patterning the conductors H01L21/3213
• CPC Class Codes: H01L 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76846 Layer combinations
• CPC Class Codes: H01L 21/76862 Bombardment with particles, e.g. treatment in noble gas plasmas; UV irradiation
• CPC Class Codes: H01L 21/76871 Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
• CPC Class Codes: H01L 21/76873 for electroplating
• CPC Class Codes: H01L 21/76874 for electroless plating
• CPC Class Codes: H01L 21/76876 for deposition from the gas phase, e.g. CVD
• CPC Class Codes: H01L 2221/1089 Stacks of seed layers
• CPC Class Codes: H01L 23/53238 Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H01L 2924/00 Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: Y10T 428/24331 : including nonapertured component

Abstract

The present methods provide tools for growing conformal metal thin films, including metal nitride, metal carbide and metal nitride carbide thin films. In particular, methods are provided for growing such films from aggressive chemicals. The amount of corrosive chemical compounds, such as hydrogen halides, is reduced during the deposition of transition metal, transition metal carbide, transition metal nitride and transition metal nitride carbide thin films on various surfaces, such as metals and oxides. Getter compounds protect surfaces sensitive to hydrogen halides and ammonium halides, such as aluminum, copper, silicon oxide and the layers being deposited, against corrosion. Nanolaminate structures incorporating metallic thin films, and methods for forming the same, are also disclosed.

Claims

1. A process for producing an integrated circuit comprising:

forming a damascene structure including trenches in an insulating material on a substrate;

placing the substrate in a reaction chamber;

depositing a metal nitride carbide diffusion barrier by an atomic layer deposition (ALD) process; and

depositing metal over the metal carbide nitride.

2. The method of claim 1, wherein the ALD process comprises a plurality of cycles, each cycle comprising at least one pulse of a gettering agent.

3. The method of claim 2, wherein the ALD process comprises providing pulses of a metal halide and an intervening reactant, wherein a pulse of the gettering agent does not immediately follow a pulse of the metal halide.

4. The method of claim 2, wherein a pulse of the gettering agent is provided before a pulse of the metal halide and a pulse of the intervening reactant is provided after the pulse of the metal halide in each of the plurality of cycles.

5. The method of claim 4, wherein the first cycle starts with pulse of gettering agent.

6. The method of claim 4, wherein the intervening reactant pulse comprises a pulse of NH₃.

7. The method of claim 4, wherein the metal halide comprises WE₆.

8. The method of claim 4, wherein the gettering agent comprises a boron compound.

9. The method of claim 8, wherein the boron compound comprises triethylboron.

10. The method of claim 1, wherein the substrate comprises exposed copper oxide and the exposed copper oxide is reduced prior to depositing the metal nitride carbide diffusion barrier.

11. The method of claim 10, wherein the exposed copper oxide is reduced with a compound selected from the group consisting of alcohols, aldehydes and carboxylic acids.

12. The method of claim 10, wherein the exposed copper oxide is reduced with hydrogen plasma.

13. The method of claim 10, additionally including treating surfaces of the substrate surface with ammonia following reduction of the exposed copper oxide.

14. The method of claim 1, additionally including depositing a metal oxide on the substrate and reducing the metal oxide to metal, after depositing the metal nitride carbide diffusion barrier and prior to depositing metal over the metal nitride carbide.

15. The method of claim 14, wherein reducing the metal oxide comprises exposure to a compound selected from the group consisting of alcohols, aldehydes and carboxylic acids.

16. The method of claim 1, additionally comprising depositing a seed layer over the metal nitride carbide prior to depositing metal over the metal nitride carbide.

17. The method of claim 1, wherein the metal nitride carbide is WN_xC_y.

18. The method of claim 17, wherein the WN_xC_y comprises about 55 at.-% of tungsten, about 25-30 at.-% of carbon and about 15-20 at.-% of nitrogen.

19. The method of claim 17, wherein depositing the metal nitride carbide diffusion barrier is carried out at temperatures from 275 to 350 C.

20. The method of claim 17, wherein a thickness of the WN_xC_y is less than 5 nm.

21. The method of claim 1, wherein the metal deposited over the metal nitride carbide is copper.

22. The method of claim 21, wherein the copper is deposited by a method selected from the group consisting of electroless plating, electrochemical deposition, chemical vapor deposition and catalytically enhanced chemical vapor deposition.

23. The method of claim 1, wherein the insulating material consists essentially of a low-k material.

24. The method of claim 1, wherein the insulating material comprises silicon oxide deposited by chemical vapor deposition.

25. The method of claim 23, wherein the low-k material is selected from the group consisting of polymeric materials, porous materials and fluorine-doped oxides.

26. The method of claim 1, wherein the reaction chamber is part of a cluster tool.

27. The method of claim 1, wherein the insulating material is selected from the group consisting of polymeric materials, porous materials and fluorine-doped oxides.