Deposition of transition metal carbides

• US 6,800,552 B2
• Filed: 09/17/2002
• Issued: 10/05/2004
• Est. Priority Date: 10/15/1999
• Status: Expired due to Term

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Kaipio, Sari Johanna, Elers, Kai-Erik, Haukka, Suvi P., Soininen, Pekka Juha, Saanila, Ville Antero
• Primary Examiner(s): MEEKS, TIMOTHY HOWARD
• Application Number:
  US10/246,131
• Publication Number:
  US 20030031807A1
• Time in Patent Office: 749 Days
• Field of Search: 117/74, 117/88, 427/249.1, 427/249.17, 427/249.18, 427/249.19, 438/680, 438/685
• US Class Current: 438/680
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/045 Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
• CPC Class Codes: C23C 16/08 from metal halides
• CPC Class Codes: C23C 16/14 Deposition of only one other metal element
• CPC Class Codes: C23C 16/32 Carbides
• CPC Class Codes: C23C 16/34 Nitrides C23C16/303 takes precedence
• CPC Class Codes: C23C 16/44 characterised by the method of coating C23C16/04 takes precedence
• CPC Class Codes: C23C 16/4401 Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• 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: C23C 16/45542 Plasma being used non-continuously during the ALD reactions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: C23C 16/45555 applied in non-semiconductor technology
• CPC Class Codes: C30B 25/02 Epitaxial-layer growth
• CPC Class Codes: C30B 25/14 Feed and outlet means for the gases; Modifying the flow of the reactive gases
• CPC Class Codes: C30B 29/02 Elements
• CPC Class Codes: C30B 29/36 Carbides
• CPC Class Codes: C30B 29/38 Nitrides
• 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 21/76871 : Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
• 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 23/5226 : Via connections in a multilevel interconnection structure
• CPC Class Codes: H01L 23/53223 : Additional layers associated with aluminium layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H01L 23/53228 : the principal metal being copper
• CPC Class Codes: H01L 23/53238 : Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H01L 23/53242 : the principal metal being a noble metal, e.g. gold
• CPC Class Codes: H01L 23/53252 : Additional layers associated with noble-metal layers, e.g. adhesion, barrier, cladding layers
• CPC Class Codes: H01L 23/5329 : Insulating materials
• CPC Class Codes: H01L 23/53295 : Stacked insulating 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

Abstract

The present invention relates generally to a method of depositing transition metal carbide thin films. In particular, the invention concerns a method of depositing transition metal carbide thin films by atomic layer deposition (ALD), in which a transition metal source compound and a carbon source compound are alternately provided to the substrate. A variety of metal and carbon source gases are disclosed. The methods are applicable to forming metal carbide thin films in semiconductor fabrication, and particularly to forming thin, conductive diffusion barriers within integrated circuits.

Claims

1. A method of producing a thin film by an atomic layer deposition (ALD) process, in which each of a plurality of cycles comprises exposing an adsorbed metal complex on a substrate to a carbon compound, the carbon compound reacting with the adsorbed metal complex to form no more than about one monolayer of metal carbide, wherein the carbon compound is selected from the group consisting of organic boron compounds, organic silicon compounds and organic phosphorus compounds.

2. The method of claim 1, wherein at least a portion of the metal source gas adsorbs upon the substrate, thereby producing the adsorbed metal complex.

3. The method of claim 1, wherein the metal complex comprises a metal selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and W.

4. The method of claim 1, wherein vapor-phase pulses are alternately introduced in a cycle comprising:

introducing a metal source gas into a reaction space containing the substrate to form the adsorbed metal complex;

removing excess metal source gas and any gaseous reaction byproducts from the reaction space;

introducing the carbon compound into the reaction space; and

removing excess carbon compound and any gaseous reaction byproducts from the reaction space.

5. The method of claim 4, wherein the adsorbed metal complex forms no more than about one monolayer.

6. The method of claim 4, wherein the carbon compound reacts with the adsorbed metal complex to leave a transition metal carbide.

7. The method of claim 4, wherein gaseous reaction byproducts are formed by the reaction of the adsorbed metal complex with the carbon compound.

8. The method of claim 4, wherein the metal source gas and carbon compound are each fed into the reaction space with the aid of an inert carrier gas.

9. The method of claim 4, further comprising feeding an inert gas pulse to the reaction space after each pulse of metal source gas and carbon compound.

10. The method of claim 4, wherein the metal source gas is a transition metal halide.

11. The method of claim 10, wherein the metal source gas is tungsten hexafluoride.

12. The method of claim 1, wherein the carbon compound comprises a volatile boron compound comprising at least one boron atom and at least one carbon atom.

13. The method of claim 12, wherein the boron compound is an alkyl boron compound.

14. The method of claim 13, wherein the boron compound is triethylboron.

15. The method of claim 1, wherein the carbon compound comprises a volatile silicon compound comprising at least one silicon atom and at least one carbon atom.

16. The method of claim 15, wherein the silicon compound is an alkylsilicon compound.

17. The method of claim 1, wherein the carbon compound comprises a volatile phosphorous compound comprising at least one phosphorous atom and at least one carbon atom.

18. The method of claim 17, wherein the phosphorous source compound is an alkylphosphorus compound.

19. The method of claim 1, wherein the metal carbide forms part of a conductive diffusion barrier in an integrated circuit.

20. The method of claim 19, wherein the conductive diffusion barrier comprises a liner in a dual damascene void.

21. The method of claim 1, wherein the metal carbide forms part of a hard coating on a substrate to protect against mechanical wear.

22. The method of claim 1, wherein the metal carbide forms part of a corrosion protection layer.

23. The method of claim 1, wherein the metal carbide forms part of a chemical reaction catalyst.

24. The method of claim 1, wherein the carbon compound comprises radicals generated in a plasma formed from an organic boron compound.

25. The method of claim 24, wherein the organic boron compound is an alkyl boron compound.

26. The method of claim 25, wherein the alkyl boron compound is triethylboron.

27. A method of producing a metal carbide thin film in an integrated circuit by an atomic layer deposition (ALD) process, in which each of a plurality of cycles comprises:

introducing a metal source gas into a reaction space containing a substrate to form an adsorbed metal complex;

removing excess metal source gas and any gaseous reaction byproducts from the reaction space;

introducing an organic boron compound into the reaction space; and

removing excess organic boron compound and any gaseous reaction byproducts from the reaction space.

28. The method of claim 27, wherein the metal source gas comprises a transition metal halide.

29. The method of claim 28, wherein the transition metal halide comprises a transition metal fluoride.

30. The method of claim 29, wherein the transition metal fluoride comprises tungsten fluoride.

31. The method of claim 29, wherein the transition metal fluoride comprises tantalum fluoride.

32. The method of claim 29, wherein the transition metal fluoride comprises titanium fluoride.

33. The method of claim 27, wherein the organic boron compound is selected from the group consisting of carboranes, amine-borane adducts, aminoboranes, alkyl borons and alkyl boranes.

34. The method of claim 27, wherein the organic boron compound comprises an alkyl boron.

35. The method of claim 34, wherein the alkyl boron comprises triethylboron.