Method for depositing nanolaminate thin films on sensitive surfaces

• US 6,902,763 B1
• Filed: 10/16/2000
• Issued: 06/07/2005
• 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): La Villa, Michael
• Application Number:
  US10/049,125
• Time in Patent Office: 1,695 Days
• Field of Search: 428/216, 428/938, 427/250, 427/252, 427/253, 427/255.11, 427/255.15, 427/255.23, 427/255.26, 427/255.28, 427/255.39, 427/255.391, 427/255.392, 427/255.394, 427/255.7, 438/245, 438/607, 257/E21.586, 257/751, 257/499
• US Class Current: 427/250
• 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 16/45529 specially adapted for making a layer stack of alternating different compositions or gradient 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: C30B 25/02 Epitaxial-layer growth
• 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 21/76843 formed in openings in a dielectric
• CPC Class Codes: H01L 21/76846 Layer combinations
• CPC Class Codes: H01L 21/76877 Filling of holes, grooves or trenches, e.g. vias, with conductive material

Abstract

The present method provides tools for growing conformal metal nitride, metal carbide and metal thin films, and nanolaminate structures incorporating these 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 and transition metal nitride thin films on various surfaces, such as metals and oxides. Getter compounds protect surface sensitive to hydrogen halides and ammonium halides, such as aluminum, copper, silicon oxide and the layers being deposited, against corrosion. Nanolaminate structures (20) incorporating metal nitrides, such as titanium nitride (30) and tungsten nitride (40), and metal carbides, and methods for forming the same, are also disclosed.

Claims

1. A method of forming a conductive nanolaminate structure on a substrate within a reaction space comprising depositing at least three adjacent thin film layers by atomic layer deposition (ALD) type processes comprising sequential and alternating self-saturating surface reactions, including at least one metal compound layer, wherein each of the at least three thin film layers is in a different phase from directly adjacent ones of the at least three thin film layers.

2. The method of claim 1, wherein the nanolaminate structure comprises at least four adjacent thin film layers deposited by the atomic layer deposition (ALD) type processes.

3. The method of claim 1, wherein each of the at least three adjacent thin film layers has a different composition from directly adjacent ones of the at least three thin film layers.

4. The method of claim 1, wherein the at least one metal compound thin film layer comprises a metal carbide.

5. The method of claim 1, wherein the at least one metal compound thin film layer comprises a metal nitride.

6. The method of claim 1, wherein at least one thin film layers of the at least three adjacent thin film layers comprises an elemental metal.

7. The method of claim 1, wherein the nanolaminate structure is a diffusion barrier in an integrated circuit.

8. The method of claim 1, wherein the nanolaminate is a conductive diffusion barrier.

9. The method of claim 1, wherein the nanolaminate structure is formed on a substrate susceptible to halide attack.

10. The method of claim 9, wherein the ALD type process comprises providing alternating pulses of reactants in a plurality of deposition cycles, each cycle comprising:

supplying a first reactant to chemisorb no more than about one monolayer of a halide-terminated species over a surface of the substrate;

removing excess first reactant from the reaction space; and

gettering halides from the monolayer prior to repeating the cycle.

11. The method of claim 10, wherein each cycle further comprises supplying a hydrogen-bearing second reactant.

12. The method of claim 11, wherein the hydrogen bearing second reactant comprises a source of nitrogen.

13. The method of claim 12, wherein the source of nitrogen comprises ammonia.

14. The method of claim 12, wherein the first reactant comprises a metal halide.

15. The method of claim 10, wherein the surface comprises metal.

16. The method of claim 10, wherein gettering comprises reducing.

17. A method of forming a conductive nanolaminate structure on a substrate susceptible to halide attack within a reaction space by an atomic layer deposition (ALD) process, the nanolaminate structure comprising at least two adjacent thin film layers, including at least one metal compound layer, wherein each of the at least two adjacent thin film layers is in a different phase from directly adjacent ones of the at least two adjacent thin film layers, and wherein the atomic layer deposition process comprises providing alternating pulses of reactants in a plurality of deposition cycles, each cycle comprising:

supplying a first reactant to chemisorb no more than about one monolayer of a halide species over a surface of the substrate,

removing excess first reactant from the reaction space; and

gettering halides from the monolayer prior to repeating the cycle,

wherein the surface comprises copper.

18. The method of claim 17, wherein the surface further comprises a form of silicon oxide.

19. A method of forming a conductive nanolaminate structure on a substrate susceptible to halide attack within a reaction space by an atomic layer deposition (ALD) process, the nanolaminate structure comprising at least two adjacent thin film layers, including at least one metal compound layer, wherein each of the at least two adjacent thin film layers is in a different phase from directly adjacent ones of the at least two adjacent thin film layers, and wherein the atomic layer deposition process comprises providing alternating pulses of reactants in a plurality of deposition cycles, each cycle comprising:

supplying a first reactant to chemisorb no more than about one monolayer of a halide species over a surface of the substrate,

removing excess first reactant from the reaction space; and

gettering halides from the monolayer prior to repeating the cycle,

wherein the surface is formed by a material less than 5 nm thick over copper.

20. A method of forming a conductive nanolaminate structure on a substrate susceptible to halide attack within a reaction space by an atomic layer deposition (ALD) process, the nanolaminate structure comprising at least two adjacent thin film layers, including at least one metal compound layer, wherein each of the at least two adjacent thin film layers is in a different phase from directly adjacent ones of the at least two adjacent thin film layers, and wherein the atomic layer deposition process comprises providing alternating pulses of reactants in a plurality of deposition cycles, each cycle comprising:

supplying a first reactant to chemisorb no more than about one monolayer of a halide species over a surface of the substrate,

removing excess first reactant from the reaction space; and

gettering halides from the monolayer prior to repeating the cycle,

wherein gettering comprises reducing by exposing the halide-terminated species to a boron compound.

21. The method of claim 20, wherein the boron compound comprises triethyl boron (TEB).