Selective formation of metallic films on metallic surfaces

• US 10,157,786 B2
• Filed: 11/18/2016
• Issued: 12/18/2018
• Est. Priority Date: 12/09/2011
• Status: Active Grant

• Current Assignee: ASM International NV
• Original Assignee: ASM International NV
• Inventors: Haukka, Suvi P., Niskanen, Antti, Tuominen, Marko
• Primary Examiner(s): Nicely, Joseph C
• Assistant Examiner(s): Vuong, Thai T
• Application Number:
  US15/356,306
• Publication Number:
  US 20170069527A1
• Time in Patent Office: 760 Days
• Field of Search: 438777, 438632
• CPC Class Codes: C23C 16/04 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 16/14 Deposition of only one other metal element
• CPC Class Codes: C23C 16/45536 Use of plasma, radiation or electromagnetic fields
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02068 during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
• CPC Class Codes: H01L 21/28518 the conductive layers comprising silicides H01L21/28537 takes precedence
• 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 21/3105 After-treatment
• CPC Class Codes: H01L 21/76826 by contacting the layer with gases, liquids or plasmas
• CPC Class Codes: H01L 21/76849 the layer being positioned on top of the main fill metal
• CPC Class Codes: H01L 21/7685 the layer covering a conductive structure H01L21/76849 takes precedence
• CPC Class Codes: H01L 21/76864 Thermal treatment
• CPC Class Codes: H01L 21/76867 characterized by methods of formation other than PVD, CVD or deposition from a liquids PVD H01L21/2855; CVD H01L21/28556; deposition from liquids H01L21/288
• CPC Class Codes: H01L 21/76883 Post-treatment or after-treatment of the conductive material
• CPC Class Codes: H01L 21/76886 Modifying permanently or temporarily the pattern or the conductivity of conductive members, e.g. formation of alloys, reduction of contact resistances
• CPC Class Codes: H01L 21/76889 by forming silicides of refractory metals
• CPC Class Codes: H01L 23/53238 Additional layers associated with copper layers, e.g. adhesion, barrier, cladding layers

Abstract

Metallic layers can be selectively deposited on one surface of a substrate relative to a second surface of the substrate. In some embodiments, the metallic layers are selectively deposited on copper instead of insulating or dielectric materials. In some embodiments, a first precursor forms a layer on the first surface and is subsequently reacted or converted to form a metallic layer. The deposition temperature may be selected such that a selectivity of above about 50% or even about 90% is achieved.

Claims

1. A method for selectively depositing a film on a first metal surface of a substrate relative to a second dielectric surface of the substrate, the method comprising:

contacting the substrate with one or more silanes; and

carrying out one or more deposition cycles at a temperature of less than 150°

C., each cycle comprising;

contacting the substrate with a first precursor comprising tungsten (W); and

contacting the substrate with a second precursor,

wherein deposition on the first metal surface relative to the second dielectric surface has a selectivity of greater than 50%.

2. The method of claim 1, wherein at least one deposition cycle comprises contacting the substrate with the second precursor prior to contacting the substrate with the first precursor.

3. The method of claim 1, wherein the substrate is contacted with a silane having the formula Si_nH_2n+2, where n is equal to or greater than 1.

4. The method of claim 1, wherein the substrate is contacted with a silane selected from silane and trisilane.

5. The method of claim 1, wherein the substrate is contacted with disilane.

6. The method of claim 1, wherein the substrate is contacted with a silane having the formula SiH_xL_y, where L is a ligand selected from alkyl, alkenyl, alkynyl, alkoxide and amide groups.

7. The method of claim 1, wherein substrate is contacted with an alkylhalosilane having the formula R_3-xSiL, wherein L is a halide, x is from 1 to 3 and each R can be independently selected from C1-C5 hydrocarbons.

8. The method of claim 7, wherein L is chloride.

9. The method of claim 1, wherein contacting the substrate with at least one silane forms —

Si(CH₃)₃ groups on the second dielectric surface.

10. The method of claim 1, wherein the substrate is contacted with one or more silanes after carrying out one or more deposition cycles.

11. The method of claim 1, wherein the one or more deposition cycles are carried out subsequent to contacting the substrate with one or more silanes.

12. The method of claim 1, wherein the second precursor comprises silicon or boron.

13. The method of claim 1, wherein the first precursor comprises a tungsten halide.

14. The method of claim 1, wherein the first precursor comprises WF₆.

15. The method of claim 1, additionally comprising cleaning the substrate prior to contacting the substrate with the one or more silanes.

16. The method of claim 15, wherein cleaning comprises exposing the substrate to a plasma.

17. The method of claim 15, wherein cleaning comprises removing a passivation layer from the first metal surface.

18. The method of claim 1, wherein the first metal surface comprises copper.

19. The method of claim 1, wherein the film comprises elemental tungsten.

20. The method of claim 1, wherein deposition on the first metal surface relative to the second dielectric surface has a selectivity of greater than 90%.

21. The method of claim 1, wherein contacting the substrate with one or more silanes and the deposition cycles are carried out in different reaction spaces.