REACTIVE SITE DEACTIVATION AGAINST VAPOR DEPOSITION

• US 20110198736A1
• Filed: 02/17/2010
• Published: 08/18/2011
• Est. Priority Date: 02/17/2010
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM America Incorporated (ASM International NV)
• Inventors: Muscat, Anthony, SHERO, ERIC, Miller, Shawn, Verghese, Mohith
• Granted Patent: US 8,293,658 B2
• Time in Patent Office: Days
• US Class Current: 257/629
• CPC Class Codes: B05D 1/32 using means for protecting parts of a surface not to be coated, e.g. using stencils, resists
• CPC Class Codes: B05D 1/60 Deposition of organic layers from vapour phase vapour phase deposition in general C23C14/00, C23C16/00
• CPC Class Codes: B05D 5/08 to obtain an anti-friction or anti-adhesive surface rendering particulate materials free-flowing in general, e.g. making them hydrophobic B01J2/30
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C23C 16/04 Coating on selected surface areas, e.g. using masks
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: H01L 21/02181 the material containing hafnium, e.g. HfO2
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/02304 formation of intermediate layers, e.g. buffer layers, layers to improve adhesion, lattice match or diffusion barriers
• CPC Class Codes: H01L 21/28194 by deposition, e.g. evaporation, ALD, CVD, sputtering, laser deposition H01L21/28202 takes precedence
• CPC Class Codes: H01L 21/76826 by contacting the layer with gases, liquids or plasmas
• CPC Class Codes: H01L 21/76834 formation of thin insulating films on the sidewalls or on top of conductors H01L21/76831 takes precedence
• CPC Class Codes: H01L 29/517 the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence

Abstract

Methods and structures relating to the formation of mixed SAMs for preventing undesirable growth or nucleation on exposed surfaces inside a reactor are described. A mixed SAM can be formed on surfaces for which nucleation is not desired by introducing a first SAM precursor having molecules of a first length and a second SAM precursor having molecules of a second length shorter than the first. Examples of exposed surfaces for which a mixed SAM can be provided over include reactor surfaces and select surfaces of integrated circuit structures, such as insulator and dielectric layers.

Claims

1. A method of processing, comprising:

providing an exposed surface;

supplying a first organic precursor having a first molecular chain length to adsorb a self-assembled monolayer over the exposed surface; and

supplying a second organic precursor having a second molecular chain length that is shorter than the first molecular chain length to adsorb onto reactive sites of the exposed surface on which a self-assembled monolayer is not adsorbed.

2. The method of claim 1, wherein the exposed surface is a surface of a reaction chamber.

3. The method of claim 1, wherein the exposed surface is a surface of a patterned substrate.

4. The method of claim 3, wherein the exposed surface is an insulating surface of an integrated circuit structure.

5. The method of claim 1, wherein the first molecular chain length is a length greater than or equal to 8 carbon atoms.

6. The method of claim 1, wherein the second molecular chain length is a length less than 8 carbon atoms.

7. The method of claim 1, wherein the first molecular chain length is a length greater than or equal to 12 carbon atoms and the second molecular chain length is a length less than or equal to 6 carbon atoms.

8. The method of claim 3, further comprising performing a selective ALD process on the patterned substrate in the reaction chamber, wherein a negligible amount of material is deposited on the self-assembled monolayer during the selective ALD process.

9. The method of claim 8, wherein the amount of material deposited on the self-assembled monolayer is less than 10% of that deposited on similar surfaces without the self-assembled monolayer.

10. The method of claim 8, wherein the self-assembled monolayer is formed on a first surface of the patterned substrate without forming the self-assembled monolayer on a second surface of the patterned substrate.

11. The method of claim 1, further comprising performing a hydroxylation process on the exposed surface prior to introducing the first organic precursor.

12. The method of claim 11, wherein the hydroxylation process comprises exposing the exposed surface to ozone gas.

13. The method of claim 11, further comprising repeating the hydroxylation process and introducing the first organic precursor and/or second organic precursor one or more times.

14. The method of claim 13, wherein repeating the hydroxylation process and introducing the first organic precursor and/or second organic precursor occurs once every 2-3 days as part of an in situ repair process.

15. The method of claim 13, further comprising periodically stripping the self-assembled monolayer and a first molecular chain length and a second molecular chain length adsorbed over the exposed substrate ex situ.

16. The method of claim 15, wherein periodically stripping ex situ is conducted with periods of at least fifteen weeks between from deposition runs.

17. The method of claim 15, wherein periodically stripping ex situ is conducted with periods of at least four weeks between from deposition runs involving ALD deposition of HfO₂.

18. The method of claim 1, wherein the first organic precursor and the second organic precursor are supplied simultaneously.

19. The method of claim 1, further comprising removing unreacted first organic precursor that is not adsorbed over the exposed surface prior to supplying the second organic precursor.

20. The method of claim 1, further comprising removing unreacted second organic precursor that is not adsorbed onto reactive sites.

21. The method of claim 1, further comprising extracting unadsorbed molecules from the exposed surface after supplying the first organic precursor and/or second organic precursor.

22. The method of claim 21, further comprising re-supplying the first organic precursor and/or the second organic precursor after extracting the unadsorbed molecules.

23. A method of processing with a vapor deposition reactor, comprising:

supplying a first organic precursor to deposit a self-assembled monolayer over portions of a reactor surface; and

supplying a second organic precursor to react with portions of the reactor surface on which the self-assembled monolayer was not deposited, wherein the chain of molecules in the second organic precursor is shorter than the chain of molecules in the first organic precursor.

24. The method of claim 23, wherein the first organic precursor and the second organic precursor are introduced simultaneously.

25. The method of claim 23, further comprising performing an ALD process on an integrated circuit structure in the reactor, wherein one or more monolayers are deposited onto the integrated circuit structure and not on the self-assembled monolayer on the reactor surface.

26. The method of claim 23, wherein the first organic precursor is supplied in situ within the reactor.

27. The method of claim 23, wherein the first organic precursor is introduced ex situ outside the reactor.

28. The method of claim 23, further comprising removing reacted molecules of the first organic precursor and reacted molecules of the second organic precursor over portions of the reactor surface in situ using ozone, oxygen, N_xO_y, or other oxidizing plasma species after supplying the first organic precursor and second organic precursor.

29. A method of forming a semiconductor device, comprising:

providing an integrated circuit structure into a reaction chamber having a first surface and a second surface different from the first surface;

introducing a first organic precursor into the reaction chamber to coat portions of the first surface with a self-assembled monolayer without coating the second surface;

purging unreacted first organic precursor that does not coat the first surface from the reaction chamber;

introducing a second organic precursor into the reaction chamber to react with reactive sites of the first surface that are not coated with the first organic precursor; and

purging unreacted second organic precursor that does not react with reactive sites from the reaction chamber.

30. The method of claim 29, further comprising performing a selective ALD process, wherein material is deposited on the second surface and not on the first surface coated with the self-assembled monolayer.

31. The method of claim 30, further comprising performing a thermal anneal to remove the self-assembled monolayer.

32. The method of claim 29, wherein the first organic precursor is selected from the group consisting of octadecyltrichlorosilane (ODTS), tridecafluororo-1,1,2,2-tetrahydrooctyltrichlorosilane (FOTS) and tetradecyltrichlorosilane (TTS).

33. The method of claim 32, wherein the second organic precursor is selected from the group consisting of trichloromethylsilane (TCMS), trimethylchlorosilane (TMCS) and FOMB(DMA)S.

40. The integrated film structure of claim 32, wherein the ALD film has a step coverage of greater than 98%.

34. An integrated film structure, comprising:

a first surface and a second adjacent surface different from the first exposed surface; and

a mixed hydrophobic film adsorbed on the first surface without forming on the second surface, the film comprising a plurality of first chain organic molecules and a plurality of second chain organic molecules, the second chain organic molecules being shorter than the first chain organic molecules

35. The integrated film structure of claim 34, wherein the first exposed surface comprises a dielectric material and the second exposed surface comprises a semiconductor material.

36. The integrated film structure of claim 34, wherein the mixed hydrophobic film has a water contact angle of greater than 100 degrees.

37. The integrated film structure of claim 34, further comprising an overlying atomic layer deposition (ALD) film deposited on the second exposed surface and negligibly over the mixed hydrophobic film on the first exposed surface

38. The integrated film structure of claim 37, wherein the ALD film has a thickness of between 10 Å

and 30 Å

.

39. The integrated film structure of claim 37, wherein the ALD film has a thickness uniformity of greater than 98%.