Reactor surface passivation through chemical deactivation

• US 7,118,779 B2
• Filed: 05/07/2004
• Issued: 10/10/2006
• Est. Priority Date: 05/09/2003
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM America Incorporated (ASM International NV)
• Inventors: Verghese, Mohith, Shero, Eric J.
• Primary Examiner(s): Meeks, Timothy
• Assistant Examiner(s): ABRAMOWITZ, HOWARD E
• Application Number:
  US10/841,585
• Publication Number:
  US 20040221807A1
• Time in Patent Office: 886 Days
• Field of Search: 427/248.1, 427/237, 427/255.23, 427/255.26, 427/255.27
• US Class Current: 427/230
• CPC Class Codes: B05D 1/185 applying monomolecular layers B05D1/204 takes precedence
• CPC Class Codes: B05D 1/36 Successively applying liquids or other fluent materials, e.g. without intermediate treatment
• 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 2203/30 Other inorganic substrates, e.g. ceramics, silicon
• CPC Class Codes: B05D 2518/12 Ceramic precursors (polysiloxanes, polysilazanes)
• CPC Class Codes: B05D 3/044 Pretreatment
• CPC Class Codes: B05D 3/0466 the gas being a non-reacting gas B05D3/0406 takes precedence
• CPC Class Codes: B05D 3/104 Pretreatment of other substrates
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C23C 16/403 of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 16/4404 Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 22/68 using aqueous solutions with pH between 6 and 8
• CPC Class Codes: C30B 25/14 Feed and outlet means for the gases; Modifying the flow of the reactive gases
• CPC Class Codes: H01J 37/32477 characterised by the means for protecting vessels or internal parts, e.g. coatings

Abstract

Protective layers are formed on a surface of an atomic layer deposition (ALD) or chemical vapor deposition (CVD) reactor. Parts defining a reaction space for an ALD or CVD reactor can be treated, in situ or ex situ, with chemicals that deactivate reactive sites on the reaction space surface(s). A pre-treatment step can maximize the available reactive sites prior to the treatment step. With reactive sites deactivated by adsorbed treatment reactant, during subsequent processing the reactant gases have reduced reactivity or deposition upon these treated surfaces. Accordingly, purge steps can be greatly shortened and a greater number of runs can be conducted between cleaning steps to remove built-up deposition on the reactor walls.

Claims

1. A method of operating a deposition reactor having a reaction space, the method comprising:

contacting a reaction space surface of the reactor with a treatment chemical, thereby forming a protective layer over the reaction space surface;

loading a substrate into the reaction space;

flowing a deposition reactant gas over the protective layer and the substrate; and

preferentially reacting the reactant gas with the substrate as compared to the protective layer, thereby selectively depositing a layer on the substrate;

wherein contacting comprises an ex situ treatment of reactor parts prior to assembly of the reaction space and wherein the treatment chemical is an organic molecule and the protective layer is a self-assembled monolayer.

2. The method of claim 1, wherein preferentially reacting comprises chemical vapor deposition.

3. The method of claim 1, wherein the chemical treatment gas is selected from the group consisting of

4. The method of claim 1, wherein the protective layer defines a hydrophobic outer surface.

5. The method of claim 1, further comprising contacting the reaction space surface with a pre-treatment chemical, thereby densifying a plurality of reactive sites on the reaction space surface, prior to contacting the reaction space surface with the treatment chemical.

6. The method of claim 5, wherein the pre-treatment chemical comprises an oxygen containing chemical.

7. A method of deposition with reduced coating on portions of a reaction space, the method comprising:

applying a treatment chemical to one or more portions of the reaction space;

loading a substrate into the reaction space;

conducting a plurality of cycles of atomic layer deposition reactions, each cycle comprising;

introducing a first reactant into the reaction space, at least a portion of the first reactant adsorbing on the substrate,

removing excess first reactant from the reaction space,

introducing a second reactant gas into the reaction space, and

forming a first monolayer of a material on the surface of the substrate from the second reactant gas and the adsorbed portion of the first reactant gas;

removing excess second reactant from the reaction space;

removing the substrate from the reactor

wherein the treatment chemical deactivates the portion of the reaction space to the atomic layer deposition reactions and wherein the treatment chemical comprises octadecyltrichlorosilane.

8. The method of claim 7, wherein applying the treatment chemical comprises ex situ exposure of reactor components to the treatment chemical.

9. The method of claim 7, wherein ex situ exposure comprises dipping the reactor components into a liquid mixture including the treatment chemical.

10. The method of claim 7, further comprising assembling the treated reactor components to form the reaction space.

11. The method of claim 7, wherein each cycle further comprises introducing a third reactant to the reaction space and removing excess third reactant from the reaction space.

12. The method of claim 7, wherein applying the treatment chemical comprises introducing a gas phase of the treatment chemical into the reaction space prior to loading the substrate into the reaction space.

13. The method of claim 7, further comprising re-treating the portions of the reaction space after a predetermined number of substrates have been processed sequentially in the reaction space.

14. The method of claim 7, further comprising re-treating the portions of the reaction space after a predetermined duration of deposition reactions has lapsed.

15. The method of claim 7, wherein applying the treatment chemical comprises a pre-treatment reaction to prepare the portions of the reaction space for the treatment chemical.

16. The method of claim 15, wherein the portions of the reaction space are exposed to the pre-treatment reaction prior to applying the treatment chemical.

17. The method of claim 15, wherein the pre-treatment reaction comprises exposing the portions of the reaction space to an oxygen containing agent.

18. The method of claim 17, wherein the oxygen containing agent comprises ozone.

19. A method of operating a deposition reactor having a reaction space, the method comprising:

contacting a reaction space surface of the reactor with a treatment chemical, thereby forming a protective layer over the reaction space surface;

loading a substrate into the reaction space;

flowing a deposition reactant gas over the protective layer and the substrate; and

preferentially reacting the reactant gas with the substrate as compared to the protective layer, thereby selectively depositing a layer on the substrate;

wherein contacting comprises an in situ treatment of reactor parts after assembly of the reaction space and wherein the treatment chemical is an organic molecule and the protective layer is a self-assembled monolayer.

20. The method of claim 19, wherein contacting the reaction space surface of the reactor with a treatment chemical comprises entraining the treatment chemical in an inert gas flow.