Reactor surface passivation through chemical deactivation

• US 7,799,135 B2
• Filed: 10/06/2006
• Issued: 09/21/2010
• 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): Cleveland; Michael
• Assistant Examiner(s): Chen; Keath T
• Application Number:
  US11/539,312
• Publication Number:
  US 20070084404A1
• Time in Patent Office: 1,446 Days
• Field of Search: 118/715
• US Class Current: 118/715
• 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. An atomic layer deposition apparatus, comprising:

a plurality of reaction space surfaces defining a reaction space;

a substrate support structure housed within the reaction space;

a plurality of feed lines connecting the reaction space to sources of vapor phase reactants suitable for a vapor deposition process,

wherein at least some of the reactant space surfaces comprise a surface modification deactivating the at least some surfaces against the vapor deposition process, the surface modification comprising a protective self-assembled monolayer (SAM) layer that comprises adsorbed organic reactant molecules, wherein one end of each reactant molecule is adsorbed onto a hydrophilic surface whereas the other end of each reactant molecule is hydrophobic; and

a control system programmed to operate said reaction space at temperatures in excess of approximately 200°

C., the control system configured to provide alternated and repeated pulses of the vapor phase reactants to the reaction space in accordance with an atomic layer deposition sequence.

2. The apparatus of claim 1, wherein the protective layer comprises an adsorbed treatment chemical having a thickness of no more than about two monolayers.

3. The apparatus of claim 1, wherein the protective layer defines a hydrophobic outer surface.

4. The apparatus of claim 1, wherein the surface modification renders the vapor deposition process selective to a semiconductor substrate relative to the at least some surfaces.

5. The apparatus of claim 1, further comprising an inlet leading from a source of a treatment reactant to the reaction space, the treatment reactant providing the surface modification to the at least some surfaces.

6. The apparatus of claim 5, wherein the treatment reactant is an alkyldisilazane.

7. The apparatus of claim 5, wherein the treatment reactant is an alkylhalosilane.

8. The apparatus of claim 5, wherein the treatment reactant is an aryldisilazane.

9. The apparatus of claim 5, wherein the treatment reactant is an arylhalosilane.

10. The apparatus of claim 5, further comprising an inlet leading from a source of a pre-treatment reactant to the reaction space, the pre-treatment reactant rendering the at least some surfaces more reactive to the treatment reactant.

11. The apparatus of claim 10, wherein the pre-treatment reactant comprises an oxygen-containing reactant.

12. The apparatus of claim 1, further comprising separate inlets to the reaction space for the sources of the vapor phase reactants.

13. The apparatus of claim 1, wherein a portion of the reactant molecule comprises an alkyl group with 1 to 20 carbon atoms.

14. The apparatus of claim 1, wherein a portion of the reactant molecule comprises an aryl group with 6 to 10 carbon atoms.

15. A treated component of an atomic layer deposition (ALD) reactor that forms a portion of a reaction surface, the component comprising a portion of a surface having a protective self-assembled monolayer (SAM) layer thereon, the protective layer comprising an adsorbed treatment chemical having a thickness of less than about 5 molecular monolayers, the protective layer configured to inhibit reaction with ALD deposition reactants and comprising adsorbed organic reactant molecules, wherein one end of each reactant molecule is adsorbed onto a hydrophilic surface whereas the other end of each reactant molecule is hydrophobic, the component elevated to a temperature in excess of approximately 200°

C.

16. The apparatus of claim 15, wherein a portion of the reactant molecule comprises an alkyl group with 1 to 20 carbon atoms.

17. The apparatus of claim 15, wherein a portion of the reactant molecule comprises an aryl group with 6 to 10 carbon atoms.

18. An atomic layer deposition apparatus, comprising:

a plurality of reaction space surfaces defining a reaction space;

a substrate support structure housed within the reaction space;

a plurality of feed lines connecting the reaction space to sources of vapor phase reactants suitable for a vapor deposition process,

wherein at least some of the reactant space surfaces comprise a surface modification deactivating the at least some surfaces against the vapor deposition process, the surface modification comprising a protective self-assembled monolayer (SAM) layer that comprises adsorbed organic reactant molecules, wherein one end of each reactant molecule is adsorbed onto a hydrophilic surface whereas the other end of each reactant molecule is hydrophobic; and

a control system programmed for atomic layer deposition by alternated and repeated pulses of the vapor phase reactants.

19. The apparatus of claim 18, further comprising separate inlets to the reaction space for the sources of the vapor phase reactants.

20. The apparatus of claim 18, wherein a portion of the reactant molecule comprises an alkyl group with 1 to 20 carbon atoms.

21. The apparatus of claim 18, wherein a portion of the reactant molecule comprises an aryl group with 6 to 10 carbon atoms.