SELF-ASSEMBLED MONOLAYER BLOCKING WITH INTERMITTENT AIR-WATER EXPOSURE

• US 20170256402A1
• Filed: 03/01/2017
• Published: 09/07/2017
• Est. Priority Date: 03/03/2016
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: KAUFMAN-OSBORN, Tobin, WONG, Keith Tatseun
• Granted Patent: US 10,192,752 B2
• Time in Patent Office: Days
• CPC Class Codes: H01L 21/3105 After-treatment
• CPC Class Codes: H01L 21/32 using masks
• 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

Abstract

Implementations described herein generally relate to processes for the fabrication of semiconductor devices in which a self-assembled monolayer (SAM) is used to achieve selective area deposition. Methods described herein relate to alternating SAM molecule and hydroxyl moiety exposure operations which may be utilized to form SAM layers suitable for blocking deposition of subsequently deposited materials.

Claims

1. A method of processing a substrate, comprising:

exposing a substrate to a self-assembled monolayer (“

SAM”

) molecule to achieve selective deposition of a SAM on a first material, wherein the substrate comprises an exposed first material and an exposed second material;

exposing the substrate to a hydroxyl moiety;

repeating the exposing the substrate to a SAM molecule and the exposing the substrate to a hydroxyl moiety in a time ratio of between about 1;

1 and about 100;

1, respectively;

after performing the repeating, exposing the substrate to the SAM molecule;

selectively depositing a third material on the exposed second material; and

removing the SAM from the first material.

2. The method of claim 1, wherein a hydroxyl moiety precursor is selected from the group consisting of ambient air, water solution, water vapor, hydrogen peroxide solution, hydrogen peroxide vapor, organic alcohol solutions, and organic alcohol vapors.

3. The method of claim 2, wherein the hydroxyl moiety precursor is selected from the group consisting of water solution, water vapor, and ambient air.

4. The method of claim 1, wherein a hydroxyl moiety precursor is water vapor.

5. The method of claim 1, wherein a hydroxyl moiety precursor is ambient air.

6. The method of claim 1, wherein the time ratio of the exposing the substrate to a SAM molecule and the exposing the substrate to a hydroxyl moiety is about 10:

1.

7. The method of claim 1, wherein the exposing the substrate to the SAM molecule performed after the repeating is performed for an amount of time substantially equal to the amount of time the exposing the substrate to a SAM molecule was performed during one cycle of the repeating.

8. The method of claim 1, wherein the SAM molecule is selected from the group consisting of carboxylic acid materials, phosphonic acid materials, thiol materials, silylamine materials, chlorosilane materials, oxysilane materials, and combinations thereof.

9. The method of claim 8, wherein the phosphonic acid materials are selected from the group consisting of methylphosphonic acid, ethylphosphonic acid, propylphosphonic acid, butylphosphonic acid, pentylphosphonic acid, hexylphosphonic acid, heptylphosphonic acid, octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid, undecylphosphonic acid, dodecylphosphonic acid, tridecylphosphonic acid, tetradecyphosphonic acid, pentadecylphosphonic acid, hexadecylphosphonic acid, heptadecylphosphonic acid, octadecylphosphonic acid, nonadecylphosphonic acid, and combinations thereof.

10. The method of claim 8, wherein the thiol materials are selected from the group consisting of methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, heptadecanethiol, octadecanethiol, nonadecanethiol, and combinations thereof.

11. The method of claim 8, wherein the silylamine materials are selected from the group consisting of tris(dimethylamino)methylsilane, tris(dimethylamino)ethylsilane, tris(dimethylamino)propylsilane, tris(dimethylamino)butylsilane, tris(dimethylamino)pentylsilane, tris(dimethylamino)hexylsilane, tris(dimethylamino)heptylsilane, tris(dimethylamino)octylsilane, tris(dimethylamino)nonylsilane, tris(dimethylamino)decylsilane, tris(dimethylamino)undecylsilane tris(dimethylamino)dodecylsilane, tris(dimethylamino)tridecylsilane, tris(dimethylamino)tetradecylsilane, tris(dimethylamino)pentadecylsilane, tris(dimethylamino)hexadecylsilane, tris(dimethylamino)heptadecylsilane, tris(dimethylamino)octadecylsilane, tris(dimethylamino)nonadecylsilane and combinations thereof.

12. The method of claim 8, wherein the chlorosilane materials are selected from the group consisting of methyltrichlorosilane, ethyltrichlorosilane, propyltrichlorosilane, butyltrichlorosilane, pentyltrichlorosilane, hexyltrichlorosilane, heptyltrichlorosilane, octyltrichlorosilane, nonyltrichlorosilane, decyltrichlorosilane, undecyltrichlorosilane, dodecyltrichlorosilane, tridecyltrichlorosilane, tetradecyltrichlorosilane, pentadecyltrichlorosilane, hexadecyltrichlorosilane, heptadecyltrichlorosilane, octadecyltrichlorosilane, nonadecyltrichlorosilane, and combinations thereof.

13. The method of claim 8, wherein the oxysilane materials are selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyltrimethoxysilane, undecyltrethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, tridecyltrimethoxysilane, tridecyltriethoxysilane, tetradecyltrimethoxysilane, tetradecyltriethoxysilane, pentadecyltrimethoxysilane, pentadecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltroethoxysilane, heptadecyltrimethoxysilane, heptadecyltriethoxysilane, octadecyltrimethoxylsilane octadecyltriethoxysilane, nonadecyltrimethoxysilane, nonadecyltriethoxysilane, and combinations thereof.

14. A method of processing a substrate, comprising:

exposing a substrate to a self-assembled monolayer (“

SAM”

) molecule to achieve selective deposition of a SAM on a first material in a first processing chamber, wherein the substrate comprises an exposed first material and an exposed second material;

transferring the substrate to a second processing chamber;

exposing the substrate to a hydroxyl moiety formed from water vapor in the second processing chamber;

repeating the exposing the substrate to a SAM molecule in the first processing chamber and the exposing the substrate to a hydroxyl moiety in the second processing chamber in a time ratio of between about 1;

1 and about 100;

1, respectively;

after performing the repeating, exposing the substrate to the SAM molecule in the first processing chamber;

selectively depositing a third material on the exposed second material; and

removing the SAM from the first material.

15. The method of claim 14, wherein the transferring the substrate is performed under vacuum.

16. The method of claim 14, wherein the exposing the substrate to a hydroxyl moiety formed from water vapor is performed at a temperature of between about 25°

C. and about 300°

C., at a pressure between about 1 T and about 600 T, and for an amount of time between about 1 second and about 600 seconds.

17. The method of claim 14, wherein the time ratio of the exposing the substrate to a SAM molecule and the exposing the substrate to a hydroxyl moiety formed from water vapor is between about 1:

1 and about 10;

1.

18. A method of processing a substrate, comprising:

exposing a substrate to a self-assembled monolayer (“

SAM”

) molecule to achieve selective deposition of a SAM on a first material in a processing chamber, wherein the substrate comprises an exposed first material and an exposed second material;

transferring the substrate to an ambient air environment;

exposing the substrate to a hydroxyl moiety formed from ambient air in the ambient air environment;

repeating the exposing the substrate to a SAM molecule in the processing chamber and the exposing the substrate to a hydroxyl moiety in the ambient air environment in a time ratio of between about 1;

1 and about 100;

1, respectively;

after performing the repeating, exposing the substrate to the SAM molecule in the processing chamber;

selectively depositing a third material on the exposed second material; and

removing the SAM from the first material.

19. The method of claim 18, wherein the exposing the substrate to a hydroxyl moiety formed from ambient air is performed at temperature of between about 25°

C. and about 400°

C., at a pressure of between about 1 mT and about 1520 T, and for an amount of time between about 30 second and about 600 seconds.

20. The method of claim 18, wherein the time ratio of the exposing the substrate to a SAM molecule and the exposing the substrate to a hydroxyl moiety formed from ambient air is between about 1:

10 and about 10;

1.