METHODS AND APPARATUS FOR IN-SITU CLEANING OF COPPER SURFACES AND DEPOSITION AND REMOVAL OF SELF-ASSEMBLED MONOLAYERS

• US 20170062210A1
• Filed: 09/01/2015
• Published: 03/02/2017
• Est. Priority Date: 09/01/2015
• Status: Active Grant

• Current Assignee: Applied Materials Incorporated
• Original Assignee: Applied Materials Incorporated
• Inventors: GORADIA, Prerna, VISSER, Robert Jan, ARNEPALLI, Ranga Rao
• Granted Patent: US 9,673,042 B2
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: C23C 16/0227 by cleaning or etching
• CPC Class Codes: C23C 16/0236 by etching with a reactive gas
• CPC Class Codes: C23C 16/0272 Deposition of sub-layers, e.g. to promote the adhesion of the main coating
• CPC Class Codes: C23C 16/24 Deposition of silicon only
• CPC Class Codes: C23C 16/56 After-treatment
• CPC Class Codes: H01L 21/02043 Cleaning before device manufacture, i.e. Begin-Of-Line process
• 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 21/02118 carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC polymers per se C08G, photoresist per se G03F
• CPC Class Codes: H01L 21/02271 deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/02277 the reactions being activated by other means than plasma or thermal, e.g. photo-CVD
• CPC Class Codes: H01L 21/02301 in-situ cleaning
• 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 21/02312 treatment by exposure to a gas or vapour
• CPC Class Codes: H01L 21/76829 characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
• CPC Class Codes: H01L 21/76831 in via holes or trenches, e.g. non-conductive sidewall liners
• 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 21/76883 Post-treatment or after-treatment of the conductive material

Abstract

A method of processing includes: providing a substrate having a contaminant material disposed on the copper surface to a substrate support within a hot wire chemical vapor deposition (HWCVD) chamber; providing hydrogen (H₂) gas to the HWCVD chamber; heating one or more filaments disposed in the HWCVD chamber to a temperature sufficient to dissociate the hydrogen (H₂) gas; exposing the substrate to the dissociated hydrogen (H₂) gas to remove at least some of the contaminant material from the copper surface; cooling the one or more filaments to room temperature; exposing the substrate in the HWCVD chamber to one or more chemical precursors to deposit a self-assembled monolayer atop the copper surface; and depositing a second layer atop the substrate.

Claims

1. A method of processing a substrate having an exposed copper surface, comprising:

(a) providing a substrate having a contaminant material disposed on the copper surface to a substrate support within a hot wire chemical vapor deposition (HWCVD) chamber;

(b) providing hydrogen (H₂) gas to the HWCVD chamber;

(c) heating one or more filaments disposed in the HWCVD chamber to a temperature sufficient to dissociate the hydrogen (H₂) gas;

(d) exposing the substrate to the dissociated hydrogen (H₂) gas to remove at least some of the contaminant material from the copper surface;

(e) cooling the one or more filaments to room temperature;

(f) exposing the substrate in the HWCVD chamber to one or more chemical precursors to deposit a self-assembled monolayer atop the copper surface; and

(g) depositing a second layer atop the substrate.

2. The method of claim 1, wherein depositing the second layer further comprises:

after depositing the self-assembled monolayer, selectively depositing a dielectric layer atop an exposed silicon-containing surface of the substrate in the HWCVD chamber;

providing hydrogen (H₂) gas to the HWCVD chamber;

heating the one or more filaments disposed in the HWCVD chamber to a temperature sufficient to dissociate the hydrogen (H₂) gas; and

exposing the substrate to the dissociated hydrogen (H₂) gas to remove the self-assembled monolayer from the copper surface.

3. The method of claim 1, wherein depositing the second layer further comprises:

depositing a UV Block layer atop the self-assembled monolayer.

4. The method of claim 1, wherein the filament temperature is about 1000 to about 2400 degrees Celsius.

5. The method of claim 1, wherein the one or more filaments comprise 20 to 32 filaments.

6. The method of claim 1, wherein the one or more filaments are composed of tantalum, tungsten, or iridium.

7. The method of claim 1, wherein during (b)-(d), the substrate support is heated to about 50 to about 400 degrees Celsius.

8. The method of claim 1, wherein the self-assembled monolayer has a thickness of about 12 to about 13 angstroms.

9. The method of claim 1, wherein the one or more chemical precursors comprise at least one of 3-mecaptopropyltrimethoxysilane, 11-mercaptoundecyltrimethoxysilane, Octadecyltrimethoxysilane (ODTMS), Nonafluorohexylmethyltrimethoxysilane (NFHTMS), 1H,1H,2H,2H-Perfluorodecyltrichlorosilane (PFTS), (3-Aminopropyl)triethoxysilane (APTES), (3-Aminopropyl)trimethoxysilane (APTMS), octadecyltrichlorosilane [CH₃(CH₂)₁₇SiCl₃], oxydiphthalic acid (ODPA), Octadecyltrimethoxysilane (ODTMS), Nonafluorohexylmethyltrimethoxysilane (NFHTMS), 1H,1H,2H,2H-Perfluorodecyltrichlorosilane (PFTS), Chlorodimethyloctadecylsilane (CDODS), (3-mercaptopropyl)methyldimethoxysilane, Octadecyltrimethoxysilane (OTMS) (CH₃(CH₂)₁₇Si(OCH₃)₃, (17-aminoheptadecyl) trimethoxysilane(H₂N(CH₂)₁₇Si(OCH₃)₃ (AHTMS) Butyltrichlorosilane (BTS)(Chloro silane), or (Trichlorosilyl) Tricosanoate (MTST) (H₃CO₂C(CH₂)₂₂SiCl₃).

10. The method of claim 1, wherein exposing the substrate to one or more chemical precursors further comprises:

heating one or more ampoules containing one or more chemical precursors; and

drawing a vapor of the one or more chemical precursors from the one or more ampoules using a carrier gas.

11. The method of claim 10, further comprising heating the one or more ampoules to a temperature of about 45 degrees Celsius to about 200 degrees Celsius.

12. The method of claim 1, wherein a temperature of the substrate during deposition of the self-assembled monolayer is about 25 to about 350 degrees Celsius.

13. The method of claim 1, wherein a pressure in the HWCVD chamber during deposition of the self-assembled monolayer is about 80 mTorr to about 500 Torr.

14. The method of claim 1, wherein the substrate is exposed to the one or more chemical precursors for about 30 seconds to about 600 seconds.

15. The method of claim 2, wherein a temperature of the substrate during removal of the self-assembled monolayer from the copper surface is about 25 to about 350 degrees Celsius.

16. A method of processing a substrate having an exposed copper surface, comprising:

providing a substrate having a contaminant material disposed on the copper surface to a substrate support within a hot wire chemical vapor deposition (HWCVD) chamber;

providing hydrogen (H₂) gas to the HWCVD chamber;

heating one or more filaments disposed in the HWCVD chamber to a temperature of about 1000 to about 2400 degrees Celsius to dissociate the hydrogen (H₂) gas and heating the substrate support to a temperature of about 50 to about 400 degrees Celsius;

exposing the substrate to the dissociated hydrogen (H₂) gas to remove at least some of the contaminant material from the copper surface;

cooling the one or more filaments to room temperature;

heating one or more ampoules coupled to the HWCVD chamber and containing one or more chemical precursors to a temperature of about 25 to about 200 degrees Celsius;

drawing a vapor of the one or more chemical precursors from the one or more ampoules using a carrier gas;

exposing the substrate in the HWCVD chamber to one or more chemical precursors to deposit a self-assembled monolayer atop the copper surface, wherein the substrate is heated to a temperature of about 25 to about 350 degrees Celsius;

wherein a pressure in the HWCVD chamber during deposition of the self-assembled monolayer is about 80 mTorr to about 500 Torr, and wherein the substrate is exposed to the one or more chemical precursors for about 30 to about 600 seconds; and

depositing a second layer atop the substrate.

17. The method of claim 16, wherein depositing the second layer further comprises:

after depositing the self-assembled monolayer, selectively depositing a dielectric layer atop an exposed silicon-containing surface of the substrate in the HWCVD chamber;

providing hydrogen (H₂) gas to the HWCVD chamber;

heating the one or more filaments disposed in the HWCVD chamber to a temperature sufficient to dissociate the hydrogen (H₂) gas; and

exposing the substrate to the dissociated hydrogen (H₂) gas to remove the self-assembled monolayer from the copper surface, wherein a temperature of the substrate during removal of the self-assembled monolayer from the copper surface is about 150 to about 350 degrees Celsius.

18. The method of claim 16, wherein depositing the second layer further comprises:

depositing a UV Block layer atop the self-assembled monolayer.

19. A non-transitory computer readable medium, having instructions stored thereon which, when executed, cause a process chamber to perform a method of processing a substrate having an exposed copper surface and an exposed silicon-containing surface, the method comprising:

(a) providing a substrate having a contaminant material disposed on the copper surface to a substrate support within a hot wire chemical vapor deposition (HWCVD) chamber;

(b) providing hydrogen (H₂) gas to the HWCVD chamber;

(c) heating one or more filaments disposed in the HWCVD chamber to a temperature sufficient to dissociate the hydrogen (H₂) gas;

(d) exposing the substrate to the dissociated hydrogen (H₂) gas to remove at least some of the contaminant material from the copper surface;

(e) cooling the one or more filaments to room temperature;

(f) exposing the substrate in the HWCVD chamber to one or more chemical precursors to deposit a self-assembled monolayer atop the copper surface; and

(g) depositing a second layer atop the substrate.

20. The non-transitory computer readable medium of claim 19, wherein depositing the second layer further comprises:

after depositing the self-assembled monolayer, selectively depositing a dielectric layer atop the silicon-containing surface of the substrate in the HWCVD chamber;

providing hydrogen (H₂) gas to the HWCVD chamber;

heating the one or more filaments disposed in the HWCVD chamber to a temperature sufficient to dissociate the hydrogen (H₂) gas; and

exposing the substrate to the dissociated hydrogen (H₂) gas to remove the self-assembled monolayer from the copper surface.