US20020048950A1 - Application of vapor phase HFACAC-based compound for use in copper decontamination and cleaning processes - Google Patents

Application of vapor phase HFACAC-based compound for use in copper decontamination and cleaning processes Download PDF

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Publication number
US20020048950A1
US20020048950A1 US09/882,677 US88267701A US2002048950A1 US 20020048950 A1 US20020048950 A1 US 20020048950A1 US 88267701 A US88267701 A US 88267701A US 2002048950 A1 US2002048950 A1 US 2002048950A1
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United States
Prior art keywords
copper
compound
decontamination
elemental
found
Prior art date
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Abandoned
Application number
US09/882,677
Inventor
Yakub Aliyu
Simon Chooi
Mei Zhou
John Sudijono
Subhash Gupta
Sudipto Roy
Paul Ho
Yi Xu
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GlobalFoundries Singapore Pte Ltd
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Chartered Semiconductor Manufacturing Pte Ltd
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Filing date
Publication date
Application filed by Chartered Semiconductor Manufacturing Pte Ltd filed Critical Chartered Semiconductor Manufacturing Pte Ltd
Priority to US09/882,677 priority Critical patent/US20020048950A1/en
Publication of US20020048950A1 publication Critical patent/US20020048950A1/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02043—Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02046—Dry cleaning only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/12—Gaseous compositions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041—Cleaning
    • H01L21/02079—Cleaning for reclaiming
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S438/00—Semiconductor device manufacturing: process
    • Y10S438/906—Cleaning of wafer as interim step

Definitions

  • the invention relates to a method of copper decontamination and cleaning of surfaces and tools in the fabrication of integrated circuits, and more particularly, to a method of copper decontamination and cleaning of surfaces and tools by dissolving copper in a vapor phase.
  • U.S. Pat. No. 5,939,334 to Nguyen et al teaches cleaning of copper oxides on copper lines by using ⁇ -diketone vapor. This method uses a reaction that is almost exclusively to copper oxide and not to copper.
  • U.S. Pat. Nos. 5,744,192 to Nguyen et al and 5,767,301 to Senzaki et al teach the use of hfac as a precursor in copper deposition.
  • Another object of the present invention is to provide an effective and very manufacturable method of removing copper contamination of tools and equipment in the fabrication of integrated circuits by dissolving copper contamination in a vapor phase.
  • Yet another object of the present invention is to provide an effective and very manufacturable method of removing copper contamination from any equipment without corroding or destroying equipment parts.
  • a still further object is to provide a novel copper decontamination process using an organic-based HFACAC compound in vapor phase.
  • an effective copper decontamination method in the fabrication of integrated circuits is achieved.
  • a decontamination compound in vapor form is sprayed over elemental copper wherein the compound dissolves all of the elemental copper and forms a volatile compound that can be flushed away thereby completing copper decontamination.
  • a novel organic-based HFACAC decontamination compound in vapor phase is provided.
  • the HFACAC decontamination compound in vapor phase is sprayed over elemental copper wherein the compound dissolves all of the elemental copper and forms a volatile compound that can be flushed away thereby completing copper decontamination.
  • FIG. 1 schematically illustrates in cross-sectional representation equipment from which copper contamination is removed in the process of the present invention.
  • Copper spills and contamination may be found in many places in a factory, such as on copper dedicated tools and on shared tools and equipment, and in both open and remote sites. It is to be understood by those skilled in the art that the process of the present invention is not limited to the applications illustrated in the drawing figure. Rather, the process of the invention can be used in any application in which it is desired to provide an effective method of copper removal.
  • the copper decontamination process of the invention can be performed on any equipment found in a wafer fabrication plant. Copper decontamination can be performed after the wafer or wafers have been processed, during preventive maintenance, or after breakage of a wafer or wafers in the equipment.
  • FIG. 1 illustrates a typical tool or piece of equipment used in semiconductor manufacturing.
  • a chamber 10 contains a wafer chuck 12 on which a wafer is held for processing. Copper contamination 14 is shown on the wafer chuck and on the walls of the chamber.
  • An organic-based hexafluoroacetylacetone (HFACAC) or 1,1,1,5,5,5-hexafluoro-2,4-pentanedione compound is flowed through a spray nozzle 20 in a vapor phase combined with an inert gas, such as nitrogen, which serves as a carrier.
  • hexafluoroacetylacetate (HFAC) can be introduced into the chamber 10 in a pressurized state.
  • the HFACAC—CF 3 COCH 2 COCF 3 is sprayed at about 0.1 to 100 liters per minute at a temperature of between about 20 and 100° C. for 1 second to 10 minutes.
  • the vapor phase compound 25 is sprayed over the copper contaminated sites and/or surfaces of equipment and tools to react with the elemental copper and/or copper oxides and form a readily volatile compound that can be flushed away.
  • the decontamination removal compound is in vapor phase, it can be used to clean both open areas and remote locations that are not easily accessible. It is also an effective decontaminant after spills. In addition, this process may be used for removing copper from the surface of a wafer for reclaiming of the wafer.
  • the decontamination removal compound of the invention may be used during copper metallic trace detection and analysis for formation of a preconcentrate.
  • a preconcentrate is a copper-containing solution that can be treated by evaporating water and solvents to leave copper concentrates.
  • the HFACAC of the invention can be used to dissolve the contaminents so that the preconcentrate can be analyzed using any of numerous techniques, such as total X-ray Flouresence Spectroscopy (VDP/TXRF), Inactively Coupled Mass Spectroscopy (ICMS), and Atomic Absorption Spectroscopy (AAS).
  • VDP/TXRF total X-ray Flouresence Spectroscopy
  • ICMS Inactively Coupled Mass Spectroscopy
  • AAS Atomic Absorption Spectroscopy

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

An effective copper decontamination method in the fabrication of integrated circuits is achieved. An organic-based HFACAC decontamination compound in vapor phase is sprayed over elemental copper found on equipment or tools or as a spill wherein the compound reacts with all of the elemental copper and forms a volatile compound that can be flushed away thereby completing copper decontamination.

Description

    BACKGROUND OF THE INVENTION
  • (1) Field of the Invention [0001]
  • The invention relates to a method of copper decontamination and cleaning of surfaces and tools in the fabrication of integrated circuits, and more particularly, to a method of copper decontamination and cleaning of surfaces and tools by dissolving copper in a vapor phase. [0002]
  • (2) Description of the Prior Art [0003]
  • The evolution of copper interconnect processes in the semiconductor manufacturing industry involves integrating copper into the existing fabrication process, which consists mainly of aluminum processes. In such dual-metal Fabs, incidents of copper spills and factory-wide cross-contamination must be contained. At present, Isopropyl Alcohol is commonly used to wipe and clean copper. This method is inadequate as traces of copper are usually left in minute quantities sufficient to cause further contamination. It is desired to provide an effective method of cleaning copper spills and completely removing copper contamination from the surface of tools and equipment. [0004]
  • U.S. Pat. No. 5,939,334 to Nguyen et al teaches cleaning of copper oxides on copper lines by using β-diketone vapor. This method uses a reaction that is almost exclusively to copper oxide and not to copper. U.S. Pat. Nos. 5,744,192 to Nguyen et al and 5,767,301 to Senzaki et al teach the use of hfac as a precursor in copper deposition. [0005]
    • SUMMARY OF THE INVENTION
  • A principal object of the present invention is to provide an effective and very manufacturable method of removing copper contamination of tools and equipment in the fabrication of integrated circuits. [0006]
  • Another object of the present invention is to provide an effective and very manufacturable method of removing copper contamination of tools and equipment in the fabrication of integrated circuits by dissolving copper contamination in a vapor phase. [0007]
  • Yet another object of the present invention is to provide an effective and very manufacturable method of removing copper contamination from any equipment without corroding or destroying equipment parts. [0008]
  • A still further object is to provide a novel copper decontamination process using an organic-based HFACAC compound in vapor phase. [0009]
  • In accordance with the objects of this invention an effective copper decontamination method in the fabrication of integrated circuits is achieved. A decontamination compound in vapor form is sprayed over elemental copper wherein the compound dissolves all of the elemental copper and forms a volatile compound that can be flushed away thereby completing copper decontamination. [0010]
  • Also in accordance with the objects of the invention, a novel organic-based HFACAC decontamination compound in vapor phase is provided. The HFACAC decontamination compound in vapor phase is sprayed over elemental copper wherein the compound dissolves all of the elemental copper and forms a volatile compound that can be flushed away thereby completing copper decontamination.[0011]
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • In the accompanying drawings forming a material part of this description, there is shown: [0012]
  • FIG. 1 schematically illustrates in cross-sectional representation equipment from which copper contamination is removed in the process of the present invention.[0013]
    • DESCRIPTION OF THE PREFERRED EMBODIMENTS
  • Copper spills and contamination may be found in many places in a factory, such as on copper dedicated tools and on shared tools and equipment, and in both open and remote sites. It is to be understood by those skilled in the art that the process of the present invention is not limited to the applications illustrated in the drawing figure. Rather, the process of the invention can be used in any application in which it is desired to provide an effective method of copper removal. [0014]
  • The copper decontamination process of the invention can be performed on any equipment found in a wafer fabrication plant. Copper decontamination can be performed after the wafer or wafers have been processed, during preventive maintenance, or after breakage of a wafer or wafers in the equipment. [0015]
  • FIG. 1 illustrates a typical tool or piece of equipment used in semiconductor manufacturing. A [0016] chamber 10 contains a wafer chuck 12 on which a wafer is held for processing. Copper contamination 14 is shown on the wafer chuck and on the walls of the chamber.
  • The process of the invention proposes a novel method for safe and effective removal of copper in any application. The process of the invention can be employed without corroding or destroying the equipment. [0017]
  • An organic-based hexafluoroacetylacetone (HFACAC) or 1,1,1,5,5,5-hexafluoro-2,4-pentanedione compound is flowed through a [0018] spray nozzle 20 in a vapor phase combined with an inert gas, such as nitrogen, which serves as a carrier. Alternatively, hexafluoroacetylacetate (HFAC) can be introduced into the chamber 10 in a pressurized state. The HFACAC—CF3COCH2COCF3—is sprayed at about 0.1 to 100 liters per minute at a temperature of between about 20 and 100° C. for 1 second to 10 minutes. The vapor phase compound 25 is sprayed over the copper contaminated sites and/or surfaces of equipment and tools to react with the elemental copper and/or copper oxides and form a readily volatile compound that can be flushed away.
  • This volatile compound can be removed from the [0019] chamber 10 in the figure through a drain 30, such as by a vacuum pump 32, or otherwise exhausted from the chamber. Vapor 27, comprising CF3COCH2COCF3 and nitrogen, is allowed to escape and no residues are left on the contaminated sites, equipment, or tools.
  • Since the decontamination removal compound is in vapor phase, it can be used to clean both open areas and remote locations that are not easily accessible. It is also an effective decontaminant after spills. In addition, this process may be used for removing copper from the surface of a wafer for reclaiming of the wafer. [0020]
  • The decontamination removal compound of the invention may be used during copper metallic trace detection and analysis for formation of a preconcentrate. A preconcentrate is a copper-containing solution that can be treated by evaporating water and solvents to leave copper concentrates. The HFACAC of the invention can be used to dissolve the contaminents so that the preconcentrate can be analyzed using any of numerous techniques, such as total X-ray Flouresence Spectroscopy (VDP/TXRF), Inactively Coupled Mass Spectroscopy (ICMS), and Atomic Absorption Spectroscopy (AAS). [0021]
  • The process of the present invention provides a method for effective copper decontamination for any application. An organic-based HFACAC decontamination compound in vapor phase is employed to effect the desired copper decontamination. [0022]
  • While the invention has been particularly shown and described with reference to the preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made without departing from the spirit and scope of the invention.[0023]

Claims (20)

What is claimed is:
1. A method of copper decontamination in the fabrication of an integrated circuit comprising:
introducing a decontamination compound in vapor form over elemental copper wherein said compound reacts with all of said elemental copper and forms a volatile compound that can be flushed away thereby completing said copper decontamination.
2. The method according to claim 1 wherein said decontamination compound comprises an organic-based HFACAC compound.
3. The method according to claim 1 wherein said decontamination compound comprises an organic-based HFAC compound.
4. The method according to claim 1 wherein said step of introducing said decontamination compound is done by spraying said decontamination compound from a nozzle.
5. The method according to claim 1 wherein said step of introducing said decontamination compound is done under pressure.
6. The method according to claim 1 wherein said step of spraying said decontamination compound comprises combining said decontamination compound with an inert gas as a carrier.
7. The method according to claim 1 wherein said elemental copper is found on surfaces of equipment and tools.
8. The method according to claim 1 wherein said elemental copper is found on wafers to be reclaimed.
9. The method according to claim 1 wherein said elemental copper is found on surfaces after a spill.
10. A method of copper decontamination in the fabrication of an integrated circuit comprising:
spraying an organic-based HFACAC compound in vapor form over elemental copper wherein said compound reacts with all of said elemental copper and forms a volatile compound that can be flushed away thereby completing said copper decontamination.
11. The method according to claim 10 wherein said step of spraying said organic-based HFACAC compound comprises combining said compound with an inert gas as a carrier.
12. The method according to claim 10 wherein said elemental copper is found on surfaces of equipment and tools.
13. The method according to claim 10 wherein said elemental copper is found on wafers to be reclaimed.
14. The method according to claim 10 wherein said elemental copper is found on surfaces after a spill.
15. A copper decontamination compound comprising:
an organic-based HFACAC compound in vapor form.
16. The compound according to claim 15 further comprising an inert gas as a carrier.
17. The copper decontamination compound according to claim 15 wherein said copper decontamination compound reacts with elemental copper found on surfaces of equipment and tools and forms a volatile compound that can be flushed away thereby completing copper decontamination.
18. The copper decontamination compound according to claim 15 wherein said copper decontamination compound reacts with elemental copper found on wafers to be reclaimed and forms a volatile compound that can be flushed away thereby completing copper decontamination.
19. The copper decontamination compound according to claim 15 wherein said copper decontamination compound reacts with elemental copper found on surfaces after a spill and forms a volatile compound that can be flushed away thereby completing copper decontamination.
20. The copper decontamination compound according to claim 15 wherein said copper decontamination compound is used to dissolve contaminants in a copper preconcentrate wherein said copper preconcentrate can then be subjected to copper metallic trace detection and analysis.
US09/882,677 2000-07-18 2001-06-18 Application of vapor phase HFACAC-based compound for use in copper decontamination and cleaning processes Abandoned US20020048950A1 (en)

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US09/618,262 US6261955B1 (en) 2000-07-18 2000-07-18 Application of vapor phase HFACAC-based compound for use in copper decontamination and cleaning processes
US09/882,677 US20020048950A1 (en) 2000-07-18 2001-06-18 Application of vapor phase HFACAC-based compound for use in copper decontamination and cleaning processes

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Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5939334A (en) * 1997-05-22 1999-08-17 Sharp Laboratories Of America, Inc. System and method of selectively cleaning copper substrate surfaces, in-situ, to remove copper oxides
US6929637B2 (en) * 2002-02-21 2005-08-16 Spiration, Inc. Device and method for intra-bronchial provision of a therapeutic agent
US6843893B2 (en) * 2002-12-12 2005-01-18 International Business Machines Corporation Metal dry etch using electronic field
CN114126731A (en) * 2020-05-29 2022-03-01 昭和电工株式会社 Dry etching method, method for manufacturing semiconductor element, and cleaning method

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US5087485A (en) * 1990-08-14 1992-02-11 Texas Instruments Incorporated Isopropanol catalyst for copper chemical vapor deposition
US5431774A (en) * 1993-11-30 1995-07-11 Texas Instruments Incorporated Copper etching
US5744192A (en) 1996-11-08 1998-04-28 Sharp Microelectronics Technology, Inc. Method of using water vapor to increase the conductivity of cooper desposited with cu(hfac)TMVS
US5767301A (en) 1997-01-21 1998-06-16 Sharp Microelectronics Technology, Inc. Precursor with (alkyloxy)(alkyl)-silylolefin ligand to deposit copper
US5939334A (en) 1997-05-22 1999-08-17 Sharp Laboratories Of America, Inc. System and method of selectively cleaning copper substrate surfaces, in-situ, to remove copper oxides

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SG87939A1 (en) 2002-04-16

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