WO2000075402A1 - Hydrophobic and hydrophilic membranes to vent trapped gases in a plating cell - Google Patents

Hydrophobic and hydrophilic membranes to vent trapped gases in a plating cell Download PDF

Info

Publication number
WO2000075402A1
WO2000075402A1 PCT/US2000/014976 US0014976W WO0075402A1 WO 2000075402 A1 WO2000075402 A1 WO 2000075402A1 US 0014976 W US0014976 W US 0014976W WO 0075402 A1 WO0075402 A1 WO 0075402A1
Authority
WO
WIPO (PCT)
Prior art keywords
anode
membrane
cell
hydrophobic
plating
Prior art date
Application number
PCT/US2000/014976
Other languages
French (fr)
Inventor
David Windsor Stockbower
Original Assignee
Mykrolis Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mykrolis Corporation filed Critical Mykrolis Corporation
Priority to AU53088/00A priority Critical patent/AU5308800A/en
Priority to US10/009,744 priority patent/US6846392B1/en
Publication of WO2000075402A1 publication Critical patent/WO2000075402A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/12Semiconductors
    • C25D7/123Semiconductors first coated with a seed layer or a conductive layer
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/001Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C25D17/002Cell separation, e.g. membranes, diaphragms
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00Processes for servicing or operating cells for electrolytic coating
    • C25D21/04Removal of gases or vapours ; Gas or pressure control
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/003Electroplating using gases, e.g. pressure influence

Definitions

  • a plating tool uses a negatively charged anode (usually a copper anode) to plate a positively charged (cathode) silicon wafer.
  • the anode provides a source of replenishing metal ions.
  • the metal ions are reduced to metal and deposited on the 0 cathode surface.
  • Sulfuric acid and a plating solution flows through a chamber around the anode and is used to dissolve a metal (copper) plate. As fluid flows past the anode, it becomes enriched with metal ions .
  • the present invention provides a plating anode cup filter 0 design that vents unwanted gases from the plating solution before they exit the cell and reach the wafer. More specifically, in a first embodiment of the present invention, in the chamber where the fluid flows into the plating tool cell and contacts the anode, it encounters a hydrophobic membrane 5 and a hydrophilic membrane spaced from the hydrophobic membrane. A driving force such as a vacuum applied in the space between the membranes removes unwanted gases therein. In a second embodiment of the present invention, a single membrane is used that is both hydrophobic and hydrophilic. Preferably the hydrophobic portion of the membrane is located at or near the perimeter of the fluid chamber in the plating tool cell, and gas to be vented is directed toward the hydrophobic portion (s).
  • Figure 1 is a cross-sectional view of the anode holder in accordance with the present invention.
  • Figure 2 is a cross-sectional view of the anode holder in accordance with another embodiment of the present invention.
  • Figure 3 is a top view of a membrane having hydrophilic and a hydrophobic portions in accordance with one embodiment of the present invention
  • Figure 4 is a cross-sectional view of an anode holder using the membrane of Figure 3 ;
  • Figure 5 is a cross-sectional view of still another embodiment of the present invention.
  • a plating tool cell 10 is the housing for the anode 50, which is preferably a copper anode, and includes one or more fluid inlets 12.
  • the plating tool cell 10 serves as an anode holder and as a means for fluid distribution to the substrate being plated, such as a wafer (not shown) which is typically rotating for uniform plating.
  • the plating tool cell 10 is made of plastic, and includes an optional fluid inlet 12 and a fluid outlet 13.
  • a fluid plating solution or ion source such as copper sulfate, is introduced into a chamber defined by the plating tool cell 10 through optional fluid inlet 12, and contacts the anode 50.
  • the resulting reaction between the plating solution and the metal anode generates hydrogen gas.
  • situated in the fluid path is a hydrophobic membrane 14.
  • the hydrophobicity of the membrane 14 inhibits or prevents passage of the fluid.
  • the porosity of the hydrophobic membrane 14 is such that gases, generally air and hydrogen, entrapped in the fluid are able to pass through the hydrophobic membrane 14 easily.
  • a second membrane 15 is positioned downstream of the first membrane (in the direction away from the anode 50) .
  • the second membrane 15 is spaced from the first membrane 14, and is hydrophilic. Once the hydrophilic membrane 15 is wetted, it does not allow the passage of gases through it. Accordingly, most or all of the gases remain in the gap 16 between the two membranes.
  • the gap 16 can be filled with a open mesh type separation material, and may be 1/16 to 1/4 inch wide, on average.
  • a driving force such as a vacuum source in communication with the gap 16 with suitable plumbing draws off the gases, thereby preventing them from contacting the wafer and causing defects.
  • high velocity air can be used to create a vacuum by the venturi effect to draw off the gases.
  • Figure 2 shows another embodiment where the gases are vented in gap 16 by creating a high spot 23 in the gap 16 mechanically.
  • the high spot 23 is a portion of the gap 16 that is wider, from membrane 14 to membrane 15, than the total average width of the gap 16.
  • the air tends to collect in the high spot 23 and vent naturally, or can be assisted with a vacuum or high velocity air pressure.
  • the high spot 23 also can be created by bowing the membrane with external fluid pressure, leaving high spots during processing.
  • FIG 3 illustrates another embodiment of the present invention.
  • the membrane 14' is patterned such that only a portion 28 thereof is hydrophobic.
  • Conventional techniques to render portions of the membrane hydrophobic well known to those skilled in the art can be used.
  • the hydrophobic portion (s) are located at or near the perimeter of the cell 10, and the fluid flow is directed towards the perimeter, as shown in Figure 4.
  • FIG 5 illustrates another embodiment of the present invention, where a high spot 23 is created and a small hydrophobic membrane patch 15' is used in a vertical orientation.
  • the hydrophobic membrane 15 is optional, and a bowed hydrophilic membrane 14 is positioned to create a high spot 23 as in the embodiment of Figure 2.
  • the air trapped in gap 16 vents naturally through hydrophobic patch 15' without the use of an external driving force such as a vacuum.

Abstract

A plating tool cell anode for venting unwanted gases from a fluid plating solution. In a first embodiment, the solution is introduced into a chamber, defined by the plating tool cell (10), by fluid inlet (12) and contacts the anode (50). The fluid encounters a hydrophobic membrane (14) and a hydrophilic membrane (15) spaced from the hydrophobic membrane. A driving force, such as a vacuum, is applied to the gap (16) between the membranes to remove unwanted gases therein. In a second embodiment, a single membrane is used that is both hydrophobic and hydrophilic. Preferably, the hydrophobic portion of the membrane is located at or near the perimeter of the chamber and gas to be vented is directed toward the hydrophobic portion(s).

Description

HYDROPHOBIC AND HYDROPHILIC MEMBRANES TO VENT TRAPPED GASES IN A PLATING CELL
BACKGROUND OF THE INVENTION
5. In semiconductor manufacturing, a plating tool uses a negatively charged anode (usually a copper anode) to plate a positively charged (cathode) silicon wafer. The anode provides a source of replenishing metal ions. At the cathode, the metal ions are reduced to metal and deposited on the 0 cathode surface. Sulfuric acid and a plating solution flows through a chamber around the anode and is used to dissolve a metal (copper) plate. As fluid flows past the anode, it becomes enriched with metal ions .
During the chemical reaction that dissolves the metal 5 (e.g., copper), hydrogen gas is liberated. In addition, entrapped gases are generally present during start-up. These gases must be vented so that they do not effect the electrical field or the wafer plating uniformity. Indeed, a separate upstream degasser removes most dissolved air from the main 0 fluid flow path. The generated hydrogen gas, if not removed, becomes entrapped in the plating solution as bubbles or microbubbles and may interfere with the plating operation.
It therefore would be desirable to provide a means for venting hydrogen gas and any other trapped gases out of the 5 plating solution before the solution reaches the wafer.
SUMMARY OF THE INVENTION
The problems of the prior art have been overcome by the present invention, which provides a plating anode cup filter 0 design that vents unwanted gases from the plating solution before they exit the cell and reach the wafer. More specifically, in a first embodiment of the present invention, in the chamber where the fluid flows into the plating tool cell and contacts the anode, it encounters a hydrophobic membrane 5 and a hydrophilic membrane spaced from the hydrophobic membrane. A driving force such as a vacuum applied in the space between the membranes removes unwanted gases therein. In a second embodiment of the present invention, a single membrane is used that is both hydrophobic and hydrophilic. Preferably the hydrophobic portion of the membrane is located at or near the perimeter of the fluid chamber in the plating tool cell, and gas to be vented is directed toward the hydrophobic portion (s).
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a cross-sectional view of the anode holder in accordance with the present invention;
Figure 2 is a cross-sectional view of the anode holder in accordance with another embodiment of the present invention;
Figure 3 is a top view of a membrane having hydrophilic and a hydrophobic portions in accordance with one embodiment of the present invention;
Figure 4 is a cross-sectional view of an anode holder using the membrane of Figure 3 ; and
Figure 5 is a cross-sectional view of still another embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION Turning now to Figure 1, there is shown an anode for use in semiconductor manufacturing. A plating tool cell 10 is the housing for the anode 50, which is preferably a copper anode, and includes one or more fluid inlets 12. Thus, the plating tool cell 10 serves as an anode holder and as a means for fluid distribution to the substrate being plated, such as a wafer (not shown) which is typically rotating for uniform plating. Preferably the plating tool cell 10 is made of plastic, and includes an optional fluid inlet 12 and a fluid outlet 13.
A fluid plating solution or ion source, such as copper sulfate, is introduced into a chamber defined by the plating tool cell 10 through optional fluid inlet 12, and contacts the anode 50. The resulting reaction between the plating solution and the metal anode generates hydrogen gas. In the embodiment shown, situated in the fluid path is a hydrophobic membrane 14. The hydrophobicity of the membrane 14 inhibits or prevents passage of the fluid. However, the porosity of the hydrophobic membrane 14 is such that gases, generally air and hydrogen, entrapped in the fluid are able to pass through the hydrophobic membrane 14 easily. A second membrane 15 is positioned downstream of the first membrane (in the direction away from the anode 50) . The second membrane 15 is spaced from the first membrane 14, and is hydrophilic. Once the hydrophilic membrane 15 is wetted, it does not allow the passage of gases through it. Accordingly, most or all of the gases remain in the gap 16 between the two membranes. The gap 16 can be filled with a open mesh type separation material, and may be 1/16 to 1/4 inch wide, on average. A driving force such as a vacuum source in communication with the gap 16 with suitable plumbing draws off the gases, thereby preventing them from contacting the wafer and causing defects. Alternatively, high velocity air can be used to create a vacuum by the venturi effect to draw off the gases. Figure 2 shows another embodiment where the gases are vented in gap 16 by creating a high spot 23 in the gap 16 mechanically. The high spot 23 is a portion of the gap 16 that is wider, from membrane 14 to membrane 15, than the total average width of the gap 16. The air tends to collect in the high spot 23 and vent naturally, or can be assisted with a vacuum or high velocity air pressure. The high spot 23 also can be created by bowing the membrane with external fluid pressure, leaving high spots during processing.
Figure 3 illustrates another embodiment of the present invention. In this embodiment, the membrane 14' is patterned such that only a portion 28 thereof is hydrophobic. Conventional techniques to render portions of the membrane hydrophobic well known to those skilled in the art can be used. Preferably, the hydrophobic portion (s) are located at or near the perimeter of the cell 10, and the fluid flow is directed towards the perimeter, as shown in Figure 4.
Figure 5 illustrates another embodiment of the present invention, where a high spot 23 is created and a small hydrophobic membrane patch 15' is used in a vertical orientation. The hydrophobic membrane 15 is optional, and a bowed hydrophilic membrane 14 is positioned to create a high spot 23 as in the embodiment of Figure 2. The air trapped in gap 16 vents naturally through hydrophobic patch 15' without the use of an external driving force such as a vacuum.
The removal of bubbles from the plating solution prior to their reaching the wafer contributes to lower plating defects on the wafer.

Claims

What is claimed is:
1. An anode plating cell, comprising: an anode ; a housing for said anode, said housing having a fluid 5. inlet and a fluid outlet; a hydrophobic membrane in said housing downstream of said anode ; a hydrophilic membrane in said housing downstream of and spaced from said hydrophobic membrane by a gap; 0 whereby gases entrapped in said fluid pass through said hydrophobic membrane into said gap and are prevented from passing through said hydrophilic membrane.
2. The anode plating cell of claim 1, further comprising a driving force for removing said entrapped gases from said 5 gap .
3. The anode plating cell of claim 2, wherein said driving force is a vacuum.
4. The anode plating cell of claim 1, wherein said anode comprises copper. 0
5. An anode plating cell, comprising: an anode; a housing for said anode, said housing having a fluid inlet and a fluid outlet; a membrane in said housing downstream of said anode, said 5 membrane having a hydrophobic portion permeable to said fluid and to gases entrapped in said fluid, and a hydrophilic portion permeable to said fluid but not to said gases.
6. The anode plating cell of claim 5, further comprising a driving force for removing said entrapped gases from said 0 housing.
7. The anode plating cell of claim 6, wherein said driving force is a vacuum.
8. The anode plating cell of claim 5, wherein said anode comprises copper. 5
9. A method of removing gases entrapped in a plating solution from an anode plating cell, comprising: providing an anode in said cell; providing a hydrophobic membrane in said cell downstream of said anode; providing a hydrophilic membrane in said cell spaced from and downstream of said hydrophobic membrane; circulating plating solution in said anode plating cell to contact said plating solution with said anode; causing gases entrapped in said plating solution to pass through said hydrophobic membrane but not through said hydrophilic membrane; and removing said gases from said cell.
10. A method of removing gases entrapped in a plating solution from an anode plating cell, comprising: providing an anode in said cell; circulating a plating solution in said cell; causing said plating solution to contact said anode; providing a membrane in said cell downstream of said anode, said membrane having a hydrophobic portion permeable to said plating solution and to entrapped gases in said plating solution, and a hydrophilic portion permeable to said plating solution but not to gases entrapped in said plating solution; causing gases entrapped in said plating solution to pass through said hydrophobic portion of said membrane but not through said hydrophilic portion; and removing said gases from said cell.
PCT/US2000/014976 1999-06-04 2000-05-31 Hydrophobic and hydrophilic membranes to vent trapped gases in a plating cell WO2000075402A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU53088/00A AU5308800A (en) 1999-06-04 2000-05-31 Hydrophobic and hydrophilic membranes to vent trapped gases in a plating cell
US10/009,744 US6846392B1 (en) 1999-06-04 2000-05-31 Hydrophobic and hydrophilic membranes to vent trapped gases in a plating cell

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US13755899P 1999-06-04 1999-06-04
US60/137,558 1999-06-04

Publications (1)

Publication Number Publication Date
WO2000075402A1 true WO2000075402A1 (en) 2000-12-14

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004097929A2 (en) * 2003-04-29 2004-11-11 Asm Nutool, Inc. Method and apparatus for reduction of defects in wet processed layers
DE10340012A1 (en) * 2003-08-30 2005-04-07 Roche Diagnostics Gmbh Device for gas or liquid separation from microfluidic flow systems
US7138014B2 (en) * 2002-01-28 2006-11-21 Applied Materials, Inc. Electroless deposition apparatus

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075069A (en) * 1975-04-10 1978-02-21 Mitsui Mining & Smelting Co., Ltd. Processes for preventing the generation of a mist of electrolyte and for recovering generated gases in electrowinning metal recovery, and electrodes for use in said processes
US4201653A (en) * 1977-10-11 1980-05-06 Inco Limited Electrowinning cell with bagged anode
US4522695A (en) * 1982-12-23 1985-06-11 Neefe Charles W Vapor phase hydrogen generator
US5112465A (en) * 1990-12-04 1992-05-12 George Danielson Electrodeposition apparatus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4075069A (en) * 1975-04-10 1978-02-21 Mitsui Mining & Smelting Co., Ltd. Processes for preventing the generation of a mist of electrolyte and for recovering generated gases in electrowinning metal recovery, and electrodes for use in said processes
US4201653A (en) * 1977-10-11 1980-05-06 Inco Limited Electrowinning cell with bagged anode
US4522695A (en) * 1982-12-23 1985-06-11 Neefe Charles W Vapor phase hydrogen generator
US5112465A (en) * 1990-12-04 1992-05-12 George Danielson Electrodeposition apparatus

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7138014B2 (en) * 2002-01-28 2006-11-21 Applied Materials, Inc. Electroless deposition apparatus
US7189146B2 (en) 2003-03-27 2007-03-13 Asm Nutool, Inc. Method for reduction of defects in wet processed layers
US7503830B2 (en) 2003-03-27 2009-03-17 Novellus Systems, Inc. Apparatus for reduction of defects in wet processed layers
WO2004097929A2 (en) * 2003-04-29 2004-11-11 Asm Nutool, Inc. Method and apparatus for reduction of defects in wet processed layers
WO2004097929A3 (en) * 2003-04-29 2004-12-29 Asm Nutool Inc Method and apparatus for reduction of defects in wet processed layers
DE10340012A1 (en) * 2003-08-30 2005-04-07 Roche Diagnostics Gmbh Device for gas or liquid separation from microfluidic flow systems

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Publication number Publication date
AU5308800A (en) 2000-12-28

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