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WO2002007244A1 - Single crystal electrolyte for fuel cells - Google Patents

Single crystal electrolyte for fuel cells Download PDF

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Publication number
WO2002007244A1
WO2002007244A1 PCT/US2001/004590 US0104590W WO0207244A1 WO 2002007244 A1 WO2002007244 A1 WO 2002007244A1 US 0104590 W US0104590 W US 0104590W WO 0207244 A1 WO0207244 A1 WO 0207244A1
Authority
WO
WIPO (PCT)
Prior art keywords
wafers
electrolyte
single crystal
yttria
crystal
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/US2001/004590
Other languages
French (fr)
Inventor
John W. Berthold
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sofco LP
Original Assignee
Sofco LP
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 Sofco LP filed Critical Sofco LP
Priority to AU2001238201A priority Critical patent/AU2001238201A1/en
Publication of WO2002007244A1 publication Critical patent/WO2002007244A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
    • H01M8/1253—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides the electrolyte containing zirconium oxide
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/16—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
    • H01M2008/1293—Fuel cells with solid oxide electrolytes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates generally to the field of fuel cells and in particular to a new and useful fuel cell electrolyte material.
  • Fuel cells generate electricity by reacting a fuel with an oxidant, generally hydrogen and air or oxygen, on the surface an anode and a cathode in the cell, separated by an electrolyte. Many single cells are connected in series in a cell stack.
  • an oxidant generally hydrogen and air or oxygen
  • pSOFC Plant Solid Oxide Fuel Cells
  • fuel cell electrolyte Yttria-stabilized Zirconia
  • the finished electrolyte is known to be brittle and may contain pinholes through the thickness that result in fuel leaks.
  • Fig. 1 illustrates a typical sintered YSZ electrolyte.
  • the scale bar represents lO ⁇ m length. The lack of uniformity in the electrolyte is obvious, as evidenced by the individual grains and grain boundaries that are clearly visible on the sintered electrolyte.
  • a less brittle electrolyte that is more durable is needed for fuel cells, and would allow such cells to be viable in a larger number of commercial and consumer applications.
  • a single crystal YSZ electrolyte which is produced by first growing single YSZ crystals to form a single crystal boule.
  • the boule is sliced into wafers between about 100 ⁇ m and 200 ⁇ m thick.
  • the surfaces of the wafers are ground to a matte finish with a root-mean-square (rms) roughness of about 10 ⁇ m.
  • the area specific resistance of the wafers can be tested by printing electrode patterns onto the wafer surfaces and firing the assembly. Platinum mesh current collectors are attached to each electrode and fired.
  • the resulting electrolyte has improved durability over tape cast and sintered electrolytes.
  • the electrolyte wafers produced by this method do not exhibit bleed through between the anode and cathode.
  • Fig. 1 is a scanning electron microscope image of a standard sintered YSZ material made by prior art methods
  • Fig. 2 is a scanning electron microscope image of the single crystal YSZ electrolyte material of the invention.
  • Fig. 3 is a diagram of a single crystal electrolyte wafer bonded to an electrode and platinum mesh current collector.
  • Fig. 2 illustrates a single crystal YSZ electrolyte produced according to the method of the invention.
  • the electrolyte surface is very uniform, especially compared to the surface of the prior art tape cast and sintered electrolyte of Fig. 1.
  • the particles on the surface of the electrolyte shown in Fig. 2 are surface defects of 1 ⁇ m or less in size.
  • the scale bar represents a 10 ⁇ m length.
  • the electrolyte shown in Fig. 2 is made according to the following steps.
  • Single crystals of yttria-stabilized zirconia (YSZ) are first grown using established crystal growth methods with standard crystal growth equipment as known in the art, including but not limited to Model 7000CZ sold by Thermal Technology Incorporated.
  • Single crystal boules (solid cylinders) of YSZ are formed.
  • those skilled in the art will be able to readily identify appropriate equipment and methods.
  • Standard wafer slicing equipment are then used to cut slices (wafers) of material from the boule at the desired thickness.
  • One such wafer slicing machine is the Ultraslice 6000 sold by Ultra Tec Manufacturing Incorporated.
  • An example of the electrolyte wafers which can be produced by the present invention include single crystal wafers, having a diameter of 1.57 inches and a thicknesses of between approximately 100 ⁇ m and 200 ⁇ m. Single crystal wafers having these dimensions were manufactured and evaluated. The surfaces of the wafers were ground to a matte finish with an rms roughness of about 3 ⁇ m to 10 ⁇ m, which ensures that there is large surface area available for contact with porous electrodes deposited on the single crystal electrolyte surfaces.
  • the yttria concentration in the wafers produced was approximately 9.5% by total weight (wt%).
  • the yttria concentration in standard sintered material produced by the tape casting methods is about 10.5 wt%.
  • the crystalline structure of the single crystal wafers is cubic, with the (1 ,0,0) direction being perpendicular to the wafer surface.
  • the wafers were selected for testing.
  • the wafers were cleaned, electrode patterns were screen printed on the wafer surfaces and the electrodes were fired at high temperature (about 1300°C) to bond the electrodes to the wafer surfaces.
  • platinum mesh current collectors were attached to each electrode and fired at 1250°C.
  • the purpose of the current collectors is to enable measurement of area specific resistance (ASR), which may then be used to compare performance of different electrolyte materials.
  • a diagram of the single crystal electrolyte wafer with bonded electrode and platinum mesh current collector is shown in Figure 3.
  • a single crystal YSZ electrolyte material offers several advantages compared to tape cast and sintered material. The advantages include: greater fracture resistance and higher tensile strength, freedom from pinholes and leak paths, and relatively easy production of wafers with thickness in the 100 ⁇ m to 200 ⁇ m range of interest for fuel cell applications.
  • Electrode printing and for attachment of platinum mesh current collectors can be used as well, which may facilitate processing, reduce time required for ASR testing measurement, and reduce the stresses in the single crystal YSZ material.
  • a screen printer capable of printing circular rather than square electrode patterns should help to significantly lower stresses in the wafers. With square electrodes, stresses are highest at the electrode corners.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Fuel Cell (AREA)

Abstract

A single crystal yttria-stabilized zirconia (YSZ) electrolyte is provided which is produced by first growing single YSZ crystals to form a single crystal boule. The boule is sliced into wafers between 100mm and 200mm thick. The surfaces of the wafers are ground to a matte finish with an rms roughness of about 10mm.

Description

SINGLE CRYSTAL ELECTROLYTE FOR FUEL CELLS
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates generally to the field of fuel cells and in particular to a new and useful fuel cell electrolyte material.
Fuel cells generate electricity by reacting a fuel with an oxidant, generally hydrogen and air or oxygen, on the surface an anode and a cathode in the cell, separated by an electrolyte. Many single cells are connected in series in a cell stack.
Present pSOFC (Planar Solid Oxide Fuel Cells) fuel cell electrolyte (Yttria-stabilized Zirconia) material is made by tape casting methods. The finished electrolyte is known to be brittle and may contain pinholes through the thickness that result in fuel leaks. Fig. 1 illustrates a typical sintered YSZ electrolyte. The scale bar represents lOμm length. The lack of uniformity in the electrolyte is obvious, as evidenced by the individual grains and grain boundaries that are clearly visible on the sintered electrolyte.
A less brittle electrolyte that is more durable is needed for fuel cells, and would allow such cells to be viable in a larger number of commercial and consumer applications.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a single crystal to replace tape cast electrolyte material, which are typically made from sintered grains.
Accordingly, a single crystal YSZ electrolyte is provided which is produced by first growing single YSZ crystals to form a single crystal boule. The boule is sliced into wafers between about 100 μm and 200 μm thick. The surfaces of the wafers are ground to a matte finish with a root-mean-square (rms) roughness of about 10 μm.
The area specific resistance of the wafers can be tested by printing electrode patterns onto the wafer surfaces and firing the assembly. Platinum mesh current collectors are attached to each electrode and fired.
The resulting electrolyte has improved durability over tape cast and sintered electrolytes. The electrolyte wafers produced by this method do not exhibit bleed through between the anode and cathode.
The various features of novelty which characterize the invention are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and specific objects attained by its uses, reference is made to the accompanying drawings and descriptive matter in which a preferred embodiment of the invention is illustrated.
BRIEF DESCRIPTION OF THE DRA WINGS
In the drawings:
Fig. 1 is a scanning electron microscope image of a standard sintered YSZ material made by prior art methods;
Fig. 2 is a scanning electron microscope image of the single crystal YSZ electrolyte material of the invention; and
Fig. 3 is a diagram of a single crystal electrolyte wafer bonded to an electrode and platinum mesh current collector.
DESCRIPTION OF THE PREFERRED EMBODIMENTS Referring now to the drawings, in which like reference numerals are used to refer to the same or similar elements, Fig. 2 illustrates a single crystal YSZ electrolyte produced according to the method of the invention. The electrolyte surface is very uniform, especially compared to the surface of the prior art tape cast and sintered electrolyte of Fig. 1. The particles on the surface of the electrolyte shown in Fig. 2 are surface defects of 1 μm or less in size. The scale bar represents a 10 μm length.
The electrolyte shown in Fig. 2 is made according to the following steps. Single crystals of yttria-stabilized zirconia (YSZ) are first grown using established crystal growth methods with standard crystal growth equipment as known in the art, including but not limited to Model 7000CZ sold by Thermal Technology Incorporated. Single crystal boules (solid cylinders) of YSZ are formed. Ultimately, those skilled in the art will be able to readily identify appropriate equipment and methods.
Standard wafer slicing equipment are then used to cut slices (wafers) of material from the boule at the desired thickness. One such wafer slicing machine is the Ultraslice 6000 sold by Ultra Tec Manufacturing Incorporated. As before, those skilled in the art will be able to readily identify appropriate equipment and methods. An example of the electrolyte wafers which can be produced by the present invention include single crystal wafers, having a diameter of 1.57 inches and a thicknesses of between approximately 100 μm and 200 μm. Single crystal wafers having these dimensions were manufactured and evaluated. The surfaces of the wafers were ground to a matte finish with an rms roughness of about 3 μm to 10 μm, which ensures that there is large surface area available for contact with porous electrodes deposited on the single crystal electrolyte surfaces.
The yttria concentration in the wafers produced was approximately 9.5% by total weight (wt%). The yttria concentration in standard sintered material produced by the tape casting methods is about 10.5 wt%. The crystalline structure of the single crystal wafers is cubic, with the (1 ,0,0) direction being perpendicular to the wafer surface.
After manufacturing, several of the wafers were selected for testing. The wafers were cleaned, electrode patterns were screen printed on the wafer surfaces and the electrodes were fired at high temperature (about 1300°C) to bond the electrodes to the wafer surfaces.
Subsequent examination of one of the wafers showed that there was no evidence of bleed through of the anode or cathode material from one side of the electrolyte to the other.
This result was unexpected and is a remarkable difference between single crystal YSZ electrolyte material and standard tape cast and sintered material. The bleed through in tape cast material is believed to occur along the grain boundaries, which is further supported by the fact that no bleed through occurs in the single crystal YSZ material of the present invention, which has no grain boundaries.
After electrode firing, platinum mesh current collectors were attached to each electrode and fired at 1250°C. The purpose of the current collectors is to enable measurement of area specific resistance (ASR), which may then be used to compare performance of different electrolyte materials. A diagram of the single crystal electrolyte wafer with bonded electrode and platinum mesh current collector is shown in Figure 3.
Two separate platinum mesh current collectors were placed in contact with the electrodes on both sides of one of the 200 μm thick wafers to balance the stresses during firing. The area specific resistance was then tested with good results.
Scanning electron microscope (SEM) photos were produced from samples of the single crystal YSZ electrolyte material to verify that the material was indeed single crystal. Detailed examination of the SEM images confirmed that the wafers are single crystals. A single crystal YSZ electrolyte material offers several advantages compared to tape cast and sintered material. The advantages include: greater fracture resistance and higher tensile strength, freedom from pinholes and leak paths, and relatively easy production of wafers with thickness in the 100 μm to 200 μm range of interest for fuel cell applications.
Application of single crystal YSZ to pSOFC offers potential to significantly improve performance of solid electrolyte.
Other methods for electrode printing and for attachment of platinum mesh current collectors can be used as well, which may facilitate processing, reduce time required for ASR testing measurement, and reduce the stresses in the single crystal YSZ material. For example, a screen printer capable of printing circular rather than square electrode patterns should help to significantly lower stresses in the wafers. With square electrodes, stresses are highest at the electrode corners.
While a specific embodiment of the invention has been shown and described in detail to illustrate the application of the principles of the invention, it will be understood that the invention may be embodied otherwise without departing from such principles.

Claims

CLAIMS:I claim:
1. An electrolyte for a solid oxide fuel cell comprising: a wafer sliced from a boule of a single crystal of yttria-stabilized zirconia, the crystal having a discernible crystalline structure and a selected concentration of yttria therein and the crystal lacking any discernible grain boundaries therein.
2. An electrolyte according to claim 1 , wherein the wafer is between about 100 μm to 200 μm thick.
3. An electrolyte according to claim 1, wherein the concentration of yttria is less than about 10.5 % by total weight.
4. An electrolyte according to claim 3, wherein the crystalline structure of the crystal is cubic.
5. An electrolyte according to claim 1, wherein the crystalline structure of the crystal is cubic.
6. A method of making an electrolyte for a solid oxide fuel cell, comprising: growing a single crystal of yttria-stabilized zirconia; forming a boule of the single crystal yttria-stabilized zirconia; and slicing the boule of the single crystal yttria-stabilized zirconia into wafers.
7. A method according to claim 6, wherein the wafers are between about 100 μm to 200 μm thick and wherein the crystal has a yttria concentration of less than about 10.5 % by total weight.
8. A method according to claim 6, further comprising shaping the wafers into a selected geometry for integration into a solid oxide fuel cell system.
9. A method according to claim 8, wherein the selected geometry is one of: circular and rectangular.
10. A method according to claim 6, further comprising treating the wafers to ensure that there is a large surface area on the wafers for contact with at least one porous solid oxide fuel electrode.
11. A method according to claim 10, wherein the treating of the wafers comprises grinding a matte finish onto a surface of the wafers.
12. A method according to claim 11, wherein the matte finish has a rms roughness between about 3 μm and 10 μm.
13. A method according to claim 12, further comprising shaping the wafers into a selected geometry for integration into a solid oxide fuel cell system.
14. A method according to claim 13, wherein the selected geometry is one of: circular and rectangular.
15. A method according to claim 14, wherein the wafers are between about 100 μm to 200 μm thick and wherein the crystal has a yttria concentration of less than about 10.5 % by total weight.
PCT/US2001/004590 2000-07-14 2001-02-13 Single crystal electrolyte for fuel cells Ceased WO2002007244A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2001238201A AU2001238201A1 (en) 2000-07-14 2001-02-13 Single crystal electrolyte for fuel cells

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US61685400A 2000-07-14 2000-07-14
US09/616,854 2000-07-14

Publications (1)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100407404C (en) * 2003-12-26 2008-07-30 株式会社瑞萨科技 Method for manufacturing semiconductor integrated circuit device

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0864216A (en) * 1994-08-25 1996-03-08 Tonen Corp Oxygen ion conductor thin film and method for producing the same
WO1997026684A1 (en) * 1996-01-18 1997-07-24 The Arizona Board Of Regents On Behalf Of The University Of Arizona Single-crystal oxygen ion conductor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0864216A (en) * 1994-08-25 1996-03-08 Tonen Corp Oxygen ion conductor thin film and method for producing the same
WO1997026684A1 (en) * 1996-01-18 1997-07-24 The Arizona Board Of Regents On Behalf Of The University Of Arizona Single-crystal oxygen ion conductor

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MANNING ET AL.: "The kinetics of oxygen transport in... zirconia", SOLID STATE IONICS, vol. 100, 1997, pages 1 - 10, XP002941098 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100407404C (en) * 2003-12-26 2008-07-30 株式会社瑞萨科技 Method for manufacturing semiconductor integrated circuit device

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