US20040187984A1 - Metallic material, electronic component, electronic device and electronic optical component manufactured by using the metallic material and working method of the metallic material - Google Patents

Metallic material, electronic component, electronic device and electronic optical component manufactured by using the metallic material and working method of the metallic material Download PDF

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US20040187984A1
US20040187984A1 US10/791,569 US79156904A US2004187984A1 US 20040187984 A1 US20040187984 A1 US 20040187984A1 US 79156904 A US79156904 A US 79156904A US 2004187984 A1 US2004187984 A1 US 2004187984A1
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weight
metallic material
electrode
wiring pattern
contact
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Takashi Ueno
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Department Corp
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Department Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/01—Alloys based on copper with aluminium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/10—Alloys based on copper with silicon as the next major constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
    • H01L23/49866—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers characterised by the materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
    • H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
    • H01L23/53204—Conductive materials
    • H01L23/53209—Conductive materials based on metals, e.g. alloys, metal silicides
    • H01L23/53228—Conductive materials based on metals, e.g. alloys, metal silicides the principal metal being copper
    • H01L23/53233—Copper alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern

Definitions

  • the present invention relates to an electronic component, an electronic device and an electric optical component as well as a liquid crystal display device, various types of semiconductor product and component, a printed writing board and an IC chip, and also a metallic alloy material used for the same and a working method of the metallic alloy material. And, more particularly, it relates to a metallic alloy material with lower electrical resistance than that of conventional metallic alloy materials and having a heat stable and workable property as well as a widely applicable property, and an electronic component and the likes manufactured by using the metallic alloy material.
  • wiring patterns and electrodes are formed by using a pure metallic material, such as Cu, Al, Ti, Mo, Ta, W and Cr, or a metallic alloy material, such as Al—Cu, Al—Cu—Si, Al—Pd, TaSi, WSi and TiN, as a material for wiring patterns, electrodes and contacts.
  • a pure metallic material such as Cu, Al, Ti, Mo, Ta, W and Cr
  • a metallic alloy material such as Al—Cu, Al—Cu—Si, Al—Pd, TaSi, WSi and TiN, as a material for wiring patterns, electrodes and contacts.
  • pure Al having a good etching property and a low electrical resistance is commonly used as a material for wiring patterns.
  • pure Al has a melting point as low as 660° C.
  • defects such as hillock and whisker, may occur during a heat-treatment in the temperatures in a range of from 300 to 500° C., such as chemical vapor deposition (CVD) after a film forming process for wiring patterns.
  • CVD chemical vapor deposition
  • pure Al due to pure Al having superiority of lower electrical resistance than that of other metallic materials and a complicated manufacturing method, a substitute material for pure Al has not been developed.
  • pure Al is sandwiched in between materials having a heat stability and having a high melting point, such as Ta, Mo, Cr and W, to form wiring patterns.
  • Au, Cu and Ag are known as a material having a lower electrical resistance than that of pure Al.
  • Au has disadvantages such that its expensive cost leads to heighten manufacturing cost and its poor atmospheric corrosion resistance, poor workability in an etching process and poor workability in fining process.
  • Ag has also disadvantages such that it is easy to react with chloride, sulfur and sulfide, and has poor workability in fining process and poor atmospheric corrosion resistance.
  • Cu reacts easily, for example, when Cu contacts oxygen atom deposited on a substrate material, such as a Silicone oxide film on a Silicon wafer, or Cu is subjected to various types of manufacturing process carried out under an environment containing moisture and other oxygen, Cu reacts with oxygen under an environment containing atmosphere to form CuOx at a surface and a boundary of wiring patterns.
  • the CuOx causes damage to advantageous properties of Cu, such as high electric conductivity and high thermal conductivity.
  • Cu contacts a transparent conductive film directly and reacts with oxygen at a boundary to form CuOx, which causes damage to physical stability of Cu.
  • a barrier layer is formed on a substrate, or Cu is sandwiched in between barrier layers, similar to the case of Al.
  • an electrode made of a metallic is oxidized, and a gate insulation film is formed between the oxidized electrode and a silicon active element (that is anodic oxidation).
  • materials capable of forming the gate insulation film are Al and Ta.
  • Ta possibly forms an oxide insulation film with a high yield and having no defects such as pinhole.
  • Ta is a high-resistance material, it is required that electrodes are constructed of two-layer wiring patterns formed by an anode oxidation method which uses Al having a low electrical resistance, whereby an extra manufacturing step is required. In the case of the two-layer wiring patterns, the resistance of the wiring patterns is dependent on the resistance of Al.
  • a semiconductor device such as DRAM, flash memory, CPU, MPU and ASIC, except for above-mentioned display devices, increases in the integration and the size of chips cause the wire width of the wiring patterns to narrow and the arrangement thereof to be complicated, whereby the wire length of the wiring patterns becomes long. Accordingly, such semiconductor device requires the wiring patterns to be formed by using a material having low electrical resistance and heat stable and workable property.
  • Cu or Ag is used as a material for wiring patterns, electrodes and contacts. These materials have insufficient atmospheric corrosion resistance for practical use and are rarely recyclable.
  • an object of the present invention is to provide a metallic material having lower electrical resistance than that of conventional metallic materials as well as having heat stable and workable property, manufacturing methods of electronic component, electronic devices and electronic optical components by using said metallic material, and a working method of said metallic material.
  • a metallic material for an electronic component according to the present invention consists of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight and a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight.
  • the metallic material for an electronic component according to the present invention, Mo is added to Cu so that Mo will be homogeneously mixed in a grain boundary of Cu, resulting in improvement of atmospheric corrosion resistance. Further, addition of a plurality of elements selected from the group consisting of Al, Au, Ag, Ti, Ni Co and Si makes electrical resistance of the metallic material lower. And, an increase in electrical resistance caused by addition of Mo as a second element can be controlled by addition of a third element. At this time, since a weight of the third element added to Cu is set in an amount of 0.1 to 3.0% by weight, the atmospheric corrosion resistance can be improved. Accordingly, a metallic material for an electronic component, which has lower resistance than that of conventional metallic materials as well as heat stable and workable property can be provided.
  • a metallic material for an electronic component according to the present invention consists of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight.
  • a metallic material for electronic components according to the present invention consists of an alloy including mainly Cu, one or a plurality of elements selected from the group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight.
  • the metallic material for an electronic component according to the present invention has electrical resistance lower than 10 ⁇ cm.
  • a metallic material for an electronic component according to the present invention consists of a ternary alloy including mainly of Cu, Mo in an amount of 0.1 to 3.0% by weight and one element selected from a group consisting of Al, Au, Ag, Ti, Ni, Co and Si in an amount of 0.1 to 3.0% by weight.
  • the metallic material for an electronic component according to the present invention, Mo is added to Cu so that Mo will be homogeneously mixed in a grain boundary of Cu, resulting in improvement of atmospheric corrosion resistance. Further, addition of one element selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si makes electrical resistance of the metallic material lower. And, an increase in electrical resistance caused by addition of Mo as a second element can be controlled by addition of a third element. At this time, since a weight of the third element added to Cu is set in an amount of 0.1 to 3.0% by weight, the atmospheric corrosion resistance can be improved. Accordingly, a metallic material for an electronic component, which has lower electrical resistance than that of conventional metallic materials as well as heat stable and workable property, can be provided.
  • the metallic material for an electronic component according to the present invention has electrical resistance higher than 1.5 ⁇ ⁇ cm and lower than 7.0 ⁇ cm.
  • the metallic material for an electronic component according to the present invention is used as a material for any one of a wiring pattern, an electrode, a contact and a target for a sputtering process.
  • An electronic component according to the present invention has a wiring pattern, an electrode or a contact using a metallic material, which consists of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni, Co and Si in a total amount of 0.1 to 3.0% by weight.
  • the metallic material used for above-mentioned electronic component has lower electrical resistance than that of conventional metallic material as well as heat stable and workable property.
  • An electronic component according to the present invention has a wiring pattern, an electrode or a contact using a metallic material, which consists of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight.
  • An electronic component according to the present invention has a wiring pattern, an electrode or a contact using a metallic material, which consists of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight.
  • the electronic component according to the present invention has a wiring pattern, an electrode or a contact which are formed by an etching process using a solution including phosphoric acid and nitric acid.
  • the metallic material consisting of alloy including three or more elements used for the electronic component according to the present invention can be subjected to an etching process using phosphoric etchant, such as H 3 PO4+HNO 3 +CH 3 COOH. And, an addition of phosphoric acid, nitric acid, acetic acid, water, cerium nitrate, silver nitrate to the etchant allows the etching rate to be controlled. Accordingly, a patterning process suitable for such kind of metallic material can be added to conventional pattering processes.
  • phosphoric etchant such as H 3 PO4+HNO 3 +CH 3 COOH.
  • the electronic component according to the present invention has a wiring pattern, an electrode or a contact which are formed by an etching process under a gas atmosphere including chlorine.
  • the metallic material consisting of alloy including three or more elements used for the electronic component according to the present invention can be subjected to an dry etching process under a gas atmosphere including chlorine, for instance RIE (reactive ion etching) and a plasma etching process under a gas atmosphere including chlorine such as Cl 2 , CCl 4 , BCl 3 and SiCl 4 . Accordingly, a patterning process suitable for such the metallic materials can be added to conventional pattering processes.
  • RIE reactive ion etching
  • the electronic component according to the present invention has region other than a wiring pattern, an electrode and a contact are formed by an etching process under a gas atmosphere including fluorine.
  • the metallic material consisting of alloy including three or more elements used for the electronic component is advantageous in that it is hardly damaged by a gas including fluorine under the etching process. Therefore, when subjected to an etching process such as RIE and plasma etching, which are carried out under a gas atmosphere including fluorine such as CF 4 , C 3 F 8 , C 4 F8 and SF 6 and not including chlorine, the metallic material consisting of an alloy including three or more elements is not etched and another materials such as Si, poly-crystalline Si, amorphous Si, SiO 2 , Si 3 N 4 , Mo, W, Ta, Ti and Pt are etched. Accordingly, a patterning process available for device made of such metallic material and another materials can be provided.
  • the electronic component according to the present invention has a wiring pattern, an electrode or a contact which are formed by a heat treatment in the range of the temperatures from 100° C. to 750° C.
  • the electronic component according to the present invention has a wiring pattern, an electrode or a contact which are formed on a backing layer made of one of Ti, W, Ta, Mo, indium tin oxide, titanium nitride, oxidation silicon and silicon nitride.
  • the electronic component according to the present invention has a wiring pattern, an electrode or a contact which are directly formed on a substrate made of one of glass or plastic resin. Because, the a wiring pattern, an electrode or a contact which formed by the metallic material according to the present invention shows a sufficiently adhesion.
  • the alloy consisting of CuMo alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight, further including one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight, has an excellent heat conductivity inherent for pure Cu.
  • the alloy can be subjected to a conventional deposition process such as a sputtering process, a vapor deposition process, a CVD process and a plating process, and a patterning can be easily carried out by a wet etching process and a dry etching process while its heat stability being maintained under high temperatures. Accordingly, an electronic component which uses an metallic material having a low electrical resistance and excellent properties in a heat stability and a workability, for a wiring pattern, an electrode or a contact can be provided.
  • An electronic device has a wiring pattern, an electrode or a contact using a metallic material, which consists of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight.
  • the above-mentioned metallic material used for the above-mentioned electronic device has lower electrical resistance than that of conventional metallic materials as well as heat stable and workable property.
  • the electronic device means a condenser component having a certain capacitor such as a lamination chip condenser and an electrolytic condenser, a semiconductor package component which a semiconductor element is mounted (or bonded) on a cupper sheet or a plastic substrate, and a product which combined these components.
  • An electronic device has a wiring pattern, an electrode or a contact using a metallic material, which consists of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight.
  • An electronic device has a wiring pattern, an electrode or a contact using a metallic material, which consists of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight.
  • the electronic device according to the present invention has a wiring pattern, an electrode or a contact which are formed by an etching process using a solution including phosphoric acid and nitric acid.
  • the electronic device according to the present invention has a wiring pattern, an electrode or a contact which are formed by an etching process under a gas atmosphere including chlorine.
  • the electronic device according to the present invention has region other than a wiring pattern, an electrode and a contact, are formed by an etching process under a gas atmosphere including fluorine.
  • the electronic device according to the present invention has a wiring pattern, an electrode or a contact which are formed by a heat treatment in the range of the temperatures from 100° C. to 750° C.
  • the electronic device according to the present invention has a wiring pattern, an electrode or a contact which are formed on a backing layer made of one of Ti, W, Ta, Mo, indium tin oxide, titanium nitride, oxidation silicon and silicon nitride.
  • the electronic device according to the present invention has a wiring pattern, an electrode or a contact which are directly formed on a substrate made of one of glass or plastic resin.
  • a working method of a metallic material according to the present invention is a method in which a metallic film consisting of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% byweight and one or aplurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is etched by using a solution including phosphoric acid and nitric acid to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film consisting of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight is etched by using a solution including phosphoric acid and nitric acid to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film consisting of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is etched by using a solution including phosphoric acid and nitric acid to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film consisting of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is etched under a gas atmosphere including hydrochloric acid to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film consisting of an alloy including mainly of Cu and Mo in an amount of 0.1 to 3.0% by weight is etched under a gas atmosphere including hydrochloric acid to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film consisting of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is etched under a gas atmosphere including hydrochloric acid to form a wiring pattern, an electrode or a contact.
  • a manufacturing method of electronic component according to the present invention is a method in which a metallic film is consisted of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight, and a film other than said metallic film is worked by an etching process under a gas atmosphere including fluorine.
  • a manufacturing method of an electronic component according to the present invention is a method in which a metallic film is consisted of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight, and a film other than said metallic film is worked by an etching process under a gas atmosphere including fluorine.
  • a manufacturing method of an electronic component according to the present invention is a method in which a metallic film is consisted of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight, and a film other than said metallic film is worked by an etching process under a gas atmosphere including fluorine.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is subjected to a heat treatment in the range of temperatures to 100° C. to 750° C. to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight is subjected to a heat treatment in a range of temperatures to 100° C. to 750° C. to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is subjected to a heat treatment in a range of temperatures to 100° C. to 750° C. to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% byweight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is deposited on a backing layer made of one of Ti, W, Ta, Mo, indium tin oxide, titanium nitride, oxidation silicon and silicon nitride to form a wiring pattern, an electrode or a contact.
  • a metallic film formed by the above-mentioned alloy is deposited on the above-mentioned substrate to form a wiring pattern, an electrode or a contact, and then is subjected to a conventional working process so that a sufficient adhesion can be obtained. Therefore, wiring pattern and the likes having a low electrical resistance as well as excellent properties in heat stability and workability can be formed.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight is deposited on a backing layer made of one of Ti, W, Ta, Mo, indium tin oxide, titanium nitride, oxidation silicon and silicon nitride to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is deposited on a backing layer made of one of Ti, W, Ta, Mo, indium tin oxide, titanium nitride, oxidation silicon and silicon nitride to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is directly deposited on a substrate made of glass or resin such as plastic to form a wiring pattern, an electrode or a contact.
  • a metallic film formed by the above-mentioned alloy is directly deposited on a substrate made of glass or resin such as plastic to form a wiring pattern, an electrode or a contact. Since the alloy which forms the metallic film is hardly reacted with oxygen, increase in en electrical resistance, which may occur in the case of Al, can be eliminated. Accordingly, wiring pattern and the like having a low electrical resistance can be easily formed by a simple manufacturing method.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight is directly deposited on a substrate made of glass or resin such as plastic to form a wiring pattern, an electrode or a contact.
  • a working method of a metallic material according to the present invention is a method in which a metallic film formed by said metallic material consisting of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight is directly deposited on a substrate made of glass or resin such as plastic to form a wiring pattern, an electrode or a contact.
  • An electronic optical component according to the present invention has reflective film, an electrode or a wiring pattern which are formed by a metallic film consisting of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni, Co and Si in a total amount of 0.1 to 3.0% by weight.
  • reflective film, a wiring pattern or electrode can be formed by a metallic film consisting of an alloy having a low electrical resistance as well as excellent properties in a heat stability, a workability and a high reflectance.
  • An electronic optical component according to the present invention has reflective film, an electrode or a wiring pattern which are formed by a metallic film consisting of an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight.
  • An electronic optical component according to the present invention has reflective film, an electrode or a wiring pattern which are formed by a metallic film consisting of an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight.
  • an alloy including mainly of Cu, Mo in an amount of 0.1 to 3.0% by weight and Al and the like in a total amount of 0.1 to 3.0% by weight a metallic material with a lower electrical resistance than that of conventional metallic materials as well as having excellent properties in a heat stability and a workability can be provided.
  • an electronic component, an electronic device and an electronic optical component which are formed by using the metallic material can be provided. Further, a working method of the metallic materials can be provided.
  • an alloy including mainly of Cu and Mo in an amount of 0.1 to 3.0% by weight a metallic material with a lower electrical resistance than that of conventional metallic materials as well as having excellent properties in a heat stability and a workability can be provided.
  • an electronic component, an electronic device and an electronic optical component which are formed by using the metallic material can be provided. Further, a working method of the metallic materials can be provided.
  • an alloy including mainly of Cu, one or a plurality of elements selected from the group consisting of Cr, Ta, W and Ti in a total of an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from the group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight
  • a metallic material with a lower electrical resistance than that of conventional metallic materials as well as having excellent properties in a heat stability and a workability can be provided.
  • an electronic component, an electronic device and an electronic optical component which are formed by using the metallic material can be provided. Further, a working method of the metallic materials can be provided.
  • FIG. 1(A) is a plan view schematically showing a sample for evaluation in adhesion of copper alloy according to an example
  • FIG. 1(B) is a cross sectional drawing schematically showing a sample as shown in FIG. 1(A) in the evaluation.
  • FIG. 2 is a sectional drawing schematically showing an electronic component of which a metallic film is formed on an under layer.
  • FIG. 3 is a sectional drawing schematically showing an electronic component of which a wiring pattern is formed on a plastic substrate or a glass substrate.
  • FIG. 4(A) is a sectional drawing schematically showing a reflective film of an optical modulator
  • FIG. 4(B) is a sectional drawing schematically showing an electrode of an optical modulator
  • FIG. 4(C) is a sectional drawing schematically showing a wiring pattern of an optical modulator.
  • FIG. 5(A) is a sectional drawing schematically showing an electronic component of which a wiring pattern is formed on a printed writing board
  • FIG. 5(B) is a sectional drawing schematically showing an electrode of a chip or contacts of a relay.
  • a metallic material according to the present invention consists of an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight, and is usable as metallic parts of various types of electronic component.
  • the various types of electronic component include a transparent liquid crystal display element, an organic EL (electronic luminescence) panel, a plasma display, a display device such as an electronic optical component using a micro mirror, various types of semiconductor device, a printed writing board, a chip condenser and a relay.
  • the metallic material according to the present invention is applicable for wiring patterns, electrodes, high reflective films, contacts and a target material used for a sputtering process.
  • Mo is added to Cu so that Mo will be homogeneously mixed in a grain boundary of Cu, resulting in improvement of an atmospheric corrosion resistance.
  • electric resistance will increase.
  • a suitable amount of the third element to improve atmosphere corrosion resistance is 0.1 to 3.0% by weight, but adding the third element 3.0% by weight or more will make the atmosphere corrosion resistance lower.
  • the metallic material according to the present invention consists of the cupper alloy so as to have atmosphere corrosion resistance as well as advantageous properties of pure Cu such as electrical conductivity and heat conductivity. Accordingly, the metallic material according to the present invention can have enhanced atmosphere corrosion resistance as well as low electrical resistance and high heat conductivity.
  • the metallic material according to the present invention when used as wiring patterns and electrodes, it is required that electrical resistance thereof is the same value as that of AlSi, which is conventionally used as wiring patterns and electrodes.
  • the electrical resistance less than that of Cr is thought to allow the metallic material to be put in practical use.
  • the metallic material according to the present invention has electrical resistance over 1.6 ⁇ ⁇ cm, and possibly has electrical resistance lower than 3.5 ⁇ ⁇ cm of AlSi alloy if required.
  • the metallic material according to the present invention can have suitable electrical resistance for a material used as wiring patterns and electrodes.
  • the Cu alloy consisted the metallic material does not have a perfectly solid-solution type structure but a Cu grain boundary precipitation type structure. While an alloy having a perfectly solid-solution type structure is assumed to be physically stable, physical property of thereof is often dependent on property of a main element included in the alloy if an amount of an added element is little. That is to say, if the main element such as Cu will have disadvantage in its property, it is difficult for the alloy to solve such disadvantage perfectly.
  • the metallic material according to the present invention can have more workable, heat stable and reliable property than that of conventionally-used materials such as Al, Mo, Cr, Ti, Ta and Cu.
  • a dry etching process using a combined gas including chlorine, and a wet etching process using an etchant such as chlorine solution or alkali solution, like NH OH, are known.
  • the Cu alloy can be worked by such the etching processes, and can be subjected to various types of working process by which pure Al or Al alloy is worked conventionally.
  • the combined chlorine gas includes Cl 2 , CCl 4 , BCl 3 or SiCl 4 .
  • the Cu alloy can be worked by RIE or plasma etching under atmosphere containing such the combined gas to form a film.
  • chlorine included in the combined gas reacts with Cu during etching processing, resulting in a formation of CuCl 2 at a boundary of the wiring patterns.
  • the CuCl 2 damages electrical conductivity and heat conductivity.
  • the film formed by using the Cu alloy does not cause such reaction of Cu with chlorine.
  • a pattering process can be carried out by an etching process under atmosphere including chlorine.
  • region formed by the other material than the alloy including three or more elements can be selectivity etched by an etching process under gas atmosphere including fluorine and not including chlorine. So, by using the metallic material according to the present invention, a suitable method for pattering can be obtained.
  • the Cu alloy including mainly Cu, Mo in an amount of 0.1 to 3.0 % by weight and one or a plurality of element selected from a group consisting of Al, Au, Ag, Ti, Co and Si in a total amount of 0.1 to 3.0% by weight can be etched by using the complex including phosphoric acid. Therefore, the Cu alloy can be subjected to an etching process by utilizing a conventionally-used etching equipment for working Al. And, by adding phosphoric acid, nitric acid, acetic acid, water, cerium nitrate or hydrochloric acid copper, an etching rate can be controlled similar to a conventional process.
  • the Cu alloy can be subjected to the same post-process such as cleaning process after an etching process as pure Al and Al alloy. In addition, contamination can be eliminated compared with pure Al or Al alloy. So, the Cu alloy has workable property compared with a conventionally-used material such as Al, Mo, Cr, Ti, Ta or Cu.
  • the Cu alloy possibly forms a film easily and steadily by a conventionally-used deposition process such as sputtering process, vapor process, CVD process and plating process.
  • a conventionally-used deposition process such as sputtering process, vapor process, CVD process and plating process.
  • the Cu alloy can be sputtered at about 2.3 to 2.5 times faster than a material including Al. So, the Cu alloy is characterized in its fast sputtering rate. Therefore, a film forming time can be shortened and a total manufacturing time also can be shortened.
  • a heat-treatment process is required for alloying.
  • the heat-treatment process is carried out in the temperatures in a range of 100° C. to 750° C.
  • a metallic film 1 shown in FIG. 2, having low electric resistance as well as heat stable and workable property can be provided.
  • a working process requires sufficiently adhesion of the Cu alloy to an under layer 2 shown in FIG. 2
  • the Cu alloy can have satisfactory adhesion by using the under layer made of one of Ti, W, Ta, Mo, indium tin oxide, titanium nitride, oxidation silicon or silicon nitride so as to be possibly used as wiring patterns of various types of semiconductor elements in place of Al. Accordingly, the wiring patterns can have reliability.
  • the Cu alloy hardly reacts with oxygen, when directly deposited on a plastic substrate or a glass substrate to form a film, increase in electrical resistance of the film can be prevented. In addition, because of satisfactory adhesion of the film to the substrate, peeling off or chipping after the film formation dose not occur. Accordingly, as shown in FIG. 3, it becomes possible that the Cu alloy is directly deposited on a plastic 3 or a glass 4 to form a wiring pattern 5 . And, the wiring patterns have low electric resistance and can be formed by a simple producing process.
  • a transmittable liquid crystal display panel when wiring patterns thereof are formed by using the Cu alloy, even if wire length of wiring patterns is lengthened and narrow as its display area and its integration increase, the display panel can be easily and accurately driven. Accordingly, a transmittable liquid crystal panel having reliability and requiring little electric power can be provided.
  • a reflective liquid crystal display panel when wiring patterns thereof are formed by using the Cu alloy, the same effect as the transmittable liquid crystal panel can be obtained.
  • a high reflective films formed by using the Cu alloy allows high reflectance, whereby a display area of the reflective liquid crystal display will be brightened.
  • the present invention refers not only to an alloy including mainly Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight, but also to an alloy including mainly Cu and Mo in an amount of 0.1 to 3.0% by weight, and an alloy including mainly Cu, one or a plurality of elements selected from a group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from a group consisting of Al, Au, Ag, Ti, Ni Co and Si in a total amount of 0.1 to 3.0% by weight.
  • the following three alloys were prepared; a Cu alloy including Mo in an amount of 1.8% by weight, a Cu alloy including Mo in an amount of 1.8% by weight and Al in an amount of 1.5% by weight, and a Cu alloy including Mo in an amount of 1.8% by weight and Ag in an amount of 1.2% by weight.
  • film samples were prepared in the following manner.
  • Each of the alloy samples was deposited on three kinds of substrates to form a film with a thickness of 250 nm by a magnetron sputtering method respectively.
  • the substrate included a glass substrate, an indium oxide tin film with a thickness of 200 nm and a silicon oxide film with a thickness of 500 nm. Then, total nine film samples formed by using the Cu alloys were prepared.
  • each of the film samples was cut into a plurality of gridironed pieces as shown in FIG. 1(A) by using a cutter knife.
  • a size of the gridironed piece was about 1 mm ⁇ 1 mm.
  • a tape (trade mark CT405A-18 manufactured by Nichiban Co., Ltd.) was adhered on each of the film samples of the Cu alloy, and then peeled off, thereby to examine whether or not the gridironed pieces were peeled off the substrate with the tape. As a result, none of the films was peeled off.
  • the following material samples were prepared; pure Al, pure Cu, pure Au, a Cu alloy including Mo in an amount of 1.8% by weight (a CuMo alloy), a Cu alloy including Mo in an amount of 1.8% by weight and Al in an amount of 1.5% by weight (a CuMoAl alloy) and a Cu alloy including Mo in an amount of 1.8% by weight and Ag in an amount of 1.2% by weight (a CuMoAg alloy).
  • a CuMo alloy a Cu alloy including Mo in an amount of 1.8% by weight and Al in an amount of 1.5% by weight
  • a CuMoAl alloy a Cu alloy including Mo in an amount of 1.8% by weight and Ag in an amount of 1.2% by weight
  • a CuMoAg alloy a CuMoAg alloy
  • each of the material samples was deposited on an adhesion layer made of Cr with a thickness of 100 nm, wherein the adhesion layer was formed on the glass substrate. Then, a pure Cu film, a pure Al film, a pure Au film, a CuMo alloy film, a CuMoAl film and a CuMoAg film were prepared.
  • each of the aforesaid films was set in a vacuum furnace, an atmosphere furnace and a nitrogen atmosphere furnace respectively, and after heated to 100° C., further heated to 800° C. And, changes of the film samples were observed every 100° C.
  • the reason why the film showed turbidness is as follows. In the case the pure Al film, an oxide film is generated on its surface, and particles included in the film are bonded each other and grown by heat, resulting in an irregularly and uneven surface which causes turbidness.
  • the Cu alloy according to the present invention has higher heat stability than other metallic materials having low electrical resistance. Also, since particle growing is not substantially observed, it is confirmed that the Cu alloy has heat stability.
  • the following material samples were prepared; pure Al, pure Cu, pure Au, a Cu alloy including Mo in an amount of 1.8% by weight (a CuMo alloy), a Cu alloy including Mo in an amount of 1.8% by weight and Al in an amount of 1.5% by weight (a CuMoAl alloy) and a Cu alloy including Mo in an amount of 1.8% by weight and Ag in an amount of 1.2% by weight (a CuMoAg alloy).
  • a CuMo alloy a Cu alloy including Mo in an amount of 1.8% by weight and Al in an amount of 1.5% by weight
  • a CuMoAl alloy a Cu alloy including Mo in an amount of 1.8% by weight and Ag in an amount of 1.2% by weight
  • a CuMoAg alloy a CuMoAg alloy
  • each of the material samples was deposited on an adhesion layer made of Cr with a thickness of 100 nm, wherein the adhesion layer was formed on the glass substrate. Then, as film samples, a pure Al film, a pure Cu film, a pure Au film, a CuMo alloy film, a CuMoAl film and a CuMoAg film were prepared.
  • each of the film samples was set in a container at a temperature of 80° C. and a humidity of 85% and left for 100 hours or more, up to 800 hours. And, each of changes of the films was observed every 100 hours.
  • the pure Al film was oxidized to show white turbidness at its surface after 200 hours, and showed black spots locally after 700 hours, resulting in an appearance of white turbidness and loss in metallic luster.
  • the pure Ag film began to blacken after 300 hours, and changed in yellowy black color at its all surface after 800 hours, resulting in loss in metallic luster.
  • the pure Au film showed black spots locally at its surface after 800 hours. But, obviously changes in its surface were hardly observed and metallic luster was maintained.
  • the pure Cu film began to blacken at its surface before 100 hours, and blackened at its all surface after 400 hours.
  • the CuMo alloy film and the CuMoAg alloy film hardly changed until 800 hours like the pure Au film, but showed black spots locally at its surface and thinner metallic luster.
  • the following material samples were prepared; pure Al, pure Cu, pure Au, a Cu alloy including Mo in an amount of 1.8% by weight (a CuMo alloy), a Cu alloy including Mo in an amount of 1.8% by weight and Al in an amount of 1.5% by weight (a CuMoAl alloy) and a Cu alloy including Mo in an amount of 1.8% by weight and Ag in an amount of 1.2% by weight (a CuMoAg alloy).
  • a CuMo alloy a Cu alloy including Mo in an amount of 1.8% by weight and Al in an amount of 1.5% by weight
  • a CuMoAl alloy a Cu alloy including Mo in an amount of 1.8% by weight and Ag in an amount of 1.2% by weight
  • a CuMoAg alloy a CuMoAg alloy
  • each of the material samples was deposited on an adhesion layer made of Cr with a thickness of 100 nm, wherein the adhesion layer was formed on the glass substrate. Then, as film samples, a pure Al film, a pure Cu film, a pure Au film, a CuMo alloy film, a CuMoAl film and a CuMoAg film were prepared.
  • each of the film samples were immersed in a 3% NaCl solution, a 5% NaOH solution, a 1% KOH solution and a 1% H 2 SO 4 solution respectively, and then left to stand at room temperature for 100 hours. And, changes of the samples were observed after 24-hour and 100-hour immersions.
  • the pure Au film did not change up to 24-hour immersion by visual observation, and after 100 hours all films showed black turbidness or become translucent.
  • the CuMo alloy film, the CuMoAg alloy film and the CuMoAl alloy film hardly changed, except black spots shown locally.
  • Al, Ag and Cu which are conventionally used materials, reacted chemically to show loss in metallic luster, white turbdiness, blackening or translucence. That is to say, these materials are easily influenced or significantly changes over time by high temperatures and high humidity environments or chemicals, suggesting that these materials have little physical stability.
  • the three kinds of Cu alloys which consist of mainly pure Cu and an added element such as Mo, Al or Ag in an amount of 0.1% by weight, have enhanced heat resistances, high-temperature and high-humidity environment resistance and chemical resistance.
  • addition of Mo, Al or Ag to pure Cu in a small amount will dramatically improve physical instability of pure Cu.
  • the Cu alloys are stable even at a high temperature of about 750° C., it is not required to form a protective film after forming a film by using the Cu alloy. So, a post heat-treatment process after the film formation can be simplified.
  • Table 2 shows a measurement for chemical resistance in photolithography.
  • film sample was prepared in the following manner. A Cu alloy including Mo in an amount of 1.0% by weight and Al in an amount of 1.0% by weight is deposited on a silicone substrate to form a film having a thickness of 150 nm. And, the film was subjected to a development process in a lithography process, and after baking, the electrical resistance of the film was measured.
  • the film was immersed in a 5% silicic acid sodium and 3% phosphoric acid hydrogen disodium solution, which are main elements of the developer. And, in the baking process, the film on which to coat a resist was baked for 30 minutes at a temperature of 87° C.
  • Al and Al alloy, or, Cu, Ag and their alloys, which conventionally tested as a substitute material having low electrical resistance for Al and Al alloys, are used for wiring patterns and electrodes.
  • the plasma ashing process requires specific operating conditions.
  • the plasma ashing process is an important process to improve reliability of single-layered wiring patterns and electrodes when the wiring patterns and electrodes are formed by a plurality of layers.
  • a mixed gas in which oxygen and argon are mixed at a specific flow rate, is splayed on wiring patterns and electrodes by using plasma.
  • contamination and moisture on an upper surface of the wiring patterns and electrode are removed, and particles present at a grain boundary of wiring patterns and electrodes are removed.
  • conventionally-used materials having low electrical resistance are instable for oxygen plasma, the plasma ashing process requires specific operation condition. Consequently, materials for end products will not be sufficiently reliable, or, to provide higher integrated wiring patterns will be difficult.
  • these film samples were set in an ashing device and subjected to a plasma ashing process in the following condition: RF power is 500 W; ashing gas is a mixed gas of oxygen with argon (mixing ration is 50:50% by volume); flow rate is 5 ml/m; ° C. of vacuum is 1.0 to 1.5 torr during the ashing process; ashing time is 300 seconds (5 minutes).
  • the temperature on the surface of the substrate is about 160° C. by measurement using thermo couple.
  • the plasma ashing device left without being opened for 20 minutes to cool down. Then, the samples were retrieved from the device and the surfaces thereof were visually observed. Further, the electrical resistance of each of the films was measured by using a four-prove method.
  • the CuMo alloy film, the CuMoAg alloy film and the CuMoAl alloy film did not change in metallic luster or color before and after the plasma ashing process. Also, the electrical resistance thereof did not change.
  • the Cu alloy according to the present invention can be subjected to a plasma ashing process without physical change or deterioration thereof. Accordingly, wiring patterns and electrodes formed by the Cu alloy according to the present invention can have higher reliability than that of conventionally used materials, and can be manufactured easily by a conventionally way.
  • Table 3 shows an evaluation for film forming rate by a DC magnetron sputtering method.
  • each of target materials formed by the CuMO alloy, the CuMoAl alloy and the CuMoAg alloy has a film formation rate of 2.3 to 2.5 times faster than that of Al. Accordingly, when the Cu alloy according to the present invention is used in the place of Al, a film formation time can be reduced to half and also a manufacturing time can be reduced.
  • a film formation rate of the Cu alloy is faster than that of pure Cu.
  • plastic material can be used as a substrate.
  • the Cu alloy according to the present invention does not only refer to an alloy including mainly of Cu, Mo and one or a plurality of elements selected from the group consisting of Al, Au, Ti, Ni, Co and Si in a total amount of 0.1 to 3.0% by weight, but also refers to an alloy including mainly of Cu, Mo in an amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from the group consisting of Al, Au, Ti, Ni, Co and Si in a total amount of 0.1 to 3.0% by weight, an alloy including mainly of Cu, Mo in an amount of 0.1 to 3.0% by weight, an alloy including mainly of Cu, one or a plurality of elements selected from the group consisting of Cr, Ta, W and Ti in a total amount of 0.1 to 3.0% by weight and one or a plurality of elements selected from the group consisting of Al, Au, Ti, Ni, Co and Si in a total amount of 0.1 to 3.0% by weight.
  • a film formation process does not only refer to a sputtering process but also to refer to another film formation process and a thick film formation process.

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EP1953250A1 (fr) 2008-08-06
CA2497395A1 (fr) 2004-03-18
TWI253475B (en) 2006-04-21
EP1918391A3 (fr) 2009-01-07
EP1956104A1 (fr) 2008-08-13
CN1678765A (zh) 2005-10-05
DE60324830D1 (de) 2009-01-02
EP1559801A4 (fr) 2005-11-30
JP3754011B2 (ja) 2006-03-08
EP1559801A1 (fr) 2005-08-03
TW200404905A (en) 2004-04-01
JP2004091907A (ja) 2004-03-25
EP1559801B1 (fr) 2008-11-19
KR100673401B1 (ko) 2007-01-24
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CN1318626C (zh) 2007-05-30
WO2004022803A1 (fr) 2004-03-18

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