WO2007018052A1 - Planar electronic display device and process for producing the same - Google Patents

Abstract

This invention provides a planar electronic display device comprising a wiring with high electric conductivity, an electrode and the like in which an element added to Cu can be preferentially reacted with oxygen contained in a gas atmosphere or a solid, which comes into contact with a Cu member, to form an oxide film which can suppress the oxidation of Cu. In an active matrix-type liquid crystal display device comprising a plate, electrode wires (17, 18) which cross each other in a matrix form on the plate, liquid crystal pixels (20) disposed at the intersection points, and a terminal electrode connected to an external drive circuit, at least one of the electrode wires (17, 18), the electrode, the wiring layer, and the terminal electrode is formed of a copper alloy that is composed mainly of copper and forms an oxide layer of an addition element added to copper at the interface thereof with the substrate. The addition element is such that the oxide forming free energy is smaller than Cu, the diffusion coefficient in Cu is larger than the self-diffusion coefficient of Cu, the percentage increase in electric resistance based on 1 at.% in Cu is not more than 5 μΩ·cm, and the activity coefficient Ϝ in Cu satisfies a relationship represented by activity coefficient Ϝ > 1.

Description

 Specification

 Planar electronic display device and manufacturing method thereof

 Technical field

 TECHNICAL FIELD [0001] The present invention relates to a flat electronic display device and a manufacturing method thereof, and in particular, a liquid crystal display device (LCD) that displays an image on a flat screen, a plasma display device (PDP), an organic EL display device (O LED), a field The present invention relates to a flat-panel electronic display device such as an emission display device (FED) and a manufacturing method thereof.

 Background art

 In recent years, liquid crystal display devices (LCDs) that are thin and lightweight, can be driven at low voltage, and consume less power are widely used as flat display devices (flat panel displays). The liquid crystal display device normally has a structure in which liquid crystal is sealed between two transparent glass substrates. A black matrix, a color filter, a common electrode, an alignment film, etc. are provided on the inner surface of one substrate, and a thin film transistor (TFT), gate wiring, signal wiring, pixel electrode, alignment film, etc. are provided on the inner surface of the other substrate. Is provided. For example, a flat color display device is formed by arranging three pixel electrodes aligned with a power filter of three primary colors, defining one pixel unit, and arranging them in a matrix of many pixel units. Is done. In the actual image, pixel rows are sequentially selected by applying a gate voltage pulse as a scanning signal to the gate wiring, and the signal wiring force image signal is simultaneously supplied to the pixel electrodes in the same row, so that the three primary colors of each pixel An image is formed by operating the pixel electrodes.

A thin film transistor (TFT) used for a liquid crystal display device is formed as follows, for example. That is, a gate wiring is first formed on a substrate, and a gate insulating film, an amorphous silicon layer that is a thin film semiconductor, and an n-type amorphous silicon layer are formed on the gate wiring. After forming the TFT structure by a photoetching process, a channel protective layer is formed on the channel region of the amorphous silicon layer, and then a high impurity concentration amorphous silicon layer for contact and source on the source Z drain region on both sides of the channel region After forming and patterning a metal layer to be a Z drain electrode and signal wiring, it is covered with an insulating protective layer. In the liquid crystal display device, several thousand pixels are arranged in one row. For the gate wiring, a gate voltage noise is applied to the end of the wiring to simultaneously excite multiple TFTs arranged in one row. The gate voltage pulse also propagates to the TFT gate electrode of each pixel. The propagation speed decreases as the resistance value of the gate wiring and the capacitance parasitic on the gate wiring increase. This is called the propagation delay of the gate voltage pulse. When this propagation delay increases, the brightness of each pixel becomes more conspicuous. Therefore, by reducing the resistance value of the gate wiring, the propagation delay of the gate voltage pulse is reduced. As a result, uneven brightness is suppressed.

 With the increase in the screen size of liquid crystal display devices, the gate wiring material was changed from molybdenum alloy to aluminum alloy or aluminum cladding. Aluminum (A1) has problems such as hillock and electo port migration. Thereafter, as disclosed in Patent Document 1, for example, a wiring material made of an Al—Nd alloy has been proposed, and anodized Al, Al that has been gradated or double-layered with a Mo alloy, has come to be used. It was. In addition, copper has attracted attention as a material having a lower electrical resistance than these gate electrode materials, but copper has poor adhesion to glass, which is the substrate of a liquid crystal display device. There is a problem that it is easily oxidized by the process gas when forming the insulating layer.

Therefore, in order to solve such a problem, a technique using an alloyed copper wiring has been attempted. This technology ensures the adhesion between the alloy element and the substrate by forming a reaction product with the substrate, and at the same time, the additive element forms an oxide on the Cu surface, thereby forming an acid-resistant Cu film. It aims to act as.

 However, with the conventionally proposed technology, the targeted characteristics are not sufficiently developed, and the alloy element remains in Cu, resulting in an increase in the electrical resistance of Cu, which is superior to the wiring material using A1 or A1 alloy. There was no sex.

That is, Patent Document 2 discloses that 0.3 to 10% by weight of Ag is added to Cu to improve the acid resistance, but the adhesion to the glass substrate is improved. In addition, there is a problem that sufficient oxidation resistance that can withstand the liquid crystal process cannot be obtained.

Patent Document 3 discloses a copper alloy in which at least one element of Ti, Mo, Ni, Al, and Ag is added to Cu in an amount of 0.5 to 5% by weight in order to improve adhesion. Proposed help There is a problem that the electrical resistance of the wiring increases due to the added element.

Further, Patent Document 4 discloses a technique for forming a Mo film between Cu and a substrate, thereby ensuring adhesion and barrier properties with the substrate. However, there is a problem that the effective resistance of the wiring increases as the number of steps for forming Mo increases.

Furthermore, Patent Document 5 discloses that adhesion and acid resistance are improved by adding one or more elements of Mg, Ti, and Cr to Cu. There is a problem that the wiring resistance increases as a result. There is also a problem that the additive element reduces the oxides of the substrate, and the reduced element diffuses into the wiring to increase the wiring resistance.

 Furthermore, Patent Document 6 proposes a technique for forming high melting point nitrides such as TaN, TIN, and WN around Cu in order to solve these problems related to Cu wiring. The technology requires a material and an additional process for forming the barrier layer compared to the conventional wiring material, and the effective resistance of the wiring increases because the high-resistance noria layer is formed thick. There is a problem.

Furthermore, Patent Document 7 proposes that 0.1 to 3. Owt% of Mo is added to Cu, and that Mo is segregated to the grain boundary to suppress acidification due to grain boundary diffusion. However, although this technology can improve the acid resistance of Cu, there is a problem that the wiring resistance increases.

 On the other hand, as a wiring board composition, for example, Patent Document 8 discloses a composite oxide containing 0.5 to 8 parts by mass of a glass component, Zn, Mg and Ti as main components with respect to 100 parts by mass of copper powder. A copper metallized composition containing 0.05 to 3 parts by mass of copper is disclosed, thereby improving the adhesive strength, suppressing warping of the wiring board, and having excellent solder wettability. It is hoped that a composition and a ceramic wiring board using the composition will be provided.

Further, in Patent Documents 9 and 10, Au and / or Co used for the wiring board and Cu alloy which is powerful with Cu, the composition ratio of Cu is 80 to 99.5 wt%, the composition ratio of Au and C A wiring material having a Cu alloy strength in which the sum of the composition ratios of o is 0.5 to 20 wt% is disclosed. This means that an alloy with improved adhesion to a glass substrate or silicon film can be provided. Furthermore, in Patent Document 11, the wiring layer is mainly composed of at least one first metal selected from the group consisting of Ag, Au, Cu, A1, and Pt, and Ti, Zr, Hf, Ta, Nb, Si, B, La, Nd, Sm, Eu, Gd, Dy, Y, Yb, Ce, Mg, Th, and a conductive layer made of a material containing at least one second metal selected from the group consisting of Cr And a liquid crystal display device having an oxide layer made of a material mainly composed of a second metal that covers the surface of the conductive layer. This means that high resistance to chemical treatment in the manufacturing process and good adhesion to the substrate can be obtained, and disconnection of the wiring layer can be suppressed.

 [0006] However, there is a problem that the Cu oxide in the above-mentioned prior art does not form a protective film without an oxidation inhibiting function because it easily permeates oxygen. In particular, in the technique disclosed in Patent Document 11, the additive element forms a protective film by adding an appropriate additive element to Cu and alloying it, thereby suppressing Cu oxidation. Although there is a possibility, it is difficult to form a strong oxide film due to insufficient diffusion of additive elements in the copper alloy.

 [0007] As a flat display device other than a liquid crystal display device (LCD), for example, a plasma display (PDP) which is a display device using gas discharge, a display device using organic substances such as diamines which emit light when a current is passed Field emission display (FED), which is a self-luminous display based on the same principle as the organic EL display (OLED) and cathode ray tube (CRT), which basically emits light based on the same principle as the CRT. Can be mentioned.

 Here, the plasma display device has discharge cells separated by barrier ribs (ribs) and is covered with a phosphor, and the discharge cells discharge fluorescence accumulated between the address electrodes and the scan electrodes. Lights the body. In addition, in an organic EL display device, a pixel circuit composed of TFTs similar to a liquid crystal display device is arranged for each pixel. On the other hand, in the field emission display device, a voltage is applied between the emitter electrode and the anode electrode connected to the force sword electrode, and the emitted electrons controlled by the gate voltage cause the phosphor to emit light. In these flat electronic display devices as well as the electrode wiring for TFT of the liquid crystal display device described above, the adhesion between the glass substrate and the wiring is increased, the wiring resistance is reduced, the oxidation resistance is increased, and the terminal is further improved. It is necessary to simplify the process of forming the part.

[0008] Patent Document 1: JP 2000-199054 A Patent Document 2: Japanese Patent Laid-Open No. 2002-69550

 Patent Document 3: Japanese Patent Laid-Open No. 2005-158887

 Patent Document 4: Japanese Unexamined Patent Application Publication No. 2004-163901

 Patent Document 5: Japanese Unexamined Patent Application Publication No. 2005-166757

 Patent Document 6: Japanese Unexamined Patent Application Publication No. 2004-139057

 Patent Document 7: Japanese Unexamined Patent Application Publication No. 2004-91907

 Patent Document 8: Japanese Patent Laid-Open No. 2003-277852

 Patent Document 9: Japanese Patent Laid-Open No. 2003-332262

 Patent Document 10: Japanese Patent Laid-Open No. 2003-342653

 Patent Document 11: Japanese Patent Laid-Open No. 10-153788

 Disclosure of the invention

 Problems to be solved by the invention

[0009] As described above, in the above prior art, an attempt was made to ensure adhesion and oxidation resistance with a substrate by adding an alloy additive element to Cu. However, sufficient results were obtained even in the case of V deviation. Not obtained. In addition, if the electrical resistance of the wiring increases due to the additive elements remaining in Cu, the problem remains unresolved.

 The present invention has been made in view of the situation to be covered, and the problem is that the adhesion to the substrate is high, and an acid film can be formed to prevent the acid such as the wiring material. An object of the present invention is to provide a flat electronic display device having a high conductivity V wiring, electrode or terminal electrode, and a method for manufacturing the same.

 Means for solving the problem

[0010] In order to solve the above problems, a flat electronic display device according to the present invention includes a pixel unit in which a plurality of pixels as a minimum unit for forming an image are arranged in a matrix on a substrate. As a wiring material for at least one of a signal electrode, a scan electrode, and a terminal electrode that connects the signal electrode or the scan electrode and an external circuit, Cu as a main component, its surface or A copper alloy for forming an oxide layer of the additive element added with Cu is applied to the interface with the substrate. In this case, the additive element has an oxide free formation energy smaller than that of Cu. The diffusion coefficient force in Cu is greater than the self-diffusion coefficient of Cu. The rate of increase in electrical resistance per lat.% In Cu is 5 Ω'cm or less, and the activity coefficient γ in Cu is the activity coefficient. The relationship of γ> 1 is satisfied, and the amount added in the copper alloy is preferably 0.5 to 25 at.%.

The electrode to which the copper alloy is applied is an electrode that drives and controls at least one of a liquid crystal pixel, a gas discharge cell, an organic EL element, and a field emission display display pixel. A liquid crystal display device, a plasma display device, an organic EL display device, or a field emission display device can be used.

A liquid crystal display device according to the present invention includes an electrode line crossing in a matrix on a substrate, a pair of substrates, a liquid crystal layer sandwiched between the substrates, a liquid crystal layer sandwiched between the substrates, A number of liquid crystal pixels each having an electrode formed on the surface on the liquid crystal layer side, a wiring layer electrically connected to the electrode and disposed on the surface of the substrate, and connected to an external driving circuit. And at least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode, the copper being a main component, and the copper at the interface with the substrate. It is characterized by being a copper alloy that forms an oxide layer of an additive element added to the above.

In this case, the oxide layer is preferably formed by a reaction between oxygen contained in the substrate and the additive element.

In addition, it is preferable that at least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode includes an oxide layer of the additive element at the interface with the insulating layer.

Furthermore, at least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode includes an oxide layer in which the additive element and a constituent element of the insulating layer are reacted at an interface with the insulating layer containing oxygen. You can do it.

Furthermore, at least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode may have an oxide layer in which the additive element and oxygen in the atmosphere gas react on the surface. Good.

Furthermore, it is preferable that the additive element has an oxide formation free energy smaller than that of Cu and a diffusion coefficient in Cu larger than that of Cu. Furthermore, the additive element preferably has an electrical resistance increase rate per lat.% In Cu of 5 μΩ · cm or less.

 Furthermore, the additive element preferably satisfies the relationship of activity coefficient γ force activity coefficient γ> 1 in Cu.

Furthermore, the copper alloy is preferably a copper alloy in which an additive element diffuses on the surface of the copper alloy to form an oxide film layer of the additive element.

 Furthermore, the additive element may be at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr and Nd. .

Furthermore, the additive element is preferably Mn.

Furthermore, the amount of Mn added can be 0.5 to 25 at.%.

A method of manufacturing a liquid crystal display device according to the present invention includes an electrode line intersecting in a matrix on a substrate, a pair of substrates disposed at an intersection of the electrode lines, and a liquid crystal layer sandwiched between the substrates, A plurality of liquid crystal pixels each having an electrode formed on the surface of the substrate on the liquid crystal layer side, and a wiring layer electrically connected to the electrode and disposed on the surface of the substrate; and an external drive circuit In the manufacturing method of an active matrix type liquid crystal display device having connected terminal electrodes, Cu is a main component on the substrate, and an additive element added to the Cu is added to the surface or the interface with the substrate. A step of forming a copper alloy for forming an oxide layer by physical vapor deposition or chemical vapor deposition, and etching the obtained copper alloy film to form an electrode wire, an electrode, a wiring layer, or a terminal electrode. Form at least one of And having a degree, the.

 In this case, the copper alloy is at least one metal in which the additive element is selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr and Nd. It is preferable that it exists.

 In this case, the method may further include a step of forming an oxide layer on at least one surface of the formed electrode wire, electrode, wiring layer, and terminal electrode. In addition, the oxygen concentration in the atmospheric gas in the oxide layer forming step is ΙΟρρπ! It is preferably ~ 1%.

Furthermore, the oxide layer forming step includes few electrode wires, electrodes, wiring layers, and terminal electrodes. After forming at least one, heat at 150 to 400 ° C. for 5 minutes to 50 hours to form an acid solution of the additive element in the copper alloy on at least one surface of the electrode wire, electrode, wiring layer, and terminal electrode. It can be a step of forming a material layer.

[0013] A plasma display device according to the present invention includes an address electrode wiring formed inside a back glass substrate, a display electrode wiring formed inside the front glass substrate, the address electrode wiring, and the display electrode wiring. In a plasma display device having a plurality of electric discharge cells respectively arranged at intersections intersecting in a matrix and terminal electrodes connected to an external drive circuit, the address electrode wiring, display electrode wiring, terminal At least one of the electrodes is made of a copper alloy containing copper as a main component and forming an oxide layer of an additive element added to the copper at the interface with the substrate.

 In this case, the oxide layer is preferably formed by a reaction between oxygen contained in the substrate and the additive element.

 In addition, at least one of the address electrode wiring, the display electrode wiring, and the terminal electrode reacts with oxygen in the atmospheric gas or oxygen contained in the insulating layer and the additive element at the surface or the interface with the insulating layer. It may be provided with an oxide layer formed in this way.

 Furthermore, the additive element preferably has an oxide formation free energy smaller than that of Cu, and the diffusion coefficient of the additive element in Cu is larger than the self-diffusion coefficient of Cu.

 Furthermore, the additive element preferably has an electrical resistance increase rate per lat.% In Cu of 5 μΩ · cm or less.

 Furthermore, the additive element preferably satisfies the relationship of activity coefficient γ force activity coefficient γ> 1 in Cu.

 Furthermore, the copper alloy may be a copper alloy in which an additive element diffuses on the surface of the copper alloy to form an oxide film layer of the additive element.

 Furthermore, the additive element is at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr and Nd. be able to. Furthermore, it is preferable that the additive element is Mn.

 Furthermore, the amount of Mn added can be 0.5 to 25 at.%.

[0014] Note that, as a method of manufacturing a plasma display device, for example, a back glass substrate Address electrode wiring formed on the side, display electrode wiring formed on the inner side of the front glass substrate, and a plurality of electric discharges arranged at each intersection where the address electrode wiring and display electrode wiring intersect in a matrix In a method of manufacturing a plasma display device having a cell and a terminal electrode connected to an external drive circuit, cu is a main component on the substrate, and Cu is added to the surface or the interface with the substrate. The process of forming the copper alloy forming the oxide layer of the additive element by physical vapor deposition or chemical vapor deposition, and etching the obtained copper alloy film to address electrode wiring, display electrode wiring, terminal electrode And a step of forming at least one of the following. In this case, a step of forming a dielectric layer on the formed address electrode wiring, display electrode wiring, and Z or terminal electrode may be included.

Furthermore, after forming at least one of the address electrode wiring, the display electrode wiring, and the terminal electrode, it is heated at 150 to 400 ° C. for 5 minutes to 50 hours to at least the address electrode wiring, the display electrode wiring, and the terminal electrode. You may further have the process of forming the oxide layer of the additive element contained in the said copper alloy on one surface.

In this case, the oxygen concentration in the atmospheric gas in the oxide layer formation step is 1 Ορρπ! ~ 1% preferred!

 The organic EL display device according to the present invention is arranged at the intersection of the electrode lines intersecting in a matrix on the substrate and the electrode lines, and the glass substrate, and the positive electrode and the hole transport sequentially stacked on the glass substrate. A plurality of organic EL elements each having a layer, an organic light emitting layer, an electron transport layer, and a cathode, wherein the anode and the cathode are electrically connected to electrode lines intersecting in a matrix through a TFT circuit; In an active matrix type organic EL display device having terminal electrodes connected to an external driving circuit, at least one of the electrode lines, wirings, and terminal electrodes is mainly composed of copper and has an interface with the substrate. Further, it is characterized by comprising a copper alloy that forms an oxide layer of an additive element added to the copper.

In this case, the oxide layer is preferably formed by a reaction between oxygen contained in the substrate and the additive element.

In addition, at least one of the electrode wire, the wiring, and the terminal electrode has a reaction between oxygen in the atmospheric gas or oxygen contained in the insulating layer and the additive element on the surface or the interface with the insulating layer. It may be provided with an acid oxide layer.

 Furthermore, the additive element preferably has an oxide formation free energy smaller than that of Cu, and the diffusion coefficient of the additive element in Cu is larger than the self-diffusion coefficient of Cu.

 Furthermore, the additive element preferably has an electrical resistance increase rate per lat.% In Cu of 5 μΩ ′ cm or less.

 Furthermore, the additive element preferably satisfies the relationship of activity coefficient γ force activity coefficient γ> 1 in Cu.

 Furthermore, the copper alloy may be a copper alloy in which an additive element diffuses on the surface of the copper alloy to form an oxide film layer of the additive element.

 Furthermore, the additive element may be at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr and Nd. .

 Furthermore, it is preferable that the additive element is Mn.

 Furthermore, the amount of Mn added can be 0.5 to 25 at.%.

[0016] Note that, as a method for manufacturing an organic EL display device, for example, electrode lines that intersect in a matrix on a substrate, and are arranged at intersections of the electrode lines, and are sequentially laminated on the glass substrate. A plurality of organic layers, each having an anode, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode, wherein the anode and the cathode are electrically connected to electrode lines that intersect in a matrix through a TFT circuit. According to a method for manufacturing an active matrix organic EL display device having an EL element and a terminal electrode connected to an external drive circuit, Cu is a main component on the substrate, and the surface thereof or the substrate Forming a copper alloy that forms an oxide layer of the additive element added to Cu at the interface with the substrate by physical vapor deposition or chemical vapor deposition, and etching the obtained copper alloy film to form the electrode wire , Wiring, end Forming at least one electrode, and a method that features have a. In this case, after forming at least one of the electrode wire, wiring, and terminal electrode, heating at 150 to 400 ° C. for 5 minutes to 50 hours to at least one surface of the electrode wire and wiring terminal electrode And a step of forming an oxide layer of an additive element contained in the copper alloy.

[0017] A field emission display device according to the present invention includes a force sword side glass substrate and the cathode. A plurality of anode side glass substrates provided opposite to the glass side glass substrate, an anode electrode and a phosphor film provided on the inner surface of the anode side glass substrate, and a matrix on the inner surface of the force sword side glass substrate. A force sword electrode disposed; a gate electrode disposed in a vacuum space between the anode electrode and the force sword electrode; an electrode wire connecting the force sword electrode and the anode electrode; and the force In a field emission display device having an electrode line connecting a sword electrode and a gate electrode and a terminal electrode connected to an external drive circuit, at least one of the electrode, electrode line, and terminal electrode is made of copper. The main component is made of a copper alloy that forms an oxide layer of an additive element added to the copper at the interface with the substrate.

In this case, the oxide layer is preferably formed by a reaction between oxygen contained in the substrate and the additive element.

In addition, at least one of the electrode, the electrode wire, and the terminal electrode is formed on the surface or the interface with the insulating layer, in which oxygen in the atmosphere gas or oxygen contained in the insulating layer reacts with the additive element. It may have a physical layer.

Furthermore, the additive element preferably has an oxide formation free energy smaller than that of Cu, and the diffusion coefficient of the additive element in Cu is larger than the self-diffusion coefficient of Cu.

Furthermore, the additive element preferably has an electrical resistance increase rate per lat.% In Cu of 5 μΩ · cm or less.

Furthermore, the additive element preferably satisfies the relationship of activity coefficient γ force activity coefficient γ> 1 in Cu.

Furthermore, the copper alloy may be a copper alloy in which an additive element diffuses on the surface of the copper alloy to form an oxide film layer of the additive element.

Furthermore, the additive element may be at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr and Nd. .

Furthermore, it is preferable that the additive element is Mn.

Furthermore, the amount of Mn added can be 0.5 to 25 at.%.

As a method for manufacturing the field emission display device, for example, a force sword side glass substrate, an anode side glass substrate provided opposite to the force sword side glass substrate, The anode electrode and phosphor film provided on the inner surface of the anode side glass substrate, a plurality of force sword electrodes arranged in a matrix on the inner surface of the cathode side glass substrate, the anode electrode and the A gate electrode disposed in a vacuum space between the force sword electrode, an electrode line connecting the force sword electrode and the anode electrode, an electrode line connecting the force sword electrode and the gate electrode, and an external drive In a method for manufacturing a field emission display device having a terminal electrode connected to a circuit, the substrate surface is mainly composed of Cu, and oxidation of an additive element added to the Cu on the surface or the interface with the substrate is performed. Forming a physical layer A process of forming a copper alloy by physical vapor deposition or chemical vapor deposition, and etching the obtained copper alloy film to form at least one of an electrode, an electrode wire, and a terminal electrode A step of forming, and a method that features have a.

 In this case, after forming at least one of the electrode, electrode wire, and terminal electrode, heating at 150 to 400 ° C. for 5 minutes to 50 hours to at least one of the electrode, electrode wire, and terminal electrode It may have a step of forming an oxide layer of an additive element contained in the copper alloy on the surface.

 The invention's effect

 According to the present invention, a liquid crystal display device having a wiring in which an oxide film layer having high adhesion to the substrate is formed on the surface of the wiring without lowering the electrical conductivity while preventing oxidation of Cu. In addition, it is possible to provide flat electronic display devices such as plasma display devices, organic EL display devices, and field emission display devices. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be noted that it is easy for those skilled in the art to change and modify the present invention within the scope of the claims to make other embodiments, and the following description is an example of the best mode of the present invention. It does not limit the scope of claims.

 FIG. 1 is a schematic diagram showing a configuration of a liquid crystal display device as a first embodiment of the present invention.

This liquid crystal display (LCD) is a reverse stagger type TFT type. The copper alloy wiring applied in the present invention is not limited to this etching stopper Z reverse stagger type, back channel Z reverse stagger type The same applies to stagger type TFT and planar type TFT Can be applied to. The copper alloy wiring can be used not only for gate lines but also for signal lines, source / drain electrodes, electrode terminals, and the like. Further, the TFT semiconductor film is not limited to the a-Si film but may be a polysilicon film.

 In FIG. 1, the liquid crystal display device includes a pair of substrates 11 and 12, a liquid crystal layer 15 sandwiched between the substrates, an electrode formed on the surface of the substrate 12 on the liquid crystal layer side, and an electrode electrically And a wiring layer disposed on the surface of the substrate. That is, the liquid crystal display device of FIG. 1 includes a glass transparent substrate 11 having an ITO (indium stannate) film transparent common electrode 13 formed on one surface, and an ITO film pixel electrode on one surface. The transparent substrate 12 on which 14 is formed is arranged so that the electrode surfaces face each other. The pixel electrode 14 formed on the transparent substrate 12 includes a TFT 16 as a switch and a storage capacitor 19. Hundreds of thousands of such pixel electrodes 14 are arranged on the transparent substrate 12. The substrates 11 and 12 are arranged with a gap of several meters by a substrate gap agent (spacer), the periphery thereof is sealed, and the liquid crystal layer 15 is filled in the inner gap. That is, the liquid crystal layer 15 is sandwiched between a pair of substrates.

 FIG. 2 is a schematic diagram showing a configuration of a pixel of the liquid crystal display device of FIG.

 In FIG. 2, a pixel electrode 14, a TFT switching element 16, a gate wiring 17, a source wiring 18, and a storage capacitor line 19 are arranged on a transparent substrate in a secondary plane arrangement that is planarly equivalent to the circuit. The intersection of the gate wiring 17 and the source wiring 18 is insulated by an insulating film 24. In other words, the gate wiring 17 extended in the row direction on the screen display and the source wiring 18 extended in the column direction are arranged in a matrix, and the storage capacitor line 19 is arranged in parallel with each gate wiring 17. Yes. The TFT switching element 16 and the pixel electrode 14 are formed in the region unit surrounded by the gate wiring 17 and the source wiring 18, and the TFT switching element 16 is electrically connected to the gate wiring 17 and the source wiring 18 at the intersection of the region unit. . That is, the TFT source electrode 22 is connected to the source wiring 18, the drain electrode 23 is connected to the pixel electrode 14, and the gate electrode 21 is connected to the gate line 17.

 FIG. 3 is an enlarged cross-sectional view showing a main part of the pixel configuration in FIG. 2, and shows a cross section (1) of the TFT transistor element portion and a cross section (2) of the storage capacitor line portion.

In FIG. 3, a TFT switching element 16 and a gate line 17 are formed on a transparent substrate 12 made of glass. A gate electrode 21 and a storage capacitor line 19 connected to are connected. The gate electrode 21 is composed of a conductive layer 211 of a metal portion made of a Cu alloy and oxide film layers 212 and 213 covering the conductive layer 211. The acid coating layer 213 is interposed between the conductive layer 211 and the substrate 12. Similarly, the storage capacitor line 19 includes a conductive layer 191 having a Cu alloy force and oxide film layers 192 and 193 covering the conductive layer 191.

 An insulating film 24 composed of a plurality of layers 241 and 242 is deposited on the transparent substrate 12 on which the gate electrode 21, the storage capacitor line 19 and the like are formed, and an a-Si layer 25 is formed in the TFT region on the upper surface. A source electrode 22 and a drain electrode 23 are formed thereon. The source electrode layer 22 is electrically connected to the source wiring 18 (FIG. 3 (1)). A pixel electrode 14 having ITO force is formed in the pixel region on the insulating film 24 composed of the storage capacitor line 19 and a plurality of layers 241 and 242 provided thereon, and is electrically connected to the drain electrode 23. (Figure 3 (2)).

 FIG. 4 is a diagram showing an equivalent circuit of a TFT liquid crystal panel in which a large number of liquid crystal pixels (hereinafter also referred to as TFT elements) 20 configured as described above are arranged. Normally, a TFT liquid crystal panel is shown as a 3 × 3 pixel for the sake of convenience in FIG. 4, for example, as a force consisting of 640 × 3 × 480 TFT elements. In FIG. 4, the gate wiring 17 and the source wiring 18 are shared by the respective rows and columns. When a certain gate wiring 17 and source wiring 18 are selected, the combination is determined. When an arbitrary pixel among the TFT pixels 20 is displayed to form a character or an image, a plurality of scanning lines are scanned line-sequentially using the gate wiring 17 as a scanning line. In accordance with this principle, the gate lines 17 are sequentially scanned, and the necessary liquid crystal pixels 20 are applied by applying voltages according to the driving states of the respective pixels to all the source lines 18 at the same timing. Is displayed, and one frame is displayed. This is repeated to display a movie.

 Next, the wiring forming method in the present embodiment will be described.

For example, a Cu alloy is sputtered on the glass transparent substrate 12 and etched to form a Cu alloy layer pattern of the gate wiring 17, the gate electrode 21, and the storage capacitor line 19. Next, this contains a trace amount of oxygen. Heat treatment is performed in an oxidizing atmosphere to oxidize the surface of the gate electrode wire 211 made of Cu alloy (see Fig. 3 (1)) to form oxide film layers 212 and 213. Let The acid coating layer 213 is formed between the conductive layer 211 and the substrate 12.

 Thereafter, a SiOx insulating layer 241 and a SiNx film 242 are laminated as the insulating film 24 by sputtering or CVD, and an undoped a-Si layer 25 is further formed thereon.

Next, a metal layer to be the source electrode 22 and the drain electrode 23 is formed on the surface, and then the source electrode 22 and the drain electrode 23 are formed with an etching solution. Next, the a-Si layer 25 was etched by CDE to form a SiNx protective film, and an opening was formed in the contact portion to form a TFT switching element 16.

 In this embodiment, the gate electrode 21, the source electrode 22, the drain electrode 23 of the TFT switching element 16, and the gate wiring 17, the source wiring 18, and the heat storage capacity line 19 connected to these are the same using the same copper alloy. It is formed by the procedure. As an additive element in a copper alloy, the free energy of formation of oxides is smaller than that of Cu, and the diffusion coefficient of the additive element in Cu (hereinafter simply referred to as the diffusion coefficient unless otherwise specified) A metal greater than the self diffusion coefficient is applied.

The free energy (A G: kjZmol) for forming an oxide is higher in reactivity with oxygen (O 2) as the negative value increases. Therefore, in order to form an oxide film layer on the surface of the Cu alloy, an additive element having a larger absolute value of the oxide formation free energy than Cu, in other words, an additive element having a lower oxide formation free energy. Apply.

 In addition, by making the diffusion coefficient of the additive element larger than the self-diffusion coefficient of Cu, it is possible to quickly reach the Cu surface and to preferentially form an acid-oxide film layer with the additive element on the Cu alloy surface. . If the diffusion coefficient of the additive element is smaller than the self-diffusion coefficient of Cu, a considerable amount of time is required for the additive element to reach the surface of the Cu alloy. Therefore, a Cu oxide film such as CuO or Cu20 is formed on the surface of the Cu alloy. Form a layer. Since this Cu oxide film layer is not strong, oxygen penetrates from the surface of the Cu oxide film layer and forms an oxide with an additive element inside the Cu alloy. Furthermore, as Cu oxidation progresses, there is a problem that Cu in the metal state gradually decreases, and when it is used for wiring of a liquid crystal display device, the electrical resistance gradually increases.

Therefore, in the present embodiment, a metal element having a diffusion coefficient larger than the self-diffusion coefficient of Cu is used as an additive element. In addition, by using an additive element that is a metal element that has a larger absolute value than that of Cu and has a higher absolute value than that of Cu. An oxide film layer is formed.

 [0027] Further, according to the present embodiment, when the Cu alloy used as the wiring material of the liquid crystal display device is applied in contact with an oxide layer or another metal layer, the oxide layer and the Cu alloy are used. An oxide film layer containing an additive element is formed at the interface with the substrate. At this time, the oxide forming the oxide layer is reduced by reducing the oxide forming the oxide layer by setting the additive element to have an oxide formation free energy larger than that of the oxide layer element. In an oxidizing atmosphere, an oxide coating layer can be formed without reducing the oxide. Note that an oxide film layer can be formed at the interface even in contact with another metal layer in an oxidizing atmosphere.

 Further, in this embodiment, when a Cu alloy applied as a wiring material or the like is brought into contact with an insulating layer containing oxygen, the Cu alloy diffuses at the interface, and the additive element is oxidized and an oxide film is formed. Form a layer. In addition, the metal element contained in the insulating layer, Cu in the Cu alloy, and the additive element may each form an oxide to form a composite oxide film layer. For example, when the substrate of the liquid crystal display device includes an oxide such as Si02, a Cu alloy gate wiring is provided on the substrate, and when this is heat-treated, the additive element in the Cu alloy that forms the gate wiring is not in contact with the substrate. It diffuses to the interface with the Cu alloy gate wiring and reacts with oxygen on the substrate containing the oxide to form an oxide, whereby an oxide film layer can be formed. Further, for example, a gate insulating film 24 made of SiNO or the like is provided on the gate electrode 21. By performing heat treatment in the manufacturing process, the gate electrode 21 and the gate insulating film 24 made of Cu alloy are provided. (Cu, Si, additive elements) Oxide oxide layer expressed by Ox is formed at the interface. In this manner, an oxide layer can be provided on the surface of a Cu alloy as a wiring material or the like for a liquid crystal display device.

[0028] As the additive element in the copper alloy, an additive element that is solid-solved in an amount of additive in the Cu alloy in the range of 0.1 to 25 at.% Is preferably used. This is because the additive element is difficult to diffuse unless it is in a solid solution state in the Cu alloy. In particular, when an intermetallic compound is formed with Cu, the additive element is hardly diffused. Furthermore, the additive amount of the additive element in the Cu alloy is 0. lat.% If it is less than this, the formed oxide film layer becomes too thin to prevent the progress of Cu oxidation. On the other hand, if the amount of the additive element exceeds 25 at.%, The α element of the additive element may precipitate near room temperature.

Further, in the present embodiment, an additive element whose electrical resistance increase rate per lat.% In Cu is 5 μΩ ′ cm or less is applied. The rate of increase in electrical resistance of the additive element is determined, for example, by the relationship between the atomic radius of the element applied as the additive element, the electronic state, and the Cu atom. If the rate of increase in electrical resistance per lat.% In Cu exceeds 5 Ω 'cm, the electrical resistance is equivalent to that of the aluminum alloy currently used, and the advantage of using a copper alloy is lost.

 Further, the Cu alloy as the wiring and electrode material applied to the present embodiment contains an additive element having an activity coefficient exceeding 1.0 in Cu. This activity coefficient is also called activity and is defined by the following formula (1).

 i = io + RTln y iNi …… Formula (1)

 (Where i is the chemical potential of the i component, io is the chemical potential of the standard state of the i component, y i is the activity coefficient, and Ni is the mole fraction)

 The activity coefficient represents the interaction in Cu. When the activity coefficient γ ί> 1 of the i component, it repels in Cu and separates from Cu. When the activity coefficient of the i component is γ ί <1, it attracts in Cu and stays in Cu. Here, the additive element added to the Cu alloy has an activity coefficient of more than 1 with respect to Cu, so that Cu nuclear energy is released and diffusion is made. In addition, it reaches the surface of the Cu alloy and is more easily oxidized than Cu, thereby forming an oxide film layer on the surface of the Cu alloy. If the activity coefficient is less than 1, the formation of an oxide film layer that hardly reaches the surface of the Cu alloy is delayed due to a strong tendency to remain in Cu, and the oxidation of Cu proceeds.

 The activity coefficient was measured as follows, for example. That is, the copper alloy was dissolved in a Knudsen cell, the composition dependence of the ionic current value was measured with a mass spectrometer, and the obtained results were analyzed using Belton and Fruehan integral formulas to obtain activity coefficients.

In the present embodiment, the additive element in the Cu alloy is specifically at least one selected from the group consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr, and Nd. so is there. These may be used alone or a plurality of additive elements may be applied simultaneously. Each of these additive elements has an absolute value of the free energy of formation of oxides larger than that of Cu, and the diffusion coefficient of the additive element in Cu is larger than the self-diffusion coefficient of Cu. The rate of increase in electrical resistance per lat.% is 5 Ω'cm or less. Further, these additive elements satisfy the relationship of activity coefficient γ force activity coefficient γ> 1 in Cu. As a result, these metals added to the Cu alloy diffuse in the Cu and reach the surface of the Cu alloy to form a strong and highly adherent oxide film layer ahead of the Cu. The Cu alloy is inevitably mixed with impurities such as S, Se, Te, Pb, Sb, Bi, etc. These may cause a decrease in the electrical conductivity, tensile strength, etc. of the copper alloy. As long as it is not.

[0030] In the present embodiment, the method of applying the Cu alloy is not particularly limited. A plating method such as an electric field plating method or a melting plating method, or a physical vapor deposition method such as a vacuum deposition method or a sputtering method can be used. By heat-treating the Cu alloy provided in this way, the additive elements diffuse and reach the surface of the Cu alloy, and are oxidized preferentially over Cu to form an oxide film layer. . Here, the additive element used in the copper alloy is at least one selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr and Nd. In particular, manganese (Mn) is preferable.

 The heat treatment temperature is, for example, 150 to 400 ° C., and the heat treatment period is, for example, in the range of 5 minutes to 5 hours. When the heat treatment temperature is less than 150 ° C, it takes time to form an oxide film, and productivity is lowered. On the other hand, when the temperature exceeds 400 ° C, Cu additive elements diffuse and reach the surface, causing Cu to oxidize and form an acid film layer. In addition, if the heat treatment time is less than 5 minutes, it takes too much time to form the acid film, whereas if it exceeds 5 hours, the acid film layer is sufficiently formed, so that there is no need for heat treatment.

[0031] Specific examples of the present invention will be described below.

 Example 1

A Cu-2at.% Mn alloy thin film is formed on a cleaned glass substrate using a Cu-2at.% Mn alloy consisting of 99.9999% pure Cu and 99.98% pure Mn as a target material. The film was then heat-treated at a temperature of 150 ° C or higher and 400 ° C or lower. After that The composition distribution in the depth direction of the thin film surface was analyzed by spectroscopy. Furthermore, cross-sectional samples were prepared, and microstructure observation and composition analysis were performed using a transmission electron microscope and an X-ray energy dispersive spectrometer (XEDS).

 FIG. 5 is a diagram schematically showing a cross-sectional structure after heat treatment at 400 ° C. for 30 minutes. A stable oxide layer containing Mn as a main element is formed near the interface between the Cu-Mn alloy and the glass substrate and near the Cu-Mn alloy surface.

[0032] Example 2

 A p-Si film was deposited on the cleaned glass substrate by plasma enhanced chemical vapor deposition (PECVD), and then the entire surface was laser-annealed. After p-Si film was patterned, Si02 gate insulating film was formed by CVD method. Thereafter, a Cu-2at.% Mn alloy was formed by sputtering, and a gate electrode was formed by etching. Next, heat treatment was performed at 400 ° C. for 30 minutes in a vacuum. Further, impurities were implanted by an ion doping method, the source electrode and the drain electrode were formed in a self-aligned manner, and an interlayer insulating film was formed. Thereafter, heat treatment was performed at 400 ° C. for 30 minutes. FIG. 6 is a schematic cross-sectional view of a planar type polysilicon (p-Si) type TFT liquid crystal display device switching element portion formed by the above process. In FIG. 6, a noria layer made of Mn oxide was formed in the vicinity of the interface between the gate insulating film and the interlayer insulating film and the gate electrode 21 which is the Cu—Mn alloy wiring portion.

[0033] A second embodiment of the present invention will be described below.

 FIG. 7 is a schematic diagram showing the structure of a gas discharge cell (hereinafter, simply referred to as a discharge cell) of the plasma display device.

 In FIG. 7, the discharge cell 105 includes an address (data) electrode 103 formed inside the rear glass substrate 101 and a transparent electrode 104 formed inside the front glass substrate 102 in a matrix form on the substrate. Discharge cells arranged at each crossing point, which are a back glass substrate 101, a protective layer 106 that protects the transparent electrode 104 formed on the surface of the front glass substrate 102, and a predetermined gap therebetween. It has a discharge space surrounded by the arranged barrier ribs 107.

The discharge space is filled with, for example, a mixed gas of neon (Ne) and xenon (Xn) or a mixed gas of helium (He) and xenon (Xn). The inner wall of the discharge cell 105 has three light sources. A phosphor corresponding to the color (R, G, B) is applied. When a voltage is applied between the address electrode 103 and the transparent electrode 104, a discharge is generated, and the generated ultraviolet light hits the phosphor and emits visible light. . The three colors of light mix delicately to create various colors.

FIG. 8 is an explanatory view showing a plasma display panel in which a large number of discharge cells are arranged. In FIG. 8, for convenience of explanation, a total of nine discharge cells 111 are arranged in a matrix form with three pixels in each of the horizontal and vertical directions. In such a plasma display panel, the same Cu alloy as that used in the first embodiment, for example, Cu-Mn, is used as the wiring material for the address electrode wiring 113, the display electrode wiring 114, and the terminal electrode 115 of the switch portion. Applies.

 That is, for example, a Cu-Mn alloy is formed on the surface of a glass substrate by a physical vapor deposition method such as a sputtering method or an electron beam method or a chemical vapor deposition method, and is then etched by, for example, a photolithography method to form an address electrode wiring. At least one of 113, display electrode wiring 114, and terminal electrode 115 is formed. Thereafter, if necessary, a dielectric layer is formed on the upper surface, and heated at 150 ° C. to 400 ° C. for 5 minutes to 50 hours, for example, in the constituent elements of the glass substrate and the copper alloy. Mn, which is an additive element of the above, is reacted to form an oxide layer containing Mn as a main element at the interface between the glass substrate and the Cu alloy material. Improve interfacial adhesion and increase oxidation resistance of electrodes and wiring parts.

 At this time, by setting the oxygen concentration in the atmospheric gas in the dielectric layer forming step to 10 ppm to 1%, the above-described heat treatment step can be omitted.

 [0035] According to this embodiment, the copper oxide is prevented from being oxidized on the surface of the wiring without lowering the electrical conductivity, and the brazing having the wiring in which the oxide film layer is formed with high adhesion to the substrate. A zuma display device can be provided.

 Hereinafter, a third embodiment of the present invention will be described.

FIG. 9 is a schematic diagram showing the structure of an organic EL element. In FIG. 9, the organic EL device includes a glass substrate 201, an anode (ITO) 202, a hole transport layer (HTL) 203, a light emitting layer (EML) 204, and an electron transport layer sequentially stacked on the glass substrate 201. (ETL) 205 and a cathode 206 disposed on the electron transport layer 205. As a light emitting layer For example, organic substances such as diamines are used. The anode 22 and the cathode 206 are electrically connected by an electrode line through a power source. The thickness of each layer is, for example, about several tens of nm.

 FIG. 10 is an explanatory view showing an organic EL display panel in which a large number of organic EL elements are arranged in a matrix. Each organic EL element is provided with a transistor as an active element, and the active organic EL element is turned on and off by this active element. As the transistor, for example, an amorphous silicon or polysilicon thin film transistor (TFT) is used. Each organic EL element and active element are connected by a vertical X electrode line 212 and a horizontal Y electrode line 213.

 In such an organic EL display panel, a copper alloy similar to that used in the first embodiment and the second embodiment described above as a wiring material such as the X electrode line 212 and the Y electrode line 213, such as a Cu-Mn alloy, is used. Applied.

 That is, for example, a Cu-Mn alloy is formed on the surface of a glass substrate by a physical vapor deposition method such as a sputtering method or an electron beam method or a chemical vapor deposition method, and then etched by, for example, a photolithography method to form an X electrode wire. 212, Y electrode wire 213, etc. are formed, and then, if necessary, for example, by heating at 150 ° C to 400 ° C for 5 minutes to 50 hours, the organic EL elements are arranged in a matrix. A display panel is formed. At this time, for example, a constituent element of the glass substrate reacts with Mn which is an additive element in the copper alloy to form an oxide layer containing Mn as a main element at the interface between the glass substrate and the Cu alloy material. In addition to improving the interfacial adhesion between the substrate and the electrode and wiring material, it also increases the acid resistance of the electrode and wiring parts, and also prevents the wiring material from increasing in electrical resistance.

[0038] In the organic EL display panel having such a configuration, when a voltage is applied between the anode 202 and the negative electrode 206 of the organic EL element, holes injected from the anode and electrons injected from the cathode cover emit light. The organic material recombined in the body 204 and excited by the energy emits light. By repeating such light emission under predetermined conditions in each organic EL element, an image is formed on the organic EL display panel.

According to the present embodiment, Cu oxidation is prevented from occurring on the surface of the wiring without lowering the electrical conductivity, and adhesion to the substrate is high!有機 Organic with wiring with oxide coating layer An EL display device can be provided.

 [0039] A fourth embodiment of the present invention will be described below.

 Fig. 11 is a schematic diagram showing the structure of a field emission display (hereinafter referred to as FED). In FIG. 11, this FED uses carbon nanotubes as a force sword electrode, and includes a force sword side glass substrate 301 and an anode side glass substrate 302 provided to face the force sword side glass substrate 301. An anode electrode film 304 provided on the inner surface of the anode side glass substrate 302, a phosphor film 306 applied to the surface of the anode electrode film 304, and a matrix on the inner side surface of the force sword side glass substrate 301. A plurality of force sword electrodes 303 arranged in a shape, and a gate electrode 307 disposed in a vacuum space between the phosphor film 306 and the force sword electrode.

 A plurality of cathode electrodes arranged in a matrix, for example, on the surface of the force sword side glass substrate 301 are electrically connected by electrode wires, and the gate electrode 307 and the force sword electrode 301 are electrode wires to which a gate voltage is applied. Connected by. The anode electrode film 304 is connected by an electrode line through a power source. Further, terminal electrodes (not shown) are provided at the connection portions with the external power supply circuit and the signal circuit.

 In such an FED display device, as at least one wiring member such as an electrode wire or an electrode terminal, copper similar to the alloy used in the first embodiment, the second embodiment, and the third embodiment described above is used. Alloys such as Cu-Mn alloys are applied.

 That is, for example, a Cu-Mn alloy is formed on a glass substrate surface by, for example, a physical vapor deposition method such as a sputtering method or an electron beam method or a chemical vapor deposition method, and then etched by, for example, a photolithography method to form an electrode wire, At least one of the terminal electrodes is formed, and then the wiring portion of the FED display device is formed by heating, for example, at 150 ° C. to 400 ° C. for 5 minutes to 50 hours as necessary. At this time, the constituent element of the glass substrate reacts with the additive element Mn in the copper alloy to form an oxide layer containing Mn as a main element at the interface between the glass substrate and the Cu alloy material. In addition to improving the interfacial adhesion between the substrate and electrodes and wiring materials, it also increases the oxidation resistance of the electrodes and wiring parts.

In the FED display device having such a configuration, when a predetermined voltage is applied between the force sword electrode 301 and the anode electrode 302, electrons are emitted from the force sword electrode 301 by field emission. It is. At this time, the current of the emitted electron beam is controlled by the voltage difference between the force sword electrode 301 and the gate electrode 307. Electrons emitted into the vacuum traveled toward the anode electrode 302 and emitted visible light as a set of three phosphors of R (red), G (green), and B (blue). An image is formed on the display screen by visible light.

 According to the present embodiment, Cu oxidation is prevented from occurring on the surface of the wiring without lowering the electrical conductivity, and adhesion to the substrate is high! It is possible to provide a field emission display device having a wiring on which an oxide film layer is formed. Brief Description of Drawings

FIG. 1 is a schematic view showing a configuration of a liquid crystal display device of the present invention.

 FIG. 2 is a schematic diagram showing a configuration of a pixel of a liquid crystal display device of the present invention.

 FIG. 3 is a schematic cross-sectional view showing a configuration of a pixel of the liquid crystal display device of the present invention. (1) is a TFT transistor element portion, and (2) is a storage capacitor line portion.

 FIG. 4 is a diagram showing an equivalent circuit of a TFT liquid crystal panel.

 FIG. 5 is a schematic view showing a state in which an oxide is formed in the vicinity of the interface between the Cu—Mn alloy surface and the glass substrate.

 FIG. 6 is a schematic diagram of a planar type p-Si TFT.

 FIG. 7 is a schematic diagram showing the structure of a gas discharge element.

 FIG. 8 is an explanatory diagram showing a PDP.

 FIG. 9 is a schematic diagram showing the structure of an organic EL device.

 FIG. 10 is an explanatory diagram of an organic EL display.

 FIG. 11 is an explanatory diagram showing FED.

 Explanation of symbols

[0043] 1 Liquid crystal display device

 11, 12 Transparent substrate

 13 Transparent common electrode

 14 Pixel electrode

 15 Liquid crystal layer

16 TFT switching element Gate wiring Source wiring Storage capacitance (line) Liquid crystal pixel

 Gate electrode Gate electrode line a Oxide film layer b Conductive layer

 Source electrode Drain electrode Insulating film

 1st insulating layer 2nd insulating layer a—Si layer

 Rear glass substrate Front glass substrate Address (data) electrode Transparent electrode

 Discharge cell

 Protective layer

 Bulkhead (rib) discharge cell

 Stray capacitance

 Address electrode wiring Display electrode wiring Terminal electrode

Glass electrode Anode 203 Hole transport layer

204 Light-emitting layer

 205 Electron transport layer

 206 cathode

 212 X electrode wire

 213 Y electrode wire

 301 Power sword side glass substrate

302 Anode glass substrate

303 force sword electrode

304 Anode electrode

306 Phosphor film

 307 Gate electrode

Claims

The scope of the claims  [1] A planar electronic display device having a pixel portion in which a plurality of pixels as a minimum unit for forming an image are arranged in a matrix on a substrate.  As a wiring material for at least one of the signal electrode, the scan electrode, and the terminal electrode that connects the signal electrode or the scan electrode and an external circuit, intersecting in the pixel portion A flat electronic display device characterized by applying a copper alloy containing Cu as a main component and forming an oxide layer of an additive element added to Cu on the surface or the interface with the substrate.  [2] In the flat electronic display device according to claim 1,  The additive element has less free energy of formation of oxides than Cu  Diffusion coefficient force in Cu. Greater than the self-diffusion coefficient of SCu.  The rate of increase in electrical resistance per lat.% In Cu is 5 Ω'cm or less, and satisfies the relationship of activity coefficient γ force activity coefficient γ> 1 in Cu. Additive amount is 0.5-25at.%  A flat-panel electronic display device.  [3] The flat electronic display device according to claim 1 or 2,  The electrode to which the copper alloy is applied is an electrode that drives or controls at least one of a liquid crystal pixel, a gas discharge cell, an organic EL element, and a display pixel for field emission display. apparatus. [4] electrode wires crossing in a matrix on the substrate;  A pair of substrates disposed at the intersection of the electrode lines, a liquid crystal layer sandwiched between the substrates, an electrode formed on the surface of the substrate on the liquid crystal layer side, and electrically connected to the electrodes A plurality of liquid crystal pixels having a wiring layer disposed on the surface of the substrate; a terminal electrode connected to an external drive circuit;  In an active matrix liquid crystal display device having  At least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode has copper as a main component, and an oxide layer of an additive element added to the copper is formed at an interface with the substrate. Copper alloy strength A liquid crystal display device characterized by the above. [5] The liquid crystal display device according to claim 4,  The liquid crystal display device, wherein the oxide layer is formed by a reaction between oxygen contained in the substrate and the additive element. [6] In the liquid crystal display device according to claim 4 or 5,  At least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode includes an oxide layer of the additive element at an interface with the insulating layer.  A liquid crystal display device characterized by the above. [7] In the liquid crystal display device according to any one of claims 4 to 6,  At least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode is an oxide in which the additive element and the constituent element of the insulating layer react with each other at the interface with the insulating layer containing oxygen With layers  A liquid crystal display device characterized by the above. [8] In the liquid crystal display device according to any one of claims 4 to 7,  At least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode includes an acid layer on the surface of which the additive element and oxygen in the atmosphere gas react. A liquid crystal display device. [9] In the liquid crystal display device according to any one of claims 4 to 8,  The additive element has an oxide free formation energy smaller than that of Cu, and a diffusion coefficient in Cu is larger than that of Cu.  A liquid crystal display device characterized by the above. [10] In the liquid crystal display device according to any one of claims 4 to 9,  The additive element has an electrical resistance increase rate of 5 μΩ-cm or less per lat.% In Cu.  A liquid crystal display device characterized by the above. [11] Claim 4 ~: The liquid crystal display device according to any one of claims 1, wherein:  In the additive element, the activity coefficient γ in Cu satisfies the relationship of activity coefficient γ> 1. A liquid crystal display device characterized by the above. [12] Claim 4 ~: The liquid crystal display device according to any one of LI, wherein in the copper alloy, the additive element diffuses on the surface of the copper alloy, and an oxide film layer of the additive element is formed. Copper alloy  A liquid crystal display device characterized by the above. [13] In the liquid crystal display device according to any one of claims 4 to 12,  The additive element is at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr, and Nd.  A liquid crystal display device characterized by the above. 14. The liquid crystal display device according to claim 13, wherein the additive element is Mn, and the amount of Mn added is 0.5 to 25 at.%. [15] electrode wires crossing in a matrix on the substrate;  A pair of substrates disposed at the intersection of the electrode lines, a liquid crystal layer sandwiched between the substrates, an electrode formed on the surface of the substrate on the liquid crystal layer side, and electrically connected to the electrodes A plurality of liquid crystal pixels having a wiring layer disposed on the surface of the substrate; a terminal electrode connected to an external drive circuit;  In the manufacturing method of an active matrix type liquid crystal display device having  On the substrate, a copper alloy containing Cu as a main component and forming an oxide layer of the additive element added to the surface or the interface with the substrate is formed by physical vapor deposition or chemical vapor deposition. And a process of  Etching the obtained copper alloy film to form at least one of an electrode wire, an electrode, a wiring layer, and a terminal electrode.  A method for manufacturing a liquid crystal display device. [16] In the method of manufacturing a liquid crystal display device according to claim 15,  The copper alloy is at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr and Nd.  A method for manufacturing a liquid crystal display device. [17] In the method of manufacturing a liquid crystal display device according to claim 15 or 16, At least of the formed electrode wire, the electrode, the wiring layer, and the terminal electrode A method for manufacturing a liquid crystal display device comprising a step of forming an oxide layer on one surface.  [18] In the method of manufacturing a liquid crystal display device according to claim 17,  The method for manufacturing a liquid crystal display device, wherein the oxygen concentration in the atmospheric gas in the oxide layer forming step is 10 ppm to l%.  [19] In the method of manufacturing a liquid crystal display device according to claim 17 or 18,  The oxide layer forming step includes forming at least one of the electrode wire, the electrode, the wiring layer, and the terminal electrode, and then heating the electrode at 150 to 400 ° C. for 5 minutes to 50 hours. Manufacturing of a liquid crystal display device, characterized in that it is a step of forming an oxide layer of an additive element in the copper alloy on the surface of at least one of an electrode wire, the electrode, the wiring layer, and the terminal electrode Method.  [20] Address electrode wiring formed inside the rear glass substrate;  Display electrode wiring formed inside the front glass substrate;  A plurality of electric discharge cells arranged at each intersection where the address electrode wiring and the display electrode wiring cross in a matrix;  A terminal electrode connected to an external drive circuit;  In a plasma display device having  At least one of the address electrode wiring, the display electrode wiring, and the terminal electrode is made of copper as a main component, and a copper alloy that forms an oxide layer of an additive element added to the copper at an interface with the substrate Consist of  A plasma display device. [21] In the plasma display device according to claim 20,  The plasma display apparatus, wherein the oxide layer is formed by a reaction between oxygen contained in the substrate and the additive element. [22] In the plasma display device according to claim 20 or 21, At least one of the address electrode wiring, the display electrode wiring, and the terminal electrode has a reaction between oxygen in the atmosphere gas or oxygen contained in the insulating layer and the additive element at the surface or the interface with the insulating layer. An oxide layer formed A plasma display device.  [23] The plasma display device according to any one of [20] to [22], wherein the additive element is Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr, and Nd. Group power consisting of at least one metal selected  A plasma display device. [24] electrode wires crossing in a matrix on the substrate;  The glass substrate and an anode, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode, which are disposed at the intersections of the electrode lines, are sequentially laminated on the glass substrate, and the anode and the cathode are TFT circuits. A plurality of organic EL elements electrically connected to the electrode wires crossing in a matrix via the matrix,  A terminal electrode connected to an external drive circuit;  In an active matrix organic EL display device having  At least one of the electrode wire, the wiring, and the terminal electrode is made of copper alloy, and a copper alloy that forms an oxide layer of an additive element added to the copper at an interface with the substrate. Become  An organic EL display device characterized by that. [25] The organic EL display device according to claim 24,  The organic EL display device, wherein the oxide layer is formed by a reaction between oxygen contained in the substrate and the additive element. [26] The organic EL display device according to claim 24 or 25,  At least one of the electrode wire, the wiring, and the terminal electrode has reacted with oxygen in the atmosphere gas or oxygen contained in the insulating layer and the added calo element at the surface or the interface with the insulating layer. With oxide layer  An organic EL display device characterized by that. [27] In the organic EL display device according to any one of claims 24 to 26, The copper alloy is a copper alloy in which an additive element diffuses on the surface of the copper alloy and an oxide film layer of the additive element is formed. An organic EL display device characterized by that. [28] In the organic EL display device according to any one of claims 24 to 27,  The additive element is at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr, and Nd.  An organic EL display device characterized by that. [29] a force sword side glass substrate;  An anode side glass substrate provided opposite to the force sword side glass substrate, an anode electrode and a phosphor film provided on the inner surface of the anode side glass substrate, and an inner surface of the force sword side glass substrate on a matrix A plurality of force sword electrodes, a gate electrode disposed in a vacuum space between the anode electrode and the force sword electrode, an electrode wire connecting the force sword electrode and the anode electrode, and the force sword electrode An electrode line connecting the gate electrode;  A terminal electrode connected to an external drive circuit;  In a field emission display device having  At least one of the electrode, the electrode wire, and the terminal electrode is made of copper as a main component, and is a copper alloy that forms an oxide layer of an additive element added to the copper at an interface with the substrate. Become  A field emission display device characterized by that. [30] The field emission display device according to claim 29,  The field oxide display device, wherein the oxide layer is formed by a reaction between oxygen contained in the substrate and the additive element. [31] The field emission display device according to claim 29 or 30,  At least one of the electrode, the electrode wire, and the terminal electrode has reacted with oxygen in the atmospheric gas or oxygen contained in the insulating layer and the added calo element at the surface or the interface with the insulating layer. With oxide layer A field emission display device characterized by that. [32] The field emission display device according to any one of claims 29 to 31, wherein:  The copper alloy is a copper alloy in which an additive element diffuses on the surface of the copper alloy and an oxide film layer of the additive element is formed.  A field emission display device characterized by that. [33] In the field emission display device according to any one of claims 29 to 32,  The additive element is at least one metal selected from the group force consisting of Mn, Zn, Ga, Li, Ge, Sr, Ag, In, Sn, Ba, Pr, and Nd.  A field emission display device characterized by that.