JP2004158442A - Laminate, substrate with wiring, organic el display element, connecting terminal of the element, and their manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminate suitable for an FPD such as an organic EL display element, a circuit structure showing excellent low resistivity using the laminate, and an organic EL display element which can maintain a low resistivity contact property against a wiring electrode through which a large current flows, can achieve a reliable contact property, and has high reliability with improved corrosion resistance. <P>SOLUTION: The laminate for forming a substrate with wiring is provided with a first conductive layer composed mainly of Al or an Al alloy on the substrate and with a cap layer composed mainly of Ni-Mo alloy on the 1st conductive layer. <P>COPYRIGHT: (C)2004,JPO

Description

  The present invention relates to a laminate, a substrate with wiring, an organic electroluminescence (EL) display element, a connection terminal of an organic EL display element, and a method for producing them.

  As a next-generation thin display element (FPD), an organic EL display element has begun to be used in a mobile phone or the like. An organic EL display element is provided with an organic light emitting material and displays by spontaneous light emission, and is significantly superior to conventional LCDs and PDPs in terms of high-speed response, visibility, brightness, and the like.

  The basic configuration and operation principle are as follows (for example, see Non-Patent Document 1). In order to emit light, an organic layer such as a hole transport layer, a light-emitting layer, and an electron transport layer is formed from the anode side between at least one transparent electrode (for example, tin-doped indium oxide (ITO)) and another electrode. Is provided. Currently, further research is being carried out so that the organic EL display element can have a long life, high brightness, full color, and the like.

  The organic EL display element is a current-driven display. In particular, in the passive drive type organic EL display element, a current flows only during a selection period of each row, and the light emitting layer emits light in accordance with the current and display is performed. As a result, a larger current flows into the electrode than in the case of a voltage driven LCD.

For example, it is assumed that a panel having a pixel size of 300 μm × 300 μm and 100 anodes is driven with a 1/64 duty ratio. In order to light up with an emission efficiency of 1 cd / A and an average luminance of 300 cd / m ² , the total current flowing into the cathode during the selection period is 172.8 mA.

  With the recent demand for full color and high definition display in thin display devices (FPD), further reduction in resistance of transparent electrodes is desired. However, lowering the resistance of ITO conventionally used for LCDs and the like is approaching its limit. Therefore, a low resistance wiring technique in which a low resistance metal widely used in TFT-LCD or the like is used in combination with ITO has been introduced.

  Thus, a low resistance wiring technique is required between the cathode of the organic EL display element and the connection terminal in order to suppress a voltage increase due to a large current. Generally, an auxiliary wiring is provided between the cathode and the connection terminal, and a structure is adopted in which current flows to the connection terminal via the auxiliary wiring.

  However, there is a strong demand for an increase in display panel size, definition, and brightness. In order to achieve this, it is necessary to further reduce the resistance of the auxiliary wiring. In general, Al or an Al alloy is often used as a low-resistance wiring material for FPD. However, hillocks are likely to occur in Al or Al alloys, and Al oxides are likely to be formed on the surface. Moreover, even if it is intended to make electrical contact with another metal, the contact resistance is high and it is difficult to use it as it is.

  Therefore, in many cases, a method of capping Al or an Al alloy with Mo or an Mo alloy (Cr, Ti, Ta, Zr, Hf, or an alloy of V and Mo) is employed (for example, see Patent Document 1). ). This is because Mo can be etched with the same etching solution as Al. Therefore, in the case of a combination of Mo and Al, patterning of Al and Mo can be performed collectively in a photolithography process for forming a display panel.

  However, in general, Mo has low moisture resistance and is easily corroded by moisture in the air. Therefore, when Mo is used as an FPD wiring material, there is a problem that wiring is likely to deteriorate. On the other hand, when Al is capped with Cr having high moisture resistance, it cannot be etched with the same etching solution as Al, and it is difficult to perform batch patterning in the manufacturing process.

  Further, Ni having high moisture resistance has almost no change in resistance value even when left under high humidity conditions. However, Ni cannot practically be etched with a certain etching solution (phosphoric acid: nitric acid: acetic acid: water = 16: 1: 2: 1 (volume ratio)) (see, for example, Non-Patent Document 2). .

  Further, since Ni is a ferromagnetic material, it is difficult to use a magnetron sputtering method which is a general thin film forming method. Therefore, it is difficult to use the Ni thin film as an FPD wiring material.

  Further, in the organic EL display element, the contact between the cathode and the auxiliary wiring and the reduction in resistance between the connection terminal and the auxiliary wiring become a new problem. In particular, the contact characteristics between the cathode and the auxiliary wiring need to be stable not only with low resistance characteristics but also with respect to Joule heat generated in the contact portion due to the flowing current.

  That is, it is necessary that the contact resistance does not easily increase due to Joule heat. The increase in contact resistance due to Joule heat is believed to be due to oxidation of the metal used for the auxiliary wiring and the like.

  Here, FIG. 17 shows a partial cross-sectional view of an organic EL display element according to the prior art. An anode 20a is provided on a transparent substrate 1 such as glass. Connection between the electrode inside the element and the drive circuit is made by using the auxiliary wiring 30x. It is composed of a connection terminal side pattern 30b and an inner pattern portion 30a. The cathode 70 is electrically connected to the external connection wiring 150 through the auxiliary wiring 30x. The organic EL layer 60 emits light by supplying a current between the anode 20a and the cathode 70. A counter substrate 80 is provided to seal the organic EL layer 60 and the like.

  The insulating film 40 has a role of defining an opening portion 40a where the organic EL layer 60 and the anode 20a are in contact with each other. In such a structure, ITO (indium oxide-tin oxide) is usually used for the anode 20a, and a metal that is easily oxidized, such as Al, Mg, or Ag, is used for the cathode. A metal such as Cr is used for the auxiliary wiring.

  In this case, for example, when a Cr pattern having a film thickness of 300 nm, a width of 150 μm, a length of 4 mm, and a resistivity of 20 μΩcm is used as the auxiliary wiring, the resistance value becomes 17.7Ω, and when a current as described above is applied, 3 A voltage drop of about 1 V is generated according to the wiring resistance, and rises from a desired potential.

  Also, as shown in FIG. 17, a surface oxide layer is formed on the auxiliary wiring 30x as it goes through the manufacturing process, thereby increasing the contact resistance between the cathode 70 and the auxiliary wiring 30x. These voltage rises are considered to cause adverse effects such as display unevenness at the time of gradation display and an increase in the withstand voltage of the anode driver used.

  Here, the auxiliary wiring technique disclosed in Japanese Patent Laid-Open No. 11-317292 (hereinafter referred to as Patent Document 2) will be described. This patent document 2 is characterized in that a transparent electrode material is used for a connection terminal with a drive circuit, and the cathode material and the auxiliary wiring material are made the same. In this case, it is considered that the problem of contact resistance between the cathode and the auxiliary wiring does not occur unless the cathode surface and the auxiliary wiring surface are oxidized before the connection between the cathode material and the auxiliary wiring material.

  However, generally, a material that is easily oxidized is used for the cathode of the organic EL display element. For this reason, when the auxiliary wiring is made of the same material as that of the cathode, the surface of the auxiliary wiring is oxidized during the manufacturing process of the organic EL display element, resulting in a problem that the contact resistance with the cathode is increased. In particular, when the temperature is maintained at a high temperature, the contact resistance is remarkably increased. When Al or an Al alloy is applied to the cathode and the auxiliary wiring, the contact resistance is remarkably increased by holding at about 100 ° C.

  Japanese Patent Laid-Open No. 11-329750 (hereinafter referred to as Patent Document 3) discloses a technique for reducing the contact resistance between the cathode and the auxiliary wiring. In this Patent Document 3, the auxiliary wiring is formed by dividing into two of a base pattern and an electrode pattern, TiN or Cr is applied to the base pattern, Al is applied to the electrode pattern, and contacted with the cathode. It is said that low resistance contact characteristics can be obtained.

  However, in Patent Document 3, two photolithography processes are required to form the auxiliary wiring. In addition, in order to use TiN as a wiring material, it is necessary to apply dry etching to patterning, which causes a problem in productivity. Further, when Cr is used for the base pattern, even if the initial contact characteristics are good, the contact resistance may be remarkably increased when left at a high temperature of about 100 ° C.

  In the organic EL display element, as described above, it is necessary to flow a large current through the electrode, and the cathode connection wiring is preferably formed of a low-resistance metal. Since the connection terminal portion is exposed not in the sealed element but in the use environment, it is desirable that the connection terminal portion has excellent environmental resistance, particularly moisture resistance.

  In this way, when the auxiliary wiring material is applied to an organic EL display element, not only good contact with the cathode is required, but also it extends outside the seal of the display panel, so that corrosion due to moisture is suppressed as much as possible. It is necessary to do.

Japanese Patent Laid-Open No. 13-311954 JP 11-317292 A JP 11-329750 A Appl. Phys. Lett. , 51, 913 (1987) “Photoetching and microfabrication” Kiyoi Takaoka and 1 other, General Electronic Publishing Company (issued on May 10, 1977) pages 82-83

  In this invention, it is going to obtain the laminated body applicable to an organic EL display element. Basically, a substrate with wiring having excellent moisture resistance can be configured. Moreover, it has low resistance and excellent patterning performance. And it aims at providing the board | substrate with wiring formed using this laminated body.

  To provide a manufacturing method for manufacturing a substrate with wiring, and a substrate with wiring obtained by forming a layered body suitable for an FPD such as an organic EL element display in particular and then easily etching the layered body into a planar shape. With the goal.

  In addition, like an organic EL display element, when a driving current for light emission is passed, a circuit configuration showing excellent low resistance is obtained at a contact portion constituting the circuit.

  Another object of the present invention is to realize a contact characteristic that can maintain a low resistance contact property with respect to a wiring electrode through which a large current flows, and that is reliable. It is another object of the present invention to provide a highly reliable organic EL display element with improved corrosion resistance for metal materials constituting electrodes and wiring.

  Aspect 1 of the present invention is a laminated body for forming a substrate with wiring, wherein a first conductor layer mainly composed of Al or Al alloy is formed on the substrate, and Ni is formed on the first conductor layer. A laminate comprising a cap layer mainly composed of a Mo alloy is provided.

  Aspect 2 provides the laminate according to aspect 1, comprising an ITO layer and a base layer in this order from the substrate side between the first conductor layer and the substrate.

  Aspect 3 provides the laminate according to aspect 2, wherein the main component of the underlayer is Mo or a Mo alloy.

  Aspect 4 provides the laminate according to aspect 2 or 3, wherein the underlayer is composed mainly of NiMo and includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon. .

  Aspect 5 is the aspect 2, 3 or 4 in which the Ni content in the undercoat layer is 20 to 90% by mass with respect to all components and the Mo content is 10 to 80% by mass with respect to all components. A laminate is provided.

  Aspect 6 provides the laminate according to aspects 1, 2, 3, 4 or 5 in which a Ni diffusion prevention layer not containing Ni is provided between the first conductor layer and the cap layer.

  Aspect 7 provides the laminate according to aspect 6, wherein the Ni diffusion prevention layer contains Mo as a main component and does not contain Ni.

  Aspect 8 provides the laminate according to aspect 6 or 7, wherein the Ni diffusion preventing layer is MoNb, MoTa, MoV, or MoW.

  Aspect 9 is that the conductive material of the Ni diffusion prevention layer contains Mo and Nb or Ta, the Mo content is 80 to 98% by mass, and the Nb or Ta content is 2 to 20% by mass. A laminate according to aspect 6, 7 or 8 is provided.

  A tenth aspect provides the laminate according to any one of the first to ninth aspects, wherein the cap layer includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon.

  Aspect 11 has a Ni content in the cap layer of 20 to 90% by mass with respect to all components, and a Mo content of 10 to 80% by mass with respect to all components. A laminate according to item 1 is provided.

  Aspect 12 is an organic EL display element formed by using the laminated body according to any one of aspects 1 to 11, wherein the second electrode layer is formed on the substrate so as to face the first electrode layer. An organic EL display device comprising: an organic EL layer disposed between a first electrode layer and a second electrode layer; and a substrate, a first conductor layer, and a cap layer disposed in this order from the substrate side I will provide a.

  Aspect 13 includes an organic EL device in which a first electrode layer and a second electrode layer facing each other are provided on a substrate, and an organic EL layer is disposed between the first electrode layer and the second electrode layer. An EL display element comprising a first conductor layer conductively connected to a first electrode layer, a cap layer above the first conductor layer, the main component of the first conductor layer being Al Alternatively, an organic EL display element which is an Al alloy and the main component of the cap layer is a Ni—Mo alloy is provided.

  Aspect 14 provides the organic EL display element according to Aspect 13, wherein the cap layer includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon.

  Aspect 15 provides the organic EL display element according to Aspect 13 or 14, wherein a Ni diffusion prevention layer not containing Ni is provided between the first conductor layer and the cap layer.

  Aspect 16 provides the organic EL display element according to Aspect 13, 14 or 15, wherein the Ni diffusion preventing layer is one selected from MoNb, MoTa, MoV, and MoW.

  Aspect 17 provides the organic EL display element according to Aspect 13, 14, 15 or 16, wherein a base layer containing Mo or a Mo alloy is provided below the first conductor layer.

  Aspect 18 provides the organic EL display element according to any one of Aspects 13 to 17, wherein the second electrode layer is an ITO layer.

  Aspect 19 is a connection terminal of the organic EL display element for connecting the first electrode layer provided on the substrate of the organic EL display element and the drive circuit, and is a first terminal mainly composed of Al or Al alloy. 1 conductor layer and a cap layer mainly composed of a Ni—Mo alloy on the upper side of the first conductor layer, and the circuit is configured so that current is supplied from the drive circuit to the first electrode layer. A connection terminal of an organic EL display element is provided.

  Aspect 20 provides the connection terminal of the organic EL display element according to Aspect 19, wherein the cap layer includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon. .

  Aspect 21 provides the connection terminal of the organic EL display element according to Aspect 19 or 20, wherein a Ni diffusion preventing layer not containing Ni is provided between the first conductor layer and the cap layer.

  In the aspect 22, the circuit is configured such that current flows from the plurality of second electrodes to one first electrode, and the instantaneous maximum current flowing in one first electrode layer is 50 mA or more. A connection terminal of the organic EL display element according to 19, 20, or 21 is provided.

Aspect 23 is a method for manufacturing a multilayer body according to any one of aspects 1 to 11, wherein the first conductor layer is formed on a substrate and then a cap layer is formed. I will provide a.
Aspect 24 provides the method for producing a laminate according to aspect 23, in which a transparent second conductor layer is formed and patterned, and then the first conductor layer is formed.

  Aspect 25 provides the method for producing a laminate according to Aspect 23 or 24, in which a treatment of oxidation, nitridation, oxynitridation, oxycarbonization, nitrocarburization, or oxynitrocarburization is performed when forming the cap layer.

  Aspect 26 provides a substrate with wiring, in which the laminate according to any one of aspects 1 to 11 is patterned in a planar shape.

  Aspect 27 is a method for manufacturing a connection terminal of an organic EL display element according to Aspect 19, 20, 21, or 22, wherein a transparent second conductor layer is formed, patterned, and then the first conductor layer and Provided is a method for manufacturing a connection terminal of an organic EL display element, in which a laminated film including a cap layer is formed and the laminated film is patterned.

  Aspect 28 is a manufacturing method for manufacturing the organic EL display element according to any one of aspects 12 to 18, wherein a transparent second conductor layer is formed on a substrate, and the first conductor layer and the cap layer are formed. Patterning of the laminated film so that the second conductive layer is used as the second electrode and the laminated film is used for at least a part of the wiring from the first conductive layer to the connection terminal. Provided is a method for producing an organic EL display element.

  In aspect 29, a transparent second conductor layer is formed on a substrate and patterned as a second electrode layer, and then a first conductor layer and a cap layer are formed to form a laminated film. Then, the manufacturing method of the organic electroluminescent display element of the aspect 28 which patterns a laminated film is provided.

Aspect 30 provides an organic EL display element in which a drive circuit is connected to the organic EL display element according to any one of aspects 12 to 18 and display is performed at a luminance of 100 cd / m ² or more.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings, examples and the like. In addition, these figures and Examples illustrate this invention, and do not restrict | limit the scope of the present invention. It goes without saying that other embodiments may belong to the category of the present invention as long as they match the gist of the present invention.

  The substrate used in the present invention is not necessarily flat and plate-like, and may be curved or atypical. Examples of the substrate include a transparent or opaque glass substrate, a ceramic substrate, a plastic substrate, and a metal substrate.

  When used for an organic EL device having a structure that emits light from the substrate side, the substrate is preferably transparent, and a glass substrate is particularly preferable from the viewpoint of strength and heat resistance. Examples of the glass substrate include a colorless and transparent soda lime glass substrate, a quartz glass substrate, a borosilicate glass substrate, and an alkali-free glass substrate. When used for an organic EL element, the thickness of the glass substrate is preferably 0.2 to 1.5 mm from the viewpoint of strength and transmittance.

  The laminate for forming a substrate with wiring of the present invention has a conductor layer mainly composed of Al or an Al alloy (hereinafter also referred to as Al-based metal) on the substrate, and Ni—Mo is mainly formed on the conductor layer. It is a laminate of two or more layers that necessarily include two layers of a cap layer as a component. Since the conductor layer is made of an Al-based metal, the wiring can have a low resistance. In particular, an Al—Nd alloy is preferable because generation of Al hillocks can be prevented while maintaining low resistance. The Al alloy is an alloy of Al and a metal such as Nd, Ag, or Cu, and is preferably a metal that has few problems such as increasing the resistance value of the wiring.

  The Al metal layer may contain Ti, Mn, Si, Cu, Na, and O as impurities, and the total content is preferably 1% by mass or less. The Al content of the Al alloy layer is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, from the viewpoint of reducing the wiring resistance.

  The thickness of the conductor layer is preferably from 100 to 600 nm and from 100 to 400 nm, more preferably from 150 to 400 nm, and even more preferably from 150 to 300 nm so that sufficient conductivity and good patterning properties can be obtained.

  The cap layer formed on the conductor layer is a layer mainly composed of a Ni—Mo alloy. Since the Ni-Mo alloy layer has excellent moisture resistance, the cap layer maintains the low resistance of the wiring, and suppresses the generation of an Al oxide layer on the surface of the Al-based metal layer, thereby preventing an increase in contact resistance. Have

  Therefore, the reliability of the electronic device using the obtained substrate with wiring can be improved. In addition, the resulting laminate can be finely patterned. Furthermore, when patterning the Ni-Mo alloy layer using photolithography, the conductor layer (Al-based metal layer) and the cap layer (Ni-Mo alloy layer) are etched at the same rate with the same etching solution (acid aqueous solution). can do. That is, it is possible to perform patterning together with the conductor layer.

  If the etching rates of the conductor layer and the cap layer are greatly different, it is not preferable because it causes over-etching and residue when forming the wiring. The etching rate of the Ni—Mo alloy layer can be easily adjusted by changing the composition ratio of Ni and Mo according to the type of the etchant. The larger the ratio of Mo to Ni, the faster the etching rate.

  The thickness of the cap layer is preferably 10 to 200 nm, more preferably 15 to 50 nm, from the viewpoint of moisture resistance and patterning properties.

  The Ni content in the Ni-Mo alloy layer is preferably 20 to 90% by mass, more preferably 55 to 75% by mass. When the Ni content is less than 20% by mass, the moisture resistance of the Ni—Mo alloy layer is insufficient, and when it exceeds 90% by mass, the etching rate by the etching solution is slow and is adjusted to be the same as the etching rate of the conductor layer. It becomes difficult. Moreover, the Mo content of the Ni—Mo alloy layer is preferably 10 to 80% by mass, more preferably 20 to 40% by mass.

  When the Mo content is less than 10% by mass, the etching rate with the etching solution is slow, and it becomes difficult to adjust to the etching rate of the conductor layer. When the Mo content exceeds 80% by mass, the moisture resistance of the Ni—Mo alloy layer Sex is not enough. The total content of Ni and Mo in the Ni—Mo alloy layer is preferably 90 to 100% by mass.

  The Ni—Mo alloy layer is one or more metals such as Ti, V, Cr, Fe, Co, Zr, Nb, Ta, and W, and does not deteriorate the moisture resistance, etching property, etc., for example, 10 mass. % Or less may be contained.

  The laminate for forming a substrate with wiring of the present invention is formed using a sputtering method. For example, a step of forming a conductor layer by sputtering in an inert gas atmosphere using an Al target on one surface of a glass substrate, and a Ni-Mo alloy target on the conductor layer Thus, sputtering is performed in combination with the step of forming the cap layer.

  Examples of the Al target include an Al metal target, an Al alloy target containing Nd, and an Al non-alloy target containing Nd. The Ni—Mo alloy target is, for example, a Ni—Mo alloy target, a Ni—Mo alloy target containing Fe, a Ni—Mo non-alloy target containing Fe, or the like.

  As a Ni-Mo non-alloy target containing Fe, for example, a combination of a Ni plate, a Mo plate, and a Fe plate smaller than the target area in a mosaic shape, or a combination of a Ni-Mo alloy target plate and a Fe plate Including those. A laminated body for forming a substrate with wiring having a uniform film thickness over a large area can be formed by sputtering.

  The laminate for forming a substrate with wiring of the present invention is formed by the following method, for example, when an Al layer is formed as a conductor layer and a Ni-Mo alloy layer is formed as a cap layer.

An Al target and a Ni—Mo alloy target are separately attached to the cathode of the DC magnetron sputtering apparatus. Further, the base is attached to the substrate holder. Next, after the film formation chamber is evacuated to vacuum, Ar gas is introduced as a sputtering gas. In addition to Ar gas, He, Ne, Kr gas, and the like can be used. However, inexpensive Ar gas is preferable because of stable discharge. The sputtering pressure is suitably from 0.1 to 2 Pa. The back pressure is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻² Pa. The substrate temperature is preferably room temperature to 400 ° C. A high deposition temperature is preferable because the resistance value is generally low. However, the surface roughness increases. When it is necessary to reduce the surface roughness, it is preferable to lower the substrate temperature. In addition, there exists an advantage that the coverage of the NiMo layer formed in the upper part of Al layer becomes favorable when surface roughness is made low.

  When forming an Al metal layer, an Al metal target may be used, and when forming an Al alloy layer, an alloy layer may be formed using Al and another metal forming the alloy as separate targets. However, from the viewpoint of improving the controllability and uniformity of the composition of the conductor layer, it is preferable to prepare an Al alloy having a desired composition in advance and use it as a target.

  First, an Al metal layer as a conductor layer is formed on a substrate by sputtering using an Al metal target. Next, a Ni—Mo alloy layer is formed by sputtering using a Ni—Mo based target thereon, thereby forming a laminate.

  As described above, the laminate of the present invention is basically one having two layers on a substrate, but is not limited thereto, and further comprises three or more layers having other layers as described below. The thing which has is also included. The other layers are preferably formed by sputtering.

  The laminate of the present invention comprises a Ni diffusion prevention layer having a composition different from that of the cap layer between the Ni-Mo alloy layer (cap layer) and the Al metal layer (conductor layer) mainly composed of Al or Al alloy. You may have. When heat treatment is performed when the cap layer and the conductor layer are in contact with each other, Ni diffuses from the cap layer to the conductor layer, and the resistance of the conductor layer increases. The increase in resistance can be prevented by the Ni diffusion preventing layer. The Ni diffusion preventing layer is also preferably formed by sputtering. Also, when forming the Ni diffusion prevention layer, it is preferable to form it under the same conditions (sputtering pressure, etc.) as the Al layer.

  The thickness of the Ni diffusion preventing layer is preferably 10 to 200 nm from the viewpoint of barrier properties and patterning properties, more preferably 15 to 80 nm, and even more preferably 15 to 50 nm.

  The Ni diffusion preventing layer is preferably a Mo-based metal layer containing Mo as a main component from the point that it can be etched together with the cap layer and the conductor layer. When the Mo-based metal layer is formed as a Ni diffusion preventing layer between the conductor layer and the cap layer, Mo is exposed in the pattern cross-section after patterning, but most of the Mo-based metal layer is composed of the cap layer and the conductor layer. Since it is covered with, the improvement of moisture resistance is hardly hindered.

  However, for the purpose of further improving the moisture resistance, the Ni diffusion preventing layer is made of one or more metals such as Nb, Ta, V, W, Cr, Zr and Ti in addition to Mo, and 2 to 20 masses. % Can be contained. If it is less than 2% by mass, the effect of improving moisture resistance by adding elements is not sufficient, and if it is 20% by mass or more, the etching property is deteriorated, which is not preferable in production. The Mo content of the Mo-based alloy layer containing Mo as a main component is preferably 80 to 98% by mass.

  In the laminate of the present invention, the cap layer is preferably subjected to treatment such as oxidation, nitridation, oxynitridation, oxycarbonization, nitrocarbonization, or oxynitrocarbonization. That is, by performing such a treatment at the time of forming the cap layer, the Ni-Mo alloy layer is made into a Ni-Mo alloy layer that is oxidized, nitrided, oxynitrided, oxycarbonized, nitrocarburized, oxynitrocarburized, etc. Like the Ni diffusion preventing layer, it is possible to prevent an increase in resistance.

This treatment is performed by a method using a mixed gas of a reactive gas such as O ₂ , N ₂ , CO, CO ₂ and Ar gas as a sputtering gas when the Ni—Mo alloy layer is formed by sputtering. The content of the reactive gas is preferably 5 to 50% by volume, more preferably 20 to 40% by volume from the viewpoint of the Ni diffusion preventing effect.

  Moreover, the laminated body of this invention may have a tin dope indium oxide layer (ITO layer). In that case, since the Al-based metal layer has a disadvantage that the contact resistance with the ITO layer is large, in practice, the cap layer / conductor layer / underlayer / ITO layer / substrate is interposed through the underlayer. preferable.

  Since the ITO layer can be used as a transparent electrode, in the laminate of the present invention, after forming the ITO layer on the substrate, masking necessary portions when forming the underlayer, the conductor layer, and the cap layer. The masked portion has no base layer, conductor layer and cap layer, and only the ITO layer. By using this as an electrode, for example, if necessary, an organic layer can be formed thereon to form an organic EL element. On the other hand, in a portion not masked, an underlayer, a conductor layer, and a cap layer are formed on the ITO layer, and the ITO layer as an electrode and the underlayer, conductor layer, and cap layer as a wiring are connected without a step.

The ITO layer is formed, for example, by forming an ITO layer on a glass substrate by using an electron beam method, a sputtering method, an ion plating method, or the like. The ITO layer is preferably formed by sputtering using, for example, an ITO target containing 3 to 15% by mass of SnO ₂ with respect to the total amount of In ₂ O ₃ and SnO ₂ . The sputtering gas is preferably a mixed gas of O ₂ and Ar, and the O ₂ gas concentration is preferably 0.2 to 2% by volume.

  The thickness of the ITO layer is preferably 50 to 300 nm, more preferably 100 to 200 nm.

  Then, by further forming a conductor layer and a cap layer on the ITO film by sputtering, a laminate for forming a substrate with wiring having an ITO layer can be obtained.

  Since the conductor layer has a disadvantage that the contact resistance with the ITO layer is large, when the ITO layer is formed between the substrate and the conductor layer, the conductor layer is used to prevent an increase in the contact resistance between the ITO layer and the wiring. A base layer is formed below the substrate. The underlayer is preferably a layer mainly composed of Mo or Mo alloy. The layer mainly composed of Mo or Mo alloy means that the content of Mo or Mo alloy is 90 to 100% by mass in the layer. Also, when forming the base layer, it is preferable to form it under the same conditions (sputtering pressure, etc.) as the Al layer.

  The film thickness of the underlayer is preferably from 10 to 200 nm, more preferably from 15 to 50 nm, from the viewpoints of barrier properties and patterning properties.

  The layer mainly composed of Mo or Mo alloy is preferably a Ni—Mo alloy layer, and when the Ni—Mo alloy layer is used as a base layer, the Ni content of the alloy layer is preferably 20 to It is 90 mass%, More preferably, it is 55-75 mass%, Mo content rate becomes like this. Preferably it is 10-80 mass% with respect to all the components, More preferably, it is 20-40 mass%.

  Further, one or more metals such as Ti, V, Cr, Fe, Co, Zr, Nb, Ta, and W are contained in a range not deteriorating moisture resistance, etching property, etc., for example, 10% by mass or less. May be.

  The composition of the Ni—Mo alloy layer of the underlayer formed under the conductor layer may be the same as or different from the composition of the Ni—Mo alloy layer of the cap layer. If it is the same composition, the target of the same material can be used and it is excellent in economical efficiency. The composition of the upper and lower Ni—Mo alloy layers is adjusted so that the etching rate increases in the order of the Ni—Mo alloy layer (cap layer), the Al-based metal layer (conductor layer), and the Ni—Mo alloy layer (underlayer). In this case, the pattern cross-sectional shape can be processed into a taper shape at the time of patterning. Therefore, it is preferable in terms of improving wear resistance and adhesion. Further, a Ni diffusion preventing layer may be provided between the conductor layer and the Ni—Mo alloy layer as the base layer. The structure of the Ni diffusion preventing layer is the same as that of the Ni diffusion preventing layer provided between the conductor layer and the cap layer.

  When a layer mainly composed of Mo or Mo alloy is formed under the conductor layer as an underlayer, Mo is exposed in the pattern cross-section after patterning, but most of the layer mainly composed of Mo or Mo alloy is formed. Since it is covered with the substrate or ITO film and the conductor layer, the improvement in moisture resistance is not hindered.

  A layered product having desired characteristics can be formed by performing oxidation treatment, nitridation treatment, carbonization treatment (or a combination thereof) when forming a film without forming the Ni diffusion preventing layer. . In this case, there is an advantage that a laminate can be formed with a small number of layers.

Alternatively, in the case of forming a four-layer or five-layer metal laminated film, there is an advantage that continuous production is possible using an in-line type continuous film forming system.
The laminate of the present invention may have a silica layer between the conductor layer and the substrate. The silica layer may or may not be in contact with the substrate. The silica layer is usually formed by sputtering using a silica target. When the substrate is a glass substrate, the alkali component in the glass substrate is prevented from moving to the conductor layer and deteriorating the conductor layer. The film thickness is preferably 5 to 30 nm.

  The laminate of the present invention has low resistance, excellent patterning performance, and high moisture resistance. When an organic EL display element is manufactured using the laminate, the organic EL display element can be formed with a low resistance and highly reliable wiring, and thus an organic EL display element with a long element life and improved light emission characteristics can be obtained. The laminate of the present invention thus obtained is preferably formed on a substrate with wiring by etching by photolithography.

  For the laminate, apply a photoresist on the cap layer, which is the outermost surface, baked the wiring pattern, and remove unnecessary parts of the metal layer with an etching solution according to the photoresist pattern to form a substrate with wiring Is done. The etching solution is preferably an acidic aqueous solution, and is phosphoric acid, nitric acid, acetic acid, sulfuric acid, hydrochloric acid or a mixture thereof, ceric ammonium nitrate, perchloric acid or a mixture thereof.

  A mixed solution of phosphoric acid, nitric acid, acetic acid, sulfuric acid and water is preferred, and a mixed solution of phosphoric acid, nitric acid, acetic acid and water is more preferred.

When forming the substrate with wiring, each layer of the laminate, for example, (1) cap layer / conductor layer / substrate, (2) cap layer / conductor layer / underlayer / ITO layer / substrate, (3) cap layer / Each layer of Ni diffusion prevention layer / conductor layer / Ni diffusion prevention layer / underlayer / ITO layer / substrate is formed in the same pattern by the etching solution.
When the laminate has an ITO layer, the cap layer / conductor layer and the ITO layer may be removed together with the etching solution, but the cap layer and the conductor layer are removed first, and the ITO layer is separately provided. Alternatively, the ITO layer may be patterned first, the conductor layer and the cap layer may be sputtered, and then the cap layer / conductor layer other than the wiring portion may be removed.

  Next, although the suitable example which forms a base | substrate with wiring using the laminated body of this invention and produces an organic EL display element is demonstrated using FIGS. 1-3, this invention is not limited to this.

  First, an ITO film is formed on the glass substrate 1. The ITO film is etched to form an ITO anode 3 as a stripe pattern. Next, a Ni—Mo alloy layer (not shown) is formed by sputtering so as to cover the entire surface of the glass substrate 1. On the alloy layer, a Mo-based metal layer (not shown) as an underlayer, an Al-based metal layer 2a as a conductor layer, a Mo-based metal layer (not shown) as a Ni diffusion preventing layer, and a cap layer The Ni—Mo layer 2b is formed by sputtering in this order to obtain a laminate for forming a substrate with wiring. Of course, the ITO film may be formed on the entire surface of the glass substrate 1 or a part thereof.

  A photoresist is applied on the laminated body, an unnecessary portion of the metal layer is etched according to the pattern of the photoresist, the resist is peeled off, a Ni-Mo alloy layer, a Mo-based metal layer, an Al-based metal layer 2a, A wiring 2 made of a Mo-based metal layer and a Ni—Mo alloy layer 2b is formed. Thereafter, ultraviolet irradiation cleaning is performed, and the entire laminate is subjected to ultraviolet-ozone treatment or oxygen plasma treatment. In the ultraviolet irradiation cleaning, the organic substance is usually removed by irradiating ultraviolet rays with an ultraviolet lamp.

  Next, an organic layer 4 having a hole transport layer, a light emitting layer, and an electron transport layer is formed on the ITO anode 3. When the cathode separator (partition wall) is provided, the partition wall is formed by photolithography before the organic layer 4 is vacuum-deposited.

  The Al cathode 5 as the cathode back electrode is formed by sputtering so as to be orthogonal to the ITO anode 3 after the wiring 2, the ITO anode 3 and the organic layer 4 are formed.

  Next, a portion surrounded by a broken line is sealed with resin to form a sealing can 6.

  Since the substrate with wiring of the present invention uses the above laminate, that is, low resistance Al or Al alloy is used for the conductor layer, and Ni-Mo alloy having high moisture resistance is used for the cap layer. Low resistance, excellent patterning, and high moisture resistance prevent wiring deterioration.

  Moreover, when using the laminated body of this invention as a base | substrate for organic EL display elements, it is necessary to perform the ultraviolet-ozone process which is a process peculiar to organic EL to a base | substrate with wiring, Since it has tolerance also to a process, it is preferable.

  By using the laminate of the present invention, a substrate with wiring having low resistance, excellent patterning performance, and high moisture resistance can be formed. And a high-definition and highly reliable display can be manufactured. In particular, it can be effectively used in an organic EL display element that has a long element life and is desired to have low wiring resistance in order to improve light emission characteristics.

  EXAMPLES Examples will be given below to describe each aspect of the present invention, but the present invention is not limited to these.

  Hereinafter, the present invention will be described in detail with reference to examples. However, it goes without saying that the present invention is not limited to this.

(Reference Examples 1-5)
A soda lime glass substrate having a thickness of 0.7 mm × length 100 mm × width 100 mm was washed. Then, it set to the sputter apparatus, the silica layer of thickness 20nm was formed on this board | substrate by the high frequency magnetron sputtering method using the silica target, and the glass substrate with a silica layer was obtained.

Next, an ITO layer having a thickness of 160 nm is formed by a direct current magnetron sputtering method using an ITO target (containing 10 mass% of SnO _{2 with} respect to the total amount of In ₂ O ₃ and SnO ₂ ). A substrate (also simply referred to as a substrate) was obtained. Ar gas containing 0.5% by volume of O ₂ gas was used as the sputtering gas.

Next, on the entire surface of the glass substrate with the ITO layer (excluding the portion not formed for holding the substrate), as shown in Table 1, Ar gas was formed by DC magnetron sputtering using five types of targets. Five types of single-layer films were formed in an atmosphere to obtain a glass substrate with a film. The back pressure was 1.3 × 10 ⁻³ Pa, the sputtering pressure was 0.3 Pa, and the substrate was not heated. The Ni target made magnetron sputtering possible by reducing the thickness of the target to 1 mm.

  The film thickness, sheet resistance, etching rate and moisture resistance (1) of the film-coated glass substrate were measured and the results are shown in Table 1.

  The sheet resistance was measured by a 4-probe method using Loresta IP MCP-T250 manufactured by Mitsubishi Yuka Co., Ltd.

  The etching rate is determined by immersing the glass substrate with a film in an etching solution having a volume ratio of 16: 1: 2: 1 in order of phosphoric acid, nitric acid, acetic acid, and water for 5 minutes until the film is dissolved. Determined by measurement. The case where the etching was not completed after 5 minutes was evaluated as x.

  Moisture resistance (1) is a constant temperature and humidity chamber (manufactured by ESPEC Co., Ltd., PR-1S), and the film-coated glass substrate is allowed to stand for 1 day under the conditions of 60 ° C.-95% RH. Measured and evaluated. The case where the sheet resistance change rate was less than 5% was evaluated as ◯, and the case where it was 5% or more was evaluated as ×.

  From Table 1, it can be seen that the Mo layer has low moisture resistance, and the Ni layer and the Ni—Mo alloy layer have excellent moisture resistance. In the case of the Mo layer, corrosion could be visually observed on the surface. On the other hand, in the Ni layer and the Ni—Mo alloy layer, no corrosion was visually confirmed on the surface.

  The Ni layer was not etched even after being immersed for 5 minutes. On the other hand, the Ni—Mo alloy layer was etched at an etching rate comparable to or higher than that of the Al layer, and was excellent in etching property. In particular, when a Ni—Mo—Fe alloy target was used, an etching rate substantially equal to that of the Al layer was obtained. Therefore, in the following examples, a Ni—Mo—Fe alloy target (hereinafter also referred to as a Ni—Mo target) having a mass percentage of 65% -32% -3% was used for forming the Mo alloy layer. In addition, the layer formed with the Ni-Mo target is called a Ni-Mo alloy layer.

(Examples 1-2)
A soda lime glass substrate having a thickness of 0.7 mm × length 100 mm × width 100 mm was washed. Then, it set to the sputter apparatus, the silica layer of thickness 20nm was formed on this board | substrate by the high frequency magnetron sputtering method using the silica target, and the glass substrate with a silica layer was obtained. An Al layer (conductor layer) is formed on the entire surface of the glass substrate with a silica layer (excluding portions not formed for holding the substrate) in an Ar gas atmosphere using an Al metal target by DC magnetron sputtering. did. The back pressure was 1.3 × 10 ⁻³ Pa, the sputtering pressure was 0.3 Pa, and the substrate was not heated.

Using the Mo substrate (Example 1) or Ni-Mo target (Example 2) on the obtained substrate with a conductor layer, the Mo layer (Example 1) or Ni as a cap layer in an Ar gas atmosphere by DC magnetron sputtering. A Mo alloy layer (Example 2) was formed to obtain a laminate for forming a substrate with wiring. The back pressure was 1.3 × 10 ⁻³ Pa, the sputtering pressure was 0.3 Pa, and the substrate was not heated. The film thickness, moisture resistance (1), sheet resistance and heat resistance of the laminate before heat treatment were measured for the laminate for forming a substrate with wiring, and the results are shown in Table 2.

  Evaluation of moisture resistance (1) was performed in the same manner as in Reference Example 1. In addition, when the cap layer was a Mo layer (Example 1), corrosion was visually observed on the surface. However, when the cap layer was a Ni—Mo alloy layer (Example 2), corrosion was visually confirmed on the surface. could not. Regardless of the cap layer, the evaluation of moisture resistance (1) (rate of change in sheet resistance) was good.

  In addition, heat treatment of the laminate was performed by using a thermostatic bath (manufactured by ESPEC Co., Ltd., PMS-P101) by allowing the laminate to stand at 320 ° C. for 1 hour in an air atmosphere. The sheet resistance of the body and the resistance change rate (heat resistance) before and after heat treatment were measured. A case where the sheet resistance change rate was 10% or less was evaluated as ◯, 10% was exceeded, 100% or less was evaluated as Δ, and 100% was evaluated as ×.

(Example 3)
A Ni—Mo alloy in an Ar gas atmosphere is formed on the entire surface of the glass substrate with an ITO layer in Reference Example 1 (except for a portion that is not formed for holding the substrate) by a direct current magnetron sputtering method using a Ni—Mo target. A layer (underlayer) was formed to obtain a glass substrate with an underlayer.

The back pressure was 1.3 × 10 ⁻³ Pa, the sputtering pressure was 0.3 Pa, and the substrate was not heated. Thereafter, an Al layer (conductor layer) and a Ni—Mo alloy layer (cap layer) were formed on the underlayer in the same manner and conditions as in Example 2 to obtain a laminate for forming a substrate with wiring. . The film thickness, moisture resistance (1) of the laminate, sheet resistance and heat resistance of the laminate before heat treatment were measured in the same manner as in Example 1, and the results are shown in Table 2.

  Moreover, the ESCA depth profile of this laminated body before and after the heat treatment of Example 3 is shown in FIGS. In the laminated body of Example 3, it can be seen that Ni metal diffuses into the Al layer (conductor layer) by heat treatment.

(Examples 4-7)
On the underlayer of the glass substrate with the underlayer of Example 3, a Mo layer (Ni diffusion prevention layer) was formed in an Ar gas atmosphere by a direct current magnetron sputtering method using a Mo target. Thereafter, an Al layer (conductor layer) is formed on the Ni diffusion prevention layer in the same manner as in Example 2, and the Mo layer is formed on the conductor layer by the same method and conditions as the Ni diffusion prevention layer. (Ni diffusion prevention layer) was formed.

  Further, a Ni—Mo alloy layer (cap layer) is formed on the Ni diffusion preventing layer using a Ni—Mo target in the same manner and under the same conditions as in Example 2, and a laminate for forming a substrate with wiring is formed. Obtained. The film thickness, moisture resistance (1) of the laminate, sheet resistance and heat resistance of the laminate before heat treatment were measured in the same manner as in Example 1, and the results are shown in Table 2.

  From Table 2 and FIGS. 4 (a) and 4 (b), when the cap layer is a Mo layer as in Example 1, the moisture resistance is poor, but when it is a Ni—Mo alloy layer as in Example 2, the moisture resistance is excellent. It is clear. Furthermore, it can be seen that when heat treatment is performed with the Ni—Mo alloy layer and the Al layer in contact as in Example 3, Ni diffuses into the Al layer and heat resistance deteriorates.

  On the other hand, as the results of Examples 4 to 7 show, it is clear that the heat resistance can be prevented from deteriorating when the Mo layer is interposed between the Ni—Mo alloy layer and the Al layer. Further, it can be seen that the film thickness of the Mo layer may be 10 nm or more and 60 nm or less.

(Examples 8 to 11)
In Example 3, sputtering was performed under the same method and conditions as in Example 3 except that the mixed gas having the composition shown in Table 3 was used instead of Ar gas as the sputtering gas for forming the base layer and the cap layer. A laminate for forming a substrate with wiring was obtained. The film thickness, moisture resistance (1), sheet resistance and heat resistance of the laminate before heat treatment were measured in the same manner as in Example 1, and the results are shown in Table 3.

  From Table 3, it can be seen that when the Ni—Mo alloy layer is nitrided or oxycarburized, Ni is prevented from diffusing into the Al-based metal layer, and deterioration in heat resistance can be prevented.

(Example 12)
The laminated body for forming a substrate with wiring in Example 5 was patterned using an Al etching solution by a photolithographic method using a mask pattern with a line / space of 25 μm / 65 μm to form a substrate with wiring. The thickness of the laminate, the sheet resistance before patterning, and the resistance change rate (heat resistance) of the laminate before and after heat treatment were measured in the same manner as in Example 1. The results are shown in Table 4.

  The patterning property was measured by measuring the distance that etching progressed beyond the patterning line in a direction perpendicular to the line, and observing overetching. A case where the overetching was 2 μm or less was evaluated as ◯, and a case where the overetching exceeded 2 μm was evaluated as ×.

  The moisture resistance (2) of the substrate with wiring after patterning is determined by using the constant temperature and humidity chamber (PR-1S, manufactured by Espec Co., Ltd.) under the condition of 60 ° C.-95% RH for one day. This was evaluated by observing the wiring using a laser microscope. The case where corrosion was not recognized in the wiring was evaluated as “◯”, and the case where corrosion was observed was evaluated as “X”. Table 4 shows the evaluation results of the patterning property and moisture resistance (2). Moreover, the observation result (500-times multiplication factor) by the laser microscope after evaluation of the moisture resistance (2) of the board | substrate with a wiring of Example 12 was shown to Fig.5 (a).

(Example 13)
Ar—with the composition shown in Table 4 was applied to the entire surface of the glass substrate with an ITO layer in Reference Example 1 (except for the portion not formed for holding the substrate) by a direct current magnetron sputtering method using a Ni—Mo target. A Ni—Mo alloy layer (underlayer) was formed in a CO ₂ mixed gas atmosphere. The back pressure was 1.3 × 10 ⁻³ Pa, the sputtering pressure was 0.3 Pa, and the substrate was not heated.

  Thereafter, an Al layer (conductor layer) is formed on the base layer using an Al metal target, and a Mo layer (Ni diffusion prevention layer) is formed on the conductor layer using a Mo target. Furthermore, a Ni—Mo alloy layer (cap layer) was formed on the Ni diffusion preventing layer using a Ni—Mo target to obtain a laminate for forming a substrate with wiring. The thickness of the laminate, the sheet resistance before patterning, and the resistance change rate (heat resistance) of the laminate before and after heat treatment were measured in the same manner as in Example 1. The results are shown in Table 4.

  Thereafter, patterning was performed by the same method and conditions as in Example 12 to obtain a substrate with wiring. The patternability and moisture resistance (2) of the substrate with wiring were measured in the same manner as in Example 12, and the evaluation results are shown in Table 4. Further, the moisture resistance (3) of the substrate with wiring after patterning the laminate was evaluated in the same manner as the moisture resistance (2) except that it was left for 5 days, and the results are shown in Table 5.

(Example 14)
Ar—with the composition shown in Table 4 was applied to the entire surface of the glass substrate with an ITO layer in Reference Example 1 (except for the portion not formed for holding the substrate) by a direct current magnetron sputtering method using a Ni—Mo target. A Ni—Mo alloy layer (underlayer) was formed in a CO ₂ mixed gas atmosphere. The back pressure was 1.3 × 10 ⁻³ Pa, the sputtering pressure was 0.3 Pa, and the substrate was not heated.

Thereafter, an Al layer (conductor layer) was formed on the underlayer using an Al metal target. Further, a Ni—Mo alloy layer (cap layer) is formed on the conductor layer by a direct current magnetron sputtering method using an Ni—Mo target in an Ar—CO ₂ mixed gas atmosphere having a composition shown in Table 4. A laminate for forming a substrate with wiring was obtained. The thickness of the laminate, the sheet resistance before patterning, and the resistance change rate (heat resistance) of the laminate before and after heat treatment were measured in the same manner as in Example 1. The results are shown in Table 4.

  Thereafter, patterning was performed by the same method and conditions as in Example 12 to obtain a substrate with wiring. The patterning property and moisture resistance (2) of the substrate with lines were measured in the same manner as in Example 12, and the evaluation results are shown in Table 4.

(Example 15)
On the entire surface of the glass substrate with an ITO layer in Reference Example 1 (except for the portion that is not deposited for holding the substrate), a Mo layer was formed in an Ar gas atmosphere by a direct current magnetron sputtering method using a Mo target. The back pressure was 1.3 × 10 ⁻³ Pa, the sputtering pressure was 0.3 Pa, and the substrate was not heated.

  Thereafter, an Al layer (conductor layer) is formed on the base layer using an Al metal target, and a Mo layer (cap layer) is formed on the conductor layer using a Mo target. A laminate for forming an attached substrate was obtained. The thickness of the laminate, the sheet resistance before patterning, and the resistance change rate (heat resistance) of the laminate before and after heat treatment were measured in the same manner as in Example 1. The results are shown in Table 4.

  Thereafter, patterning was performed by the same method and conditions as in Example 12 to obtain a substrate with wiring. The patterning property and moisture resistance (2) of the substrate with wiring were measured in the same manner as in Example 12, and the evaluation results are shown in Table 4. Moreover, the observation result (500-times multiplication factor) by the laser microscope after evaluation of the moisture resistance (2) of the board | substrate with wiring of Example 15 was shown in FIG.5 (b).

  From Table 4 and FIG.5 (b), when a cap layer is Mo layer, it turns out that moisture resistance is low.

(Example 16)
Sputtering was performed in the same manner and conditions as in Example 13 except that the Ni diffusion prevention layer was not formed in Example 13 to form a laminate according to the present invention. The film thickness of the laminate, the sheet resistance before patterning, and the resistance change rate (heat resistance) of the laminate before and after heat treatment were measured in the same manner as in Example 1, and the results are shown in Table 4.

Thereafter, patterning was performed under the same method and conditions as in Example 13 to form a substrate with wiring. The patternability, moisture resistance (2) and moisture resistance (3) of this substrate with wiring were measured in the same manner as in Example 13, and the results are shown in Table 5. The moisture resistance (2) is a test for 1 day, and the moisture resistance (3) is a continuous 5 days test. In the table, ○ means no corrosion, Δ means slightly corrosion, and X means corrosion.
(Example 17)
In Example 13, the Ni diffusion preventing layer was formed using a Mo—Nb alloy target having a Nb content of 5 mass%. A laminate was formed by sputtering under the same method and conditions as in Example 13 except that the Ni diffusion preventing layer was a MoNb alloy layer. The film thickness of the laminate, the sheet resistance before patterning, and the resistance change rate (heat resistance) of the laminate before and after heat treatment were measured in the same manner as in Example 1, and the results are shown in Table 4.

  Thereafter, patterning was performed by the same method and conditions as in Example 13 to obtain a substrate with wiring. The patternability, moisture resistance (2) and moisture resistance (3) of this substrate with wiring were measured in the same manner as in Example 13, and the evaluation results are shown in Table 5 above.

(Example 18)
In Example 13, the Ni diffusion preventing layer was formed using a Mo—Nb alloy target having a Nb content of 10 mass%. A laminate was formed by sputtering under the same method and conditions as in Example 13 except that the Ni diffusion preventing layer was a MoNb alloy layer. The film thickness of the laminate, the sheet resistance before patterning, and the resistance change rate (heat resistance) of the laminate before and after heat treatment were measured in the same manner as in Example 1, and the results are shown in Table 4.

  Thereafter, patterning was performed by the same method and conditions as in Example 13 to obtain a substrate with wiring. The patternability, moisture resistance (2) and moisture resistance (3) of this substrate with wiring were measured in the same manner as in Example 13, and the evaluation results are shown in Table 5 above.

(Example 19)
In Example 13, except that the substrate temperature was 200 ° C., sputtering was performed in the same manner and conditions as in Example 13 to obtain a laminate. The film thickness, sheet resistance before patterning, heat resistance, patternability, moisture resistance (2) and moisture resistance (3) of the laminate were measured in the same manner as in Example 13, and the results are shown in Table 5.

  From Table 5, it can be seen that the moisture resistance can be further improved by using the Ni diffusion preventing layer as the MoNb alloy.

  In addition, the surface roughness (Ra) was measured using an atomic force microscope (manufactured by Digital Instruments, NanoScope 3a). The Ra of Example 13 was 3 nm, and the Ra of Example 19 was 21 nm. From this result, it is understood that the resistance value decreases when the substrate is heated. On the other hand, it can be seen that the surface roughness is increased by heating the substrate.

  In the above example, when the treatment of oxidation, nitridation, carbonization, oxynitridation, nitrocarburization, oxynitride carbonization is performed, the atoms contained in the formed metal film are, for example, about several% to 30%. This is considered good.

21 and 22 are partial cross-sectional views of the laminated body according to the present invention. In FIG. 21, the laminated film 35 of the laminated body has a three-layer structure. For example, a layer structure of NiMo—O _x / Al-based metal / NiMoN _y can be given. In FIG. 22, the laminated film 35 has a four-layer structure. For example, a layer structure of NiMo—O _x / Al-based metal / Mo / NiMo or NiMo—O _x / Al-based metal / MoNb / NiMo can be given. Further, as in the above-described embodiment, a multilayer film having a five-layer structure is also included. For example, a layer structure of NiMo—O _x / Mo / Al-based metal / Mo / NiMo can be given.
FIG. 23 is a schematic diagram showing a state in the vicinity of the connection terminal of the organic EL display element. An external connection lead 41 is connected to the connection terminal according to the present invention. Next, Examples B1 to B4 in the case of forming an organic EL display element will be described. Examples B1 to B4 are passive drive organic EL display elements, but it goes without saying that they can be applied to TFT drive organic EL display elements using low-resistance electrodes.

(Example B1)
FIG. 6 shows a plan view of an example of the organic EL display element according to the present invention. FIG. 7 is a CC ′ cross section of FIG. In FIG. 6, the counter substrate and the TCP are not shown. FIG. 20 is a flowchart of a method for forming an organic EL display element according to the present invention. Hereinafter, description will be made in accordance with the order of steps in FIG. 20 with reference to FIGS.

In addition, partial cross-sectional views of the organic EL display element corresponding to each step are shown in FIGS. 24 to 28, and plan views are shown in FIGS. In this example, first, a transparent conductive film (ITO layer) is formed on a substrate and patterned to form an electrode layer that becomes the anode 20a. The connection terminal portion 20b is located at the end on the substrate. Next, a metal laminated film 35 is formed on almost the entire substrate surface (FIG. 29). Thereafter, the laminated film 35 is patterned to form the auxiliary wiring 30 (FIG. 30).
Then, an insulating film 40 is formed so as to cover the entire substrate surface including the auxiliary wiring 30 and the anode 20a (FIG. 31). Then, the pixel opening 40a and the insulating film opening pattern 40b are formed (FIG. 32). Further, the metal pattern of the cathode 70 is formed so as to be in contact with those portions, and connected to the auxiliary wiring 30 (FIG. 33). The end of the auxiliary wiring becomes a connection terminal side pattern and is connected to an external drive circuit.

The laminate of the present invention may be one obtained by patterning an anode and then forming a metal laminate film on the substrate surface (see FIG. 29). Alternatively, a desired film can be appropriately formed depending on the region of the substrate surface.
First, in accordance with step S _1, forming a conductive layer on the silica-coated layer of the glass substrate 1 having a silica coating layer. This conductive layer corresponds to the second electrode layer described above. As the glass substrate, for example, soda lime glass can be used. The thickness of the silica coat layer is usually 5 to 30 nm, and can be formed by sputtering, for example.

  In general, the conductive layer has translucency. Having translucency means that it can include a case of having a certain degree of transparency other than the case where the light transmittance is as high as 90 to 100% as in the case of a so-called transparent conductive layer. The second electrode layer is preferably a transparent conductive layer. This is because the function as a display element can be sufficiently exhibited.

  The thickness of the conductive layer is usually 50 to 300 nm. More preferably, it is 100-200 nm. Typically, it is an ITO film produced by a DC sputtering method. In this example, an ITO film is used. In addition, the conductive layer can generally be produced by physical vapor deposition (PVD) such as vacuum deposition or ion plating.

Then, according to step _{S 2,} a resist is patterned by a photolithographic process, then in accordance with step _{S 3,} the ITO film is etched, and then the resist is removed in accordance with step _{S 4,} to obtain the anode patterns 20a and anode wiring connection terminals 20b. Any known resist may be used as long as it does not violate the gist of the present invention. For the etching, for example, a mixed aqueous solution of hydrochloric acid and nitric acid can be used. Any known stripping agent may be used for stripping the resist as long as it does not violate the gist of the present invention.

Then, according to step S _5, for example by a DC sputtering method, forming a metal stacked film comprising a cap layer formed of a low-resistance layer and a Ni alloy of Al or Al alloy. In order to reduce the wiring resistance, it is desirable that the low resistance layer be made of Al. At this time, in order to improve the corrosion resistance, it is also possible to use an Al alloy such as AlNd or AlSiCu. Detailed film formation examples will be described later.

Then, according to step S _6, and the resist is patterned by a photolithographic process, then, according to step S _7, by etching the laminated metal film, according to step S _8, the resist is removed. Any known resist may be used as long as it does not contradict the spirit of the present invention.

  For the etching, for example, an etching solution made of a mixed aqueous solution of phosphoric acid, acetic acid and nitric acid can be used. Any known stripping agent may be used for stripping the resist as long as it does not violate the gist of the present invention. The laminated film according to the present invention can be collectively etched with this etching solution. Thereby, the auxiliary wiring 30 is formed. An inner side pattern portion 30a and a connection terminal side pattern portion 30b located inside the element are formed.

The deposition in place of the step of patterning the above ITO film (step _S 2 to S ₄₎ and the step of patterning the laminated metal film (Step _S 6 to S _8), in order to the ITO film and the laminated metal film by sputtering Then, the laminated metal film and the ITO film can be patterned in this order. However, if ITO is etched after the auxiliary wiring patterning, the ITO etchant is a strong acid, so if there is a pinhole in the resist, the auxiliary wiring pattern may disappear. It is preferable that the manufacturing method precedes patterning.

Thereafter, in accordance with step S _9, the insulating film, for example, a photosensitive polyimide film was spin-coated was patterned by a photolithographic process in accordance with step S _10, and cured according to step S _11, as shown in FIGS. 6 and 7, An insulating film pattern 40 having a pixel opening 40a in the pixel portion is obtained. The film thickness of the insulating film pattern 40 after curing is usually about 1.0 μm. In the case where the pixel opening is about 300 μm × 300 μm, it is preferable that the contact forming portion 40b between the cathode and the auxiliary wiring is 200 μm × 200 μm or less because the size of the entire display element is not affected.

Then, according to step S _12, for example, a photosensitive acrylic resin is spin-coated was patterned by photolithography, and cured to form a cathode separation pattern 50 (see FIG. 9). When forming this cathode separation pattern, it is preferable to use a negative photosensitive resin so as to have an inversely tapered structure. When using negative type photosensitive resin, when light is irradiated from above, the deeper the curing becomes insufficient, and as a result, when viewed from above, the cross-sectional area of the cured part is lower than the upper one. Has a narrow structure. This means that it has an inverted taper structure.

  When such a reverse taper structure is provided, in a subsequent process, the deposition does not reach the shadowed portion when viewed from above when the cathode mask is deposited. As a result, the cathodes can be separated from each other. Note that the photosensitive polyimide resin and the photosensitive acrylic resin may be interchangeable with each other. Any known insulating film resin such as an epoxy resin or a phenolic resin can be used as long as it does not contradict the gist of the present invention.

Then, according to step S _13, for example, using a parallel plate RF plasma (RF plasma) apparatus, to implement the oxygen plasma irradiation, conducted surface modification of the ITO film, then, according to step S _14, for example using the vapor deposition apparatus Then, the organic EL layer 60 and the cathode 70 are mask-deposited (see FIGS. 27 to 28 and FIGS. 29 to 33).
This cathode corresponds to the first electrode layer according to the present invention. The organic EL layer often includes an interface layer, a hole transport layer, a light emitting layer, an electron injection layer, and the like as constituent elements. However, a different layer configuration can be applied. The thickness of the organic EL layer is usually 100 to 300 nm.

  Note that the end portion of the anode 20a is covered with the insulating film by the formation of the insulating film pattern. For this reason, the surface where the organic EL layer is in contact with the anode 20a is flattened, the possibility of disconnection of the organic EL layer or the cathode due to electric field concentration or the like is reduced, and the withstand voltage between the anode and the cathode is improved. Al is often used for the cathode, but an alkali metal such as Li, Ag, Ca, Mg, Y, In or an alloy containing them can be used instead.

  The thickness of the cathode is usually 50 to 300 nm. Note that it is not necessary for all of the cathodes to contain Al or an Al alloy, and it is sufficient that the portion where the conductive layer is connected to the auxiliary wiring contains Al or an Al alloy. In addition, the cathode may be produced by physical vapor deposition (PVD) such as sputtering or ion plating.

  Thereby, the organic EL pattern 60 and the cathode pattern 70 which consist of an organic EL layer are formed (refer the top view of FIG. 6). By applying the laminated film of the present invention to the auxiliary wiring and the cathode terminal portion, the resistance is low, and the low contact resistance can be maintained with respect to the cathode and the drive circuit connection terminal. In addition, an organic EL display element having an auxiliary wiring having reliable contact characteristics, and an organic EL display element and a driving circuit for driving the organic EL display element can be obtained.

Thereafter, as S ₁₅ , a film in which CaO is kneaded into the resin as the water capturing material 100 is attached to the counter substrate 80. Therefore, it is desirable that the counter substrate 80 has a structure in which a glass substrate is partially dug by sandblasting or the like. Next, after the ultraviolet curable resin is dispensed around the element substrate, it is bonded to the counter substrate 8 and irradiated with ultraviolet rays to form a peripheral seal 90 to fix the counter substrate 80. These steps are performed in a nitrogen atmosphere so that moisture and oxygen do not enter the display panel. Thereafter, the substrate is cut, separated into panels, and the mounting terminal portions are exposed.
_Then, as _{S 16,} to implement the drive circuit to the outside. Specifically, the anisotropic conductive film 110 is attached to the connection terminal side pattern portion 30b to be the connection terminal, and then the TCP copper foil wiring is arranged so that the terminal and the TCP side connection wiring overlap, and then thermocompression bonding is performed. And paste.

  Here, a sealing process and a subsequent mounting process which are important in the organic EL display element will be described with reference to FIG. Since the organic LED element deteriorates due to moisture, the counter substrate 80 is sealed with a peripheral seal 90. The sealing material used at this time is preferably a photosensitive epoxy resin.

  Next, the water capturing material in the organic EL display element will be described. In the organic EL display element, it is preferable to add a water catching material in order to remove moisture when sealing. Examples of the water catching material include barium oxide, calcium oxide, and zeolite. For example, the water capturing material film 100 in which calcium oxide is kneaded into the resin film is bonded to the concave portion on the inner surface side of the counter substrate 80 (see FIG. 17).

  Thereafter, the anode and the cathode are connected to the external drive circuit. Thereafter, a drive circuit is mounted on the anode and cathode terminal portions by TCP. As a method of connecting the organic EL display element to the drive circuit, a terminal electrically connected to the in-element wiring is provided and connected to the drive circuit.

  For high-density connections, an external drive circuit is connected to one of the polyimide films patterned with copper thin wiring, and the other is connected to the element terminals via an anisotropic conductive film (ACF) (TCP mounting) A method has been adopted in which gold bumps are provided on a drive circuit bare chip and connected to a terminal via an ACF (COG mounting).

  TCP is a form in which a drive IC and connection wiring are provided on a film such as polyimide. FIG. 18 is a plan view of a terminal portion on which TCP mounting is performed, and FIG. 19 is a cross-sectional view taken along line E-E ′ of FIG. A terminal 30C is formed on the glass substrate 1, an anisotropic conductive film (ACF) 110 is pasted thereon, and a connection wiring 150 formed on the polyimide film of TCP12 is aligned with the terminal from above. Paste. An anisotropic conductive film is one in which conductive particles 130 are dispersed in a resin. In general, an epoxy resin is used as the resin, and conductive particles coated with plastics such as Ni and Au, or those using Ni particles are used.

  The TCP is obtained by forming the driving IC 140 and the connection wiring 150 on the polyimide tape 160. Cu is mainly used for the connection wiring 150. In the TCP connection process, first, ACF is temporarily pressure-bonded to the terminal portion. The temperature at that time is about 50 to 150 ° C., and the pressure is generally 1 to 2 MPa.

  Thereafter, the positional relationship between the TCP connection wiring 150 and the terminal 30 </ b> C is adjusted, and the TCP is finally bonded. The temperature at that time is about 150 to 250 ° C., and the pressure is generally 2 to 3 MPa. After the main pressure bonding, the conductive particles existing between the connection wiring 150 and the terminal 30C are crushed to obtain an electrical connection. In addition, after the mounting is completed, a method of preventing the corrosion by covering the mounting portion with a resin is also used. Generally, a silicone resin, a UV curable epoxy resin, or the like is used.

  In this way, an organic EL display element is produced. On the other hand, a test element group (hereinafter referred to as TEG) may be formed in order to confirm the functions of individual parts and grasp the performance of each process. A TEG created in the same manner as the above process is shown in FIGS.

These, while being formed by a part of the constituent material, it is formed through all the steps up to S ₁₅ in FIG. 20. This makes it possible to evaluate not only the performance and workability of the material, but also the influence of the material on the process history. In FIG. 8, the ITO film is removed by etching at S _{1 to} S ₈ , and then the pattern of the auxiliary wiring 30 which is a metal laminated film is formed. With this pattern, it is possible to know the resistance of the wiring formed of the laminated film. Here, the wiring width is 40 μm, and the length of the wiring is 6.8 mm. FIG. 9 is formed by the processes of S _{1 to} S ₁₄ . FIG. 10 shows a cross section taken along the line DD ′ of FIG.

First remove the ITO film at _S 1 to S _4. Next, the auxiliary wiring 30 is formed in a laminated film pattern in S _{5 to} S ₈ , and then the insulating film pattern 40 and the insulating film opening pattern 40 b are formed in S _{9 to} S ₁₁ . The insulating film opening pattern is a square having a side of 200 μm. _Then, a cathode separation pattern 50 according to _{S 12.} This pattern has a slit 50a in the vicinity of the opening of the insulating film.

_Thereafter, a pattern of the cathode 70 in _{S 14,} TEG is completed. In this TEG, the auxiliary wiring 30 which is a pattern of a metal laminated film is connected to the cathode pattern 70 through the insulating film opening 40b. When a voltage is applied to the adjacent auxiliary wiring (laminated film pattern) 30, the current flows from the opening pattern 40b to the cathode pattern, and further passes through the slit 50a of the partition wall pattern to adjoin the auxiliary wiring (laminated film pattern). ) Flow into 30.

At this time, the current flows through the connection between the two metal patterns (a part of the laminated film) and the cathode pattern, and the resistance of the junction (contact resistance) can be calculated by subtracting the resistance of the other part. . The reason why the cathode separation pattern is provided here is that there is a possibility that the developer may be accumulated in the insulating film opening pattern 40b at the time of developing the cathode separation pattern, and the contact resistance may be affected. Because there is. From these, it becomes possible to evaluate the wiring resistance and the contact resistance between the auxiliary wiring and the cathode metal.
An organic EL display element was produced according to the above description. The contents of each step are the same as described above unless otherwise specified.

(Example B2)
In accordance with the above description, the wiring resistance TEG and the contact resistance TEG shown in FIGS. 8, 9, and 10 were created. First, a 150 nm ITO film was formed and removed in accordance with S _{1 to} S ₄ . Thereafter, NiMo, Mo, Al, Mo, and NiMo were sequentially formed by DC sputtering. When the NiMo film for the underlayer was formed, CO ₂ was flowed to cause oxycarbonization.

  Each film thickness is 50 nm for the NiMo layer, 20 nm for Mo, and 400 nm for the Al layer. This laminated film can be etched at once with phosphoric acid, acetic acid, and aqueous nitric acid. Thereby, the laminated metal pattern 3 was obtained. Thereafter, an insulating film pattern 40 was obtained. At this time, the insulating film pattern is not formed in FIG. Thereafter, a cathode separation pattern 50 was obtained. As before, the cathode separation pattern is not formed in FIG. At this time, the slit 50a of the cathode separation pattern is 300 μm.

  Then, oxygen plasma irradiation was implemented on the surface modification conditions of ITO film | membrane using the parallel plate RF plasma apparatus. Specifically, RIE (reactive ion etching) mode plasma treatment was performed for 60 seconds under plasma treatment conditions of an oxygen flow rate of 50 sccm (50 mL / min in the standard state), a total gas pressure of 6.7 Pa, and 1.5 kW.

  Then, using a vapor deposition apparatus, Al was deposited as a cathode in a 300 nm mask to obtain a cathode pattern 70. The wiring resistance TEG created in this way was measured by the four-terminal method and found to be 25.5Ω. When this is converted into sheet resistance, it becomes 0.15Ω / □. The sheet resistance immediately after sputtering of this film was 0.13Ω / □.

  This indicates that although a slight increase in resistance is observed through the process of forming the organic EL display element, a low-resistance wiring is formed. FIG. 11 shows the current-voltage characteristics at the contact TEG, and FIG. 12 shows the contact resistance. The contact resistance is obtained by subtracting the resistance of the wiring portion at room temperature from the obtained resistance.

  When a voltage was applied to the adjacent metal pattern of the TEG using a probe, the terminal burned out when the probe and the terminal were in contact at 4.8 V, and no more voltage could be applied. As can be seen from the measurement results, when the above five-layer laminated film is applied to the auxiliary wiring, it is estimated that the contact resistance is as low as about 0.5 to 3.0Ω and the current can flow at 350 mA or more. . The reason why the current value gradually reaches a peak here is considered that the wiring portion is heated by the current, the temperature rises, and the resistance value rises.

  When a similar pattern was made of Cr and evaluated, the contact resistance could be suppressed to about 10Ω, but when a current of about 10 mA was passed, the pattern was burned out at the contact portion.

  Thus, if the above-mentioned laminated metal film is applied to the auxiliary wiring of the organic EL display element, it is possible to flow a large current with a low resistance and a low contact resistance as compared with conventionally used Cr. It is considered that a display capable of displaying with high luminance and high duty can be created.

(Example B3)
Similar to Example B1, another metal laminate film was applied to make a TEG. The used metal laminated film was formed of NiMo, Al, and NiMo in this order. When NiMo was formed as the underlayer, CO ₂ was flown to oxidize and carbonized, and when NiMo was formed as the cap, nitriding was performed by flowing N ₂ . Each film thickness is 50 nm for the NiMo layer and 400 nm for the Al layer. The other processes are the same as in Example B1.

  The wiring resistance TEG created in this way was measured by the four-terminal method and found to be 18.7Ω. When this is converted into sheet resistance, it is 0.11Ω / □. FIG. 11 shows the current-voltage characteristics at the contact TEG, and FIG. 12 shows the contact resistance. In this example, when a voltage of 4.2 V was applied, the positively applied wiring was burned out, and a voltage higher than that could not be applied. If this laminated film is applied to the auxiliary wiring of the organic EL display element, it is considered that a display having a high performance similar to or higher than that in Example B1 can be produced.

(Example B4)
An organic EL display element and a TEG were produced according to the above description. The creation of the TEG is omitted. A plan view of the organic EL display element of this example is shown in FIG. 6, and a CC ′ cross section is shown in FIG.

  First, a 150 nm ITO film was formed by DC sputtering on a silica coat layer of a 0.7 mm thick soda lime glass substrate 1 having a 20 nm silica coat layer formed by sputtering. Thereafter, the resist was patterned by a photolithography process, and then the ITO film was etched using a mixed aqueous solution of hydrochloric acid and nitric acid, and then the resist was peeled off to obtain a pattern of the anode 20a and the anode wiring connection terminal 20b.

A phenol novolac resin was used as the resist, and monoethanolamine was used as the resist stripper. Thereafter, a laminated metal film made of NiMo, Al, Mo, and NiMo was sequentially formed by DC sputtering. The thickness of the laminated metal film is 50 nm for the NiMo layer, 20 nm for the Mo layer, and 360 nm for Al. Here, the NiMo film of the underlayer was acid carbonized by flowing CO ₂ .

  Thereafter, the resist was patterned by a photolithography process, and then the laminated metal film was etched using an etching solution made of a mixed aqueous solution of phosphoric acid, acetic acid and nitric acid, and then the resist was peeled off. As a result, an internal pattern 30 a and a connection terminal pattern 30 b were formed as the auxiliary wiring 30. A phenol novolac resin was used as the resist, and monoethanolamine was used as the resist stripper. Thereafter, an insulating film pattern 40 having a pixel opening 40a was obtained. As shown in FIG. 6, the insulating film pattern 40 is also provided on the pattern of the auxiliary wiring 30 so that the auxiliary wiring contact forming portion 40b is formed.

  The pixel opening was 300 μm × 300 μm, and the contact forming portion 40b between the cathode and the auxiliary wiring was 200 μm × 200 μm. Thereafter, a cathode separation pattern 50 was obtained. Thereafter, oxygen plasma irradiation was performed using a parallel plate RF plasma apparatus to modify the surface of the ITO film, and then the organic EL layer and the cathode were vapor-deposited using an evaporation apparatus. Specifically, plasma processing in RIE (reactive ion etching) mode was performed for 60 seconds under plasma processing conditions of an oxygen flow rate of 50 sccm (50 mL / min in a standard state), a total gas pressure of 6.7 Pa, and 1.5 kW.

  Thereafter, an interface layer composed of copper phthalocyanine (hereinafter referred to as CuPc), hole transport composed of N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine (hereinafter referred to as α-NPD) A light emitting layer made of tris (8-quinolinolato) aluminum (hereinafter abbreviated as Alq), an electron injection layer made of LiF, and a cathode made of Al, 10 nm and 60 nm, respectively. 50 nm, 0.5 nm, and 200 nm were formed.

  Among these, the hole transport layer in which the organic EL layer is formed with the interface layer made of CuPc, the hole transport layer made of α-NPD, the light emitting layer made of Alq, and the electron injection layer made of LiF, α-NPD Instead of this, a triphenylamine-based substance such as triphenyldiamine (hereinafter referred to as TPD) can be used.

  Thereby, the organic EL pattern 60 and the cathode pattern 70 which consist of an organic EL layer were formed. Thereafter, the organic EL display element and the counter substrate 80 are bonded together with a peripheral seal 90 made of an ultraviolet curable resin. Specifically, a film in which CaO is kneaded is attached to the counter substrate as the water catching material 100, an ultraviolet curable resin is applied to the periphery of the organic EL display element using a dispenser, and then irradiated with ultraviolet rays. Then, the two substrates were bonded together. Nagasetiva XNR5516 was used as the ultraviolet curable resin.

  Thereafter, an anisotropic conductive film is attached to the terminal portion, and TCP is connected via the anisotropic conductive film. Specifically, the anisotropic conductive film 110 is temporarily pressure-bonded to the mounting terminal portion. An anisotropic conductive film is, for example, Hitachi Chemical Anisolm 7106U. The temporary pressure bonding temperature is 80 ° C., the pressure bonding pressure is 1.0 MPa, and the pressure bonding time is 5 seconds.

  Next, the TCP containing the drive circuit is finally bonded to the connection terminal portion. The main pressure bonding temperature is 170 ° C., the pressure bonding pressure is 2.0 MPa, and the pressure bonding time is 20 seconds. The organic EL display element thus produced can form an auxiliary wiring having a low resistance and a low contact resistance with the cathode and a terminal excellent in moisture resistance.

  As a laminate according to the present invention, a TEG to which a metal film was applied was prepared in the same manner as described above, and the wiring resistance was 0.14Ω / □. The sheet resistance during sputtering was 0.11Ω / □. Further, the contact resistance obtained from the contact TEG was 0.5 to 0.8Ω / 200 μm □, and the metal pattern was burned out at about 350 mA.

  Moreover, the terminal part which was not mounted with the board | substrate of this example was preserve | saved in the 80 degreeC * 90% RH high temperature high humidity environment. As a comparison, a metal using MoNb (10 atomic%), Al, and MoNb (10 atomic%) as the metal of the terminal portion was also evaluated in the same manner. The film thickness at this time is 70 nm for MoNb and 350 nm for Al. The state of corrosion when 100 hours have elapsed is shown in FIGS. Here, FIG. 15 shows the pattern of the laminated film of this example, and FIG. 16 shows the laminated film formed of MoNb and Al.

  Thus, it can be seen that when the laminated film according to the present invention is used, corrosion is reduced as compared with the case where MoNb is used as the cap film. Further, as a result of observing the mounted FPC and ACF after removing the mounted one after 700 hours, the corrosion was further reduced.

  This suggests that the NiMo alloy is excellent in corrosion resistance as a cap film. Further, when the pattern is formed of the laminated metal, Mo of the Ni diffusion preventing layer is exposed at the pattern end face. If this Mo is made of a metal with improved corrosivity such as MoNb, diffusion of Ni into Al can be prevented and corrosion can be suppressed.

  By using the laminate of the present invention, a substrate with wiring having low resistance, excellent patterning performance, and high moisture resistance can be formed, which is useful. And a high-definition and highly reliable display can be manufactured. In particular, it is useful for an organic EL display element that has a long element life and is desired to have low wiring resistance for improving light emission characteristics.

The partially notched front view which shows an example of the base | substrate with wiring formed using the laminated body of this invention. FIG. 2 is a partial cross-sectional view taken along the line A-A ′ of FIG. 1. FIG. 2 is a partial cross-sectional view taken along the line B-B ′ of FIG. 1. (A) ESCA depth profile figure before heat processing of the laminated body for board | substrate formation with wiring of Example 3, (b) ESCA depth profile figure after heat processing of the laminated body for board | substrate formation with wiring of Example 3. (A) A photograph showing the observation result by a laser microscope after the moisture resistance test of the substrate with wiring of Example 12 of the present invention, (b) A photograph showing the observation result by a laser microscope after the moisture resistance test of the substrate with wiring of Example 15 . The top view of an example of the organic electroluminescent display element by this invention. FIG. 7 is a partial cross-sectional view taken along the line C-C ′ of FIG. 6. The top view of wiring resistance evaluation TEG. The top view of TEG which evaluates the contact resistance of a cathode and auxiliary wiring. FIG. 10 is a partial cross-sectional view taken along the line D-D ′ in FIG. 9. The current-voltage characteristic view of contact TEG obtained in Example B2. Contact resistance of contact TEG obtained in Example B2. The current-voltage characteristic view of contact TEG obtained in Example B3. Contact resistance of contact TEG obtained in Example B3. The photograph after the high-temperature, high-humidity evaluation of the terminal part in the organic EL display element obtained in Example B4. The photograph after the high-temperature, high-humidity evaluation of the terminal part in the organic EL display element made into the comparative example in Example B4. Sectional drawing of the cathode contact part of the organic electroluminescent display element produced with the prior art. The top view of the terminal part which gave TCP mounting. The fragmentary sectional view in the E-E 'cut line of FIG. The flowchart of the manufacturing method in an example of this invention. Sectional drawing of the structural example 1 of the laminated body concerning this invention. Sectional drawing of the structural example 2 of the laminated body concerning this invention. The perspective view of the example of the board | substrate with wiring concerning this invention. The fragmentary sectional view which shows the formation process 1 of the cathode side extraction circuit of an organic electroluminescent display element. The fragmentary sectional view which shows the formation process 2 of the cathode side extraction circuit of an organic electroluminescent display element. The fragmentary sectional view which shows the formation process 3 of the cathode side extraction circuit of an organic electroluminescent display element. The fragmentary sectional view which shows the formation process 4 of the cathode side extraction circuit of an organic electroluminescent display element. The fragmentary sectional view which shows the formation process 5 of the cathode side extraction circuit of an organic electroluminescent display element. The typical top view in the manufacturing process 1 of the organic electroluminescent display element of this invention. The typical top view in the manufacturing process 2 of the organic electroluminescent display element of this invention. The typical top view in the manufacturing process 3 of the organic EL display element of this invention. The typical top view in the manufacturing process 4 of the organic EL display element of this invention. The typical top view in the manufacturing process 5 of the organic EL display element of this invention.

Explanation of symbols

1: Glass substrate 2: Wiring 2a: Al-based metal layer 2b: Ni—Mo alloy layer 3: Anode (ITO layer)
4: Organic layer 5: Cathode (Al)
6: Sealing can 20a: Anode 20b: Anode wiring connection terminal 30: Auxiliary wiring (metal pattern)
30a: Internal side pattern 30b: Connection terminal side pattern 30x: Auxiliary wiring 35: Laminated film 40: Insulating film 40a: Pixel opening 40b: Insulating film opening pattern 41: Connection lead 50: Cathode separation pattern 50a: Cathode separation pattern slit part 60: Organic EL layer 70: Cathode 80: Counter substrate 90: Counter substrate adhesive resin 100: Water catching material 110: ACF
120: TCP
130: Conductive particles 140: Driving IC
150: TCP connection wiring 160: TCP polyimide film

Claims (30)

  A laminate for forming a substrate with wiring, comprising: a first conductor layer mainly composed of Al or Al alloy on the substrate; and a Ni—Mo alloy as a major component on the first conductor layer. And a laminated body provided with a cap layer.   The laminate according to claim 1, comprising an ITO layer and a base layer in this order from the substrate side between the first conductor layer and the substrate.   The laminate according to claim 2, wherein the main component of the underlayer is Mo or Mo alloy.   The laminate according to claim 2 or 3, wherein the underlayer contains NiMo as a main component and includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon.   The laminate according to claim 2, 3 or 4, wherein the Ni content in the underlayer is 20 to 90 mass% with respect to all components, and the Mo content is 10 to 80 mass% with respect to all components. .   The laminate according to claim 1, 2, 3, 4, or 5, wherein a Ni diffusion preventing layer not containing Ni is provided between the first conductor layer and the cap layer.   The laminate according to claim 6, wherein the Ni diffusion preventing layer contains Mo as a main component and does not contain Ni.   The laminate according to claim 6 or 7, wherein the Ni diffusion preventing layer is MoNb, MoTa, MoV, or MoW.   The conductive material of the Ni diffusion preventing layer contains Mo and Nb or Ta, the Mo content is 80 to 98% by mass, and the Nb or Ta content is 2 to 20% by mass. The laminate according to 7 or 8. The laminate according to any one of claims 1 to 9, wherein the cap layer includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon.
.   The content rate of Ni in a cap layer is 20-90 mass% with respect to all the components, and the content rate of Mo is 10-80 mass% with respect to all the components, The any one of Claims 1-10. Laminated body. An organic EL display element formed by using the laminate according to any one of claims 1 to 11,
On the substrate, a second electrode layer is provided opposite the first electrode layer,
An organic EL layer is disposed between the first electrode layer and the second electrode layer,
An organic EL display element in which a substrate, a first conductor layer, and a cap layer are arranged in this order from the substrate side. A first electrode layer and a second electrode layer facing each other are provided on the substrate,
An organic EL display element in which an organic EL layer is disposed between a first electrode layer and a second electrode layer,
A first conductor layer conductively connected to the first electrode layer is provided;
A cap layer is provided on the upper side of the first conductor layer;
The main component of the first conductor layer is Al or Al alloy,
The organic EL display element whose main component of a cap layer is a Ni-Mo alloy.   The organic EL display element according to claim 13, wherein the cap layer includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon.   The organic EL display element according to claim 13, wherein a Ni diffusion preventing layer not containing Ni is provided between the first conductor layer and the cap layer.   The organic EL display element according to claim 15, wherein the Ni diffusion preventing layer is one selected from MoNb, MoTa, MoV, and MoW.   The organic EL display element according to claim 13, 14, 15, or 16, wherein a base layer containing Mo or an Mo alloy is provided below the first conductor layer.   The organic EL display element according to claim 13, wherein the second electrode layer is an ITO layer. A connection terminal of the organic EL display element for connecting the first electrode layer provided on the base of the organic EL display element and the drive circuit,
A first conductor layer mainly composed of Al or Al alloy, and a cap layer composed mainly of a Ni-Mo alloy on the upper side of the first conductor layer;
A connection terminal of an organic EL display element in which a circuit is configured such that a current is supplied from the drive circuit to the first electrode layer.   The connection terminal of the organic EL display element according to claim 19, wherein the cap layer includes one selected from oxygen, nitrogen, oxygen and nitrogen, oxygen and carbon, or oxygen, nitrogen and carbon.   21. The connection terminal of the organic EL display element according to claim 19, wherein a Ni diffusion preventing layer not containing Ni is provided between the first conductor layer and the cap layer.   The circuit is configured such that a current flows from a plurality of second electrodes to one first electrode, and an instantaneous maximum current flowing to one first electrode layer is 50 mA or more, The connection terminal of the organic EL display element of 20 or 21.   It is a manufacturing method of the laminated body of any one of Claims 1-11, Comprising: The manufacturing method of the laminated body which forms a 1st conductor layer on a base | substrate and forms a cap layer after that.   The method for producing a laminate according to claim 23, wherein a transparent second conductor layer is formed and patterned, and then the first conductor layer is formed.   The method for producing a laminate according to claim 23 or 24, wherein the cap layer is formed by oxidation, nitridation, oxynitridation, oxycarbonization, nitrocarburization, or oxynitrocarburization.   A substrate with wiring, wherein the laminate according to any one of claims 1 to 11 is patterned in a planar shape.   The transparent second conductor layer is formed and patterned, and then a laminated film including the first conductor layer and the cap layer is formed, and then the laminated film is patterned. The manufacturing method of the connection terminal of the organic electroluminescent display element of description. It is a manufacturing method which manufactures the organic EL display element of any one of Claims 12-18,
A transparent second conductor layer is formed on the substrate, a laminated film including the first conductor layer and the cap layer is formed, the second conductor layer is used as the second electrode, and the first conductor layer is formed. A method for manufacturing an organic EL display element, wherein the laminated film is patterned so that the laminated film is used for at least a part of the wiring extending from the wiring to the connection terminal.   A transparent second conductor layer is formed on the substrate and patterned as a second electrode layer. Thereafter, a first conductor layer and a cap layer are formed to form a laminated film, and then the laminated film is formed. The manufacturing method of the organic electroluminescent display element of Claim 28 patterned. An organic EL display element, wherein a drive circuit is connected to the organic EL display element according to any one of claims 12 to 18 and display is performed at a luminance of 100 cd / m ² or more.

Images