TWI576454B - Spraying target for forming wiring film and coating layer for electronic parts - Google Patents

Description

Multilayer wiring film for electronic parts and sputtering target forming sputtering target

The present invention relates to a sputtering target for a laminated wiring film for an electronic component such as a touch panel, and a coating layer for forming a conductive layer covering the laminated wiring film for the electronic component.

In recent years, as a new portable terminal, a smart phone or a tablet computer (Tablet Personal Computer) has been produced, and the new portable terminal is a liquid crystal display (Liquid Crystal) which forms a thin film element on a glass substrate. Display: Hereinafter, a flat panel display device such as an electrophoretic display used in an organic electroluminescence (EL) display or an electronic paper (flat panel display, Flat Panel Display: hereinafter referred to as "FPD") ") It is a combination of a touch panel that can directly manipulate the screen while viewing the screen. In the sensor film which is the position detecting electrode of the touch panel, indium tin oxide (hereinafter referred to as "ITO") is used as a transparent conductive film. Further, in the bridge wiring or the lead wiring, for example, a laminated wiring film in which Mo or a Mo alloy and Al or an Al alloy are laminated is used as a metal wiring film having a lower resistance value (hereinafter referred to as low resistance).

In recent years, LCDs or FPDs used in smart phones or tablet computers are rapidly developing large screens, high definition, and high-speed response year by year. For sensor films and metal wiring films, further reduction is required. Resistance. Therefore, a metal mesh film method in which a metal layer having a lower electric resistance than ITO is formed into a mesh shape has been proposed for the sensor film. As a result of investigating the application of Cu or Ag having a lower electric resistance than Al to the metal mesh film, in addition to the problem of oxidation resistance and adhesion, Cu has a problem as moisture resistance which is one of weather resistance, and thus it is difficult to handle this. A problem. On the other hand, the price of Ag is higher than that of Cu, but it is promising because oxidation resistance or moisture resistance is superior to Cu. However, since Ag has low adhesion to a substrate and is easily peeled off, and it is easy to react with chlorine or sulfur, there is a problem in weather resistance. Therefore, in order to solve the problem unique to Ag, such as adhesion or weather resistance, it has been proposed to coat Ag by a coating layer containing another metal. In addition, in order to reduce the thickness of a smart phone or a tablet, the substrate of the touch panel is also a resin film substrate which is thinner than a glass substrate, and the coating layer also needs to have adhesion to the resin film substrate.

As a method of forming the metal wiring film or the cladding layer, a sputtering method using a sputtering target is most suitable. The sputtering method is one of physical vapor deposition methods, and is a method for easily forming a large area as compared with other vacuum evaporation or ion plating, and is effective in obtaining a film layer having a small variation in composition. method. Further, it is a method in which the thermal influence on the substrate is small and can be applied to the resin film substrate.

The inventors of the present invention have proposed a laminated wiring film in which a conductive layer containing Cu or Ag having low adhesion to glass or the like and a coating layer containing a Mo alloy containing V and/or Nb as a Mo main body are laminated. The low electrical resistance of Cu or Ag is maintained, and corrosion resistance, heat resistance, or adhesion to a glass substrate is improved (see Patent Document 1). This technique is effective as a wiring film of a thin film transistor (TFT) formed on a glass substrate.

Further, the present inventors have proposed an element selected from Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, and W which contains 1 atom% to 25 atom% of Cu, and 1 atom% to 25 atom% of Cu. In addition, a laminated wiring film in which a Ni alloy of a total of 35 atom% or less is laminated on a conductive layer containing Ag or Cu (see Patent Document 2). The coating layer proposed in Patent Document 2 is a technique useful for achieving weak magnetic magnetization by using a Ni alloy to which a predetermined amount of a transition metal such as Ti, V, or Cr is added, and is stable. Film formation by sputtering is performed for a long period of time. [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-140319 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-310814

[Problems to be Solved by the Invention] As described above, in recent years, FPD is rapidly developing in high definition. Therefore, in a touch panel, it is also desired to perform etching processing with a narrow wiring width with high precision. However, dry etching of Cu or Ag as an etching method with high precision is not easy, and therefore wet etching is mainly used. Further, since the resin film substrate has moisture permeability, when formed on a glass substrate, a coating layer laminated with a conductive layer of Cu or Ag is required to have higher weather resistance.

According to the investigation by the inventors of the present invention, in the laminated wiring film in which the conductive layer containing Cu or Ag and the coating layer containing the Mo alloy are laminated, the corrosion may occur on the resin film substrate. The inventors of the present invention have confirmed that the electrode potential of Cu or Ag in the conductive layer is high. Therefore, when Mo is mixed with the electrode potential or the Mo alloy is laminated, Mo or Mo alloy is formed in the resin film having moisture permeability. The battery reacts easily and is corroded, and the reliability under a long period of time has a problem. In addition, the inventors of the present invention have confirmed that when wet etching is performed on a laminated wiring film in which a Ni alloy having an electrode potential close to Cu or Ag is used for a coating layer, etching of the coating layer existing in the surface of the substrate becomes uneven. In the case where the unevenness is likely to occur, the wiring width is deviated, or the amount of side etching is increased, and there is a new problem that it is difficult to stably obtain a wiring film having a narrow width expected in the future.

An object of the present invention is to provide a conductive layer having one selected from the group consisting of low-resistance Ag, Ag alloy, Cu, and Cu alloy, and to ensure adhesion, weather resistance, oxidation resistance, and stable high precision A wet-etched new type of coated wiring layer for electronic parts, and a sputtering target for forming a cladding layer. [Means for solving the problem]

In view of the above-described problems, the present inventors have made an effort to study the alloy composition of a coating layer which is laminated with a conductive layer containing one selected from the group consisting of low-resistance Ag, Ag alloy, Cu, and Cu alloy. As a result, it has been found that by adding a specific element to Ni and optimizing the amount of addition thereof, adhesion, weather resistance, oxidation resistance, and high-precision wet etching can be stably performed. The novel coating layer thus completed the present invention.

That is, the present invention is a laminated wiring film for an electronic component, comprising: a conductive layer including one selected from the group consisting of Ag, an Ag alloy, Cu, and a Cu alloy; and a coating layer covering at least one surface of the conductive layer, the coating The layer contains 5 atom% to 50 atom% of Mo, and the total content contains 60 atom% or less of the Mo and Cu, and the remainder contains Ni and unavoidable impurities. Moreover, it is preferable that the coating layer contains 5 atom% to 25 atom% of the Cu, and a total of 36 atom% or more of the Mo and the Cu. Further, the coating layer preferably contains 26 atom% to 40 atom% of the Mo.

Further, the present invention is an invention of a sputtering target for forming a cladding layer for forming a conductive covering covering one selected from the group consisting of Ag, Ag alloy, Cu, and Cu alloy. The sputtering target of the coating layer of the layer contains 5 atom% to 50 atom% of Mo, and the total content contains 60 atom% or less of the Mo and Cu, and the remainder contains Ni and unavoidable impurities, and the Curie point ( Curie point) is below normal temperature. Further, the sputtering target preferably contains 5 to 25 atom% of the Cu, and a total of 36 atom% or more of the Mo and the Cu. Further, the sputtering target preferably contains 26 atom% to 40 atom% of the Mo. [Effects of the Invention]

The present invention can provide a conductive layer comprising one of Ag, Ag alloy, Cu, and Cu alloy selected from a low resistance, and can ensure adhesion, weather resistance, and high oxidation resistance, and can stably perform high precision A wet-etched coating layer of a novel laminated wiring film for electronic parts and a coating layer for forming a sputtering target. As a result, it is a very useful technique for various electronic components such as a touch panel formed on a resin film substrate or a flexible FPD, and can contribute greatly to stable manufacturing or reliability improvement of electronic components.

An example of a schematic cross-sectional view of the laminated wiring film for an electronic component of the present invention is shown in Fig. 1 . The multilayer wiring film for an electronic component of the present invention includes a conductive layer 3 including one selected from the group consisting of Ag, an Ag alloy, Cu, and a Cu alloy, and a coating layer 2 and a coating layer 4 covering at least one surface of the conductive layer 3. And formed on the substrate 1, for example. In FIG. 1, the cladding layer 2 and the cladding layer 4 are formed on both surfaces of the conductive layer 3. However, the cladding layer 2 and the cladding layer 4 may be formed as a base layer or a cover layer only on the conductive layer 3. On either side, it is suitable for selection. Further, when only one side of the conductive layer is covered by the coating layer of the present invention, the other side of the conductive layer may be covered with a coating layer having a composition different from the present invention in accordance with the use of the electronic component.

An important feature of the present invention is that it is found in the coating layer of the laminated wiring film for an electronic component shown in Fig. 1 that a specific amount of Ni, Mo, or Cu is added to ensure adhesion, weather resistance, and resistance. Oxidizing property, and it is difficult to produce an uneven coating layer during wet etching. Hereinafter, the wiring film for electronic parts of the present invention will be described in detail. In the following description, "adhesiveness" refers to the difficulty in peeling off the coating layer, the glass substrate, and the resin film substrate, or the difficulty in peeling off the conductive layer and the coating layer, and can be peeled off by the adhesive tape. To evaluate. The term "weather resistance" refers to the difficulty of deterioration of electrical contact properties caused by surface deterioration in a high-temperature and high-humidity environment, and can be confirmed by discoloration of the wiring film, and can be quantitatively evaluated by, for example, reflectance. . In addition, the term "oxidation resistance" refers to the difficulty of deterioration of electrical contact properties of surface oxidation during heating in an environment containing oxygen, and can be confirmed by discoloration of the wiring film, for example, by reflectance. To quantitatively evaluate.

The present invention is characterized in that the conductive layer containing one selected from the group consisting of Ag, Ag alloy, Cu, and Cu alloy and the coating layer covering at least one surface of the conductive layer contain 5 atom% to 50 atom% of Mo, Further, Cu is contained in a total amount of 60 atom% or less, and the remainder contains Ni and unavoidable impurities. Ni which is one of the main elements is an element which has high adhesion to a glass substrate, ITO which is a transparent conductive film, an oxide which is an insulating protective film, etc., and is excellent in weather resistance and oxidation resistance, compared with Cu or Ag. Further, by coating a conductive layer containing one selected from the group consisting of Ag, an Ag alloy, Cu, and a Cu alloy, an element having an effect of improving adhesion, weather resistance, and oxidation resistance can be obtained. However, Ni cannot be etched by an etchant for Cu or Ag, and therefore it is necessary to improve etching properties. In the present invention, Mo and Cu, which are elements other than Ni contained in the coating layer, have an effect of improving the etching rate for an etchant for Cu or Ag. If the content is increased, the improvement effect can be further improved. In addition, when the total content exceeds 60 atom%, the moisture resistance originally possessed by Ni is largely lowered. Therefore, the total of Mo and Cu is set to 60 atom% or less.

Mo is an element which has a solid solution region in a high temperature region with respect to Ni and which can easily form an alloy with Ni. If Mo is contained in the coating layer, the effect of improving the adhesion and the etching rate is improved, and the uniformity is also greatly improved. Further, Mo is an element having an effect of also improving oxidation resistance, and is an element which cannot be lacked in the present invention. The improvement effect is exhibited when it contains 5 atom% or more, and becomes more clear when it is 15 atom% or more. On the other hand, when Mo is contained in an amount of more than 50 atom%, the moisture resistance which is one of the weather resistance is drastically lowered. Therefore, in the present invention, Mo is contained in the coating layer in a range of 5 atom% to 50 atom%. In addition, the effect of improving the uniformity of etching is remarkable when the content of Mo is 15 atom% or more. However, in order to improve etching unevenness with respect to an etchant of both Cu and Ag which become a conductive layer, it is more preferable to use Mo. The content is set to be 26 atom% or more. On the other hand, when Mo is contained in an amount of more than 40% by atom, residue may be easily generated during etching due to the type of the etchant. Therefore, the Mo contained in the coating layer is more preferably from 26 atom% to 40 atom%.

When Cu is added to the coating layer of the laminated wiring film for electronic parts of the present invention, the effect of improving the etching rate can be obtained. The effect of the improvement is clear when the content of Cu is 5 atom%. However, when Cu is contained in an amount of more than 25 atom%, the oxidation resistance is lowered in addition to the adhesion, and the etchant is easily wetted, so that it exists. The amount of side etching increases and the etching accuracy decreases. Further, when Cu is contained in the coating layer in an amount of more than 25 atom%, the etching rate may be lowered in particular in the etchant of Ag. Therefore, in the present invention, it is preferred that the Cu contained in the coating layer be in the range of 5 atom% to 25 atom%. In addition, in order to suppress the etching rate of Ag or Cu which is a conductive layer to be laminated with respect to the etchant of both Cu and Ag, high-precision etching is performed, and it is more preferable to set the total of Mo and Cu to 36. More than atomic %. In addition, when the content of Cu is larger than the content of Mo, the effect of improving the oxidation resistance, the adhesion, and the uniformity during etching of Mo may not be sufficiently obtained. Therefore, the content of Cu is preferably less than the content of Mo, more preferably 0.7 times or less the content of Mo. In addition, the coating layer of the laminated wiring film for electronic components of the present invention may be substituted for a part of Ni, Mo, and Cu by one or more elements selected from the group consisting of Ti, V, Nb, Ta, Cr, and W. These elements are elements having a high effect of improving weather resistance, and on the other hand, if excessively added, the etching rate may be lowered. Therefore, the substitution amount of these elements is preferably in the range of 1 atom% to 5 atom% in total.

In order to stably obtain low electrical resistance, weather resistance, or oxidation resistance, the laminated wiring film for electronic components of the present invention preferably has a thickness of a conductive layer containing one selected from the group consisting of Ag, Ag alloy, Cu, and Cu alloy. 100 nm to 1000 nm. If the film thickness of the conductive layer is thinner than 100 nm, the resistance value is likely to increase due to the influence of scattering of electrons unique to the film. On the other hand, when the film thickness of the conductive layer is thicker than 1000 nm, it takes time to form a film, or warpage is likely to occur in the substrate due to film stress. The film thickness of the conductive layer is more preferably in the range of 200 nm to 500 nm. In the conductive layer of the present invention, it is preferable to obtain pure Ag or pure Cu having a low electric resistance value, but in addition to the weather resistance or oxidation resistance, in consideration of reliability such as heat resistance or corrosion resistance, it may be used. An Ag alloy or a Cu alloy obtained by adding a transition metal or a semimetal or the like to Ag or Cu. In this case, in order to obtain a low electric resistance as much as possible, it is preferable to add it in a total amount of 5 atom% or less.

In order to stably obtain low electrical resistance, weather resistance, or oxidation resistance, the laminated wiring film for an electronic component of the present invention preferably has a thickness of the coating layer of 10 nm to 100 nm. When the coating layer is used as the underlayer, the adhesion to the substrate can be improved by setting the film thickness to 10 nm or more. In addition, when the coating layer is used as the coating layer, the film thickness is 20 nm or more, and the disappearance of defects or the like of the coating layer is sufficient, and weather resistance or oxidation resistance can be improved. On the other hand, when the film thickness of the coating layer exceeds 100 nm, the electric resistance value of the coating layer becomes high, and when laminated with the electrically conductive layer, it is difficult to obtain a low electric resistance as a laminated wiring film for an electronic component. Therefore, the film thickness of the coating layer is more preferably set to 20 nm to 100 nm.

In forming each layer of the build-up wiring film for an electronic component of the present invention, a sputtering method using a sputtering target is most suitable. When the coating layer is formed, for example, a method of forming a film using a sputtering target having the same composition as that of the coating layer, or using a sputtering target of each element and cosputtering is used. A method of forming a film. Further, a method of forming a film by co-sputtering using a sputtering target such as a Ni-Mo alloy or a Ni-Cu alloy may be applied. From the viewpoint of the ease of setting the conditions of the sputtering or the fact that the coating layer of the desired composition is easily obtained, it is more preferable to use a sputtering target having the same composition as that of the coating layer to perform sputtering. Further, in the sputtering method, in order to perform efficient and stable sputtering, it is necessary to set the non-magnetic, that is, the Curie point to a normal temperature or lower at a normal temperature using a sputtering target. In addition, the "Curie point is below normal temperature" means that it is non-magnetic when the magnetic properties of the sputtering target are measured at normal temperature (25 ° C). Since Ni which is one component of the sputtering target forming target of the present invention is a magnetic material, in order to perform efficient and stable sputtering, it is necessary to adjust the type and addition of the additive element so that the Curie point becomes below normal temperature. the amount.

In the sputtering target for forming a coating layer of the present invention, Mo which is a non-magnetic element has the highest effect of lowering the Curie point of Ni as a magnetic material, and when 8 atom% of Mo is separately added to Ni, The Curie point becomes below normal temperature. However, as described above, in the characteristics of the coating layer, when the amount of Mo added is 5 atom% for the purpose of ensuring adhesion, etching property, or oxidation resistance, in order to make the Curie of the sputtering target The point becomes below normal temperature, and the content of Cu is set to 15 atom% or more. Further, Ni dissolves about 30 atom% of Mo in a high temperature region, and the amount of solid solution decreases in a low temperature region. In addition, when the amount of Mo added exceeds 30 atom%, the compound phase appears. As an alloy phase of Ni and Mo, when the amount of Mo added exceeds about 50 atom%, the compound phase becomes a main component and the ductility or toughness decreases. It is brittle and difficult to perform stable machining. Further, in the characteristics of the coating layer, when the amount of Mo added exceeds 50 atom%, the weather resistance may be greatly lowered. Therefore, in the present invention, the upper limit of the amount of addition of Mo is set to 50 atom%. Further, Cu is an element which is completely dissolved in Ni, and the effect of lowering the Curie point is lower than Mo. When Cu is added to Ni in an amount of about 30 at%, the Curie point becomes below normal temperature. However, as described above, in order to secure oxidation resistance or adhesion in the characteristics of the coating layer, the amount of Cu added is preferably in the range of 5 atom% to 25 atom%.

According to the above, the sputtering target forming sputtering target material contains 5 atom% to 50 atom% of Mo, and the total content contains 60 atom% or less of the Mo and Cu, and the balance contains Ni and unavoidable impurities. , set the Curie point below normal temperature. Thereby, the sputtering target forming sputtering target of the present invention can stably sputter the coating layer. In addition, the more the type and amount of the added element, the more the amount of the compound phase in the sputtering target increases, and the more likely the damage occurs during machining or joining in the production of a large-sized sputtering target required for FPD applications. . Further, Mo and Cu added in the present invention are elements which are phase-separated, and if the content of both Mo and Cu exceeds a certain fixed amount, phase separation may be easily performed, and it is difficult to obtain a uniform alloy, and the sputtering target is also required. The material is easily broken. Therefore, the total content of Mo and Cu in the sputtering target of the present invention is 60 atom% or less.

In the method for producing a sputtering target for forming a coating layer of the present invention, for example, a method or a powder for producing a sputtering target by subjecting an ingot prepared by melting a raw material adjusted to a predetermined composition to a sputtering target may be applied. Sintering method. In the powder sintering method, for example, a alloy powder can be produced by a gas atomization method as a raw material powder, or a mixed powder obtained by mixing a plurality of alloy powders or pure metal powders as a final composition of the present invention as a raw material powder. As the sintering method of the raw material powder, pressure sintering such as hot isostatic pressing, hot pressing, spark plasma sintering, or extrusion sintering can be used. In the present invention, since the amount of addition of Mo or Cu is large and the plastic workability is lowered, in order to stably produce a large-sized sputtering target for FPD, it is preferable to carry out pressure sintering of an alloy powder having a specific composition. method. In addition, since Ni is contained as a magnetic material, it is preferable to select an element to be added, and to press-sinter the alloy powder having a Curie point of a normal temperature or lower. The alloy powder having a Curie point below normal temperature can be easily obtained by an atomization method using a Ni alloy adjusted to a final composition. Alternatively, the melted ingot may be pulverized to produce an alloy powder. Further, a method of producing various alloy powders and mixing them in a final composition can also be applied. Further, if the average particle diameter of the alloy powder is less than 5 μm, impurities in the obtained sputtering target increase. On the other hand, if the average particle diameter of the alloy powder exceeds 300 μm, it is difficult to obtain a sintered body having a high density. Therefore, the average particle diameter of the alloy powder is preferably set to 5 μm to 300 μm. Further, the average particle diameter described in the present invention is represented by a sphere equivalent diameter obtained by a light scattering method using laser light as defined in JIS Z 8901.

The sputtering target forming sputtering target of the present invention preferably has a small content of unavoidable impurities other than Ni, Mo, and Cu as a main constituent element, and may contain oxygen, nitrogen, and the like insofar as the effects of the present invention are not impaired. Inevitable impurities such as carbon, Fe, Al, and Si. Here, each of the main constituent elements is represented by the atomic % with respect to the entire main constituent element, and the unavoidable impurities other than the main element are represented by the mass ppm in the entire target. For example, oxygen and nitrogen are each 1000 ppm by mass or less, carbon is 200 ppm by mass or less, Al and Si are 100 ppm by mass or less, and the purity other than the gas component is preferably 99.9% by mass or more. [Example 1]

First, a sputtering target for forming a coating layer is formed. The composition of the produced coating layer is shown in Table 1. In addition, the sputtering target of No. 4 to No. 10 is obtained by weighing electrolytic Ni and a block of Mo raw material and oxygen-free copper into a predetermined amount, and then casting by a melting and melting furnace by a melting and melting method. ingot. In addition, Ni-30 atom% Cu, Ni-35 atom% Cu-3 atom% Ti, and Ni-8 atom% Mo which are No. 1 to No. 3 of the comparative example are similarly vacuum-deposited by electrolysis. Ni was weighed to a predetermined amount with a block of Mo raw material and oxygen-free copper, and then an ingot was produced by a melt-melting furnace using a vacuum melting furnace. The SmCo magnet was brought close to the obtained ingot of each alloy, and as a result, it was confirmed that it did not adhere to the magnet. In addition, a part of the ingot obtained above was placed in a box for measuring magnetic properties, and a vibrating sample type magnetometer (model: VSM-5) manufactured by Riken Electronics Co., Ltd. was used at room temperature (25 ° C). The magnetic properties were measured and the results were confirmed to be non-magnetic. Further, a sputtering target of Mo-30 at% Ni was produced by a powder metallurgy method. In this method, Mo powder having an average particle diameter of 6 μm is mixed with Ni powder having an average particle diameter of 100 μm, and after being filled in a can made of mild steel, the mixture is vacuum-exhausted while being heated, and then sealed. Then, the sealed can was placed in a hot isostatic pressing apparatus, and sintered at 1100 ° C, 100 MPa, and 3 hours to prepare a sintered body. Further, a sintered body of pure Mo was also produced by the same method.

Each of the ingots and the sintered bodies obtained above were machined to prepare a sputtering target having a diameter of 100 mm and a thickness of 5 mm. In addition, the sputter target of pure Ag was prepared to have a purity of 4 N manufactured by Mitsubishi Materials Co., Ltd. In addition, a pure Cu sputtering target is prepared by machining a plate containing oxygen-free copper having a purity of 4 N. Then, each of the sputtering targets was welded to a support plate made of copper, and then mounted on a sputtering apparatus (model: CS-200) manufactured by ULVAC Co., Ltd. in an Ar environment at a pressure of 0.5 Pa. The sputtering test was carried out under the condition of 500 W of electric power, and as a result, any of the sputtering targets was sputtered.

A 25 mm × 50 mm glass substrate (product number: EagleXG) manufactured by Corning Co., Ltd. was attached to a substrate holder of the sputtering apparatus to form a coating layer having a thickness of 100 nm, and adhesion and etching properties were evaluated. Further, No. 11 and No. 13 were formed by a co-sputtering method in which a sputtering target of Mo and Ni-30 at% Cu was simultaneously sputtered. No. 12 was formed by co-sputtering Mo-30 atom% Ni and Ni-30 atom% Cu, and the composition shown in Table 1 was an inductively coupled plasma luminescence analyzer manufactured by Shimadzu Corporation. (Inductively Coupled Plasma, ICP) (Model: ICPV-1017) A value obtained by analyzing the formed coating layer.

The evaluation of the adhesion was carried out by the method specified in JIS K 5400. First, a transparent adhesive tape (product name: transparent beauty) manufactured by Sumitomo 3M Co., Ltd. was attached to the surface of the above-mentioned coating layer, and a 2 mm square grid was formed by a cutter, and then a transparent adhesive tape was used. Peel off and evaluate with the presence or absence of a coating layer. One of the grids in which the coating layer was not peeled off was evaluated as ○, and one of the grids to 10 grids was evaluated as Δ, and those having 11 or more grids were evaluated as ×. In the evaluation of the etching property, nitric acid, phosphoric acid, acetic acid, and water were mixed and used as an etchant for Ag. The etchant for Cu is Cu02 manufactured by Kanto Chemical Industry. In order to form a coating layer having less side etching, it is necessary to suppress uneven etching time, reduce over-etching time, and moderately suppress wettability to an etchant. Each sample was immersed in an etching solution, and the time taken until the entire surface of the coating layer was completely transmitted was measured as an appropriate etching time. Further, at the same time, the etching unevenness was visually confirmed, and in order to form a clearer difference, the time difference between the time when a part of the film was transmitted and the appropriate etching time was measured. The smaller the time difference, the less the etching unevenness. Separately, 20 μl of an etchant was added dropwise to the surface of the film, and the diameter expansion after 2 minutes was measured. The smaller the diameter is, the more the side etching can be suppressed, and the higher the precision etching can be performed.

[Table 1]

As shown in Table 1, the adhesion of Sample No. 1, Sample No. 2, and Sample No. 4 was low. Further, it was found that Sample No. 3 improved the adhesion by containing 8 atom% of Mo, but an appropriate amount of etching time was long. On the other hand, it was confirmed that the coating layer of the present invention contains a specific amount of Mo and Cu in Ni, and the adhesion is greatly improved. Further, regarding the etching property, it is understood that the coating layers of the sample No. 1 and the sample No. 2 can be etched by the etching agent of Cu within 2 minutes, but if it is an Ag etchant, it takes 18 minutes or more. Not suitable. Further, it is understood that there is a portion which is etched fast and a portion which is slow, and etching unevenness occurs, so that the time difference is large and the etchant is easily spread. Therefore, it is understood that it is difficult to perform uniform etching, and it is not suitable for etching with high precision. In addition, in the composition in which the Mo content of the sample No. 13 and the sample No. 14 exceeded 50 atom%, the generation of the residue was confirmed after the etching. On the other hand, it was confirmed that the coating layers of Sample No. 5 to Sample No. 12 of the present invention were etched in an etchant of both Cu and Ag for 90 seconds or less. In addition, it is confirmed that the coating layer of sample No. 8 to sample No. 12 increases the amount of Mo added, and the total amount of Mo and Cu is 36 atom% or more, and the appropriate etching time is shortened, and the time difference is obtained. The diameter is also reduced, and etching unevenness and side etching are small, so that high-precision etching can be performed. [Embodiment 2]

Evaluation of oxidation resistance was performed. Each sample was heat-treated at 150 ° C, 250 ° C, 300 ° C, and 350 ° C for 30 minutes in an atmospheric environment, and the reflectance and the resistance value were measured. The reflectance was measured using a spectrophotometer (model: CM2500d) manufactured by Konica Minolta Co., Ltd., and the resistance value was a four-terminal thin film resistivity meter manufactured by DIA Instruments. (Model: MCP-T400) to measure. Using the sputtering targets prepared in Example 1, a substrate having a film thickness of 30 nm, a Cu conductive layer having a film thickness of 300 nm, and a film thickness of 50 nm were prepared in the composition shown in Table 2. A sample of a laminated wiring film formed by sequentially coating a film on a glass substrate. Furthermore, the base layer and the cover layer are composed of the material of the cover layer of Table 2.

[Table 2]

As shown in Table 2, it was confirmed that the oxidation resistance can be greatly improved by using the coating layer of the present invention. On the film substrate, oxidation resistance from the heat resistant temperature of the film to 250 ° C is required. As shown in Table 2, in the sample No. 4, the reflectance at 250 ° C or higher began to decrease. However, the laminated wiring film for electronic components of the present invention maintains a high reflection of 50% or more even after heating at 250 ° C in the atmosphere. Rate, and has high oxidation resistance. In particular, it was confirmed that the effect is large if the amount of addition of Mo is increased. In addition, it has been confirmed that the laminated wiring film for an electronic component of the present invention is heated at 250 ° C, 300 ° C, and 350 ° C, and the increase in the resistance value is suppressed, and the oxidation resistance can be improved. [Example 3]

Then, the laminated wiring film for each electronic component of Example 2 was used to evaluate the weather resistance. The weather resistance was measured by placing the laminated wiring film for each electronic component in an environment of a temperature of 85 ° C and a relative humidity of 85% for 100 hours, 200 hours, and 300 hours, and then measuring the reflectance in the same manner as in the second embodiment. Further, the base layer and the cover layer shown in Table 3 are those of the cover layer material of Table 3.

[table 3]

As shown in Table 3, in the sample No. 13 and the sample No. 14 which were comparative examples, since the content of Mo exceeded 50 atom%, the reflectance decreased with the passage of time. On the other hand, it was confirmed that the laminated wiring film for electronic components of Sample No. 5 to Sample No. 12 which is an example of the present invention does not discolor even when exposed to a high-temperature and high-humidity environment, and remains high after 300 hours. Reflectivity and high moisture resistance. As described above, it has been confirmed that by using the laminated wiring film for an electronic component of the present invention, adhesion to the conductive layer, oxidation resistance, and weather resistance can be ensured, and stable wet etching can be performed. [Example 4]

Then, using the sputtering target prepared in Example 1, a base layer having a film thickness of 30 nm and an Ag conductive layer having a film thickness of 200 nm and a film thickness of 30 were prepared in the composition shown in Table 4. The coating layer of nm is a sample of a laminated wiring film formed by sequentially forming a film on a film substrate or a glass substrate with an ITO film. Furthermore, the base layer and the cover layer are composed of the material of the cover layer of Table 4. The evaluation of the adhesion was carried out by attaching a transparent adhesive tape (product name: transparent beauty) manufactured by Sumitomo 3M Co., Ltd. to the laminated wiring film, rubbing the surface with an eraser, and then peeling off the transparent adhesive tape, and evaluating the presence or absence of the coating layer. Remaining. The uncoated layer was evaluated as ○, about 10% of the flaking was evaluated as Δ, and 20% or more of the flaking was evaluated as ×. Unlike Ag, the Ag does not greatly increase the electric resistance value even when heated at 350 ° C in the atmosphere. Therefore, in the same manner as in the second embodiment, Ag is 150 ° C, 250 ° C, and 350 ° C in the atmosphere. Each sample was subjected to heat treatment for 30 minutes, and the reflectance was measured. In addition, in the same manner as in Example 3, the weather resistance was measured by allowing each sample to stand in an environment of a temperature of 85 ° C and a relative humidity of 85% for 100 hours, 200 hours, and 300 hours.

[Table 4]

As shown in Table 4, the adhesion of the sample No. 4 was low. On the other hand, it is understood that Sample No. 5 to Sample No. 12 which are examples of the present invention are improved in adhesion by the content of Mo, and in particular, Sample No. 8 to Sample having a Mo content of 22 at% or more. In No. 12, high adhesion was obtained. Further, when heat resistance is performed at 350 ° C, wrinkles are generated in the film substrate. In addition, when Ag was used as the conductive layer, it was confirmed that the sample which is an example of the present invention suppresses discoloration of the Ag conductive layer by high oxidation resistance during heating up to 250 °C. Further, regarding the weather resistance, it was confirmed that the sample which is an example of the present invention suppresses discoloration of the Ag conductive layer by high weather resistance.

1‧‧‧Substrate
2‧‧‧coating layer (base layer)
3‧‧‧ Conductive layer
4‧‧‧coating (covering)

1 is an example of a schematic cross-sectional view of a laminated wiring film for an electronic component according to the present invention.

1‧‧‧Substrate

2‧‧‧coating layer (base layer)

3‧‧‧ Conductive layer

4‧‧‧coating (covering)

Claims (6)

A laminated wiring film for an electronic component, comprising: a conductive layer containing one selected from the group consisting of Ag, an Ag alloy, Cu, and a Cu alloy; and a coating layer covering at least one surface of the conductive layer, the coating The layer contains 5 atom% to 50 atom% of Mo, and the total content contains 60 atom% or less of the Mo and Cu, and the remainder contains Ni and unavoidable impurities. The laminated wiring film for electronic components according to the first aspect of the invention, wherein the coating layer contains 5 atom% to 25 atom% of the Cu, and a total of 36 atom% or more of the Mo and the Cu. The laminate wiring film for an electronic component according to the above aspect of the invention, wherein the coating layer contains 26 atom% to 40 atom% of the Mo. A sputtering target forming sputtering target, which is a sputtering target for forming a coating layer covering a conductive layer containing one selected from the group consisting of Ag, Ag alloy, Cu, and Cu alloy, characterized in that it contains 5 atom% to 50 atom% of Mo, and a total of 60 atom% or less of said Mo and Cu are contained, and the remainder contains Ni and unavoidable impurities, and the Curie point is normal temperature or less. The sputtering target forming sputtering target according to claim 4, which contains 5 atom% to 25 atom% of the Cu, and a total of 36 atom% or more of the Mo and the Cu. The sputtering target forming sputtering target according to claim 4, wherein the coating layer contains 26 atom% to 40 atom% of the Mo.