TW201715054A - Laminated wiring film for electronic components and sputtering target material for forming coating layers the new coating layer ensures sealing ability, corrosion resistance, and oxidation resistance while stably performing high-precision wet etching. - Google Patents

Abstract

The present invention provides a laminated wiring film for electronic components and sputtering target material for forming coating layers, the multilayer wiring film for electronic components comprising: a conductive layer comprising aluminum or aluminum alloy; a coating layer covering at least one surface of the conductive layer has a new coating layer, in which the new coating layer can ensure adhesion, corrosion resistance, and oxidation resistance while stably performing high-precision wet etching. The laminated wiring film for electronic components comprises a conductive layer comprising aluminum or aluminum alloy and a coating layer covering at least one surface of the conductive layer, in which the above-mentioned coating layer comprises 30~75 atom percent of Nickel and one or more elements selected from manganese and copper, and the remainder comprises molybdenum and inevitable impurities; and a sputtering target material for forming coating layers which comprises 30~75 atom percent of Nickel, one or more elements selected from manganese and copper, and the remainder comprising molybdenum and inevitable impurity.

Description

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

The present invention relates to, for example, a laminated wiring film for an electronic component that can be applied to a touch panel or the like, and a sputtering target for forming a coating layer covering the conductive layer of the laminated wiring film for the electronic component.

In recent years, the smart phone (smartphone) and the tablet PC (tablet personal computer), which are new type of portable terminal devices, have been commercialized, and the above-mentioned new portable terminal device forms a liquid crystal display of a thin film device on its glass substrate ( Liquid Crystal Display: hereinafter referred to as "LCD"), organic electroluminescence display (organic electroluminescence display), or flat display device such as electrophoretic display for electronic paper (flat panel display): A touch panel is incorporated in the "FPD", which can directly manipulate the screen while viewing its screen. In the sensing film which is the position detecting electrode of the touch panel, indium tin oxide (hereinafter referred to as "ITO") is generally used as the transparent conductive film. Further, in the bridge wire or the traction wire, as the metal wiring film having a lower resistance value (hereinafter referred to as low resistance), for example, Al (aluminum) or an Al alloy which is a conductive layer is used as a coating. A laminated wiring film obtained by laminating pure Mo (molybdenum) or Mo alloy of a layer.

As a method of forming the above-mentioned laminated wiring film, a sputtering method using a sputtering target is most suitable. The sputtering method is one of the physical vapor deposition methods. Compared with other vacuum evaporation or ion plating, the sputtering method can easily form a large-area film and has a small variation in composition, and is an effective method for obtaining an excellent thin film layer. . Further, the sputtering method has little thermal influence on the substrate, and is also applicable to the resin film substrate.

As a method for improving the characteristics of pure Mo, the present inventors have proposed a Mo alloy film in which 3 to 50 atom% of V (vanadium) or Nb (yttrium) is added to Mo, and the corrosion resistance and heat resistance of the Mo alloy film are improved. Moreover, it is excellent in adhesiveness with a board|substrate, and it is low resistance (refer patent document 1). Further, the inventors have also proposed to combine a conductive layer containing Al and a Ni (nickel) alloy as a face-centered cubic lattice structure of a coating layer on a base film, the Ni alloy containing 7 to 30 atom% of a selected from Ti (titanium), Zr (zirconium), Hf (铪), V, Nb, Ta (钽), Cr (chromium), Mo, W (tungsten), Cu (copper), Si (矽), Ge (锗) One or two or more elements can thereby suppress the hillock of Al and improve heat resistance. (Refer to Patent Document 2). The present inventors have further proposed a Mo alloy represented by Mo _{100 - x - y -} Ni _{x -} Ti _y (10 _{≤ x ≤} 30, 3 _{≤ y ≤} 20) on a conductive layer containing Al as a main component. As the coating layer, oxidation resistance and moisture resistance can be improved more than Mo or Mo-Nb. (Refer to Patent Document 3). [Prior Art Document] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. JP-A-2006-280022 (Patent Document 3): JP-A-2006-27956

In order to reduce the thickness of a portable terminal device such as a smart phone or a tablet PC, the substrate of the touch panel is also in such a manner that a resin film substrate which can be further thinned by a glass substrate is used, and the above-mentioned coating layer needs to have Adhesion of the resin film substrate. In addition, an operation panel or a remote control that is a conditioning device for home electric appliances is operated with a wet hand, or an operation panel of an industrial device or an in-vehicle device is operated under high temperature and high humidity, and is compatible with a portable terminal device. More time than use. In particular, since the in-vehicle device is placed outdoors during periods of no operation, and sometimes placed in a high temperature condition or an extremely cold condition for a long period of time, it is required to further improve the high corrosion resistance of the laminated wiring film. On the other hand, in the manufacture of the touch panel described above, the laminated wiring film formed on the substrate may be left in the atmosphere for a long time when it enters the next process. In addition, when a signal cable is attached to a terminal portion of the FPD or the like, it may be heated in the air. Therefore, it is required to improve the oxidation resistance of the laminated wiring film. In addition, with the high definition of the LCD which is a display device, the metal wiring film for a touch panel is also required to have etching property to perform processing with a narrow width and high precision along the display pixels.

According to the study by the present inventors, it has been confirmed that when the Mo-V, the Mo-Nb alloy or the pure Mo of the above-mentioned Patent Document 1 is applied to the coating layer, the adhesion between the coating layer and the flexible substrate and the oxidation resistance are obtained. Insufficient, there is a problem that the surface of the coating layer is discolored by oxidation. In addition, in the case where the grease or salt adhering after contact with a person remains, corrosion may occur in a high-temperature and high-humidity environment for a long period of time, and in particular, long-term reliability related to corrosion resistance is confirmed in the in-vehicle device. There are problems. Further, when the coating layer containing the Ni alloy described in Patent Document 2 is subjected to wet etching to form an elongated wiring or a square spacer, it is easy to cause uneven etching in the substrate surface depending on the added element. Since the wiring width varies, it has been confirmed in recent years that there is a new problem that it is difficult to stably obtain a wiring film having a narrow width. Further, in the case where the build-up wiring film of Patent Document 3 remains in a high-temperature and high-humidity environment in a state of being left in a high-temperature and high-humidity environment, the laminated wiring film of the patent document 3 may be corroded in a high-temperature and high-humidity environment, and in particular, it is confirmed in the in-vehicle device that corrosion resistance is observed. There are problems with regard to long-term reliability related to sex.

[Problem to be Solved by the Invention] An object of the present invention is to provide a laminated wiring film for an electronic component and a sputtering target for forming a coating layer, wherein the laminated wiring film covers at least one of conductive layers containing Al or an Al alloy. A new coating layer is provided on the coating layer, and the new coating layer can stably perform wet etching with high precision while ensuring adhesion, corrosion resistance, and oxidation resistance. [Means for solving the problem]

In view of the above problems, the inventors conducted intensive studies on the alloy composition of a coating layer laminated on a conductive layer containing Al or an Al alloy. As a result, by adding a specific element to Mo, it has been found that a new coating layer capable of stably performing high-precision wet etching while ensuring adhesion, corrosion resistance, and oxidation resistance is completed, thereby completing the present invention. .

In other words, the present invention relates to a laminated wiring film for an electronic component, comprising: a conductive layer containing Al or an Al alloy; and a coating layer covering at least one surface of the conductive layer, wherein the coating The layer contains 30 to 75 atom% of Ni, and one or more elements selected from the group consisting of Mn and Cu, and the remainder contains Mo and unavoidable impurities. The coating layer preferably contains 30 to 75 atom% of the above-mentioned Ni and 3 to 25 atom% of the above-mentioned Mn, and contains the above-mentioned Ni and the above-mentioned Mn in a total amount of less than 80 atom%. The coating layer preferably contains 30 to 65 atom% of the above Ni and 5 to 25 atom% of the above Cu, and contains the above-described Ni and the Cu in a total amount of less than 75 atom%. The coating layer preferably contains the above-mentioned Mn and the above-mentioned Cu in a total amount of 5 to 40% by atom, and contains the above-mentioned Cu, the above-mentioned Mn, and the above-mentioned Ni in a total amount of less than 75 atom%. More preferably, a part of the above-mentioned Mo is substituted with one or more elements selected from the group consisting of Ti, V, Nb, Ta, Cr, and W in a range of 1 to 15 atom% in total.

The present invention relates to a coating target for forming a coating layer for forming a coating layer covering a conductive layer containing Al or an Al alloy in a laminated wiring film for an electronic component, comprising 30 to 30 75 atom% of Ni, and one or more elements selected from the group consisting of Mn and Cu, the remainder containing Mo and unavoidable impurities. The sputtering target formation sputtering target preferably contains 30 to 75 atom% of the above-mentioned Ni and 3 to 25 atom% of the above-mentioned Mn, and contains the above-mentioned Ni and the above-mentioned Mn in a total amount of less than 80 atom%. The sputtering target formation sputtering target preferably contains 30 to 65 atom% of the above-mentioned Ni and 5 to 25 atom% of the above-mentioned Cu, and contains the above-described Ni and the above-mentioned Cu in a total amount of less than 75 atom%. The sputtering target formation sputtering target preferably contains the above-mentioned Mn and the above-mentioned Cu in a total amount of 5 to 40% by atom, and contains the above-mentioned Cu, the above-mentioned Mn, and the above-mentioned Ni in a total amount of less than 75 atom%. More preferably, a part of the above-mentioned Mo is replaced with one or more elements selected from the group consisting of Ti, V, Nb, Ta, Cr, and W in a range of 1 to 15 atom% in total. [Effects of the Invention]

The present invention can provide a novel laminated wiring film for an electronic component obtained by laminating a coating layer and a conductive layer containing Al or an Al alloy, and a sputtering target for forming a coating layer, and the adhesion and corrosion resistance of the coating layer It is excellent in oxidation resistance and can perform high-precision wet etching stably. Thereby, it is a very useful technique for various electronic components, for example, a touch panel formed on a resin film substrate, and contributes greatly to stable manufacturing of electronic components or improvement of reliability.

Fig. 1 shows an example of a schematic cross-sectional view of a laminated wiring film for an electronic component according to the present invention. The build-up wiring film for an electronic component of the present invention has a conductive layer 3 containing Al or an Al alloy, and a coating layer covering at least one surface of the conductive layer 3, for example, formed on the substrate 1. In FIG. 1, when the coating layer (base layer 2, cover layer 4) is formed on both surfaces of the conductive layer 3, only one of the base layer 2 or the cover layer 4 may be formed, and may be appropriately selected. It should be noted that when only one surface of the conductive layer is covered by the coating layer of the present invention, the other surface of the conductive layer may be covered with a coating layer different from the composition of the present invention depending on the use of the electronic component.

An important feature of the present invention is that, in the multilayer wiring film for an electronic component shown in FIG. 1, by adding Ni, Mn, and Cu to Mo, it is found that adhesion, corrosion resistance, and oxidation resistance are ensured. When the wet etching is performed, uneven coating layers are less likely to occur. Next, the laminated wiring film for electronic parts of the present invention will be described in detail. In the following description, "adhesiveness" means difficulty in peeling off from a glass substrate or a resin film substrate, and can be evaluated according to the peeling of the tape used. "Corrosion resistance" refers to the difficulty of deterioration of electrical contact properties due to 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 based on, for example, reflectance. In addition, "oxidation resistance" refers to the difficulty of deterioration of electrical contact property accompanying surface oxidation when heated in an oxygen-containing environment, and can be confirmed based on the discoloration of the wiring film, and can be quantitatively evaluated based on the reflectance, for example.

The present invention is characterized in that the coating layer covering at least one surface of the conductive layer containing Al or an Al alloy contains 30 to 75 atom% of Ni, and one or more elements selected from the group consisting of Mn and Cu, and the remainder contains Mo. And inevitable impurities.

The Mo element contained in the coating layer of the present invention is excellent in electrical contact property, wet etching property, and uniformity with the ITO film as a transparent conductive film, but on the other hand, it is inferior in corrosion resistance and oxidation resistance. In the present invention, in order to ensure corrosion resistance and oxidation resistance, Ni must be 30 atom% or more. On the other hand, when Ni exceeds 75 atom%, Ni is easily thermally diffused into Al of the conductive layer, and the resistance value of the laminated wiring film is increased, and the wet etching property is lowered. Therefore, Ni added to the coating layer of the present invention is 30 to 75 atom%. Further, the Mn element is excellent in adhesion to a glass substrate or a resin film substrate, and the effect of improving wet etching property is good. On the other hand, when the amount of addition of Mn is increased, oxidation resistance is lowered. Further, Cu can improve the adhesion to the ITO film and the wet etching property. On the other hand, when the amount of Cu added is large, the adhesion to the glass substrate is lowered, and the oxidation resistance is also lowered. Further, Cu and Ni are more likely to thermally diffuse into the Al of the conductive layer, and it is easy to increase the resistance value of the build-up wiring film. In addition to Mo and Ni, the coating layer of the present invention contains one or more elements selected from the group consisting of Mn and Cu, thereby ensuring oxidation resistance and also improving adhesion to a glass substrate, a resin film substrate or an ITO film. Sexual and wet etching. Next, the reason for selecting Mn and Cu will be described.

First, a case where Mn is selected as an element added other than Mo or Ni constituting the coating layer of the present invention will be described. The effect of improving adhesion and wet etching property of Mn starts from 3 atom%. On the other hand, when Mn exceeds 25 atom%, oxidation resistance may fall. Therefore, the amount of Mn added to the coating layer is preferably 3 to 25 atom%, and more preferably 7 to 20 atom%. Further, in order to secure the contact property with the ITO film and the uniformity of the wet etching, it is preferable that Ni and Mn are less than 80 atom% in total.

Next, a case where Cu is selected as an element to be added other than Mo or Ni constituting the coating layer of the present invention will be described. The effect of improving the adhesion to the ITO film and the wet etching property of Cu exhibited from 5 atom%. On the other hand, when Cu exceeds 25 atom%, the adhesion to the glass substrate is lowered, the oxidation resistance is also lowered, and the etchant is easily wetted, and the amount of side etching is increased. The etching accuracy sometimes decreases. Therefore, the amount of Cu added to the coating layer is preferably 5 to 25 atom%, and more preferably 10 to 20 atom%. At this time, in consideration of thermal diffusion with Al of the conductive layer, the amount of Ni added is preferably 65 atom% or less. Further, in order to ensure uniformity of wet etching of Mo, it is preferable that Ni and Cu total less than 75 atom%.

Next, a case where Mn and Cu are selected as elements other than Mo and Ni constituting the coating layer of the present invention will be described. When the total amount of Mn and Cu in the coating layer is 5 atom% or more, the adhesion and the wet etching property can be suppressed from being lowered. On the other hand, when the total amount of Mn and Cu of the coating layer exceeds 40 atom%, oxidation resistance and adhesion may be lowered. Therefore, it is preferable that Mn and Cu have a total of 5 to 40% by atom and contain Ni, Mn, and Cu in a total amount of less than 75 atom%. In order to ensure higher wet etching property, the total amount of Mn and Cu is more preferably 20 atom% or more. Further, the total of Ni, Mn, and Cu is more preferably 50 atom% or more. Further, in the coating layer of the present invention, a part of the above Mo may be substituted with one or more elements selected from the group consisting of Ti, V, Nb, Ta, Cr, and W. These selected elements have a good effect of improving corrosion resistance, but sometimes the etching rate is lowered. Therefore, the amount of substitution is preferably in the range of 1 to 15 atom% in total.

In order to stably obtain low resistance, corrosion resistance, and oxidation resistance, the multilayer wiring film for electronic parts of the present invention preferably has a thickness of a conductive layer containing Al or an Al alloy of 100 to 1000 nm. When the film thickness of the conductive layer is less than 100 nm, the resistance value is likely to increase due to the influence of electron scattering specific to the film. On the other hand, when the film thickness of the conductive layer is more than 1000 nm, it takes time to form a film, or the substrate tends to warp due to film stress. A more preferable range of the film thickness of the conductive layer is 200 to 500 nm. In the conductive layer of the present invention, it is preferable to obtain a low-resistance pure Al. However, in addition to the above-mentioned corrosion resistance and oxidation resistance, reliability such as heat resistance is considered, and a transition metal or a half may be added to Al. An Al alloy such as a metal. At this time, it is preferable that the added elements reach a total of 5 atom% or less in total, so that the lowest possible electric resistance is obtained.

In order to stably obtain low resistance, corrosion resistance, and oxidation resistance, the laminated wiring film for electronic parts of the present invention preferably has a thickness of the coating layer of 10 to 100 nm. When the coating layer is used as the underlayer, the adhesion to the substrate can be improved by making the film thickness 10 nm or more. In addition, when the coating layer is used as a cap film, by making the film thickness 20 nm or more, defects or the like of the coating layer can be sufficiently eliminated, and corrosion resistance and 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 increases, and when laminated with the electrically conductive layer, it is difficult to obtain low electrical resistance as a laminated wiring film for electronic parts. Therefore, the film thickness of the coating layer is more preferably 20 to 100 nm.

In the formation of each layer of the laminated wiring film for electronic parts of the present invention, a sputtering method using a sputtering target is most suitable. In forming the coating layer, a method of forming a film using a sputtering target having the same composition as that of the coating layer, or a sputtering target using each element, or Mo, a Mo-Ni alloy, or Ni may be employed. A method in which a sputtering target such as a Cu alloy or a Ni-Mn alloy is formed by co-sputtering. From the viewpoint of the ease of setting the conditions of the sputtering or the coating layer having a desired composition, it is more preferable to perform sputtering using a sputtering target having the same composition as that of the coating layer.

In order to obtain the coating layer described above, the present invention relates to a sputtering target for forming a coating layer, the sputtering target containing 30 to 75 atom% of Ni, and one or more elements selected from the group consisting of Mn and Cu, and the remainder Contains Mo and unavoidable impurities. In the Mo, Ni, Mn, and Cu which are constituent elements of the present invention, Ni is a magnetic material, but in the composition range of the present invention, the Curie temperature of the sputtering target for forming a coating layer of the present invention (Curie) Since the temperature is below normal temperature (25 ° C), it is non-magnetic, so sputtering can be easily performed by ordinary magnetron sputtering. Further, the coating target forming sputtering target of the present invention preferably contains 30 to 75 atom% of Ni, 3 to 25 atom% of Mn, and contains less than 80 atom% of Ni and Mn in total, and the remainder contains Mo and is inevitable. Impurities. Further, the sputtering target forming sputtering target of the present invention preferably contains 30 to 65 atom% of Ni and 5 to 25 atom% of Cu, and the total of Ni and Cu is less than 75 atom%, and the remainder contains Mo and unavoidable impurities. . In addition, the sputtering target forming target of the present invention preferably contains Mn and Cu in a total amount of 5 to 40% by atom, and contains Ni, Mn, and Cu in a total amount of less than 75 atom%, and the remainder contains Mo and inevitable impurities. . Further, in the sputtering target for forming a coating layer of the present invention, a part of the Mo may be substituted with one or more elements selected from the group consisting of Ti, V, Nb, Ta, Cr, and W. The amount of substitution is preferably in the range of 1 to 15 atom% in total.

In the equilibrium state diagram, the Mo and Ni elements have almost no solid solution zone on the Mo side, but have a wide solid solution zone on the Ni side, and various intermetallic compounds are found in the intermediate composition. Further, the Mo and Mn elements have a wide solid solution region on the Mo side and a wide solid solution region on the Mn side in the high temperature region. The Mo and Cu elements hardly have a solid solution region on the Mo side and the Cu side. Moreover, Ni and Mn, Ni and Cu, Mn and Cu are all elements having a wide solid solution region. Further, Ni and Cu are completely solid-melted, and Ni and Mn, Mn and Cu are also elements which are completely solid-melted in a high temperature region and are easily alloyed, but if Mn is contained, an intermetallic compound is easily found in a low temperature region due to a phase transition. . From the above results, it is understood that the sputtering target for forming a coating layer of the present invention contains Mo and Cu which are not easily alloyed, but can be alloyed depending on the composition by containing Ni or Mn. In the present invention, an optimum manufacturing method of the sputtering target can be selected according to the composition adjusted in accordance with the film characteristics of the necessary coating layer. Next, a method of producing a sputtering target for forming a coating layer of the present invention will be described.

In the method for producing a coating target for forming a coating layer according to the present invention, for example, a method of dissolving a raw material adjusted to a predetermined composition into an ingot may be employed, and the ingot is machined to produce a splash. Plating target; or powder sintering method. In the powder sintering method, for example, an alloy powder can be produced by a gas atomization method as a raw material powder; or a plurality of alloy powders or pure metal powders can be mixed to achieve the final composition of the present invention, and the obtained mixed powder can be used as a raw material. powder. The sintering method of the raw material powder may be pressure sintering using hot hydrostatic pressure press, hot press, spark plasma sintering, extrusion pressurization sintering, or the like. As described above, since the present invention contains Mo and Cu which are not easily alloyed, and an intermetallic compound is likely to occur depending on the composition ratio of Mo and Ni, plastic workability is lowered, so that large-scale sputtering such as a touch panel is stably manufactured. The target is preferably a method for producing a pressure-sintered alloy powder in which a final composition is formed. In addition, since the sputtering target for forming a coating layer of the present invention contains Ni 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 at a normal temperature or lower. At this time, the above alloy powder can easily obtain an alloy metal solution adjusted to the final composition by an atomization method. Further, alloying with Mo by an atomization method is effective for forming an alloy powder having a Curie point below normal temperature. In addition, the alloy powder can also be produced by pulverizing the dissolved ingot. Further, a method of mixing various Ni alloy powders with Mo powder or making various alloy powders and mixing them to achieve a final composition may be employed. If the average particle diameter of the alloy powder is less than 5 μm , impurities in the resulting 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 from 5 to 300 μm . It should be noted that the average particle diameter referred to in the present invention is represented by a sphere equivalent diameter which is obtained by a light scattering method using laser light as defined in JIS Z 8901.

In the coating layer for forming a coating layer of the present invention, it is preferable that the content of unavoidable impurities other than the main constituent elements Mo, Ni, Mn, and Cu is small, and oxygen and nitrogen may be contained in a range that does not impair the effects of the present invention. Inevitable impurities such as carbon, iron (Fe), aluminum (Al), and bismuth (Si). Here, each of the main constituent elements is represented by atomic % with respect to the entire main constituent element, and unavoidable impurities other than the main element are represented by the mass ppm thereof in the entire sputtering target. For example, oxygen and nitrogen are each preferably 1000 ppm by mass or less, carbon is preferably 200 ppm by mass or less, and Al and Si are preferably 100 ppm by mass or less. Further, the purity of the entire metal component in the sputtering target for forming a coating layer of the present invention is preferably 99.9% by mass or more. [Example 1]

First, a sputtering target for forming a coating layer shown in Table 1 was produced. It should be noted that No. 4, No. 5, and No. 8 are weighing electrolytic Ni and bulk Mo raw materials, oxygen-free copper blocks, Mn sheets, and Ti blocks to a predetermined amount, and then using a vacuum melting furnace. The ingot was produced by a melt casting method. Further, No. 1 to No. 3, No. 6, No. 7, No. 9, No. 10, and No. 11 are non-magnetic Ni-30 atom% Mo atomized powder, Mo powder, and Cu. The powder, the Mn powder, and the Ti powder were mixed to obtain a predetermined composition, and filled in a can made of mild steel, and then vacuum-exhausted while heating to perform sealing. Next, the sealed can was placed in a hot hydrostatic pressurizing apparatus, and sintered at 900 ° C, 100 MPa, and 3 hours to prepare a sintered body. When the SmCo magnet was brought close to each of the obtained ingots and the respective sintered bodies, it was confirmed that they did not adhere to the magnet. In addition, each of the obtained ingots and a part of each of the sintered bodies were placed in a magnetic property measuring box, and a vibrating sample magnetometer (model: VSM-5) manufactured by Riken Electronics Co., Ltd. was used at room temperature (25 ° C). When the magnetic properties were measured, it was confirmed that they were non-magnetic. These ingots and sintered bodies were machined into a sputtering target having a diameter of 100 mm and a thickness of 5 mm by mechanical processing. Further, a sputtering target of pure Al for forming a conductive layer was made of a material having a purity of 4 N manufactured by Mitsubishi Material Co., Ltd.

Next, each of the above-described coating layer forming sputtering targets was welded to a copper backing plate, 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. When the sputtering test is performed under a power of 500 W, all the sputtering targets can be sputtered. Next, a 25 mm × 50 mm glass substrate (product number: EagleXG) manufactured by Corning Co., Ltd. was mounted on the substrate holder of the above sputtering apparatus, and a base film having a thickness of 50 nm, an Al conductive layer having a thickness of 300 nm, and a thickness of 50 nm were sequentially formed. The cover layer was used to make a sample, and the adhesion and oxidation resistance were evaluated. Further, regarding the film substrate and the film substrate with the ITO film, samples were also produced in the same manner as the glass substrate. The adhesion was evaluated on a glass substrate in accordance with the method specified in JIS K 5400. First, a square having a side length of 2 mm was inscribed on the surface of the coating layer formed by using a cutter, and a scotch tape (product name: transparent color) manufactured by Sumitomo 3M Co., Ltd. was attached, and the scotch tape was peeled off, depending on whether or not a coating remained. Layers are evaluated. A sample in which one square coating layer was not peeled off was evaluated as ○, a sample in which 1 to 10 square coating layers were peeled off was evaluated as Δ, and a sample in which 11 or more square coating layers were peeled off was evaluated as ×. In the film substrate and the film substrate with the ITO film, a transparent tape (product name: transparent color) was attached to the surface of the film, and then the scotch tape was peeled off, and the sample which was not peeled at all was evaluated as ○, and the area of 10% or less was The peeled sample was evaluated as Δ, and the sample having more than 10% of the area peeled off was evaluated as ×. Further, in the evaluation of oxidation resistance, each sample was subjected to heat treatment in an air atmosphere at a temperature of 150 ° C to 300 ° C for 30 minutes, and the reflectance and the resistance value were measured. The reflectance was measured using a spectrophotometer (model: CM2500d) manufactured by KONICA MINOLTA Co., Ltd. In addition, the resistance value was measured using a four-terminal thin film resistivity meter (model: MCP-T400) manufactured by DIA Instrument. The evaluation results are shown in Table 1.

【Table 1】

As shown in Table 1, the sample No. 1 as a comparative example had low adhesion on a film substrate or a film substrate with ITO, and film peeling occurred. Further, Sample No. 3 as a comparative example was partially peeled off on the glass substrate or the film substrate. On the other hand, it has been confirmed that the laminated wiring film of Sample No. 4 to No. 9 in which a coating layer containing a predetermined amount of Ni, Mn, and Cu is contained in Mo is not peeled off in the base film. Has a high adhesion. Further, it was found that Sample No. 2, No. 3, No. 10, No. 11, No. 12, No. 14, and No. 17 which are comparative examples have a low reflectance at 250 ° C or higher and poor oxidation resistance. Further, when samples No. 3, No. 10, No. 11, and No. 17 were heated at 300 ° C, the resistance value increased. On the other hand, in samples No. 4 to No. 9, No. 13, No. 15, and No. 16 which are examples of the present invention, the decrease in reflectance and the increase in resistance value were small and high. Oxidation resistance. [Embodiment 2]

Next, the corrosion resistance was evaluated using each sample produced in Example 1. In the evaluation of the corrosion resistance, each sample was allowed 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, and the reflectance was measured in the same manner as in Example 1. The results are shown in Table 2.

【Table 2】

As shown in Table 2, it was confirmed that when the samples No. 1 to No. 3, No. 12, No. 14, and No. 17 as comparative examples were allowed to stand in a high-temperature and high-humidity environment for 100 hours or more, the reflectance was greatly lowered. Poor corrosion resistance. On the other hand, it was confirmed that samples No. 4 to No. 9, No. 13, No. 15, and No. 16 which are examples of the present invention have little discoloration even when exposed to a high-temperature and high-humidity environment, and are maintained after 300 hours. High reflectivity with high corrosion resistance. [Example 3]

Next, using the sputtering target for forming a coating layer prepared in Example 1, a single layer film of the coating layer was formed on the glass substrate, and the wet etching property was evaluated. The etchant uses an etchant obtained by mixing nitric acid, phosphoric acid, acetic acid, and water for the Al film. 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 etchant solution, and the time taken until the entire surface of the coating layer was completely transmitted was measured as an appropriate etching time. Further, the etching unevenness was visually confirmed, and the time difference between the time when a part of the film was transmitted and the appropriate etching time was measured to determine a more clear difference. The smaller the time difference, the less the etching unevenness. Further, an etchant of 20 μm was dropped on the surface of the film of the coating layer, and the diffusion diameter after 2 minutes was measured. The smaller the diffusion diameter, the more the side etching can be suppressed, which means that high-precision wet etching can be performed. The evaluation results of the wet etching of each sample are shown in Table 3.

【table 3】

Regarding the wet etching property, the Al film of the sample No. 11 as a comparative example was less diffused at 200 seconds, and uniform etching occurred. On the other hand, the sample No. 1 as a comparative example was blistered, but it was etched in a short time of 35 seconds. Further, in the sample No. 10 as a comparative example, it was confirmed that the etching time was as long as 156 seconds as compared with the other coating layers, and there was a portion where etching was fast and a portion where etching was slow, and etching unevenness occurred, so the time difference was also Large, the etchant is easy to spread. Therefore, it is understood that it is difficult to perform uniform etching, and it is not suitable for etching with high precision. On the other hand, samples No. 4 to No. 9, No. 13, No. 15, and No. 16 which are examples of the present invention were able to be wet-etched within 75 seconds, and the time difference was small, and the diffusion diameter was also small. From the above results, it was confirmed that the coating layer of the present invention has less etching unevenness and side etching, and it is possible to perform etching with high precision.

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

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

1‧‧‧Substrate

2‧‧‧ basal layer (coating layer)

3‧‧‧ Conductive layer

4‧‧‧ Covering layer (covering layer)

Claims (10)

A laminated wiring film for an electronic component comprising: a conductive layer containing a layer of Al or an Al alloy, and a coating layer covering at least one surface of the conductive layer, the laminated wiring film for an electronic component characterized by: the coating The layer contains 30 to 75 atom% of Ni, and one or more elements selected from the group consisting of Mn and Cu, and the remainder contains Mo and unavoidable impurities. The laminated wiring film for an electronic component according to the first aspect of the invention, wherein the coating layer contains 30 to 75 atom% of the Ni, 3 to 25 atom% of the Mn, and contains less than 80 atoms in total. % of said Ni and said Mn. The laminated wiring film for electronic components according to the first aspect of the invention, wherein the coating layer contains 30 to 65 atom% of the Ni, 5 to 25 atom% of the Cu, and contains less than 75 atoms in total. % of the Ni and the Cu. The laminated wiring film for electronic parts according to the above aspect, wherein the coating layer contains the Mn and the Cu in a total amount of 5 to 40% by atom, and the total amount is less than 75 atom%. Cu, the Mn, and the Ni. The laminated wiring film for an electronic component according to any one of the first aspect, wherein the part of the Mo of the coating layer is selected from the group consisting of Ti, V, Nb, Ta, Cr, One or more elements of W are substituted in the range of 1 to 15 atom% in total. A coating layer for forming a coating layer for forming a coating layer covering a conductive layer containing Al or an Al alloy in a laminated wiring film for an electronic component, comprising 30 to 75 atom% of Ni, and selected from the group consisting of More than one element of Mn and Cu, and the remainder contains Mo and unavoidable impurities. The sputtering target for forming a coating layer according to claim 6, wherein the Ni is contained in an amount of 30 to 75 atom%, the Mn is 3 to 25 atom%, and the total amount is less than 80 atom%. The Ni and the Mn. The sputtering target for forming a coating layer according to claim 6, wherein the Ni is contained in an amount of 30 to 65 atom%, and the Cu is contained in an amount of 5 to 25 atom%, and the total amount is less than 75 atom%. The Ni and the Cu. The sputtering target for forming a coating layer according to claim 6, wherein the Mn and the Cu are contained in a total amount of 5 to 40% by atom, and the Cu is contained in a total amount of less than 75 atom%. The Mn and the Ni. The sputtering target for forming a coating layer according to any one of claims 6 to 9, wherein a part of the Mo is selected from the group consisting of Ti, V, Nb, Ta, Cr, and W. The above elements are substituted in the range of 1 to 15 atom% in total.