CN105986233B - Wiring membrane and coating formation sputtering target material is laminated in electronic component-use - Google Patents

Abstract

The present invention provides electronic component-use stacking wiring membrane and coating is formationed sputtering target material, the electronic component-use be laminated wiring membrane with using low-resistance Ag or Cu as conductive layer, the novel coating of high-precision wet etching can be steadily carried out while ensuring adaptation, weatherability, oxidative resistance.A kind of electronic component-use stacking wiring membrane, it includes the coating of conductive layer and a face at least covering the conductive layer made of a kind of in Ag, Ag alloy, Cu and Cu alloys, Mo that the coating contains 5~50 atom %, containing add up to 60 atom % Mo and Cu below, surplus is made of Ni and inevitable impurity；The coating can with the Mo containing 5~50 atom %, containing add up to 60 atom % Mo and Cu below, surplus is made of Ni and inevitable impurity and curie point is formed in room temperature coating formation below with sputtering target material.

Description

Wiring membrane and coating formation sputtering target material is laminated in electronic component-use

Technical field

Wiring membrane is laminated the present invention relates to the electronic component-use that for example can be used for touch panel etc. and is used to form covering The sputtering target material of the coating of the conductive layer of wiring membrane is laminated in the electronic component-use.

Background technology

In recent years, commercialization is realized as smart mobile phone, tablet computer of Novel portable type end etc., is to be glass Liquid crystal display (the Liquid Crystal Display of film apparatus are formed on glass substrate：Hereinafter referred to as " LCD "), be used in The flat display apparatus such as the electrophoresis escope of organic el display, Electronic Paper etc. (flat-panel monitor, Flat Panel Display：Hereinafter referred to as " FPD ") on combination can assign directly operational touch panel while watching its picture Obtained from.It is typically used as transparent conductive film on the sensing membrane as the position detection electrode of these touch panels Indium-tin-oxide (Indium Tin Oxide：Hereinafter referred to as " ITO ").Moreover, on its bridge joint wiring, lead-out wiring, as With lower resistance value (hereinafter referred to as low resistance.) metal line film, used for example be laminated with Mo, Mo alloy and Al, The stacking wiring membrane of Al alloys.

In recent years, LCD, FPD of smart mobile phone, tablet computer etc. etc. is used for year by year in large screen, High precision, high speed Rapidly develop in terms of responseization, further low resistance is required to its sensing membrane and metal line film.Therefore, it was also proposed that will pass Sense film is made the scheme of metal nethike embrane mode etc., the metal nethike embrane make will metal layer more low-resistance than ITO be made it is netted and It obtains.

Being applicable in for Cu, Ag more low-resistance than Al is had studied in the metal nethike embrane, as a result, Cu is in addition to oxidative resistance, close It closes except sex chromosome mosaicism, there are projects in the moisture-proof as one of weatherability, therefore exist and be difficult to handle this problem.Separately On the one hand, Ag ratios Cu is expensive, but because with better than Cu oxidative resistance, moisture-proof due to foreground.

However, Ag is low with the adaptation of substrate, it is easily peeled off, and then easy and chlorine, reaction of Salmon-Saxl, therefore weatherability presence is asked Topic.Therefore, in order to solve project specific to this Ag of adaptation, weatherability, it is proposed that with the covering formed by other metals The scheme of layer covering Ag.

In addition, for the slimming of smart mobile phone, tablet computer etc., the substrate of touch panel can also be used by glass substrate Become the mode using the resin film substrate that can be more thinned, above-mentioned coating also requires closely sealed with resin film substrate Property.

As the method for forming above-mentioned metal line film, coating, the sputtering method using sputtering target material is most appropriate. Sputtering method be physical vapor deposition one kind, compared with other vacuum evaporations, ion plating, be can easily be done large area at The method of film, and be that component fluctuation is few, can get the effective method of excellent film layer.In addition, being the hot shadow to substrate It rings few, it can also be used to the method for resin film substrate.

Present inventors have proposed following schemes：It is made of Cu, the Ag low with the adaptation of glass etc. by being made to be laminated with Conductive layer and the coating made of the Mo alloys using Mo as main body and containing V and/or Nb stacking wiring membrane, to It is able to maintain that low resistance possessed by Cu, Ag, and improves the adaptation of resistance to feeding habits, heat resistance and glass substrate (referring to patent text It offers 1).The technology is effective technology as the wiring membrane for forming TFT on the glass substrate.

In addition, present inventors have proposed a kind of stacking wiring membrane, be on the conductive layer made of Ag, Cu stacking with by Made of coating made of Ni alloys, in the Ni alloys Cu be 1~25 atom %, selected from Ti, Zr, Hf, V, Nb, Ta, Cr, The element of Mo, W are 1~25 atom % and their total addition level is 35 atom % or less (referring to patent document 2.).To this For the coating proposed in patent document 2, by using the Ni alloys of the transition metal such as Ti, V, the Cr for being added to specified amount Weak magnetization is realized, it is stable in the film forming ability based on sputtering method and be for a long time useful technology on this aspect.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2004-140319 bulletins

Patent document 2：Japanese Unexamined Patent Publication 2006-310814 bulletins

Invention content

Problems to be solved by the invention

As noted previously, as the High precision of FPD in recent years rapidly develops, thus it is also desirable that with more in touch panel Narrow wiring width is precisely etched processing.

However, for Cu, Ag, the dry etching not a duck soup for belonging to high-precision etching method is carried out, thus is mainly made Use wet etching.In addition, since resin film substrate has penetrability, thus, for the covering with the stacking of the conductive layer of Cu, Ag For layer, when being formed on glass substrate, it is desirable that higher weatherability.

Through the present inventor's the study found that disclosed in patent document 1 be laminated with the conductive layer made of Cu, Ag and by Mo The stacking wiring membrane of coating made of alloy corrodes on resin film substrate sometimes.The inventors discovered that conductive layer The electrode potential of Cu, Ag are high, thus when the Mo low with electrode potential, above-mentioned Mo alloys are laminated, with penetrability Resin film substrate in, due to cell reaction, Mo, Mo alloy become easy corrosion, and there are problems in long-term reliability.

In addition, the inventors discovered that, to using Ni alloy of the electrode potential closer to Cu, Ag compared with Mo in coating Obtained from stacking wiring membrane when carrying out wet etching, the etching that is present in real estate inner covering layer is inhomogenous, it is uneven to generate, Can exist the case where generating deviation in wiring width or the case where side etching quantity becomes larger and be difficult to steadily obtain institute's phase from now on Narrow wiring membrane this new project of the width that waits for.

The purpose of the present invention is to provide electronic component-use stacking wiring membrane and coating formation sputtering target material, the electricity Subassembly has conductive layer and coating with stacking wiring membrane, and conductive layer is by being selected from low-resistance Ag, Ag alloy, Cu and Cu alloys In one kind be made, coating be can steadily be carried out while ensuring adaptation, weatherability, oxidative resistance it is high-precision The novel coating of wet etching.

The solution to the problem

The present inventor in view of the above subject, for by one kind in low-resistance Ag, Ag alloy, Cu and Cu alloys The composition of alloy of the coating of manufactured conductive layer stacking has made intensive studies.As a result, by adding specific member into Ni Element optimizes its additive amount, it was found that can while ensuring adaptation, weatherability, oxidative resistance steadily into The novel coating of the high-precision wet etching of row, so as to complete the present invention.

That is, the present invention, which is a kind of electronic component-use, is laminated wiring membrane comprising by being selected from Ag, Ag alloy, Cu and Cu alloys In it is a kind of made of conductive layer and a face at least covering the conductive layer coating, it is former that above-mentioned coating contains 5~50 The Mo of sub- %, containing 60 atom % Mo and Cu below are added up to, surplus is made of Ni and inevitable impurity.

In addition, above-mentioned coating preferably comprises the above-mentioned Cu of 5~25 atom %, containing adding up to the upper of 36 atom % or more State Mo and above-mentioned Cu.

In addition, above-mentioned coating preferably comprises the above-mentioned Mo of 26~40 atom %.

In addition, the present invention is the invention of coating formation sputtering target material, it is the sputtering target material for being used to form coating, A kind of coating covering conductive layer made of in Ag, Ag alloy, Cu and Cu alloys, the coating form use Mo that sputtering target material contains 5~50 atom %, containing 60 atom % Mo and Cu below are added up to, surplus is by Ni and can not keep away The impurity composition exempted from, the curie point of the coating formation sputtering target material is below room temperature.

In addition, above-mentioned sputtering target material preferably comprises the above-mentioned Cu of 5~25 atom %, containing adding up to 36 atom % or more Above-mentioned Mo and above-mentioned Cu.

In addition, above-mentioned sputtering target material preferably comprises the above-mentioned Mo of 26~40 atom %.

The effect of invention

The present invention is capable of providing novel electronic component-use stacking wiring membrane and its coating formation sputtering target material, described Electronic component-use stacking wiring membrane is laminated with conductive layer and coating, and the conductive layer is by being selected from low-resistance Ag, Ag alloy, Cu It is made with one kind in Cu alloys, coating oxidative resistance while ensuring adaptation, weatherability is high, can be steadily Carry out high-precision wet etching.The touch surface accordingly, for various electronic units, for example formed on resin film substrate Plate, FPD flexible are highly useful technologies, can to electronic unit stablize manufacture, the raising of reliability bring it is huge Contribution.

Description of the drawings

Fig. 1 is an example of the schematic cross-section of the electronic component-use stacking wiring membrane of the present invention.

Reference sign

1. substrate

2. coating (basal layer)

3. conductive layer

4. coating (cap layer)

Specific implementation mode

Fig. 1 shows an example of the schematic cross-section of the electronic component-use stacking wiring membrane of the present invention.The electricity of the present invention Subassembly stacking wiring membrane includes the conductive layer 3 made of a kind of in Ag, Ag alloy, Cu and Cu alloys and covers The coating 2,4 at least one face of the conductive layer 3 is covered, the electronic component-use stacking wiring membrane is for example formed on substrate 1. In Fig. 1 coating 2,4 is regard as basal layer or cap layer in the case that the two sides of conductive layer 3 forms coating 2,4, it also can be only It is formed in the arbitrary one side of conductive layer 3, it can be suitable for selection.

It should be noted that when only covering a face of conductive layer with the coating of the present invention, in another of conductive layer Face can also be covered according to the purposes of electronic unit with the coating for the composition being different from the present invention.

The important feature of the present invention is：It is found that the coating of electronic component-use stacking wiring membrane shown in Fig. 1 In, by adding Ni, Mo, Cu of specific quantity, wet etching while ensuring adaptation, weatherability, oxidative resistance can be formed in When be difficult to generate non-uniform coating.The electronic component-use wiring membrane of the present invention is described in detail below.

It should be noted that in the following description, " adaptation " refers to coating and glass substrate, resin film substrate Stripping degree of difficulty or conductive layer and coating stripping degree of difficulty, can be by using the stripping of adhesive tape It is evaluated." weatherability " refers to the degree of difficulty that the envenomation under hot and humid environment causes electrical contact to deteriorate, can Confirmed by the discoloration of wiring membrane, such as quantitative evaluation can be carried out by reflectivity.In addition, " oxidative resistance " refer to The degree of difficulty of the adjoint electrical contact deterioration of surface oxidation when being heated under the atmosphere containing oxygen, can pass through cloth The discoloration of line film is confirmed, such as can carry out quantitative evaluation by reflectivity.

The present invention is characterized in that：The conductive layer made of a kind of in Ag, Ag alloy, Cu and Cu alloys, and, In covering the coating at least one face of the conductive layer, the Mo containing 5~50 atom % and then contain Cu, they are total Containing 60 atom % hereinafter, surplus is made of Ni and inevitable impurity.

Ni as one of the chief elements compared with Cu, Ag, with as glass substrate, transparent conductive film ITO, as exhausted The adaptation of the oxide of edge protective film etc. is high, into but weatherability, oxidative resistance also excellent element, be by covering by selecting A kind of made of in Ag, Ag alloy, Cu and Cu alloys conductive layer and can get adaptation, weatherability, oxidative resistance and change The element of kind effect.On the other hand, Ni cannot be etched with the etchant used Cu, Ag, it is therefore desirable to improve etching.

As Mo, Cu of the element other than Ni contained by coating to the etchant tool for Cu, Ag in the present invention Having improves the effect of etching speed.The improvement can be further increased when increasing content.In addition, total content is more than 60 When atom %, the moisture-proof that Ni has originally can be greatly reduced.Therefore, the total amount of Mo and Cu is set as 60 atom % or less.

Mo has solid solution region to Ni in high-temperature area, is the element that alloy can be easily formed with Ni.If covering Contain Mo in layer, then while having the effect of improving adaptation and improving etching speed, the improvement for its uniformity Have very great help.In turn, Mo is the element for having the effect of also improving oxidative resistance, is the indispensable member of the present invention Element.Its improvement shows when containing 5 atom % or more, can become more clear when more than 15 atom %.On the other hand, If containing the Mo for having more than 50 atom %, the moisture-proof as one of weatherability can be greatly reduced.Therefore, in the present invention, exist Mo is contained with the range of 5~50 atom % in coating.

In addition, the improvement of etch uniformity becomes notable when the content of Mo is 15 atom % or more, and to becoming For the etchant of the Cu and both Ag of conductive layer, the content of Mo is more preferably set as 26 originals when improvement etching is uneven Sub- % or more.On the other hand, it when containing the Mo for having more than 40 atom %, according to the difference of the type of etchant, is etching sometimes When easy to produce residue.Therefore, Mo contained in coating is more preferably 26~40 atom %.

If being laminated in the coating of wiring membrane in the electronic component-use of the present invention and adding Cu, can obtain improving etching speed Effect.The improvement becomes clear when the content of Cu is 5 atom % or more, if containing more than 25 atom %, removes Except adaptation reduces, oxidative resistance can also reduce, and become easy and soaked to etchant, therefore there are side etching quantity increasing Add, etch the case where precision reduces.

In addition, when containing the Cu for having more than 25 atom % in coating, especially in the etchant of Ag, there is etching instead The case where speed reduces.Therefore, Cu contained in coating is preferably set as to the range of 5~25 atom % in the present invention.Separately Outside, for the etchant of both Cu and Ag, in order to inhibit with the etching speed of the Ag or Cu of the conductive layer as stacking it is poor, into Row etching with high accuracy, is more preferably set as 36 atom % or more by the total amount of Mo and Cu.

In addition, if the content of Cu is more than the content of Mo, oxidative resistance possessed by Mo, closely sealed cannot be fully obtained sometimes Property, improve etching when uniformity effect.Therefore, the content that the content of Cu is set as less than Mo is preferred, more preferably Mo's 0.7 times or less of content.

In addition, the coating of the electronic component-use stacking wiring membrane of the present invention also can be used in Ti, V, Nb, Ta, Cr, W More than one element substitution Ni, Mo and Cu a part.These elements are the good elements of the improvement of weatherability, if but It added and at most there is the case where making etching speed reduce.Therefore, the replacement amount of these elements is preferably set to 1~5 in the total amount The range of atom %.

For the electronic component-use of present invention stacking wiring membrane, in order to steadily obtain low resistance and weatherability, resistance to Oxidisability, a kind of film thickness of the conductive layer made of in Ag, Ag alloy, Cu and Cu alloys is preferably set as 100~ 1000nm.If the Film Thickness Ratio 100nm of conductive layer is thin, due to the influence of the scattering of the distinctive electronics of film, resistance value can become It is easy to increase.On the other hand, it if the Film Thickness Ratio 1000nm of conductive layer is thick, forms film and needs to spend the time, or can be answered because of film Power and so that substrate is easy tod produce bending.The film thickness of conductive layer is more preferably the range of 200~500nm.

The pure Ag of low resistance value, pure Cu can be preferably obtained in the conductive layer of the present invention, and in above-mentioned weatherability, resistance to oxidation Property on the basis of further consider the reliabilities such as heat resistance, resistance to feeding habits, can also use in Ag, Cu added with transition metal, Ag alloys, Cu alloys obtained from semimetal etc..At this point, in order to obtain low resistance as much as possible, preferably with total 5 atom % with Under range be added.

For the present invention electronic component-use be laminated wiring membrane, in order to steadily obtain low resistance and weatherability, oxytolerant The property changed, is preferably set as 10~100nm by the film thickness of coating.When coating is used as basal layer, by the way that film thickness is set as 10nm or more can improve the adaptation with substrate.In addition, when coating is used as cap layer, by the way that film thickness is set as 20nm More than, defect of coating etc. can be made fully to disappear, weatherability, oxidative resistance is made to improve.

On the other hand, if the film thickness of coating is more than 100nm, the resistance value of coating is got higher, and layer is carried out with conductive layer When folded, it is difficult to obtain low resistance as electronic component-use stacking wiring membrane.Therefore, the film thickness of coating be more preferably 20~ 100nm。

When each layer of wiring membrane is laminated in the electronic component-use for forming the present invention, it is the most to have used the sputtering method of sputtering target Suitable.When forming coating, it can apply and for example be carried out into as the sputtering target of same composition using the group with coating The method of film, the sputtering target using each element and the method that is formed a film by cosputtering.In addition, also can be using Ni-Mo The sputtering target material of alloy, Ni-Cu alloys etc. and the method to be formed a film by cosputtering.

From the viewpoint of the simplicity that the condition of sputtering is set, be easily obtained the desired coating formed, more preferably Using the group with coating spatter film forming is carried out as the sputtering target of same composition.

In addition, in sputtering method, in order to efficiently carry out stable sputtering, under the room temperature using sputtering target material, need It is set as non magnetic, curie point is set as room temperature or less.It should be noted that " curie point is below room temperature " refers in room temperature It is non magnetic when the magnetic characteristic for measuring sputtering target material under (25 DEG C).

Since the Ni of an ingredient of the coating formation sputtering target material as the present invention is magnetic substance, thus for height Stable sputtering is carried out to effect, needs the type for adjusting addition element and additive amount that curie point is made to become room temperature or less.

In the coating formation sputtering target material of the present invention, for the effect for making the curie point of the Ni as magnetic substance reduce For fruit, belong to the Mo highests of nonmagnetic elements, if only individually adding the Mo of 8 atom % to Ni, curie point become room temperature with Under.However, as described above, in the characteristic of coating, by Mo's for the purpose of ensuring adaptation, etching characteristic, oxidative resistance When additive amount is set as 5 atom %, the content of Cu is set as 15 originals in order to which the curie point of sputtering target material is set as room temperature or less Sub- % or more.

In addition, Ni is dissolved the Mo of about 30 atom % in high-temperature area, can be reduced in low-temperature region solid solution capacity.If moreover, Mo Additive amount be more than 30 atom %, then find compound phase, if the additive amount of the Mo of the alloy phase as Ni and Mo be more than about 50 Atom %, then exist compound coordinate based on, ductility, toughness reduces, becomes fragile and be difficult to carry out stable mechanical processing Situation.

In addition, in the characteristic of above-mentioned coating, if the additive amount of Mo is more than 50 atom %, there are weatherabilities substantially The case where reduction.Therefore, in the present invention, the upper limit of the additive amount of Mo is set as 50 atom %.

In addition, Cu is the element being dissolved completely with Ni, the effect that curie point reduces is set to be less than Mo, if individually adding to Ni Add the Cu of about 30 atom %, then curie point becomes room temperature or less.However, as described above, in the characteristic of coating, in order to ensure Oxidative resistance, adaptation, the additive amount of Cu is preferably in the range of 5~25 atom %.

According to the above, coating formation sputtering target material of the invention contains the Mo of 5~50 atom %, containing total It is made of Ni and inevitable impurity for 60 atom % Mo and Cu below, surplus, curie point is room temperature or less.As a result, The coating formation of the present invention can steadily sputter coating with sputtering target material.

In addition, the type and additive amount of addition element are more, then the appearance amount of the compound phase in sputtering target material can more increase Add, easier mechanical processing when manufacturing the sputtering target material of the required large size of FPD purposes cracks in welding.Moreover, The Mo and Cu added in the present invention is the element being separated, if both Mo and Cu content be more than it is a certain amount of if be easy hair The case where raw phase separation, exists and is not only difficult to obtain uniform alloy, but also sputtering target material easy tos produce crackle.Therefore, this hair The total amount of the content of the Mo and Cu of bright sputtering target material is set as 60 atom % or less.

The manufacturing method of coating formation sputtering target material as the present invention, such as can also apply and be adjusted to being liquefied Implement mechanical processing for the ingot casting that the raw material of composition requirement makes to manufacture method, the powder sintering of sputtering target material.In powder In last sintering process, such as alloy powder can be manufactured with gas atomization raw material powder is made or can will be to become this The mode of invention finally formed makes the mixed mixed-powder of a variety of alloy powders, pure metal powder that raw material powder be made.Make For the sintering method of raw material powder, hot isostatic pressing can be used, hot pressing, discharge plasma sintering, squeeze out the pressure sinterings such as sintering. As noted previously, as the additive amount of Mo, Cu of the present invention is more, plastic processing reduces, so in order to steadily manufacture FPD's Large-scale sputtering target material preferably carries out the alloy powder with specific composition the manufacturing method of pressure sintering.

It is room temperature to curie point it is therefore preferable that selecting element to be added in addition, due to containing the Ni of magnetic substance is belonged to Alloy powder below carries out pressure sintering.Curie point can use in room temperature alloy powder below and be adjusted to finally to form Ni alloys are readily available by atomization.In addition, can also be crushed to the ingot casting after melting to make alloy powder.Separately Outside, it can also apply and manufacture various alloy powders and be mixed into the method finally formed.

In addition, if the average grain diameter of alloy powder, less than 5 μm, the impurity in obtained sputtering target material can increase.It is another Aspect is difficult to obtain densely sintered body if the average grain diameter of alloy powder is more than 300 μm.Therefore, alloy powder is flat Equal grain size is preferably 5~300 μm.It is advised it should be noted that heretofore described average grain diameter is expressed as JIS Z 8901 The ball equivalent diameter of light scattering method fixed, by using laser.

For the present invention coating formation sputtering target material for, it is preferred that in addition to the Ni of main composition element, The content of inevitable impurity other than Mo, Cu is few, do not damage the present invention effect in the range of, can contain aerobic, nitrogen, The inevitable impurity such as carbon, Fe, Al, Si.Herein, each main composition element is with the original relative to main composition element entirety Sub- % indicates that the inevitable impurity in addition to essential element is indicated with the quality ppm relative to target entirety.Such as oxygen, Nitrogen is respectively 1000 mass ppm hereinafter, carbon is 200 mass ppm hereinafter, Al, Si are that 100 mass ppm are such as the following, except gas componant Except purity be preferably 99.9 mass % or more.

[embodiment 1]

First, the sputtering target material for being used to form coating is made.Table 1 shows the composition of made coating.It needs It is bright, about the sputtering target material of No.4~No.10, electrolysis Ni and block-like Mo raw materials, oxygen-free copper block are being weighed by specified amount Afterwards, using steel vacuum melting stoves ingot casting is made by melting casting.In addition, the Ni-30 of No.1~No.3 as comparative example Atom %Cu, Ni-35 atom %Cu-3 atom %Ti, Ni-8 atom %Mo are similarly pressing specified amount using vacuum melting method After weighing electrolysis Ni and block-like Mo raw materials, oxygen-free copper block, ingot casting is made by melting casting using steel vacuum melting stoves.

When SmCo magnetites to be approached to the ingot casting of obtained each alloy, confirm non-cohesive on magnetite.In addition, will be above-mentioned A part for obtained ingot casting is put into the container of magnetic characteristic measurement, the vibrating example manufactured using Riken Densi K. K. Magnetometer (model：VSM-5), magnetic characteristic is measured under room temperature (25 DEG C), be as a result confirmed as non magnetic.

In addition, having made the sputtering target material of Mo-30 atoms %Ni using powder metallurgic method.It is 6 μm that this, which is by average grain diameter, Mo powder and average grain diameter be 100 μm Ni powder mix, in filling to the tank of mild steel after, carried out while heating very Idle discharge gas simultaneously seals.Then, the tank after sealing is put into heat isostatic apparatus, 1100 DEG C, 100MPa, 3 hours conditions Under so that its sintering is made sintered body.In addition, also having made the sintered body of pure Mo of identical method.

Each ingot casting obtained above and each sintered body are fabricated to the sputtering of diameter 100mm, thickness 5mm by being machined Target.In addition, the substance that the sputtering target material of pure Ag is 4N using the purity that Mitsubishi Materials Co., Ltd. manufactures. In addition, the sputtering target material of pure Cu is machined to plate made of the oxygen-free copper by purity for 4N to prepare.

Then, above-mentioned each sputtering target material is brazed on backboard made of copper, is mounted on ULVAC Co., Ltd. later and manufactures Sputter equipment (model：CS-200 on), implement sputtering experiment, knot under conditions of Ar atmosphere, pressure 0.5Pa, electric power 500W The arbitrary sputtering target material of fruit can be sputtered.

Glass substrate (the product type for 25mm × 50mm that Corning companies are manufactured：EagleXG) it is mounted on above-mentioned splash On the substrate holder of injection device, the coating of thickness 100nm is formed, adaptation and etching are had rated.In addition, No.11 and No.13 is formed by the cosputtering method for the sputtering target material for sputtering Mo and Ni-30 atoms %Cu simultaneously.No.12 is similarly to Mo-30 Atom %Ni and Ni-30 atom %Cu carries out cosputtering and is formed, and composition shown in table 1 is to utilize Shimadzu Scisakusho Ltd Inductively coupled plasma emission spectrometer (ICP) (model of manufacture：ICPV-1017 it) is carried out to forming the coating after these The value obtained after analysis.

Method as defined in the Appreciation gist JIS K 5400 of adaptation carries out.First, in the table of the coating of above-mentioned formation Paste the transparent adhesion band (ProductName of Sumitomo 3M Co., Ltd. manufacture in face：Transparent beauty), the square of 2mm square is cut out with cutter Notch, remove transparent adhesion band, have rated the residual of intectate.1 piece of coating also unstripped situation is evaluated as △ zero, will be evaluated as the case where having removed 1~10 piece, be evaluated as the situation for having removed 11 pieces or more ×.

About the evaluation of etching, nitric acid, phosphoric acid, acetic acid and water are carried out to mix the etchant as Ag.Cu's Etchant uses the CuO of Northeast chemical industry system₂.In order to make the few coating of lateral erosion, the unevenness for inhibiting etching period is needed It is even, overetch time is reduced, and suitably inhibit the wetability to etchant.

Each sample is impregnated in etchant liquid, measures the coating whole face time required completely through until as best Etching period.In addition, simultaneously on one side by visual observation observation etching it is uneven, on one side in order to obtain more specific difference and determine Time difference between time through a part for film and optimal etch time.It indicates that the time difference is smaller, etches uneven get over It is few.In addition, drip 20 μ l etchants to film surface, the diffusion diameter after measuring 2 minutes.This indicates that the smaller expression of diffusion diameter is got over It can inhibit lateral erosion, can more carry out etching with high accuracy.

[table 1]

As shown in table 1, the adaptation of sample No.1, No.2, No.4 is low.In addition, understanding sample No.3 by containing 8 originals The Mo of sub- % and improve adaptation, but the optimal etch time is long.

In contrast, it can be confirmed that the coating of the present invention substantially changes due to Mo and Cu containing specific quantity in Ni It has been apt to adaptation.

In addition, for etching, it is known that be：The coating of sample No.1, No.2 can be with the etchants of Cu 2 It is etched within minute, but Ag etchants then need 18 minutes or more time, thus it is not applicable.In addition, understanding to exist etching soon Part and etch slow part, because generate etching it is uneven due to so that the time difference is become larger, etchant is easy diffusion.Therefore, it is known that It is difficult to uniformly be etched, is unsuitable for etching with high accuracy.In addition, the Mo contents for confirming sample No.13, No.14 are more than The composition of 50 atom % produces residue after the etching.

In contrast, though can be confirmed as the present invention sample No.5~No.12 coating Cu and Ag this It can also be etched at 90 seconds or less in the etchant of the two.In addition it confirmed that the coating of sample No.8~No.12 is logical It crosses and increases the additive amount of Mo, the total amount of Mo and Cu is set as 36 atom % or more and the optimal etch time is made to shorten, the time Difference and diffusion diameter also become smaller, and etching is uneven and lateral erosion is few, thus can carry out etching with high accuracy.

[embodiment 2]

The evaluation of oxidative resistance is carried out.By each sample in air atmosphere with 50 DEG C, 250 DEG C, 300 DEG C, 350 DEG C of progress Heat treatment in 30 minutes, determines reflectivity and resistance value.Reflectivity is manufactured using Konica Minolta Co., Ltd. Spectral photometric colour measuring meter (model：CM2500d it) measures, resistance value uses the film resiativity meter (type of 4 terminal of diamond instruments system Number：MCP-T400 it) measures.

Using each sputtering target material prepared in embodiment 1, be formed in shown in table 2 made on glass substrate according to Secondary film forming has the sample of the stacking wiring membrane of the cap layer of the basal layer of film thickness 30nm, the Cu conductive layers of film thickness 300nm, film thickness 50nm Product.It should be noted that above-mentioned basal layer and cap layer is the coating material composition of table 2.

[table 2]

As shown in table 2, the coating by using the present invention, which can be confirmed, can greatly improve oxidative resistance.

On film substrate, the oxidative resistance until 250 DEG C is needed based on the heat resisting temperature of film.As shown in table 2, it is known that Although sample No.4 reflectivity at 250 DEG C or more starts to reduce, though the present invention electronic component-use stacking wiring membrane through The air heating for crossing 250 DEG C, can also maintain 50% or more high reflectance, have high oxidation resistance.Especially it can be confirmed The effect is big in the case of increasing the additive amount of Mo.

Furthermore it is possible to which wiring membrane is laminated even across 250 DEG C, 300 DEG C, 350 DEG C in the electronic component-use for confirming the present invention Air heating can also inhibit resistance value rising, oxidative resistance can be improved.

[embodiment 3]

Then, the evaluation of weatherability has been carried out using each electronic component-use of embodiment 2 stacking wiring membrane.About weatherability Evaluation, by each electronic component-use stacking wiring membrane placed under 85 DEG C of temperature, the atmosphere of relative humidity 85% 100 hours, 200 Hour after 300 hours, determines reflectivity similarly to Example 2.It should be noted that being shown in the basal layer and cap layer of table 3 It is the coating material composition of table 3.

[table 3]

As shown in table 3, as sample No.13, No.14 of comparative example since the content of Mo is more than 50 atom %, so with The process of time, reflectivity reduces.

On the other hand, the electronic component-use stacking wiring of sample No.5~No.12 as example of the present invention can be confirmed Film can also maintain high reflectivity even when exposed to that will not change colour under high temperature and humidity atmosphere after 300 hours, have high Moisture-proof.

According to the above, it can be confirmed and wiring membrane is laminated by using the electronic component-use of the present invention, can ensure Wet etching is steadily carried out while with the adaptation, oxidative resistance, weatherability of conductive layer.

[embodiment 4]

Then, using each sputtering target material prepared in embodiment 1, to be shown in the composition of table 4, in band ito film film base Film forming successively is made on plate or glass substrate the cover of the basal layer of film thickness 30nm, the Ag conductive layers of film thickness 200nm, film thickness 30nm The sample of the stacking wiring membrane of layer.It should be noted that above-mentioned basal layer and cap layer refers to the coating material composition of table 4.

The evaluation of adaptation, the transparent adhesion band (ProductName that Sumitomo 3M Co., Ltd. is manufactured：Transparent beauty) it is affixed on layer On folded wiring membrane, surface is wiped with rubber, transparent adhesion band is removed, has rated the residual of intectate.Coating is not shelled From the case where be evaluated as zero, about 10% or so will have been removed the case where be evaluated as △, will remove 20% or more situation evaluation For ×.

Ag is different from Cu, even if carrying out 350 DEG C of heating in air, resistance value will not be significantly increased, so oxytolerant Change property evaluation similarly to Example 2, by each sample in air atmosphere with 150 DEG C, 250 DEG C, 350 DEG C carry out 30 minutes plus Heat treatment, determines reflectivity.

In addition, the evaluation of weatherability is similarly to Example 3, by each sample in 85 DEG C of temperature, the atmosphere of relative humidity 85% After lower placement 100 hours, 200 hours, 300 hours, reflectivity is determined.

[table 4]

As shown in table 4, the adaptation of sample No.4 is low.

On the other hand, it is known that sample No.5~No.12 as example of the present invention is improved close by increasing the content of Mo Conjunction property, especially sample No.8~No.12 of the Mo contents more than 22 atom % has obtained high adaptation.

It should be noted that for heat resistance, when carrying out 350 DEG C of heating, pleat is produced on film substrate Wrinkle.Furthermore it is possible to confirm in the case where using Ag as conductive layer, the sample as example of the present invention is being heated to 250 DEG C When, the discoloration of Ag conductive layers is inhibited because of high oxidative resistance.In addition it can be confirmed for weatherability, as this hair The sample of bright example similarly inhibits the discoloration of Ag conductive layers due to high-weatherability.

Claims (4)

1. wiring membrane is laminated in a kind of electronic component-use, which is characterized in that include by Ag, Ag alloy, Cu and Cu alloys The coating of conductive layer and a face at least covering the conductive layer, the coating made of a kind of containing 22~50 atom % Mo, 5~20 atom % Cu, containing adding up to 36 atom % or more and the 60 atom % Mo below and Cu, it is remaining Amount is made of Ni and inevitable impurity, wherein the content of the Cu in the coating is less than the content of the Mo.

2. wiring membrane is laminated in electronic component-use according to claim 1, which is characterized in that the coating contains 26~40 The Mo of atom %.

3. a kind of coating formation sputtering target material, which is characterized in that it is the sputtering target material for being used to form coating, described to cover A kind of cap rock covering conductive layer made of in Ag, Ag alloy, Cu and Cu alloys, the coating formation sputtering target Material contains the Mo of 22~50 atom %, the Cu of 5~20 atom %, containing adding up to 36 atom % or more and 60 atom % are below The Mo and Cu, surplus are made of Ni and inevitable impurity, and the content of the Cu in the coating is less than institute The content of Mo is stated, the curie point of the coating formation sputtering target material is below room temperature.

4. coating formation sputtering target material according to claim 3, which is characterized in that the institute containing 26~40 atom % State Mo.