CN105986233A - Stacked wireing film for electronic member and sputtering target material for formation of coating layer - Google Patents
Stacked wireing film for electronic member and sputtering target material for formation of coating layer Download PDFInfo
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- CN105986233A CN105986233A CN201610159285.2A CN201610159285A CN105986233A CN 105986233 A CN105986233 A CN 105986233A CN 201610159285 A CN201610159285 A CN 201610159285A CN 105986233 A CN105986233 A CN 105986233A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/002—Alloys based on nickel or cobalt with copper as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/005—Alloys based on nickel or cobalt with Manganese as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
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Abstract
The invention provides a stacked wiring film for electronic members and a sputtering target material for formation of a coating layer. The stacked wiring film has a novel coating layer, which uses low resistance Ag or Cu as a conductive layer and can perform high accuracy wet etching while guaranteeing sealing, weather resistance and oxidation resistance. The stacked wiring film for the electronic member comprises a conductive layer made from at least one of Ag, Ag alloy, Cu and Cu alloy and a coating layer coating at least one surface of the conductive layer; the coating layer contains Mo of 5-50% of atoms and Mo and Cu with 60% of atoms in total, and residual consists of Ni and inventible foreign matters; the coating layer can be constituted by Mo of 5-50% of atoms and Mo and Cu with 60% of atoms in total, and residual consisting of Ni and inventible foreign matters.
Description
Technical field
The present invention relates to such as can be used for the electronic component-use stacking wiring membrane of touch panel etc. and for forming covering
The sputtering target material of the cover layer of the conductive layer of this electronic component-use stacking wiring membrane.
Background technology
In recent years, achieving commercialization as the smart mobile phone of Novel portable type end, panel computer etc., it is to be glass
Form the liquid crystal display (Liquid Crystal Display: hereinafter referred to as " LCD ") of film apparatus on glass substrate, be used in
Flat display apparatus (flat faced display, the Flat Panel such as the electrophoretype display of organic el display, Electronic Paper etc.
Display: hereinafter referred to as " FPD ") upper combination can watch its picture and give the touch panel of direct operability
And obtain.Sensing membrane as the position detecting electrode of these touch panels is typically used as nesa coating
Indium-tin-oxide (Indium Tin Oxide: hereinafter referred to as " ITO ").And, on its bridge joint wiring, lead-out wiring, as
There is lower resistance value (hereinafter referred to as low resistance.) metal line film, employ such as be laminated with Mo, Mo alloy and Al,
The stacking wiring membrane of Al alloy.
In recent years, for LCD, FPD etc. of smart mobile phone, panel computer etc. year by year in large screen, high-precision refinement, at a high speed
Responseization aspect develops rapidly, and its sensing membrane and metal line film are required further low resistance.Therefore, it was also proposed that will pass
Sense film makes the scheme of metal nethike embrane mode etc., described metal nethike embrane make to make metal level more low-resistance than ITO netted and
Obtain.
Being suitable for as a result, Cu is except oxidative resistance, close of Cu, Ag more low-resistance than Al is have studied in this metal nethike embrane
Close outside sex chromosome mosaicism, as there is problem in the moisture-proof of one of weatherability, therefore existing and being difficult to process such problem.Separately
On the one hand, Ag is more expensive than Cu, but because of have be better than the oxidative resistance of Cu, moisture-proof and there is prospect.
But, Ag is low with the adaptation of substrate, is easily peeled off, and then easy and chlorine, reaction of Salmon-Saxl, and therefore weatherability existence is asked
Topic.Therefore, in order to solve problem specific to adaptation, this Ag of weatherability, it is proposed that with the covering formed by other metal
Layer covers the scheme of Ag.
It addition, for the slimming of smart mobile phone, panel computer etc., the substrate of touch panel also can use by glass substrate
Become using can the mode of the more resin film substrate of slimming, it is closely sealed that above-mentioned cover layer also requires with resin film substrate
Property.
As forming above-mentioned metal line film, the method for cover layer, the sputtering method using sputtering target material is most widely suited.
Sputtering method is the one of physical vapor deposition, compared with vacuum evaporation with other, ion plating, is can easily to carry out large area one-tenth
The method of film, and be the effective method that component fluctuation is few, can obtain the thin layer of excellence.It addition, be the hot shadow to substrate
Ring less it can also be used to the method for resin film substrate.
Present inventors have proposed following scheme: make by making Cu, the Ag being laminated with by low with the adaptation of glass etc.
Conductive layer and by using Mo as main body the stacking wiring membrane of cover layer made containing the Mo alloy of V and/or Nb, thus
It is able to maintain that the low resistance that Cu, Ag are had, and the adaptation improving resistance to feeding habits, thermostability and glass substrate (sees patent literary composition
Offer 1).This technology is effective technology as the wiring membrane of the TFT formed on the glass substrate.
It addition, present inventors have proposed a kind of stacking wiring membrane, its be on the conductive layer being made up of Ag, Cu stacking with by
The cover layer that Ni alloy is made, in described Ni alloy Cu be 1～25 atom %, selected from Ti, Zr, Hf, V, Nb, Ta, Cr,
The element of Mo, W is 1～25 atom % and their total addition level is that 35 below atom % (see patent documentation 2.).To this
For the cover layer proposed in patent documentation 2, be with the addition of by employing the transition metal such as Ti, V, Cr of ormal weight Ni alloy and
Achieve weak magnetization, stable at film forming ability based on sputtering method and be useful technology on this aspect for a long time.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-140319 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2006-310814 publication
Summary of the invention
The problem that invention is to be solved
The high-precision refinement being as noted previously, as FPD in recent years develops rapidly, thus is also desirable that in touch panel with more
Narrow wiring width precision is etched processing well.
But, for Cu, Ag, carry out belonging to the dry etching not a duck soup of high-precision etching method, thus mainly make
Use wet etching.Further, since resin film substrate has poisture-penetrability, thus, for the covering with the conductive layer stacking of Cu, Ag
For Ceng, when being formed on glass substrate, it is desirable to higher weatherability.
Find through the research of the present inventor, be laminated with the conductive layer being made up of Cu, Ag and by Mo disclosed in patent documentation 1
The stacking wiring membrane of the cover layer that alloy is made corrodes sometimes on resin film substrate.The inventors discovered that, conductive layer
The electrode potential of Cu, Ag is high, thus when the Mo low with electrode potential, above-mentioned Mo alloy carry out stacking, has poisture-penetrability
Resin film substrate in, due to cell reaction, Mo, Mo alloy becomes easily to corrode, in long-term reliability have problems.
It addition, the inventors discovered that, to using compared with Mo electrode potential closer to the Ni alloy of Cu, Ag in cover layer
And the stacking wiring membrane obtained is when carrying out wet etching, be present in real estate inner covering layer etching heterogeneity, produce uneven,
The situation of deviation, or the situation that lateral erosion quantitative change is big can be produced in wiring width, exist and be difficult to stably obtain institute's phase from now on
This new problem of the wiring membrane of the narrow width treated.
It is an object of the invention to provide electronic component-use stacking wiring membrane and cover layer formation sputtering target material, described electricity
Subassembly stacking wiring membrane has conductive layer and cover layer, and conductive layer is by selected from low-resistance Ag, Ag alloy, Cu and Cu alloy
In one make, cover layer be can stably carry out while guaranteeing adaptation, weatherability, oxidative resistance high-precision
The cover layer that wet etching is novel.
For solving the scheme of problem
The present inventor in view of above-mentioned problem, for by the one in low-resistance Ag, Ag alloy, Cu and Cu alloy
The alloy composition of the cover layer of the conductive layer stacking made conducts in-depth research.As a result, by adding specific unit in Ni
Element, carries out optimization to its addition, it was found that stably can enter while guaranteeing adaptation, weatherability, oxidative resistance
The novel cover layer of the high-precision wet etching of row, thus complete the present invention.
That is, the present invention is a kind of electronic component-use stacking wiring membrane, and it includes by selected from Ag, Ag alloy, Cu and Cu alloy
In a kind of conductive layer made and at least cover the cover layer in a face of this conductive layer, it is former that above-mentioned cover layer contains 5～50
The Mo of sub-%, containing adding up to this Mo and Cu of 60 below atom %, surplus is made up of Ni and inevitable impurity.
It addition, above-mentioned cover layer preferably comprises the above-mentioned Cu of 5～25 atom %, containing adding up to the upper of 36 more than atom %
State Mo and above-mentioned Cu.
It addition, above-mentioned cover layer preferably comprises the above-mentioned Mo of 26～40 atom %.
Additionally, the invention that the present invention is cover layer formation sputtering target material, it is the sputtering target material for forming cover layer,
Described cover layer covers by a kind of conductive layer made in Ag, Ag alloy, Cu and Cu alloy, and described cover layer is formed to be used
Mo that sputtering target material contains 5～50 atom %, containing adding up to this Mo and Cu of 60 below atom %, surplus is by Ni and can not keep away
The impurity composition exempted from, the curie point of described cover layer formation sputtering target material is below room temperature.
It addition, above-mentioned sputtering target material preferably comprises the above-mentioned Cu of 5～25 atom %, containing adding up to 36 more than atom %
Above-mentioned Mo and above-mentioned Cu.
It addition, above-mentioned sputtering target material preferably comprises the above-mentioned Mo of 26～40 atom %.
The effect of invention
The present invention can provide novel electronic component-use stacking wiring membrane and cover layer formation sputtering target material thereof, described
Electronic component-use stacking wiring membrane is laminated with conductive layer and cover layer, and described conductive layer is by selected from low-resistance Ag, Ag alloy, Cu
Making with the one in Cu alloy, described cover layer oxidative resistance while guaranteeing adaptation, weatherability is high, can be stably
Carry out high-precision wet etching.Accordingly, for various electronic units, the such as touch surface of formation on resin film substrate
Plate, flexible FPD are highly useful technology, it is possible to stable manufacture, the raising of reliability to electronic unit bring huge
Contribution.
Accompanying drawing explanation
Fig. 1 is an example of the schematic cross-section of the electronic component-use stacking wiring membrane of the present invention.
Description of reference numerals
1. substrate
2. cover layer (basal layer)
3. conductive layer
4. cover layer (cap layer)
Detailed description of the invention
Fig. 1 illustrates 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 by a kind of conductive layer 3 made in Ag, Ag alloy, Cu and Cu alloy and covers
Covering the cover layer 2,4 at least one face of this conductive layer 3, described electronic component-use stacking wiring membrane is formed the most on substrate 1.
Formed cover layer 2,4 in the two sides of conductive layer 3 in FIG in the case of cover layer 2,4 as basal layer or cap layer, it is possible to only
Arbitrarily one side at conductive layer 3 is formed, and can suitably select.
During it should be noted that only cover a face of conductive layer with the cover layer of the present invention, at another of conductive layer
Face, it is also possible to cover with the cover layer of the composition different from the present invention according to the purposes of electronic unit.
The important feature of the present invention is: be found that the cover layer at the electronic component-use stacking wiring membrane shown in Fig. 1
In, by adding Ni, Mo, Cu of specified quantitative, can be formed in and guarantee wet etching while adaptation, weatherability, oxidative resistance
Time be difficult to produce uneven cover layer.Hereinafter the electronic component-use wiring membrane of the present invention is described in detail.
It should be noted that in the following description, " adaptation " refers to cover layer and glass substrate, resin film substrate
The degree of difficulty of stripping or the degree of difficulty of conductive layer and the stripping of cover layer, 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 variable color of wiring membrane, such as, can carry out quantitative evaluation by reflectance.It addition, " oxidative resistance " refers to
The degree of difficulty of the electrical contact deterioration that surface oxidation when heating under the atmosphere containing oxygen is adjoint, can pass through cloth
The variable color of line film confirms, such as, can carry out quantitative evaluation by reflectance.
It is a feature of the present invention that: by a kind of conductive layer made in Ag, Ag alloy, Cu and Cu alloy, and,
In covering the cover layer at least one face of this conductive layer, Mo containing 5～50 atom % and then containing Cu, they add up to
Containing 60 below atom %, surplus is made up of Ni and inevitable impurity.
Compared with Ni with Cu, the Ag of one of the chief elements, with as glass substrate, the ITO of nesa coating, as absolutely
The adaptation of the oxide etc. of edge protecting film is high, and then is the element that weatherability, oxidative resistance are also excellent, is by covering by selecting
A kind of conductive layer made in Ag, Ag alloy, Cu and Cu alloy and adaptation, weatherability, the changing of oxidative resistance can be obtained
The element of kind effect.On the other hand, Ni can not be etched with the etchant that Cu, Ag are used, it is therefore desirable to improve etching.
In the present invention, the etchant for Cu, Ag is had by Mo, Cu as the element in addition to Ni contained by cover layer
There is the effect improving etching speed.This improvement effect can improve further when increasing content.It addition, add up to content more than 60
During atom %, the moisture-proof that Ni has originally can be greatly reduced.Therefore, the total amount of Mo and Cu is set to 60 below atom %.
Mo has solid solution region to Ni at high-temperature area, is easily can to form the element of alloy with Ni.If covering
Containing Mo in Ceng, then while there is the effect improving adaptation and improve etching speed, for its uniformity improvement also
Have very great help.And then, Mo is the element with the effect that oxidative resistance is also carried out improvement, is the indispensable unit of the present invention
Element.It improves effect and manifests when containing 5 more than atom %, can become the clearest and the most definite when 15 more than atom %.On the other hand,
If containing the Mo having more than 50 atom %, then the moisture-proof as one of weatherability can be greatly reduced.Therefore, in the present invention, exist
Cover layer contains Mo with the scope of 5～50 atom %.
It addition, the effect of improving of etch uniformity becomes notable when the content of Mo is 15 more than atom %, and to becoming
For the etchant of both Cu and Ag of conductive layer, more preferably the content of Mo is set to 26 when improving etching and being uneven former
Sub-more than %.On the other hand, when containing the Mo having more than 40 atom %, according to the difference of the kind of etchant, sometimes in etching
Shi Rongyi produces residue.Therefore, contained in cover layer Mo is more preferably 26～40 atom %.
If adding Cu in the cover layer of the electronic component-use stacking wiring membrane of the present invention, then can obtain improving etching speed
Effect.This improvement effect becomes clear and definite when the content of Cu is 5 more than atom %, if containing more than 25 atom %, then removes
Outside adaptation reduces, oxidative resistance also can reduce, and becomes easily etchant moistening, therefore there is side etching quantity and increases
Add, etch the situation that precision reduces.
During it addition, cover layer contains the Cu having more than 25 atom %, particularly in the etchant of Ag, there is etching on the contrary
The situation that speed reduces.Therefore, the most preferably Cu contained in cover layer is set to the scope of 5～25 atom %.Separately
Outward, for the etchant of both Cu and Ag, in order to the etching speed of Ag or Cu of the conductive layer suppressed and become stacking is poor, enter
The etching that row precision is high, is more preferably set to 36 more than atom % by the total amount of Mo and Cu.
If it addition, the content of Cu more than the content of Mo, can not fully obtain oxidative resistance that Mo had, closely sealed the most sometimes
Property, the effect of uniformity when improving etching.Therefore, the content that the content of Cu is set to less than Mo is preferred, more preferably Mo's
Less than 0.7 times of content.
It addition, the cover layer of the electronic component-use stacking wiring membrane of the present invention also can be with in Ti, V, Nb, Ta, Cr, W
A part of more than one element substitution Ni, Mo and Cu.These elements be weatherability improve effective element, if but
Added the situation that existence makes etching speed reduce at most.Therefore, the replacement amount of these elements is preferably set to 1～5 in terms of total amount
The scope of atom %.
For the electronic component-use stacking wiring membrane of the present invention, in order to stably obtain low resistance and weatherability, resistance to
Oxidisability, preferably by by the thickness of a kind of conductive layer made in Ag, Ag alloy, Cu and Cu alloy be set to 100～
1000nm.If Film Thickness Ratio 100nm of conductive layer is thin, then due to the impact of scattering of the distinctive electronics of thin film, resistance value can become
Easily increase.On the other hand, if Film Thickness Ratio 1000nm of conductive layer is thick, then forming film needs the cost time, or can answer because of film
Power and make substrate easily produce bending.The thickness of conductive layer is more preferably the scope of 200～500nm.
The conductive layer of the present invention preferably can obtain the pure Ag of low resistance value, pure Cu, and in above-mentioned weatherability, resistance to oxidation
Consider the reliability such as thermostability, resistance to feeding habits on the basis of property further, it is possible to use be added with in Ag, Cu transition metal,
Semimetal etc. and obtain Ag alloy, Cu alloy.Now, in order to obtain low resistance as much as possible, preferably with add up to 5 atom % with
Under scope be added.
For the electronic component-use stacking wiring membrane of the present invention, for the low resistance stably obtained and weatherability, oxytolerant
The property changed, is preferably set to 10～100nm by the thickness of cover layer.When cover layer is used as basal layer, by thickness is set to
More than 10nm, it is possible to improve the adaptation with substrate.It addition, when cover layer is used as cap layer, by thickness is set to 20nm
Above, it is possible to make the defect etc. of cover layer fully disappear, make weatherability, oxidative resistance improve.
On the other hand, if the thickness of cover layer is more than 100nm, then the resistance value of cover layer uprises, and carries out layer with conductive layer
Time folded, it is difficult to obtain low resistance as electronic component-use stacking wiring membrane.Therefore, the thickness of cover layer be more preferably 20～
100nm。
When forming each layer of electronic component-use stacking wiring membrane of the present invention, the sputtering method employing sputtering target is the most
Suitable.When forming cover layer, can apply and such as use to become with the sputtering target consisting of same composition of cover layer
The method of film, the sputtering target using each element the method carrying out film forming by cosputtering.Additionally, it is possible to application uses Ni-Mo
The sputtering target material of alloy, Ni-Cu alloy etc. the method carrying out film forming by cosputtering.
From the viewpoint of the simplicity that sets from the condition of sputtering, the cover layer being easily obtained desired composition, more preferably
Use the sputtering target consisting of same composition with cover layer to carry out spatter film forming.
It addition, in sputtering method, in order to carry out stable sputtering efficiently, under the room temperature using sputtering target material, need
Be set as non magnetic, curie point will be set to below room temperature.It should be noted that " curie point is below room temperature " refers at room temperature
It is non magnetic when measuring the magnetic characteristic of sputtering target material under (25 DEG C).
Owing to the Ni of a composition of the cover layer formation sputtering target material as the present invention is magnetic, thus for height
Effect ground carries out stable sputtering, needs to regulate the kind of addition element and addition makes curie point become below room temperature.
In the cover layer formation sputtering target material of the present invention, for the effect making the curie point of the Ni as magnetic reduce
For Guo, the Mo belonging to nonmagnetic elements is the highest, if Ni the most individually to be added the Mo of 8 atom %, then curie point become room temperature with
Under.But, as it has been described above, in the characteristic of cover layer, by Mo's for the purpose of guaranteeing adaptation, etching characteristic, oxidative resistance
When addition is set to 5 atom %, in order to the curie point of sputtering target material being set as below room temperature, the content of Cu is set to 15 former
Sub-more than %.
It addition, Ni is at the Mo of high-temperature area solid solution about 30 atom %, can reduce at low-temperature region solid solution capacity.And, if Mo
Addition more than 30 atom %, then find compound phase, if the addition as the Mo of the alloy phase of Ni and Mo exceedes about 50
Atom %, then there is compound becomes main body, ductility, toughness reduction mutually, becomes fragile and be difficult to stable machining
Situation.
It addition, in the characteristic of above-mentioned cover layer, if the addition of Mo is more than 50 atom %, then there is weatherability significantly
Situation about reducing.Therefore, in the present invention, the upper limit of the addition of Mo is set to 50 atom %.
It addition, Cu is to carry out the element of complete solid solution with Ni, make the effect that curie point reduces less than Mo, if Ni is individually added
Add the Cu of about 30 atom %, then curie point becomes below room temperature.But, as it has been described above, in the characteristic of cover layer, in order to ensure
Oxidative resistance, adaptation, the addition of Cu is preferably in the scope of 5～25 atom %.
According to foregoing, the cover layer formation sputtering target material of the present invention contains the Mo of 5～50 atom %, containing adding up to
Be this Mo and Cu of 60 below atom %, surplus by Ni and inevitably impurity form, curie point is below room temperature.Thus,
The cover layer formation sputtering target material of the present invention can stably sputter cover layer.
It addition, the kind of addition element and addition are the most, then the appearance amount of the compound phase in sputtering target material more can increase
Add, the easiest machining when manufacturing the required large-scale sputtering target material of FPD purposes, welding crack.And,
Mo and Cu added in the present invention is by the element being separated, if the content of both Mo and Cu exceedes a certain amount of, easily sends out
Raw separated, exist and be not only difficult to obtain uniform alloy, and the situation that sputtering target material easily cracks.Therefore, this
The total amount of the content of Mo and Cu of bright sputtering target material is set to 60 below atom %.
As the manufacture method of the cover layer formation sputtering target material of the present invention, such as, can also apply being liquefied regulation
The ingot casting made for the raw material of composition requirement implements machining to manufacture the method for sputtering target material, powder sintering.At powder
In the sintering process of end, such as, can manufacture alloy powder with gas atomization and make material powder or can be by become this
The mode of the final composition of invention makes the mixed mixed-powder of multiple alloy powder, pure metal powder make material powder.Make
For the sintering method of material powder, the pressure sinterings such as high temperature insostatic pressing (HIP), hot pressing, discharge plasma sintering, extrusion sintering can be used.
The addition of Mo, Cu of being as noted previously, as the present invention is many, and plastic working reduces, so in order to stably manufacture FPD's
Large-scale sputtering target material, preferably carries out the manufacture method of pressure sintering to the alloy powder with specific composition.
Further, since contain the Ni belonging to magnetic, it is therefore preferable that select element to be added, it is room temperature to curie point
Following alloy powder carries out pressure sintering.Curie point alloy powder below room temperature can use and be adjusted to finally to form
Ni alloy is readily available by atomization.Additionally, it is possible to the ingot casting after melting is carried out pulverizing to make alloy powder.Separately
Outward, it is possible to application manufactures various alloy powders the method being mixed into final composition.
If it addition, the mean diameter of alloy powder can increase less than 5 μm, the then impurity in the sputtering target material obtained.Another
Aspect, if the mean diameter of alloy powder is more than 300 μm, then is difficult to obtain densely sintered body.Therefore, alloy powder is flat
All particle diameters are preferably 5～300 μm.Advised it should be noted that heretofore described mean diameter is expressed as JIS Z 8901
Fixed, by utilizing the ball equivalent diameter of the light scattering method of laser.
For the cover layer formation sputtering target material of the present invention, it is preferred that except main composition element Ni,
The content of the inevitable impurity beyond Mo, Cu is few, in the range of the effect not damaging the present invention, can contain aerobic, nitrogen,
The inevitably impurity such as carbon, Fe, Al, Si.Herein, each main composition element is with overall relative to main composition element former
Sub-% represents, the inevitable impurity in addition to essential element represents with quality ppm overall relative to target.Such as oxygen,
Nitrogen is respectively below 1000 mass ppm, and carbon is below 200 mass ppm, and Al, Si are that 100 mass ppm are such as the following, except gas componant
Outside purity be preferably more than 99.9 mass %.
[embodiment 1]
First, the sputtering target material for forming cover layer is made.Table 1 illustrates the composition of made cover layer.Need
Bright, about the sputtering target material of No.4～No.10, weighing electrolysis Ni and block Mo raw material, oxygen-free copper block by ormal weight
After, utilize vacuum melting stove to make ingot casting by melting casting.It 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, is utilizing vacuum melting method by ormal weight too
After weighing electrolysis Ni and block Mo raw material, oxygen-free copper block, vacuum melting stove is utilized to make ingot casting by melting casting.
When by SmCo Magnetitum close to the ingot casting of each alloy obtained, confirm non-cohesive on Magnetitum.It addition, will be above-mentioned
A part for the ingot casting obtained is put in the container that magnetic characteristic measures, and uses the vibrating example that Riken Densi K. K. manufactures
Gaussmeter (model: VSM-5), measures magnetic characteristic under room temperature (25 DEG C), and results verification is non magnetic.
It addition, utilize powder metallurgic method to make the sputtering target material of Mo-30 atom %Ni.This is to be 6 μm by mean diameter
Mo powder mix with the Ni powder that mean diameter is 100 μm, fill to after in the tank of mild steel, heat and carry out very
Idle discharge gas also seals.Then, will seal after tank put in heat isostatic apparatus, 1100 DEG C, 100MPa, the condition of 3 hours
Under make it sinter to make sintered body.It addition, also made the sintered body of pure Mo by identical method.
By machining, each ingot casting obtained above and each sintered body are fabricated to diameter 100mm, the sputtering of thickness 5mm
Target.It addition, the sputtering target material of pure Ag uses the material that purity is 4N that Mitsubishi Materials Co., Ltd. manufactures.
It addition, the sputtering target material of pure Cu is the plate being made up of the oxygen-free copper that purity is 4N to be carried out machining prepare.
Then, by above-mentioned each sputtering target material soldering on backboard made of copper, it is arranged on ULVAC Co., Ltd. afterwards and manufactures
Sputter equipment (model: CS-200) on, under conditions of Ar atmosphere, pressure 0.5Pa, electric power 500W implement sputtering test, knot
Fruit arbitrarily sputtering target material all can sputter.
The glass substrate (product type: EagleXG) of 25mm × 50mm Corning company manufactured is arranged on above-mentioned spattering
On the substrate holder of injection device, form the cover layer of thickness 100nm, have rated adaptation and etching.It addition, No.11 and
No.13 is formed by the cosputtering method of the sputtering target material of sputtering Mo and Ni-30 atom %Cu simultaneously.No.12 is similarly to Mo-30
Atom %Ni and Ni-30 atom %Cu carries out cosputtering and is formed, and the composition being shown in table 1 is to utilize Shimadzu Scisakusho Ltd
Cover layer after forming these is carried out by the inductively coupled plasma emission spectrometer (ICP) (model: ICPV-1017) manufactured
The value obtained after analysis.
The method of Appreciation gist JIS K 5400 regulation of adaptation is carried out.First, at the table of cover layer of above-mentioned formation
The transparent adhesion band (ProductName: transparent beauty) that stickup Sumitomo, face 3M Co., Ltd. manufactures, cuts out the square square of 2mm with cutting knife
Otch, peel off transparent adhesion band, have rated intectate residual.1 piece of situation the most unstripped of cover layer is evaluated as
Zero, the situation having peeled off 1～10 piece is evaluated as △, the situation having peeled off more than 11 pieces is evaluated as ×.
About the evaluation of etching, carry out mixing the etchant as Ag using nitric acid, phosphoric acid, acetic acid and water.Cu's
Etchant uses the CuO of Northeast chemical industry2.The cover layer few in order to make lateral erosion, needs to suppress the inequality of etching period
Even, reduce overetch time, and suitably suppress the wettability to etchant.
Each sample be impregnated in etchant liquid, measure whole of cover layer completely through till required time as most preferably
Etching period.It addition, simultaneously while etched uneven by visualization, determine to obtain more specific difference
Through the time difference between time and the optimal etch time of a part for film.Its express time difference is the least, etch uneven more
Few.The 20 μ l etchants it addition, drip to film surface, the diffusion diameter after measuring 2 minutes.This represents the least expression of diffusion diameter more
Lateral erosion can be suppressed, more can carry out the etching that precision is high.
[table 1]
As shown in table 1, the adaptation of sample No.1, No.2, No.4 is low.It addition, understand sample No.3 by former containing 8
The Mo of sub-% and improve adaptation, but the optimal etch time is long.
On the other hand, can confirm that the cover layer of the present invention due in Ni Mo and Cu containing specified quantitative and significantly change
It is apt to adaptation.
It addition, for etching, it is known that: the cover layer of sample No.1, No.2 can be with the etchant of Cu 2
Etch within minute, but Ag etchant then needs the time of more than 18 minutes, thus inapplicable.It addition, it is fast to understand existence etching
Part and the slow part of etching, uneven and make time difference become big because producing etching, etchant easily spreads.Therefore, it is known that
It is difficult to etch uniformly, is unsuitable for the etching that precision is high.It addition, the Mo content confirming sample No.13, No.14 exceedes
The composition of 50 atom % creates residue after the etching.
On the other hand, though can confirm that the cover layer of sample No.5～No.12 as the present invention Cu and Ag this
Both etchants can also be etched below 90 seconds.The cover layer additionally confirming sample No.8～No.12 leads to
Cross the addition of increase Mo, the total amount of Mo and Cu be set to 36 more than atom % and make the optimal etch time shorten, its time
Difference and diffusion diameter also diminish, and etch uneven and lateral erosion is few, thus can carry out the etching that precision is high.
[embodiment 2]
Carry out the evaluation of oxidative resistance.Each sample is carried out with 50 DEG C, 250 DEG C, 300 DEG C, 350 DEG C in air atmosphere
The heat treated of 30 minutes, determines reflectance and resistance value.Reflectance uses Konica Minolta Co., Ltd. to manufacture
Spectral photometric colour measuring meter (model: CM2500d) measure, resistance value use diamond instruments system 4 terminal film resiativity meter (type
Number: MCP-T400) measure.
Use each sputtering target material of preparing in embodiment 1, with being formed on glass substrate to have made and depend on shown in table 2
Secondary film forming has the sample of the stacking wiring membrane of the cap layer of the basal layer of thickness 30nm, the Cu conductive layer of thickness 300nm, thickness 50nm
Product.It should be noted that above-mentioned basal layer and cap layer are the cover layer material compositions of table 2.
[table 2]
As shown in table 2, can confirm that the cover layer of the application of the invention can greatly improve oxidative resistance.
On film substrate, heat resisting temperature based on thin film and need until the oxidative resistance of 250 DEG C.As shown in table 2, it is known that
Although when sample No.4 is more than 250 DEG C, reflectance starts to reduce, even if but the electronic component-use stacking wiring membrane warp of the present invention
Cross the air heating of 250 DEG C, it is possible to maintain the high reflectance of more than 50%, there is high oxidation resistance.Especially can confirm that
In the case of increasing the addition of Mo, this effect is big.
Furthermore it is possible to confirm the electronic component-use stacking wiring membrane of the present invention even across 250 DEG C, 300 DEG C, 350 DEG C
Air heating also can suppress the rising of resistance value, oxidative resistance can be improved.
[embodiment 3]
Then, each electronic component-use stacking wiring membrane of embodiment 2 is used to carry out the evaluation of weatherability.About weatherability
Evaluation, by each electronic component-use stacking wiring membrane temperature 85 DEG C, relative humidity 85% atmosphere under place 100 hours, 200
Hour, after 300 hours, determine reflectance similarly to Example 2.It should be noted that be shown in basal layer and the cap layer of table 3
It it is the cover layer material composition of table 3.
[table 3]
As shown in table 3, as sample No.13, No.14 of comparative example owing to the content of Mo is more than 50 atom %, so with
The process of time, reflectance reduction.
On the other hand, can confirm that the electronic component-use stacking wiring of sample No.5～No.12 as example of the present invention
Film even when exposed under hot and humid atmosphere also will not variable color, after 300 hour, also can maintain high reflectance, have high
Moisture-proof.
According to foregoing, can confirm that the electronic component-use stacking wiring membrane of the application of the invention, it is possible to guaranteeing
Wet etching is stably carried out with while the adaptation of conductive layer, oxidative resistance, weatherability.
[embodiment 4]
Then, each sputtering target material prepared in embodiment 1 is used, to be shown in the composition of table 4, at band ito film thin film base
Make film forming successively on plate or glass substrate and have the basal layer of thickness 30nm, the Ag conductive layer of thickness 200nm, the cover of thickness 30nm
The sample of the stacking wiring membrane of layer.It should be noted that above-mentioned basal layer and cap layer refer to the cover layer material composition of table 4.
The evaluation of adaptation, is affixed on layer by the transparent adhesion band (ProductName: transparent beauty) that Sumitomo 3M Co., Ltd. manufactures
On folded wiring membrane, with rubber wiping surface, peel off transparent adhesion band, have rated intectate residual.Cover layer is not shelled
From situation be evaluated as zero, the situation having peeled off about about 10% is evaluated as △, the situation evaluation of more than 20% will have been peeled off
For ×.
Ag from Cu is different, even if carrying out the heating of 350 DEG C in atmosphere, resistance value also will not be significantly increased, so oxytolerant
Each sample similarly to Example 2, is carried out 30 minutes add with 150 DEG C, 250 DEG C, 350 DEG C by the evaluation of the property changed in air atmosphere
Heat treatment, determines reflectance.
It addition, the evaluation of weatherability is similarly to Example 3, by each sample in temperature 85 DEG C, the atmosphere of relative humidity 85%
Lower placement 100 hours, 200 hours, after 300 hours, determine reflectance.
[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 improves close by increasing the content of Mo
Conjunction property, particularly Mo content has obtained high adaptation at sample No.8～No.12 of 22 more than atom %.
It should be noted that for thermostability, when carrying out the heating of 350 DEG C, film substrate creates pleat
Wrinkle.Furthermore it is possible to confirm in the case of using Ag as conductive layer, the sample as example of the present invention is being heated to 250 DEG C
Time, inhibit the variable color of Ag conductive layer because of high oxidative resistance.Additionally can confirm that for weatherability, as this
The sample of bright example inhibits the variable color of Ag conductive layer too because having high-weatherability.
Claims (6)
1. an electronic component-use stacking wiring membrane, it is characterised in that include by Ag, Ag alloy, Cu and Cu alloy
A kind of conductive layer made and at least cover the cover layer in a face of this conductive layer, described cover layer contains 5～50 atom %
Mo, containing adding up to this Mo and Cu of 60 below atom %, surplus is made up of Ni and inevitable impurity.
Electronic component-use stacking wiring membrane the most according to claim 1, it is characterised in that described cover layer contains 5～25
The described Cu of atom %, containing the described Mo and described Cu adding up to 36 more than atom %.
3. according to the electronic component-use stacking wiring membrane described in claim 1 or claim 2, it is characterised in that described covering
The layer described Mo containing 26～40 atom %.
4. a cover layer formation sputtering target material, it is characterised in that it is for forming the sputtering target material of cover layer, described in cover
Cap rock covers by a kind of conductive layer made in Ag, Ag alloy, Cu and Cu alloy, described cover layer formation sputtering target
Mo that material contains 5～50 atom %, containing adding up to this Mo and Cu of 60 below atom %, surplus is by Ni and the most miscellaneous
Matter forms, and the curie point of described cover layer formation sputtering target material is below room temperature.
Cover layer formation sputtering target material the most according to claim 4, it is characterised in that containing the institute of 5～25 atom %
State Cu, containing the described Mo and described Cu that add up to 36 more than atom %.
6. according to the cover layer formation sputtering target material described in claim 4 or claim 5, it is characterised in that containing 26～
The described Mo of 40 atom %.
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| JP2015-057552 | 2015-03-20 | ||
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| JP (1) | JP6706418B2 (en) |
| KR (1) | KR101840109B1 (en) |
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| JP6443220B2 (en) * | 2015-05-25 | 2018-12-26 | 住友金属鉱山株式会社 | Alloy target for sputtering |
| AT15574U3 (en) * | 2017-05-11 | 2018-05-15 | Plansee Se | Flexible component with layer structure with metallic layer |
| JP6950447B2 (en) * | 2017-10-20 | 2021-10-13 | 大同特殊鋼株式会社 | Semiconductor device |
| CN111183508A (en) * | 2017-11-09 | 2020-05-19 | 三井金属矿业株式会社 | Wiring structure and target material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006310814A (en) * | 2005-03-29 | 2006-11-09 | Hitachi Metals Ltd | Thin film wiring layer |
| CN104425416A (en) * | 2013-09-10 | 2015-03-18 | 日立金属株式会社 | Stacked wiring film and manufacturing method thereof, and Ni alloy sputtering target material |
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| JPS5522948A (en) * | 1978-08-09 | 1980-02-19 | Toyo Kasei Kk | Manufacture of record disc with picture |
| JP4496518B2 (en) | 2002-08-19 | 2010-07-07 | 日立金属株式会社 | Thin film wiring |
| JP5203908B2 (en) | 2008-12-04 | 2013-06-05 | 新日鉄住金マテリアルズ株式会社 | Ni-Mo alloy sputtering target plate |
| JP2012222166A (en) * | 2011-04-08 | 2012-11-12 | Ulvac Japan Ltd | Wiring film, thin film transistor, target, wiring film formation method |
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2016
- 2016-02-10 JP JP2016023190A patent/JP6706418B2/en active Active
- 2016-02-24 TW TW105105341A patent/TWI576454B/en active
- 2016-03-16 KR KR1020160031260A patent/KR101840109B1/en active IP Right Grant
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006310814A (en) * | 2005-03-29 | 2006-11-09 | Hitachi Metals Ltd | Thin film wiring layer |
| CN104425416A (en) * | 2013-09-10 | 2015-03-18 | 日立金属株式会社 | Stacked wiring film and manufacturing method thereof, and Ni alloy sputtering target material |
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| Publication number | Publication date |
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| JP2016178286A (en) | 2016-10-06 |
| TW201706432A (en) | 2017-02-16 |
| TWI576454B (en) | 2017-04-01 |
| KR101840109B1 (en) | 2018-04-26 |
| CN105986233B (en) | 2018-08-07 |
| KR20160112995A (en) | 2016-09-28 |
| JP6706418B2 (en) | 2020-06-10 |
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