CN104611615B - Ni-Cu ALLOY TARGET MATERIAL FOR Cu ELECTRODE PROTECTIVE FILM AND LAMINATED FILM - Google Patents
Ni-Cu ALLOY TARGET MATERIAL FOR Cu ELECTRODE PROTECTIVE FILM AND LAMINATED FILM Download PDFInfo
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Abstract
The invention aims to provide a Ni-Cu alloy target material used in a Cu electrode protection film and a laminated film manufactured by using the target material, wherein, the target material can be used as a protection film of the Cu electrode, can restrain an electrical characteristic degradation caused by the electrolytic corrosion or atomic diffusion of the Cu electrode, can form patterns in a higher precision via a wet etching method, can form a protection film having good attachment performance on a transparent electrode and can carry out sputtering effectively. The invention relates to the Ni-Cu alloy target material used in the Cu electrode protection film and the laminated film manufactured by using the target material, the target material comprises, by mass, 15%≤Cu≤55%, and 0.5%≤Cr, Ti≤10.0%, with the balance being Ni and unavoidable impurities..
Description
The application is the applying date for August in 2011 30 days, Application No. 201110261494.5, entitled " Cu is electric
The divisional application of the application of pole protecting film NiCu alloy target materials and stack membrane ".
Technical field
The present invention relates to Cu electrode protective membranes NiCu alloy target materials and stack membrane, specifically, the present invention relates to
Cu electrode protective membranes NiCu alloy target materials in the Cu electrode protective membranes for forming the electrode as touch panel or liquid crystal panel,
And the stack membrane manufactured using the target.
Background technology
Liquid crystal panel used in touch panel and slim big frame TV etc. has between 2 pieces of transparency carriers
It is closed with structure as liquid crystal.The working electrode as liquid crystal is formed with the inner side (one side of liquid crystal side) of transparency carrier
Transparency electrode.In transparency electrode, tin indium oxide (ITO) is generally used.In addition, in the substrate surface for being formed with transparency electrode
Metal electrode or metal wiring as outside lead-out terminal are formed with a part and (they are referred to as below " metal electricity
Pole ").In substrate surface, metal electrode is formed in part (for example, the peripheral part of the substrate) place for not needing printing opacity.
In the case of the metal electrode of formation directly on a surface of transparency electrode, when between transparency electrode and metal electrode
When standard electric potential difference (potential difference) is larger, there is electrolytic etching in metal electrode.In addition, being sometimes formed at the bottom of substrate surface
There is the phase counterdiffusion of atom between metal electrode, so as to the electrical characteristics of metal electrode are deteriorated.Therefore, typically in metal
The two sides of electrode is respectively formed the protecting film (barrier layer) for protecting metal electrode.In existing liquid crystal panel, generally use
Al-Nd systems alloy as metal electrode, and using Mo-Nb systems alloy as protecting film.
With regard to the metal electrode used in this liquid crystal panel, protecting film and for forming their material, one
There are various motions since straight.
For example, Patent Document 1 discloses such thin film formation sputtering target：It contains 2～50 atom %'s altogether
Selected from one of V and Nb or both, balance of Mo and inevitable impurity, and its relative density is more than 95%.
Describe in the publication：During using the Mo alloys targets containing Nb or V, can obtain without harmful Cr, resistance
The high metallic film of low and corrosion resistance.
In addition, Patent Document 2 discloses such sputtering target material：Its using Mo as main body, containing 0.5～50 atom %
The metallic element M in Ti, Zr, V, Nb, Cr, and with predetermined tissue.
Describe in the publication：By raw material powder mixture compression molding to form formed body, the formed body is crushed
Powder is formed again, and by the powder pressure sintering, thereby inhibiting the segregation of composition, and also improve the plasticity of sintered body
Processability.
In addition, Patent Document 3 discloses such target part：The target part is not the protecting film target of metal electrode
Material, it contains Ni：70～85 weight %, Cu：2～10 weight % and Mo：1～6 weight % and/or Cr：0.5～3 weight
Amount %, surplus is substantially made up of Fe, and the grain size number in the face of Jing sputterings is than JIS austinite grain size numbering No.3
It is little.
Describe in the publication：During using this target, it is possible to obtain coercive force is low and uniform Fe-Ni alloy/C thin film.
In addition, Patent Document 4 discloses such evaporation Ni-Fe based alloys：The alloy is not the guarantor of metal electrode
Cuticula target, it contains Ni：35～85 weight %, more than a kind in Mo, Cr, Cu and Nb：3～15 weight %, Al：1
Below weight %, Ca and/or Mg：Below 300ppm, O：Below 30ppm, N：Below 30ppm, surplus is substantially Fe.
Describe in the publication：By using this target, it is possible to obtain the thin magnetic film of the high characteristic of very high purity.
In addition, disclosing such method in non-patent literature 1：Using Ar+O2 mixed gas to by Cu-2 weight %
The target that Zr alloys, Cu-1 weight %Mo alloy or Cu-0.7 weight %Mg alloy are constituted is sputtered.
Describe in the publication：By adopting the method, can the layer (metal electrode) that is made up of Cu based materials with
Interface between bottom forms the barrier layer (oxide layer) good with the adhesion of bottom.
In addition, Patent Document 5 discloses such sputtering target：It is not the protecting film target of metal electrode, its by
Ni-7.5 mass %Ti-4～40 mass %Cu alloy is constituted, and can be used to form the electrode of chip resister.
Describe in the publication：When adding Cu in Ni-Ti alloys, because saturation magnetization diminishes, therefore can be with
Obtain long-life target.
In addition, Patent Document 6 discloses such nickel alloy sputtering target for forming barrier layer：It is not metal electricity
The protecting film target of pole, its by
(a) Ni-25 atom %Cu-2 atom %Cr alloys (Ni-26.6 mass %Cu-1.7 mass %Cr alloys) or
B () Ni-25 atom %Cu-12 atom %Ti alloys (Ni-27.1 mass %Cu-9.8 mass %Ti alloys) is formed.
Describe in the publication：Formed using the target with such composition during barrier layer, the expansion of Sn can be suppressed
Dissipate.
With the maximization of liquid crystal panel, people's demand material lower than the resistance of Al based material.In addition, matching somebody with somebody in Al systems
Mo-Nb systems alloy used in the protecting film of line is expensive, becomes the obstacle of liquid crystal panel cost degradation.On the other hand, Cu
Based material is lower than the resistance of Al based material, expects the low resistance wiring material of Al based materials as an alternative.
As the forming method of the metal electrode and Cu electrode protective membranes for having used Cu based materials, such as in non-patent literature 1
As disclosed, it is known in Ar+O2The target formed by Cu systems alloy is sputtered method under atmosphere.The document is remembered
The method of load has the advantage that：Can be while forming Cu electrodes and protecting film by once sputtering.
But, in Ar+O2Reactive sputtering under atmosphere increases the resistance of Cu electrode films itself, causes deterioration in characteristics.
Further, since O2Easily it is captured in vacuum equipment room, therefore, it is difficult to control oxygen partial pressure, uneven so as to become product quality
The reason for.
In addition, in general, metal electrode and protecting film are formed by such method：It is being formed with the base of transparency electrode
Protecting film and electrode layer are formed in plate whole surface, and pattern is formed with predetermined shape.When the cost of liquid crystal panel is reduced,
It is preferred that forming pattern using wet etching.Further, in order to accurately form pattern with wet etching, preferably
It is that the etch-rate of protecting film and electrode layer is of substantially equal.
But, using in metal electrode and protecting film that method disclosed in non-patent literature 1 is obtained, both etchings are fast
Rate difference is larger, therefore there is a problem that accurately forming pattern.
In addition, in the case of liquid crystal panel, Cu electrode protective membranes are formed on the transparency electrode being made up of ITO.Cause
This, it is desirable to Cu electrode protective membranes have high adhesion with ITO.In addition, in order to effectively be sputtered, it is desirable to the saturating magnetic of target
Rate is low.But, so far, still nobody proposes all possess the Cu electrode protective membranes target of these conditions and make simultaneously
The example of the stack membrane manufactured with this target.
[prior art literature]
[patent documentation]
Patent documentation 1：Japanese Unexamined Patent Publication 2002-327264 publications
Patent documentation 2：Japanese Unexamined Patent Publication 2005-290409 publications
Patent documentation 3：Japanese Unexamined Patent Application 62-186511 publication
Patent documentation 4：Japanese Unexamined Patent Application 63-100148 publication
Patent documentation 5：Japanese Unexamined Patent Publication 2005-171341 publications
Patent documentation 6：International Publication WO2005/041290
[non-patent literature]
Non-patent literature 1：High pool is realized, etc.；Ulvac Technical Journal, the 69th phase, page 7,2009
The content of the invention
Problems to be solved by the invention
The problem to be solved in the present invention is to provide a kind of Cu electrode protective membranes Ni-Cu alloy target materials and use this
The stack membrane of target manufacture is planted, wherein the target
A () can act as the protecting film of Cu electrodes, can suppress by Cu electrodes electrolytic etching or atoms permeating caused
Electrical characteristics deterioration, and can pass through wet etching formed can with higher precision pattern protecting film；
B () can form the protecting film good with the adhesion of transparency electrode, and
C () can effectively be sputtered.
The means of solve problem
In order to solve the above problems, the Cu electrode protective membranes according to the present invention first aspect of Ni-Cu alloy target materials
It is characterized by：
Containing 15.0 mass %≤Cu≤55.0 mass % and 0.5 mass %≤mass % (its of (Cr, Ti)≤10.0
In, Cr>0, Ti>0), balance of Ni and inevitable impurity.
Cu electrode protective membranes involved in the present invention are characterized by with the second aspect of Ni-Cu alloy target materials：
Containing 15.0 mass %≤Cu≤55.0 mass % and 0.5 mass %≤Cr≤10.0 mass %, balance of Ni
And inevitable impurity.
Cu electrode protective membranes involved in the present invention are characterized by with the third aspect of Ni-Cu alloy target materials：
Containing 15.0 mass %≤Cu≤55.0 mass % and 0.5 mass %≤Ti≤10.0 mass %, balance of Ni
And inevitable impurity.
Moreover, it relates to stack membrane have：Cu electrodes and the Cu electrodes one or both sides formed
Protecting film, the protecting film is by thin with Ni-Cu alloy target material film forming using Cu electrode protective membranes involved in the present invention
Film is formed.
Invention effect
When Cr and/or Ti of scheduled volume is added to Ni-15～55Cu alloys, the etching rate difference of the alloy and Cu electrodes
Diminish, while also diminishing with the potential difference between the peripheral parts such as Cu electrodes or ITO.Therefore, the alloy is used as into liquid crystal panel
In Cu electrodes used protecting film when, can suppress by Cu electrodes electrolytic etching or atoms permeating institute caused by electrical characteristics it is bad
Change, and pattern can accurately be formed by wet etching.
In addition, when Cr and/or Ti of scheduled volume is added to Ni-15～55Cu alloys, the patch of the alloy and transparency electrode
Attached property is improved.Further, since the maximum magnetic susceptibility of Ni-15～55Cu alloys diminishes, when using it for target, can effectively carry out
Sputtering.
Description of the drawings
[Fig. 1] Fig. 1 (A) be illustrate the Cu contents of Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys with it is relative
The figure of the relation between the potential difference △ V of ITO.Fig. 1 (B) is to illustrate Ni-35 mass %Cu-x mass %Cr (x=0～11)
The Cr contents of alloy and the figure relative to the relation between the potential difference △ V of ITO.
[Fig. 2] Fig. 2 (A) be illustrate the Cu contents of Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys with it is relative
The figure of the relation between the potential difference △ V of Cu.Fig. 2 (B) is closed to illustrate Ni-35 mass %Cu-x mass %Cr (x=0～11)
The Cr contents and the figure relative to the relation between the potential difference △ V of Cu of gold.
[Fig. 3] Fig. 3 (A) is Cu contents and the etching for illustrating Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys
The figure of the relation between speed difference.Fig. 3 (B) is to illustrate that the Cr of Ni-35 mass %Cu-x mass %Cr (x=0～11) alloys contains
The figure of the relation between amount and etching rate difference.
[Fig. 4] Fig. 4 (A) is to illustrate the Cu contents of Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys and peel off
Rate (ITO：20nm, NiCuCr：The figure of the relation between 50nm).Fig. 4 (B) is to illustrate Ni-35 mass %Cu-x mass %Cr (x
=0～11) the Cr contents of alloy and stripping rate (ITO：20nm, NiCuCr：The figure of the relation between 50nm).
[Fig. 5] Fig. 5 (A) is to illustrate the Cu contents of Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys and peel off
Rate (ITO：20nm, NiCuCr：The figure of the relation between 200nm).Fig. 5 (B) is to illustrate Ni-35 mass %Cu-x mass %Cr (x
=0～11) the Cr contents of alloy and stripping rate (ITO：20nm, NiCuCr：The figure of the relation between 200nm).
[Fig. 6] Fig. 6 (A) is to illustrate the Cu contents of Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys and peel off
Rate (ITO：150nm, NiCuCr：The figure of the relation between 50nm).Fig. 6 (B) is to illustrate Ni-35 mass %Cu-x mass %Cr (x
=0～11) the Cr contents of alloy and stripping rate (ITO：150nm, NiCuCr：The figure of the relation between 50nm).
[Fig. 7] Fig. 7 (A) is to illustrate the Cu contents of Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys and peel off
Rate (ITO：150nm, NiCuCr：The figure of the relation between 200nm).Fig. 7 (B) is to illustrate Ni-35 mass %Cu-x mass %Cr
The Cr contents of (x=0～11) alloy and stripping rate (ITO：150nm, NiCuCr：The figure of the relation between 200nm).
[Fig. 8] Fig. 8 (A) is the Cu content and maximum for illustrating Ni-x mass %Cu-3 mass %Cr (x=10～60) alloys
The figure of the relation between magnetic susceptibility μ.Fig. 8 (B) is to illustrate that the Cr of Ni-35 mass %Cu-x mass %Cr (x=0～11) alloys contains
The figure of the relation between amount and maximum magnetic susceptibility μ.
[Fig. 9] Fig. 9 (A) be illustrate the Cu contents of Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys with it is relative
The figure of the relation between the potential difference △ V of ITO.Fig. 9 (B) is closed to illustrate Ni-35 mass %Cu-x mass %Ti (x=0～7)
The Ti contents and the figure relative to the relation between the potential difference △ V of ITO of gold.
[Figure 10] Figure 10 (A) is the Cu content and phase for illustrating Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys
The figure of the relation between potential difference △ V for Cu.Figure 10 (B) is to illustrate Ni-35 mass %Cu-x mass %Ti (x=0～7)
The Ti contents of alloy and the figure relative to the relation between the potential difference △ V of Cu.
[Figure 11] Figure 11 (A) is Cu contents and the erosion for illustrating Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys
The figure of the relation between etching speed difference.Figure 11 (B) is the Ti for illustrating Ni-35 mass %Cu-x mass %Ti (x=0～7) alloys
The figure of the relation between content and etching rate difference.
[Figure 12] Figure 12 (A) is Cu contents and the stripping for illustrating Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys
From rate (ITO：20nm, NiCuTi：The figure of the relation between 50nm).Figure 12 (B) is to illustrate Ni-35 mass %Cu-x mass %Ti
The Ti contents of (x=0～7) alloy and stripping rate (ITO：20nm, NiCuTi：The figure of the relation between 50nm).
[Figure 13] Figure 13 (A) is Cu contents and the stripping for illustrating Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys
From rate (ITO：20nm, NiCuTi：The figure of the relation between 200nm).Figure 13 (B) is to illustrate Ni-35 mass %Cu-x mass %
The Ti contents of Ti (x=0～7) alloy and stripping rate (ITO：20nm, NiCuTi：The figure of the relation between 200nm).
[Figure 14] Figure 14 (A) is Cu contents and the stripping for illustrating Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys
From rate (ITO：150nm, NiCuTi：The figure of the relation between 50nm).Figure 14 (B) is to illustrate Ni-35 mass %Cu-x mass %
The Ti contents of Ti (x=0～7) alloy and stripping rate (ITO：150nm, NiCuTi：The figure of the relation between 50nm).
[Figure 15] Figure 15 (A) is Cu contents and the stripping for illustrating Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys
From rate (ITO：150nm, NiCuTi：The figure of the relation between 200nm).Figure 15 (B) is to illustrate Ni-35 mass %Cu-x mass %
The Ti contents of Ti (x=0～7) alloy and stripping rate (ITO：150nm, NiCuTi：The figure of the relation between 200nm).
[Figure 16] Figure 16 (A) be illustrate the Cu contents of Ni-x mass %Cu-3 mass %Ti (x=10～60) alloys with most
The figure of the relation between big magnetic susceptibility μ.Figure 16 (B) is the Ti for illustrating Ni-35 mass %Cu-x mass %Ti (x=0～7) alloys
The figure of the relation between content and maximum magnetic susceptibility μ.
Specific embodiment
One embodiment of the invention is described in detail below.
[1.Cu electrode protective membranes are with Ni-Cu alloys targets (1)：NiCuCr alloys]
[1.1. compositions]
The Cu electrode protective membrane Ni-Cu alloy target materials that first embodiment of the invention is related to contain following element, and
Surplus is made up of Ni and inevitable impurity.The species of addition element and the restriction reason of addition are as described below.
(1) 15.0 mass %≤Cu≤55.0 mass %
Cu contents in NiCu alloys can affect the difference (current potential of the normal potential between the alloy and Cu electrodes or ITO
Difference) or the etching rate difference that affects between the alloy and Cu electrodes.In addition, Cu contents can also affect the saturating magnetic of NiCu alloys
Rate.
In general, Cu contents are fewer, and the potential difference between peripheral parts is bigger, and resistance to electrolytic etching is reduced.
In addition, etch-rate is slack-off compared with Cu electrodes, the credibility of electrode is reduced.It is wet if the etch-rate of protecting film is excessively slow
The section of the protecting film/electrode/protecting film after formula etching becomes concavity.And, Cu contents are fewer, and the resistance of protecting film is bigger,
The credibility of electrode is reduced.In addition, Cu contents are fewer, maximum magnetic susceptibility μm increases.
Therefore, Cu contents are needed more than 15.0 mass %.Cu contents are further excellent more preferably more than 25.0 mass %
It is selected in more than 30.0 mass %.
On the other hand, if Cu contents surplus, become big with the potential difference of peripheral parts on the contrary.In addition, compared with Cu electrodes
Etch-rate is too fast, and the credibility of electrode is reduced.If the etch-rate of protecting film is too fast, the protecting film after Wet-type etching/
The section of electrode/protecting film becomes convex.And, if Cu contents surplus, due to compound between precipitating metal, thus processability
Reduce.
Therefore, Cu contents are needed below 55.0 mass %.Cu contents are further excellent more preferably below 45.0 mass %
It is selected in below 40.0 mass %, still more preferably below 35.0 mass %.
(2) 0.5 mass %≤Cr≤10.0 mass %
Potential difference between the NiCu alloys of the Cu containing relative more amount and peripheral parts (particularly Cu electrodes) becomes big,
And, etch-rate is accelerated compared with Cu electrodes.Cr has makes the potential difference between the NiCu alloys and peripheral parts diminish,
And making the etch-rate of NiCu alloys reduces the effect of (close to Cu electrodes).In addition, Cr also has improving and transparency electrode
(ITO) effect of adhesion.
In general, Cr contents are fewer, and the potential difference between peripheral parts becomes big, and resistance to electrolytic etching is reduced.In addition,
Etch-rate is too fast compared with Cu electrodes, and the credibility of electrode is reduced.And, Cr contents are fewer, the adhesion with transparency electrode
Reduce.
Therefore, Cr contents are needed more than 0.5 mass %.Cr contents more preferably more than 1.0 mass %, further preferably
More than 3.0 mass %.
On the other hand, if Cr contents surplus, become big with the potential difference of peripheral parts on the contrary.In addition, compared with Cu electrodes
Etch-rate is too fast, and the credibility of electrode is reduced.
Therefore, Cr contents are needed below 10.0 mass %.Cr contents are further excellent more preferably below 7.0 mass %
It is selected in below 5.0 mass %.
[1.2. purposes]
The target that first embodiment of the invention is related to can be used for forming protecting film, and the protecting film is used to protect Cu electric
Pole.
Herein, " Cu electrodes " refers to such electrode：It is (concrete next by pure Cu or with the resistance equal with pure Cu
Say, about 2～3 μ Ω cm) Cu alloys constitute.
In addition, the target that the present embodiment is related to can be used for the purposes beyond Cu electrode protective membranes.As other
Purposes, specifically there is electrode film, reflectance coating etc..
Cu electrode protective membranes are typically incorporated in the two sides of Cu electrodes.For example, it is pre- using having in the case of liquid crystal panel
The target of fixed composition, in the substrate surface for being formed with transparency electrode Cu electrode protective membranes, Cu electrodes and Cu electrodes are sequentially formed
Protecting film.Then, using wet etching, Cu electrode protective membranes/Cu electrodes/Cu electrode protective membranes are formed with predetermined shape
Pattern.
On the other hand, according to purposes, also on the one side of Cu electrodes protecting film is formed sometimes.For example, in the situation of TFT
Under, using the target with predetermined composition, in the substrate surface for being formed with transparency electrode Cu electrode protective membranes and Cu are sequentially formed
Electrode.Then, using wet etching, Cu electrode protective membranes/Cu electrodes are formed by pattern with predetermined shape.
[2.Cu electrode protective membranes are with Ni-Cu alloy target materials (2)：NiCuTi alloys]
[2.1. compositions]
The Cu electrode protective membrane Ni-Cu alloy target materials that second embodiment of the invention is related to contain following element, and
Surplus is made up of Ni and inevitable impurity.The species of addition element and the restriction reason of addition are as described below.
(1) 15.0 mass %≤Cu≤55.0 mass %
Cu contents in NiCu alloys can affect the difference (current potential of the normal potential between the alloy and Cu electrodes or ITO
Difference) or the etching rate difference that affects between the alloy and Cu electrodes.In addition, Cu contents can also affect the saturating magnetic of NiCu alloys
Rate.
In general, Cu contents are fewer, and the potential difference between peripheral parts is bigger, and resistance to electrolytic etching is reduced.
In addition, etch-rate is slack-off compared with Cu electrodes, the credibility of electrode is reduced.It is wet if the etch-rate of protecting film is excessively slow
The section of the protecting film/electrode/protecting film after formula etching becomes concavity.And, Cu contents are fewer, and the resistance of protecting film is bigger,
The credibility of electrode is reduced.In addition, Cu contents are fewer, maximum magnetic susceptibility μm increases.
Therefore, Cu contents are needed more than 15.0 mass %.Cu contents are further excellent more preferably more than 25.0 mass %
It is selected in more than 30.0 mass %.
On the other hand, if Cu contents surplus, become big with the potential difference of peripheral parts on the contrary.In addition, compared with Cu electrodes
Etch-rate is too fast, and the credibility of electrode is reduced.If the etch-rate of protecting film is too fast, the protecting film after Wet-type etching/
The section of electrode/protecting film becomes convex.And, if Cu contents surplus, due to compound between precipitating metal, thus processability
Reduce.
Therefore, Cu contents are needed below 55.0 mass %.Cu contents are further excellent more preferably below 45.0 mass %
It is selected in below 40.0 mass %, still more preferably below 35.0 mass %.
(2) 0.5 mass %≤Ti≤10.0 mass %
Potential difference between the NiCu alloys of the Cu containing relative more amount and peripheral parts (particularly Cu electrodes) becomes big,
And, etch-rate is accelerated compared with Cu electrodes.Ti has makes the potential difference between the NiCu alloys and peripheral parts diminish,
And making the etch-rate of NiCu alloys reduces the effect of (close to Cu electrodes).In addition, Ti also has improving and transparency electrode
(ITO) effect of adhesion.
In general, Ti contents are fewer, and the potential difference between peripheral parts becomes big, and resistance to electrolytic etching is reduced.In addition,
Etch-rate is too fast compared with Cu electrodes, and the credibility of electrode is reduced.And, Ti contents are fewer, the adhesion with transparency electrode
Reduce.
Therefore, Ti contents are needed more than 0.5 mass %.Ti contents more preferably more than 1.0 mass %, further preferably
More than 3.0 mass %.
On the other hand, if Ti contents surplus, become big with the potential difference of peripheral parts on the contrary.In addition, compared with Cu electrodes
Etch-rate is excessively slow, and the credibility of electrode is reduced.
Therefore, Ti contents are needed below 10.0 mass %.Ti contents are further excellent more preferably below 7.0 mass %
It is selected in below 5.0 mass %.
[2.2. purposes]
The purposes of the target being related to regard to second embodiment of the invention, due to identical with the first embodiment, therefore saves
Omit detailed description thereof.
[3.Cu electrode protective membranes are with Ni-Cu alloy target materials (3)：NiCuCrTi alloys]
[3.1. compositions]
The Cu electrode protective membrane Ni-Cu alloy target materials that third embodiment of the invention is related to contain following element, and
Surplus is made up of Ni and inevitable impurity.The species of addition element and the restriction reason of addition are as described below.
(1) 15.0 mass %≤Cu≤55.0 mass %
Cu contents in NiCu alloys can affect the difference (current potential of the normal potential between the alloy and Cu electrodes or ITO
Difference) or the etching rate difference that affects between the alloy and Cu electrodes.In addition, Cu contents can also affect the saturating magnetic of NiCu alloys
Rate.
In general, Cu contents are fewer, and the potential difference between peripheral parts is bigger, and resistance to electrolytic etching is reduced.
In addition, etch-rate is slack-off compared with Cu electrodes, the credibility of electrode is reduced.It is wet if the etch-rate of protecting film is excessively slow
The section of the protecting film/electrode/protecting film after formula etching becomes concavity.And, Cu contents are fewer, and the resistance of protecting film is bigger,
The credibility of electrode is reduced.In addition, Cu contents are fewer, maximum magnetic susceptibility μm increases.
Therefore, Cu contents are needed more than 15.0 mass %.Cu contents are further excellent more preferably more than 25.0 mass %
It is selected in more than 30.0 mass %.
On the other hand, if Cu contents surplus, become big with the potential difference of peripheral parts on the contrary.In addition, compared with Cu electrodes
Etch-rate is too fast, and the credibility of electrode is reduced.If the etch-rate of protecting film is too fast, the protecting film after Wet-type etching/
The section of electrode/protecting film becomes convex.And, if Cu contents surplus, due to compound between precipitating metal, thus processability
Reduce.
Therefore, Cu contents are needed below 55.0 mass %.Cu contents are further excellent more preferably below 45.0 mass %
It is selected in below 40.0 mass %, still more preferably below 35.0 mass %.
(2) 0.5 mass %≤mass % of (Cr, Ti)≤10.0, but Cr>0、Ti>0
As described above, Cr and Ti are respectively provided with following effect：
A () makes the effect that the potential difference between NiCu alloys and peripheral parts reduces；
B () makes the etch-rate of NiCu alloys slow down the effect of (close to Cu electrodes)；And
C () improves the effect with the adhesion of transparency electrode (ITO).
If adding Cr and Ti simultaneously in NiCu alloys, with such effect：Etch-rate and patch are kept same
While attached property so that further reduce with the potential difference of peripheral parts.
In general, Cr and/or Ti contents are fewer, and the potential difference between peripheral parts becomes big, resistance to electrolytic etching drop
It is low.In addition, etch-rate is too fast compared with Cu electrodes, the credibility of electrode is reduced.Therefore, the total content of Cr and Ti needs
It is more than 0.5 mass %.The total content of Cr and Ti more preferably more than 1.0 mass %, further preferably more than 3.0 mass %.
On the other hand, if the content surplus of Cr and/or Ti, become big with the potential difference of peripheral parts on the contrary.In addition, and Cu
Electrode compares that etch-rate is excessively slow, and the credibility of electrode is reduced.Therefore, Cr and Ti total content need 10.0 mass % with
Under.The total content of Cr and Ti more preferably below 7.0 mass %, further preferably below 5.0 mass %.
[3.2. purposes]
The purposes of the target being related to regard to third embodiment of the invention, due to identical with the first embodiment, therefore saves
Omit detailed description thereof.
[4. stack membrane]
Stack membrane according to the present invention has Cu electrodes and the protection formed on the one or both sides of the Cu electrodes
Film, the protecting film with the thin film after Ni-Cu alloy target material film forming using Cu electrode protective membranes involved in the present invention by being constituted.
[4.1.Cu electrodes]
The thickness of Cu electrodes preferably selects optimal thickness according to purpose.In general, Cu electrodes are thicker, work more steady
It is fixed.But, if Cu electrodes are blocked up, not only etching or adhesion are reduced, and also result in film rupture.Therefore, Cu electrodes
Thickness is preferably 50～500nm.The thickness of Cu electrodes is more preferably 100～400nm, more preferably 150～250nm.
With regard to the other side of Cu electrodes, due to it is described above as, therefore omit its description.
[4.2. protecting film]
The thickness of protecting film preferably selects optimal thickness according to purpose.In general, protecting film is thicker, and durability is got over
It is high.But, if protecting film is blocked up, then etching or adhesion are reduced.Therefore, the thickness of protecting film be preferably 5～
100nm.The thickness of protecting film is more preferably 5～70nm, more preferably 5～50nm.
In the case where the two sides of Cu electrodes forms protecting film, the composition of the protecting film in each face can with mutually the same or
Can be with difference.That is, in the case where the two sides of Cu electrodes forms protecting film, the target of same composition can be adopted to form each face
Protecting film.Or, the first target can be adopted to form the protecting film of one side, and using different from the composition of the first target the
Two targets form the protecting film of another side.
With regard to the film build method of protecting film, there is no particular limitation, can adopt various methods according to purpose.As using
The film build method of the protecting film of target, specifically there is sputtering method, in addition also using nanoparticle nano-imprint method or
Wet plating method etc..
With regard to the protecting film and Cu electrode protective membranes other side of Ni-Cu alloy target materials, due to it is recited above
Like that, thus omit its description.
The effect of Ni-Cu alloy target materials and stack membrane [5.Cu electrode protective membranes with]
Potential difference between Ni-15～55Cu alloys and peripheral parts (particularly Cu electrodes) is larger, and, with Cu electrodes
Compare, etch-rate is fast.
On the other hand, if adding the Cr and/or Ti of scheduled volume in Ni-15～55Cu alloys, etch-rate is slack-off
(close to the etch-rate of Cu electrodes), meanwhile, diminish with the potential difference between the peripheral parts such as Cu electrodes or ITO.Therefore, will
The alloy is used as in the protecting film of the Cu electrodes used in liquid crystal panel, can suppress the electrolytic etching by Cu electrodes or atom
Electrical characteristics deterioration caused by diffusion institute, and pattern can accurately be formed by wet etching.
In addition, if add the Cr and/or Ti of scheduled volume in Ni-15～55Cu alloys, then with the attaching of transparency electrode
Property improve.Further, because the maximum magnetic susceptibility of Ni-15～55Cu alloys diminishes, therefore when using it for target, can be effective
Sputtered.
Embodiment
(embodiment 1)
[the 1. preparation of sample]
Using dissolving casting, the Ni-Cu-Cr alloy target materials with predetermined composition are prepared.Cu contents are set as 10～60
Quality %.Cr contents are set as 0～11 mass %.In addition, using dissolving casting, preparing Ni-35 mass %Cu-1.5 matter
Amount %Cr-1.5 mass %Ti alloy target materials.Further, as a comparison, using pure Cu and ITO.
[2. test method]
[2.1. potential differences]
Ni-Cu-Cr alloys, Ni-Cu-Cr-Ti alloys, the normal potential of Cu and ITO are determined respectively.Using carbon electrode as
It is permanent using current potential in the 200g/L ammonium sulfate solutions for remaining 40 DEG C using calomel electrode as reference electrode to electrode
Stream device method bioassay standard current potential.
Using the normal potential of resulting each material, calculate Ni-Cu-Cr alloys or Ni-Cu-Cr-Ti alloys and Cu it
Between potential difference △ V (V), and the potential difference △ V (V) between Ni-Cu-Cr alloys or Ni-Cu-Cr-Ti alloys and ITO.
In addition, compared with prior art, potential difference is more little more preferred, but potential difference is same as the prior art or slightly larger one
Also have no problem in practical a bit.Specifically, with the potential difference of ITO below 0.35V and Cu potential difference in below 1.0V
.
[2.2. etching rate differences]
The test film of the complete each material of shape is immersed in into the time predetermined in 40 DEG C of ammonium sulfate 200g/L aqueous solutions.
Etch-rate is calculated according to the decrement of thickness after dipping.Further, using resulting etch-rate, calculate between Cu
Etching rate difference (nm/ seconds).
In addition, compared with prior art, etching rate difference is more little more preferred, but etching rate difference is same as the prior art
Or somewhat larger also have no problem in practical.Specifically, etch-rate is the 1.2nm/ seconds.
[2.3. stripping rates]
Ito film (thickness is formed on the glass substrate：20nm or 150nm).Then, Ni- is further formed in ito film
Cu-Cr alloy films or Ni-Cu-Cr-Ti alloy film (thickness：50nm or 200nm).
Using resulting film, scratch test is carried out.Experimental condition is according to JIS K5600 settings.That is, put on the surface of the film
The crosscutting device of 1mm spacing is put, 100 grids are formed.Adhesive tape is sticked on the surface of the film, after stripping tape, calculates peeled off grid
Number n (=stripping rate (%)).
In addition, when stripping rate is 0% preferably, however, it is preferred to be less than 10% (1 digit).
[2.4. maximum magnetic susceptibilities]
Using the complete test film of shape, maximum magnetic susceptibility μ is determined by sample oscillating mode magnetometer (VSM).Determine
When magnetic field Hm be set as 20 [MOe].
In addition, having no problem in practical when maximum magnetic susceptibility is below 100.
[3. result]
[3.1. potential difference △ V]
The potential difference △ V between Ni-Cu-Cr alloys and ITO is shown in Fig. 1.In Fig. 1, what dotted line was represented is existing skill
The potential difference △ V (0.16V) being used as in art between the Mo-10Nb and ITO of Al systems wiring material protecting film.
The potential difference △ V between Ni-Cu-Cr alloys and Cu is shown in Fig. 2.In Fig. 2, that dotted line is represented is Mo-10Nb
With the potential difference △ V (0.62V) being used as in prior art between the Al-3Nd of Al systems wiring material.
In addition, also also show the result of Ni-Cu-Cr-Ti alloys in Fig. 1 and Fig. 2.
As shown in Figure 1：
(1) as the combination of protecting film/electrode/transparency electrode, using Ni-Cu-Cr alloys/Cu/ITO combination when, with
Existing combination (Mo-10Nb/Al-3Nd/ITO) is compared, and diminishes relative to the potential difference △ V of ITO.
(2) in order that becoming the value (0.35V) that has no problem in practicality below relative to the potential difference △ V of ITO, Cu contents
Lower limit be preferably 15 mass % or 20 mass %.In addition, the upper limit of Cu contents is preferably 55 mass % or 50 mass %.
(3) in order that equal with existing combination or less than existing combination, Cu contents relative to the potential difference △ V of ITO
Lower limit be preferably 23.5 mass %, 24 mass % or 25 mass %.In addition, the upper limit of Cu contents be preferably 44 mass %,
40 mass % or 38 mass %.
(4) in order that becoming the value (0.35V) that has no problem in practicality below relative to the potential difference of ITO, Cr contents
The upper limit is preferably 10 mass %, 8 mass % or 7 mass %.
(5) in order that equal with existing combination or less than existing combination, Cr contents relative to the potential difference △ V of ITO
Lower limit be preferably 0.2 mass %, 0.5 mass % or 1 mass %.In addition, the upper limit of Cr contents be preferably 6.5 mass %,
6 mass % or 5 mass %.
(6) compared with Ni-35Cu-3Cr alloys, potential difference △ relative to ITO of Ni-35Cu-1.5Cr-1.5Ti alloys
V is less.
As shown in Figure 2：
(1) as the combination of protecting film/electrode/transparency electrode, using Ni-Cu-Cr alloys/Cu/ITO combination when, with
Existing combination (Mo-10Nb/Al-3Nd/ITO) is compared, and diminishes relative to the potential difference △ V of Cu.
(2) in order that becoming the value (1.0V) that has no problem in practicality below relative to the potential difference △ V of Cu, Cu contents
Lower limit is preferably 15 mass % or 20 mass %.
(3) in order that equal with existing combination or less than existing combination relative to the potential difference △ V of Cu, Cu contents
Lower limit is preferably 23 mass %, 24 mass % or 25 mass %.In addition, the upper limit of Cu contents is preferably 45 mass %, 42 matter
Amount % or 40 mass %.
(4) in order that equal with existing combination or less than existing combination relative to the potential difference △ V of Cu, Cr contents
Lower limit is preferably 0.2 mass %, 0.5 mass % or 1 mass %.In addition, the upper limit of Cr contents be preferably 5.5 mass %, 5
Quality % or 4 mass %.
(5) the potential difference △ V and Ni-35Cu-3Cr alloys relative to Cu of Ni-35Cu-1.5Cr-1.5Ti alloys are basic
It is identical.
[3.2. etching rate differences]
The etching rate difference between Ni-Cu-Cr alloys and Cu is shown in Fig. 3.In Fig. 3, what dotted line was represented is the erosion of Cu
The value (0.6nm/ seconds) of the 1/2 of etching speed.The etch-rate R of each material1With the etch-rate R of Cu2Difference (=R1-R2) it is exhausted
The smaller the better to being worth, in terms of practicality, etching rate difference is also not necessarily 0.The etch-rate R of each material1With the etch-rate R of Cu2
Difference absolute value for Cu etch-rate R2Less than 1/2 when (that is, | R1-R2|≤R2When/2), can be obtained by Wet-type etching
Obtain concavo-convex relatively small number of good section.
In addition, also together showing the result of Ni-Cu-Cr-Ti alloys in Fig. 3.
As shown in Figure 3：
(1) as the combination of protecting film/electrode/transparency electrode, using Ni-Cu-Cr alloys/Cu/ITO combination when, its
Value (1.2nm/ second) of the etching rate difference less than existing combination (Mo-10Nb/Al-3Nd/ITO).
(2) in order that etching rate difference becomes the value (1.2nm/ seconds) having no problem in practicality below, the lower limit of Cu contents
Preferably 15 mass % or 20 mass %.In addition, the upper limit of Cu contents is preferably 55 mass %, 50 mass % or 47 matter
Amount %.
(3) in order that etching rate difference is less than or equal to Cu/2, the lower limit of Cu contents is preferably 24 mass %, 24.5 matter
Amount % or 25 mass %.In addition, the upper limit of Cu contents is preferably 42 mass %, 40 mass % or 38 mass %.
(4) in order that etching rate difference becomes the value (1.2nm/ seconds) having no problem in practicality below, the upper limit of Cr contents
Preferably 10 mass %, 9 mass % or 8 mass %.
(5) in order that etching rate difference is less than or equal to Cu/2, the lower limit of Cr contents is preferably 0.5 mass %, 1 matter
Amount % or 2 mass %.In addition, the upper limit of Cr contents is preferably 6.5 mass %, 6 mass % or 5 mass %.
(6) etching rate difference of Ni-Cu-Cr-Ti alloys is more slightly higher than Ni-Cu-Cr alloy, but closes significantly less than Ni-Cu
Gold.
[3.3. stripping rates]
Fig. 4 to Fig. 7 shows the thickness formed in the ito film that thickness is 20nm or 150nm for 50nm's or 200nm
The stripping rate of Ni-Cu-Cr alloy films.In addition, also together showing the result of Ni-Cu-Cr-Ti alloys in Fig. 4 to Fig. 7.
From Fig. 4 to Fig. 7：
(1) the stripping rate of Ni-Cu-Cr alloy films is significantly less than Ni-Cu alloy films.In addition, the stripping of Ni-Cu-Cr alloy films
From rate not too dependent on thickness.
(2) the stripping rate of Ni-Cu-Cr alloy films does not rely on Cu contents and shows good value.Particularly, contain in Cu
Measure as good result can be obtained in the range of 15～40 mass %.Cu contents are more preferably 23～25 mass %.
(3) by adding Cr, peel resistance can be greatly improved.Even if the Cr of 1 mass % of addition, it is also possible to confirm that it fills
The effect divided, if Cr more than 3 mass % of addition, substantially not peeling-off.Particularly, in the scope of 3～7 mass %
It is interior to obtain good result.
(4) if adding Ti in Ni-Cu-Cr alloys, although stripping rate somewhat increases than Ni-Cu-Cr alloy, but it is aobvious
Write and be less than Ni-Cu alloys.
[3.4. maximum magnetic susceptibilities]
The maximum magnetic susceptibility of Ni-Cu-Cr alloys is shown in Fig. 8.In addition, also together showing Ni-Cu-Cr-Ti in Fig. 8
The result of alloy.
As shown in Figure 8：
(1) in order that maximum magnetic susceptibility μ is below 100, the lower limit of Cu contents can be 15 mass %.The lower limit of Cu contents
More preferably 20 mass %.In addition, the upper limit of Cu contents is preferably 50 mass %.
(2) in order that maximum magnetic susceptibility μ is below 20, the lower limit of Cu contents is preferably 24 mass % or 25 mass %.
In addition, the upper limit of Cu contents is preferably 47 mass % or 45 mass %.
(3) even if making Cr contents change in 0～11 mass %, maximum magnetic susceptibility μ also has almost no change.
(embodiment 2)
[the 1. preparation of sample]
Using dissolving casting, the Ni-Cu-Ti alloy target materials with predetermined composition are prepared.Cu contents are set as 10～60
Quality %.Ti contents are set as 0～7 mass %.In addition, as a comparison, using pure Cu and ITO.
[2. test method]
According to operation same as Example 1, potential difference △ V, the Ni-Cu-Ti between Ni-Cu-Ti alloys and Cu is determined
The etching rate difference between potential difference △ V, Ni-Cu-Ti alloy and Cu, stripping rate and maximum magnetic thoroughly between alloy and ITO
Rate μ.
[3. result]
[3.1. potential difference △ V]
The potential difference △ V between Ni-Cu-Ti alloys and ITO is shown in Fig. 9.In Fig. 9, what dotted line was represented is existing skill
The potential difference △ V (0.16V) being used as in art between the Mo-10Nb and ITO of Al systems wiring material protecting film.
The potential difference △ V between Ni-Cu-Ti alloys and Cu is shown in Figure 10.In Figure 10, that dotted line is represented is Mo-
The potential difference △ V (0.62V) being used as in 10Nb and prior art between the Al-3Nd of Al systems wiring material.
In addition, also showing the result of Ni-Cu-Cr-Ti alloys in Fig. 9 and Figure 10 in the lump.
As shown in Figure 9：
(1) as the combination of protecting film/electrode/transparency electrode, using Ni-Cu-Ti alloys/Cu/ITO combination when, with
Existing combination (Mo-10Nb/Al-3Nd/ITO) is compared, and diminishes relative to the potential difference △ V of ITO.
(2) in order that becoming the value (0.35V) that has no problem in practicality below relative to the potential difference △ V of ITO, Cu contents
Lower limit can be 15 mass %.The lower limit of Cu contents is more preferably 20 mass % or 23 mass %.
(3) in order that equal with existing combination or less than existing combination, Cu contents relative to the potential difference △ V of ITO
Lower limit be preferably 23.5 mass %, 24 mass % or 25 mass %.In addition, the upper limit of Cu contents be preferably 50 mass %,
45 mass % or 42 mass %.
(4) no matter the content of Ti is how many, relative to the potential difference △ V of ITO good value is shown.
(5) in order that equal with existing combination or less than existing combination, Ti contents relative to the potential difference △ V of ITO
Lower limit be preferably 0.2 mass %, 0.3 mass % or 0.5 mass %.In addition, the upper limit of Ti contents is preferably 5.5 matter
Amount %, 5 mass % or 4.5 mass %.
(6) compared with Ni-35Cu-3Ti alloys, potential difference △ relative to ITO of Ni-35Cu-1.5Cr-1.5Ti alloys
V is less.
As shown in Figure 10：
(1) as the combination of protecting film/electrode/transparency electrode, using Ni-Cu-Ti alloys/Cu/ITO combination when, with
Existing combination (Mo-10Nb/Al-3Nd/ITO) is compared, and diminishes relative to the potential difference △ V of Cu.
(2) in order that becoming the value (1.0V) that has no problem in practicality below relative to the potential difference △ V of Cu, Cu contents
Lower limit can be 15 mass %.The lower limit of Cu contents is more preferably 20 mass %.
(3) in order that equal with existing combination or less than existing combination relative to the potential difference △ V of Cu, Cu contents
Lower limit is preferably 23.5 mass % or 24 mass %.In addition, the upper limit of Cu contents be preferably 46 mass %, 45 mass % or
Mass % of person 40.
(4) no matter the content of Ti is how many, relative to the potential difference △ V of Cu good value is shown.
(5) in order that equal with existing combination or less than existing combination relative to the potential difference △ V of Cu, Ti contents
Lower limit is preferably 0.2 mass %, 0.5 mass % or 1 mass %.In addition, the upper limit of Ti contents be preferably 5.5 mass %, 5
Quality % or 4.5 mass %.
(6) the potential difference △ V and Ni-35Cu-3Ti alloys relative to Cu of Ni-35Cu-1.5Cr-1.5Ti alloys are basic
It is identical.
[3.2. etching rate differences]
The etching rate difference between Ni-Cu-Ti alloys and Cu is shown in Figure 11.In Figure 11, that dotted line is represented is Cu
The value (0.6nm/ seconds) of the 1/2 of etch-rate.In addition, also showing the result of Ni-Cu-Cr-Ti alloys in Figure 11 in the lump.
As shown in Figure 11：
(1) as the combination of protecting film/electrode/transparency electrode, using Ni-Cu-Ti alloys/Cu/ITO combination when, its
Value (1.2nm/ second) of the etching rate difference less than existing combination (Mo-10Nb/Al-3Nd/ITO).
(2) in order that etching rate difference becomes the value (1.2nm/ seconds) having no problem in practicality below, the lower limit of Cu contents
Can be 15 mass %.The lower limit of Cu contents is more preferably 20 mass %.In addition, the upper limit of Cu contents can be 55 mass %.
The upper limit of Cu contents is more preferably 50 mass % or 45 mass %.
(3) in order that etching rate difference is less than or equal to Cu/2, the lower limit of Cu contents is preferably 24 mass % or 25 matter
Amount more than %.In addition, the upper limit of Cu contents is preferably 40 mass % or 38 mass %.
(4) no matter the content of Ti is how many, good etching rate difference is shown.
(5) in order that etching rate difference is less than or equal to Cu/2, the lower limit of Ti contents is preferably 1.5 mass % or 2 matter
Amount %.In addition, the upper limit of Ti contents is preferably 5 mass % or 4.5 mass %.
(6) etching rate difference of Ni-Cu-Cr-Ti alloys is less than Ni-Cu-Ti alloys.
[3.3. stripping rates]
Figure 12 to Figure 15 shows the thickness formed in the ito film that thickness is 20nm or 150nm for 50nm's or 200nm
The stripping rate of Ni-Cu-Ti alloy films.In addition, also showing the result of Ni-Cu-Cr-Ti alloys in Figure 12 to Figure 15 in the lump.
From Figure 12 to Figure 15：
(1) the stripping rate of Ni-Cu-Ti alloy films depends on thickness, and the thickness of Ni-Cu-Ti alloy films is thicker, and stripping rate increases
Greatly.
(2) in the case where the thickness of Ni-Cu-Ti alloy films is 50nm, in order that stripping rate is less than 10%, Cu contents
Lower limit can be 15 mass %.The lower limit of Cu contents is more preferably 20 mass %, 23 mass %, 24 mass % or 25 matter
Amount %.In addition, the upper limit of Cu contents is preferably 47 mass %, 45 mass % or 40 mass %.
(3) in the case where the thickness of Ni-Cu-Ti alloy films is 50nm, in order that stripping rate is less than 10%, Ti contents
Lower limit be preferably 1.0 mass %, 1.5 mass %, 2 mass % or 3 mass %.
(4) if adding Cr in Ni-Cu-Ti alloys, stripping rate is with Ni-Cu-Ti alloys identical or less than Ni-Cu-Ti
Alloy.
[3.4. maximum magnetic susceptibilities]
The maximum magnetic susceptibility of Ni-Cu-Ti alloys is shown in Figure 16.In addition, also showing Ni-Cu-Cr- in Figure 16 in the lump
The result of Ti alloys.
As shown in Figure 16：
(1) in order that maximum magnetic susceptibility μ is below 100, the lower limit of Cu contents is preferably 24 mass %.
(2) in order that maximum magnetic susceptibility μ is below 20, the lower limit of Cu contents is preferably 24.5 mass % or 25 matter
Amount %.In addition, the upper limit of Cu contents is preferably 47 mass %, 45 mass % or 40 mass %.
(3) even if making Ti contents change in 0～11 mass %, maximum magnetic susceptibility μ also has almost no change.
(embodiment 3)
[the 1. preparation of sample]
Using the target prepared by embodiment 1 or 2, touch panel stack membrane is prepared.That is, using sputtering method, in substrate
Surface (from bottom to up) forms barrier layer, electrode layer and coating successively.As substrate, using ITO/ underlying membranes/pet substrate,
Or ITO/ underlying membranes/glass substrate (being commercially available product).The Cu containing scheduled volume is used in barrier layer and coating respectively
Or the NiCu alloys of Ti, used in electrode layer Cu (5N).
As a comparison, being prepared for such stack membrane：Wherein, Mo-10Nb conjunctions have been used respectively in barrier layer and coating
Gold, Al-3Nd used in electrode layer.
The membrance casting condition of touch panel stack membrane is shown in table 1.
Table 1
| Material | Power | Gas | Sputter rate | Film thickness |
| NiCu alloys | DC300W | Ar 0.3Pa | 55nm/ minutes | 20nm |
| Cu(5N) | RF500W | Ar 0.3Pa | 48nm/ minutes | 200nm |
| MoNb | DC300W | Ar 0.3Pa | 31nm/ minutes | 20nm |
| AlNd | DC300W | Ar 0.3Pa | 60nm/ minutes | 200nm |
[2. test method]
[2.1. adhesions]
Scratch test (according to JIS K5600 standards) is carried out under the same conditions as example 1, determines stripping rate.
[2.2. weatherabilities]
Substrate with stack membrane is kept for 1000 hours under conditions of 65 DEG C, 95% humidity.After off-test, visually
Judge whether discoloration.
[2.3. etchings]
Substrate with stack membrane is immersed in 40 DEG C of Ammonium persulfate. 200g/L aqueous solutions, stack membrane is dissolved.Survey
Fixed required time when substrate bleach (until stack membrane all dissolves).
[2.4. electrode portion film resistors]
Electrode portion film resistor is determined using 4 terminal methods.
[3. result]
Result is shown in table 2 and table 3.From table 2 and table 3：
(1) regardless of the composition of barrier layer/electrode layer/coating, electrode portion film resistor is relatively low.
(2) in the case where the Cu contents of NiCuCr alloys are certain, Cr contents are more, and adhesion and weatherability are higher, but
It is that etching is reduced.In addition, in the case where the Cr contents of NiCuCr alloys are certain, if Cu contents are superfluous, weatherability drop
It is low.That is, if Ni-25～40Cu-3～5Cr alloys is used in barrier layer and coating, adhesion, resistance to can be obtained
The excellent touch panel stack membrane of time property and etching.
(3) in the case where the Cu contents of NiCuTi alloys are certain, Ti contents are more, and adhesion and weatherability are higher, but
It is that etching is reduced.In addition, in the case where the Ti contents of NiCuTi alloys are certain, if Cu contents are superfluous, weatherability drop
It is low.That is, if Ni-25～40Cu-3～5Ti alloys is used in barrier layer and coating, adhesion, resistance to can be obtained
The excellent touch panel stack membrane of time property and etching.
(table 2)
Adhesion (stripping rate)：Zero=be more than or equal to less than 3%, △=more than or equal to 3% and less than 10%, X=
10%
Weatherability：Zero=without discoloration, X=has discoloration
Etching (time required for substrate bleach)：Zero=less than 1 minute, X=1 is more than minute
(table 3)
Adhesion (stripping rate)：Zero=be more than or equal to less than 3%, △=more than or equal to 3% and less than 10%, X=
10%
Weatherability：Zero=without discoloration, X=has discoloration
Etching (time required for substrate bleach)：Zero=less than 1 minute, X=1 is more than minute
(embodiment 4)
[the 1. preparation of sample]
Using the target prepared by embodiment 1 or 2, TFT stack membranes are prepared.That is, using sputtering method, substrate surface according to
Secondary (from bottom to up) forms barrier layer and electrode layer.As substrate, using ITO/ underlying membranes/glass substrate (commercially available product).Intercept
NiCu alloys of the Cu containing scheduled volume or Ti used in layer, used in electrode layer Cu (5N).
As a comparison, being prepared for such stack membrane：Wherein, Mo-50Ti alloys used in barrier layer, make in electrode layer
With Cu.
The membrance casting condition of TFT stack membranes is shown in table 4.
Table 4
| Material | Power | Gas | Sputter rate | Film thickness |
| NiCu alloys | DC300W | Ar 0.3Pa | 55nm/ minutes | 20nm |
| Cu(5N) | RF500W | Ar 0.3Pa | 48nm/ minutes | 200nm |
| MoTi | DC300W | Ar 0.3Pa | 28nm/ minutes | 20nm |
[2. test method]
[2.1. adhesions, etching and electrode portion film resistor]
At the same conditions as example 3, adhesion, etching and electrode portion film resistor are determined.
[2.2. blocks]
The vacuum heat of 250 DEG C × 30 minutes is carried out to the substrate with stack membrane.After heat treatment, using Auger point
Analysis, detects the diffusion of near interface Cu, Si.Using auger analysis, judged according to the slope of Cu, Si detected level on depth direction
The quality of block.With regard to the evaluation of block, zero represents the difference of the slope of Cu, Si detected level on depth direction before and after heat treatment
For less than 3% when situation, X represent the slope of Cu, Si detected level on depth direction before and after heat treatment difference be more than 3% when feelings
Condition.
[3. result]
Result is shown in table 5.As shown in Table 5：
(1) regardless of the composition of barrier layer/electrode layer, electrode portion film resistor is relatively low.
(2) in the case where the Cu contents of NiCuCr alloys are certain, Cr contents are more, and adhesion and block are higher, but
It is that etching is reduced.In addition, in the case where the Cr contents of NiCuCr alloys are certain, if Cu contents are superfluous, block drop
It is low.That is, if Ni-25～40Cu-3～5Cr alloys are used for into barrier layer, adhesion, block and etching can be obtained
The excellent TFT stack membranes of property.
(3) in the case where the Cu contents of NiCuTi alloys are certain, Ti contents are more, and adhesion and block are higher, but
It is that etching is reduced.In addition, in the case where the Ti contents of NiCuTi alloys are certain, if Cu contents are superfluous, block drop
It is low.That is, if Ni-25～40Cu-3～5Ti alloys are used for into barrier layer, adhesion, block and etching can be obtained
The excellent TFT stack membranes of property.
(table 5)
Adhesion (stripping rate)：Zero=be more than or equal to less than 3%, △=more than or equal to 3% and less than 10%, X=
10%
The block difference of the slope of Cu, Si detected level (before and after heat treatment on depth direction)：Less than zero=3%, X=exceed
3%
Etching (time required for substrate bleach)：Zero=less than 1 minute, X=1 is more than minute
Embodiment of the present invention is illustrated in detail above, but, the embodiment above is the invention is not limited in,
Without departing from various changes can be carried out in the scope of spirit of the present invention.
Industrial applicibility
Cu electrode protective membranes according to the present invention NiCu alloy target materials can be used as being formed on the two sides of Cu electrodes and protect
The sputtering target material of cuticula, wherein the Cu electrodes are used for touch pad electrode portion, liquid crystal panel TFT portions, organic EL panel electricity
In pole portion, plasma display electrode portion, solar battery panel electrode portion, semi-conducting electrode portion etc..
Claims (6)
1. a kind of panel Cu electrode protective membranes Ni-Cu alloy target materials, its following composition：
30.0 mass %≤Cu≤55.0 mass %,
3.0 mass %≤mass % of (Cr, Ti)≤5.0, wherein, Cr>0、Ti>0,
Balance of Ni and inevitable impurity.
2. Cu electrode protective membranes Ni-Cu alloy target materials of the panel described in claim 1, wherein
30.0 mass %≤Cu≤40.0 mass %.
3. a kind of panel Cu electrode protective membranes Ni-Cu alloy target materials, its following composition：
30.0 mass %≤Cu≤55.0 mass %,
3.0 mass %≤Cr≤5.0 mass %,
Balance of Ni and inevitable impurity.
4. Cu electrode protective membranes Ni-Cu alloy target materials of the panel described in claim 3, wherein
30.0 mass %≤Cu≤40.0 mass %.
5. a kind of panel Cu electrode protective membranes Ni-Cu alloy target materials, its following composition：
30.0 mass %≤Cu≤55.0 mass %,
3.0 mass %≤Ti≤5.0 mass %,
Balance of Ni and inevitable impurity.
6. Cu electrode protective membranes Ni-Cu alloy target materials of the panel described in claim 5, wherein
30.0 mass %≤Cu≤40.0 mass %.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
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| JP2010-192370 | 2010-08-30 | ||
| JP2010192370 | 2010-08-30 | ||
| JP2011041885 | 2011-02-28 | ||
| JP2011-041885 | 2011-02-28 | ||
| JP2011134616A JP5895370B2 (en) | 2010-08-30 | 2011-06-16 | NiCu alloy target material for Cu electrode protective film for panel and laminated film |
| JP2011-134616 | 2011-06-16 | ||
| CN201110261494.5A CN102321832B (en) | 2010-08-30 | 2011-08-30 | Ni-cu alloy target material used in cu electrode protection film and laminated film |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201110261494.5A Division CN102321832B (en) | 2010-08-30 | 2011-08-30 | Ni-cu alloy target material used in cu electrode protection film and laminated film |
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| CN104611615A CN104611615A (en) | 2015-05-13 |
| CN104611615B true CN104611615B (en) | 2017-04-12 |
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| CN201410850977.2A Active CN104611615B (en) | 2010-08-30 | 2011-08-30 | Ni-Cu ALLOY TARGET MATERIAL FOR Cu ELECTRODE PROTECTIVE FILM AND LAMINATED FILM |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2013133489A (en) * | 2011-12-26 | 2013-07-08 | Sumitomo Metal Mining Co Ltd | Cu ALLOY SPUTTERING TARGET, METHOD FOR PRODUCING THE SAME, AND METAL THIN FILM |
| JP6149712B2 (en) * | 2012-11-28 | 2017-06-21 | 住友金属鉱山株式会社 | Cu wiring protective film and Cu alloy sputtering target |
| JP6028540B2 (en) * | 2012-11-28 | 2016-11-16 | 住友金属鉱山株式会社 | Cu wiring protective film and Cu alloy sputtering target |
| JP5979034B2 (en) | 2013-02-14 | 2016-08-24 | 三菱マテリアル株式会社 | Sputtering target for protective film formation |
| JP6135275B2 (en) | 2013-04-22 | 2017-05-31 | 三菱マテリアル株式会社 | Sputtering target for protective film formation |
| JP5757318B2 (en) * | 2013-11-06 | 2015-07-29 | 三菱マテリアル株式会社 | Protective film forming sputtering target and laminated wiring film |
| JP6398594B2 (en) | 2014-10-20 | 2018-10-03 | 三菱マテリアル株式会社 | Sputtering target |
| JP2017049482A (en) * | 2015-09-03 | 2017-03-09 | 凸版印刷株式会社 | Color filter and liquid crystal display using the same |
| JP6531596B2 (en) * | 2015-09-28 | 2019-06-19 | 住友金属鉱山株式会社 | Laminate substrate, conductive substrate, method of producing laminate substrate, method of producing conductive substrate |
| JP6950447B2 (en) * | 2017-10-20 | 2021-10-13 | 大同特殊鋼株式会社 | Semiconductor device |
| CN108456844B (en) * | 2018-02-07 | 2019-11-08 | 中国原子能科学研究院 | A method of it being coated with high-purity N i/Cu bilayer target membrane on high-boron-silicon glass |
| JP2019183251A (en) | 2018-04-17 | 2019-10-24 | 三菱マテリアル株式会社 | Cu-Ni alloy sputtering target |
| CN114107921A (en) * | 2021-10-22 | 2022-03-01 | 广东电网有限责任公司广州供电局 | Coating method of copper electrode |
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| CN1993488A (en) * | 2004-08-02 | 2007-07-04 | 住友金属工业株式会社 | Weld joint and weld material thereof |
| CN101121976A (en) * | 2006-08-09 | 2008-02-13 | 海恩斯国际公司 | Hybrid corrosion-resistant nickel alloys |
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| WO2005041290A1 (en) * | 2003-10-24 | 2005-05-06 | Nikko Materials Co., Ltd. | Nickel alloy sputtering target and nickel alloy thin film |
| JP4355743B2 (en) * | 2006-12-04 | 2009-11-04 | 株式会社神戸製鋼所 | Cu alloy wiring film, TFT element for flat panel display using the Cu alloy wiring film, and Cu alloy sputtering target for producing the Cu alloy wiring film |
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| CN1993488A (en) * | 2004-08-02 | 2007-07-04 | 住友金属工业株式会社 | Weld joint and weld material thereof |
| CN101121976A (en) * | 2006-08-09 | 2008-02-13 | 海恩斯国际公司 | Hybrid corrosion-resistant nickel alloys |
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| CN104611615A (en) | 2015-05-13 |
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