CN104611615A - 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 divisional application that the application is the applying date is on August 30th, 2011, application number is 201110261494.5, denomination of invention is the application of " Cu electrode protective membrane NiCu alloy target material and stack membrane ".
Technical field
The present invention relates to Cu electrode protective membrane NiCu alloy target material and stack membrane; the Cu electrode protective membrane NiCu alloy target material that specifically, the present invention relates to the Cu electrode protective membrane forming the electrode being used as touch panel or liquid crystal panel and the stack membrane using this target and manufacture.
Background technology
The liquid crystal panel used in touch panel and slim large frame TV etc. has be closed with the such structure of liquid crystal between 2 pieces of transparency carrier.The transparency electrode of the working electrode as liquid crystal is formed in the inner side (one side of liquid crystal side) of transparency carrier.In transparency electrode, generally use tin indium oxide (ITO).In addition, in the part for substrate surface being formed with transparency electrode, be formed with the metal electrode as outside output terminal or metal wiring (they being referred to as " metal electrode " below).In substrate surface, metal electrode is formed in part (such as, the peripheral part of the substrate) place not needing printing opacity.
The surface of transparency electrode is directly formed metal electrode, when the standard electric potential difference (potential difference) between transparency electrode and metal electrode is larger, metal electrode generation electrolytic corrosion.In addition, be sometimes formed at the phase mutual diffusion that atom occurs between the bottom of substrate surface with metal electrode, thus there is deterioration in the electrical characteristic of metal electrode.Therefore, the protective membrane (barrier layer) for the protection of metal electrode is generally all formed on the two sides of metal electrode.In existing liquid crystal panel, the general Al-Nd system alloy that uses as metal electrode, and uses Mo-Nb system alloy as protective membrane.
About the metal electrode used in this liquid crystal panel, protective membrane and the material for the formation of them, there is various motion all the time.
For example, Patent Document 1 discloses such film formation sputtering target: it contains the one or both be selected from V and Nb of 2 ~ 50 atom % altogether, and surplus is Mo and inevitable impurity, and its relative density is more than 95%.
Describe in the publication: when using containing the Mo alloys target of Nb or V, not low containing harmful Cr, resistance and the metallic film that erosion resistance is high can be obtained.
In addition, Patent Document 2 discloses such sputtering target material: it is using Mo as main body, the metallic element M be selected from Ti, Zr, V, Nb, Cr containing 0.5 ~ 50 atom %, and there is predetermined tissue.
Describe in the publication: by raw material powder mixture compression molding to be formed into body, this molding is pulverized and again forms powder, and by this powder pressure sintering, thereby inhibiting the segregation of composition, and improve the plastic working of sintered compact.
In addition; Patent Document 3 discloses such target part: this target part is not the protective membrane target of metal electrode; it contains Ni:70 ~ 85 % by weight, Cu:2 ~ 10 % by weight and Mo:1 ~ 6 % by weight and/or Cr:0.5 ~ 3 % by weight; surplus is made up of Fe substantially, and less than JIS austinite grain size numbering No.3 through the grain size number in face of sputtering.
Describe in the publication: when using this target, the low and uniform Fe-Ni alloy/C film of coercive force can be obtained.
In addition; Patent Document 4 discloses such evaporation Ni-Fe base alloy: this alloy is not the protective membrane target of metal electrode; it contains Ni:35 ~ 85 % by weight, is selected from more than a kind: 3 ~ 15 in Mo, Cr, Cu and Nb % by weight, Al:1 less than % by weight, Ca and/or below Mg:300ppm, below O:30ppm, below N:30ppm, and surplus is essentially Fe.
Describing in the publication: by using this target, the magneticthin film of the high characteristic of very high purity can be obtained.
In addition, in non-patent literature 1, such method is disclosed: use Ar+O2 mixed gas to sputter the target be made up of Cu-2 % by weight Zr alloy, Cu-1 % by weight Mo alloy or Cu-0.7 % by weight Mg alloy.
Describing in the publication: by adopting the method, the barrier layer (zone of oxidation) good with the attaching of bottom can be formed in the interface between the layer be made up of Cu based material (metal electrode) and bottom.
In addition, Patent Document 5 discloses such sputtering target: it is not the protective membrane target of metal electrode, and it is made up of Ni-7.5 quality %Ti-4 ~ 40 quality %Cu alloy, can be used for the electrode forming chip resister.
Describe in the publication: when adding Cu in Ni-Ti alloy, because saturation magnetization diminishes, therefore can obtain long-life target.
In addition, Patent Document 6 discloses such nickel alloy sputtering target for the formation of barrier layer: it is not the protective membrane target of metal electrode, its by
(a) Ni-25 atom %Cu-2 atom %Cr alloy (Ni-26.6 quality %Cu-1.7 quality %Cr alloy) or
B () Ni-25 atom %Cu-12 atom %Ti alloy (Ni-27.1 quality %Cu-9.8 quality %Ti alloy) is formed.
Describe in the publication: use there is such composition target to form barrier layer time, the diffusion of Sn can be suppressed.
Along with the maximization of liquid crystal panel, the material that people's demand is lower than the resistance of Al based material.In addition, Mo-Nb system alloy used in the protective membrane of Al system distribution 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 material as an alternative.
As the formation method of the metal electrode and Cu electrode protective membrane that employ Cu based material, as disclosed in non-patent literature 1, there will be a known at Ar+O
2to the method that the target formed by Cu system alloy sputters under atmosphere.Method described in the document has such advantage: by once sputtering and can form Cu electrode and protective membrane simultaneously.
But, at Ar+O
2reactive sputtering under atmosphere makes the resistance of Cu electrode film itself increase, and causes deterioration in characteristics.In addition, due to O
2indoor easily captured at vacuum unit, be therefore difficult to control oxygen partial pressure, thus become the reason of quality product inequality.
In addition, in general, form metal electrode and protective membrane by such method: on the whole surface of the substrate being formed with transparency electrode, form protective membrane and electrode layer, and form pattern with predetermined shape.When reducing the cost of liquid crystal panel, wet etching is preferably adopted to form pattern.Further, in order to form pattern accurately with wet etching, preferably, the etch-rate of protective membrane and electrode layer is substantially equal.
But adopt in the metal electrode and protective membrane that disclosed in non-patent literature 1, method obtains, both etching rate differences are comparatively large, therefore there is the problem that can not form pattern accurately.
In addition, when liquid crystal panel, Cu electrode protective membrane is formed in by the transparency electrode that ITO is formed.Therefore, require that Cu electrode protective membrane and ITO have high attaching.In addition, in order to effectively sputter, require that the magnetic susceptibility of target is low.But, up to now, the still example of nobody's Cu electrode protective membrane target of proposing simultaneously all to possess these conditions and the stack membrane that uses this target to manufacture.
[prior art document]
[patent documentation]
Patent documentation 1: Japanese Unexamined Patent Publication 2002-327264 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2005-290409 publication
Patent documentation 3: Japanese Laid-Open Patent Publication 62-186511 publication
Patent documentation 4: Japanese Laid-Open Patent Publication 63-100148 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2005-171341 publication
Patent documentation 6: No. WO2005/041290, International Publication
[non-patent literature]
Non-patent literature 1: Gao Zewu, etc.; Ulvac Technical Journal, the 69th phase, the 7th page, 2009
Summary of the invention
The problem that invention will solve
The problem to be solved in the present invention is the stack membrane providing a kind of Cu electrode protective membrane Ni-Cu alloy target material and use this target to manufacture, wherein said target
A () can be used as the protective membrane of Cu electrode, can suppress the electrical characteristic deterioration caused by the electrolytic corrosion of Cu electrode or atomic diffusion, and can form the protective membrane can with more high-precision pattern by wet etching;
B () can form the protective membrane good with the attaching of transparency electrode, and
C () can sputter effectively.
The means of dealing with problems
In order to solve the problem, the main points of the first aspect of the Cu electrode protective membrane Ni-Cu alloy target material that the present invention relates to are:
Containing 15.0 quality %≤Cu≤55.0 quality % and 0.5 quality %≤(Cr, Ti)≤10.0 quality % (wherein, Cr>0, Ti>0), surplus is Ni and inevitable impurity.
The main points of the second aspect of Cu electrode protective membrane Ni-Cu alloy target material involved in the present invention are:
Containing 15.0 quality %≤Cu≤55.0 quality % and 0.5 quality %≤Cr≤10.0 quality %, surplus is Ni and inevitable impurity.
The main points of the third aspect of Cu electrode protective membrane Ni-Cu alloy target material involved in the present invention are:
Containing 15.0 quality %≤Cu≤55.0 quality % and 0.5 quality %≤Ti≤10.0 quality %, surplus is Ni and inevitable impurity.
In addition, the stack membrane that the present invention relates to has: the protective membrane that Cu electrode and the one or both sides at described Cu electrode are formed, and described protective membrane is formed by using the film of Cu electrode protective membrane Ni-Cu alloy target material film forming involved in the present invention.
Invention effect
When adding Cr and/or Ti of predetermined amount to Ni-15 ~ 55Cu alloy, the etching rate difference of this alloy and Cu electrode diminishes, and the potential difference simultaneously and between the peripheral parts such as Cu electrode or ITO also diminishes.Therefore, when this alloy is used as the protective membrane of Cu electrode used in liquid crystal panel, the electrical characteristic deterioration caused by the electrolytic corrosion of Cu electrode or atomic diffusion can be suppressed, and pattern can be formed accurately by wet etching.
In addition, when adding Cr and/or Ti of predetermined amount to Ni-15 ~ 55Cu alloy, the attaching of this alloy and transparency electrode improves.In addition, because the maximum magnetic susceptibility of Ni-15 ~ 55Cu alloy diminishes, when using it for target, can effectively sputter.
Accompanying drawing explanation
[Fig. 1] Fig. 1 (A) for illustrate Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy Cu content and relative to ITO potential difference △ V between the figure of relation.Fig. 1 (B) for illustrate Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy Cr content and relative to ITO potential difference △ V between the figure of relation.
[Fig. 2] Fig. 2 (A) for illustrate Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy Cu content and relative to Cu potential difference △ V between the figure of relation.Fig. 2 (B) for illustrate Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy Cr content and relative to Cu potential difference △ V between the figure of relation.
[Fig. 3] Fig. 3 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy and etching rate difference.Fig. 3 (B) is for illustrating the figure of the relation between the Cr content of Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy and etching rate difference.
[Fig. 4] Fig. 4 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy and stripping rate (ITO:20nm, NiCuCr:50nm).Fig. 4 (B) is for illustrating the figure of the relation between the Cr content of Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy and stripping rate (ITO:20nm, NiCuCr:50nm).
[Fig. 5] Fig. 5 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy and stripping rate (ITO:20nm, NiCuCr:200nm).Fig. 5 (B) is for illustrating the figure of the relation between the Cr content of Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy and stripping rate (ITO:20nm, NiCuCr:200nm).
[Fig. 6] Fig. 6 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy and stripping rate (ITO:150nm, NiCuCr:50nm).Fig. 6 (B) is for illustrating the figure of the relation between the Cr content of Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy and stripping rate (ITO:150nm, NiCuCr:50nm).
[Fig. 7] Fig. 7 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy and stripping rate (ITO:150nm, NiCuCr:200nm).Fig. 7 (B) is for illustrating the figure of the relation between the Cr content of Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy and stripping rate (ITO:150nm, NiCuCr:200nm).
[Fig. 8] Fig. 8 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Cr (x=10 ~ 60) alloy and maximum magnetic susceptibility μ.Fig. 8 (B) is for illustrating the figure of the relation between the Cr content of Ni-35 quality %Cu-x quality %Cr (x=0 ~ 11) alloy and maximum magnetic susceptibility μ.
[Fig. 9] Fig. 9 (A) for illustrate Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy Cu content and relative to ITO potential difference △ V between the figure of relation.Fig. 9 (B) for illustrate Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy Ti content and relative to ITO potential difference △ V between the figure of relation.
[Figure 10] Figure 10 (A) for illustrate Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy Cu content and relative to Cu potential difference △ V between the figure of relation.Figure 10 (B) for illustrate Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy Ti content and relative to Cu potential difference △ V between the figure of relation.
[Figure 11] Figure 11 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy and etching rate difference.Figure 11 (B) is for illustrating the figure of the relation between the Ti content of Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy and etching rate difference.
[Figure 12] Figure 12 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy and stripping rate (ITO:20nm, NiCuTi:50nm).Figure 12 (B) is for illustrating the figure of the relation between the Ti content of Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy and stripping rate (ITO:20nm, NiCuTi:50nm).
[Figure 13] Figure 13 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy and stripping rate (ITO:20nm, NiCuTi:200nm).Figure 13 (B) is for illustrating the figure of the relation between the Ti content of Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy and stripping rate (ITO:20nm, NiCuTi:200nm).
[Figure 14] Figure 14 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy and stripping rate (ITO:150nm, NiCuTi:50nm).Figure 14 (B) is for illustrating the figure of the relation between the Ti content of Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy and stripping rate (ITO:150nm, NiCuTi:50nm).
[Figure 15] Figure 15 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy and stripping rate (ITO:150nm, NiCuTi:200nm).Figure 15 (B) is for illustrating the figure of the relation between the Ti content of Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy and stripping rate (ITO:150nm, NiCuTi:200nm).
[Figure 16] Figure 16 (A) is for illustrating the figure of the relation between the Cu content of Ni-x quality %Cu-3 quality %Ti (x=10 ~ 60) alloy and maximum magnetic susceptibility μ.Figure 16 (B) is for illustrating the figure of the relation between the Ti content of Ni-35 quality %Cu-x quality %Ti (x=0 ~ 7) alloy and maximum magnetic susceptibility μ.
Embodiment
Below one embodiment of the invention are described in detail.
[1.Cu electrode protective membrane with Ni-Cu alloys target (1): NiCuCr alloy]
[1.1. composition]
The Cu electrode protective membrane Ni-Cu alloy target material that first embodiment of the invention relates to contains following element, and surplus is made up of Ni and inevitable impurity.The kind of Addition ofelements and the restriction reason of addition as described below.
(1) 15.0 quality %≤Cu≤55.0 quality %
The difference (potential difference) that Cu content in NiCu alloy can affect the standard potential between this alloy and Cu electrode or ITO or the etching rate difference affected between this alloy and Cu electrode.In addition, Cu content also can affect the magnetic susceptibility of NiCu alloy.
In general, Cu content is fewer, and potential difference between peripheral parts is larger, and resistance to electrolytic corrosion reduces.In addition, etch-rate is slack-off compared with Cu electrode, and the confidence level of electrode reduces.If when the etch-rate of protective membrane is crossed slow, the section of the protective membrane/electrode/protective membrane after Wet-type etching becomes concavity.And Cu content is fewer, the resistance of protective membrane is larger, and the confidence level of electrode reduces.In addition, Cu content is fewer, and maximum magnetic susceptibility μm increases.
Therefore, Cu content needs at more than 15.0 quality %.Cu content is more preferably at more than 25.0 quality %, preferred at more than 30.0 quality % further.
On the other hand, Cu content surplus, becomes large with the potential difference of peripheral parts on the contrary.In addition, etch-rate is too fast compared with Cu electrode, and the confidence level of electrode reduces.If the etch-rate of protective membrane is too fast, then the section of the protective membrane/electrode/protective membrane after Wet-type etching becomes convex.And Cu content surplus, due to compound between precipitating metal, thus processibility reduces.
Therefore, Cu content needs at below 55.0 quality %.Cu content is more preferably at below 45.0 quality %, preferred at below 40.0 quality % further, further preferred at below 35.0 quality %.
(2) 0.5 quality %≤Cr≤10.0 quality %
The potential difference contained between the NiCu alloy of the relatively Cu of volume and peripheral parts (particularly Cu electrode) becomes greatly, and etch-rate is accelerated compared with Cu electrode.Cr has to be made the potential difference between described NiCu alloy and peripheral parts diminish and makes the etch-rate of NiCu alloy reduce the effect of (close to Cu electrode).In addition, Cr also has the effect improved with the attaching of transparency electrode (ITO).
In general, Cr content is fewer, and the potential difference between peripheral parts becomes greatly, and resistance to electrolytic corrosion reduces.In addition, etch-rate is too fast compared with Cu electrode, and the confidence level of electrode reduces.And Cr content is fewer, reduce with the attaching of transparency electrode.
Therefore, Cr content needs at more than 0.5 quality %.Cr content is more preferably at more than 1.0 quality %, preferred at more than 3.0 quality % further.
On the other hand, Cr content surplus, becomes large with the potential difference of peripheral parts on the contrary.In addition, etch-rate is too fast compared with Cu electrode, and the confidence level of electrode reduces.
Therefore, Cr content needs at below 10.0 quality %.Cr content is more preferably at below 7.0 quality %, preferred at below 5.0 quality % further.
[1.2. purposes]
The target that first embodiment of the invention relates to may be used for forming protective membrane, and this protective membrane is for the protection of Cu electrode.
Herein, " Cu electrode " refers to such electrode: it is made up of pure Cu or the Cu alloy with the resistance (specifically, about 2 ~ 3 μ Ω cm) equal with pure Cu.
In addition, the target that the present embodiment relates to also may be used for the purposes beyond Cu electrode protective membrane.As other purposes, there are electrode film, reflectance coating etc. specifically.
Cu electrode protective membrane is generally formed in the two sides of Cu electrode.Such as, when liquid crystal panel, use the target with predetermined composition, form Cu electrode protective membrane, Cu electrode and Cu electrode protective membrane successively at the substrate surface being formed with transparency electrode.Then, adopt wet etching, with predetermined shape, Cu electrode protective membrane/Cu electrode/Cu electrode protective membrane is formed pattern.
On the other hand, according to purposes, sometimes also on the one side of Cu electrode, form protective membrane.Such as, when TFT, use the target with predetermined composition, form Cu electrode protective membrane and Cu electrode successively at the substrate surface being formed with transparency electrode.Then, adopt wet etching, with predetermined shape, Cu electrode protective membrane/Cu electrode is formed pattern.
[2.Cu electrode protective membrane with Ni-Cu alloy target material (2): NiCuTi alloy]
[2.1. composition]
The Cu electrode protective membrane Ni-Cu alloy target material that second embodiment of the invention relates to contains following element, and surplus is made up of Ni and inevitable impurity.The kind of Addition ofelements and the restriction reason of addition as described below.
(1) 15.0 quality %≤Cu≤55.0 quality %
The difference (potential difference) that Cu content in NiCu alloy can affect the standard potential between this alloy and Cu electrode or ITO or the etching rate difference affected between this alloy and Cu electrode.In addition, Cu content also can affect the magnetic susceptibility of NiCu alloy.
In general, Cu content is fewer, and potential difference between peripheral parts is larger, and resistance to electrolytic corrosion reduces.In addition, etch-rate is slack-off compared with Cu electrode, and the confidence level of electrode reduces.If when the etch-rate of protective membrane is crossed slow, the section of the protective membrane/electrode/protective membrane after Wet-type etching becomes concavity.And Cu content is fewer, the resistance of protective membrane is larger, and the confidence level of electrode reduces.In addition, Cu content is fewer, and maximum magnetic susceptibility μm increases.
Therefore, Cu content needs at more than 15.0 quality %.Cu content is more preferably at more than 25.0 quality %, preferred at more than 30.0 quality % further.
On the other hand, Cu content surplus, becomes large with the potential difference of peripheral parts on the contrary.In addition, etch-rate is too fast compared with Cu electrode, and the confidence level of electrode reduces.If the etch-rate of protective membrane is too fast, then the section of the protective membrane/electrode/protective membrane after Wet-type etching becomes convex.And Cu content surplus, due to compound between precipitating metal, thus processibility reduces.
Therefore, Cu content needs at below 55.0 quality %.Cu content is more preferably at below 45.0 quality %, preferred at below 40.0 quality % further, further preferred at below 35.0 quality %.
(2) 0.5 quality %≤Ti≤10.0 quality %
The potential difference contained between the NiCu alloy of the relatively Cu of volume and peripheral parts (particularly Cu electrode) becomes greatly, and etch-rate is accelerated compared with Cu electrode.Ti has to be made the potential difference between described NiCu alloy and peripheral parts diminish and makes the etch-rate of NiCu alloy reduce the effect of (close to Cu electrode).In addition, Ti also has the effect improved with the attaching of transparency electrode (ITO).
In general, Ti content is fewer, and the potential difference between peripheral parts becomes greatly, and resistance to electrolytic corrosion reduces.In addition, etch-rate is too fast compared with Cu electrode, and the confidence level of electrode reduces.And Ti content is fewer, reduce with the attaching of transparency electrode.
Therefore, Ti content needs at more than 0.5 quality %.Ti content is more preferably at more than 1.0 quality %, preferred at more than 3.0 quality % further.
On the other hand, Ti content surplus, becomes large with the potential difference of peripheral parts on the contrary.In addition, etch-rate is excessively slow compared with Cu electrode, and the confidence level of electrode reduces.
Therefore, Ti content needs at below 10.0 quality %.Ti content is more preferably at below 7.0 quality %, preferred at below 5.0 quality % further.
[2.2. purposes]
About the purposes of the target that second embodiment of the invention relates to, due to identical with the first embodiment, therefore omit detailed description thereof.
[3.Cu electrode protective membrane with Ni-Cu alloy target material (3): NiCuCrTi alloy]
[3.1. composition]
The Cu electrode protective membrane Ni-Cu alloy target material that third embodiment of the invention relates to contains following element, and surplus is made up of Ni and inevitable impurity.The kind of Addition ofelements and the restriction reason of addition as described below.
(1) 15.0 quality %≤Cu≤55.0 quality %
The difference (potential difference) that Cu content in NiCu alloy can affect the standard potential between this alloy and Cu electrode or ITO or the etching rate difference affected between this alloy and Cu electrode.In addition, Cu content also can affect the magnetic susceptibility of NiCu alloy.
In general, Cu content is fewer, and potential difference between peripheral parts is larger, and resistance to electrolytic corrosion reduces.In addition, etch-rate is slack-off compared with Cu electrode, and the confidence level of electrode reduces.If when the etch-rate of protective membrane is crossed slow, the section of the protective membrane/electrode/protective membrane after Wet-type etching becomes concavity.And Cu content is fewer, the resistance of protective membrane is larger, and the confidence level of electrode reduces.In addition, Cu content is fewer, and maximum magnetic susceptibility μm increases.
Therefore, Cu content needs at more than 15.0 quality %.Cu content is more preferably at more than 25.0 quality %, preferred at more than 30.0 quality % further.
On the other hand, Cu content surplus, becomes large with the potential difference of peripheral parts on the contrary.In addition, etch-rate is too fast compared with Cu electrode, and the confidence level of electrode reduces.If the etch-rate of protective membrane is too fast, then the section of the protective membrane/electrode/protective membrane after Wet-type etching becomes convex.And Cu content surplus, due to compound between precipitating metal, thus processibility reduces.
Therefore, Cu content needs at below 55.0 quality %.Cu content is more preferably at below 45.0 quality %, preferred at below 40.0 quality % further, further preferred at below 35.0 quality %.
(2) 0.5 quality %≤(Cr, Ti)≤10.0 quality %, but Cr>0, Ti>0
As mentioned above, Cr and Ti all has following effect:
A effect that () makes the potential difference between NiCu alloy and peripheral parts reduce;
B () makes the etch-rate of NiCu alloy slow down the effect of (close to Cu electrode); And
C () improves the effect with the attaching of transparency electrode (ITO).
If add Cr and Ti in NiCu alloy simultaneously, there is such effect: while same maintenance etch-rate and attaching property, make to reduce further with the potential difference of peripheral parts.
In general, Cr and/or Ti content is fewer, and the potential difference between peripheral parts becomes greatly, and resistance to electrolytic corrosion reduces.In addition, etch-rate is too fast compared with Cu electrode, and the confidence level of electrode reduces.Therefore, the total content of Cr and Ti needs at more than 0.5 quality %.The total content of Cr and Ti is more preferably at more than 1.0 quality %, preferred at more than 3.0 quality % further.
On the other hand, the content surplus of Cr and/or Ti, becomes large with the potential difference of peripheral parts on the contrary.In addition, etch-rate is excessively slow compared with Cu electrode, and the confidence level of electrode reduces.Therefore, the total content of Cr and Ti needs at below 10.0 quality %.The total content of Cr and Ti is more preferably at below 7.0 quality %, preferred at below 5.0 quality % further.
[3.2. purposes]
About the purposes of the target that third embodiment of the invention relates to, due to identical with the first embodiment, therefore omit detailed description thereof.
[4. stack membrane]
The protective membrane that the stack membrane that the present invention relates to has Cu electrode and formed on the one or both sides of described Cu electrode, described protective membrane is made up of the film after using Cu electrode protective membrane Ni-Cu alloy target material film forming involved in the present invention.
[4.1.Cu electrode]
The thickness of Cu electrode preferably selects best thickness according to object.In general, Cu electrode is thicker, works more stable.But if Cu electrode is blocked up, not only etching or attaching property reduce, but also cause film rupture.Therefore, the thickness of Cu electrode is preferably 50 ~ 500nm.The thickness of Cu electrode is more preferably 100 ~ 400nm, more preferably 150 ~ 250nm.
About the other side of Cu electrode, due to recited above, therefore omit its description.
[4.2. protective membrane]
The thickness of protective membrane preferably selects best thickness according to object.In general, protective membrane is thicker, and weather resistance is higher.But if protective membrane is blocked up, then etching or attaching property reduce.Therefore, the thickness of protective membrane is preferably 5 ~ 100nm.The thickness of protective membrane is more preferably 5 ~ 70nm, more preferably 5 ~ 50nm.
When the two sides of Cu electrode forms protective membrane, the composition of the protective membrane of each can be mutually the same or can be different.That is, when the two sides of Cu electrode forms protective membrane, the target of same composition can be adopted to form the protective membrane of each.Or, the first target can be adopted to form the protective membrane of one side, and adopt the second target different from the composition of the first target to form the protective membrane of another side.
About the film of protective membrane, there is no particular limitation, can adopt various method according to object.As the film of protective membrane employing target, there is sputtering method specifically, also have the nano-imprint method using nanoparticle or wet plating method etc. in addition.
About protective membrane and the Cu electrode protective membrane other side of Ni-Cu alloy target material, due to recited above, therefore omit its description.
[effect of Ni-Cu alloy target material and stack membrane of 5.Cu electrode protective membrane]
Potential difference between Ni-15 ~ 55Cu alloy and peripheral parts (particularly Cu electrode) is comparatively large, and compared with Cu electrode, etch-rate is fast.
On the other hand, if add Cr and/or Ti of predetermined amount in Ni-15 ~ 55Cu alloy, then etch-rate slack-off (etch-rate close to Cu electrode), meanwhile, and the potential difference between the peripheral parts such as Cu electrode or ITO diminishes.Therefore, when this alloy being used as the protective membrane of the Cu electrode used in liquid crystal panel, the electrical characteristic deterioration caused by the electrolytic corrosion of Cu electrode or atomic diffusion can being suppressed, and pattern can be formed accurately by wet etching.
In addition, if add Cr and/or Ti of predetermined amount in Ni-15 ~ 55Cu alloy, then improve with the attaching of transparency electrode.Further, because the maximum magnetic susceptibility of Ni-15 ~ 55Cu alloy diminishes, when therefore using it for target, can effectively sputter.
Embodiment
(embodiment 1)
[1. the preparation of sample]
Adopt and dissolve casting, preparation has the Ni-Cu-Cr alloy target material of predetermined composition.Cu content is set as 10 ~ 60 quality %.Cr content is set as 0 ~ 11 quality %.In addition, adopt and dissolve casting, preparation Ni-35 quality %Cu-1.5 quality %Cr-1.5 quality %Ti alloy target material.Further, as a comparison, use pure Cu and ITO.
[2. test method]
[2.1. potential difference]
Measure the standard potential of Ni-Cu-Cr alloy, Ni-Cu-Cr-Ti alloy, Cu and ITO respectively.Use carbon dioxide process carbon electrode as to electrode, use mercurous chloride electrode as reference electrode, in the 200g/L ammonium sulfate solution remaining 40 DEG C, adopt current potential galvanostat method bioassay standard current potential.
Utilize the standard potential of each material obtained, calculate Ni-Cu-Cr alloy or the potential difference △ V (V) between Ni-Cu-Cr-Ti alloy and Cu, and Ni-Cu-Cr alloy or the potential difference △ V (V) between Ni-Cu-Cr-Ti alloy 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 also no problem in practical.Specifically, with the potential difference of ITO below 0.35V, with the potential difference of Cu at below 1.0V.
[2.2. etching rate difference]
The test film of each material complete for shape is immersed in predetermined time in the ammonium sulfate 200g/L aqueous solution of 40 DEG C.Etch-rate is calculated according to the reduction of thickness after dipping.Further, utilize the etch-rate obtained, calculate the etching rate difference (nm/ second) between Cu.
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 slightly larger also no problem in practical.Specifically, etch-rate is 1.2nm/ second.
[2.3. stripping rate]
Form ito film (thickness: 20nm or 150nm) on the glass substrate.Then, ito film forms Ni-Cu-Cr alloy film or Ni-Cu-Cr-Ti alloy film (thickness: 50nm or 200nm) further.
Utilize the film obtained, carry out scratch test.Test conditions is according to JIS K5600 setting.That is, place 1mm spacing crosscut device on the surface of the film, form 100 grids.Stick adhesive tape on the surface of the film, after stripping tape, calculate the number n (=stripping rate (%)) of the grid peeled off.
In addition, best when stripping rate is 0%, but, be preferably less than 10% (1 figure place).
[the maximum magnetic susceptibility of 2.4.]
Use the test film that shape is complete, measure maximum magnetic susceptibility μ by sample oscillating mode magnetometer (VSM).Magnetic field Hm during mensuration is set as 20 [MOe].
In addition, it is no problem in practical when maximum magnetic susceptibility is below 100.
[3. result]
[3.1. potential difference △ V]
Potential difference △ V between Ni-Cu-Cr alloy and ITO has been shown in Fig. 1.In Fig. 1, the potential difference △ V (0.16V) between what dotted line represented is is used as Al system wiring material protective membrane Mo-10Nb and ITO in prior art.
Potential difference △ V between Ni-Cu-Cr alloy and Cu has been shown in Fig. 2.In Fig. 2, the potential difference △ V (0.62V) between the Al-3Nd being used as Al system wiring material in what dotted line represented is Mo-10Nb and prior art.
In addition, also also show the result of Ni-Cu-Cr-Ti alloy in Fig. 1 and Fig. 2.
As shown in Figure 1:
(1) as the combination of protective membrane/electrode/transparency electrode, when using the combination of Ni-Cu-Cr alloy/Cu/ITO, compared with existing combination (Mo-10Nb/Al-3Nd/ITO), diminish relative to the potential difference △ V of ITO.
(2) become practical no problem value (0.35V) below in order to make relative to the potential difference △ V of ITO, the lower limit of Cu content is preferably 15 quality % or 20 quality %.In addition, the upper limit of Cu content is preferably 55 quality % or 50 quality %.
(3) in order to make equal with existing combination relative to the potential difference △ V of ITO or be less than existing combination, the lower limit of Cu content is preferably 23.5 quality %, 24 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 44 quality %, 40 quality % or 38 quality %.
(4) become practical no problem value (0.35V) below in order to make relative to the potential difference of ITO, the upper limit of Cr content is preferably 10 quality %, 8 quality % or 7 quality %.
(5) in order to make equal with existing combination relative to the potential difference △ V of ITO or be less than existing combination, the lower limit of Cr content is preferably 0.2 quality %, 0.5 quality % or 1 quality %.In addition, the upper limit of Cr content is preferably 6.5 quality %, 6 quality % or 5 quality %.
(6) with Ni-35Cu-3Cr alloy phase ratio, Ni-35Cu-1.5Cr-1.5Ti alloy less relative to the potential difference △ V of ITO.
As shown in Figure 2:
(1) as the combination of protective membrane/electrode/transparency electrode, when using the combination of Ni-Cu-Cr alloy/Cu/ITO, compared with existing combination (Mo-10Nb/Al-3Nd/ITO), diminish relative to the potential difference △ V of Cu.
(2) become practical no problem value (1.0V) below in order to make relative to the potential difference △ V of Cu, the lower limit of Cu content is preferably 15 quality % or 20 quality %.
(3) in order to make equal with existing combination relative to the potential difference △ V of Cu or be less than existing combination, the lower limit of Cu content is preferably 23 quality %, 24 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 45 quality %, 42 quality % or 40 quality %.
(4) in order to make equal with existing combination relative to the potential difference △ V of Cu or be less than existing combination, the lower limit of Cr content is preferably 0.2 quality %, 0.5 quality % or 1 quality %.In addition, the upper limit of Cr content is preferably 5.5 quality %, 5 quality % or 4 quality %.
(5) Ni-35Cu-1.5Cr-1.5Ti alloy is substantially identical with Ni-35Cu-3Cr alloy relative to the potential difference △ V of Cu.
[3.2. etching rate difference]
Etching rate difference between Ni-Cu-Cr alloy and Cu has been shown in Fig. 3.In Fig. 3, the value (0.6nm/ second) of what dotted line represented is 1/2 of the etch-rate of Cu.The etch-rate R of each material
1with the etch-rate R of Cu
2difference (=R
1-R
2) absolute value the smaller the better, in practical, etching rate difference also need not be 0.The etch-rate R of each material
1with the etch-rate R of Cu
2the absolute value of difference be the etch-rate R of Cu
2less than 1/2 time (that is, | R
1-R
2|≤R
2when/2), concavo-convex relatively less good section can be obtained by Wet-type etching.
In addition, the result of Ni-Cu-Cr-Ti alloy is also together shown in Fig. 3.
As shown in Figure 3:
(1) as the combination of protective membrane/electrode/transparency electrode, when using the combination of Ni-Cu-Cr alloy/Cu/ITO, its etching rate difference is less than the value (1.2nm/ second) of existing combination (Mo-10Nb/Al-3Nd/ITO).
(2) in order to make etching rate difference become practical no problem value (1.2nm/ second) below, the lower limit of Cu content is preferably 15 quality % or 20 quality %.In addition, the upper limit of Cu content is preferably 55 quality %, 50 quality % or 47 quality %.
(3) in order to make etching rate difference be less than or equal to Cu/2, the lower limit of Cu content is preferably 24 quality %, 24.5 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 42 quality %, 40 quality % or 38 quality %.
(4) in order to make etching rate difference become practical no problem value (1.2nm/ second) below, the upper limit of Cr content is preferably 10 quality %, 9 quality % or 8 quality %.
(5) in order to make etching rate difference be less than or equal to Cu/2, the lower limit of Cr content is preferably 0.5 quality %, 1 quality % or 2 quality %.In addition, the upper limit of Cr content is preferably 6.5 quality %, 6 quality % or 5 quality %.
(6) etching rate difference of Ni-Cu-Cr-Ti alloy is slightly higher than Ni-Cu-Cr alloy, but is significantly less than Ni-Cu alloy.
[3.3. stripping rate]
Fig. 4 to Fig. 7 shows the stripping rate at thickness to be the thickness that the ito film of 20nm or 150nm is formed the be Ni-Cu-Cr alloy film of 50nm or 200nm.In addition, the result of Ni-Cu-Cr-Ti alloy is also together shown in Fig. 4 to Fig. 7.
From Fig. 4 to Fig. 7:
(1) the stripping rate of Ni-Cu-Cr alloy film is significantly less than Ni-Cu alloy film.In addition, the stripping rate of Ni-Cu-Cr alloy film not too depends on thickness.
(2) the stripping rate of Ni-Cu-Cr alloy film does not rely on Cu content and demonstrates good value.Particularly, good result can be obtained in the scope that Cu content is 15 ~ 40 quality %.Cu content is more preferably 23 ~ 25 quality %.
(3) by adding Cr, significantly peel resistance can be improved.Even if add the Cr of 1 quality %, also can confirm its sufficient effect, if add the Cr of more than 3 quality %, then substantially not peel off.Particularly, good result can be obtained in the scope of 3 ~ 7 quality %.
(4) if add Ti in Ni-Cu-Cr alloy, although stripping rate increases a little than Ni-Cu-Cr alloy, Ni-Cu alloy is significantly less than.
[the maximum magnetic susceptibility of 3.4.]
The maximum magnetic susceptibility of Ni-Cu-Cr alloy has been shown in Fig. 8.In addition, the result of Ni-Cu-Cr-Ti alloy is also together shown in Fig. 8.
As shown in Figure 8:
(1) in order to make maximum magnetic susceptibility μ below 100, the lower limit of Cu content can be 15 quality %.The lower limit of Cu content is more preferably 20 quality %.In addition, the upper limit of Cu content is preferably 50 quality %.
(2) in order to make maximum magnetic susceptibility μ below 20, the lower limit of Cu content is preferably 24 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 47 quality % or 45 quality %.
(3) even if make Cr content change in 0 ~ 11 quality %, maximum magnetic susceptibility μ also has almost no change.
(embodiment 2)
[1. the preparation of sample]
Adopt and dissolve casting, preparation has the Ni-Cu-Ti alloy target material of predetermined composition.Cu content is set as 10 ~ 60 quality %.Ti content is set as 0 ~ 7 quality %.In addition, as a comparison, use pure Cu and ITO.
[2. test method]
According to the operation identical with embodiment 1, measure etching rate difference, stripping rate and the maximum magnetic susceptibility μ between potential difference △ V, Ni-Cu-Ti alloy between potential difference △ V, Ni-Cu-Ti alloy between Ni-Cu-Ti alloy and Cu and ITO and Cu.
[3. result]
[3.1. potential difference △ V]
Potential difference △ V between Ni-Cu-Ti alloy and ITO has been shown in Fig. 9.In Fig. 9, the potential difference △ V (0.16V) between what dotted line represented is is used as Al system wiring material protective membrane Mo-10Nb and ITO in prior art.
Potential difference △ V between Ni-Cu-Ti alloy and Cu has been shown in Figure 10.In Figure 10, the potential difference △ V (0.62V) between the Al-3Nd being used as Al system wiring material in what dotted line represented is Mo-10Nb and prior art.
In addition, the result of Ni-Cu-Cr-Ti alloy is also shown in Fig. 9 and Figure 10 in the lump.
As shown in Figure 9:
(1) as the combination of protective membrane/electrode/transparency electrode, when using the combination of Ni-Cu-Ti alloy/Cu/ITO, compared with existing combination (Mo-10Nb/Al-3Nd/ITO), diminish relative to the potential difference △ V of ITO.
(2) become practical no problem value (0.35V) below in order to make relative to the potential difference △ V of ITO, the lower limit of Cu content can be 15 quality %.The lower limit of Cu content is more preferably 20 quality % or 23 quality %.
(3) in order to make equal with existing combination relative to the potential difference △ V of ITO or be less than existing combination, the lower limit of Cu content is preferably 23.5 quality %, 24 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 50 quality %, 45 quality % or 42 quality %.
(4) content regardless of Ti is how many, all shows good value relative to the potential difference △ V of ITO.
(5) in order to make equal with existing combination relative to the potential difference △ V of ITO or be less than existing combination, the lower limit of Ti content is preferably 0.2 quality %, 0.3 quality % or 0.5 quality %.In addition, the upper limit of Ti content is preferably 5.5 quality %, 5 quality % or 4.5 quality %.
(6) with Ni-35Cu-3Ti alloy phase ratio, Ni-35Cu-1.5Cr-1.5Ti alloy less relative to the potential difference △ V of ITO.
As shown in Figure 10:
(1) as the combination of protective membrane/electrode/transparency electrode, when using the combination of Ni-Cu-Ti alloy/Cu/ITO, compared with existing combination (Mo-10Nb/Al-3Nd/ITO), diminish relative to the potential difference △ V of Cu.
(2) become practical no problem value (1.0V) below in order to make relative to the potential difference △ V of Cu, the lower limit of Cu content can be 15 quality %.The lower limit of Cu content is more preferably 20 quality %.
(3) in order to make equal with existing combination relative to the potential difference △ V of Cu or be less than existing combination, the lower limit of Cu content is preferably 23.5 quality % or 24 quality %.In addition, the upper limit of Cu content is preferably 46 quality %, 45 quality % or 40 quality %.
(4) content regardless of Ti is how many, all shows good value relative to the potential difference △ V of Cu.
(5) in order to make equal with existing combination relative to the potential difference △ V of Cu or be less than existing combination, the lower limit of Ti content is preferably 0.2 quality %, 0.5 quality % or 1 quality %.In addition, the upper limit of Ti content is preferably 5.5 quality %, 5 quality % or 4.5 quality %.
(6) Ni-35Cu-1.5Cr-1.5Ti alloy is substantially identical with Ni-35Cu-3Ti alloy relative to the potential difference △ V of Cu.
[3.2. etching rate difference]
Etching rate difference between Ni-Cu-Ti alloy and Cu has been shown in Figure 11.In Figure 11, the value (0.6nm/ second) of what dotted line represented is 1/2 of the etch-rate of Cu.In addition, the result of Ni-Cu-Cr-Ti alloy is also shown in Figure 11 in the lump.
As shown in Figure 11:
(1) as the combination of protective membrane/electrode/transparency electrode, when using the combination of Ni-Cu-Ti alloy/Cu/ITO, its etching rate difference is less than the value (1.2nm/ second) of existing combination (Mo-10Nb/Al-3Nd/ITO).
(2) in order to make etching rate difference become practical no problem value (1.2nm/ second) below, the lower limit of Cu content can be 15 quality %.The lower limit of Cu content is more preferably 20 quality %.In addition, the upper limit of Cu content can be 55 quality %.The upper limit of Cu content is more preferably 50 quality % or 45 quality %.
(3) in order to make etching rate difference be less than or equal to Cu/2, the lower limit of Cu content is preferably more than 24 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 40 quality % or 38 quality %.
(4) content regardless of Ti is how many, all shows good etching rate difference.
(5) in order to make etching rate difference be less than or equal to Cu/2, the lower limit of Ti content is preferably 1.5 quality % or 2 quality %.In addition, the upper limit of Ti content is preferably 5 quality % or 4.5 quality %.
(6) etching rate difference of Ni-Cu-Cr-Ti alloy is less than Ni-Cu-Ti alloy.
[3.3. stripping rate]
Figure 12 to Figure 15 shows the stripping rate at thickness to be the thickness that the ito film of 20nm or 150nm is formed the be Ni-Cu-Ti alloy film of 50nm or 200nm.In addition, the result of Ni-Cu-Cr-Ti alloy is also shown in Figure 12 to Figure 15 in the lump.
From Figure 12 to Figure 15:
(1) the stripping rate of Ni-Cu-Ti alloy film depends on thickness, and the thickness of Ni-Cu-Ti alloy film is thicker, and stripping rate increases.
(2) when the thickness of Ni-Cu-Ti alloy film is 50nm, be the lower limit of less than 10%, Cu content to make stripping rate can be 15 quality %.The lower limit of Cu content is more preferably 20 quality %, 23 quality %, 24 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 47 quality %, 45 quality % or 40 quality %.
(3) when the thickness of Ni-Cu-Ti alloy film is 50nm, be that the lower limit of less than 10%, Ti content is preferably 1.0 quality %, 1.5 quality %, 2 quality % or 3 quality % in order to make stripping rate.
(4) if add Cr in Ni-Cu-Ti alloy, stripping rate and Ni-Cu-Ti alloy phase with or be less than Ni-Cu-Ti alloy.
[the maximum magnetic susceptibility of 3.4.]
The maximum magnetic susceptibility of Ni-Cu-Ti alloy has been shown in Figure 16.In addition, the result of Ni-Cu-Cr-Ti alloy is also shown in Figure 16 in the lump.
As shown in Figure 16:
(1) in order to make maximum magnetic susceptibility μ below 100, the lower limit of Cu content is preferably 24 quality %.
(2) in order to make maximum magnetic susceptibility μ below 20, the lower limit of Cu content is preferably 24.5 quality % or 25 quality %.In addition, the upper limit of Cu content is preferably 47 quality %, 45 quality % or 40 quality %.
(3) even if make Ti content change in 0 ~ 11 quality %, maximum magnetic susceptibility μ also has almost no change.
(embodiment 3)
[1. the preparation of sample]
Use the target prepared by embodiment 1 or 2, prepare touch panel stack membrane.That is, sputtering method is adopted, at substrate surface successively (from bottom to up) formation barrier layer, electrode layer and tectum.As substrate, use ITO/ underlying membrane/pet substrate or ITO/ underlying membrane/glass substrate (being commercially available product).Employ the NiCu alloy of Cu or Ti containing predetermined amount in barrier layer and tectum respectively, in electrode layer, employ Cu (5N).
As a comparison, prepared such stack membrane: wherein, employ Mo-10Nb alloy respectively in barrier layer and tectum, in electrode layer, employed Al-3Nd.
The filming condition of touch panel stack membrane has been shown in table 1.
Table 1
| Material | Power | Gas | Sputter rate | Film thickness |
| NiCu alloy | DC300W | Ar 0.3Pa | 55nm/ minute | 20nm |
| Cu(5N) | RF500W | Ar 0.3Pa | 48nm/ minute | 200nm |
| MoNb | DC300W | Ar 0.3Pa | 31nm/ minute | 20nm |
| AlNd | DC300W | Ar 0.3Pa | 60nm/ minute | 200nm |
[2. test method]
[2.1. attaching property]
Carry out scratch test (according to JIS K5600 standard) under the same conditions as example 1, measure stripping rate.
[2.2. weathering resistance]
By the substrate with stack membrane 65 DEG C, keep 1000 hours under the condition of 95% humidity.After off-test, visually judge whether variable color.
[2.3. etching]
The substrate with stack membrane is immersed in the ammonium persulphate 200g/L aqueous solution of 40 DEG C, stack membrane is dissolved.Measure until substrate bleach (until stack membrane all dissolves) time required time.
[2.4. electrode part sheet resistance]
4 terminal methods are adopted to measure electrode part sheet resistance.
[3. result]
In table 2 and table 3, result is shown.From table 2 and table 3:
(1) no matter barrier layer/electrode layer/tectal composition how, electrode part sheet resistance is all lower.
(2) when the Cu content of NiCuCr alloy is certain, Cr content is more, attach property and weathering resistance higher, but etching reduce.In addition, when the Cr content of NiCuCr alloy is certain, if Cu content is superfluous, then weathering resistance reduces.That is, if when being used in barrier layer and tectum by Ni-25 ~ 40Cu-3 ~ 5Cr alloy, then the touch panel stack membrane that attaching property, weathering resistance and etching are all excellent can be obtained.
(3) when the Cu content of NiCuTi alloy is certain, Ti content is more, attach property and weathering resistance higher, but etching reduce.In addition, when the Ti content of NiCuTi alloy is certain, if Cu content is superfluous, then weathering resistance reduces.That is, if when being used in barrier layer and tectum by Ni-25 ~ 40Cu-3 ~ 5Ti alloy, then the touch panel stack membrane that attaching property, weathering resistance and etching are all excellent can be obtained.
(table 2)
Attaching property (stripping rate): zero=less than 3%, △=be more than or equal to 3% and be less than 10%, X=is more than or equal to 10%
Weathering resistance: zero=without variable color, X=has variable color
Etching (until the time required for substrate bleach): zero=less than 1 minute, more than X=1 minute
(table 3)
Attaching property (stripping rate): zero=less than 3%, △=be more than or equal to 3% and be less than 10%, X=is more than or equal to 10%
Weathering resistance: zero=without variable color, X=has variable color
Etching (until the time required for substrate bleach): zero=less than 1 minute, more than X=1 minute
(embodiment 4)
[1. the preparation of sample]
Use the target prepared by embodiment 1 or 2, preparation TFT stack membrane.That is, sputtering method is adopted, at substrate surface successively (from bottom to up) formation barrier layer and electrode layer.As substrate, use ITO/ underlying membrane/glass substrate (commercially available product).Employ the NiCu alloy of Cu or Ti containing predetermined amount in barrier layer, in electrode layer, employ Cu (5N).
As a comparison, prepared such stack membrane: wherein, employ Mo-50Ti alloy in barrier layer, employ Cu in electrode layer.
The filming condition of TFT stack membrane has been shown in table 4.
Table 4
| Material | Power | Gas | Sputter rate | Film thickness |
| NiCu alloy | DC300W | Ar 0.3Pa | 55nm/ minute | 20nm |
| Cu(5N) | RF500W | Ar 0.3Pa | 48nm/ minute | 200nm |
| MoTi | DC300W | Ar 0.3Pa | 28nm/ minute | 20nm |
[2. test method]
[2.1. attaching property, etching and electrode part sheet resistance]
At the same conditions as example 3, attaching property, etching and electrode part sheet resistance is determined.
[2.2. block]
The substrate with stack membrane is carried out to the vacuum heat treatment of 250 DEG C × 30 minutes.After thermal treatment, adopt auger analysis, detect the diffusion of near interface Cu, Si.Utilize auger analysis, judge the quality of block according to the slope of Cu, Si detected level on depth direction.About the evaluation of block, situation when zero difference representing the slope of Cu, Si detected level on depth direction before and after thermal treatment is less than 3%, situation when X represents that the difference of the slope of Cu, Si detected level on depth direction before and after thermal treatment is greater than 3%.
[3. result]
Result has been shown in table 5.As shown in Table 5:
(1) no matter the composition of barrier layer/electrode layer how, electrode part sheet resistance is all lower.
(2) when the Cu content of NiCuCr alloy is certain, Cr content is more, attach property and block higher, but etching reduce.In addition, when the Cr content of NiCuCr alloy is certain, if Cu content is superfluous, then block reduces.That is, if when Ni-25 ~ 40Cu-3 ~ 5Cr alloy being used for barrier layer, then the TFT stack membrane that attaching property, block and etching are all excellent can be obtained.
(3) when the Cu content of NiCuTi alloy is certain, Ti content is more, attach property and block higher, but etching reduce.In addition, when the Ti content of NiCuTi alloy is certain, if Cu content is superfluous, then block reduces.That is, if when Ni-25 ~ 40Cu-3 ~ 5Ti alloy being used for barrier layer, then the TFT stack membrane that attaching property, block and etching are all excellent can be obtained.
(table 5)
Attaching property (stripping rate): zero=less than 3%, △=be more than or equal to 3% and be less than 10%, X=is more than or equal to 10%
The block difference of the slope of Cu, Si detected level (before and after the thermal treatment on depth direction): less than zero=3%, X=is more than 3%
Etching (until the time required for substrate bleach): zero=less than 1 minute, more than X=1 minute
Below understand embodiment of the present invention in detail, but the present invention is not limited to above-mentioned embodiment, can carry out various change without departing from the spirit of the scope of the invention.
Industrial applicibility
The Cu electrode protective membrane NiCu alloy target material that the present invention relates to can be used as the sputtering target material for forming protective membrane on the two sides of Cu electrode, and wherein said Cu electrode is used in touch pad electrode portion, liquid crystal panel TFT portion, organic EL panel electrode part, plasma display electrode part, solar battery panel electrode part, semi-conducting electrode portion etc.
Claims (6)
1. a panel Cu electrode protective membrane Ni-Cu alloy target material, it is formed as follows:
30.0 quality %≤Cu≤55.0 quality %,
0.5 quality %≤(Cr, Ti)≤10.0 quality %, wherein, Cr>0, Ti>0,
Surplus is Ni and inevitable impurity.
2. panel Cu electrode protective membrane Ni-Cu alloy target material according to claim 1, wherein
30.0 quality %≤Cu≤40.0 quality % and
1.0 quality %≤(Cr, Ti)≤5.0 quality %, wherein, Cr>0, Ti>0.
3. a panel Cu electrode protective membrane Ni-Cu alloy target material, it is formed as follows:
30.0 quality %≤Cu≤55.0 quality %,
0.5 quality %≤Cr≤10.0 quality %,
Surplus is Ni and inevitable impurity.
4. panel Cu electrode protective membrane Ni-Cu alloy target material according to claim 3, wherein
30.0 quality %≤Cu≤40.0 quality % and
1.0 quality %≤Cr≤5.0 quality %.
5. a panel Cu electrode protective membrane Ni-Cu alloy target material, it is formed as follows:
30.0 quality %≤Cu≤55.0 quality %,
0.5 quality %≤Ti≤10.0 quality %,
Surplus is Ni and inevitable impurity.
6. panel Cu electrode protective membrane Ni-Cu alloy target material according to claim 5, wherein
30.0 quality %≤Cu≤40.0 quality % and
1.0 quality %≤Ti≤5.0 quality %.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2011041885 | 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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| 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 |
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| 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 |
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| 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 |
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| JP2019183251A (en) | 2018-04-17 | 2019-10-24 | 三菱マテリアル株式会社 | Cu-Ni alloy sputtering target |
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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 |
| JP2008166742A (en) * | 2006-12-04 | 2008-07-17 | Kobe Steel Ltd | Cu-alloy interconnection film, tft element for flat panel display using the film, and cu alloy sputtering target for manufacturing the film |
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- 2011-08-30 CN CN201410850977.2A patent/CN104611615B/en active Active
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| US20070074790A1 (en) * | 2003-10-24 | 2007-04-05 | Nikko Materials Co., Ltd. | Nickel alloy sputtering target and nickel alloy thin film |
| 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 |
| JP2008166742A (en) * | 2006-12-04 | 2008-07-17 | Kobe Steel Ltd | Cu-alloy interconnection film, tft element for flat panel display using the film, and cu alloy sputtering target for manufacturing the film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108456844A (en) * | 2018-02-07 | 2018-08-28 | 中国原子能科学研究院 | A method of it being coated with high-purity N i/Cu bilayer target membranes on high-boron-silicon glass |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5895370B2 (en) | 2016-03-30 |
| CN104611615B (en) | 2017-04-12 |
| JP2012193444A (en) | 2012-10-11 |
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