TW201211276A - NiCu alloy target for Cu electrode protection membrane and lamination membrane - Google Patents

Abstract

The present invention provides a protection membrane, which is suitable for use as a Cu electrode protection membrane, capable of inhibiting the electrolytic corrosion or degradation of electrical property caused by atomic diffusion of the Cu electrode, allowing high precision patterning through wet etching and having desirable adhesion with transparent electrodes, a NiCu alloy target for the Cu electrode protection membrane allowing high performance sputtering, and a lamination membrane made thereby. The present invention relates to a NiCu alloy target for the Cu electrode protection membrane, containing 15.0 ≤ Cu ≤ 55.0 mass%, 0.5 ≤ (Cr, Ti) ≤ 10.0 mass%, and the remaining part having Ni and unavoidable impurities, and a lamination membrane made thereby.

Description

201211276 VI. Description of the Invention: [Technical Field] The present invention relates to a NiCu alloy target for Cu electrode protection film and a laminated film. In detail, the present invention relates to the use of a touch panel. Or a Cu electrode for a protective film of a Cu electrode of an electrode of a liquid crystal panel, a NiCu alloy target for a film, and a laminated film produced using the same. [Prior Art] A liquid crystal panel used in a touch panel, a thin-sized large-faced television, or the like is provided with a liquid crystal structure enclosed between two transparent substrates. A transparent electrode serving as a working electrode of the liquid crystal is formed on the inner side (the surface on the liquid crystal side) of the transparent substrate. In general, indium tin oxide (JTO, jndium tin Oxide) is used in the & Further, a metal electrode or a metal wiring serving as an external turn-out terminal is formed in a portion of the surface of the substrate on which the transparent electrode is formed (hereinafter, these are collectively referred to as "metal electrodes" collectively). The metal electrode forms a portion (e.g., a peripheral portion of the substrate) in which the light is not required to pass through the surface of the substrate. In the case where a metal electrode is directly formed on the surface of the transparent electrode, when the difference (potential difference) between the standard potentials between the moving electrode and the metal electrode is large, the electrolysis of the metal electrode is caused. Further, there is an interdiffusion of atoms between the underlayer formed on the surface of the substrate and the metal electrode, and the electric shape of the metal electrode is I-like. Therefore, a film (transfer layer) useful for protecting the metal electrode is formed on both sides of the metal electrode. In the liquid crystal panel, 吏Nd series & gold is used as the metal electrode. The Mo-Nb alloy is used as the 100128318 201211276. Protective film. Various proposals have been made for metal electrodes, protective films, and materials for forming such liquid crystal panels. For example, Patent Document 1 discloses a film formation method comprising a total of 2 to 50 atom% selected from V and Nb, and the balance containing Mo and unavoidable impurities and having a relative density of 95% or more. Sputter target. It is described in the same document that when a Mo alloy target containing Nb or V is used, a metal thin film containing no harmful Cr and having low electrical resistance and high corrosion resistance can be obtained. Further, Patent Document 2 discloses a metal element lanthanum selected from the group consisting of (Ti, Zr, V, Nb, Cr) of 0.5 to 50 atom%, and having a specific structure. material. In the same document, a mixture of raw material powders is compression-molded to obtain a molded body, and the molded body is pulverized and powdered, and the powder is subjected to pressure sintering to suppress segregation of components and plastic processing of the sintered body. Sex also improved. Further, although Patent Document 3 does not disclose a target for a protective film for a metal electrode, it is disclosed that Ni contains 70:85 to 85% by weight, Cu: 2 to 10% by weight, and Mo: 1 to 6% by weight and / or Cr: 0.5 to 3% by weight, the remainder containing Fe substantially, and the crystal grain size of the sputtered face is smaller than the target member of JIS austenite crystal grain size No. 3. 100128318 4 201211276 In the same literature, § has been used to obtain a Fe-Ni alloy thin film with low magnetic constant force and uniformity when such a dry material is used. Further, although Patent Document 4 does not disclose a target for a protective film for a metal electrode, it is disclosed that Ni contains 35:85 wt%, self, &

One or more selected from the group consisting of Cu and Nb: 3 to 15% by weight, A1: i% by weight or less, Ca and/or Mg: 3〇〇ppm or less, 〇: 3〇ppm or less, N: 30 PPm or less, and remaining Part of it is essentially a base alloy for vapor deposition. A magnetic film which is described in the same document and has high characteristics is also disclosed in Non-Patent Document i using a mixture of Αγ+〇2 gas containing Cu-2 wt% Zr alloy, wt% M〇 alloy or Cu 〇7 wt. The method of splashing the dry material of %Mg alloy. In the same document, a barrier layer (oxidation layer) having a good adhesion to the underlayer is formed at the interface between the layer (metal electrode) containing the Cu-based material and the underlayer by using such a method. Further, although Patent Document 5 does not disclose a dry material for a protective film for a metal electrode, it discloses a crucible containing Ni_7.5 mass% TM to 40 mass% Cu alloy' and used to form an electrode for a wafer resistor. Remaining materials.于 In the same literature, it is described that if the addition of d in the alloy 1 is reduced, the saturation magnetization is reduced, so that a long-life target is obtained. Further, although the patent for the secret patent, the protective film for the 6-wire metal electrode is used for the target of 100128318 201211276, but it is revealed that one contains (a) Ni-25 at%Cu-2 at%Cr ^ α , Λ γ. Νι<6·6 maSS%CU-l.7 mass%Cr alloy), or (b) Ni-25 at%Cu-12 at%Ti Renren/χτ· 3 gold (Ν卜27)mass%Cu mass% Ti alloy) · The nickel alloy splash material is formed by the barrier layer. In the same reading towel, Lin Qianxi has a barrier layer, which inhibits the spread of %. The formation of the leather material is formed. With the enlargement of the liquid crystal panel, a low-resistance A material is sought. Further, since it is used in the film of the A1 wiring, the price of the material is high, and the cost of the liquid crystal panel is hindered. The phase =: alloy-based material is compared with the A1-based material; it is expected to be a low-resistance wiring material instead of the A1 bismuth material when the cu is low. 'S A1 is used as a metal electrode and a method using a metal material, and as disclosed in Non-Patent Document i, a tree having a material/argon Ar2 gas ring έ Cl^ alloy is sputtered. The method of 6 in the same literature has the advantage of being able to be plated with money and the same as the red protective film. * However, reactive sputtering in an Ar + 〇 2 gas atmosphere increases the electrical resistance of the Cu electrode itself, resulting in deterioration of characteristics. Moreover, since it is easy to capture the vacuum chamber t of the product, the control of the oxygen is difficult, and it is a cause of unevenness in the quality of the product. 100128318 6 201211276 The metal-electricity reduction _ system—the protective film and the electrode layer are formed on the entire surface of the substrate surface of the remedy electrode of Laiyi County, and patterned into a specific shape. In order to reduce the cost of the liquid crystal panel, it is preferable to carry out the pattern (4) by means of (4). Further, in order to perform high-precision patterning using wet fineness, it is preferable that the etching rates of the protective film and the electrode layer are almost equal. However, the gold shoulder electrode obtained by the method disclosed in Non-Patent Document 1 has a large difference in the rate between the two, so that it is impossible to perform high-precision patterning. Further, in the case of a liquid crystal panel, the 'Cu electrode protective film is formed on the transparent electrode of the package: ITO. Therefore, it is required for the Cu electrode protective film to have a readability of π and ΠΌ. Further, in order to perform (10) efficiently, the required magnetic permeability is low. However, the material for the electrode protective film and the laminated film produced using the wire material have not been previously provided. [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open No. 2 [Patent Document 2] Japanese Patent Laid-Open Publication No. JP-A No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open No. (8) 孓丨 7^4 公报 [Publication Document 6] International Publication No. WO 〇 2〇〇 5/〇 4129 [ [Non-Patent Document] 100128318 7 201211276 Literature 1] Yan Zewu et al., Ulvac Technical Journal, No. 69, P7, 2009 [Summary of the Invention] (The problem to be solved by the invention) ^ The object of the invention is to provide a protection of the seven-degree to CU electrode. The film 'suppresses the deterioration of the electrical characteristics of the electrolytic corrosion of the Cu electrode, and forms a protective film that can be highly precise by the wet type, and the adhesion is made. A good protective film, and () can be effectively sputtered: Electrode protective film, alloy material, and the like (the means for solving the problem) The flute of the present invention for solving the above problems is a NiCu alloy target for a Cu electrode protective film, which comprises: 15,0$ CuS 55.0 mass%, and 0·5 zero r, Tl)^1〇.〇mass% (its ten, C^O'TbO), and the remainder contains Ni and unavoidable impurities. 2 Inventive-type Cu electrode; composite film for coating, comprising 15.0$CuS55.0 mass%, and 0.5$CrS 10·0 mass%, and 100128318 201211276 The remainder contains Ni and unavoidable impurities. According to a third aspect of the present invention, there is provided a NiCu alloy target for a Cu electrode protective film comprising 15.0% Cu$55.0 mass% and 0.5STi$10.0 mass%, and the remainder comprising Ni and unavoidable impurities. Further, the laminated film of the present invention includes a Cu electrode and a protective film formed on one surface or both surfaces of the Cu electrode, and the protective film includes a NiCu alloy material for using the Cu electrode protective film of the present invention. Film of film. (Effect of the Invention) When a specific amount of Cr and/or Ti is added to the Ni-15 to 55Cu alloy, the difference in etching rate from the Cu electrode is reduced, and the potential difference from the peripheral member such as the Cu electrode or ITO is reduced. small. Therefore, if it is used as a protective film for a Cu electrode used for a liquid crystal panel, it is possible to suppress electrolytic corrosion of the Cu electrode = deterioration of electrical characteristics due to atomic diffusion, and high precision by wet etching. Patterning. Further, when a specific amount of Cr and/or Ti is added to the Ni-15 to 55Cu alloy, the adhesion to the transparent electrode is improved. Further, since the Ni-15 to 55Cu alloy has a small maximum magnetic permeability, it can be efficiently splattered if it is used for a dry material. 100128318 9 201211276 [Embodiment] An embodiment of the following ten inventions will be described in detail. [1. NiCu alloy target for the protection of the galvanic electrode (1): NiCuCr alloy] [1.1. Component] The NiCu alloy target for the Cu electrode protection film of the first embodiment of the present invention is the element described below and the remainder Contains Ni and unavoidable impurities. The reasons for limiting the type and amount of added elements are as follows. (1) 15.0$ Cug 55.0 mass%.

The Cu content in the NiCu alloy affects the difference (potential difference) between the standard potential between the Cu electrode and the IT electrode or the etching rate difference between the Cu electrode and the Cu electrode. Further, the Cu content affects the magnetic permeability of the NiCu alloy. In general, the smaller the Cu content becomes, the larger the potential difference from the peripheral member becomes, and the lower the electrolytic corrosion resistance. Further, the etching rate is slower than that of the Cu electrode, and the reliability of the electrode is lowered. If the etching rate of the protective film is too slow, the cross section of the protective film/electrode/protective film after the wet etching becomes concave. Further, as the Cu content becomes smaller, the electrical resistance of the protective film increases, and the reliability of the electrode decreases. Further, as the Cu content becomes smaller, the maximum magnetic permeability // increases. Therefore, it is necessary to make the Cu content 15.0 mass% or more. The Cu content is more preferably 25.0 mass% or more, further preferably 30.0 mass% or more. On the other hand, if the Cu content is excessive, the potential difference from the peripheral member becomes large. Moreover, compared with the Cu electrode, the surname rate becomes too fast, and the electrode can be reduced by 100128318 10 201211276. If the etching rate of the protective film is too fast, the cross section of the protective film/electrode/protective film after the wet etching becomes convex. Further, when the Cu content is excessive, the workability is deteriorated due to the precipitation of the intermetallic compound. Therefore, it is necessary to make the Cu content 55.0 mass% or less. The Cu content is more preferably 45.0 mass% or less, further preferably 40.0 mass% or less, and still more preferably 35.0 mass% or less. (2) 0.5 SCrS 10.0 mass%. The potential difference between the NiCu alloy containing a relatively large amount of Cu and the peripheral member (especially the Cu electrode) is large, and the etching rate is faster than that of the Cu electrode. Cr has the effect of reducing the potential difference between the NiCu alloy and the peripheral member, and slowing down the etching rate of the NiCu alloy (near the Cu electrode). Further, Cr has an effect of improving adhesion to a transparent electrode (ITO). In general, the smaller the content of Cr becomes, the larger the potential difference from the peripheral member becomes, and the lower the electrolytic corrosion resistance. Further, if the silver engraving rate becomes too fast as compared with the Cu electrode, the reliability of the electrode is lowered. Further, as the Cr content becomes smaller, the adhesion to the transparent electrode decreases. Therefore, it is necessary to make the content of Cr 0.5 mass% or more. The content of Cr is more preferably 1.0 mass% or more, further preferably 3.0 mass% or more. On the other hand, if the content of Cr becomes excessive, the potential difference from the peripheral member becomes large. Further, if the etching rate becomes too slow as compared with the Cu electrode, the reliability of the electrode is lowered. Therefore, the content of Cr must be 10·0 mass% or less. The content of Cr is better. 100128318 11 201211276 is 7, 〇 mass% or less, and then the light society is 5. 〇 mass ° / 〇 below. Π2. Use] The protective film of the first embodiment of the present invention is used. Material material (4) (4) 〇 electrode electrical specific resistance (specifically, about 2 ' 'so-called "Cu electrode" refers to an electrode containing pure cu or a Cu alloy having the same # Qcm), and the target of the present embodiment may also be J Used for applications other than Cu electrode protection film. As another use, the organic + & ° has an electrode film, a reflective film, and the like.

A Cu electrode protective film is generally formed on both sides of the u electrode. For example, in the case of a liquid crystal panel, a Cu electrode protective film, an electrode, and a Cu electrode protective film are sequentially formed on the surface of the substrate on which the transparent electrode is formed by using a specific composition. Then, the c u-polar protective film / c u electrode / CU electrode protective film is patterned into a specific shape by wet button carving. *In other respects, there is also protection on one side of the Cu electrode depending on the application. For example, a TFT (Thin Film Transistor) is used to exaggerate the surface of a substrate on which a transparent electrode is formed, and a specific composition is used. The Cu electrode protective film and the Cu electrode film are formed in sequence. Then, the CU electrode protective film/Cu electrode is patterned into a specific shape by the thirst. [2. NiCu alloy target for CU electrode protective film (2) : NiCuTi alloy] [2·1 · Component] The present invention is a NiCu alloy target for a Cu electrode protective film of the second embodiment 100128318 12 201211276 The top element, and the feed Μ% impurity. Add the type of element and the amount of addition (l) 15^Cu^55.〇mass〇/〇o (5).

The difference in the Cu content in the NiCu alloy (potential difference...": =::: ring. In addition, the Cu content causes a difference in the magnetic permeability of the NlCu alloy. In general, the Cu content becomes less. The difference becomes larger, and the resistance to electrolytic corrosion is decreased. Also, if the potential between the components becomes slower, the reliability of the electrode decreases. If the (four) Cu electrode is 'too slow', then the wire is inscribed The protective film/electrode (4) rate-like. In addition, the heart content is changed, the county protection shape = the surface becomes concave ^, the electric resistance is increased, and the sex is decreased. In addition, the cu content becomes less, then the second Therefore, the Cu content must be 15 〇% or more. The α content is more preferably 25.0 mass% or more, and further preferably 3 〇〇 mass% or more. ',, change = surface 2, the amount of cr is excessive, and the potential difference from the peripheral member Instead: /, compared with the Cu electrode, the etching rate becomes too fast, and the electrode can be reduced. The right protective film is too fast, and the film is protected after the wet film/electrode/protective film. When the surface becomes convex, the content of m is excessive, and the workability is deteriorated due to the precipitation of the intermetallic compound. Therefore, the CU content must be 55.0 mas. s% or less. The CU content is more preferably 45.0 mass/〇 or less, further preferably 3% or less, and more preferably 100128318 13 201211276 35.0 mass% by ητ. (2) 0.5ι〇〇mass%. The NiCu alloy system containing a large amount of Cu has a large _ potential difference with the peripheral member (especially the electrode), and has a faster _ rate than ^. The Τι has a reduced ratio between the NiCll and the surrounding members. The difference in potential, and slowing down the etching of the NiCu alloy - near the CU electrode. Further, the effect of the adhesion of the transparent electrode (ITO) is less than that of the ITO. Then, the potential between the peripheral member and the peripheral member is increased, and the electrolytic corrosion resistance is lowered, and the etching rate becomes Na, and the reliability of the electrode is lowered. The less the content becomes, the lower the hunting performance of the I 11 and the transparent electrodes. Therefore, the combination of Ti and, the meaning of, must be 0.5 mass% or more. The content of bismuth is better than that of painting, and Dmass%w. — The other part of the <5" face ‘ *τ· 1 is excessive, and the potential difference from the peripheral member is increased. Further, if the address rate is too slow compared to the Lu electrode and the Lu electrode, the reliability of the electrode is lowered. Therefore, the content of 'Tl must be 10.0 mass% or less. The content of Ti is more preferably 7. 〇 11% or less, and further preferably 5 〇 or less. [2.2. Use] The use of the target according to the second embodiment of the present invention is the same as that of the first embodiment, and thus detailed description thereof will be omitted. [3. Cu-electrode protection, NiCu alloy, material (3) · NiCuCrTi alloy] 100128318 201211276 [3.1. Component] The element described in the NiCu alloy target for the Cu electrode protection film of the third embodiment of this month The reasons for limiting the type of Ni and the inevitable ", the type of the element, and the amount of addition are as follows. (l) 15.0g Cu^55. 〇mass〇/〇0 in the amount of gold in the gold electrode or ITO between the ladder, JS difference), or the difference between the etching rate between the Cu electrode The effect of U & star on the magnetic permeability of NlCu alloy. In general, the smaller the θ and 3 are, the larger the potential difference from the peripheral member becomes, and the lower the resistance to electrolytic corrosion is. The etch rate is reduced, the sundial, + 屯仪邪t匕 ^ can be recorded down. If the cross section of the (four)-like etch rate protective film/electrode/protective film becomes a concave electrode, the reliability =: = less: : _ the gas resistance increases, the more "the more the summer becomes less, the maximum permeance Therefore, it is necessary to make the Cu content 15.0 mass% or more. W is more than 〇, and more preferably 3 〇〇% or more. Soil change = surface: excessive u content is the difference between the potential difference of the peripheral member and the reliability. ^Ultra material '_ rate becomes too fast, then the electrode with the protective film (four) rate is too fast, the cross section of the _ type _ after the retention / electrode / Bao _ becomes more remaining, then because of the gold ^ ^ and then, right Cu The content is too high, and the precipitation of the intergeneric compound causes the processability to decrease. 100128318 201211276 Therefore, the 'Cu content must be 55.0 mass% or less. The Cu content is more preferably 45.0 mass% or less and further preferably 40.0 mass% or less, and more preferably 35.0 mass% or less. (2) 0.5S (Cr, Ti) S 10.0 mass〇/〇. Among them, Cr>〇, Ti> As described above, both Cr and Ti have (a) a function of reducing the potential difference between the NiCu alloy and the peripheral member, (b) a function of slowing down the etching rate of the NiCu alloy (near the Cu electrode), and (c) an increase and The role of the adhesion of the transparent electrode (ITO). When such Cr and Ti are simultaneously added to the NiCu alloy, the etching rate and the adhesion are maintained at the same level, and the potential difference from the peripheral member is further reduced. In general, the smaller the content of Cr and/or Τι, the larger the potential difference from the peripheral member, and the lower the electrolytic corrosion resistance. Further, if the etching rate becomes too fast as compared with the CU electrode, the reliability of the electrode is lowered. Therefore, the content of Cr and Ti must be 〇.5 mass% or more in total. The total content of Cr and Ti is more preferably 1.0% or more and further preferably 3.0 mass% or more. On the other hand, if the content of Cr and/or Ti is excessive, the potential difference from the peripheral member becomes large. Further, if the etch rate becomes too slow as compared with the Cu electrode, the reliability of the electrode is lowered. Therefore, the contents of Cr and Ti must be 10.0 mass% or less in total. The total content of Cr and Ti is more preferably 7.0 mass% or less, further preferably 5.0 mass% or less. [3.2. Uses] 100128318 16 201211276 The use of the target according to the third embodiment of the present invention is the same as that of the first embodiment, and therefore detailed description thereof will be omitted. [4. Laminated film] The laminated film of the present invention includes a Cu electrode and a protective film formed on one surface or both surfaces of the Cu electrode, and the protective film includes a NiCu alloy target for using the Cu electrode protective film of the present invention. Film formed film. [4.1.Cu electrode]

The thickness of the Cu electrode is preferably selected to be the most suitable thickness depending on the purpose. In general, s, the thicker the Cu electrode becomes, the more stable the operation. However, if the Cu electrode is too thick, the etching property or the adhesion is lowered, and film cracking is caused. Therefore, the thickness of the Cu electrode is preferably 50 to 500 nm. The thickness of the Cu electrode is more preferably 1 〇〇 to 4 〇〇 nm, and further preferably 15 〇 to 25 〇 nm. Other aspects regarding the Cu electrode are as described above, and thus the description is omitted. [4.2. Protective film] It is preferred to ensure the thickness of the A film to be the most suitable thickness depending on the purpose. In general, the thicker the film is, the more profitable it will be. However, if the protective film is too thick, the ship's engraving or adhesion is degraded. Therefore, the thickness of the protective film is preferably 5 to 1 〇〇 nm. The thickness of the protective film is preferably 5 to 7 Å, and more preferably 5 to 50 nm. 100128318 17 201211276 When a protective film is formed on both surfaces of the Cu electrode, the composition of the protective film on each side may be the same or different. That is, in the case where a protective film is formed on both surfaces of the Cu electrode, a protective film of each surface can be formed using a target of the same composition. Alternatively, a protective film may be formed by using the first target material, and another protective film may be formed by using the second target having a composition different from that of the first target. The film formation method of the protective film is not particularly limited, and various methods can be used depending on the purpose. Specific examples of the film forming method using the protective film of the target include a sputtering method, and other methods such as a nanoimprint method using a nanoparticle or a wet plating method. The other aspects of the protective film and the NiCu alloy target for the Cu electrode protective film are as described above, and thus the description thereof is omitted. [5. Effect of NiCu alloy target and laminated film for Cu electrode protection film]

The potential difference between the Ni-15~55Cu alloy system and the peripheral members (especially the Cu electrode) is large, and the etching rate is faster than that of the Cu electrode. On the other hand, if a specific amount of Cr and/or Ti' is added to the Ni-15 to 55Cu alloy, the surname rate becomes slower (close to the etching rate of the Cu electrode), and at the same time, with a peripheral member such as a Cu electrode or ITO. The potential difference is reduced. Therefore, if it is used as a protective film of a Cu electrode used in a liquid crystal panel, electrolytic corrosion of the Cu electrode or deterioration of electrical characteristics due to atomic diffusion can be suppressed, and high-precision pattern can be performed by wet etching. Chemical. Further, when a specific amount of Cr and/or 100128318 18 201211276 is added to the Ni-15 to 55Cu alloy, the adhesion of the Ni-15 to 55Cu alloy to the transparent electrode is improved. Since the maximum residual conductivity is small, if it is used in a dry material, sputtering can be performed efficiently. [Examples] (Example 1) [1. Preparation of sample material] A Ni-Cu-Cr alloy having a specific composition was produced by a refining and casting method. The Cu content was set to 10 to 60 mass%. The Cr content was set to 0 to 11 maSS%. In addition, Ni-35 mass% Cu-1.5 was produced by dazzle and casting.

maSS%CM.5 mass%Ti alloy dry material. Further, pure Cu and ITO were used as comparisons. [2. Test method] [2.1. Potential difference]

Hanging Ni C _ U, Cr alloy, Ni-Cu-Cr-Ti alloy, Cu, and bismuth

Use the resulting materials. The standard potential system uses a carbon electrode as a counter electrode, and is dissolved in 200 g/L ammonium sulfate maintained at 40 ° C.

Furthermore, the potential difference between the Ni-Cu-Cr alloys and the Ni-Cu-Cr is calculated from the standard potential of the electric grid material.

The potential difference between the Cr_Ti alloy and no. Practical problems. The potential difference is better than the previous one, but the same or a little more is not a problem. Specifically, the potential difference from ITO is 0.35 v 100128318 19 201211276 or less, and the potential difference between Cu and Cu is 1. 〇v or less. [2.2. Etch rate difference] The test piece of each material of the adjusted shape was immersed in a sulphuric acid sulphuric acid 2 〇〇g/L aqueous solution for a specific day of immersion, and the residual rate was calculated from the decrease in thickness. Further, the difference in the rate of money (nm/sec) between & is calculated using the resulting button rate. Furthermore, the difference in the rate of surnames is better than that of the former, but there is no practical problem in the equivalent or large part. Specifically, as long as the difference in the chain rate is I] nm/sec. [2.3. Stripping rate] nm or 150 nm). Then, a film or a Ni-Cu-Cr-Ti alloy is formed on the glass substrate to form an ITO film (thickness: 2 Å on the ITO film to form a Ni-Cu-Cr alloy film (thickness: 50 nm or 200 nm). The film was subjected to a scratch test. The test conditions were in accordance with JIS K56. That is, 'a cross-cut of 1 mm pitch was added to the surface of the film to form a grid of ι. A tape was attached to the surface of the film to peel off the tape. The number n of the grids to be separated is measured (= peeling rate (%)). Further, the peeling rate is preferably 0%, preferably less than 1% (1 digit). [2.4. Maximum Permeance Rate] Using the test piece of the adjusted shape, the maximum magnetic permeability # was measured using a vibrating-samle-magnetometer (VSM, vibrating-samle-magnetometer). The magnetic field Hm at the time of measurement was set to 20 [MOe]. 100128318 20 201211276 When the magnetic permeability is 100 or less, there is no practical problem. [3. Results] [3.1. Potential difference AV] Fig. 1 shows the potential difference / \V between the Ni-Cu-Cr alloy and ITO. The potential difference ΔV (0.16 V) between Μο-lONb and ΙΤΟ used as a protective film for the Α1 wiring material. Fig. 2 shows a Ni-Cu-Cr alloy. The potential difference AV between Cu. The dotted line in Fig. 2 indicates the potential difference ΔV (0.62 V) between Μο-lONb and Al-3Nd previously used as the wiring material of the A1 system. Further, Ni-Cu-Cr-Ti alloy The results are also shown in Fig. 1 and Fig. 2. The following can be seen from Fig. 1. (1) If a combination of Ni-Cu-Cr alloy/Cu/ITO is used as a combination of a protective film/electrode/transparent electrode, Compared with the previous combination (Mo-10Nb/Al-3Nd/ITO), the potential difference AV with respect to ITO is decreased. (2) In order to set the potential difference AV with respect to ITO to a value that has no practical problem (0· 35 V) Hereinafter, it is preferable to set the lower limit of the Cu content to 15 mass% or 20 mass%. Further, it is preferable to set the upper limit of the Cu content to 55 mass% or 50 mass%. The potential difference AV of ITO is equal to or lower than the previous combination, and the lower limit of the Cu content is preferably set to 23.5 mass%, 24 mass% or 25 mass%. Further, it is preferable to set the upper limit of the Cu content to 44 mass%. 40 mass% or 38 mass%. 100128318 21 201211276 (4) In order to set the potential difference with respect to ITO to a value below the practical problem (0.35 V), it is preferable to set the upper limit of the Cr content to 10 ma. Ss%, 8 mass% or 7 mass%. (5) In order to make the potential difference AV with respect to ITO equal to or lower than the previous combination, it is preferable to set the lower limit of the Cr content to 0.2 mass%, 0.5 mass% or 1 mass%. Further, it is preferable to set the upper limit of the Cr content to 6.5 mass%, 6 mass% or 5 mass%. (6) The potential difference AV of the Ni-35Cu-1.5Cr-1.5Ti alloy with respect to ITO is reduced as compared with the potential difference AV of the Ni-35Cu-3Cr alloy. The following can be seen from Fig. 2 . (1) If a combination of Ni-Cu-Cr alloy/Cu/ITO is used as a combination of a protective film/electrode/transparent electrode, it is compared with Cu in comparison with the previous combination (Mo-10Nb/Al-3Nd/ITO). The potential difference ΔV decreases. (2) In order to set the potential difference AV with respect to Cu to a value (1.0 V) or less which is not a practical problem, it is preferable to set the lower limit of the Cu content to 15 mass% or 20 mass% 〇(3) in order to The potential difference AV of Cu is equal to or lower than the previous combination, and it is preferable to set the lower limit of the Cu content to 23 mass%, 24 mass% or 25 mass%. Further, it is preferable to set the upper limit of the Cu content to 45 mass%, 42 mass% or 40 mass%. (4) In order to make the potential difference AV with respect to Cu equal to or lower than the previous combination, it is preferable to set the lower limit of the Cr content to 0.2 mass%, 0.5 mass% or 100128318 22 201211276 1 mass%. Further, it is preferable to set the upper limit of the Cr content to 5.5 mass%, 5 mass% or 4 mass%. (5) The potential difference Αν of Ni-35Cu-1.5Cr-1.5Ti alloy with respect to Cu

The Ni-35Cu-3Cr alloy is roughly equivalent. [3.2. Etching Rate Difference] FIG. 3 shows the difference in the etch rate between the Ni-Cu-Cr alloy and Cu. The dotted line in Fig. 3 indicates the value of 1/2 of the buttoning rate of Cu (〇·6 nm/sec). The smaller the absolute value of the difference between the rate of the surname of each material and the rate R of Cu (two hearts - anti-2), the better the practical etch rate difference does not have to be zero. When the absolute value of the difference between the etching rate of each material and the etching rate of Cu and the etching rate of Cu is less than 1/2 of the etching rate of ampere (ie, the case of |R), The etching obtains a good cross section with relatively few irregularities. Further, the results of the Ni-Cu-Cr-Ti alloy are also shown in Fig. 3. The following can be seen from Fig. 3. (1) If a combination of Ni-Cu-Cr alloy/Cu/ITO is used as a combination of the protective film/electrode/transparent electrode, the difference in etching rate becomes smaller than the previous combination (Mo-l〇Nb/Al-3Nd/ITO) Value (1.2 nm/sec). (2) In order to set the etching rate difference to a value that does not have a practical problem (丨2 nm/sec) or less, it is preferable to set the lower limit of the Cu content to 15 mass% or 2 〇 mass%. Further, it is preferable to set the upper limit of the Cu content to 55 mass%, 50 mass% or 47 mass%. (3) In order to make the etching rate difference equal to or lower than cu/2, it is preferable to set the lower limit of Cu to 100128318 23 201211276 24 to 24 mass%, 24.5 mass% or 25 mass%. Further, it is preferable to set the upper limit of the Cu content to 42 mass%, 40 mass%, or 38 mass% 〇(4) to set the difference in the rice cooking rate to a value that is not practical (1.2 nm/sec) or less. It is preferred to set the upper limit of the Cr content to 1 〇 mass%, 9 mass% or 8 mass%. (5) In order to make the etching rate difference equal to or lower than Cu/2, it is preferable to set the lower limit of the Cr content to 〇 5 mass%, 1 mass% or 2 mass%. Further, it is preferable to set the upper limit of the Cr content to 6 $ mass%, 6 mass% or 5 mass%. (6) The etching rate difference of Ni-Cu-Cr-Ti alloy is slightly higher than that of Ni-Cu-Cr alloy, but it is significantly smaller than that of Ni-Cii alloy. [3.3. Peeling Rate] Figs. 4 to 7 show the peeling ratio of the Ni-Cu-Cr alloy film having a thickness of 50 nm or 200 nm which was raised/formed on the ITO film having a thickness of 2 〇 nm or 150 nm. The results of the 'Ni_Cu-Cr-Ti alloy are also shown in Figures 4 to 7. The following can be seen from Figures 4 to 7. (1) The peeling rate of the Nl'Cu_Cr alloy film is significantly lower than that of the Ni-Cu alloy film, and the peeling rate of the N'-Cu-Cr alloy film is not excessively dependent on the film thickness. The peeling rate of the C2) Nl_Cu-Cr alloy film does not show a good value depending on the Cu content. Especially in the case of Cu content of 15~40 mass ° /. Good results are obtained within the scope. The Cu content is further preferably 23 to 25 maSS〇/o. (3) The peeling resistance is greatly improved by the addition of Ci*. Even if 1 100128318 24 201211276 mass% is added, sufficient effect can be confirmed, and if 3 mass% or more is added, peeling hardly occurs. Especially in the range of 3 to 7 mass%, good results are obtained. (4) When Ti is added to the Ni-Cu-Cr alloy, the peeling rate is slightly increased as compared with the Ni-Cu-Cr alloy, but is significantly reduced as compared with the Ni-Cu alloy. [3.4. Maximum Magnetic Permeability] Fig. 8 shows the maximum magnetic permeability of the Ni-Cu-Cr alloy. Further, the results of the Ni-Cu-Cr-Ti alloy are also shown in Fig. 8. The following can be seen from Fig. 8. (1) In order to set the maximum magnetic permeability / / to 100 or less, the lower limit of the Cu content is set to 15 mass %. It is preferable to further set the lower limit of the Cu content to 20 mass%. Further, it is preferable to set the upper limit of the Cu content to 50 mass%. (2) In order to set the maximum magnetic permeability μ to 20 or less, it is preferable to set the lower limit of the Cu content to 24 mass% or 25 mass%. Further, it is preferable to set the lower limit of the Cu content to 47 mass% or 45 mass%. (3) Even if the Cr content is changed to 0 to 11 mass%, the maximum magnetic permeability // is also slightly changed. (Example 2) [1. Preparation of sample] A Ni-Cu-Ti alloy material having a specific composition was produced by a melting or casting method. The Cu content is set to 10 to 60 mass%. The Ti content was set to 0 to 7 mass%. Also, pure Cu and ITO were used as comparisons. 100128318 25 201211276 [2. Test method] The potential difference ΔV between the Ni-Cu-Ti alloy and Cu and the potential difference ΔV between the Ni-Cu-Ti alloy and ITO were measured in the same order as in Example 1. The etching rate difference, the peeling rate, and the maximum magnetic permeability between the Ni-Cu-Ti alloy and Cu//. [3. Results] [3.1. Potential Difference AV] Fig. 9 shows a potential difference Λν between the Ni-Cu-Ti alloy and ITO. The dotted line in Fig. 9 indicates the potential difference ΔV (0.16 V) between Μο-lONb and ITO which was previously used as a protective film for the Α1 wiring material. Fig. 10 shows a potential difference AV between the Ni-Cu-Ti alloy and Cu. The dotted line in Fig. 10 indicates the potential difference Δν (0.62 V) between Μο-lONb and Al-3Nd which was previously used as the wiring material of the A1 system. Further, the results of the Ni-Cu-Cr-Ti alloy are also shown together in FIGS. 9 and 10. The following can be seen from Fig. 9. (1) If a combination of Ni-Cu-Ti alloy/Cu/ITO is used as a combination of the protective film/electrode/transparent electrode, compared with the previous combination (Mo-10Nb/Al-3Nd/ITO), relative to ITO The potential difference AV is reduced. (2) In order to set the potential difference AV with respect to ΙΤΟ to a value (0.35 V) or less which is not a practical problem, the lower limit of the Cu content may be 15 mass%. It is preferable to further set the lower limit of the Cu content to 20 mass% or 23 mass%. (3) In order to make the potential difference AV with respect to ITO equal to the previous combination, 100128318 26 201211276, it is preferable to set the lower limit of the Cu content to 23.5 mass%, 24 mass% or 25 mass%. Further, it is preferable to set the upper limit of the Cu content to 50 mass%, 45 mass% or 42 mass%. (4) Regardless of the content of the Ti system, the potential difference AV with respect to ITO showed a good value. (5) In order to make the potential difference AV with respect to ITO equal to or lower than the previous combination, it is preferable to set the lower limit of the Ti content to 0.2 mass%, 0.3 mass% or 0.5 mass%. Further, it is preferable to set the upper limit of the Ti content to 5.5 mass%, 5 mass% or 4.5 mass%. (6) The potential difference AV of the Ni-35Cu-1.5Cr-1.5Ti alloy with respect to ITO is reduced as compared with the Ni-35Cu-3Ti alloy. The following can be seen from Fig. 10. (1) If a combination of Ni-Cu-Ti alloy/Cu/ITO is used as a combination of the protective film/electrode/transparent electrode, compared with the previous combination (Mo-10Nb/Al-3Nd/ITO), relative to Cu The potential difference AV is reduced. (2) In order to set the potential difference AV with respect to Cu to a value (1.0 V) or less which is not a practical problem, the lower limit of the Cu content may be 15 mass%. Preferably, the lower limit of the Cu content is further set to 20 mass%. (3) In order to make the AV with respect to the potential difference of Cu equal to or lower than the previous combination, it is preferable to set the lower limit of the Cu content to 23.5 mass% or 24 mass%. Further, it is preferable to set the upper limit of the Cu content to 46 mass%, 45 mass% or 40 mass%. 100128318 27 201211276 (4) Regardless of the content of the Ti system, the potential difference ZXV with respect to Cu shows a good value. (5) In order to make the potential difference Δν with respect to the CU <the same as the previous combination, it is preferable to set the lower limit of the amount of enthalpy to 〇 2 魏%, 〇5邮岭. Or 1 mass%. Further, it is preferable to set the upper limit of the content of Τι to 5 5, '$ mass% or 4.5 mass%. (6) The potential difference of Ni-35Cu-1.5Cr-1.5Ti alloy with respect to Cu

The Ni-35Cu-3Ti alloy is almost equivalent. [3.2. Etch rate difference] Fig. 11 shows the difference in etching rate between the Ni-Cu-Ti alloy and Cu. The broken line in Fig. η indicates the value of 1/2 of the etching rate of Cu (〇6 nm/sec). The results of the Ni-Cu-Cr-Ti alloy are also shown in Fig. 9. The following can be seen from Fig. 11. (1) If a combination of Ni-CU-Ti alloy/Cu/ITO is used as the protective film/electrode/ In the combination of the transparent electrodes, the difference in etching rate becomes smaller than the value of the previous combination (Mo-l〇Nb/Al-3Nd/ITO) (1.2 nm/sec). (2) In order to set the etching rate difference to be practical The value of the above problem (1 2 nm/sec) is less as long as the lower limit of the Cu content is 15 mass%. It is preferable to further set the lower limit of the Cu content to 20 mass%. Further, as long as the upper limit of the Cu content is set to 55 mass% may be sufficient. Further, the upper limit of the Cu content is preferably 50 mass% or 45 mass%. (3) In order to make the etching rate difference equal to or less than Cu/2, it is preferable to have cu 100128318 00 201211276 The lower limit of the amount is set to 24 mass% or more. Further, it is preferable to set the upper limit of the Cu content to 40 mass% or 38 mass%. (4) The Τι system shows a good surname regardless of its content. Rate difference (5) In order to make the etching rate difference equal to or lower than Cu/2, it is preferable that the Ti content · 'lower limit ° is again I.5 mass% or 2 mass%. Further, it is preferable to set the upper limit of the Ti content. Set to 5 mass% or 4.5 mass%. (6) The difference in the rate of the NiCu-Cr-Ti alloy becomes smaller than that of the Ni Cu-Ti alloy. [3.3. Peeling rate] Fig. 15 shows the thickness at 2 〇 nm or 15 〇. The peeling rate of the Ni Cu Ti alloy film having a thickness of 5 〇 nm or fine nm formed on the IT 〇 film of nm. Furthermore, the results of the N"CU core·Ti alloy are also shown in Figs. 12 to 15 . The following will be understood from Figs. 12 to 15 .

The peeling rate of the Tl alloy film depends on the film thickness, and the film thickness of the melon (10) alloy film turns thicker, and the turn turns more and more. (2) The film separation rate of the Ni-CU-Ti alloy film is abundance. In the following, as long as Cu contains denier = 〇1, the lower limit of the CU content may be 15 or less. More than 25 mass%. Also, ^ people 0曰maSS%, 23 mass. /. The upper limit of 24 mass%, 45 mail or 4 〇 / ® is preferably set to 47 (3) The film thickness of the Ni-Cu-Ti alloy film is _ or less, preferably when Τι =0 coffee In order to set the lower limit of the stripping to 1 〇 mass%, 100128318 29 201211276 1.5 mass%, 2 mass% or 3 mass%. (4) When Cr is added to the Ni-Cu-Ti alloy, the peeling rate becomes equal to or less than that of the Ni-Cu-Ti alloy. [3.4. Maximum Magnetic Permeability] Fig. 16 shows the maximum magnetic permeability of the Ni-Cu-Ti alloy. Further, the results of the Ni-Cu-Cr-Ti alloy are also shown in Fig. 16. The following can be seen from Fig. 16. (1) In order to set the maximum magnetic permeability # to 100 or less, it is preferable to set the lower limit of the Cu content to 24 mass%. (2) In order to set the maximum magnetic permeability / / to 20 or less, it is preferable to set the lower limit of the Cu content to 24.5 mass% or 25 mass%. Further, it is preferable to set the lower limit of the Cu content to 47 mass% and 45 mass. /) or 40 mass%. (3) Even if the Ti content is changed to 0 to 11 mass%, the maximum magnetic permeability // is hardly changed. (Example 3) [1. Preparation of sample] A laminate film for a touch panel was produced by using the target material produced in Example 1 or 2. Namely, a barrier layer, an electrode layer, and an overcoat layer (in order from bottom to top) are sequentially formed on the surface of the substrate by sputtering. As the substrate, an ITO/base film/PET (Polyethylene Terephthalate 5 polyethylene terephthalate) substrate or an ITO/base film/glass substrate (all commercially available) was used. Barrier layer and overlying layer 100128318 30 201211276 The layer uses a NiCu alloy containing a specific amount of Cu or Ti, and the electrode layer uses Cu(5 N). As a comparison, an M〇_1〇Nb alloy was used for each of the barrier layer and the overcoat layer, and a laminated film of Al-3Nd was used for the electrode layer. The film formation conditions of the laminated film for a touch panel are shown in Table 1. [Table 1] Material-Output gas sputtering rate Film thickness NiCu alloy DC300 W Ar 0.3 Pa 55 nm/min 20 nm Cu(5 N) RF500 W Ar 0.3 Pa 48 nm/min 200 nm MoNb DC300 W Ar 0.3 Pa 31 Nm/min 20 nm AINd DC300 W Ar 0.3 Pa 60 nm/min 200 nm [2. Test method] [2.1. Adhesion] Under the same conditions as in Example 1, a trace test (according to jis K5600) was performed. Stripping rate. [2.2. Weather resistance] The substrate with the laminated film was kept at 65 ° C and a humidity of 95% for 1000 hours. After the end of the test, it was judged by visual observation whether or not there was discoloration. [2.3. Surname] The substrate with the laminated film was immersed in an ammonium persulfate 2 0 〇 g / L aqueous solution at 40 ° C and the laminated film was dissolved. The time required until the substrate became transparent (to the time when the entire laminated film was dissolved) was measured. [2.4. Electrode portion sheet resistance] The electrode portion sheet resistance was measured by a 4-terminal method. 100128318 31 201211276 [3. Results] The results are shown in Table 2 and Table 3. The following can be seen from Table 2 and Table 3. (1) The sheet resistance of the electrode portion is low regardless of the composition of the barrier layer/electrode layer/overcoat layer. (2) When the amount of Cu in the NiCuCr alloy is fixed, the more the Cr content is, the more the adhesion and the weather resistance are improved, but the etching property is lowered. Further, when the amount of Cr in the NiCuCr alloy is fixed, if the Cu content is excessive, the selectivity is lowered. In other words, when a Ni-25~40Cu-3~5Cr alloy is used for the barrier layer and the overcoat layer, a laminated film for a touch panel excellent in adhesion, weather resistance, and etching property is obtained. (3) When the amount of Cu in the NiCuTi alloy is fixed, the Ti content increases, and the adhesion and weather resistance increase, but the etching property decreases. Further, when the amount of Ti in the NiCuTi alloy is fixed, if the Cu content is excessive, the weather resistance is lowered. In other words, when a Ni-25~40Cu-3~5Ti alloy is used for the barrier layer and the overcoat layer, a laminated film for a touch panel excellent in adhesion, weather resistance, and etching property is obtained. 100128318 32 201211276 [Table 2]

No. Substrate barrier layer electrode layer overlying layer adhesion property #刻性部分部片电阻1 Ni-10Cu Ni-lOCu XX 〇2 Ni-10Cu-lCr Ni-lOCu-lCr XX 〇3 Ni-10Cu -10Cr Ni-lOCu-lOCr 〇〇X 4 Ni-25Cu Ni-25Cu XX 〇5 Ni-25Cu-lCr Ni-25Cu-lCr Δ X 〇6 Ni-25Cu-3Cr Ni-25Cu-3Cr 〇〇〇7 Ni- 25Cu-5Cr Ni-25Cu-5Cr 〇〇〇8 Ni-25Cu-7Cr Ni-25Cu-7Cr 〇〇X 9 Ni-35Cu Ni-35Cu XX 〇10 Ni-35Cu-lCr Ni-35Cu-lCr Δ X 〇11 Ni -35Cu-3Cr Ni-35Cu-3Cr 〇〇〇12 Ni-35Cu-5Cr Ni-35Cu-5Cr 〇〇〇13 Ni-35Cu-7Cr Ni-35Cu-7Cr 〇〇X 14 Ni-40Cu Ni-40Cu XX 〇15 Ni-40Cu-lCr Ni-40Cu-lCr Δ X 〇16 Ni-40Cu-3Cr Ni-40Cu-3Cr 〇〇〇17 Ni-40Cu-5Cr Ni-40Cu-5Cr 〇〇〇18 Ni-40Cu-7Cr Ni-40Cu -7Cr 〇〇X 19 Ni-60Cu Ni-60Cu XX 〇20 ITO/ Ni-60Cu-lCr Cu Ni-60Cu-lCr Δ X 〇21 bottom layer Ni-60Cu-5Cr Ni-60Cu-5Cr 〇X 〇<0.5 Ω /口22 /PET Ni-60Cu-10Cr Ni-60Cu-10Cr 〇〇X 23 Ni-lOCu-lTi Ni-lOCu- lTi XX 〇24 Ni-10Cu-3Ti Ni-10Cu-3Ti 〇〇X 25 Ni-10Cu-7Ti Ni-10Cu-7Ti 〇〇X 26 Ni-25Cu-lTi Ni-25Cu-lTi Δ X 〇27 Ni-25Cu- 3Ti Ni-25Cu-3Ti 〇〇〇28 Ni-25Cu-5Ti Ni-25Cu-5Ti 〇〇〇29 Ni-25Cu-7Ti Ni-25Cu-7Ti 〇〇X 30 Ni-35Cu-lTi Ni-35Cu-lTi Δ X 〇31 Ni-35Cu-3Ti Ni-35Cu-3Ti 〇〇〇32 Ni-35Cu-5Ti Ni-35Cu-5Ti 〇〇〇33 Ni-35Cu-7Ti Ni-35Cu-7Ti 〇〇X 34 Ni-40Cu-lTi Ni -40Cu-lTi Δ X 〇35 Ni-40Cu-3Ti Ni-40Cu-3Ti 〇〇〇36 Ni-40Cu-5Ti Ni-40Cu-5Ti 〇〇〇37 Ni-40Cu-7Ti Ni-40Cu-7Ti 〇〇X 38 Ni-60Cu-lTi Ni-60Cu-lTi XX 〇39 Ni-60Cu-3Ti Ni-60Cu-3Ti 〇X 〇40 Ni-60Cu-7Ti Ni-60Cu-7Ti 〇〇X 41 Mo-lONb Al-3Nd Mo-lONb 〇 XX Adhesion (peeling rate): 〇 = less than 3%, Δ = 3% or more and less than 10%, χ = 10% or more in the presence of: 〇 = no discoloration, x = color etchability ( The time required until the substrate becomes transparent): 〇 = less than 1 minute, more than 30 33128318 201211276 [Table 3]

No. Substrate barrier layer Electrode layer overcoating adhesion Weatherability Scratch electrode sheet resistance 1 Ni-10Cu Ni-lOCu XX 〇2 Ni-10Cu-lCr Ni-lOCu-lCr XX 〇3 Ni-10Cu- 10Cr Ni-lOCu-lOCr 〇〇X 4 Ni-25Cu Ni-25Cu XX 〇5 Ni-25Cu-lCr Ni-25Cu-lCr Δ X 〇6 Ni-25Cu-3Cr Ni-25Cu-3Cr 〇〇〇7 Ni-25Cu -5Cr Ni-25Cu-5Cr 〇〇〇8 Ni-25Cu-7Cr Ni-25Cu-7Cr 〇〇X 9 Ni-35Cu Ni-35Cu XX 〇10 Ni-35Cu-lCr Ni-35Cu-lCr Δ X 〇11 Ni- 35Cu-3Cr Ni-35Cu-3Cr 〇〇〇12 Ni-35Cu-5Cr Ni-35Cu-5Cr 〇〇〇13 Ni-35Cu-7Cr Ni-35Cu-7Cr 〇〇X 14 Ni-40Cu Ni-40Cu XX 〇15 Ni -40Cu-lCr Ni-40Cu-lCr Δ X 〇16 Ni-40Cu-3Cr Ni-40Cu-3Cr 〇〇〇17 Ni-40Cu-5Cr Ni-40Cu-5Cr 〇〇〇18 Ni-40Cu-7Cr Ni-40Cu- 7Cr 〇〇X 19 Ni-60Cu Ni-60Cu XX 〇20 ITO/ Ni-60Cu-lCr Cu Ni-60Cu-lCr Δ X 〇21 bottom layer / Ni-60Cu-5Cr Ni-60Cu-5Cr 〇X 〇<0.5 Ω 〇22 Glass Ni-60Cu-10Cr Ni-60Cu-10Cr 〇〇X 23 Ni-lOCu-lTi Ni-l OCu-lTi XX 〇24 Ni-10Cu-3Ti Ni-10Cu-3Ti 〇〇X 25 Ni-10Cu-7Ti Ni-10Cu-7Ti 〇〇X 26 Ni-25Cu-lTi Ni-25Cu-lTi Δ X 〇27 Ni- 25Cu-3Ti Ni-25Cu-3Ti 〇〇〇28 Ni-25Cu-5Ti Ni-25Cu-5Ti 〇〇〇29 Ni-25Cu-7Ti Ni-25Cu-7Ti 〇〇X 30 Ni-35Cu-lTi Ni-35Cu-lTi Δ X 〇31 Ni-35Cu-3Ti Ni-35Cu-3Ti 〇〇〇32 Ni-35Cu-5Ti Ni-35Cu-5Ti 〇〇〇33 Ni-35Cu-7Ti Ni-35Cu-7Ti 〇〇X 34 Ni-40Cu- lTi Ni-40Cu-lTi Δ X 〇35 Ni-40Cu-3Ti Ni-40Cu-3Ti 〇〇〇36 Ni-40Cu-5Ti Ni-40Cu-5Ti 〇〇〇37 Ni-40Cu-7Ti Ni-40Cu-7Ti 〇〇 X 38 Ni-60Cu-lTi Ni-60Cu-lTi XX 〇39 Ni-60Cu-3Ti Ni-60Cu-3Ti 〇X 〇40 Ni-60Cu-7Ti Ni-60Cu-7Ti 〇〇X 41 Mo-10Nb Al-3Nd Mo -lONb 〇 XX Adhesiveness (peeling rate): 〇 = less than 3%, ^=3% or more and less than 10%, x=10% or more and only wait: 〇 = no discoloration, X = color change etching Sex (the time required until the substrate becomes transparent): 〇 = less than 1 minute, x = 1 minute or more 34 100128318 201211276 (real Example 4) [Production of Sample 1] using the target prepared in Example 1 or 2 to prepare a laminated membrane embodiments of the TFT. That is, the barrier layer and the electrode layer are sequentially formed on the surface of the substrate by sputtering (the order from bottom to top). An ITO/base film/glass substrate (commercial product) was used for the substrate. A NiCu alloy containing a specific amount of Cu or Ti is used in the barrier layer, and Cu(5 N) is used in the electrode layer. For comparison, a film of a film of Mo-50 was used for the barrier layer and Cu was used for the electrode layer. The film formation conditions of the laminated film for TFT are shown in Table 4. [Table 4] Material Output Gas Sputtering Rate Film Thickness NiCu Alloy DC300 W Ar 0.3 Pa 55 nm/min 20 nm Cu(5 N) RF500 W Ar 0.3 Pa 48 nm/min 200 nm MoTi DC300 W Ar 0.3 Pa 28 nm /min 20 nm [2. Test method] [2.1. Adhesiveness, etching property, and electrode sheet resistance] The adhesion, the etching property, and the sheet portion sheet resistance were measured under the same conditions as in Example 3. [2.2 • Barrier property] The substrate with the laminated film was subjected to vacuum heat treatment at 250 ° C > 30 min. After the heat treatment, the diffusion of Cu and Si near the interface was investigated by Oujie analysis. Whether the barrier property is good or not is determined by using the inclination of the Cu and Si detection amounts in the depth direction of the Oujie analysis. Regarding the evaluation of the barrier property, "〇" indicates that the difference between the inclination of the Cu and Si detection amounts in the depth direction before and after the treatment is 3% or less, and "X" indicates that it is more than 3%. [3. Results] The results are shown in Table 5. The following can be seen from Table 5. (1) The electrode portion sheet resistance is low regardless of the composition of the barrier layer/electrode layer. (2) When the amount of Cu in the NiCuCr alloy is fixed, the more the Cr content is, the more the adhesion and the barrier property are improved, but the etching property is lowered. Further, when the amount of Cr in the NiCuCr alloy is fixed, if the Cu content is excessive, the barrier property is lowered. In other words, when a Ni-25~40Cu-3~5Cr alloy is used for the barrier layer, a laminate film for a TFT excellent in adhesion, barrier properties, and etching property is obtained. (3) When the amount of Cu in the NiCuTi alloy is fixed, the Ti content increases, and the adhesion and barrier properties increase, but the etching property decreases. Further, when the amount of Ti in the NiCuTi alloy is fixed, if the Cu content is excessive, the barrier property is lowered. In other words, when a Ni-25~40Cu-3~5Ti alloy is used for the barrier layer, a laminate film for a TFT excellent in adhesion, barrier properties, and etching property is obtained. 100128318 36 201211276 [Table 5]

No. Substrate barrier layer Electrode layer Adhesive etchable electrode portion Sheet resistance 101 ITO / underlayer / glass Ni-10Cu Cu XX 〇 <0.5 Ω〇102 Ni-10Cu-lCr XX 〇103 Ni-10Cu- 10Cr 〇〇X 104 Ni-25Cu XX 〇105 Ni-25Cu-lCr Δ X 〇106 Ni-25Cu-3Cr 〇〇〇107 Ni-25Cu-5Cr 〇〇〇108 Ni-25Cu-7Cr 〇〇X 109 Ni-35Cu XX 〇110 Ni-35Cu-lCr Δ X 〇111 Ni-35Cu-3Cr 〇〇〇112 Ni-35Cu-5Cr 〇〇〇113 Ni-35Cu-7Cr 〇〇X 114 Ni-40Cu XX 〇115 Ni-40Cu-lCr Δ X 〇116 Ni-40Cu-3Cr 〇〇〇117 Ni-40Cu-5Cr 〇〇〇118 Ni-40Cu-7Cr 〇〇X 119 Ni-60Cu XX 〇120 Ni-60Cu-lCr Δ X 〇121 Ni-60Cu- 5Cr 〇X 〇122 Ni-60Cu-10Cr 〇〇X 123 Ni-lOCu-lTi XX 〇124 Ni-10Cu-3Ti 〇〇X 125 Ni-10Cu-7Ti 〇〇X 126 Ni-25Cu-lTi Δ X 〇127 Ni -25Cu-3Ti 〇〇〇128 Ni-25Cu-5Ti 〇〇〇129 Ni-25Cu-7Ti 〇〇X 130 Ni-35Cu-lTi Δ X 〇131 Ni-35Cu-3Ti 〇〇〇132 Ni-35Cu-5Ti 〇 〇〇133 Ni-35Cu-7Ti 〇〇X 134 N i-40Cu-lTi Δ X 〇135 Ni-40Cu-3Ti 〇〇〇136 Ni-40Cu-5Ti 〇〇〇137 Ni-40Cu-7Ti 〇〇X 138 Ni-60Cu-lTi XX 〇139 Ni-60Cu-3Ti 〇 X 〇140 Ni-60Cu-7Ti 〇〇X 141 Ni-50Ti Cu 〇XX Adhesion (peeling rate): 〇 = less than 3%, ^=3% or more and less than 10%, χ = 10% or more Barrier (difference in the inclination of Cu and Si in the depth direction before and after heat treatment): 〇 = 3% or less, χ = more than 3% Etching (time required until the substrate becomes transparent) · 〇 = underfill The present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit and scope of the invention. (Industrial Applicability) The NiCu alloy target for a Cu electrode protective film of the present invention can be used as a touch panel electrode portion, a liquid crystal panel TFT portion, and an organic EL (Electr® Luminescence) panel electrode portion. A sputtering target for forming a protective film on both surfaces of the CU electrode used in the electrode portion of the plasma display panel, the electrode portion of the solar cell panel, and the semiconductor electrode portion. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1(A) is a graph showing the relationship between the Cu content of the Ni-χ mass% Cu-3 mass ° / 〇Cr (x = 10 to 60) alloy and the potential difference with respect to IT0. Fig. 1(B) is a graph showing the relationship between the Cr content of the Ni-35 mass ° / 〇 Cu - x mass % Cr (x = 〇 〜 11) alloy and the potential difference with respect to ITO. Fig. 2(A) is a graph showing the relationship between the Cu content of the Ni-χ mass% Cu-3 mass% Cr (x = 10 to 60) alloy and the potential difference with respect to Cu. Fig. 2(B) is a graph showing the relationship between the Cr content of the Ni-35 mass% Cu-x mass% Cr (x = 〇 11 11) alloy and the potential difference with respect to Cu. Fig. 3(A) is a graph showing the relationship between the Cii content of the Ni-χ mass% Cu-3 mass% Cr (x = 10 to 60) alloy and the etching rate difference. Fig. 3. (B) is a graph showing the relationship between the Cr content of the Ni_35 mass% Cu-x mass% Cr (x = 0 to 11) alloy and the etching rate difference. 100128318 38 201211276 Fig. 4(A) is a graph showing the relationship between the Cu content and the peeling rate (no: 20 nm, NiCuCr: 50 nm) of Ni-χ mass% Cu-3 mass% Cr (x = 10 to 60) alloy. . Fig. 4(B) is a view showing the relationship between the Cr content of the Ni-35 mass% Cu-x mass% Cr (x = 0 to 11) alloy and the peeling rate (ιτ〇 = 20 nm, NiCuCr: 50 nm). Fig. 5(A) is a graph showing the relationship between the Cu content and the peeling ratio (IT〇 = 20 nm, NiCuCr: 200 nm) of the Ni-xmass%Cu-3mass%Cr (x = 10 to 60) alloy. Fig. 5(B) is a graph showing the relationship between the Cr content and the peeling ratio (ΓΓΟ: 20 nm, NiCuCr: 200 nm) of the Ni-35 mass% Cu-xmass% Cr (x = 0 to 11) alloy. Fig. 6(A) is a graph showing the relationship between the Cu content of the Ni-χ mass% Cu-3 mass% Cr (x = 10 to 60) alloy and the peeling rate (ITO: 150 nm, NiCuCr: 50 nm). Fig. 6(B) is a graph showing the relationship between the Cr content of the Ni-35 mass% Cu-x mass% Cr (x = 0 to 11) alloy and the peeling rate (ΙΤ〇 = 150 nm, NiCuCr: 50 nm). Fig. 7(A) shows the relationship between the Cu content of the Ni-xmass%Cu-3 mass%Cr (x=10~60) alloy and the separation ratio (ΙΤ〇: 15〇面, NiCuCr: 2〇〇nm) Figure 7(B) is a graph showing the relationship between the Cr content and the peeling rate (IT〇: 15〇mn, NiCuCr: 200 nm) of Ni-35 mass%Cu-x mass%Cr(x = 0~11) alloy. . Fig. 8(A) is a graph showing the relationship between the Cu content of the Ni-xmass%Cu-3 mass%Cr (x = 10 to 60) alloy and the maximum magnetic permeability β. Fig. 8(B) is a graph showing the relationship between the Cr content of the alloy of Ni_35 100128318 39 201211276 mass% Cu-x mass% Cr (x = 0 to 11) and the maximum magnetic permeability. Fig. 9(A) is a graph showing the relationship between the Cu content of the Ni-x mass% Cu-3 mass% Ti (X = 10 to 60) alloy and the potential difference AV with respect to ITO. Fig. 9(B) is a graph showing the relationship between the Ti content of the Ni-35 mass% Cu-x mass% Ti (x = 0 to 7) alloy and the potential difference Δν with respect to ITO. Fig. 10(A) is a graph showing the relationship between the Cu content of the Ni-x mass% Cu-3 mass% Ti (x = 10 to 60) alloy and the potential difference AV with respect to Cu. Fig. 10(B) is a graph showing the relationship between the Ti content of the Ni-35 mass% Cu-x mass% Ti (x = 0 to 7) alloy and the potential difference Λν with respect to Cu. Fig. 11(A) is a graph showing the relationship between the Cu content of the Ni-x mass% Cu-3 mass% Ti (x = 10 to 60) alloy and the etching rate difference. Figure ιι (Β) is a graph showing the relationship between the Ti content of the Ni-35 mass% Cu-x mass% Ti (x = 0 to 7) alloy and the etching rate difference. Fig. 12(A) is a graph showing the relationship between the Cu content of the Ni-x mass% Cu-3 mass% Ti (x = 10 to 60) alloy and the peeling rate (ΙΊΌ: 20 nm, NiCuTi: 50 nm). Fig. 12(B) is a view showing the relationship between the Ti content of the Ni-35 mass% Cu-x mass% Ti (x = 〇 〜 7) alloy and the peeling rate (ΙΊΌ: 20 nm, NiCuTi: 50 nm). Fig. 13(A) is a graph showing the relationship between the Cu content of Ni-χ mass% Cu-3 mass% Ti (x = 10 to 60) alloy and the peeling rate (IT〇: 20 nm, NiCuTi: 200 nm). Fig. 13(B) is a view showing the relationship between the content of the Ni-35 mass% Cu-xmass% Ti (x = 0 to 100128318 40 201211276 7) alloy and the peeling rate (IT〇: 2〇_, NiCuTi: 200 nm). . Fig. 14(A) is a view showing the relationship between the Cu content of the massXCu-S mass% Ti (x = 10 to 60) alloy and the peeling rate (ITO: 150 nm, NiCuTi = 50 nm). Fig. 14(B) shows Ni -35 mass% Cu-x mass% Ti (x = 0 to 7) A graph of the relationship between the content of the alloy and the peeling rate (IT〇: 15〇, NiCuTi: 50 nm). Fig. 15(A) is a graph showing the relationship between the Cu content of Ni-χ mass% Cu-3 mass% Ti (x = 10 to 60) alloy and the peeling rate (IT〇: i5〇nm, NiCuTi: 200 nm). Fig. 15(B) is a graph showing the relationship between the Ti content and the peeling ratio (no: 150 nm, NiCuTi: 200 nm) of the Ni-35 mass% Cu-xmass% Ti (x = 0 to 7) alloy. Fig. 16(A) is a graph showing the relationship between the Cu content of the Ni-x mass% Cu-3 mass% Ti (x = 10 to 60) alloy and the maximum magnetic permeability. Fig. 16(B) is a graph showing the relationship between the Ti content of the Ni-35 mass% Cu-x mass% Ti (x = 0 to 7) alloy and the maximum magnetic permeability #. 100128318 41

Claims (1)

201211276 VII. Patent application scope: 1. A NiCu alloy target for Cu electrode protection film, which comprises: 15.0$Cu$55.0 mass%, and 0.5S(Cr, Ti)S 10.0 mass% (wherein, Cr>0, Ti&gt ; 0), and the remainder contains Ni and unavoidable impurities. 2. For the NiCu alloy light material for the Cu electrode protection film according to the first application of the patent scope, wherein, 25.040.0 mass%, and 1.0S (Cr, Ti) S5.0 mass% (wherein Cr>0, Ti> 0). 3. A NiCu alloy target for a Cu electrode protective film comprising: 15.0SCu$55.0 mass%, and 0.5$Cr$10.0 mass%, and the remainder comprising Ni and unavoidable impurities. 4. For NiCu alloy leather for Cu electrode protection film according to item 3 of the patent application, 25.040.0 mass%, and 1.0$ CrS 5.0 mass%. 5. A NiCu alloy target for a Cu electrode protective film comprising: 15.0$ Cu S 55.0 mass%, and 〇.5$Ti$ 10.0 mass%, and the remainder comprising Ni and unavoidable impurities. 6. For the Cu electrode protective film of claim 5, the NiCu alloy 100128318 42 201211276 dry material, wherein, 25.0 40.0 mass%, and 1.0 STi$5.0 mass%. 7. A laminated film comprising: a Cu electrode; and a protective film formed on one surface or both surfaces of the Cu electrode, wherein the protective film comprises any one of claims 1 to 6 of the patent application scope. A film formed by forming a Cu-electrode protective film with a NiCu alloy target. 100128318 43