JP2016079433A - Sputtering target material, method of manufacturing the sputtering target material, and wiring laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method by which a crack and the like do not occur during rolling treatment in a manufacturing process of a sputtering target material.SOLUTION: A method of manufacturing a sputtering target material includes a casting process of casting an ingot composed of nickel, zinc, and remnants composed of copper and inevitable impurities by using molten metal of a copper alloy generated by dissolving nickel, zinc, and copper in a crucible. In the casting process, casting is performed in an atmosphere in which an oxygen concentration is reduced to achieve a content of 0.1 mass% or less of carbon that is one of the inevitable impurities included in the ingot without coating a surface of the molten metal with a coating material including carbon.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a sputtering target material, a method for producing a sputtering target material, and a wiring laminate.

  In recent years, for example, thin film transistors (TFTs) have been used as drive circuits for organic EL, touch panels, and the like. The TFT, for example, is provided on a substrate provided with a semiconductor layer, a substrate (semiconductor layer), a protective layer for protecting a main conductive layer described later, a protective layer, and a copper wiring (wiring pattern). And a main conductive layer to be formed (see, for example, Patent Documents 1 and 2). The protective layer is formed of, for example, a sputtered film formed using a sputtering target material formed of a copper alloy material having copper (Cu) as a base material.

Japanese Patent Application Laid-Open No. 2013-133489 JP 2012-193444 A

  However, the copper alloy material may have high hardness and low rolling workability. For example, when forming a sputtering target material by rolling a copper alloy material, a crack or the like may occur in the material to be rolled. Thereby, productivity of a sputtering target material may fall.

  An object of the present invention is to solve the above problems and provide a technique for improving the productivity of a sputtering target material.

  According to one embodiment of the present invention, the sputtering target material includes nickel and zinc, and the balance is made of copper and inevitable impurities, and the content of carbon that is one of the inevitable impurities is 0.00. A sputtering target material that is 1 mass% or less is provided.

  According to another aspect of the present invention, using a molten copper alloy formed by melting nickel, zinc, and copper in a crucible, nickel and zinc are included, and the balance is made up of copper and inevitable impurities. A crucible capable of reducing the carbon content to be contained in the ingot to 0.1% by mass or less is used as the crucible in the casting step. A method for producing a sputtering target material is provided.

  According to still another aspect of the present invention, a substrate, a main conductive layer provided on any main surface of the substrate, formed of copper, and provided on any main surface of the main conductive layer are provided. The protective layer includes nickel and zinc, the balance is made of copper and inevitable impurities, and the content of carbon that is one of the inevitable impurities is 0.1 mass%. The wiring laminated body currently formed using the sputtering target material which is the following is provided.

  According to the present invention, the productivity of the sputtering target material can be improved.

It is a schematic sectional drawing of the wiring laminated body formed using the sputtering target material concerning one Embodiment of this invention. It is a graph which shows the relationship between carbon content of the copper alloy material concerning one Example of this invention, and hardness. It is a graph which shows the measurement result of the tension test done about each of the copper alloy material formed using the alumina crucible concerning one example of the present invention, and the copper alloy material formed using the carbon crucible.

(Knowledge obtained by the inventors)
Prior to the description of the embodiments of the present invention, the knowledge obtained by the present inventors will be described. As a sputtering target material, for example, a sputtering target formed by subjecting a copper alloy material such as an ingot containing a predetermined amount of Ni and a predetermined amount of Zn and the balance of Cu and inevitable impurities to rolling, etc. Materials have been proposed. The ingot is cast using, for example, a molten copper alloy produced using a high-frequency melting furnace. The high-frequency melting furnace is configured to generate a copper alloy melt by heating and melting the raw material charged in the crucible due to eddy current loss of the crucible provided in the high-frequency melting furnace. Therefore, in the high-frequency melting furnace, a crucible formed of a material having high conductivity is used in order to improve the heating efficiency of the raw material in the crucible. For example, a crucible formed using carbon is used. For this reason, when producing | generating a molten metal, the formation material of crucibles, such as carbon, may melt | dissolve in a molten metal because a molten metal (raw material) and a crucible contact. Thereby, content of carbon (C) inevitably mixed in the molten metal increases, and as a result, the content of C in the copper alloy material may increase. As a result of intensive studies by the present inventors, it has been found that as the C content in the copper alloy material increases, the hardness of the copper alloy material increases and the productivity of the sputtering target material decreases. The present invention is based on the above findings found by the present inventors.

<One Embodiment of the Present Invention>
(1) Configuration of Wiring Laminate First, regarding the configuration of the wiring stack according to an embodiment of the present invention, a wiring stack used as a wiring material of a semiconductor device such as a thin film transistor (TFT) is taken as an example. This will be described with reference to FIG.

  As shown in FIG. 1, the wiring laminated body 10 which concerns on this embodiment is equipped with the board | substrate 1 provided with a semiconductor layer, and the main conductive layer 2 provided on the board | substrate 1 (semiconductor layer). As the substrate 1, for example, a glass substrate, a silicon (Si) substrate, or the like is used. The semiconductor layer is formed of an oxide semiconductor made of oxide (IGZO) of indium (In), gallium (Ga), and zinc (Zn), for example. The main conductive layer 2 is made of, for example, copper (Cu) (pure Cu film). The main conductive layer 2 functions as a wiring film that becomes a copper wiring (wiring pattern) by removing a predetermined portion.

  Between the substrate 1 (semiconductor layer) and the main conductive layer 2, a first protective layer (base layer) 4A is provided. A second protective layer (cap layer) 4B is provided on the surface of the main conductive layer 2 opposite to the surface in contact with the first protective layer 4A. The first and second protective layers 4A and 4B each function as a protective film (electrode protective film) that protects the main conductive layer 2. For example, the first and second protective layers 4A and 4B are formed so as to suppress the main conductive layer 2 from being oxidized or corroded, respectively. That is, each of the first and second protective layers 4A and 4B is formed to function as a barrier layer (block layer) that suppresses the main conductive layer 2 from coming into contact with oxygen. Each of the first and second protective layers 4A and 4B includes a predetermined amount of nickel (Ni) and a predetermined amount of zinc (Zn), and the remainder is formed of Cu and inevitable impurities. For example, the first and second protective layers 4A and 4B are formed by sputtering (for example, magnetron sputtering) using a sputtering target material, which will be described later, containing a predetermined amount of Ni and a predetermined amount of Zn, respectively.

  In the wiring laminated body 10, predetermined portions of the main conductive layer 2 and the first and second protective layers 4A and 4B are removed by, for example, wet etching to form a copper wiring.

The wiring laminate 10 is provided with an insulating film 3 so as to cover the copper wiring formed by removing predetermined portions of the main conductive layer 2 and the first and second protective layers 4A and 4B. . The insulating film 3 is formed of an oxide film such as a silicon oxide (SiO ₂ ) film.

(2) Configuration of Sputtering Target Material The sputtering target material (hereinafter also simply referred to as “target material”) used for forming the first and second protective layers 4A, 4B and the like described above will be described below. .

  The target material is made of a copper alloy material (for example, an ingot, hereinafter also simply referred to as “copper alloy material”) containing Ni and Zn, with the balance being Cu and inevitable impurities. As a base material of the copper alloy material, for example, oxygen free copper (OFC) having a purity of 99.9% or more may be used.

  The content of carbon (C), which is one of inevitable impurities contained in the target material, may be, for example, 0.1 mass% or less. If the C content exceeds 0.1 mass%, the productivity of the target material may be reduced. Specifically, the hardness of the copper alloy material may increase. For example, the Vickers hardness (Hv) of the copper alloy material may exceed 200. Therefore, the workability (rolling workability) of the copper alloy material may be reduced. For example, when forming a target material by subjecting a copper alloy material to a rolling process such as cold rolling, a crack or the like may occur in the material to be rolled. By setting the C content to 0.1 mass% or less, the hardness of the copper alloy material can be lowered, and the productivity of the target material can be improved.

  The lower the content of C in the target material (the lower the concentration of C), the more the productivity of the target material can be improved. Accordingly, the C content in the target material is preferably 0 mass%, for example. However, as will be described later, even when the copper alloy material is formed (produced) so as not to contain C, the material (raw material) of the copper alloy material and the surrounding environment (for example, when forming the copper alloy material) C may inevitably be mixed into the target material (copper alloy material) from a crucible or the like. For example, 0.001 mass% C may be contained in the target material.

  By including both Ni and Zn in the target material, a sputtered film formed using the target material without increasing the respective contents of Ni and Zn due to the synergistic effect of Ni and Zn (for example, The performance of the first and second protective layers 4A and 4B, hereinafter simply referred to as “sputtered films”) can be improved. For example, the performance of protecting the main conductive layer 2 of the first and second protective layers 4A and 4B described above can be improved. That is, even if the total content of Ni and Zn in the target material is less than the content of Ni (or Zn) when only Ni (or only Zn) is contained, only Ni is contained in the target material. The protective performance of the first and second protective layers 4A and 4B can be improved as compared with the case where (or only Zn) is contained.

  The content (concentration) of Ni in the target material is, for example, 30 mass% or more and 45 mass% or less, preferably 35 mass% or more and 40 mass% or less.

  If the Ni content is less than 30 mass%, the desired performance of the sputtered film may not be obtained. For example, the desired protection performance of the first and second protective layers 4A and 4B cannot be obtained, and the main conductive layer 2 may be oxidized even if the first and second protective layers 4A and 4B are provided. is there. The desired sputtered film performance can be obtained by setting the Ni content to 30 mass% or more. By setting the Ni content to 35 mass% or more, the performance of the sputtered film can be further improved.

  However, if the Ni content exceeds 45 mass%, the etching rate of the sputtered film may be significantly reduced. For this reason, for example, depending on the etching solution used when wet etching is performed on the sputtered film, the remaining etching of the sputtered film after the wet etching may not be suppressed. Further, since the content of magnetic Ni is increased, the magnetic permeability of the target material is significantly reduced, and the sputtering rate may be significantly reduced. By setting the Ni content to 45 mass% or less, it is possible to suppress a decrease in the etching rate of the sputtered film while maintaining the desired performance of the sputtered film. Moreover, the fall of the magnetic permeability of a target material can be suppressed. By making the Ni content 40 mass% or less, it is possible to further suppress the decrease in the etching rate while maintaining the desired performance of the sputtered film. Moreover, the fall of the magnetic permeability of a target material can be suppressed more.

  The Zn content (concentration) in the target material is, for example, preferably 10% by mass or more, more preferably 30% by mass or less, and further preferably 20% by mass to 25% by mass.

  If the Zn content is less than 10 mass%, the desired performance of the sputtered film may not be obtained unless the Ni content is increased. By making the Zn content 10 mass% or more, the desired performance of the sputtered film can be obtained without increasing the Ni content. By setting the Zn content to 20 mass% or more, the performance of the sputtered film can be further improved.

However, when the Zn content exceeds 30 mass%, the amount of intermetallic compounds (for example, CuZn (β ′ phase) and Cu ₅ Zn ₈ (γ phase)) generated in the copper alloy material forming the target material is increased. It may increase. Such an intermetallic compound is oxidized and embrittled when heated, for example, during rolling. Therefore, the workability (rolling workability) of the copper alloy material when forming the target material may be reduced. For example, the ductility of the copper alloy material is reduced, and cracks may occur in the material to be rolled during rolling. As a result, the productivity of the target material may decrease. By making the Zn content 30 mass% or less, it is possible to suppress a decrease in the productivity of the target material while maintaining the desired performance of the sputtered film. By making the Zn content 25 mass% or less, it is possible to further suppress a decrease in the productivity of the target material while maintaining the desired performance of the sputtered film.

  The target material has Ni and Zn contents within the above-mentioned predetermined ranges, respectively, and the total of the Ni content and the Zn content (total content of Ni and Zn) is, for example, 55 mass% or more and 65 mass%. Hereinafter, it is preferably 57 mass% or more and 62 mass% or less.

  If the total content of Ni and Zn is less than 55 mass%, the desired performance of the sputtered film may not be obtained. The desired performance of the sputtered film can be obtained by setting the total content of Ni and Zn to 55 mass% or more. By making the total content of Ni and Zn 57 mass% or more, the performance of the sputtered film can be further improved.

  However, when the total content of Ni and Zn exceeds 65 mass%, the etching rate of the sputtered film may be significantly reduced. By making the total content of Ni and Zn 65 mass% or less, a decrease in the etching rate of the sputtered film can be suppressed while maintaining the desired performance of the sputtered film. By making the total content of Ni and Zn 62% by mass or more, a decrease in the etching rate of the sputtered film can be further suppressed while maintaining the desired performance of the sputtered film.

  The target material may further include a metal whose standard electrode potential is lower than that of Zn (hereinafter also simply referred to as “base metal”). The standard electrode potential is a reduction potential in a standard state of a metal that is not oxidized and is in an ideal metal state.

  The content (concentration) of the base metal is, for example, preferably 0.05% by mass or more, and more preferably 5% by mass or less. When multiple types of metals are used as the base metal, the base metal content is the total content of the base metal.

  If the content of the base metal is less than 0.05 mass%, the effect of improving the etching rate of the sputtered film due to the inclusion of the base metal cannot be sufficiently obtained, and the etching residue of the sputtered film after the wet etching is not obtained. It may not be possible to suppress. For example, depending on the etching solution used when performing wet etching, the etching residue of the sputtered film after wet etching may not be suppressed. By setting the base metal content to 0.05 mass% or more, the etching rate of the sputtered film can be increased, and the etching residue of the sputtered film can be suppressed.

  If the base metal content exceeds 5 mass%, the amount of intermetallic compounds produced in the copper alloy material may increase. For example, in a copper alloy material, the amount of an intermetallic compound produced by a reaction between a base metal and Cu, Ni, or Zn may increase. If the amount of such an intermetallic compound increases, the hardness of the copper alloy material may increase, and the productivity of the target material may decrease. In addition, the etching rate of the sputtered film may become too high. For this reason, depending on the etching solution used, overetching may occur in the sputtered film (for example, the first and second protective layers 4A and 4B). By making the content of the base metal 5 mass% or less, it is possible to suppress a decrease in the productivity of the target material and to suppress the occurrence of overetching of the sputtered film.

  As the base metal, a paramagnetic metal may be used. Thereby, it can suppress that the magnetic permeability of a target material falls. That is, a decrease in the sputtering rate of the target material can be further suppressed.

  As the base metal, for example, at least one of manganese (Mn), zirconium (Zr), titanium (Ti), aluminum (Al), magnesium (Mg), and calcium (Ca) may be used. Among these base metals, it is better to use a metal that is easily etched by itself.

  Any base metal such as Mn can be easily combined with Cu, Ni, and Zn metal atoms in the copper alloy material, so that the amount of oxide generated in the target material can be reduced. For this reason, the amount of oxide mixed in the sputtered film can be reduced. That is, the oxygen concentration in the sputtered film can be reduced. Accordingly, it is possible to further suppress a decrease in the etching rate of the sputtered film. Moreover, the performance of the sputtered film can be further improved. For example, when the above-described first and second protective layers 4A and 4B are formed using the target material, the first and second protective layers 4A and 4B can be reduced by reducing the oxygen concentration in the first and second protective layers 4A and 4B. The amount of oxygen entering the main conductive layer 2 from the second protective layers 4A and 4B can be reduced. Thereby, it can suppress that the main conductive layer 2 is oxidized.

  Further, any base metal such as Mn is easily bonded to oxygen in the sputtered film. For this reason, when oxygen is mixed in the sputtered film, a base metal such as Mn traps (traps) oxygen in the sputtered film, and the base metal and oxygen are combined in the sputtered film. Therefore, the performance of the sputtered film can be further improved by including a base metal such as Mn in the target material. For example, even if oxygen is mixed into the first and second protective layers 4A and 4B formed using the target material, the oxygen in the first and second protective layers 4A and 4B Can be prevented from entering the main conductive layer 2. Thereby, it can suppress more that the main conductive layer 2 is oxidized.

(3) Manufacturing method of sputtering target material Next, the manufacturing method of the sputtering target material concerning this embodiment is illustrated and illustrated by melt | dissolution casting method.

(Casting process)
First, an oxygen-free copper having a purity of, for example, 99.9% or more as a base material is heated and melted in a crucible in an atmosphere with a reduced oxygen concentration using, for example, a high-frequency melting furnace, to obtain a molten copper Is generated. Subsequently, a predetermined amount of Ni and a predetermined amount of Zn are added to and mixed in the molten copper (inside the crucible) to produce a molten copper alloy. At this time, the Ni content is, for example, 30 mass% or more and 45 mass% or less, the Zn content is, for example, 10 mass% or more, preferably 30 mass% or less, and the total content of Ni and Zn is, for example, 55 mass% or more and 65 mass%. The addition amounts of Ni and Zn are preferably adjusted so as to be as follows. Moreover, when producing | generating the molten metal of a copper alloy, you may add and mix a predetermined amount of base metals in a molten metal. At this time, the addition amount of the base metal may be adjusted so that the content of the base metal is, for example, 0.05 mass% or more, preferably 5 mass% or less.

  In the casting process, the casting process is carried out in a state where the surface of the molten metal (copper melt, copper alloy melt) is exposed to the atmosphere in an atmosphere with a reduced oxygen concentration (for example, an oxygen-free atmosphere). It is not necessary to cover the surface of the molten metal with a coating material (antioxidant) containing C so as to suppress the oxidation of the molten metal. For example, it is not necessary to float an antioxidant such as carbon powder (carbon flakes) on the surface of the molten metal. Thereby, content of C mixed in the copper alloy material (for example, below-mentioned ingot) which forms a target material can be reduced more.

Moreover, it is good to use the crucible formed with the material which can reduce the quantity of C derived from the crucible which will be contained in an ingot as a crucible. Specifically, it is preferable to use a crucible formed of a material capable of reducing the C content in the ingot to, for example, 0.1 mass% or less. For example, a crucible formed of ceramic (ceramic crucible) may be used. Specifically, a crucible formed of any one of alumina (Al ₂ O ₃ ), magnesia (MgO), and zirconia (ZrO ₂ ), or an inner wall of a carbon crucible is made of Al ₂ O ₃ , MgO, ZrO _2. It is good to use what was coated by either of these. Thereby, it can suppress that C melt | dissolves in a molten metal from a crucible because a crucible and molten metal (molten copper, molten copper alloy) contact. That is, the content of C in the molten metal can be reduced. For example, the C content in the molten metal can be made 0.1 mass% or less.

  Subsequently, the produced molten copper alloy is poured into a mold (taken out) and cooled to cast a copper alloy ingot having a predetermined shape. For example, it contains a predetermined amount of Ni and a predetermined amount of Zn, further includes a predetermined amount of base metal, the balance is made of Cu and inevitable impurities, and the content of C which is one of the inevitable impurities is The ingot which is 0.1 mass% or less is cast.

(Hot processing process)
After the casting process is completed, hot forging is performed on the ingot heated to a predetermined temperature (for example, 700 ° C. or higher), and the forged material is formed by changing the cast structure in the ingot to a fine structure.

(Annealing process)
After hot forging is completed, the forging material is annealed. Specifically, the forging material is heated for a predetermined time (for example, 1 hour) under a predetermined temperature (for example, 850 ° C.) in an inert gas (for example, nitrogen (N ₂ ) gas, rare gas) atmosphere.

(Cold rolling process)
After the annealing process is completed, the forging is subjected to a cold rolling process. Specifically, rolling is performed in a plurality of times to form a cold rolled material (that is, a target material) having a predetermined thickness (for example, 8 mm).

(Cutting process)
After the cold rolling process is completed, for example, using an NC mill, the cold rolled material (target material) is cooled so as to have a predetermined shape (for example, a disk shape having a thickness of 5 mm and a diameter of 100 mm). Cutting the hot rolled material. Thereby, the sputtering target material which concerns on this embodiment is formed.

(4) Effects According to the Present Embodiment According to the present embodiment, one or more effects described below are exhibited.

(A) According to the present embodiment, the target material contains a predetermined amount of Ni and a predetermined amount of Zn, the remainder is made of Cu and inevitable impurities, and contains C which is one of the inevitable impurities. The amount is reduced. For example, the C content in the target material is 0.1 mass% or less. Thereby, the productivity of the target material can be improved.

  Specifically, by reducing the content of C in the copper alloy material, curing of the copper alloy material can be suppressed, and the hardness of the copper alloy material can be lowered. Thereby, the workability (rolling workability) of the copper alloy material can be improved. For example, when forming a target material by performing a rolling process such as cold rolling on a copper alloy material, it is possible to suppress the occurrence of cracks in the material to be rolled. Therefore, the defective product rate of the target material can be reduced, and the mass productivity of the target material can be improved.

  For example, in FIG. 2, inevitable impurities of a copper alloy material (Cu-35 mass% Ni-20 mass% Zn ingot) containing 35 mass% Ni and 20 mass% Zn with the balance being Cu and inevitable impurities. The graph figure showing the relationship between content of C which is one of these, and the hardness of a copper alloy material is shown. From FIG. 2, it was confirmed that the hardness (Vickers hardness (Hv)) of the copper alloy material decreases as the content of C in the copper alloy material decreases. For example, in the case of a copper alloy material of Cu-35 mass% Ni-20 mass% Zn, it was confirmed that the Vickers hardness (Hv) is about 109 when the content of C in the copper alloy material is 0.001 mass%. . On the other hand, when the content of C in the copper alloy material exceeds 0.1 mass%, it was confirmed that the Vickers hardness (Hv) was 208 and exceeded 200. In FIG. 2, the content of C in the copper alloy material was changed by adjusting the melting temperature when generating the molten metal forming the copper alloy material, the holding time of the molten metal in the crucible, and the like. Further, the Vickers hardness of the copper alloy material was measured at room temperature.

(B) By making content of C in a copper alloy material 0.1 mass% or less, even if it cold-rolls with respect to a copper alloy material, a to-be-rolled material becomes difficult to work harden | cure. Therefore, the target material can be formed by performing a predetermined number of cold rolling operations after annealing the ingot. For example, in the cold rolling process, there is no need to repeatedly perform cold rolling and annealing treatment a predetermined number of times. As a result, the productivity of the target material can be further improved. For example, the mass productivity of the target material can be further improved. Moreover, the manufacturing cost of the target material can be reduced.

(C) By using a crucible (for example, a crucible formed of alumina, hereinafter also referred to as “alumina crucible”) formed of a material that can reduce C contained in the ingot in the casting process, The amount of C derived from the crucible mixed in the lump can be reduced. Therefore, the C content in the target material can be made 0.1 mass% or less, for example. As a result, the effects (a) and (b) can be further obtained.

  For example, a tensile test (based on JIS G 0567) was performed on each of a copper alloy material formed using an alumina crucible and a copper alloy material formed using a carbon crucible.

Specifically, a tensile test was performed when the tensile test pieces cut out from each copper alloy material were at a predetermined temperature, and the elongation (%) of the tensile test pieces was measured. Tensile test pieces were cut out from an ingot formed using an alumina crucible and an ingot formed using a carbon crucible, respectively. In the tensile test, the tensile test piece is heated so that the tensile test piece reaches a predetermined temperature (for example, 900 ° C.), and then the tensile test piece is maintained at the predetermined temperature until the tensile test piece breaks. I pulled a piece. The tensile test was performed in a nitrogen atmosphere in order to prevent oxidation of the tensile test piece. The elongation (%) was calculated from the following (Equation 1), where L ₀ was the distance between the gauge points of the tensile test piece before the tensile test and L was the butt length of the broken tensile test piece. The butt length is the length when the broken portions of the broken tensile test pieces are joined together. The distance between the gauge points was measured at room temperature before heating the tensile test piece and before pulling the tensile test piece (before applying the test force). The butt length of the fractured tensile test piece was measured at room temperature.
(Formula 1)
Elongation (%) = {(L−L ₀ ) / L ₀ } × 100

  FIG. 3 shows the results of elongation (%) calculated by conducting a tensile test when each copper alloy material (tensile test piece) is 900 ° C. From FIG. 3, it was confirmed that the copper alloy material formed using the alumina crucible had higher elongation (%) than the copper alloy material formed using the carbon crucible. That is, it was confirmed that the copper alloy material formed using the alumina crucible has a lower hardness than the copper alloy material formed using the carbon crucible. This is considered because the content of C contained in the copper alloy material is reduced in the copper alloy material formed using the alumina crucible.

(D) By performing a casting process in the atmosphere which reduced oxygen concentration, it becomes unnecessary to cover the surface of a molten metal with the coating | coated material which suppresses the oxidation of a molten metal. Thereby, the content of C in the copper alloy material can be further reduced, and as a result, the content of C in the target material can be reduced. That is, the C content in the target material can be easily reduced to 0.1 mass% or less. Therefore, the effects (a) and (b) can be obtained more easily.

(E) By including a predetermined amount of Ni and a predetermined amount of Zn in the target material, due to the synergistic effect of Ni and Zn, the respective contents of Ni and Zn are not increased (that is, Ni and Zn) Even if the total content is reduced), the performance of the sputtered film formed using the target material can be further improved. For example, when the above-described first and second protective layers 4A and 4B are formed using a target material, the performance of protecting the main conductive layer 2 of the first and second protective layers 4A and 4B is further improved. be able to. Specifically, the first and second protective layers 4A and 4B can further suppress the main conductive layer 2 from being oxidized, and can suppress the main conductive layer 2 from being corroded. As a result, an increase in the resistance value of the copper wiring can be suppressed.

(F) This embodiment is effective when the target material contains Zn that can easily harden the copper alloy material. For example, it is particularly effective when Zn is contained in the target material by 10 mass% or more. Even in such a case, the hardening of the copper alloy material can be suppressed by setting the C content in the copper alloy material to 0.1 mass% or less, for example. Therefore, the effects (a) and (b) can be further obtained. Moreover, hardening of a copper alloy material can be suppressed more by making content of Zn in a target material into 30 mass% or less. Therefore, the effects (a) and (b) can be further obtained.

(G) The Ni content in the target material is, for example, 30 mass% or more and 45 mass% or less, the Zn content is, for example, 10 mass% or more and 30 mass% or less, and the total content of Ni and Zn is 55 mass% or more and 65 mass% or less. As a result, the performance of the sputtered film can be further improved, and a decrease in the etching rate of the sputtered film can be suppressed. Furthermore, a decrease in the sputtering rate of the target material can be suppressed. For example, a sputtering rate of 70% or more of the sputtering rate of a target material (pure Cu target material) made of Cu and inevitable impurities can be maintained.

(H) This embodiment is effective when the target material further contains a base metal that easily hardens the copper alloy material. For example, it is particularly effective when the base material contains 0.05 mass% or more of a base metal. Even in such a case, the hardening of the copper alloy material can be suppressed by setting the content of C in the copper alloy material to 0.1 mass% or less, for example. Therefore, the effects (a) and (b) can be further obtained.

(I) By further including a base metal in the target material, the standard electrode potential of the sputtered film can be made lower than the standard electrode potential of the film formed using the target material containing only Ni and Zn. . That is, the etching rate of the sputtered film can be further improved. Thereby, the etching residue after performing wet etching with respect to a sputtered film can be suppressed. For example, when an etching solution (etchant) for performing wet etching on a sputtered film is used, any etching solution having different etching characteristics such as an aqueous solution of ammonium persulfate, an aqueous solution of hydrogen peroxide, or an aqueous solution of ammonia is used. Even if it exists, the etching residue of the sputtered film after wet etching can be suppressed. By increasing the etching rate of the sputtered film, a predetermined portion of the main conductive layer 2 and the first and second protective layers 4A and 4B is removed in the above-described wiring laminate 10 to form a copper wiring (wiring pattern). When the wet etching for forming is performed, the remaining etching of the first and second protective layers 4A and 4B after the wet etching can be suppressed. Therefore, a high-definition copper wiring can be formed and the reliability of the copper wiring can be improved. Moreover, the coverage of the insulating film 3 formed on the second protective layer 4B can be improved. By setting the content of the base metal in the target material to 0.05 mass% or more, for example, the etching rate of the sputtered film can be further improved.

  In addition, by increasing the etching rate of the sputtered film, for example, in the above-described wiring laminate 10, the etching rate of the first and second protective layers 4A and 4B and the pure Cu film that is the main conductive layer 2 is increased. The difference can be reduced. Thereby, when performing wet etching, it can suppress that Cu which forms the main conductive layer 2 elutes into etching liquid ahead of the copper alloy which forms the 1st and 2nd protective layers 4A and 4B. . That is, the remaining etching of the first and second protective layers 4A and 4B after wet etching can be further suppressed.

(J) By setting the content of the base metal in the target material to 5 mass% or less, the hardening of the copper alloy material can be further suppressed. Therefore, the effects (a) and (b) can be further obtained. Moreover, it can suppress that the etching rate of a sputtered film becomes high too much. Therefore, for example, when wet etching for forming a copper wiring is performed in the wiring laminate 10 described above, it is possible to suppress the occurrence of overetching in the first and second protective layers 4A and 4B. Thereby, a higher definition copper wiring can be formed. Moreover, the fall of the sputtering rate of a target material can be suppressed more.

(K) The oxygen concentration in the sputtered film can be further reduced by using oxygen-free copper (for example, oxygen-free copper having a purity of 99.9% or more) as the base material of the copper alloy forming the target material. Therefore, the performance of the sputtered film can be further improved. For example, the amount of oxygen that enters the main conductive layer 2 from the first and second protective layers 4A and 4B can be reduced. Thereby, it can suppress that the main conductive layer 2 will be oxidized.

(L) By forming the first protective layer 4A using the target material according to the present embodiment, the substrate 1 is provided with oxygen contained in the semiconductor layer formed of an oxide semiconductor such as IGZO. Even in the case of diffusion toward this direction, oxygen is captured by the first protective layer 4A. Thereby, it can suppress more that oxygen penetrate | invades into the main conductive layer 2. FIG. Thus, this embodiment is particularly effective when the semiconductor layer is formed of an oxide semiconductor.

(M) By forming the second protective layer 4B using the target material according to the present embodiment, an oxygen-containing gas used when forming the insulating film 3 formed of an oxide film such as a SiO ₂ film. Can prevent oxygen in the second protective layer 4B from entering the main conductive layer 2 even when oxygen enters the second protective layer 4B in contact with the second protective layer 4B. . Therefore, the main conductive layer 2 can be further suppressed from being oxidized. Even when oxygen contained in the insulating film 3 diffuses toward the main conductive layer 2, oxygen is captured by the second protective layer 4 </ b> B. Accordingly, it is possible to further suppress oxygen from entering the main conductive layer 2. Thus, this embodiment is particularly effective when the insulating film 3 is formed of an oxide film. Specifically, it is effective when an oxygen-containing gas is used when forming the insulating film 3. That is, this embodiment is particularly effective when used for the high-performance FPD wiring laminate 10 in which a non-oxygen-containing film such as a SiN film cannot be used as the insulating film 3.

  Hereinafter, for reference, a copper alloy material (ingot) formed by using a carbon crucible as a crucible in the casting process and covering the surface of the molten metal with carbon flakes in order to suppress the oxidation of the molten metal will be described. When the carbon crucible is used, when the molten metal is generated, the molten metal (raw material) comes into contact with the crucible, so that C contained in the crucible is melted from the crucible into the molten metal. The amount may increase. As a result, the hardening of the copper alloy material may not be suppressed. For example, in a Cu-35 mass% Ni-20 mass% Zn ingot formed by using a carbon crucible and adding an antioxidant, the content of C in the ingot is 0.17 mass%. Further, the Vickers hardness (Hv) of this copper alloy material (ingot) is 208, which exceeds 200. On the other hand, according to this embodiment, while using the material (for example, alumina crucible) which can make content of C derived from a crucible derived in an ingot into 0.1 mass% or less, for example. The copper alloy material (ingot) is formed without covering the surface of the molten metal with a coating material containing C. Thereby, content of C in a target material can be reduced. For example, in the ingot of Cu-35 mass% Ni-20 mass% Zn, the content of C in the ingot can be 0.001 mass%. The copper alloy material has a Vickers hardness (Hv) of 109.

  Moreover, in the case of a copper alloy material having a C content exceeding 0.1 mass%, the material to be rolled is work-hardened by performing the rolling treatment, and therefore, for example, a first process in which cold rolling and annealing treatment are alternately repeated a predetermined number of times. After performing this cold rolling process, it is necessary to perform a second cold rolling process in which one or more cold rolling processes are performed. On the other hand, the work hardening of a copper alloy material can be reduced by making content of C into 0.1 mass% or less like this invention.

(Other embodiments of the present invention)
As mentioned above, although one Embodiment of this invention was described concretely, this invention is not limited to the above-mentioned embodiment, In the range which does not deviate from the summary, it can change suitably.

In the above-described embodiment, the casting process is performed in an atmosphere in which the oxygen concentration is reduced without covering the surface of the molten metal with a coating material containing C. However, the present invention is not limited to this. For example, the casting process may be performed by covering the surface of the molten metal with a coating material that can suppress the oxidation of the molten metal without covering the surface with a coating material containing C. Further, for example, the casting process may be performed while supplying an inert gas (for example, nitrogen (N ₂ ) gas or rare gas) to the atmosphere without covering the surface of the molten metal with a coating material containing C. Also by these, the content of C in the copper alloy material can be reduced while suppressing the oxidation of the molten metal. Therefore, the effects (a), (b) and (d) can be obtained.

  In the above-described embodiment, the molten metal (copper melt, copper alloy melt) is generated using the high-frequency melting furnace, but is not limited thereto. For example, various melting furnaces that can melt a raw material by heating to produce a molten metal can be used. Also in this case, it is preferable to use a crucible formed of a material capable of reducing the C content to be contained in the ingot to 0.1 mass% or less as the crucible.

  In the above-described embodiment, the method for producing the sputtering target material by the melt casting method has been described. However, the present invention is not limited to this. For example, a powder sintering method using Cu, Ni, Zn powder, or a cold spray method in which Cu, Ni, Zn powder is deposited by spraying with an inert gas at high speed may be used.

  In the above-described embodiment, the wiring laminated body 10 used for the wiring material of the TFT has been described. However, the present invention is not limited to this. For example, the above-described effects can be obtained even with the wiring laminate 10 used for the wiring material of the touch panel sensor. Specifically, for example, a substrate 1 made of a polyethylene terephthalate (PET) film substrate, a first protective layer 4A provided on the substrate 1, a main conductive layer 2 provided on the first protective layer 4A, A wiring laminate including a second protective layer 4B provided on the conductive layer 2 and a transparent conductive layer provided on the second protective layer 4B and made of, for example, an ITO layer may be used.

  In the above-described embodiment, the first protective layer 4A and the second protective layer 4B are provided as the protective layer. However, the present invention is not limited to this. For example, it is sufficient that either the first protective layer 4A or the second protective layer 4B is provided.

  The above-described embodiment is particularly effective when the semiconductor layer included in the substrate 1 is formed of an oxide semiconductor. However, the semiconductor layer may be formed of amorphous silicon or the like.

  Next, examples of the present invention will be described, but the present invention is not limited thereto.

<Preparation of sample>
First, the target material which is each sample of Examples 1-19 and Comparative Examples 1-9 was produced.

Example 1
In Example 1, a copper alloy melt was generated using a high-frequency melting furnace. Specifically, an alumina crucible surrounded by a carbon heating crucible was prepared as a crucible. Then, for example, in an inert gas atmosphere, an oxygen-free copper having a purity of 99.9% or more and a Zn block (Zn block) having a purity of 99.9% are charged into an alumina crucible, and alumina is added. In a state where the crucible was surrounded by the carbon crucible, oxygen free copper and a predetermined amount of Zn block were heated to 1050 ° C. or higher and 1100 ° C. or lower in a high frequency melting furnace to produce a CuZn molten metal. Subsequently, while maintaining the heating of the CuZn melt in a high-frequency melting furnace in an inert gas atmosphere, a predetermined amount of Ni block (Ni lump) having a purity of 99.9% is put in the CuZn melt (in an alumina crucible). The Ni block was melted and mixed to form a molten copper alloy. The total amount of the molten copper alloy produced was about 15 kg. After the oxygen-free copper, Zn block, and Ni block were completely dissolved, the molten copper alloy was held for 30 minutes to 60 minutes under conditions of 1050 ° C. or higher and 1150 ° C. or lower. Thereafter, the molten copper alloy is poured into a mold having a predetermined shape (for example, an inner diameter φ of 100 mm) and cooled, and an ingot having a predetermined shape (a diameter of 100 mm and a length of 220 mmL, that is, a cylindrical shape of φ100 mm × 220 mmL). Was cast. That is, an ingot of a copper alloy (Cu-30Ni-25Zn) having a Ni content of 30 mass%, a Zn content of 25 mass%, a total content of Ni and Zn of 55 mass%, and the balance of Cu and inevitable impurities. Was cast.

  Subsequently, cutting was performed to remove the non-uniform portions of both ends of the obtained ingot, and chamfering was performed on the ingot, so that the shape of the ingot was φ96 mm × 150 mmL. Then, after heating the ingot for a predetermined time under the condition of 850 ° C., forging is performed on the ingot so that the cross section of the circular ingot having a diameter of 96 mm becomes a rectangular shape of 25 mmt × 180 mmW, and forging A material was formed. Next, the forging material was subjected to pickling treatment for removing the oxide film on the surface of the forging material. And the forging material which performed the pickling process was heated for 1 hour in 850 degreeC conditions in nitrogen gas atmosphere, the annealing process was performed, and the annealing material was formed.

  Subsequently, the annealed material was cold-rolled to form a cold-rolled material (target material). The cold rolling treatment was performed by repeating cold rolling so that the reduction amount of the material to be rolled becomes 1 mm continuously for a predetermined number of times until a crack is generated on the surface of the material to be rolled without sandwiching the annealing treatment. That is, when the material to be rolled was cracked, the cold rolling process was finished. And it cuts into cold-rolled material using NC milling, and thickness is 5 mm from a location other than the location where the crack of cold-rolled material has occurred, and the diameter is 100 mm (5 mmt × φ100 mm). A circular target material was produced. This was used as the sample of Example 1.

(Examples 2-19, Comparative Examples 1-9)
In each of Samples 2 to 19 and Comparative Examples 1 to 9, the addition amount of the Ni block, the addition amount of the Zn block, and the base block are set so that the composition of the target material, that is, the composition of the ingot is as shown in Table 1 below. The addition amounts of Mn flakes, Zr blocks, Ti blocks, Al blocks, Mg blocks, and Ca blocks were adjusted. The purity of Mn flakes, Zr blocks, Ti blocks, Al blocks, Mg blocks, and Ca blocks is 99.9%, respectively. In Comparative Examples 1 to 8, a carbon crucible was used as the crucible. Other than that, a target material was produced in the same manner as in Example 1. These were made into the sample of Examples 2-19, and the sample of Comparative Examples 1-8, respectively. In Comparative Example 9, no Ni block, Zn block, or base metal was added, and only oxygen-free copper was used. Others were the same as in Example 1, and a target material (pure Cu target material) made of copper and Cu consisting of inevitable impurities was produced. This was used as the sample of Comparative Example 9.

<Evaluation of carbon content>
About the ingot which forms each sample of Examples 1-19 and Comparative Examples 1-8, content of C in an ingot was measured, respectively. The C content was measured by analyzing the concentration of C in the ingot by an infrared absorption method. The measurement results are shown in Table 1 below.

<Evaluation of sputtered film>
Using each sample of Examples 1 to 19 and Comparative Examples 1 to 9 as a target material, etching characteristics and performance of the sputtered film were evaluated for each sputtered film (alloy film, pure Cu film) formed by sputtering. It was.

(Sputtering method)
A method of forming a sputtered film (alloy film, pure Cu film) by sputtering using the samples of Examples 1 to 19 and Comparative Examples 1 to 9 will be described. As a sputtering apparatus for performing sputtering, SH-350 manufactured by ULVAC, Inc. was used. Each sample was attached to the sputtering apparatus in a state of being bonded to the backing plate. Specifically, each sample and a pure copper backing plate were joined to each other via melted indium (In) and attached to the sputtering apparatus. Then, sputtering was performed using each sample as a target material, and a sputtered film having a predetermined thickness was formed on a 50 mm × 50 mm glass substrate. The sputtering conditions were such that the output was 1 kW (DC), argon (Ar) gas was used as the sputtering gas, and the gas pressure (pressure in the chamber where sputtering was performed) was 0.5 Pa.

(Evaluation method of etching characteristics)
Using the samples of Examples 1 to 19 and Comparative Examples 1 to 9 as target materials, a sputtered film (alloy film, pure Cu film) having a thickness of 300 nm on a 50 mm × 50 mm glass substrate by the sputtering method described above. Each was formed into a film. Then, the etching rate was measured about each sputtered film (each sputtered film) formed into a film using each sample of Examples 1-19 and Comparative Examples 1-9. First, each glass substrate on which each sputtered film is formed is immersed in an aqueous solution (APS aqueous solution) containing ammonium persulfate as an etchant at a rate of 1 mol / L until each sputtered film is completely removed from the glass substrate. The time required for the etching (etching time) was measured. Thereafter, the etching rate (nm / s) of each sputtered film was calculated by dividing the thickness (300 nm) of the sputtered film by the measured etching time. Subsequently, the ratio (etching rate ratio) of the etching rate of each alloy film or the like to the etching rate of the pure Cu film was calculated by the following (Formula 2). Note that the etching rate of the pure Cu film formed using the sample of Comparative Example 9 was used as the etching rate of the pure Cu film.
(Formula 2)
Etching rate ratio = etching rate of sputtered film / etching rate of pure Cu film

  The calculation results of the etching rate and etching rate ratio of each sputtered film are shown in Table 1 below. It shows that the sputtered film has better etching characteristics as the value of the etching rate ratio approaches 1. In this example, a sample used for forming a sputtered film having an etching rate ratio value of 0.5 or more was determined to be acceptable (◯).

(Method for evaluating sputtered film performance)
Using the sample of Comparative Example 9 as a target material, a pure Cu film having a thickness of 1000 nm was formed on a 50 mm × 50 mm glass substrate by the sputtering method described above. Next, each of the samples of Examples 1 to 19 and Comparative Examples 1 to 8 is used as a target material, and a sputtered film (alloy film) having a thickness of 50 nm is formed on the pure Cu film by the above-described sputtering method. A laminated film of a pure Cu film and an alloy film was formed. When only the sample of Comparative Example 9 was used as the target material, only a pure Cu film having a thickness of 1000 nm was formed on a 50 mm × 50 mm glass substrate.

Subsequently, for each of the laminated film formed using each sample of Examples 1 to 19 and Comparative Examples 1 to 9, and a pure Cu film (hereinafter also referred to as “each laminated film etc.”), van der der The electrical resistance (μΩcm) was measured by the pow (van der Pauw) method. Specifically, the electric resistance was measured by setting up a needle as an electrode in a 3 mm square area including each of the four corners of each laminated film. The measured value of the electrical resistance at this time was taken as the electrical resistance before heating. In addition, each laminated film was heated in the atmosphere at 400 ° C. for a predetermined time (for example, 30 minutes) in the atmosphere, and then the electrical resistance of each laminated film was measured by the van der Pau method. The measured value of the electrical resistance at this time was taken as the electrical resistance after heating. And the increase rate (%) of the electrical resistance of each laminated film etc. was calculated by the following (Formula 3), respectively.
(Formula 3)
Electric resistance increase rate (%) = ((electric resistance after heating−electric resistance before heating) / electric resistance before heating) × 100

  Table 1 below shows the electrical resistance of each laminated film before heating, the electrical resistance after heating, and the rate of increase (%) in electrical resistance. It shows that the smaller the value of the rate of increase in electrical resistance, the better the performance of the alloy film. That is, the smaller the value of the rate of increase in electrical resistance is, the more the pure Cu film is protected by the alloy film. For example, it is shown that oxygen penetration into the pure Cu film is suppressed by the alloy film, and oxidation of the pure Cu film is suppressed. In this example, a sample used for forming a laminated film having an electrical resistance increase rate of less than 7% was set to pass (◯).

<Evaluation method of sputtering rate>
A stainless steel mask having an opening (window) of 3 mm × 3 mm was placed on a glass substrate of 50 mm × 50 mm. And using each sample of Examples 1-19 and Comparative Examples 1-9 as a target material, it sputters for 1 minute with the above-mentioned sputtering method, Each sputter | spatter film | membrane (alloy film, pure Cu film | membrane) is carried out on a glass substrate. A film was formed. Thereafter, the mask was removed from the glass substrate. And the film thickness of each sputtered film (each sputtered film) formed using each sample of Examples 1-19 and comparative examples 1-9 was measured using laser microscope VK-8700 made from Keyence Corporation. . Thereafter, the film thickness of each sputtered film was divided by the sputter time (1 minute), and the sputter rate (nm / min) of the target material as each sample was calculated. Subsequently, the ratio of the sputter rate of each sample to the sputter rate of the pure Cu target material (sputter rate ratio) was calculated by the following (formula 4). Note that the sputtering rate of the sample of Comparative Example 9 was used as the sputtering rate of the pure Cu target material.
(Formula 4)
Sputter rate ratio = spatter rate of each sample / sputter rate of pure Cu target material

  The sputter rate and sputter rate ratio of each sample are shown in Table 1 below. In this example, a sample having a sputter rate ratio value of 0.7 or more was determined to be acceptable (◯).

<Processing evaluation method>
The workability of each of the copper alloy materials forming the target material, which is each sample of Examples 1 to 19 and Comparative Examples 1 to 9, was evaluated. Specifically, as an index for evaluating workability, the degree of cold rolling process (total degree of work) performed on the annealed material that is a copper alloy material when producing the target material that is each sample (%) Was calculated. The workability (%) of the cold rolling process was calculated by the following (Formula 5). In (Formula 5), the thickness of the material to be rolled when cracking occurs is the thickness of the target material. The thickness of the material to be rolled at the start of rolling is the thickness of the annealed material.
(Formula 5)
Workability of cold rolling process (%) = {1− (thickness of material to be rolled when crack is generated / thickness of material to be rolled at the start of rolling)} × 100

  Table 1 below shows the workability of the cold rolling treatment of the copper alloy material forming each sample. In the present Example, the copper alloy material which formed the sample whose workability of a cold rolling process is 40% or more was set as the pass ((circle)).

(Comprehensive evaluation)
The sample judged to be acceptable in any of the evaluation of the etching characteristics of the sputtered film, the evaluation of the performance of the sputtered film, the evaluation of the sputter rate, and the evaluation of the workability is “◯”, and any one is rejected. Samples with an evaluation of “x” were designated as “x”.

<Evaluation results>
From Examples 1 to 19, a copper alloy containing Ni and Zn, the balance being Cu and inevitable impurities, and the content of C being one of the inevitable impurities being 0.1 mass% or less It was confirmed that the hardening of the material can be suppressed and the workability of the copper alloy material forming the target material can be improved. That is, it was confirmed that even when a cold rolling treatment with a workability of 40% or more was performed on the copper alloy material, no cracks or the like occurred in the material to be rolled. Therefore, it was confirmed that the productivity of the target material can be improved. For example, it was confirmed that the defective product rate of the target material can be reduced and the mass productivity of the target material can be improved.

  In addition, from Examples 1 to 19, it was confirmed that the material to be rolled was difficult to work harden by cold rolling when the content of C in the target material was 0.1 mass% or less. For example, when performing a cold rolling process, a predetermined number of cold rolling processes can be performed continuously without interposing an annealing process. It was confirmed that it can be increased to 40% or more. That is, in the cold rolling process, it was confirmed that it is not necessary to alternately perform the cold rolling and the annealing process a predetermined number of times.

  On the other hand, from Comparative Examples 1-8, when Ni and Zn are included, the remainder consists of Cu and inevitable impurities, and the content of C, which is one of the inevitable impurities, exceeds 0.1 mass%. It was confirmed that the hardening of the copper alloy material could not be suppressed. That is, it was confirmed that the workability of the cold rolling process was less than 40%, for example, and the workability of the copper alloy material was lowered. As a result, it was confirmed that the productivity of the target material was lowered.

  Moreover, even if Zn content was increased to 10 mass% or more from Examples 1-19, it confirmed that the fall of the workability of a copper alloy material could be suppressed by reducing C content. As a result, it was confirmed that the productivity of the target material can be improved.

  Moreover, even if it increased the content of a base metal with 5 mass% from Examples 1-19, it confirmed that the fall of the workability of a copper alloy material could be suppressed by reducing C content. As a result, it was confirmed that the productivity of the target material can be improved.

  Moreover, from the comparison with Examples 1-19 and Comparative Examples 1-8, the ingot (copper alloy material) formed using the alumina crucible is in the ingot compared with the ingot formed using the carbon crucible. It was confirmed that the C content can be reduced. Therefore, it was confirmed that the content of C in the target material can be reduced.

  From the comparison between Examples 1 to 19 and Comparative Examples 1 to 8, even if the C content in the target material is reduced to, for example, 0.1 mass% or less, the etching characteristics of the sputtered film, the performance of the sputtered film, the target material It was confirmed that the sputtering rate did not decrease. That is, it was confirmed that the effect of containing a predetermined amount of Ni, a predetermined amount of Zn, and a predetermined amount of base metal was not hindered.

<Preferred embodiment>
Hereinafter, preferred embodiments of the present invention will be additionally described.

[Appendix 1]
According to one aspect of the invention,
A sputtering target material comprising nickel and zinc, with the balance being copper and inevitable impurities,
A sputtering target material having a carbon content of 0.1 mass% or less, which is one of the inevitable impurities, is provided.

[Appendix 2]
According to another aspect of the invention,
A sputtering target material comprising nickel and zinc, the balance being formed of a copper alloy material consisting of copper and inevitable impurities,
A sputtering target material having a carbon content of 0.1 mass% or less, which is one of the inevitable impurities, is provided.

[Appendix 3]
The sputtering target material according to appendix 2, preferably,
The copper alloy material has a Vickers hardness (Hv) of 200 or less.

[Appendix 4]
The sputtering target material according to any one of appendices 1 to 3, preferably,
Content of the said zinc is 10 mass% or more.

[Appendix 5]
The sputtering target material of appendix 4, preferably,
The nickel content is not less than 30 mass% and not more than 45 mass%, the zinc content is not more than 30 mass%, and the total content of the nickel and the zinc is not less than 55 mass% and not more than 65 mass%.

[Appendix 6]
The sputtering target material according to any one of appendices 1 to 5, preferably,
It further includes a metal whose standard electrode potential is lower than that of zinc.

[Appendix 7]
The sputtering target material according to appendix 6, preferably,
The content of the base metal is 0.05 mass% or more.

[Appendix 8]
The sputtering target material according to appendix 7, preferably,
The content of the base metal is 5 mass% or less.

[Appendix 9]
The sputtering target material according to any one of appendices 6 to 8, preferably,
As the base metal, at least one of manganese, zirconium, titanium, aluminum, magnesium, and calcium is used.

[Appendix 10]
The sputtering target material according to any one of appendices 1 to 9, preferably,
Oxygen-free copper is used as the copper.

[Appendix 11]
According to yet another aspect of the invention,
Casting ingots containing nickel and zinc, with the balance being copper and inevitable impurities, using a molten copper alloy produced by heating nickel in the crucible and melting it in a crucible Having a process,
In the casting step, there is provided a method for producing a sputtering target material using a crucible formed of a material capable of making the content of the carbon to be contained in the ingot to be 0.1 mass% or less as the crucible. Provided.

[Appendix 12]
A method for producing a sputtering target material according to appendix 11, preferably,
A crucible made of ceramic is used as the crucible.

[Appendix 13]
The method for producing a sputtering target material according to appendix 12, preferably,
As the crucible, a crucible formed of any one of alumina, magnesia, and zirconia is used.

[Appendix 14]
A method for producing a sputtering target material according to any one of appendices 11 to 13, preferably,
In the casting step, the crucible is heated in a state surrounded by a heating crucible.

[Appendix 15]
The method for producing a sputtering target material according to appendix 14, preferably,
As the heating crucible, a crucible formed of a material containing carbon is used.

[Appendix 16]
A method for producing a sputtering target material according to any one of appendices 11 to 15, preferably,
The casting step is performed in an atmosphere with a reduced oxygen concentration without covering the surface of the molten metal with a coating material containing carbon.

[Appendix 17]
A method for producing a sputtering target material according to any one of appendices 11 to 16, preferably,
In the casting process, the surface of the molten metal is not covered with a coating material containing carbon, but is covered with a coating material that can suppress oxidation of the molten metal.

[Appendix 18]
A method for producing a sputtering target material according to any one of appendices 11 to 17, preferably,
The casting process is performed while supplying an inert gas into the atmosphere.

[Appendix 19]
A method for producing a sputtering target material according to any one of appendices 11 to 18, preferably,
An annealing step of heating the ingot for a predetermined time under a predetermined temperature condition;
A cold rolling process in which a predetermined number of cold rolling processes are continuously performed on the ingot after the annealing process is performed.

[Appendix 20]
According to yet another aspect of the invention,
A substrate,
A main conductive layer provided on any main surface of the substrate and made of copper;
A protective layer provided on any main surface of the main conductive layer,
The protective layer includes a sputtering target material containing nickel and zinc, the balance being made of copper and inevitable impurities, and the content of carbon being one of the inevitable impurities being 0.1 mass% or less. A wiring laminate is formed.

DESCRIPTION OF SYMBOLS 1 Board | substrate 2 Main conductive layer 4A 1st protective layer 4B 2nd protective layer 10 Wiring laminated body

Claims (9)

A sputtering target material comprising nickel and zinc, with the balance being copper and inevitable impurities,
The sputtering target material whose content of carbon which is one of the inevitable impurities is 0.1 mass% or less. The sputtering target material according to claim 1 whose content of zinc is 10 mass% or more. The sputtering target material according to claim 1 or 2, further comprising a metal whose standard electrode potential is lower than that of zinc. The sputtering target material according to claim 3, wherein the content of the base metal is 0.05 mass% or more. Casting ingots containing nickel and zinc, with the balance being copper and inevitable impurities, using a molten copper alloy produced by heating nickel in the crucible and melting it in a crucible Having a process,
The said casting process WHEREIN: The manufacturing method of the sputtering target material using the crucible formed with the material which can make content of the carbon which will be contained in the said ingot into 0.1 mass% or less as the said crucible. The method for producing a sputtering target material according to claim 5, wherein the casting step is performed in an atmosphere having a reduced oxygen concentration without covering the surface of the molten metal with a coating material containing carbon. The method for producing a sputtering target material according to claim 5, wherein, in the casting step, the surface of the molten metal is not covered with a coating material containing carbon, but is covered with a coating material that can suppress oxidation of the molten metal. An annealing step of heating the ingot for a predetermined time under a predetermined temperature condition;
The manufacturing of the sputtering target material according to any one of claims 5 to 7, further comprising: a cold rolling process in which a predetermined number of cold rolling processes are continuously performed on the ingot after the annealing process is performed. Method. A substrate,
A main conductive layer provided on any main surface of the substrate and made of copper;
A protective layer provided on any main surface of the main conductive layer,
The protective layer includes a sputtering target material containing nickel and zinc, the balance being made of copper and inevitable impurities, and the content of carbon being one of the inevitable impurities being 0.1 mass% or less. A wiring laminate formed in this way.