JP2010126807A - Surface-treated metal material and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a surface-treated metal material which has adequate solder wettability and an adequate bonding strength of a soldered portion imparted to the surface of a metal substrate having a passive state film on the outermost surface, without making a process complicated, without using a chemical solution or the like for pickling, of which the treatment for industrial waste becomes troublesome and without removing the passive state film by pickling, and to provide a method for manufacturing the same. <P>SOLUTION: The surface-treated metal material has an adhesion layer 2 formed of a sputtered film which contains chromium (Cr) as a main component and has an internal residual stress that is a compressive stress or approximately zero, and a bonding layer 3 formed of a sputtered film which contains at least one type of copper (Cu), a mixed state of copper and nickel (Cu-Ni), a mixed state of copper and zinc (Cu-Zn), a mixed state of copper, nickel and zinc (Cu-Ni-Zn) as a main component, on the surface of the metal substrate 1 having the passive state film on the outermost surface layer, sequentially from the surface side of the metal substrate 1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a surface-treated metal material obtained by performing a surface treatment for improving wettability with respect to solder in a metal substrate such as aluminum (Al) or an aluminum alloy, or stainless steel, titanium, or an invar material. It relates to a manufacturing method.

In general, a metal material made of a material having a passive film on the outermost surface, such as aluminum (Al) or stainless steel, is one of the typical materials that are extremely difficult to solder. is there. This is because, for example, a passive film such as an oxide film (also referred to as a natural oxide film or a natural aluminum oxide layer) is generally formed on the outermost surface of an aluminum thin plate in combination with oxygen in the atmosphere. .
As a method for imparting good solderability (solder wettability) to the surface of an aluminum plate or the like having such characteristics, a tin (Sn) layer is applied to the surface after pickling treatment. Alternatively, a technique of forming a nickel (Ni) layer or the like by a plating method or the like has been proposed.
More specifically, after the surface of a metal substrate made of aluminum (Al) is degreased and pickled, the first underlayer mainly composed of zinc (Zn) is subjected to a zinc substitution plating method. (5-500 mg / m ² ). Then, after washing with water, a second underlayer 202 mainly composed of nickel is formed by a plating method (0.2 to 50 mg / m ² ). Further, a solder wetting layer 203 mainly composed of tin (Sn) is formed thereon by plating (0.2 to 20 mg / m ² ) (Patent Documents 1 and 2).

  In addition, as one of the technologies proposed for the purpose of improving the solderability on the surface of the electrode in an electronic component, a layer made of titanium (Ti), aluminum (Al), zinc (Zn) or an alloy thereof is formed. There is a method in which a layer made of nickel (Ni), copper (Cu), or an alloy thereof is formed on the layer by vapor deposition, and a solder layer is further coated on the layer. In this technique, a layer made of titanium having a thickness of 0.2 μm is formed as an electrode of a ceramic component, a layer having a thickness of 1 μm made of nickel is formed thereon, and further, tin: lead (Sn: Pb) is formed thereon. = A solder coating layer is formed by dipping in 60:40 molten solder (Patent Document 3).

  Further, as a wiring material for a semiconductor chip, titanium (Ti), a titanium / tungsten (Ti / W) alloy is formed as an adhesion layer on an electrode made of aluminum (Al), and nickel (Ni), An adhesion layer made of copper (Cu), nickel / vanadium (Ni / V) alloy, nickel / phosphorus (Ni / P) alloy and having a thickness of about 1 to 5 μm is formed, and copper ( A technique of forming Cu) or a copper alloy has been proposed. A sputtering method or a plating method can be applied as a method of forming each layer constituting this laminated structure. The purpose of this technique is to enable a lead-free solder ball to be bonded onto a semiconductor chip (Patent Document 4).

  Also, in order to reduce the residual compressive stress in these films by sputtering, an adhesion layer made of titanium nitride (TiN) from aluminum (Al) alloy is formed by pressure. The technique of making it 3 mTorr or less (about 0.4 Pa or less) is proposed (patent document 5).

Further, a technique has been proposed in which a titanium (Ti) film having a compressive stress is formed by vapor deposition in a film-forming atmosphere having an oxygen partial pressure of 5 × 10 ^{−5 to} 5 × 10 ⁻⁶ Torr or in a water vapor atmosphere. Yes. According to this technology, by performing a film forming process in an environment containing oxygen (O), oxygen (O) enters the titanium (Ti) layer, and compressive stress remains in the layer. (Patent Document 6).

JP 2006-206945 A JP 2006-110769 A Japanese Patent No. 3031024 JP 2002-280417 A JP-A-11-162873 JP 59-121955 A

However, all of the techniques proposed in Patent Document 1 to Patent Document 6 described above are subjected to pickling treatment on the surface of a metal substrate having a passive film such as an aluminum substrate, and plating is performed on the surface. After making it easy to perform film formation or sputter film formation, the surface treatment structure is laminated. For example, as proposed in Patent Document 1 and Patent Document 2, the surface of the aluminum base material is first subjected to pickling treatment to remove the outermost natural oxide film, and then the tin ( An Sn) plating film, a zinc (Zn) plating film, or the like is formed. As described above, in the conventional technique, it is essential to perform a pickling treatment or the like on the surface of the metal substrate.
For this reason, in the conventional techniques as described above, it is necessary to perform a complicated process of pickling in order to remove the passive film on the surface of the metal base material, and various chemical solutions such as plating solutions Therefore, not only is the pickling process itself complicated, but also the quality control of various chemicals used in the pickling process and the treatment of waste liquids are time-consuming, time-consuming, and costly. There is a problem that it ends up.
In addition, since various kinds of plating solutions including a chemical solution for pickling are used as industrial wastes as waste liquids after use, their use is not desirable from the viewpoint of environmental engineering.
Also, in order to achieve good soldering, it may be possible to use a technique such as using a flux that is strong enough to dissolve a passive film such as an oxide film on the surface of a metal substrate, Actually, such extremely strong flux is extremely undesired from the viewpoint of durability and reliability of the joint part because there is a very high possibility that the vicinity of the joint part after soldering will be significantly roughened and deteriorated. I must say.

In particular, the technique proposed by Patent Document 3 can be a technique for realizing joining using lead (Pb) -containing solder, but joining by so-called lead-free solder is difficult.
In particular, with the technique proposed by Patent Document 4, it is possible to realize the joining with lead-free solder, but a passive film is formed on the outermost surface such as an aluminum (Al) base material having a natural oxide film. It is not certain whether it can be applied to a metal base material having the material. In this case, the thickness of the surface coat film is required to be about 1 to 5 μm. However, such a thick surface coat film is actually a time-consuming process when considered as a commercial base manufacturing technique. Therefore, there is a high possibility that productivity will be remarkably lowered, and as a result, the manufacturing cost will increase.
In particular, the techniques proposed in Patent Document 5 and Patent Document 6 disclose a technique for leaving a compressive stress in the titanium film, but even if such a compressive stress is left, this structure has lead. As a result of various experiments and the like, we have confirmed that joining using free solder actually has a very high risk of joint strength being insufficient.

The present invention has been made in view of such problems, and its main purpose is to make the chemical solution for pickling without making the process complicated and handling as industrial waste complicated. Without using a material such as aluminum (Al), aluminum alloy, stainless steel, etc., which are originally difficult-to-platable and hard-to-solder materials. To provide a surface-treated metal material and a method for producing the same, which imparts good solder wettability and bonding strength to soldering without performing pickling removal of the passive film on the surface of the metal substrate. It is in.
Further, in addition to the above-mentioned purpose, it is possible to use a so-called lead-free solder which uses a flux with weak activity (equivalent to RMA or R in the flux classification) and does not contain lead (Pb) which is a RoHs related material. Another object is to provide a surface-treated metal material and a method for producing the same.
Further, in addition to the above object, to provide a surface-treated metal material having a surface treatment structure composed of an ultrathin film capable of achieving practical productivity securing and raw material cost reduction, and a method for producing the same. It is in.

  In order to solve the above problems, the inventor of the present invention originally has a passive film such as an oxide film (natural oxide film) on the outermost surface, so that it is originally a difficult-plating material and difficult to solder. Even with a passive film left on the surface of a metal base material such as aluminum (Al) or stainless steel, which is easy to attach, and thus without any pickling treatment, it is made of the following materials: It has been found that by forming a layer and an adhesive layer, it is possible to impart good solder wettability and bonding strength against soldering. And various experiments etc. were conducted and it was confirmed that the means can acquire an effect correctly, and it came to make this invention.

The surface-treated metal material of the present invention comprises a sputtered film mainly composed of chromium (Cr) in order from the surface side of the metal base material on the surface of the metal base material having a passive film on the outermost layer. An adhesion layer in which the internal residual stress of the film is compressive stress or substantially zero, a mixed state of copper (Cu), copper and nickel (Cu—Ni), a mixed state of copper and zinc (Cu—Zn), copper and nickel, It is characterized in that an adhesive layer made of a sputtered film containing as a main component at least one of mixed states of zinc (Cu—Ni—Zn) is formed.
The method for producing a surface-treated metal material according to the present invention includes a sputtered film containing chromium (Cr) as a main component in order from the surface side of the metal substrate on the surface of the metal substrate having a passive film on the outermost layer. An adhesive layer in which the internal residual stress of the film is compressive stress or substantially zero, a mixed state of copper (Cu), copper and nickel (Cu—Ni), a mixed state of copper and zinc (Cu—Zn), copper Oxygen is also used when the material of the layer to be deposited is switched between a bonding layer made of a sputtered film mainly composed of at least one of a mixed state of nickel and zinc (Cu—Ni—Zn) It is characterized in that it includes a step of continuously performing sputter film formation in the same chamber while maintaining a film formation atmosphere of an inert gas such as argon (Ar) gas that has been excluded.

  According to the present invention, on the surface of a metal base material having a passive film on the outermost layer, it is composed of a sputtered film mainly composed of chromium (Cr) in order from the surface side of the metal base material. Adhesive layer with residual stress of compressive stress or substantially zero, mixed state of copper (Cu), copper and nickel (Cu—Ni), mixed state of copper and zinc (Cu—Zn), copper, nickel and zinc (Cu -Ni-Zn) is formed with an adhesive layer composed of a sputtered film mainly composed of at least one of the mixed states. On the surface of a metal substrate having a passive film on the outermost surface, such as aluminum (Al), aluminum alloy, or stainless steel, which is a material that is difficult to solder. acid Without subjected to removal or the like, it is possible to impart bonding strength for good solder wettability and solderability.

Hereinafter, the surface-treated metal material and the manufacturing method thereof according to the present embodiment will be described with reference to the drawings.
FIG. 1 schematically shows a main laminated structure of a surface-treated metal material according to an embodiment of the present invention, and FIG. 2 shows a sputter film formation on the adhesive layer of the surface-treated metal material shown in FIG. FIG. 3 is a view schematically showing a laminated structure further provided with a protective layer, and FIG. 3 shows a laminated structure further provided with a protective layer formed by plating on the adhesive layer of the surface-treated metal material shown in FIG. It is a figure which shows a structure typically.

  As shown in FIG. 1, this surface-treated metal material basically has a laminated structure in which an adhesion layer 2 and an adhesive layer 3 are formed in this order on the surface of a metal substrate 1. It is provided as a component. With such a configuration (laminated structure), the surface on which the surface treatment is performed on the surface-treated metal material, the surface on the side where the adhesion layer 2 and the adhesive layer 3 are laminated and formed, has good solder wetting. And sufficient bonding strength with respect to soldering.

The metal substrate 1 is made of a metal material having a passive film on the outermost layer.
Specifically, for example, pure aluminum (Al), aluminum alloy, or aluminum alloy plates of 1000 series, 2000 series, 3000 series, 5000 series, 6000 series, 7000 series, etc. are applicable when expressed in JIS standards. . Further, non-JIS standard aluminum alloys, die castings, or aluminum clad plate materials having these aluminum materials as the surface layer, aluminum / SUS, aluminum / invar, aluminum / copper (Cu), etc. are also applicable.
In addition, various stainless materials, invar materials, and the like are also applicable as practical materials.
In addition, chromium (Cr), tantalum (Ta), niobium (Nb), molybdenum (Mo), and the like are also applicable from the viewpoint that the surface layer is a metal that forms a passive film.

The shape of the metal substrate 1 can be various shapes such as a plate shape, a round shape, a pipe shape, and a tape shape, and is not particularly limited.
The surface of the metal substrate 1 is not subjected to pickling treatment using a pickling chemical solution or the like which becomes industrial waste after use and is complicated to dispose of it. Such a pickling treatment is not performed at all as a pretreatment in the preparation stage. Accordingly, a passive film such as a natural oxide film still exists on the outermost surface of the metal substrate 1, and the adhesion layer 2 and the adhesive layer 3 are laminated thereon. However, it goes without saying that general so-called degreasing or washing using various detergents or pure water may be performed before forming the adhesion layer 2 or the like on the outermost surface of the metal substrate 1. .

The adhesion layer 2 is made of a sputtered film containing chromium (Cr) as a main component, and the internal residual stress of the film is a compressive stress or substantially zero. This is because, when the internal residual stress of the sputtered film of the adhesion layer 2 is tensile, there is a high possibility that the bonding strength with the solder is lowered.
The average thickness of the adhesion layer 2 is desirably 10 nm or more and 500 nm or less. This is because if the thickness of the adhesion layer 2 is less than the lower limit of 10 nm, there is a high possibility that the wettability and the bonding strength with respect to the solder will be insufficient. On the other hand, when the upper limit of 500 nm is exceeded, there is a high risk that the bonding strength may be lowered, the solder wettability may be lowered after the application of strain, or the adverse effect in a hydrogen environment may be manifested. .

The adhesive layer 3 is a pure copper (Cu) or nickel (Ni) concentration of 60 wt% or less and a zinc (Zn) concentration of 10% or less in a mixed state of copper and nickel (Cu—Ni), copper, nickel and zinc (Cu—). It is made of a sputtered film mainly composed of at least one of a mixed state of Ni—Zn) or a mixed state of copper and zinc (Cu—Zn) having a Zn concentration of 5% or less.
The characteristics obtained when using the above three kinds of metals, nickel (Ni), copper (Cu), and zinc (Zn), which are metal materials used to form the adhesive layer 3, are as follows. It ’s like that.
Generally, the material costs of these three kinds of metals are nickel (Ni)> copper (Cu)> zinc (Zn) when arranged in the order of price. Further, when nickel (Ni) is added to copper (Cu), the wettability is improved as compared with the case of pure copper (Cu), but the cost becomes high. In the case of adding zinc (Zn) to copper (Cu), the wettability with respect to solder may be reduced, but this contributes to cost reduction. In addition, in the case of adding zinc (Zn), an effect of functioning as a sacrificial anticorrosive layer can be obtained. The final alloy composition may be determined in accordance with the use environment and the required function / performance in consideration of such characteristics of each metal. However, if the nickel (Ni) concentration exceeds 60%, the Cu—Ni alloy behaves as a ferromagnetic material, which is not preferable. Moreover, since a solder wettability will fall when zinc (Zn) density | concentration becomes high, it is unpreferable. Moreover, the solder wettability at the time of adding zinc (Zn) can be adjusted by adding nickel (Ni) to copper (Cu).

  The average thickness of the adhesive layer 3 is desirably 15 nm or more. This is because if the thickness of the adhesion layer 2 is less than the lower limit of 15 nm, there is a high possibility that the wettability to solder and the bonding strength will be insufficient.

The resolution is 2 nm by a spectroscopic method such as photoelectron spectroscopy (XPS) or Auger analysis in the vicinity of the interface between the adhesion layer 2 and the adhesive layer 3 (more specifically, in the region covering the thickness of 5 nm near the interface). Based on the result of elemental spectral intensity analysis in the depth direction measured by {circle around (1)}, {Oxygen (O) strength} is {Oxygen (O) strength + Chrome (Cr) strength of adhesion layer 2 + Adhesion layer 3 strength The value obtained by dividing by the component element (strength of copper (Cu), nickel (Ni), zinc (Zn))) = X is defined as (0 ≦) X ≦ 0.02. This is a desirable numerical aspect.
However, when the metal substrate 1 is made of a material intentionally added with magnesium (Mg), such as a JIS standard 5000 series aluminum-magnesium (Al-Mg) alloy, oxygen is used. The intensity ratio X is preferably (0 ≦) X ≦ 0.04.
That is, when the oxygen strength ratio X in the vicinity of the interface between the adhesion layer 2 and the adhesion layer 3 is more than 0.02 (or more than 0.04 when the metal substrate 1 contains Mg), Even if it is set appropriately, there is a high risk that it will be difficult to obtain sufficient bonding strength, but the oxygen concentration ratio X is intentionally set to a low oxygen concentration so that it falls within the above range. This is because good bonding strength can be obtained by depositing the adhesion layer 2 in a film forming atmosphere.

Here, as shown in FIG. 2, nickel (Ni), tin (Sn), mixed state of copper and nickel (Cu—Ni), copper, nickel and zinc (Cu—Ni—) are formed on the adhesive layer 3. It is good also as a structure further equipped with the protective layer 4 which consists of a sputtered film which has as a main component at least any one of the mixed state of Zn), and the mixed state of copper and zinc (Cu-Zn).
When the protective layer 4 is made of copper and nickel (Cu—Ni), it is desirable that the nickel (Ni) concentration be 10 wt% or more and 60 wt% or less. This is because when the nickel (Ni) concentration is 60 wt% or more, the amount of use of the alloy target material for the nickel (Ni) is increased, the time required for the film forming process is increased, and the like. This is because inconveniences such as a deterioration in throughput and an increase in manufacturing cost occur, and the material of the protective layer 4 to be formed becomes a ferromagnetic material. Ferromagnetic materials generally have a strong tendency to decrease the film formation rate by sputtering, and are likely to cause a further deterioration in throughput. Further, if the entire protective layer 4 formed is a ferromagnetic material, the ferromagnetism may be a hindrance in some cases, and when this surface-treated metal material is used, for example, a member or material for electronic parts This is because there is a possibility of inconvenience that it is difficult to use as a plate.
Therefore, by using a Cu—Ni sputtered film instead of a Ni single sputtered film, the resulting protective layer 4 is a paramagnetic material, and thus it is possible to form a film without reducing the sputtering rate. In addition, it is possible to make the material magnetically neutral and easy to use.
Further, about 40 wt% of zinc (Zn) may be added to copper and nickel (Cu—Ni). By doing in this way, it becomes possible to achieve further cost reduction, and this protective layer 4 can also be provided with a function as a so-called sacrificial anticorrosive layer.

Alternatively, instead of the protective layer 4, the adhesive layer 3 may be made of a plating film containing copper (Cu), nickel (Ni), or zinc (Zn) as a main component. In addition, the protective layer 4 can be formed by, for example, a vapor deposition method.
In addition, as shown in FIG. 3, tin (Sn), tin-zinc (Sn—Zn), tin-silver is formed on the adhesive layer 3 (or on the protective layer 4 although not shown). It is good also as a structure further provided with the solder layer 5 formed by plating the tin alloy of the composition corresponding to a solder use like (Sn-Ag). By providing the solder layer 5 as described above, it is possible to further enhance the solder wettability on the surface of the surface-treated metal material according to the embodiment of the present invention.

  The main flow of the manufacturing method of the surface-treated metal material having the laminated structure shown in FIG. 1 is that the metal base material 1 to be treated is not subjected to pickling treatment (that is, the surface is naturally oxidized). In a state where a passive film such as an aluminum (Al) layer is still formed, the film is stored in a chamber of a film forming apparatus such as a sputtering apparatus (not shown; the same applies hereinafter). Then, the adhesion layer 2 is formed by a vapor phase method so that chromium (Cr) is a main component and the internal residual stress of the sputtered film becomes a compressive stress or substantially zero. Subsequently, on the adhesion layer 2, copper (Cu), a mixed state of copper and nickel (Cu—Ni), a mixed state of copper and zinc (Cu—Zn), copper, nickel and zinc (Cu—Ni—). The adhesive layer 3 mainly composed of at least one of the mixed states of Zn) is formed. The main process conditions in the sputter film formation are that oxygen is intentionally excluded so that the oxygen concentration is 0.001% or less, an inert gas such as argon (Ar) gas is the main component, and the pressure is Even when the material of the layer to be formed is switched from the adhesive layer 2 to the adhesive layer 3 while maintaining the film formation atmosphere at 1.5 Pa or less, sputtering is continuously performed in the same chamber maintaining the film formation atmosphere. That is to form a film. Here, it is needless to say that an inert element other than Ar as described above can be applied as the inert gas used as the main component of the film formation atmosphere. However, even in that case, it is necessary to keep the oxygen concentration in the film forming atmosphere at a very low concentration such as 0.001% or less as described above.

According to such a surface-treated metal material and a manufacturing method thereof according to the embodiment of the present invention, in a state where a passive film such as a natural oxide film is present on the outermost surface of the metal substrate 1, Since the adhesion layer 2, the adhesive layer 3, and the like can be laminated thereon, it is basically unnecessary to perform the pickling treatment on the outermost surface of the metal substrate 1.
Further, since the adhesion layer 2 and the adhesive layer 3 are formed in this order on the surface of the metal substrate 1, and further, the protective layer 4 and the solder layer 5 are formed on the adhesive layer 3, By providing, the wettability with respect to a solder can be improved significantly. As a result, soldering with sufficient bonding strength using so-called lead-free solder that does not contain lead (Pb) or the like, which is a RoHs-regulated substance, even if flux with weak activity or no flux is used at all. Is possible.

In addition, the thickness of the adhesion layer 2 made of chromium (Cr) is 10 nm or more and 500 nm or less, and the thickness of the adhesive layer 3 is an appropriate thickness of 15 nm or more. As a surface treatment structure for use, it is much thinner than the conventional general thickness. As a result, the adhesion layer 2 and the adhesion layer 3 can be formed in a short time, and as a result, an improvement in throughput and a reduction in manufacturing costs are achieved.
Further, by forming the protective layer 4, it is possible to suppress the formation of an oxide film on the outermost surface of the adhesive layer 3, and as a result, the bonding strength to the solder can be enhanced. Further, by adding copper (Cu) to nickel (Ni) as a forming material, it is possible to reduce material costs and improve sputtering efficiency. Alternatively, by adding copper (Cu) zinc (Zn), it is possible to obtain a reduction in material cost and a sacrificial anticorrosive effect. Alternatively, by using a Cu—Ni—Zn ternary material, it is possible to simultaneously achieve the three effects of solder wettability, material cost reduction, and sacrificial anticorrosive effect.
In addition, the adhesive layer 3 is made of a mixture or alloy of copper and nickel (Cu—Ni), or a mixture or alloy of Cu—Ni—Zn, thereby obtaining the effect of suppressing oxidation of the outermost surface of the adhesive layer 3. It becomes possible. Further, diffusion of the adhesive layer 3 can be suppressed by adding nickel (Ni). As a result, it is possible to expect an increase in bonding strength with respect to the solder. Further, by adding zinc (Zn), a sacrificial anticorrosive effect can be obtained, whereby it is possible to further improve the corrosion resistance and durability of the outermost surface of the surface-treated metal material.

  In short, according to the surface-treated metal material and the manufacturing method thereof according to the embodiment of the present invention, the adhesion layer 2 and the adhesion layer 3 are formed on the surface of the metal substrate 1 in this order. On the surface of the metal substrate 1 that has a passive film on the outermost surface, such as aluminum (Al), aluminum alloy or stainless steel, which is originally a material that is difficult to plate and is difficult to solder. Even if the passive film is not pickled and removed, the adhesive layer 2 and the adhesive layer 3 can be formed in this order to give good solder wettability and bonding strength against soldering. In addition, since the adhesion layer 2 and the adhesive layer 3 that exhibit such good actions and effects can be formed in a short time and at low cost, the throughput of the surface-treated metal material according to the embodiment of the present invention can be reduced. Improvements and cost reductions can be achieved.

As the material of the adhesion layer 2, in addition to the above chromium (Cr), detailed description is omitted here, but niobium (Nb) and titanium (Ti) can also be applied. The inventor of the present invention has confirmed by various experiments and discussions about the experiments. Therefore, the difference in performance of the adhesion layer 2 obtained corresponding to each of these materials (titanium (Ti), niobium (Nb), chromium (Cr)) will be briefly described here.
When these materials are arranged in ascending order of influence from hydrogen gas, they are in the order of chromium (Cr) <niobium (Nb) <titanium (Ti). It is chromium (Cr) that has the least adverse effect caused by hydrogen gas. Therefore, when there are concerns about adverse effects due to the hydrogen gas environment, it is desirable to select chromium (Cr) as the material of the adhesion layer 2. In particular, when the adhesion layer 2 is formed of chromium (Cr) (that is, in the case of the surface-treated metal material and the manufacturing method thereof according to the embodiment of the present invention), there is almost no performance degradation due to hydrogen gas. It is assumed that
Further, when arranged in ascending order of influence of strain application, niobium (Nb) <titanium (Ti) <chromium (Cr). Therefore, if there is a concern about the occurrence of large strain applied due to processing with plastic deformation on the workpiece, such as press molding using a mold or press punching, the adhesion layer As the material of 2, it is desirable to select niobium (Nb).
Further, when the adhesion layer 2 is formed, if the materials of the adhesion layer 2 are arranged in order of softness, niobium (Nb) <titanium (Ti) <chromium (Cr). For example, when an aluminum (Al) plate is used as the metal substrate 1, the surface treatment provided with the adhesion layer 2 is made by making the adhesion layer 2 made of a hard material such as chromium (Cr) or titanium (Ti). When press working or the like is performed on a metal material using a press die, the wear of the press die is likely to be accelerated. From such a viewpoint, it is desirable to select a material that is as soft as possible. Therefore, in such a case, it is desirable to select niobium (Nb).
In addition, for reference in consideration of material costs, chromium (Cr) <titanium (Ti) <
Niobium (Nb). Therefore, for example, when it is required to make the material cost as low as possible, it is desirable to select chromium (Cr).
Considering the advantages and disadvantages of each material, the best selection may be made according to the purpose at that time.

  Various types of surface-treated metal materials as described in the above embodiment were produced by changing the various specifications by the above manufacturing method, and this was used as a sample according to the example. In addition, for comparison with them, a surface-treated metal material with a specification / manufacturing method different from the above embodiment was also prepared separately, and this was used as a sample according to a comparative example. Then, using these samples, the solder wettability and the bonding strength of each of them were evaluated.

(Sample preparation)
The metal base 1 is prepared in two types of aluminum (Al) and stainless steel, and the adhesion layer 2 and the adhesive layer 3 are formed on the surface by the structure and the manufacturing method described in the above embodiment. Treated metal materials were prepared and their performance and the like were evaluated.
A representative aluminum (Al) system is A1050 which is pure aluminum (Al). As a variation, A5052 containing Mg was also prepared for the same experiment (this A5052 will be described later).
The stainless steel material was SUS301. A plate-shaped material having a thickness of 0.15 mm was prepared for each type. The surface of these metal substrates 1 was not subjected to pickling treatment, and the subsequent sputter film formation and the like were performed with the passive film remaining on the outermost surface.

The sputter film formation process was performed using a DC magnetron sputtering apparatus (ULVAC, Inc., model: SH-350). The atmosphere (film formation atmosphere) for forming each film was argon (Ar) gas having a pressure of 0.3 Pa or more and 9 Pa or less. The direct current power (input energy) input to the target material was appropriately adjusted according to the type of metal. The thickness of each film was controlled by measuring the average film formation speed in advance for each metal species and adjusting the film formation time. On the surface of the metal substrate 1, the adhesion layer 2, the adhesion layer 3, and, in some cases, the protective layer 4 and the solder layer 5 are formed in this order, and oxygen is also changed when the metal type is changed. The series of film forming steps were continuously performed in the same chamber so that (or air such as indoor atmosphere) was not mixed. The purity of the argon (Ar) gas during the film formation was 99.999% or more, and each film formation step was performed while a constant flow rate was continuously maintained while maintaining the purity. The oxygen concentration in the film-forming atmosphere at that time was set to 0.001% or less.
In addition, the film formation atmosphere used in the preparation of the sample according to the comparative example was two kinds of gases, argon (Ar) + oxygen mixed gas and pure argon (Ar) gas. Adjustment of the oxygen content in these film-forming atmospheres was performed by adjusting the flow rate ratio.

(Sample experiment method and evaluation method)
(1) Evaluation of solder wettability;
As a solder material, a tin-0.7 wt% copper (Sn-0.7 wt% Cu) alloy, which is a Pb-free solder, is used, and each sample is manufactured by using a Tamura Seisakusho (model: serial number 2015) by a meniscograph method. A specimen with a width of 10 mm cut out from the specimen was immersed in a flux (HOZAN model H-728) and immersed in a solder bath maintained at a temperature of 220 ° C. for 2 mm at an immersion speed of 2 mm / second. The time (zero crossing time) until the surface of the film became wet with solder and was in a state where a so-called solder coating was applied was measured. Based on the time, the solder wettability of each sample was evaluated according to the criteria shown below. This evaluation method shows that the shorter the time, the better the solder wettability.
: Less than 5 seconds
○: Less than 5-7 seconds
Δ: Less than 7 to 10 seconds
×: 10 seconds or more
(The above symbols ◎, ○, △, × are listed in the corresponding column of each table)

(2) Evaluation of initial solder joint strength (initial evaluation immediately after film formation);
Each test piece having a surface coated with a solder coating by the method described in (1) above is repeatedly bent at a bending diameter of 10 mm, and the number of times until the solder coat film peels off from the surface of the test piece is counted. Thus, the bonding strength was evaluated. In this evaluation method, repeated bending was performed up to 5 times, and the bonding strength was evaluated according to the following criteria.
◎: No peeling even 5 times
○: peeled 3-4 times
Δ: No peeling until the first bending, but peeling the second time
×: Cannot be evaluated due to peeling or soldering failure before bending
(The above symbols ◎, ○, △, × are listed in the corresponding column of each table)

(3) Evaluation of solder wettability after strain application;
Bending strain and tensile strain were applied to each sample. First, bending strain was applied. Specifically, bending strain was applied four times by a method of winding a sample around a pipe having a diameter of 15 mm (equivalent to plate thickness / diameter = 0.15 / 15 = 0.01 → 1% in terms of strain). In the second application, after the first (first) bending application, the sample is turned over so that the tension application surface (outer surface of the plate material) and the compression application surface (inner surface of the plate material) are switched. . Similarly, the sample was turned upside down for the third time and bent at the same sample position as the first time. The fourth time, the sample was turned over after the third bending, and bent at the same sample position as the second time. After the fourth bending, a tension was applied and the elongation of the sample was about 10%, and then the sample was released from the tension to complete the strain application. Then, the test of the solder wettability of each sample was performed according to the same method and standard as the above (2), and the evaluation was performed.

(4) Evaluation of solder joint strength after hydrogen test (after hydrogen pressure test);
In order to investigate the hydrogen embrittlement characteristics of each sample, each sample subjected to solder coating was sealed in a hydrogen (H) gas atmosphere environment of 1 MPa and 80 ° C. for 24 hours, and then described in (2) above. The solder joint strength of each sample was evaluated according to the same method and standard as those.

(5) Measurement of oxygen intensity ratio X;
The oxygen content concentration of the material at the interface (about 5 nm in thickness) between the adhesion layer 2 and the adhesion layer 3 was measured as an oxygen intensity ratio X by spectroscopic analysis. However, the interface (the thickness is about 5 nm) between the metal substrate 1 and the adhesion layer 2 and the outermost surface (the thickness is about 5 nm) of the adhesive layer 3 are excluded from the measurement. Specifically, argon etching is performed at a resolution of 2 nm using a photoelectron spectrometer, and the oxygen intensity ratio X value defined by the following formula is a peak value near the interface between the adhesion layer 2 and the adhesion layer 3. Asked.
Oxygen strength ratio X = oxygen strength / {strength of oxygen (O) + strength of chromium (Cr) constituting adhesion layer 2 + strength of copper (Cu) + strength of nickel (Ni) and zinc (Zn)}
And when the value of the oxygen intensity ratio X as a result of the oxygen content concentration by the spectroscopic analysis is X ≦ 0.02, “O” is indicated, and X> 0.02 is indicated as “X” (the symbols “O” and “ It is described in the corresponding column of each table).

(6) Evaluation of internal residual stress of the adhesion layer;
The internal residual stress after deposition of the adhesion layer 2 is generally determined according to various process conditions such as the material, film thickness, gas pressure during deposition, and oxygen concentration in the gas component. Varies widely from compression to compression.
Evaluation of the internal residual stress in the film | membrane of the adhesion layer 2 formed into a film was performed by the cantilever method.
The cantilever method (reference, attached: magazine vacuum J.VAC.Soc.JPN Vol.50, No6.2007, P432) is a method of applying film formation to a sheet with known mechanical properties, fixing one end, The internal stress of the film is obtained based on the deformation direction and the deformation amount of the sheet. Here, evaluation was performed so as to determine whether the stress inside the film was compression or tension. The internal residual stress of the deposited adhesion layer 2 depends mainly on the gas pressure and film thickness at the time of film formation. For this reason, an experiment was conducted in advance to evaluate whether the stress of the film is compressive or tensile under the same gas pressure and film thickness settings as the sample preparation, and based on the data, under various process conditions. It was judged (evaluated) whether the internal residual stress of the adhesion layer 2 in each of the produced samples was compression, tension, or almost zero.

  Table 1 summarizes and summarizes the evaluation results of the internal residual stress in each adhesion layer 2 for a plurality of typical samples prepared under different process conditions in accordance with such a determination method. It is a thing. Based on the evaluation results shown in Table 1, it was determined whether the internal residual stress of the adhesion layer 2 in each sample was tensile, zero, or compression. For example, taking the case shown in the second row of Table 1 as an example, if the gas in the film formation atmosphere in the sputtering process is 1.2 Pa argon (Ar) gas, the film is formed by the sputtering process. The internal residual stress in the adhesion layer 2 made of chromium (Cr) is determined to be zero when the film thickness is 15 nm, 20 nm, and 60 nm, and to be compressed when the film thickness is 120 nm, 300 nm, and 500 nm.

(Experimental results and evaluation results using each sample)
(1) When the metal substrate is a pure aluminum (Al) material;
Table 2 shows the internal residual stress of the adhesion layer 2 in a surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. The evaluation result in the case of the samples 101-107 made into stress is collectively shown as the 1st group. Here, the sample number given to each sample is given for convenience for identification of each sample, and some sort of meaning such as priority order is given to the permutation or number itself. It goes without saying that it is not. However, focusing on the purpose intended in each experiment, each sample prepared and evaluated for the same purpose shall be put together into one group, and the prefix number of the sample number shall be the number of that group. It has been granted. For example, since each sample of the first group (sample numbers 101 to 107; hereinafter referred to as samples 101 to 107) is the first group, the third digit of the sample number is 1. Yes, as the numbers after the second digit, numbers indicating the arrangement order are given as 01, 02, 03... That is, for example, if the sample number is 103, it means that it is the third sample of the first group (this also applies to Table 3 and later).

According to the results shown in Table 2, when the internal residual stress of the adhesion layer 2 is tensile, the solder joint strength is insufficient (denoted by x) regardless of the film thickness of the adhesion layer 2. It was confirmed that Further, when the adhesion layer 2 was not provided (sample 101), the bonding strength was insufficient (denoted by x).
From this result, in the case of a surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. It was confirmed that the solder joint strength was insufficient for the tensile stress regardless of other settings such as the thickness of the adhesion layer 2 being 10 nm or more.

  Table 3 shows that the film thickness of the adhesive layer 3 is 20 nm in the surface-treated metal material having a structure in which the adhesion layer 2 and the adhesive layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. The evaluation results of the samples 201 to 205 when the internal residual stress of the adhesion layer 2 is unified to zero and the film thickness of the adhesion layer 2 is variously changed are collectively shown as a second group.

  From the results shown in Table 3, it was confirmed that the initial solder joint strength is insufficient when the thickness of the adhesion layer 2 is as thin as 5 nm and as thick as 250 nm. In addition, it was confirmed that the wettability after strain application tends to decrease when the film thickness of the adhesion layer 2 is increased, with a film thickness of 500 nm as a boundary. Moreover, it was confirmed that the joint strength after the hydrogen test shows a tendency to decrease as the film thickness of the adhesion layer 2 increases.

  Table 4 shows zero internal residual stress in the adhesion layer 2 in the surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. In addition, the film thickness of the adhesion layer 2 is 10 nm (third group), 120 nm (fourth group), and 500 nm (fifth group), and the film thickness of the adhesive layer 3 is variously changed within the range of 10 to 500 nm (10 nm). , 15 nm, 60 nm, 120 nm, 500 nm).

From the results shown in Table 4, when the adhesive layer 3 is less than 15 nm, even if the thickness of the adhesive layer 2 is changed within the range of 10 to 500 nm, the solder joint strength is insufficient, and the film of the adhesive layer 3 It was confirmed that good solder joint strength and solder wettability can be achieved when the thickness is 15 nm or more.
In particular, according to the results of the samples of the fourth group and the fifth group, it was confirmed that when the film thickness of the adhesion layer 2 is 500 nm or less, the solder joint strength does not decrease after the hydrogen test.

  Table 5 shows compression of the internal residual stress of the adhesion layer 2 in the surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. The thickness of the adhesion layer 2 is 10 nm (sixth group), 120 nm (seventh group), and 500 nm, and the thickness of the adhesive layer 3 is variously changed within a range of 10 to 200 nm (10 nm, 15 nm, 60 nm, 120 nm, and 200 nm) are collectively shown.

From the results shown in Table 5, when the internal residual stress of the adhesion layer 2 is compressed and the adhesive layer 3 is 15 nm or more, the solder wettability and the solder joint strength are Δ or more (to ○, ◎). It was confirmed. It was also confirmed that the wettability after applying the strain was also good.
Moreover, it was confirmed that if the thickness of the adhesion layer 2 is within the range of 10 to 500 nm, the solder wettability is good. Further, when the adhesion layer 2 is within the thickness range, the initial bonding strength is substantially good.
In addition, it was confirmed that the solder joint strength after the hydrogen test was almost unchanged from the initial stage.

  Table 6 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When unified with copper-10 wt% nickel (Cu-10 wt% Ni) and the protective layer 4 is made of nickel (Ni) sputtered film (group 9), tin (Sn) sputtered film (group 10) ), Evaluation results of copper-60 wt% nickel (Cu-60 wt% Ni) sputtered film (group 11), and copper-20 wt% nickel (Cu-20 wt% Ni) sputtered film (group 12) Is summarized.

  From the results shown in Table 6, the thickness of the adhesion layer 2 is set to a thickness in the range of 10 nm to 500 nm and the thickness of the adhesive layer 3 made of copper-10 wt% nickel (Cu-10 wt% Ni). By setting the internal residual stress of the adhesion layer 2 to zero or compression, and providing the protective layer 4 of the material (composition) as described above, the performance can be further improved for all performance items. Was confirmed.

  Table 7 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When pure copper (Cu) is unified and the protective layer 4 is not provided, and when the material of the protective layer 4 is a copper-20 wt% nickel (Cu-20 wt% Ni) sputtered film (group 13), copper-5 wt % Nickel (Cu-5 wt% Ni) sputtered film (group 14), copper-5 wt% nickel-10 wt% zinc (Cu-5 wt% Ni-10 wt% Zn) sputtered film (group 15) In the case of a copper-10 wt% nickel-20 wt% zinc (Cu-10 wt% Ni-20 wt% Zn) sputtered film (16th group), a copper-20 wt% zinc (Cu-20 wt% Zn) sputtered film ( 17th group) It illustrates summarized the results of evaluation of the sample.

From the results shown in Table 7, the thickness of the adhesion layer 2 made of pure copper (Cu) is set to a thickness in the range of 10 nm to 500 nm, and the thickness of the adhesion layer 3 is set to 15 nm or more. It was confirmed that good performance can be achieved for all performance items by setting the internal residual stress to zero or compression and providing the protective layer 4 made of the material (composition) as described above.
In addition, by using pure copper (Cu), which is lower in material cost than the copper-nickel (Cu—Ni) system, as the material of the adhesive layer 3, the entire manufacturing cost including the material cost can be reduced without causing a decrease in performance. It can also be expected to achieve lower costs.

  Table 8 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When the protective layer 4 is not provided (samples 1801, 1802) and the protective layer 4 is made of copper-10 wt% nickel-40 wt% zinc (Cu-10 wt) % Ni-40wt% Zn) sputtered film (group 18) and copper-20wt% zinc (Zn) (Cu-20wt% Zn) sputtered film (group 19) are shown collectively. It is a thing.

From the results shown in Table 8, the thickness of the adhesive layer 2 is set to a thickness in the range of 10 nm to 500 nm, and the thickness of the adhesive layer 3 made of the above material is set to 15 nm or more. It was confirmed that good performance can be achieved for almost all performance items by setting the internal residual stress of 2 to zero or compression and providing the protective layer 4 made of each material (composition) as described above.
Further, by using copper-40 wt% nickel (Cu-40 wt% Ni) as the material of the adhesive layer 3, the material cost is higher than when pure copper (Cu) is used, but the solder wettability is further increased. Improvements can be achieved.
Further, by using a copper-zinc (Cu-Ni-Zn) alloy containing zinc (Zn), which is lower in material cost than a copper-nickel (Cu-Ni) system, as a material for the protective layer 4, performance can be improved. It can be expected that the manufacturing cost including the material cost can be reduced without causing a decrease.

  Table 9 shows that the protective layer 4 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When made of a −10 wt% nickel—40 wt% zinc (Cu—10 wt% Ni—40 wt% Zn) alloy and the material of the adhesive layer 3 is a copper—5 wt% zinc (Cu—5 wt% Zn) sputtered film ( 20th group), copper-5 wt% zinc-10 wt% nickel (Cu-5 wt% Zn-10 wt% Ni) sputtered film (21st group), copper-10 wt% zinc-10 wt% nickel (Cu-10 wt%) When Zn-10 wt% Ni) sputtered film (group 22), and when the adhesive layer 3 is made of nickel-free copper-10 wt% zinc (Cu-10 wt% Zn) sputtered film and the protective layer 4 is not provided Sample 2301) and case of the nickel (Ni) sputtering film (23 group), in which are summarized the results of evaluation of each sample.

From the results shown in Table 9, by using a material containing zinc (Zn) as a material for forming the adhesive layer 3 and the protective layer 4, various performances are as described above except for wettability after strain application. Although it may be a little lower than in the case of other structures and material settings described based on Tables 2 to 8, it was confirmed that the structure was generally good. Moreover, about material cost, it can be made cheaper than said each case.
In particular, from the results of the samples 2301 and 2302, when the material of the adhesive layer 3 is made of nickel (Ni) and contains 10 wt% or more of zinc (Zn), the solder wettability is generally good. However, it was confirmed that when the protective layer 4 is not provided (in the case of the sample 2301), the solder joint strength is insufficient, and even when the protective layer 4 is provided (in the case of the sample 2302), the solder joint strength is insufficient. .
Considering based on the results of the samples of the 23rd group and the samples of the 20th group, the 21st group, and the 22nd group, by adding about 10 wt% of nickel (Ni), there is no nickel (Ni). It has been found that the solder joint strength can be improved more than the case, and zinc (Zn) can be added up to about 10 wt%.

  Table 10 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3, and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. Copper—10 wt% nickel (Cu—10 wt% Ni) is used, and the protective layer 4 is made of either a nickel (Ni) sputtered film or a copper—40 wt% nickel (Cu—40 wt% Ni) sputtered film. When the oxygen concentration in the argon (Ar) gas used as the atmosphere gas at the time of film formation is set to 0.05% which is more than 0.001% and 0.005% (both are oxygen intensity of the finished sample) The evaluation results of the ratio X exceeds 0.02 are collectively shown.

  From the results shown in Table 10, when the oxygen concentration contained in the inert atmosphere gas at the time of sputtering film formation is more than 0.001%, the oxygen intensity ratio X of the finished sample becomes more than 0.02. It was confirmed that the initial solder joint strength was insufficient regardless of the settings of other structures, film thicknesses and various process conditions.

(2) When the metal substrate is a stainless steel (SUS) material;
Table 11 shows the internal residual stress of the adhesion layer 2 in a surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. The evaluation results in the case of stressed samples 2501 to 2507 are collectively shown as the 25th group.

According to the results shown in Table 11, when the internal residual stress of the adhesion layer 2 is tensile, the solder joint strength is insufficient (indicated by x) regardless of the film thickness of the adhesion layer 2. It was confirmed that Further, it was confirmed that the bonding strength was insufficient even when the adhesion layer 2 was not provided (sample 2501).
From this result, in the case of a surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. 1, the adhesion layer 2 is completely present. It was confirmed that the solder joint strength is insufficient regardless of other settings including the material of the metal base material 1 when there is not, or when the internal residual stress of the adhesion layer 2 is a tensile stress.

Table 12 shows that the film thickness of the adhesive layer 3 is 20 nm in the surface-treated metal material having a structure in which the adhesion layer 2 and the adhesive layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. In addition to unifying, the internal residual stress of the adhesion layer 2 is unified to zero, and the evaluation results when the film thickness of the adhesion layer 2 is variously changed are collectively shown.

  From the results shown in Table 12, it was confirmed that the initial solder joint strength is insufficient when the thickness of the adhesion layer 2 is as thin as 5 nm and as thick as 550 nm. Further, it was confirmed that the wettability after applying the strain shows a tendency to decrease when the film thickness of the adhesion layer 2 becomes thicker than 500 nm. Moreover, it was confirmed that the joint strength after the hydrogen test shows a tendency to decrease as the film thickness of the adhesion layer 2 increases.

  Table 13 shows zero internal residual stress in the adhesion layer 2 in the surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. In addition, the film thickness of the adhesion layer 2 is 10 nm (group 27), 120 nm (group 28), and 500 nm (group 29), and the film thickness of the adhesive layer 3 is variously changed within the range of 10 to 200 nm (10 nm). , 15 nm, 60 nm, 120 nm, 200 nm).

From the results shown in Table 13, when the adhesive layer 3 is less than 15 nm, even if the thickness of the adhesive layer 2 is changed within the range of 10 to 500 nm, the solder joint strength is insufficient, and the film of the adhesive layer 3 It was confirmed that good solder joint strength and solder wettability can be achieved when the thickness is 15 nm or more. However, according to the result of the 29th group in which the adhesive layer 3 is 500 nm in particular, the wettability after applying the strain is greatly reduced.
Further, it was confirmed that the solder joint strength did not decrease after the hydrogen test, and the initial solder joint strength was substantially maintained.

  Table 14 shows compression of the internal residual stress of the adhesion layer 2 in the surface-treated metal material having a structure in which the adhesion layer 2 and the adhesion layer 3 are laminated on the surface of the metal substrate 1 as shown in FIG. The thickness of the adhesion layer 2 is changed to 10 nm (30th group), 120 nm (31st group), and 500 nm (32nd group), and the thickness of the adhesive layer 3 is variously changed within a range of 10 to 200 nm. The evaluation results in the case of (10 nm, 15 nm, 60 nm, 120 nm, 200 nm) are collectively shown.

From the results shown in Table 14, when the internal residual stress of the adhesion layer 2 is compressed and the adhesive layer 3 is 15 nm or more, the solder wettability and the solder joint strength are Δ or more (˜ ○, ◎). It was confirmed.
In addition, no decrease in solder joint strength after the hydrogen test occurred.

  In particular, in the results of the samples according to the comparative example of the thirty-second group, the wettability after applying the strain, which is estimated to be caused by increasing the thickness of the adhesion layer 2 to 500 nm, occurred. Also from this, it is considered that the film thickness of the adhesion layer 2 is desirably 500 nm or less.

  Table 15 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When unified with copper-10 wt% nickel (Cu-10 wt% Ni) and the protective layer 4 is made of a nickel (Ni) sputtered film (group 33), a tin (Sn) sputtered film (group 34) ), Evaluation results of copper-60 wt% nickel (Cu-60 wt% Ni) sputtered film (group 35), copper-20 wt% nickel (Cu-20 wt% Ni) sputtered film (group 36) Is summarized.

  From the results shown in Table 15, the thickness of the adhesion layer 2 is set to a thickness in the range of 10 nm to 500 nm and the thickness of the adhesive layer 3 made of copper-10 wt% nickel (Cu-10 wt% Ni). By setting the internal residual stress of the adhesion layer 2 to zero or compression, and providing the protective layer 4 of the material (composition) as described above, the performance can be further improved for all performance items. Was confirmed.

  Table 16 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When pure copper (Cu) is unified and the protective layer 4 is not provided, and when the material of the protective layer 4 is a copper-20 wt% nickel (Cu-20 wt% Ni) sputtered film (group 37), copper-5 wt % Nickel (Cu-5 wt% Ni) sputtered film (group 38), copper-5 wt% nickel-10 wt% zinc (Cu-5 wt% Ni-10 wt% Zn) sputtered film (group 39) In the case of a copper-10 wt% nickel-20 wt% zinc (Cu-10 wt% Ni-20 wt% Zn) sputtered film (group 40), a copper-20 wt% zinc (Cu-20 wt% Zn) sputtered film ( 41st group) It illustrates summarized evaluation results of each sample.

From the results shown in Table 16, the thickness of the adhesion layer 2 made of pure copper (Cu) is set to a thickness in the range of 10 nm to 500 nm, and the thickness of the adhesion layer 3 is set to 15 nm or more. It was confirmed that good performance can be achieved for all performance items by setting the internal residual stress to zero or compression and providing the protective layer 4 made of the material (composition) as described above.
In addition, by using pure copper (Cu), which is lower in material cost than the copper-nickel (Cu—Ni) system, as the material of the adhesive layer 3, the entire manufacturing cost including the material cost can be reduced without causing a decrease in performance. It can also be expected to achieve lower costs.

  Table 17 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When copper-40 wt% nickel (Cu-40 wt% Ni) is unified and the protective layer 4 is not provided (samples 4201, 4202), and the material of the protective layer 4 is copper-40 wt% zinc (Cu-40 wt% Zn) sputtering. In the case of a film (group 42), the evaluation results when the material of the protective layer 4 is a copper-20 wt% zinc (Zn) (Cu-20 wt% Zn) sputtered film (group 43) are summarized. It is.

From the results shown in Table 17, the adhesion layer 2 has a thickness in the range of 10 nm to 500 nm, and the adhesion layer 3 made of the above material has a thickness of 15 nm or more. It was confirmed that good performance can be achieved for all performance items by setting the internal residual stress of 2 to zero or compression and providing the protective layer 4 made of each material (composition) as described above.
Further, by using copper-40 wt% nickel (Cu-40 wt% Ni) as the material of the adhesive layer 3, the material cost is higher than when pure copper (Cu) is used, but the solder wettability is further increased. Improvements can be achieved.
Further, the use of a copper-zinc (Cu-Zn) alloy containing zinc (Zn), which has a lower material cost than that of the copper-nickel (Cu-Ni) system, as the material of the protective layer 4 reduces the performance. It can be expected that the entire manufacturing cost including the material cost will be reduced without being generated.

  Table 18 shows the protective layer 4 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. When made of a −10 wt% nickel—40 wt% zinc (Cu—10 wt% Ni—40 wt% Zn) alloy and the material of the adhesive layer 3 is a copper—5 wt% zinc (Cu—5 wt% Zn) sputtered film ( (Group 44), copper-5 wt% zinc-10 wt% nickel (Cu-5 wt% Zn-10 wt% Ni) sputtered film (group 45), copper-10 wt% zinc-10 wt% nickel (Cu-10 wt%) In the case of a Zn-10 wt% Ni) sputtered film (the 46th group), and when the adhesive layer 3 is made of a copper-10 wt% zinc (Cu-10 wt% Zn) sputtered film without nickel and the protective layer 4 is not provided And when a nickel (Ni) sputtering film (47 group), in which are summarized the results of evaluation of each sample.

From the results shown in Table 18, by using a material containing zinc (Zn) as the forming material of the adhesive layer 3 and the protective layer 4, various performances are the above except for the solder wettability after strain application. Although it may be a little lower than in the case of other structures and material settings described based on Tables 11 to 17 in the above, it was confirmed that the structure was generally good. In addition, the material cost is expected to be lower than in the above cases.
In particular, from the results of samples 4701 and 4702, when the material of the adhesive layer 3 is made of nickel (Ni) and contains 10 wt% or more of zinc (Zn), the solder wettability is generally good. However, it was confirmed that when the protective layer 4 is not provided (in the case of the sample 4701), the solder joint strength is insufficient, and even when the protective layer 4 is provided (in the case of the sample 4702), the solder joint strength is insufficient. .
Then, considering the results of the samples of the 47th group and the results of the samples of the 44th, 45th, and 46th groups, by adding about 10 wt% nickel (Ni) to the material of the adhesive layer 3 It was found that the solder joint strength can be improved as compared with the case without nickel (Ni) and that zinc (Zn) can be added up to about 10 wt%.

  Table 19 shows the material of the adhesive layer 3 in the surface-treated metal material having a structure in which the adhesion layer 2, the adhesive layer 3 and the protective layer 4 are laminated on the surface of the metal substrate 1 as shown in FIG. Copper—10 wt% nickel (Cu—10 wt% Ni) is used, and the protective layer 4 is made of either a nickel (Ni) sputtered film or a copper—40 wt% nickel (Cu—40 wt% Ni) sputtered film. When the oxygen concentration in the argon (Ar) gas used as the atmosphere gas at the time of film formation is 0.05% exceeding 0.001% and 0.005% (both are oxygen intensity ratios of the finished sample) X is a summary of the evaluation results of more than 0.02.

  From the results shown in Table 19, when the oxygen concentration contained in the inert atmosphere gas at the time of sputtering film formation is more than 0.001%, the oxygen intensity ratio X of the finished sample becomes more than 0.02. It was confirmed that the initial solder joint strength was insufficient regardless of the settings of other structures, film thicknesses and various process conditions.

(3) When a solder layer made of a plating film is used instead of the protective layer;
After producing a surface-treated metal material having a structure as shown in FIG. 1, a solder layer 5 was formed by electrolytic plating.
Table 20 summarizes and summarizes the evaluation results of various performances of the sample of the surface-treated metal material obtained by forming the solder layer 5 by the plating method.
As the metal substrate 1, three types of pure aluminum (Al), stainless steel (SUS), and titanium (Ti) were prepared.
Then, an adhesion layer 2 on the surface of the metal substrate 1 and an adhesive layer 3 on the surface are formed by sputtering, and a protective layer made of the above-described sputtered film is further formed on the surface of the adhesive layer 3. Instead of 4, the solder layer 5 was formed by electrolytic plating.
The results are summarized and shown in Table 20.

In the 49th group, the material of the adhesive layer 3 is copper-10 wt% nickel (Cu-10 wt% Ni), and the material of the solder layer 5 is tin (Sn). The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 1 μm or 5 μm. The adhesion layer 2 has compressive stress.
In the sample of the 50th group, the material of the adhesive layer 3 is copper-10 wt% nickel-20 wt% zinc (Cu
−10 wt% Ni-20 wt% Zn), and the solder layer 5 is made of tin (Sn). The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 1 μm or 5 μm. The adhesion layer 2 has compressive stress.
In the 51st group, the adhesive layer 3 is made of copper-40 wt% nickel (Cu-40 wt% Ni), and the solder layer 5 is made of tin (Sn). The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 5 μm. The adhesion layer 2 was set to zero stress.
In the 52nd group, the material of the adhesive layer 3 is copper-40 wt% nickel (Cu-40 wt% Ni), and the material of the solder layer 5 is tin-9 wt% zinc (Sn-9 wt% Zn). . The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 5 μm. The adhesion layer 2 was set to zero stress.
In the 53rd group, the material of the adhesive layer 3 is copper-40 wt% nickel (Cu-40 wt% Ni), and the material of the solder layer 5 is tin-5 wt% bismuth (Sn-5 wt% Bi). . The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 5 μm. The adhesion layer 2 was set to zero stress.
In the 54th group, the material of the adhesive layer 3 is copper-40 wt% nickel (Cu-40 wt% Ni), and the material of the solder layer 5 is tin-1 wt% silver (Sn-1 wt% Ag). . The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 5 μm. The adhesion layer 2 was set to zero stress.
In the 55th group, the metal substrate 1 is only one kind of aluminum alloy (A5052), the material of the adhesive layer 3 is copper-10 wt% nickel (Cu-10 wt% Ni), and the material of the solder layer 5 is tin. −9 wt% zinc (Sn-9 wt% Zn). The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 1 μm or 5 μm. The adhesion layer 2 has compressive stress.
In the 56th group, the material of the adhesive layer 3 is copper (Cu), and the material of the solder layer 5 is nickel (Ni). The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 0.3 μm or 5 μm. The adhesion layer 2 has compressive stress.
In the sample of the 57th group, the material of the adhesive layer 3 is copper-10 wt% nickel-20 wt% zinc (Cu-10 wt% Ni-20 wt% Zn), and the solder layer 5 is nickel (Ni). . The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 0.3 μm or 5 μm. The adhesion layer 2 has compressive stress.
In the sample of the 58th group, the material of the adhesive layer 3 is copper (Cu), and the material of the solder layer 5 is zinc (Zn). The film thickness of the adhesion layer 2 was 20 nm or 60 nm, the film thickness of the adhesive layer 3 was 15 nm or 60 nm, and the film thickness of the solder layer 5 was 0.3 μm. The adhesion layer 2 was set to zero stress.
In the 59th group, the adhesive layer 3 is made of copper-40 wt% nickel (Cu-40 wt% Ni), and the solder layer 5 is made of copper (Cu). The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 0.3 μm. The adhesion layer 2 was set to zero stress.
In the 60th group, the metal substrate 1 is only one kind of aluminum alloy (A5052), the material of the adhesive layer 3 is copper-10 wt% nickel (Cu-10 wt% Ni), and the material of the solder layer 5 is nickel. (Ni). The film thickness of the adhesion layer 2 was 20 nm, the film thickness of the adhesive layer 3 was 60 nm, and the film thickness of the solder layer 5 was 0.3 μm or 5 μm. The adhesion layer 2 has compressive stress.

From the experimental results of such a sample, solder wettability and initial solder joint strength are further stabilized by forming a solder layer 5 by a plating method such as electrolytic plating instead of the protective layer 4 made of a sputtered film. It was confirmed that it was extremely good. In addition, it was confirmed that the solder wettability after application of strain was also good.
That is, by forming the solder layer 5 by a plating method such as an electrolytic plating method, an extremely thick solder layer 5 having a thickness of μm as a protective film can be formed with a good throughput. Further improvement in solder joint strength can be achieved without increasing the cost. In addition, the solder wettability, the initial bonding strength, and the wettability after applying strain can be improved.
Here, as a material for forming the solder layer 5, in addition to the above, tin-silver (Sn-Ag), tin-zinc (Sn-zinc), zinc (Zn), or the like can also be used as a plating material. is there.

From the above results, the main items are extracted and summarized as follows.
The film thickness of the adhesion layer 2 is desirably 10 nm or more and 500 nm or less. If it is thinner than 10 nm, there is a high possibility that the solder wettability will be insufficient. Conversely, if it is thicker than 500 nm, solder wettability after application of strain may be reduced. However, even if it is thicker than 500 nm, there is no problem with an adverse effect (hydrogen embrittlement) due to hydrogen.
The film thickness of the adhesive layer 3 is desirably 15 nm or more. If it is thinner than 15 nm, there is a high possibility that both the solder wettability and the solder joint strength will be insufficient. Moreover, when it is thicker than 200 nm, it tends to be weak against strain application.
Moreover, as a material of the adhesive layer 3, copper-10 wt% nickel (Cu-10 wt% Ni) can be cited as the most typical one. In particular, by adding nickel (Ni), solder wettability is improved. Tend to. However, good solder wettability and solder joint strength can be obtained even when pure copper (Cu) is used and nickel (Ni) is not used. Further, copper-40 wt% nickel (Cu-40 wt% Ni) can be said to be the upper limit of the nickel (Ni) content.
Moreover, solder wettability can be ensured by using copper-5 wt% zinc (Cu-5 wt% Zn). Further, by using a ternary composition of copper-5 wt% nickel-10 wt% Zn (Cu-5 wt% Ni-10 wt% Zn), sacrificial anticorrosive effect by adding zinc (Zn) and by adding nickel (Ni) It is possible to achieve both the improvement of solder wettability.

Even if the film thickness of the protective layer 4 and the film thickness of the solder layer 5 are thicker than 5 μm, in terms of performance as the protective layer 4 itself, in addition to the increase in manufacturing cost including the material cost. There are no disadvantages.
When nickel (Ni) alone is used as the material of the protective layer 4, the film forming process and material cost may increase, but the performance can be used without problems.
Further, when copper-60 wt% nickel (Cu-60 wt% Ni) is used, there is no problem in terms of performance, and there is an advantage that it is slightly cheaper than nickel (Ni) alone.
Alternatively, when copper-20 wt% nickel (Cu-20 wt% Ni) is used, there is no problem in terms of performance, and there is an advantage that it is cheaper than nickel (Ni) alone.
Further, when copper-5 wt% nickel (Cu-5 wt% Ni) is used and when tin (Sn) is used, there is no problem in terms of performance, and there is an advantage that the cost is significantly lower than that of nickel (Ni) alone.
Also, when using copper-5 wt% nickel-10 wt% Zn (Cu-5 wt% Ni-10 wt% Zn) and using copper-10 wt% nickel-20 wt% Zn (Cu-10 wt% Ni-20 wt% Zn) Has the merit that the zinc (Zn) component functions as a sacrificial anticorrosive material, and also has the merit that it contributes to the enhancement of solder wettability.
In addition, when copper-20 wt% zinc (Cu-20 wt% Zn) is used, there is a merit that the zinc (Zn) component functions as a sacrificial anticorrosive material, and it can contribute to the reduction of the manufacturing cost including the material cost. There is a merit. However, depending on the case, solder wettability may be reduced.
Copper-10 wt% nickel-40 wt% zinc (Cu-10 wt% Ni-40 wt% Zn) is a large amount of zinc (Zn) when the adhesive layer 3 is required to have a sufficient function as a sacrificial anticorrosive. There is a merit that the addition of components can be performed.

In the surface-treated metal material according to the present invention, the adhesion layer 2 is made of chromium (Cr). However, there is no risk of adverse effects due to so-called hydrogen embrittlement in a hydrogen environment. This is the first advantage of using chromium (Cr) for the adhesion layer 2.
If no significant strain is applied, there is no problem if the thickness of the adhesion layer 2 is 500 nm or less. However, when strain is applied, for example, when machining is performed by a die press method, the film thickness is less than 500 nm, preferably less than 120 nm, and there is a high possibility that application is not possible. Also, there is a risk that the wear of the press die is promoted.
Chromium (Cr) has the most advantageous characteristics in terms of the reduction in manufacturing cost, mainly the material cost on the left, among the above metal materials, and is therefore the cheapest in terms of material cost. is there.

  It is desirable that the oxygen concentration in the deposition atmosphere of the adhesion layer 2 is intentionally reduced to 0.001% or less. This is because, for example, if it exceeds 0.001%, the oxygen strength ratio X of the finished adhesion layer 2 exceeds 0.02, and there is a high possibility that both the solder wettability and the solder joint strength will decrease.

Then, by performing sputter deposition in such a low oxygen concentration deposition atmosphere, when the metal substrate 1 is pure aluminum (Al), stainless steel (SUS), or titanium (Ti). It is desirable that the oxygen intensity ratio X of the adhesion layer 2 obtained by sputtering film formation is 0.02 or less.
This is because if the oxygen strength ratio X is more than 0.02, there is a high possibility that the initial solder joint strength will be insufficient, regardless of other settings such as the structure, film thickness, and various process conditions.

However, here, when the metal substrate 1 is made of an alloy containing magnesium (Mg), such as A5052, which is a kind of aluminum alloy, the oxygen strength ratio X of the adhesion layer 2 is obtained by sputtering film formation. Is preferably 0.04 or less.
That is, the metal substrate 1 is made of magnesium (Mg) -containing aluminum alloy (A5052) instead of pure aluminum (Al), and all other configurations / experimental conditions are made of pure aluminum (Al The sample was prepared with the same setting as that of the above. And the experiment about the case where the oxygen intensity ratio X was 0.04 or less using the sample, and the case where it exceeded 0.04 was conducted, and the result was examined. However, the solder joint strength after hydrogen treatment was omitted. Table 21, Table 22, and Table 23 summarize and summarize the results.

From the experimental results shown in Table 21, Table 22, and Table 23, when the metal substrate 1 is an aluminum alloy containing magnesium (Mg) (A5052), the oxygen strength ratio X in the completed adhesion layer 2 is When the metal substrate 1 is pure aluminum (Al), the solder wettability and the initial solder jointability are good when the oxygen base ratio X is 0.02 or less. It was confirmed that In contrast, when the oxygen intensity ratio X exceeds 0.04, the structure, film thickness, various process conditions, etc. other than that are the same as when the metal substrate 1 is pure aluminum (Al). Regardless of the setting,
It was confirmed that the initial solder joint strength was insufficient.
From these results, when the metal substrate 1 is made of an alloy containing magnesium (Mg), such as A5052, which is a kind of aluminum alloy, the adhesion layer 2 is formed by sputtering film formation. It was confirmed that the oxygen intensity ratio X is desirably 0.04 or less.

In the surface-treated metal material and the method for producing the same according to the present invention, by providing at least the adhesion layer 2 and the adhesive layer 3 on the surface of the metal substrate 1 having the passive film on the outermost surface, Since the lead (Pb) -free solder can be joined using a flux with weak activity, the surface-treated metal material and the manufacturing method thereof according to the invention can be used in the product field as exemplified below. It is assumed that this is suitable.
(1) It is necessary to heat-join aluminum (Al) materials with lead (Pb) -free solder, for example, a heat exchanger, a heat sink, a heat dissipation material, or the like.
(2) A cross fin tube type heat exchanger, a heat sink, a heat radiating material, etc., which require heat bonding of aluminum (Al) fins and copper tube material with lead (Pb) free solder.
(3) A heat exchanger, a heat sink, a heat radiating material, etc., which requires heat bonding of stainless steel (SUS) or titanium (Ti) with lead (Pb) free solder.
(4) By forming a laminated structure including at least the adhesion layer 2 and the adhesion layer 3 according to the present invention on the outer layer of the aluminum (Al) wire, bonding such as terminal connection using lead (Pb) -free solder is also possible. Surface-treated aluminum wire.
(5) Copper (Cu) wire is soldered to an aluminum (Al) material, a stainless steel (SUS) material, or a titanium (Ti) material that has been subjected to surface treatment to provide at least the adhesion layer 2 and the adhesion layer 3 according to the present invention. Wiring materials, antenna materials, etc.
(6) An aluminum (Al) bus bar material, a flat conductor, a titanium conductor material, a stainless steel conductor material, etc., which are subjected to a surface treatment of providing at least the adhesion layer 2 and the adhesive layer 3 according to the present invention.
(7) A plate material for crimping terminals for connecting various electric wires and the like produced by processing an aluminum (Al) material that has been subjected to a surface treatment of providing at least the adhesion layer 2 and the adhesive layer 3 according to the present invention.
However, the above is an example, and it is needless to say that the scope of application of the present invention is not limited to the above.

It is a figure which shows typically the main laminated structure of the surface treatment metal material which concerns on embodiment of this invention. It is a figure which shows typically the laminated structure which further provided the protective layer formed by sputter film-forming on the adhesion layer of the surface treatment metal material shown in FIG. It is a figure which shows typically the laminated structure which further provided the protective layer formed by plating-film-forming on the adhesion layer of the surface treatment metal material shown in FIG.

Explanation of symbols

1 Metal substrate 2 Adhesion layer 3 Adhesion layer 4 Protective layer 5 Solder layer

Claims (10)

On the surface of the metal substrate having a passive film on the outermost layer, in order from the surface side of the metal substrate,
An adhesion layer comprising a sputtered film mainly composed of chromium (Cr), and the internal residual stress of the film is a compressive stress or substantially zero;
At least one of copper (Cu), a mixed state of copper and nickel (Cu—Ni), a mixed state of copper and zinc (Cu—Zn), and a mixed state of copper, nickel and zinc (Cu—Ni—Zn) A surface-treated metal material formed by forming an adhesive layer made of a sputtered film having one kind as a main component. The surface-treated metal material according to claim 1,
Oxygen (O) strength / (oxygen (O) strength + chromium of the adhesion layer (measured at a resolution of 2 nm by XPS or Auger analysis spectroscopic method at the interface between the adhesion layer and the adhesion layer) (Cr) strength + strength of component elements of the adhesive layer) = oxygen strength ratio X defined by X is X ≦ 0.02. The surface-treated metal material according to claim 1,
The metal substrate is made of a material intentionally added with magnesium (Mg),
Oxygen (O) strength / (oxygen (O) strength + chromium of the adhesion layer (measured at a resolution of 2 nm by XPS or Auger analysis spectroscopic method at the interface between the adhesion layer and the adhesion layer) (Cr) strength + strength of component elements of the adhesive layer) = oxygen strength ratio X defined by X is X ≦ 0.04. In the surface-treated metal material according to any one of claims 1 to 3,
A surface-treated metal material, wherein the adhesion layer has an average thickness of 10 nm to 500 nm. In the surface-treated metal material according to any one of claims 1 to 4,
The surface-treated metal material characterized in that an average thickness of the adhesive layer is 15 nm or more. In the surface-treated metal material according to any one of claims 1 to 5,
On the adhesive layer, nickel (Ni), tin (Sn), mixed state of copper and nickel (Cu—Ni), mixed state of copper, nickel and zinc (Cu—Ni—Zn), copper and zinc (Cu A surface-treated metal material, further comprising a protective layer made of a sputtered film containing as a main component at least one of the mixed state of -Zn). In the surface-treated metal material according to any one of claims 1 to 5,
A surface-treated metal material further comprising a protective layer made of a plating film containing copper (Cu), nickel (Ni), or zinc (Zn) as a main component on the adhesive layer. In the surface-treated metal material according to any one of claims 1 to 7,
A surface-treated metal material, further comprising a solder layer formed by plating tin (Sn) or a tin alloy having a composition suitable for a solder application on the adhesive layer or the protective layer. On the surface of the metal substrate having a passive film on the outermost layer, it is composed of a sputtered film containing chromium (Cr) as a main component in order from the surface side of the metal substrate, and the internal residual stress of the film is a compressive stress or Adhesion layer which is substantially zero, mixed state of copper (Cu), copper and nickel (Cu—Ni), mixed state of copper and zinc (Cu—Zn), copper, nickel and zinc (Cu—Ni—Zn) An inert gas deposition atmosphere in which oxygen is intentionally excluded even when the material of the layer to be deposited is switched between the adhesive layer made of a sputtered film whose main component is at least one of the mixed states. A method for producing a surface-treated metal material, comprising a step of continuously performing sputter deposition in the same chamber maintained. In the manufacturing method of the surface treatment metal material of Claim 9,
Argon (Ar) gas is used as an inert gas in the film formation atmosphere, the oxygen concentration in the film formation atmosphere is 0.001% or less, and the pressure in the film formation atmosphere is 1.5 Pa or less. A method for producing a surface-treated metal material.

Images