JP2000012762A - Electrical/electronic equipment component material superior in corrosion resistance and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electrical/electronic equipment component material which is superior in resistance against corrosion and oxidation. SOLUTION: An Ni or an Ni alloy film as thick as 0.2 μm or above is formed on one part or over the entire surface of an electrical/electronic equipment part material formed of Cu or Cu alloy material or a Fe alloy material, the crystal orientation planes (220) and (111) of an Ni or an Ni alloy film are obtained from the diffractions of X-rays impinging vertically on the surface of an electrical/electronic equipment part material with an Ni or an Ni alloy film on its surface, and the diffraction intensity ratio of the diffraction intensity I(220) of the crystal orientation plane (220) to the diffraction intensity I(111) of the crystal orientation plane (111), or the diffraction intensity ratio I(220)/I(111) is set at 0.5:1 or above, or the diffracted intensity ratio I(220)/I(200) is set at 0.5:1 or above.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a component or a material used for electric and electronic equipment and a method for manufacturing the same.

[0002]

2. Description of the Related Art Conventionally, Fe-based materials, Cu or Cu alloy materials have been used as lead materials for lead wires, lead pins, lead frames and the like for individual semiconductors and integrated circuit packages. Further, it is used as a conductive material for terminals of sockets, connectors, switches, and contact springs. These are conductive and thermal conductive, mechanical strength and workability,
Both of them make use of the excellent properties of Cu-based and Fe-Ni-based alloys such as corrosion resistance and economy. In recent years, the development of semiconductor integrated circuit technology, circuit formation technology, and component mounting technology has been remarkable, and various alloys have been developed for materials frequently used for these, particularly Cu alloy materials for use as lead materials for semiconductor packages. It is also being applied to contact material applications such as contact springs. Many of these are used after being subjected to various surface treatments such as plating in order to improve the reliability of component materials.

[0003] For example, among the above-mentioned applications, an IC lead frame requiring many required characteristics and strict reliability will be described below as an example. An example of the cross section is shown in FIG. 1 and an example of the plane is shown in FIG. 2. As shown in FIG. Is die-bonded through the adhesive layer 3 of FIG. Then, the electrode pad 4 on the element and the inner lead end 5 of the frame are wire-bonded via a thin metal wire 6 such as Au. Further, these are sealed and molded with a resin 7 such as epoxy, and most of the outer lead portions 8 of the frame are made of Sn or Sn-Pb.
Packages are made after plating and other processing such as bending.

For example, an old Kovar alloy (Fe—Ni—Co type) or 42
In addition to Fe-Ni alloys typified by alloys, recently, various Cu alloy materials having improved various properties have been frequently used. Fe-Ni alloys are inferior in thermal conductivity and electrical conductivity, but have high mechanical strength and a coefficient of thermal expansion close to that of silicon chips and encapsulating materials, while Cu-based materials are good conductors of heat and electricity. This is because the strength, which was conventionally poor, has been dramatically improved in recent years. In particular, Cu-based materials require higher-strength, higher-conductivity lead frames and contact materials as semiconductor packages, wiring materials, and joining parts become denser and smaller. Various precipitation hardening type copper alloys have been developed and used in which the alloy elements are finely precipitated in a copper matrix to improve strength and electrical conductivity. Specific examples of these copper alloys are shown below.

[0005] Cu-Sn type (for example, 4Sn-0.1P,
6Sn-0.1P, 8Sn-0.1P, 3.5Sn-
0.2Cr-0.1P), Cu-Zn type (Example 10Z)
n), Cu-Fe system (Example 2.4Fe-0.3Zn-0.
04P, 1.5Fe-0.6Sn-0.8Co-0.1
P, 1Fe-0.5Sn-0.5Zn-0.02P,
0.1Fe-0.03P), Cu-Co type (Example 0.3C
o-0.1P), Cu-Ni-Sn system (Example 9.5Ni-
2.3Sn, 0.1Ni-2.5Sn-0.1P), C
u-Zr type (Example 0.15Zr), Cu-Sn-Cr type (Example 0.25Sn-0.25Cr-0.2Zn, 0.1
5Sn-0.1Cr), Cu-Be-based (Example 1.7Be-
0.3Co, 0.5Be-2.5Co), Cu-Ni-
Si-based (Example 3Ni-0.6Si-0.52Zn) and the like.

[0006] These component materials used in electric and electronic equipment have many secondary properties mainly related to surface properties, such as oxidation resistance and bonding, in addition to the aforementioned primary properties such as conductivity and strength. In many cases, it is used after treating the entire surface or a part of the surface or forming a surface film such as plating, because of the necessity of such properties as solderability, solderability, contact characteristics, moldability, and corrosion resistance. Since these surface properties are important properties that greatly affect the manufacturing process and final performance of electrical and electronic component products, various improvement proposals have been made conventionally. The main one is film formation by plating, and many proposals have been made and put to practical use.

[0007] The surface morphology of such lead frame products conventionally put to practical use can be summarized as follows. That is, partial Ag plating on the inner lead portion or die pad portion to be wire-bonded, partial Ag plating via underlying Cu plating or underlying Ni plating, or overall Ni plating. On the other hand, methods of omitting noble metal plating and performing wire bonding directly on a substrate with Au fine wires have been used for only a few simple transistors and the like, but are not widely used because of poor reliability. Regardless of the presence or absence of plating, the outer lead portion after resin molding is provided with Sn or Sn for soldering.
-Pb plating has been applied.

Incidentally, lead frames which have recently come into practical use include Japanese Patent Publication No. Sho 63-49382 and Japanese Patent Laid-Open No.
No. 5558, the entire surface of the lead frame is covered with Ni
Alternatively, some of them are plated with Pd via Ni alloy plating, and some are further plated with Au thereafter. Since these can be directly soldered together with bonding, they have many advantages such as no need to apply Sn-Pb plating or the like to the outer lead portions in advance, and are expected to be applied to various semiconductor packages in the future. In addition to lead frame applications, Ni plating is applied to contact materials such as lead wires and contact terminals for hermetic terminals such as individual semiconductors of diodes and transistors, ICs, capacitors, resistors, crystal oscillators, etc. Ag, Au, or P
Cu or Cu with a plating film such as d or Pd alloy formed
Alloy and Fe-based alloy members are also used, and like the noble metal-plated lead frames, these tend to become more widespread in the future.

[0009]

The Ni or Ni alloy film formed on the Cu or Cu alloy or Fe-based alloy substrate has no pinholes and is smooth regardless of whether or not a film is formed on the Ni or Ni alloy film. It is desirable to have a coating that uniformly covers the entire surface of the substrate. This is because in the heating process that is always present in the subsequent component manufacturing process, if there is a pinhole, copper oxide appears on the surface layer due to thermal oxidation, reducing wire bonding property, moldability, solder wettability, and corrosion resistance over time. Because they are connected. However, 1) substrate-side factors such as material defects of the substrate or elements and compounds dispersed and precipitated on the substrate surface, and 2) a process generally based on neutralizing acid activity after degreasing. Although used for pretreatment, although the oxide layer on the surface is removed, the amorphous or fine crystal layer on the top layer of the work-affected layer remains, so that the crystal grains become too fine and the coating is easily cut. For such reasons, it always has a pinhole. In addition, since the Ni plating is generally a columnar crystal, there is a relatively large amount of microporosity smaller than that of the pinhole. In the case where the upper layer plating is further performed after the Ni plating, the plating solution permeates and remains from the pinholes during the plating, so that the reliability of the subsequent parts is reduced.

A particularly serious problem is that, after forming a Ni or Ni alloy film on a Cu or Cu alloy or Fe-based alloy substrate, a noble metal or noble metal alloy layer coating is further formed thereon. This is the case for parts or materials. These are the product forms that are about to grow significantly in the future as described above, but due to the fact that the unipolar potential difference between the respective coating elements is too large, it is far more compared to the case of the base barrier coating such as Ni alone. There is a problem that the corrosion resistance is easily reduced, the oxidation resistance during heating is lowered, and various properties such as wire bonding property and solder wettability are reduced. Even in packaged parts such as semiconductors, connectors, and switches, where lead members and contact members are used, moisture and trace anions that gradually penetrate into the interior are present, and although they are barrier coatings for substrates,
Through the pinholes of the Ni or Ni alloy film which cannot be avoided as described above, the base material components Cu and Fe are oxidized by a large unipolar potential difference from the noble metal in the upper layer as a driving force and cause a corrosion reaction, thereby causing corrosion. In severe cases, the test may be accompanied by the formation of patina or red rust. In particular, as described above, the transition from Ag plating to Pd plating, or from Pd plating to Au thin layer plating, results in a further increase in the unipolar potential difference between the base material and the outermost noble metal element. It is becoming a big problem. Corrosion resistance of the conventionally used contact members plated with Ni and then plated with Au, particularly gas corrosion degradation due to the exposure atmosphere, remains a serious problem.

On the other hand, as described above, the size and size of the pinholes in the substrate barrier coating often largely depend on the material. Usually, the material has various surface defects, and since there are residual oxides and elements that cannot be removed by ordinary plating pretreatment, plating defects are likely to occur in such places. In the case where a material in which various alloy elements are precipitated in a substrate matrix for the purpose of high strength and high conductivity in recent years is used, the cause of plating defects is further increased. In the above-mentioned Fe-Ni, Fe-Ni-Co alloys and various Cu alloys, oxides of additional metals are also formed on the surface layer by heat treatment during the manufacturing process, atmospheric oxidation, and internal oxidation. In the case of, a large number of fine crystallized and precipitated intermetallic compounds, oxides and elements are dispersed and precipitated in the surface layer or the matrix of the base material. These oxides and crystallization,
Since many of the precipitates are hardly soluble, they hinder the surface treatment. Residuals on these surfaces make it difficult to clean the component material surface and remove the oxide film, and when forming a surface film such as plating, it is likely to cause film defects such as pinholes, non-plating, and electrodeposition on protrusions. The result is a significant loss of corrosion resistance.

As described above, the presence of the pinholes in the barrier film not only causes the base material to be corroded with the noble metal, but also causes post-curing after die bonding in a packaging process and the like, and heat history after molding to prevent the base material element from being damaged. The harmful effect of oxidizing is also caused. Since the base material oxide greatly deteriorates the bonding property, the moldability, particularly the solderability, it leads to the problem that the heating conditions in the packaging step are restricted. In these cases where the base element is corroded, potential difference corrosion can easily occur even if the upper layer is a noble metal film if the Ni or Ni alloy film to be the barrier film has no film defects such as pinholes. You can think that there is no. In view of this, a method is conceivable in which the plating film is made thicker than originally required to prevent pinholes and the like. However, as mentioned above,
Even if a general columnar crystal type Ni-based coating is formed thickly, the microporosity does not disappear, so the corrosion resistance and oxidation resistance still remain unimproved, and fundamentally improved parts materials and solutions are required. I was As described above, a component material for an electric / electronic device in which a Ni or Ni alloy barrier coating is formed on a substrate made of Cu or a Cu alloy or an Fe-based alloy particularly used for an electric / electronic device, or furthermore, Part materials with a noble metal or noble metal alloy coated on the upper layer have a problem that they are particularly inferior in corrosion resistance and oxidation resistance, and properties of noble metals or platinum group elements, which are likely to be frequently used in the future, and component materials and their final products With the spread of the use environment of, for example, the high humidity, high chloride atmosphere, and the highly corrosive environment of the strong acid rain in the Southeast Asia region where the electronic component factories are growing, the tendency has been that the problem will become more and more serious in the future.

[0013]

SUMMARY OF THE INVENTION The present invention has been made in view of such current and future trends, and has at least one Ni or Ni alloy coating film having excellent corrosion resistance frequently used in electric and electronic equipment applications. In addition to the electrical or electronic equipment component material or Ni or Ni alloy coating, and further having at least one noble metal or noble metal alloy layer on the surface layer, in addition to corrosion resistance, oxidation resistance during heating, wire bonding property, solder wettability Such as Cu or Cu alloy, or Fe
It is an object of the present invention to provide a component material for electric and electronic devices, which is composed of a system alloy, and a method for producing the same.

That is, the present invention relates to (1) Cu or Cu
At least one layer of Ni or a Ni alloy film is provided on a part or the entire surface of a component material for electric / electronic equipment composed of an alloy base material or an Fe alloy base material, and the total thickness of the coating is 0. In a component material for electrical and electronic equipment having a thickness of 2 μm or more, the crystal orientation plane (2) of a Ni or Ni alloy film obtained from X-ray diffraction perpendicularly or substantially perpendicularly incident on the surface.
20) the diffraction intensity of the plane I ₍₂₂₀₎ and (111) diffraction intensity ratio of the diffraction intensity I ₍₁₁₁₎ of the plane I ₍₂₂₀₎ / or I ₍₁₁₁₎ is 0.5 or more, or the diffraction intensity I _{( 220)} and (200) plane component material for electrical and electronic equipment having excellent corrosion resistance, wherein the diffraction intensity ratio I ₍₂₂₀₎ / I ₍₂₀₀₎ is 0.5 or more between the diffraction intensity I ₍₂₀₀₎ of, (2) In the electrical / electronic device component material, at least one noble metal or noble metal alloy coating is further provided on the Ni or Ni alloy coating, and the total thickness of the noble metal or noble metal alloy coating is 0.
Characterized in that it is not less than 01 μm and not more than 1 μm (1)
Component materials for electrical and electronic equipment with excellent corrosion resistance described in section
(3) The main elements of the noble metal or noble metal alloy are Au and A
g or Pd, wherein the component material for electrical and electronic equipment having excellent corrosion resistance according to item (2), (4) a Cu or Cu alloy substrate, or an Fe alloy substrate A component material for an electric / electronic device having at least one layer of Ni or a Ni alloy plating film on at least a part or the entire surface of the component material for an electric / electronic device or further having at least one layer of a noble metal or a noble metal alloy film is manufactured. Prior to the formation of the Ni or Ni alloy plating film, the steps of alkali cathode degreasing treatment, substrate surface dissolution treatment, alkali anode treatment, and pickling treatment are performed at least once each in the order of →→→. (1), (2) or (3), a method for producing a component material for electrical and electronic equipment having excellent corrosion resistance, and (5) a method for dissolving the base material surface layer. When the treatment liquid used for the treatment contains at least one or more of an acid, a peroxide, a soluble fluoride and a persulfate, and contains an acid and a peroxide, the treatment liquid (4) A method for producing a component material for electric / electronic equipment having excellent corrosion resistance according to the item (4), wherein the content ratio is acid / peroxide ≧ 0.5 (molar ratio). . The Ni
Alternatively, the formation of the Ni alloy film is performed at a cathode current density of 15 A / d.
It is preferable to perform plating by m ^{2 to} 40 A / dm ² . The formation of the Ni or Ni alloy film is performed at a liquid temperature of 10 ° C.
° C. It is preferably carried out by plating using a plating solution to 45 ° C., it is preferably performed by plating using the plating solution of the Ni concentration ^{10g / dm 3 ~50g / dm 3} . Further, the main elements of the noble metal or noble metal alloy are Au, A
It is preferable that at least one of g and Pd be used for parts.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The base material of the present invention in the above items (1) to (5) is made of Cu or a Cu alloy, an Fe-Ni alloy, or an Fe-based alloy such as an Fe-Ni-Co alloy or stainless steel. Can be Among the Ni or Ni alloy of at least one layer formed on the surface of the base material or the surface layer of the base material of the present invention, the Ni alloy includes Ni-Co, Ni-Pd, Ni-P, and Ni-B.
An alloy such as this is used. In addition, N formed on the substrate
The noble metal or noble metal alloy further coated at least one layer on the upper layer of the i or Ni alloy coating is, for example, Au, P
Cu such as t, Ir, Pd, Ag, Rh, Ru, Os
Noble metals and platinum group elements with a standard unipolar potential, and alloys thereof, Au-Ag, Pd-Au, Pd-Ag, P
It refers to d-Ni or the like, and a suitable type according to various electric and electronic device applications is appropriately selected and applied. However, in practice, A
It is preferable to use g, Au, Pd, or an alloy containing one or more of these as main elements (components).

In the present invention, the total thickness of the Ni or Ni alloy coating is set to 0.2 μm or more. If the thickness is less than 0.2 μm, the crystal orientation plane (220) is not sufficiently formed even if pretreatment is performed because the thickness is too thin and the number of pinholes is large. There is no particular upper limit, but the thickness of the coating is determined in consideration of the cost and performance of the parts used, and is usually at most about 3 to 5 μm, and at most 1 to 2 μm for bending applications.
It is desirable to stop at. Further, when a noble metal or noble metal alloy coating is provided, its thickness is set to 0.01 to 1 μm. The reason is that if it is too thin, it will not satisfy the characteristics of electric and electronic devices such as wire bonding properties, solderability, and contact characteristics, and if it is too thick, the cost increases, which is not preferable. This is because, depending on the alloy, cracking of the coating or peeling from the underlying Ni or Ni alloy coating may occur.

The present inventors have conducted various studies and found that Ni
Alternatively, the crystal orientation plane (220) formed on the Ni alloy film is a surface on which atoms are gathered at a high density and the film is formed while growing two-dimensionally, so that it is smooth, has good leveling properties, and has excellent corrosion resistance. And the crystal orientation plane (22
0) plane diffraction intensity I ₍₂₂₀₎ and (111) plane or (2)
It has been found that the value indicated by the ratio to the ₍ 00) plane diffraction intensity I ₍₁₁₁₎ or I ₍₂₀₀₎ corresponds to the corrosion resistance of the surface plating film. Such a (220) plane is more than a certain ratio,
In the richly formed Ni or Ni alloy coating, pinholes and microporosity, which are likely to occur in the columnar crystal type of the (111) plane and the (200) plane which are simply formed by stacking atoms into a packing structure, are observed. Disappears. on the other hand,
In a normal plating film formation not using the Ni powder or the method disclosed in the present invention, the (111) plane >> (200) plane >>
Orientation occurs in the order of> (220) plane. Therefore, the (220) plane is not rich. Corrosion resistance performance level required for component materials for use in electrical and electronic equipment of the present invention is, as described above, in the crystal orientation plane of Ni or Ni alloy coating obtained from X-ray diffraction perpendicularly or substantially perpendicularly incident.
I ₍₂₂₀₎ / I ₍₁₁₁₎ ≧ 0.5 or I ₍₂₂₀₎ /
This corresponds to the case where I ₍₂₀₀₎ ≧ 0.5. (Here, “substantially perpendicular” means within a range that forms an angle of 10 ° with the perpendicular direction.) When a Ni or Ni alloy barrier film under such conditions is formed, a film having few pinholes and porosity is inevitably formed. Is done. Therefore, the above-mentioned conventional problems are solved, and when a noble metal or noble metal alloy film is formed on the upper layer, a great effect is obtained on corrosion resistance as potential difference corrosion resistance.

The specific diffraction intensity ratio of the Ni or Ni alloy film specified in the present invention is determined by performing at least an alkali cathode degreasing treatment and a substrate surface dissolution treatment prior to the formation of the Ni or Ni alloy film. And an alkali anodic treatment and an acid washing treatment in addition to the above steps. This method is based on the above steps →
Or, it is a pretreatment method in which the steps of →→→ are sequentially performed at least once each. The alkaline cathode degreasing treatment is performed by adding a surfactant and other additives to an aqueous solution such as sodium hydroxide, sodium carbonate, sodium metasilicate, and trisodium phosphate. This is to carry out electrolytic degreasing while holding.

The substrate surface layer dissolution treatment of (i) sulfuric acid or
An acid having a substrate solubility such as nitric acid, (ii) hydrogen peroxide,
Peroxides such as ozone, (iii) persulfates such as ammonium persulfate and sodium persulfate, (iv) aqueous hydrogen fluoride or acidic or neutral ammonium fluoride, acidic or neutral sodium fluoride, acidic or neutral An aqueous solution containing at least one or two or more soluble fluorides such as potassium fluoride is used. However, as described in detail below, among the acids of (i), those which can be used alone as an aqueous solution are oxidizing and substrate-soluble acids (such as nitric acid) or (iii) In the case of sulfate. These are selected depending on the type of base material, alloy composition, and product use. However, when an acid and a peroxide are contained, the content ratio is preferably set to acid / peroxide ≧ 0.5 (molar ratio). Preferred embodiments of the substrate surface layer dissolving treatment of (1) include, as a treatment liquid, 1) an acid and a peroxide, 2) an acid and a soluble fluoride, or 3) an acid, a peroxide and a soluble Or containing fluoride. in this case,
In the cases 1) and 3), the content ratio of the acid and the peroxide in the treatment liquid is preferably set to be acid / peroxide ≧ 0.5 (molar ratio). As a basic function of the substrate surface layer dissolution treatment of (1), the acid (i) has a function of dissolving the surface oxide film, and the peroxide (ii) has a function of releasing oxygen ions to oxidize the substrate. And dissolves the substrate surface layer in the presence of an acid. However, nitric acid or the like alone has oxidizing power and can be dissolved. Further, the soluble fluoride of (iv) has an action of releasing fluorine ions and decomposing and dissolving the precipitates.
When the concentration of peroxide to acid is extremely high, such as when the molar ratio of acid to peroxide is less than 0.5, an oxide film is formed on the surface instead of dissolving the substrate surface. Care must be taken because it will be oxidized by the end of the process. (ii
The persulfate of i) is used alone or in combination with (i), (ii) and (iv) as a low dissolving action or a low oxidizing action.
Usually, the immersion treatment is performed at a temperature close to room temperature. For example, in the case of ordinary copper or copper alloy, (i), (ii), (iii),
Although an aqueous solution containing any of (iv) can be used,
(I) or (ii) a 42 alloy, a Cu alloy having a high Sn content of about 4 to 10 wt%, or a Cu alloy obtained by precipitating the above-mentioned elements or intermetallic compounds to improve mechanical performance. ) Or an aqueous solution containing the soluble fluoride of (iv) together with (i) or (iii) and capable of decomposing and dissolving the precipitate is preferred. In particular, Cu-Ni-Si-based Corson alloys and Cu-Fe-P-based alloys containing hardly soluble precipitates such as Ni ₂ Si and Fe _x P are acid-peroxide-based containing fluoride, Alternatively, it is better to use an aqueous acid-persulfate solution. A known aliphatic alcohol may be added as a stabilizer to prevent or decompose peroxides such as hydrogen peroxide. These are also commercially available, such as CPB40 and CPE1000 (Mitsubishi Gas Chemical Co., Ltd.) or IC-3
33 or Evaetch CA-30 (EBARA Uzilight Co., Ltd.) or the like may be used.

The alkali anodic treatment of, for example,
This refers to a process in which the substrate is polarized toward the anode side in an aqueous solution similar to the aforementioned alkaline degreasing solution or an alkaline aqueous solution for removing smut. Thereby, the hardly soluble elements and alloys exposed on the surface, or the oxides thereof, are anodic-dissolved, and even those which are hardly anodic-eluted, due to the anodic elution of Cu, Fe, Ni and other solid-soluble components of the matrix, Alternatively, it has the effect of generating oxygen gas to physically drop the precipitated compound from the surface layer, and to remove as much as possible residual material on the surface that causes film defects such as pinholes in the film formation process such as plating. Can be done. Examples of the precipitated element include Cr, and the precipitated compound is Be-Cu, Z
r-Cu, Fe-P, Ti-Ni, Ti-Ni-Sn,
There are Ni-Si and Ni-Sn systems.

The next pickling treatment is performed after the alkali anodic treatment. According to the alkali anodic treatment, the matrix on the substrate surface and, in some cases, the precipitated elements and intermetallic compounds remaining on the surface are oxidized. Need to be activated. Therefore, pickling treatment after the anodic treatment is performed. For Cu-based alloys, a sulfuric acid aqueous solution or a soluble fluoride-containing aqueous solution is usually used, and for an Fe-based alloy, a non-oxidizing acid or a neutral dilute aqueous solution that can dissolve an oxide film, such as a hydrochloric acid aqueous solution or a sulfuric acid aqueous solution, is used. The immersion treatment is usually performed at a liquid temperature of about room temperature. Therefore, oxidizing properties such as nitric acid,
Acids having substrate solubility are not suitable for this treatment. In the present invention, performing the pretreatment of (1) to (2) is superior to the pretreatment consisting of and / or in terms of promoting preferential growth of the (220) plane.

When the processing of (1) to (4) is performed, the processing must be performed in the order of →→→. However, it is possible to perform other processing during this time or before and after.
It suffices that at least one treatment is performed in this order before a film such as plating is finally formed. That is, ~
When each of the steps is performed, the previous step is performed immediately before. For example, (1) an acid pickling step is always performed before forming a film such as plating, and (2) an alkali anodic treatment is always performed at least once after performing a substrate surface dissolution treatment.
After pickling, pickling is performed, and after the anodizing treatment, the next pickling treatment is performed without performing the substrate dissolving treatment. Before washing, the alkali anode treatment must be performed again. By performing a series of these pretreatments, the pinholes and porosity described above are reduced,
Moreover, the preferentially grown Ni of the (220) plane is excellent in corrosion resistance.
Alternatively, a Ni alloy coating is obtained. Further, it has been found that the corrosion resistance after the noble metal coating has a still greater effect as compared with the case where the pretreatment method for forming the coating is not performed. It is to be noted that a water washing treatment is required after any of the treatments, and it is desirable to carry out a washing with deionized water immediately before plating to prevent contamination of the plating solution.

For example, regarding the plating conditions, in the present invention, the cathode current density in Ni or Ni alloy plating is preferably 15 to 40 A / dm ² . The temperature of the Ni or Ni alloy plating solution is 10 to 45 ° C.
The concentration of the i-alloy plating solution is preferably 10 to 50 g / dm ³ . The corrosion resistance of the electrodeposited Ni or Ni alloy film having such plating conditions can be further improved. These plating conditions tend to allow the electrodeposition to be performed more smoothly, cover the substrate more evenly, suppress the formation of pinholes, promote preferential growth of the (220) plane, which is excellent in corrosion resistance, and promote other orientations. This results in a higher generation ratio for the surface. The higher the current density range is, the more easily a film having excellent corrosion resistance is formed. However, if the current density range is too high, the current concentration is superior, resulting in insufficient ion supply, and rather, 15 to 40 A / dm ² because pinholes and plating defects occur. Is preferred. Also, the lower the temperature of the plating solution, the better the corrosion resistance tends to be, but if the solution temperature is too low, if the current density is high, it will result in burnt-like electrodeposition, rather reducing the uniform coverage of the substrate So 1
The lower limit is 0 ° C., and the upper limit is preferably 45 ° C. as a temperature at which the smooth coatability and corrosion resistance of the coating are not deteriorated. In this temperature range, when a liquid containing a sulfamate as a main component is used, oxidative decomposition of sulfamate can be prevented. Ni or Ni
The range of the metal concentration of the alloy plating solution is limited as the lower the metal concentration, the more likely it is to obtain a plated film with less pinholes and excellent corrosion resistance. Therefore, 50 g / dm ³
It can be said that the low concentration is good, and the lower limit is preferably 10 g / dm ³ because it is necessary to maintain a certain concentration from the viewpoint of metal ion replenishment depending on the plating equipment.

When the main element of the noble metal or noble metal alloy to be formed in the present invention is at least one of Au, Ag, and Pd, these are coated on Ni or Ni alloy as a base material barrier. In particular, since the unipolar potential is high, corrosion resistance and oxidation resistance during heating tend to be particularly problematic. However, according to the constitution of the surface layer film, the film formation and the production method according to the present invention, a component material for electric and electronic equipment having excellent corrosion resistance and oxidation resistance can be obtained.

[0025]

The present invention will be described below in more detail with reference to examples. Example 1 A plate of the following Cu alloy and Fe alloy having a thickness of 0.25 mm was etched into a 28-pin 28-pin lead frame having a width of 34 mm and a length of 172 mm and used as a base for corrosion resistance evaluation. . As a lead wire evaluation, a Cu wire containing Ag having a diameter of 0.5 mm and a length of 150 mm was also used as a base material for both tests. Cu-2.3wt% Fe
-0.1wt% Zn-0.1wt% P (Cu-Fe
System), Cu-2wt% Sn-0.1wt% Fe-0.0
3wt% P (Cu-Sn-Fe system), Cu-2.5wt
% Ni-0.6 wt% Si-0.5 wt% Zn (Cu-
Ni-Si), Cu-8wt% Sn-0.2wt% P
(Cu-Sn-P type), 62wt% Cu-17wt% N
i-21 wt% Zn (Cu-Ni-Zn based), Fe-4
2wt% Ni (Fe-Ni system), Cu-0.03wt%
Ag (Cu-Ag system / wire). The following treatments were combined as the plating pretreatment. Alkaline cathode degreasing: Cleaner 160 (Meltex Co., Ltd.) 6 wt% aqueous solution, electrolytic degreasing at 60 ° C. at a cathode current density of 3 A / dm ² , base material surface dissolution treatment: as dissolution treatment solution 1)
Aqueous solution containing 10 wt% sulfuric acid and 3 wt% hydrogen peroxide, 2) aqueous solution containing 10 wt% sulfuric acid and 1 wt% ammonium acid fluoride, 3) 10 wt% sulfuric acid and 3 wt%
Three types of hydrogen peroxide and an aqueous solution containing 1 wt% ammonium ammonium fluoride were used as appropriate. In the case of performing the surface melting treatment, a 3) solution is used for the Cu-Ni-Si-based alloy and the Fe-Ni-based alloy, a 2) solution is used for the Cu-high Sn-P-based alloy, and the 1) solution is used for the others. For 20 seconds. Alkaline anodic treatment: The solution was separately prepared in a bath, and anodized at 60 ° C. with an anodic current density of 4 A / dm ² . Pickling treatment: Dipping treatment was carried out at room temperature for 30 seconds in a 10 wt% sulfuric acid aqueous solution, except for a Fe-Ni alloy, in a 5 wt% hydrochloric acid aqueous solution. The steps used were: →, →, →→, →
In each of the four cases, water washing was performed after each treatment, and deionized water washing was performed before plating. Subsequently, the cathode current density of the Ni or Ni alloy coating of the base material barrier coating was set to 8 A / dm ^{2 to} 20 A using the following plating solutions.
/ Dm ² , and the liquid temperature is 25 ° C. unless described below.
６０60 ° C., Ni concentration 30 g / dm ³ 〜90 g / dm ³
Under the conditions described above.

Ni plating solution: Ni (NH ₂ SO ₃ ) _2.
4H ₂ O 160 g / dm ³ , H ₃ BO ₃ 30 g / d
m ³ Ni-Co alloy plating _{solution: Ni (NH 2 SO 3)} 2 · 4
H ₂ O 160 g / dm ³ , Co (NH ₂ SO ₃ ) _2.
4H ₂ O 10 g / dm ³ , H ₃ BO ₃ 30 g / dm ₃
³ Ni-P alloy plating solution: NiSO ₄ · 6H ₂ O 175
g / dm ³ , H ₃ PO ₄ 50 g / dm ³ , H ₃ PO ₃
1 g / dm ³ , 75 ° C. Ni-B alloy plating solution: NiSO ₄ .6H ₂ O 175
g / dm ³ , (CH ₃ ) ₃ N · BH ₃ 50 g / dm
³ , 65 ° C Ni-Pd alloy plating solution: Parabright-TN20 (Japan High Purity Chemical Co., Ltd.)
(1) dried and used as a test material without precious metal coating,
(2) In addition, noble metal or noble metal alloy coating was performed.
The following plating solutions were used. Pd plating solution: Parabright-SST-L (Japan High Purity Chemical Co., Ltd.), 60 ° C., 3 A / dm ² Au plating solution: after plating (Japan High Purity Chemical Co., Ltd.), 50 ° C., 1 A / dm ² Ag plating solution: KAg (CN) ₂ 50 g / dm ³ , K
CN 70 g / dm ³ , KOH 10 g / dm ³ , KC
O ₃ 20 g / dm ³ , 25 ° C., 3 A / dm ² Pd-Au plating solution: AURUNA549 (Degussa Japan Co., Ltd.), 55 ° C., 0.5 A / dm ² Pd-Ag plating solution: Parabright-SST-WABP
(Japan High Purity Chemical Co., Ltd.), 65 ° C., 2 A / dm ² Pd-Ni plating solution: PdNi466 (Degussa Japan Co., Ltd.), 45 ° C., 10 A / dm ² Pt plating solution: Platanex III LS (Nippon Electron Plating Engineers), 75 ° C, 2A /
dm ² Ir plating solution: Iridex 100 (Japan Electroplating Engineers), 85 ° C., 0.15 A
/ Dm ² Rh plating solution: Rodex (Japan Electroplating Engineers), 50 ° C., 1.3 A / dm ² Ru plating solution: Lutenex (Japan Electroplating Engineers), 60 ° C., 1 A / dm ²

After washing with water and deionized water, the material was dried and dried. Examples of the present invention (Nos. 1 to 47) and comparative examples (Nos. 48 and 4) manufactured based on the above basic plating process.
9), the test materials of the conventional examples (No. 50 to 63) (each n =
Tables 1 to 3 show various conditions of 2). No. of the conventional example. 6
Ag-plated members were comparatively evaluated in Nos. 1 to 63, and a Cu strike base plating using a known Cu cyanide and Na cyanide-containing solution was performed to maintain adhesion. In addition, No. 4
5 and No. 5 No. 55 is a four-layer coating structure of Ni → Pd-Ni → Ni → Pd. 46 and no. 56 is Ni → Pd → P
It had a five-layer structure of d-Ni → Pd → Au, and the thickness of each film was measured by X-ray fluorescence to adjust the plating time. For all of the test materials, the growth surface of the Ni or Ni alloy coating was measured by the X-ray diffraction method, and the ratio of I ₍₂₂₀₎ / I ₍₁₁₁₎ to I ₍₂₂₀₎ / I ₍₂₀₀₎ was determined. It is shown in the table. X-ray is 2θ = 30 ° ～
Diffraction measurement was performed up to 100 °. The apparatus used was a Rigaku Geiger Flex RAD-B system (Rigaku Corporation) with a target of copper, an X-ray tube voltage of 40 kV, and a tube current of 30 mA. JISZ 2371 frame-shaped sample
24 hours salt spray test on Cu alloy based on
The test was performed for 3 hours for the Fe alloy. Then, as shown in the following table, the visual appearance was evaluated relatively in seven stages.
However, the evaluation of the test material having only the Ni or Ni alloy coating without the noble metal coating was stricter than the test material having the noble metal coating. The allowable level of corrosion resistance performance for electrical and electronic equipment is level 5 or higher.

[0028]

[Table 1]

[0029]

[Table 2]

[0030]

[Table 3]

As can be seen from the results of Tables 1, 2 and 3,
Conventional examples Nos. 50 to 59 have an X-ray diffraction intensity ratio I ₍₂₂₀₎ / I
_{Both (111)} and I ₍₂₂₀₎ / I ₍₂₀₀₎ are 0.5
And the corrosion resistance of the surface plating film is poor. On the other hand, Examples Nos. 1 to 47 of the present invention have I ₍₂₂₀₎ / I ₍₁₁₁₎ and I
_At least one of ₍₂₂₀₎ / I ₍₂₀₀₎ is 0.5 or more, and has good corrosion resistance. As is clear from the results of Comparative Examples Nos. 48 and 49, when the thickness of the Ni or Ni alloy coating is less than 0.2 μm, even if the X-ray diffraction intensity ratio I ₍₂₂₀₎
Even if / I ₍₁₁₁₎ and I ₍₂₂₀₎ / I ₍₂₀₀₎ were 0.5 or more, the desired surface plating film having good corrosion resistance could not be obtained. In addition, the conventional example No. As can be seen from the comparison with Nos. 61 to 63, Nos. 6 to 47 of the present invention are equivalent to the conventional examples, although the noble metal species on Ni or Ni alloy is a noble metal element having a large standard monopolar potential difference. It turns out that it has the above characteristics. In addition, they do not depend on the type of alloy, the shape of the wire or the frame. As for the pretreatment, →, →→ or →→→
, The X-ray diffraction intensity ratios I ₍₂₂₀₎ / I ₍₁₁₁₎ and / or I ₍₂₂₀₎ / I ₍₂₀₀₎ could be made 0.5 or more. In this case, no. 4 and No. 5, no. 9 and N
o. 10, No. 22 and No. 22. 23, no. 25 and N
o. 26, no. 30 and No. As is clear from the comparison of _No. 31, the X-ray diffraction intensity ratios I ₍₂₂₀₎ / I ₍₁₁₁₎ and I ₍₂₂₀₎ are higher in the case of the step →→→ than in the case of the step → or →→ in the pretreatment. / I ₍₂₀₀₎ is large, and the corrosion resistance of the surface plating film is more excellent.

Example 2 Next, with respect to a method of forming a Ni barrier film on a substrate, the corrosion resistance of a test material due to a difference in plating conditions was tested and evaluated.
The results are shown in Table 4 as 64 to No. 76. The pretreatment was performed using →→→ of Example 1, the same Ni plating solution as in Example 1 was used, and the cathode current density was 5 A / dm ² to 43.
A / dm ² , liquid temperature 8 ° C. to 50 ° C., Ni concentration 8 g / d
m ^{3 to} 70 g / dm ³ , respectively, and the frame-shaped member of Example 1 is 0.6 μm to 1.
1 μm thick Ni plating, then 0.1 μm thick P
d plated. Water washing was performed between each step, and deionized water washing was performed before plating. These were subjected to an X-ray diffraction measurement and a salt spray test in the same manner as in Example 1. Example 1
In the same manner as in the above, together with the appearance evaluation, microscopic corrosion evaluation by observation with a stereoscopic microscope was performed, and the average evaluation results are shown in the table.

[0033]

[Table 4]

As is apparent from Table 4, the test materials of the present invention all showed good corrosion resistance evaluation results in the appearance evaluation, but among the good ones, the microscopic evaluation showed Also shows a slight difference. In other words, it can be seen that under the conditions, even better corrosion resistance characteristics can be obtained depending on the Ni plating conditions, which can be obtained from the limited conditions of the cathode current density, the liquid temperature, and the Ni concentration.

[0035]

As described above in detail, the component material for electric and electronic equipment of the present invention has excellent corrosion resistance of the surface plating film.
Therefore, the use of Cu or Cu alloy, which tends to expand in the future, a barrier film such as Ni is formed on a Fe alloy base material, and a film structure in which a noble metal or a platinum group element having various properties is further coated thereon. In the member, it is possible to solve deterioration problems such as corrosion resistance and solder wettability after a heating step, which are serious problems contrary to excellent characteristics.
According to the production method of the present invention, it is possible to produce the above-mentioned novel member which is advantageous not only in the improvement of the characteristics but also in the economic efficiency.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of a package using a commonly used lead frame.

FIG. 2 is a plan view of an example of a commonly used lead frame.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Tab part 2 Element 3 Adhesive layer 4 Electrode pad 5 Inner lead end part 6 Thin metal wire 7 Resin 8 Outer lead part

Claims (5)

[Claims] At least one Ni or Ni alloy coating is provided on a part or the entire surface of a component material for electric / electronic equipment comprising a Cu or Cu alloy base or an Fe alloy base, and the coating is provided. The crystal orientation plane of the Ni or Ni alloy coating obtained by X-ray diffraction perpendicularly or substantially perpendicularly incident on the surface of the component material for electrical and electronic equipment having a total thickness of 0.2 μm or more (220) Surface diffraction intensity I
The diffraction intensity ratio I ₍₂₂₀₎ / I ₍₁₁₁₎ between the diffraction intensity I ₍₁₁₁₎ of the ₍₂₂₀₎ and (111) planes is 0.5 or more, or the diffraction intensity I ₍₂₂₀₎ and the (200) plane parts material for electrical and electronic equipment having excellent corrosion resistance, wherein the diffraction intensity ratio _{I (220) / I (200} ) is 0.5 or more between the diffraction intensity I ₍₂₀₀₎ of. 2. The electric / electronic device component material according to claim 1,
At least one layer of a noble metal or noble metal alloy coating is further provided on the Ni or Ni alloy coating, and the total thickness of the noble metal or noble metal alloy coating is 0.01 μm or more and 1
2. The component material for electrical and electronic equipment having excellent corrosion resistance according to claim 1, wherein the thickness is not more than μm. 3. The component material for electrical and electronic equipment having excellent corrosion resistance according to claim 2, wherein the main element of the noble metal or the noble metal alloy is at least one of Au, Ag, and Pd. 4. At least one layer of Ni or a Ni alloy plating film on a part or the whole surface of a component material for electric / electronic devices composed of a Cu or Cu alloy base material or an Fe alloy base material, or at least one more. In producing a component material for an electric / electronic device having one layer of a noble metal or noble metal alloy coating, prior to the formation of the Ni or Ni alloy plating film, an alkali cathode degreasing treatment, a base material surface dissolution treatment, an alkali anode treatment, an acid 4. A component material for electrical and electronic equipment having excellent corrosion resistance according to claim 1, wherein a pretreatment is carried out in which each step of the washing process is performed at least once each in the order of →→→. Method. 5. The treatment liquid used for the substrate surface layer dissolution treatment contains at least one or more of an acid, a peroxide, a soluble fluoride, and a persulfate, and 5. The component material for electrical and electronic equipment having excellent corrosion resistance according to claim 4, wherein the content ratio in the treatment liquid when acid and peroxide are included is 0.5 / molar ratio. Manufacturing method.