JPS58181888A - Silver coating material and preparation thereof - Google Patents

Abstract

PURPOSE:To enhance the close adhesiveness of a silver coating material, in the Ag coating material prepared by forming an Ag layer or an Ag alloy layer on a base member, by providing an intermediate layer comprising Zn or an alloy containing a specific amount or more of Zn between the base member and the Ag layer or the Ag alloy layer. CONSTITUTION:The surface of a base member plated with Zn or a Zn alloy with Zn content of 50% or more, for example, a Zn-Cu alloy, a Zn-Ni alloy or a Zn- Sn alloy in a thickness of 0.01-3mum and Ag or an Ag alloy is subsequently plated on the Zn or the Zn alloy layer. By this method, even if oxygen is diffused and permeated into the Ag layer or the Ag alloy layer under a high temp. environment, oxygen is inhibited by the Zn layer or the Zn alloy layer being an intermediate layer and the close adhesivensss of the base member and the Ag layer or the Ag alloy layer is not damaged.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides corrosion resistance, solderability, and other properties that do not deteriorate even when exposed to the l4i environment. This relates to a manufacturing method.

In general, Ag coating materials that form L-Ag or Ag alloys on a base material have traditionally been used for noodles because, in addition to the properties of the core material, they have the excellent corrosion resistance and solderability characteristic of Ag. There is. For example, the Affi material has a base material of Cu, Fe, Ni, or alloy wire material, and an Ag layer with a thickness of 0 Er-10 μ is formed on the material. Known as an economical performance material with excellent corrosion resistance and soldering properties, it is also used as lead material for four-piece parts and electronic *21! It is widely used as a specialized body for i-yen.

When such Ag-coated materials are subjected to a heating process such as annealing, or when used in high-temperature conditions, the oxygen in the atmosphere actively penetrates into the Ag layer. Then, the base material table Ijj′? It oxidizes, reducing the tightness between the base material and the Ag layer, resulting in low soldering strength, which impairs the reliability of the 1! bond.Especially when Cu or Cu alloy is used as the base material. In the case where the 4 material is diffused into the Ag skin, not only does the appearance of the Ag-covered 4LVi material become unsatisfactory, but also soldering has the drawback of significantly impairing the soldering properties and the gas contact resistance. In Ag 11 coating materials, the silver layer must be thicker than C1, which increases the cost of Ag coating materials by 1+%b.

The base material 52 is A in Ag coating material using Cu alloy.
In order to prevent Cu@ from diffusing into the G layer, the base material and A
A structure in which the Ni layer is made of a Ni alloy and the Ni layer is provided between the gll1 and the gll1 layer has been put into practical use. N1 or 7 alloy layer is C
Cu◆ acts as a diffusion barrier for Agjli, etc.
Table (iii) In order to suppress the oxidation, even if the thickness of Agjli is reduced, the surface quality of the λg4I11fIL material will not deteriorate and it is said to be economical. However, if NI or Ni alloy Although the intermediate layer prevents mineralization of Cu, etc., it cannot prevent oxygen from entering into the Ag layer, and the #1 element that has penetrated through the Ag layer prevents the #1 alloy intermediate layer from entering through the Ag layer. The surface of is oxidized, and a shield and Ag1 are formed in the N-based system.
There was a drawback that the adhesion with m was low.

We have developed a silver wave 81 material that does not dig into the surface of the surface, and a method for manufacturing it.

Wholesale 1 The shrimp coating material of the present invention is an Ail coated material with an Ag or Ag alloy layer formed on the base material! In asset subversion, the base material and Ag father are A.
The g-alloy layer [CZa] is characterized by providing an intermediate layer made of a Zn alloy with a 2n content of 50% or more.

Further, the method for producing the silver-coated material of the present invention is described above or M
In the production of Ag detritus formed by the alloy l1lIv,
After plating M or a Zn alloy containing 50% or more of Zn to a thickness of 0.01 to 10 μm on the surface of the V* material, plate M or an introduction plate.

The Ag11 material of the present invention is CmFζNi or its alloy, or copper-clad goods or copper metal goods coated with Cm or Cm alloy.
Hk&H, and an intermediate layer made of Zn or a Zn alloy having a Zn content of 50% or more is provided on these 41.

A Mug or λg joint layer is formed on the intermediate layer, and the intermediate layer contains not only pure Mu but also Zn-Ni with a Zn content of 50% or more.
, Zm-Cu, Zss-8m, Zn-Cd, etc.) Alloy strength Fti Irritation1. Pure AJ is used as a layer or Ag alloy layer.
Outside of i, Ag-Cu.

Alloys such as sb%AH-8e and AH-λg-In are used. However, middle school t11IIJIIf)J
There are at least 101 voices.

3. It is desirable that it be less than Ojl, and Ag or A
It is desirable that the thickness of the g-alloy layer be at least 0.1 tone or more.

In this way, the present invention Ax 11! The fee for subverting the property is for the middle class ζ2Zn
My father used a filler alloy with a Zn content of 50% or more.
When exposed to an All environmental sea, IIM elements in the atmosphere diffuse into the AH or Ag alloy layer, but Is elements are blocked by the intermediate layer of Zn or additive alloy, and the oxidation of the base material is extremely severe. Become slow. In addition, some of the Zn from the intermediate layer diffuses into both the base material and the Ag or Ag alloy layer, and the Zn diffused into the base material prevents the constituent elements of the base material from diffusing into the Ag alloy layer. Therefore, the appearance of λgM6N material, li! The benign and soldering does not damage the property 4, M or Ag
The za diffused into the alloy layer is uniformly dispersed in the sales circle and significantly reduces the diffusion of oxygen into the field, so that not only the surface of the intermediate layer but also the surface of the base material and its interior may be oxidized. There is no possibility of impairing the adhesion of Ag or the Ag layer.

-However, the reason why the thickness of the intermediate layer is set to 0, oi to 3o is that if it is less than 0.01μ, the above effect is not sufficient, and a,
Even if you hate it, you can't expect a stronger effect, and the conditions of use -
In some cases, excessive Zfi may diffuse into Ag ytah, which may impair the appearance of Ag, which is undesirable. Moreover, the intermediate layer was formed of pure Zn or a Zn alloy with an h content of 50% or more because 7. with a Za content of less than 50%. 11. The above effects cannot be effectively achieved with n alloys, and even if they could be achieved, a thick medium tmm would be required. It is practically uneconomical.

Such an Ag-coated material of the present invention is produced as follows. Pressure, cladding method, plating method, etc. on the base material ≦=Yo11
7. It can also be made by forming an intermediate layer made of Zn or Zn alloy and Zn or Zn alloy thereon. is 7. o*t/Brazed plating or chemical plating,
Furthermore, six consecutive Ag or Ag alloy t-electroplatings or chemical platings are optimal.

The present invention will now be described with reference to embodiments.

Example (A pure Cm wire with a diameter of 0.6 mm is continuously supplied, and the following treatment tank is installed on the line that winds it up, and the Cm wire is passed through it one after another to be continuously treated. After plating Zn with a thickness of OD 5, it was plated with BV of 1.s and then coated with Ag of the present invention.
lcuilt-manufactured.

(1) Cathode degreasing tank NaOH209/1 Denmaku If IQVdm treatment time io seconds (2) Washing tank 1155 seconds when processing Hayashi (3) M washing tank HI304 100#/7 times l
ll 5 seconds (4) Water washing tank Clean water processing time 5 seconds (51Zfl j 'j + tank ZuCN
601/INaCH401/I Nap! (BoVl iE flow tight If IA/am processing time 20 seconds (6) Washing tank Clean water processing time 5 seconds (7) Mug strike wood tank AgCN 3
1/IK CN 4011/1 Current density 10A/dm! %J! ! 1 hour 3 seconds (8) Ag plating tank AgCN 501/I
KCN 100N/j Current density 11"3A/dm" Treatment time 55 seconds (washing tank Clear water treatment time 10 seconds) After plating a layer with a thickness of α5 on the line, a thickness of 1
5-voice Alt Mebuki and the present invention Ag show Cu line! 1. Example <31 Example (Similarly to ri, strain 7 on the Cu wire with a thickness of 1.0
, ya, and then plated with 1.5 tones of Ag to produce a mug-coated Cu wire of the present invention.

Implementation 411+ (conversion) In Example (11), a Zn-Ni alloy plating tank was provided in place of the ZKI plating tank in (5), and 1 it of Zn-N4 alloy (containing Zn) with a thickness of 0.1 was coated on the Cu wire. Approximately 70%
After plating.

An AgM-covered Cu wire of the present invention was manufactured by plating Ag with a thickness of 1.5 tones.

Za-Ni alloy plating tank N804-6H, 018
ON/jZn80.・7H, 0809/1 Tame B0. 301/l N1 (4C1101/1 bath 1m 50"C current density #flA/dfn1 processing time i1 30 seconds Example (5) Example N (in 11, in place of the Ag plating bath in (8),
A Ag-8b alloy plating bath described in F was installed, and after plating a 0.05μ thick layer on the Cu wire, a 1.5μ thick layer was plated on the Cu wire.
The Ag-coated Cu wire 4/11 of the present invention was plated with G-8B alloy (8B content: about 2%).

Ag-8b alloy plating 4f AzCN 121/
IK CN 401/1 Antimonyl Potassium Tartrate 251/l1 Potassium Sodium Tartrate 2'd/11 EtIL Density
4A/dm" processing time 40 seconds Comparative example (I) Shorten the 11th rule of Zn plating in the Za plating tank 2 between fil and the thickness α005 on the C type line.
μ's zn plated Il, thickness 1.5 tone Ag? It was plated and coated with Ag.

Comparative example (example tl) Zn plating tank in one question ≦ Zn in two tanks
The plating time was extended, and after plating Zn with a thickness of 4.0 mm on the CIII wire (2), g4-plating with a thickness of LJ was applied, and the Ag coated RU wire was plated with l1jl.

Comparative Example (31) In Example (11), the following tnZn-Cu alloy/ff plating tank tl- was provided instead of the two plating tank C (4), Cu1I
After plating a Zll metal alloy III (containing about 30%), that is, brass with a thickness of 0.1 μm on IA, plated with Ag having a thickness of Ls, a λg coated Cu wire was produced.

Zn-Cu alloy mesh tank Cu CN 301/
IZn (CN), lOg/l NaCN 501/I Na, C0,3011/1 Bath temperature 301/1 Treatment time 30 seconds Comparative example (4) In Example + 11, instead of the Zn plating bath in (5), F was used.
After providing the treatment ellipse described above and IV plating to a thickness of 15μ on the CM wire, we plated Ag to a thickness of 1.5μ to create an Ag-Cu wire! g1! I left it behind.

Ni ) * Tank Ni 80. 2+01/lN1
Cj, 501i//1 to 4 s BOs 30 &/j1[fl'm
K 5 A/d m! Ii&! Diachronic 1′ & 13
0 second comparative example (5) Example (in 11, the Zn plating bath in (5) was omitted)
C.

Ag coated Cu wire was manufactured by directly plating Ag V to a thickness of 1.5 tones on the wire.

Comparative Example (Q) In Comparative Example (5), the plating time of (8) was approximately doubled, and Ag was plated with a thickness of 10μ directly on the Cm line.
A coated CII wire was produced.

For each of these modules gl
Heat for 5 minutes, then in air at 250°C! ! 10 in A
solder by dipping for 5 seconds into a eutectic solder bath held at a temperature of 270"C (270"C after each heating release).
Comparison was made visually. In addition, the wires after both of the above heat treatments were twisted 80 times with a cool length of 16υ, and the #g appetizing properties of the λg layer were examined by comparing the peeling pattern sv of the Ag coating. These results are shown in Table '4fl1.

1% 1 table Heating at a temperature of 110℃ for 15 minutes in Nakayama airflow is 8
This corresponds to soldering a 4F tube, and heating in the atmosphere at a temperature of 250°C for 10 hours corresponds to molding.Soldering during and after assembly of the diode indicates the properties and adhesion, respectively, and Table 41 As is clear from C2, the present invention Agl override Cu
Both lines indicate the quality of soldering on a 90% storm when soldering a Si chip, and the quality and A of soldering after assembling a diode.
g. Denseness of the film: It is found that it is excellent.

On the other hand, there is a comparative example (1) in which the thickness of the Zn intermediate layer is 0.005 μm, a comparative example (2) in which the thickness of the Zn intermediate layer is 4.0 μm, and a further Zn intermediate layer with a thickness of 7.0 μm. Comparative Example (3), Ag-coated Cu@, which was plated with Zn-Cu alloy with an n content of 30%, had poor solderability, especially Ag4Bt Enoki of Comparative Examples (1) and (3). It can be seen that the adhesion of Mugii6 is significantly low in the I-ray. Comparative Example (21) showed discoloration to yellow due to overstorm.

Moreover, λgM! of Comparative Example (4) using Ni in the intermediate layer! Cover C
In the case of U-rays, the dark layer in the atmosphere is oxidized, and not only does the adhesion of the Ag film deteriorate significantly, but also the soldering properties are extremely low F. Comparative example (5L
Also in (6), Ag? due to oxidation of Cu? The adhesion of the jI film warped, and the soldering properties were significantly reduced. It can be seen that an AgH cover with a thickness of about 3 tones is still insufficient.

Note that the above examples involve heating at a relatively low temperature, but when heating at a lower temperature, Zs
As mentioned above, it can be practically used without excessively diffusing on the surface of mug pigeons. In addition, all of the above explanations were explained using two @Ml, but they are not limited to this.
Board material 1 row Chiang, tj:! Exactly the same results can be obtained for material temples.

Ag*ff1l exposed to i1% lagoon in the atmosphere in this way
N requires an Age coating with a thickness of at least 5 tones, but according to the present invention, a thin λg coating is far superior to providing an intermediate layer made of Zn or Zo coating. It is superior in terms of sparrow Ag, and has remarkable industrial effects.

491-

Claims (2)

[Claims] (1) 1ig alloy mv formation on the base material, ri A
In GM-covered materials, the base material and the Ag parent have Z between the Ag alloy layers.
A silver-coated material characterized in that the IZn-containing company provides an intermediate layer consisting of 50% or more Zn compound. (2) The silver-coated material according to claim 1, wherein the thickness of the intermediate layer is 0.01 to 3.0μ. (31) In the production of an Ag coating material in which an Ag or Ag alloy layer is formed on a substrate, Zn or a Zn-containing layer is
A method for producing a silver-coated material having the following characteristics: Zn alloy plating of 0% or more is plated to a thickness of 0.01 to 3.0μ, and then Ag alloy plating is applied.