JPS6360537A - Metallic laminate and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain strong bonding effect by forming a metallic laminate by a first layer and a second layer consisting of ar Sn alloy, etc., a third layer and a fourth layer composed of an Ni-Si alloy, etc., and an Si substrate in succession from the surface. CONSTITUTION:A third layer made up of an Ni-Si or Ni-Si-B amorphous alloy or an Fe metal is shaped onto an Si substrate, a fourth layer consisting of ar Ni-Si or Fe-Si alloy is formed on the interface of the Si substrate and the third layer through heat treatment, a first layer composed of an Sn alloy is shaped onto the surface of the third layer, and a second layer made up of an Ni-Sn or Fe-Sn alloy layer is formed onto the interface of the first layer and the third layer through heat treatment. The third metallic layer obstructs the diffusion of Sn to the fourth metallic layer from the second metallic layer. The composition of the Ni-Si-B alloy is selected so that a reaction layer is shaped properly on the interface of Pb-Sn/Ni-Si-B at the optimum temperature of soldering. Accordingly, an ohmic contact is acquired between a soldering layer and Si, thus obtaining strong bonding effect.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a metal laminate, especially a Si chip and a lead wire.
The present invention relates to a metal laminate thin film electrode for making ohmic contact with strong bonding force by b-Sn soldering, and a method for manufacturing the same.

(Prior Art) In recent years, the development and application of semiconductor devices has become active, and in order to ensure their reliability, research on the physical properties of thin films, surfaces, and interfaces has become increasingly important. “Soldering of minute parts in the electronics industry, expressed by the term micro soldering, is a typical example.

Micro-soldering has applications such as (i) connecting semiconductor elements such as Si to conductors such as lead wires, and (11)
) Bonding of semiconductors and IC packages.

There is something like that. In particular, the bonding of semiconductor chips typified by Si to ceramic substrates and the soldering for taking out lead wires are the most important techniques for achieving high reliability of devices.

For soldering Si chips, Au-Si, Au-C; e,
In addition to Au-based eutectic solder such as Au-3rr, pb-Sn-based eutectic solder is used. Pb because it is cheap and highly productive
-Sn-based solder is commonly used. However, Pb-Sn
Since solder cannot be directly bonded onto the S1 chip, in reality, a Ni film is interposed, or in order to obtain even higher reliability, T i / Ni / A u or Cr / Ni
/ A u Soldered through a three-layer structure film. The role of each constituent element of these electrodes is as follows: Ti, Cr, etc.
Ni in the three-layer intermediate layer prevents Sn in the solder from diffusing toward the Si chip, and Au prevents oxidation and ensures good soldering. It is for this purpose.

(Problems to be Solved by the Invention) However, in either case, Sn is absorbed into the Ni layer due to poor bonding between the metal silicide and the metal layer thereon, and due to self-heating due to use in a high-temperature atmosphere. There have been problems such as "delamination 2" due to diffusion and further segregation at the interface with the metal layer.Furthermore, in the case of multilayer electrodes, not only is the productivity and cost extremely high, but also the number of interfaces is large. As a result, there have always been problems such as insufficient bonding strength between each layer.
There has been a strong desire for the emergence of a metal laminate electrode that can ensure ohmic contact by forming a metal film on a chip and subjecting it to heat treatment, and can obtain strong bonding force by soldering.

(Means for solving the problem) For the reasons mentioned above, electrode materials for semiconductor devices, especially electrode materials for S1 devices that can be installed in automobiles, are
1) Ohmic contact can be obtained between the solder layer and Si.

(it) the diffusion of Sn in the solder is prevented even during long-term use in an atmosphere of at least 150°C;
(ill) Strong bonding force? 11 is required. Metals that can be plated with Pb-Sn are Cu and Ni.

Examples include Fe alloys, and materials that form silicide with Si include Ni, Fe, and the like. However, as is well known, 1 to 2% of Cr, Si, and Mo are added to Fe.
If such impurities are mixed in, soldering becomes extremely difficult. On the other hand, among Ni alloys, the inventors found that Ni.--Si or Ni
It has been found that -Si-B alloy has excellent soldering properties. Furthermore, depending on their composition range, these alloys contain Sn
It was also found that there was a significant change in the diffusion rate of t. In addition, Ni-Si or Ni-Si-B alloy or Fe metal is Si
It was also experimentally confirmed that stable silicide is formed between the material and the chip. From these facts, after forming a Ni-Si or Ni-Si-B or Fe layer with a specific composition range on SiJ: and forming silicide by subsequent heat treatment,
If lead wires are taken out from the Si chip by soldering, Fe or Ni silicide can be formed between it and S'i, and Ni-Si or Ni-Si-
B alloy or Fe metal layer or Ni-Si or Ni-Si-B which prevents or slows down the diffusion of Sn and was originally only a layer.
Or a Ni (or Fe)-Sn layer from both sides of the Fe layer,
As a result of the growth of the Ni (or Fe) silicide layer, a metal laminated electrode with strong bonding without discontinuous interfaces was obtained, leading to the present invention.

The metal laminate of the present invention includes a first metal layer containing Sn and a first metal layer containing Sn.
(or Fe) and a second metal layer containing Sn and Ni-S
a third metal layer comprising Ni or Ni-Si-B alloy or Fe metal; and a fourth metal layer comprising Ni (or Fe) and Si; The third metal layer is characterized in that it is a layer that prevents Sn from diffusing from the second metal layer to the fourth metal layer.

The first metal layer C (hereinafter simply referred to as the first layer) is at least Sn
Refers to metals that contain That is, Sn is an essential component of the first layer. The first layer has at least a few pieces of S of 96 or higher.
Other components include Pb, Cu, Sb, and Ni.
Refers to alloys such as solder, bronze, and type alloys that contain , In, etc. Pb- is usually used as solder for electrode bonding in the semiconductor field.
Sn alloy is used, containing 5 to 90% by weight of Sn and Pb.
Contains 10 to 95% by weight. In addition, bronze is usually Cu-
Sn alloy is used, containing 2 to 35% by weight of Sn and Cu.
Contains 65 to 98% by weight. In addition, the type alloy is usually a Pb-3b-Sn alloy, and the Sn content is 1 to 10.
The second layer containing 70 to 94 weight % of Pb and 3 to 20 weight % of Sb is a metal containing Ni (or Fe) and Sn as essential components. The second layer contains 20 to 80 atomic % of Sn, as well as Si, B, Cu, and Ag.

It may contain 2 to 3 atomic % or less of In, Sb, etc.

The second layer serves to bond the first layer containing Sn and the third layer containing Nt or Fe.

The third layer is made of Ni-Si alloy, Ni-Si-B alloy, or Fe metal, and is the most prominent technical feature of the metal laminate of the present invention. FIG. 1 shows the composition range in which the Ni-Si-B alloy acts as a Sn diffusion prevention layer. Region ■ in Figure 1 is 28 atomic %≦Si+B≦50 atomic % and S
i≧10 at%, region ■ is 20 atoms 96≦Si+B<2
8 at%, and Si≧10 at%, region ■ is 10 at%
≦Si+B<20 atomic %, and B≦lO atomic %.

Region (2), region (2), and region (2) all serve as Sn diffusion prevention layers, but the difference between them is the degree of Sn diffusion prevention effect. In other words, the diffusion prevention ability is in the order of ■>■>■.

Further, in the case of a Ni-Si alloy, the effective composition range for preventing Sn diffusion is Si≦50 atomic %, excluding the case of 100% Ni.

Furthermore, the areas (1), (2), and (2) all have good wettability with Pb-Sn solder, and can be soldered.

Fe metal consists of Fe or Fe alloy (hereinafter referred to as Fe), C<0.2% by weight, Si<0.5% by weight, Mn<1% by weight, P<0.03% by weight, S.
0.03 mm%, N i < 3 AM %+
A material containing Cr<2% by weight, Mo<Q, and 5% by weight has an effect of preventing Sn diffusion. Regarding impurities contained in Fe, silicide (Fe
Although there is no problem in the formation of Pb--Sn (soldering), sufficient soldering strength cannot be obtained if each element (L) is included.

The fourth FA is a metal layer containing Ni (or Fe) and Si, and is substantially a Ni (or Fe) silicide layer. Si
Interposition of silicide is essential in order to take out the lead wires from the chip through ohmic contact. Ni-Si-B or N
An i-Si alloy layer or Fe metal is formed on Si, and then a Ni (or Fe) silicide layer (fourth layer) is formed by solid phase-solid phase metal diffusion. Ni-Si or Ni-Si-
The growth of silicide between B or Fe and Si is slightly different from the normal reaction with 100% N1 in terms of the growth temperature and the form of the silicide.

There is no problem with ohmic properties, and Si and Ni alloy layers or F
e A strong bond can be obtained between the metal layer and the metal layer.

The thickness of the third layer, which is a technical feature of the present invention, is 0.05 μm
It is preferable to set it to 20 micrometers.

If it is less than 0.05 μm, the ability to prevent Sn diffusion is insufficient, and if it exceeds 20 μm, peeling is likely to occur due to internal stress.

The metal laminate of the present invention is manufactured by the following two methods. The first method is to first use cleaned n-type or n-type Si.
Apply physical methods (e.g. sputtering, vacuum evaporation,
Ni-Si or Ni-
A Si-B or Fe film is formed and then annealed at a temperature at which solid phase-solid intermetallic diffusion occurs to form Ni (or Fe) silicide at the interface. In this case, it is important to select annealing conditions such that an unreacted Ni-Si, Ni-Si-B, or Fe layer remains. After that, alloy L4 containing Sn is applied using physical methods (sputtering, vacuum evaporation, ion blating, etc.) or chemical methods (plating method, etc.).
Ni (or Fe
) - Form a Sn layer.

Next, a second manufacturing method will be described. First, Ni is deposited on a cleaned n-type or n-type Si substrate by a physical method (e.g., sputtering, empty evaporation, ion blating, etc.).
-Si or Ni-Si-B or Fe film is formed, and then an alloy layer containing Sn is formed by a physical method or a chemical method such as plating. Then solid phase - solid tIj or solid phase -
Annealed at a temperature at which intermetallic interdiffusion occurs in the liquid phase, and N is added to the interface between the Si substrate and N1-Si or Ni-Si-B or Fe.
i (or Fe) silicide layer further Ni-Si or N
A Ni (or Fe)-Sn layer is simultaneously formed at the interface between the i-Si-B alloy or Fe metal and the alloy layer containing Sn. What is important here is the Ni (or Fe) silicide layer and the N
The annealing temperature should be determined by fully considering the growth rate of i (or Fe)-S n IA.

In any case, the final layer containing Sn, Ni
(or Fe)-Sn alloy, Ni-S
a third layer consisting of i or Ni-Si-B or Fe, and N
The metal laminate is characterized by comprising a fourth layer forming an i (or Fe) silicide layer.

When the first layer is a Pb-Sn alloy and the second layer is a Ni-Si-B alloy, Pb does not participate in the reaction between the two alloy layers, and the degree of reaction between Si and B in the Ni-Si-B film is 1'1' for increase in quantity
It decreases. Pb-Sn/N1-Si-
Although the interfacial reaction (B) can occur at a temperature of 150° C. or higher, it is usually preferably carried out at a temperature of 330° C. or higher for reasons such as solder wettability.

Further, in order to obtain Ni silicide through an interfacial reaction between the Ni-Si-B alloy layer and the Si substrate, the temperature is preferably 1, usually 300° C. or higher, although it varies slightly depending on the composition of the two alloys. However, at temperatures above 400 to 450°C, Ni-Si-B crystallizes and disconnection of wiring occurs at A in Si devices, so a reaction temperature of 300 to 450°C is preferable.

For the above reasons, the composition of the Ni-Si-B alloy is pb-8n/N for soldering at 71u degrees (330-400°C).
It is necessary to select so that a reaction layer is appropriately formed at the i-Si-B interface (the layer becomes brittle as the reaction progresses and the layer becomes thicker), and the silicide formation temperature is 300 to 45°C.
0°C is desirable.

Therefore, in the first manufacturing method, it is sufficient to form the second and fourth layers by performing optimal heat treatment on each layer independently, but in the second manufacturing method, the treatment temperature and the Ni-Si-B composition are appropriately adjusted. You need to choose.

For example, when comparing the silicide layer formation rate D and the Sn-1-9j Ni layer formation rate D when the heat treatment temperature is T-320°C in the second manufacturing method, it is found that -1-S
n Ni-Si N1-Sn. Here, Ni-Si
-D KukuD When St and Bu in B alloy are increased, D becomes 1-S
n becomes slower, so D < D or DNi-3t
Ni-Sn Ni-Si 'DNi-S
It can be n.

Also, when T-400℃, D becomes faster, but Ni-S
i D also becomes extremely fast. Therefore, Si, BQNi-S
By further increasing n and suppressing the reaction of D, DNi-Si”
It can be done as 1-8n D.

1-Sn As an example of the application of the present invention, it can be used to take out lead wires by soldering from Si chips for power transistors or diodes that conduct large currents. These semiconductor devices are specifically used as automotive ICs for controlling an igniter or an alternator.

(Operations and Effects) A first metal layer containing Sn, a second metal layer consisting of a Ni (or Fe)-Sn alloy, a third layer consisting of Ni-Si, Ni-Si-B, or Fe alloy, and a Ni (or The effects of the metal laminate including the fourth layer made of Fe) silicide will be described.

Ni-Si or Ni-Si-B or Fe layer (third layer) which is the most remarkable technical feature of the metal laminate of the present invention
We will mainly explain the role of A Ni film is usually used to take out lead wires from a Si substrate using Pb-8n solder. However, Sn exists in Ni at a relatively low temperature (approximately 150'C).
), so depending on the temperature environment in which the Si device is used, the diffusion of Sn may slow down and cause trouble. It has been found that by adding Si or Si+B to a Ni film, the microstructure of the film changes significantly, which affects interdiffusion with Sn. Furthermore, the total amount of Si and B is 5
If the content is 0 atomic % or less, the wettability with Pb-Sn solder is good, and the Si+B or SiQ of the Ni film is 'l! 14i, the growth of the Sn--Ni reaction layer can be controlled. A similar effect was also observed in the Fe film. On the other hand, it is necessary to form Ni (or Fe) silicide between the Si substrate and ensure ohmic properties.
- A stable silicide is formed by an interfacial reaction between Si--B or Fe film and Si, and B does not participate in the reaction. In this way, the Ni-Si, Ni-Si-B, or Fe layer forms Ni (or Fe) silicide with Si, and Sn-Ni (
A single layer simultaneously fulfills three roles: forming an alloy layer (or Fe) and inhibiting or controlling Sn diffusion. Also, Ni (or Fe)-Sn
layer, Ni-Si or Ni-Si-B or Fe layer and Ni
The (or Fe) silicide layer is originally composed of a single layer, so there is no discontinuous interface and the bonding property is perfect.

As described above, the metal laminate and the method for producing the same of the present invention have made it possible to significantly improve cost, productivity, and properties (thermal stability) compared to conventional products.

(Example) Common conditions for the manufacturing method and evaluation process of the metal laminate of the present invention are shown below. The Si substrate used was 10
``p type (111) doped with boron to about am-3
The surface of the wafer is mirror-finished and the resistivity is approximately 12.
It is 0Ω·cm. DC or RF on Si-based substrate at room temperature
Ni-Si or Ni-S by magnetron sputtering method
Approximately 10,000 layers of i-8 alloy film will be applied. Thereafter, it is processed in two ways. In other words, the first method is Nf-S
After forming i or Ni-Si-B or Fe film, 300℃~4
Select a temperature within the range of 50°C according to the film composition.

Heat treatment is performed in vacuum for about 1 hour to form an N interface between Ni-Si/Si or Ni-Si-B/Si or Fe/Si.
A diffusion layer of i (Ni silicide diffusion layer) or Fe silicide diffusion layer is formed. Next, the Pb-Sn alloy film is
Pb-Sn was formed to a thickness of 0,000 mm by DC or RF magnetron sputtering, and then heat-treated in a vacuum for 10 to 60 minutes at a temperature range of 300°C to 450°C.
Alloy/Ni-Si or Ni-Si-B or Fe
Interface 1: Form a Ni (or Fe)-Sn diffusion layer.

The second method is to form a Pb-Sn film on the Ni-Si, Ni-Si-B, or Fe film, and then perform heat treatment all at once to form a Pb-Sn alloy/Ni-Si or Ni-S
A Ni (or Fe)-Sn diffusion layer is provided at the i-B or Fe interface, and a Ni-Si or Ni-Si-B or Fe/
A diffusion layer of Ni (or Fe) silicide is formed at the Si interface.

The details of the heat treatment method are as shown below. That is 3
10-” Torr held at 00’C to 450°C
A sample was inserted into the following vacuum atmosphere and held there for 10 to 60 minutes, then held in the same vacuum until the temperature returned to room temperature, and then taken out into the atmosphere. In this method, it takes 2-3 minutes for the sample to reach a predetermined temperature, so the heat treatment time is actually slightly shorter by that amount.

FIG. 2 shows the cross-sectional structure of the metal laminate of the present invention produced by the above method. Also, by corresponding Auger electron analysis, P
FIG. 3 illustrates a diagram of the results of depth direction element distribution analysis from the surface of the b-Sn alloy to the inside. From Figure 3, the second layer is Ni.
It can be seen from -Sn that the fourth layer is made of Ni-Si (Ni silicide).

The evaluation as an electrode is ohmic (5, good).

Pb-Sn film or solder wettability (evaluated as excellent, Q, fair, poor), and adhesive strength (evaluated as excellent, good, fair, poor). Good and bad ohmic properties are Ni
The formation of the -Si layer (fourth Ni silicide layer) and the wettability correspond to the formation of the Ni--Sn layer (second layer).

The criteria for excellent, good, fair, and poor are as follows.

■ Regarding ohmic properties, it is necessary to discuss the relationship between current, voltage, linearity, and contact resistance.
Here, the determination was made based on contact resistance.

Contact resistance: Several meters or less, about 10 mΩ/mouth: Good number: about 10 mΩ/mouth: rIJ 10 Ω/mouth: rIJ 10Ω/mouth”-2 Not possible ■Evaluation of solder wetting was determined based on the contact angle.

Contact angle 10' or less: Excellent 10-300: Good 30-80': Possible 80' or above: Not possible ■Judgment about adhesive strength Adhesive strength 7 kg/mm or more: Excellent 2° 7-4kg/+++n+, good 2゜ 4-1kg/m+a, possible 1 kg / mm or less: Not possible And so.

Examples 1 to 12 and Comparative Example 1 in which a Ni-Sn diffusion layer was not formed are shown below. Ni silicide diffusion layer and Ni-
Comparative Example 2 in which a Sn diffusion layer is not formed is shown. Moreover, these evaluation results are shown in Table 1.

Example 1 Third layer composition: N1-15 atomic% Si-25 atomic% B,
5000 people ↓ Heat treatment: 400°C, 1 hour, in vacuum ↓ Pb-Sn layer film formation: Pb-10 tons W%Sn, too
oo person ↓ Heat treatment = 300°C, 230 minutes, in vacuum Example 2 Third layer film formation: Ni-15 atomic% Si-25 atomic% r3.
5000 people ↓ Pb-Sn layer film formation, Pb-10 heavy QXSn, 100
00 people ↓ Heat treatment, 350°C, 1 hour, in vacuum Example 3 3rd layer film formation: Nj-35 atomic% Si-10 atomic% B,
5000 people ↓ Heat treatment: 450°C, 1 hour, in vacuum ↓ Pb-Sn layer film formation: Pb-10 weight Q%Sn, 100
00 people Processing: 300°C, 130 minutes, in vacuum Example 4 Third layer film formation: Ni-15 atomic% Si-10 atomic% B,
5000 people ↓ Heat treatment: 380°C, 1 hour, in vacuum Pl)-8n layer film formation: Pb-10 city H%Sn, 10
000 people ↓ Heat treatment = 300°C, 130 minutes, in vacuum Example 5 3rd layer film formation: Nj-20 at.% Si-5 at.% B, 5
000 people ↓ Pb-Sn layer film formation: Pb-10wt%Sn, 100
00 people ↓ Heat treatment: 330°C, 1 hour, in vacuum Example 6 Third layer coating: Ni-12 atomic%Si-4 atomic%B, 5
000 people ↓ Heat treatment = 350°C, 1 hour in vacuum Pb-Snn layer film Pb-10w%sn, 1
0,000 people ↓ Heat treatment, 300°C, 30 minutes, in vacuum Example 7 Third layer film: Ni-7 atoms 96 Si-7 atoms % B, 5
000 people ↓ Pb-Snn layer film Pb-10 double% Sn, 100
00 people ↓ Heat treatment: 300°C, 30 minutes, in vacuum Example 8 Third layer film formation: Ni-42 atomic % Si, 5000 people ↓ Heat treatment: 400°C, 1 hour, in vacuum ↓ Pb-8n delaminated film: Pb-10 weight Q%Sn, 100
00 people ↓ Heat treatment, 300°C, 30 minutes, in vacuum Example 9 Third layer film formation: Nl-251 Oji%St, 5000 people Heat treatment = 350°C, 1 hour, in vacuum ↓ Pb -Snn layer film Pb- 10iT+fa%Sn,
10,000 people ↓ Heat treatment = 300°C, 130 minutes, in vacuum Example 10 3rd layer film formation: Ni-15 atomic% Si ↓ Heat treatment: 300°C, 1 hour, in vacuum ↓ Pb-Sn layer film formation: Pb-10 weight %Sn, toooo
Nyuzen heat treatment = 300°C, 30 minutes, in vacuum Example 11 Third layer film formation: Ni-15 atomic% S! , 5000 people ↓ Pb-Sn layer film formation: Pb-10 weight-%Sn, 100
00 people ↓ Heat treatment = 300°C, 1 hour, in vacuum Example 12 3rd layer film formation: FQ 5000 people ↓ Pb-Sn layer film formation: Pb-10w%sn, 10
000 Artificial heat treatment: 300'C, 1 hour, in vacuum Comparative Example 1 Third layer film formation: Ni-15 atomic% Si-15 atomic% B,
5,000 people ↓ Heat treatment: 400°C, 1 hour, in vacuum ↓ Pb-Sn layer film formation: Pb-10 wt% Sn, 10,000
Human Comparative Example 2 3rd layer film formation: N1-15 atomic% Si-15 atomic% 13.
5000 people ↓ Pb-Sn layer film formation: Pb-10wt%Sn, 1000
The metal specimens of Examples 1 to 12 were left in the atmosphere at 150°C for 4 weeks, and the diffusion prevention effect of the Ni-Si, Ni-Si-B, or Fe layer was determined by Auger electron analysis. However, no diffusion of Sn was observed, and it was found that all the examples of the present invention had good high-temperature durability.

In addition, as a comparative example with the conventional technology, the third layer contains 1100% N.
layer (5000 people), silicide formation,
The formation of the Ni-Sn layer was normal, but when left in the atmosphere at 150°C for one week, Sn passes through the Ni-Sn layer and diffuses into the unreacted Ni region, causing a bond between the Ni silicide and the Si substrate. Auger electron analysis revealed that it diffuses to the interface.

1 The thermal stability of the electrodes of Examples 1 to 12 of the present invention was evaluated by leaving them in the atmosphere at 150°C or by applying a current of 0N1.
IHI was continued for 1 to 2 weeks while repeating 0FF, and no change was observed in both the ohmic contact and interlayer density of the electrode portion. This is because the electrode structure of the present invention is stabilized by the history of heat treatment at 300° C. or higher during electrode production.

[Brief explanation of the drawing]

Figure 1 shows the composition range of the third layer of the gold-broiled laminate of the present invention, and the composition range of the second layer.
The figure shows the cross-sectional structure of the metal laminate of the present invention (Examples 1 to 12)
, FIG. 3 shows a typical example of Auger electron analysis results (depth direction distribution) corresponding to the structure shown in FIG. 2 (Examples 1 to 8), FIG. 4 shows the first manufacturing method of the metal laminate of the present invention, FIG. 5 shows a second method of manufacturing a metal laminate according to the present invention.

Claims (10)

[Claims] (1) Sequentially from the surface: a first layer made of Sn alloy;
- a second layer made of Ni alloy or Sn-Fe alloy;
-Si or Ni-Si-B amorphous alloy or F
A metal laminate comprising a third layer made of e-metal, a fourth layer made of Ni-Si or Fe-Si alloy, and a Si substrate. (2) The metal laminate according to claim 1, wherein the Ni-Si alloy has a Si content of 10 to 50 atomic %. (3) The metal laminate according to claim 2, wherein the Ni-Si alloy has a Si content of 10 to 28 at.%. (4) The Ni-Si-B alloy contains Si and B in a total amount of 1
The metal laminate according to claim 1, characterized in that the metal laminate contains 0 to 50 atom %. (5) The Ni-Si-B alloy contains Si and B in a total amount of 2
The metal laminate according to claim 4, characterized in that the metal laminate contains 8 to 50 atomic % and 10 atomic % or more of Si. (6) The above Ni-Si-B alloy contains Si and B in a total amount of 2
The metal laminate according to claim 4, characterized in that the metal laminate contains 0 to 28 atomic % and 10 atomic % or more of Si. (7) The above Ni-Si-B alloy contains Si and B in a total amount of 1
The metal laminate according to claim 4, characterized in that the metal laminate contains 0 to 20 atomic % and 10 atomic % or less of B. (8) The metal laminate according to claim 1, wherein the Fe metal does not substantially contain impurities. (9) Ni-Si or Ni-Si-B on a Si substrate
A third layer made of an amorphous alloy or Fe metal is formed, and a Ni-Si layer is formed at the interface between the Si substrate and the third layer by heat treatment.
Alternatively, a fourth layer made of Fe-Si alloy is formed, and then a first layer made of Sn alloy is formed on the surface of the third layer, and Ni-Sn or Fe is added to the interface between the first and third layers by heat treatment. −
A method for manufacturing a metal laminate, comprising forming a second layer made of an Sn alloy layer. (10) Ni-Si or Ni-Si-
A third layer made of B amorphous alloy or Fe metal is formed, a first layer made of Sn alloy is formed on the surface thereof, and then Ni-Sn or Fe-Sn is formed at the interface between the first layer and the third layer by heat treatment. A second layer made of an alloy and a third layer made of Si
A method for manufacturing a metal laminate, comprising forming a fourth layer made of a Ni-Si or Fe-Si alloy layer at an interface of a substrate.