JPH0632669A - Joined body, metallized body and production of metallized body - Google Patents

Abstract

PURPOSE:To enable the obtaining of the shape with a high adhesive strength and excellent reproducibility by forming a metallized layer containing a metallic element such as Ti or Cu on a ceramic substrate having a prescribed thin film formed thereon. CONSTITUTION:The objective metallized body is produced by successively forming a thin film of one or more of the first metallic elements selected from Ti, Zr and Hf on a ceramic substrate which is alumina and a thin film of one or more of the second metallic elements selected from Cu, Ni, Co, Fe and Mn, providing the ceramic substrate having the thin films formed thereon, then about 3 hr and forming a metallized layer 4 containing a compound containing the first metallic elements such as a Ti layer 2, Ti-Cu-Al-based compound particles 3, the second metallic elements such as Cu and oxygen in an amount of >=70 atomic % as the compositional ratio.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bonded body using a ceramic base material, a metallized body in which the surface of the ceramic base material is metalized, and a method for producing the same.

[0002]

2. Description of the Related Art The technique of joining ceramic base materials and metal base materials or ceramic base materials together has been applied in a wide range from functional materials such as semiconductors and devices to structural materials such as gas turbines. The Mo-Mn method, the DBC method, the active metal method and the like are known as conventional effective joining methods.

Among the above-mentioned joining methods, the Mo-Mn method and the DBC method have lower mechanical joining strength represented by tensile strength and the like as compared with the strength of the base material, and require strength and heat fatigue resistance. It has a problem that it is difficult to apply it to such a part. The reason why the strength of the bonded body is lower than that of the base material is mainly due to the low chemical bonding strength at the interface and the stress concentration part in the ceramic base material due to the difference in the thermal expansion coefficient between the bonded base material and the like. May occur and the strength of this part may deteriorate.

[0004] The active metal method uses a reduction effect on ceramics such as Ti and performs bonding with a high chemical bonding force at the interface. Compared with the Mo-Mn method or the DBC method,
This is an effective joining method because a joined body having high mechanical joining strength can be obtained. However, the active metal method has a problem that the mechanical strength is lower than that of the ceramic base material because the stress concentration generated in the ceramic base material is large.

As described above, in order to make the strength of the ceramics bonded body equal to that of the ceramics base material, two factors are required to improve the chemical bonding force at the interface and suppress the stress concentration on the ceramics side. Need to control,
The current joining method has not been fully satisfied with these.

On the other hand, the above-mentioned Mo-Mn method, DBC method, active metal method, etc. are applied not only to the joining of ceramic base materials but also to the metallization of the ceramic base surface. Metallization of a ceramic base material is widely used as a circuit forming means when the ceramic base material is used as a circuit board or the like. However, even in such a metallizing technique, as in the case of the above-mentioned bonded body, the conventional method has a problem that the bonding strength (adhesion) between the ceramic base material and the metallized layer cannot be sufficiently increased.

In addition, in the technique of metallizing a ceramic substrate, reproducibility of a circuit pattern, physical characteristics of a metallized layer and the like must be considered in addition to the above-mentioned bonding strength. For example, in the conventional method of forming a metallized layer using an Ag-Cu brazing filler metal containing Ti, the brazing filler metal is melted and the liquidized state of the brazing filler metal is used to form the metallized layer. It has drawbacks such that the material is likely to protrude to the side surface, it is difficult to form a fine pattern, and a Cu metallized layer with high purity cannot be formed.

[0008]

As described above, it is difficult for the conventional joining method and metallizing method to obtain a sufficiently high mechanical joining strength comparable to the strength of the ceramic base material at the joining interface. Had the problem of being.

In view of the above, there has been a strong demand for a bonding technique capable of improving the chemical bonding force at the interface and suppressing the stress concentration on the ceramic side in the ceramic bonded body. Further, in the ceramic metallized body, there is a strong demand for a metallizing technique having sufficient adhesion strength and excellent reproducibility of fine patterns.

The present invention has been made to address such a problem, and aims to improve the chemical bonding force at the interface, suppress the stress concentration on the ceramic side, and stabilize the high mechanical bonding strength. Another object of the present invention is to provide a metallized body having a high adhesion and a metallized layer which is excellent in shape reproducibility and can be stably obtained, and a method for producing the same. To do.

[0011]

Means and Actions for Solving the Problems The inventors of the present invention have conducted extensive studies on the bonding and metallization of the above-mentioned ceramics. In addition, it is possible to reduce the concentration of stress on the ceramic side by improving the chemical bonding force by the presence of a compound with a specific structure, and to reduce the alumina-based ceramic substrate with an active metal. While forming the metallized layer while performing the reduction reaction of alumina under solid-state heat treatment, to prevent Al that is generated by the reduction of alumina and interferes with the interfacial reaction remains at the bonding interface as it is. Due to
It has been found that a metallized layer having high adhesion and excellent reproducibility of a fine pattern can be obtained.

The bonded body of the present invention is made on the basis of the above-mentioned first finding.
Or it is a joined body of ceramic base materials, and Ti,
The composition ratio of the first metal element consisting of at least one selected from Zr and Hf, the second metal element consisting of at least one selected from Cu, Ni, Co, Fe and Mn, and oxygen is set. Contains a compound of 70 at% or more and has a thickness of 2 μ
It is characterized in that the ceramic base material and the metal base material or the ceramic base materials are bonded to each other through a bonding layer of m or less.

The first metallized body according to the present invention is also based on the first finding and is provided on the ceramic base material and the ceramic base material, and is selected from Ti, Zr and Hf. A composition ratio of at least one first metal element, at least one second metal element selected from Cu, Ni, Co, Fe and Mn, and oxygen
And a metallization layer containing a compound of 70 at% or more.

The above-mentioned method for producing a metallized body is characterized in that at least one selected from Ti, Zr and Hf is formed on a ceramic substrate.
A thin film of the first metal element consisting of one kind and Cu, Ni, Co, Fe
And a step of forming a thin film of at least one second metal element selected from Mn, and the ceramic substrate on which the thin film is formed is heat-treated at a temperature not higher than the melting point of the thin film, And a step of forming a metallized layer containing a compound containing the first metal element, the second metal element and oxygen in a composition ratio of 70 at% or more on the material.

The second aspect of the present invention is based on the above-mentioned second knowledge.
The metallized body of
a layer of the active metal in which compound particles containing at least one active metal selected from i, Zr, and Hf and Cu and Al as constituent elements are dispersed and formed in the vicinity of the interface with the alumina-based ceramic substrate; And a Cu layer provided on the active metal layer.

The third metallized body is provided on the alumina-based ceramic base material and the alumina-based ceramic base material, and is at least selected from Ti, Zr and Hf.
An active metal layer of one kind is provided, and at least one of the interface between the active metal layer and the alumina-based ceramic substrate, the inside of the active metal layer, and the surface of the active metal layer is bonded with Al in advance. Place a substance that is easy to
It is characterized in that a substance that easily binds to Al is arranged and that the substance that easily binds to Al is present as a bond with Al by solid-state heat treatment.

Further, the fourth metallized body comprises an alumina-based ceramic base material and an active metal layer provided on the alumina-based ceramic base material and made of at least one selected from Ti, Zr and Hf. The active metal layer is an alignment film mainly composed of crystal grains of the active metal in which the c-axis of the crystal is oriented within a range of ± 30 degrees with respect to the direction perpendicular to the surface of the alumina-based ceramic substrate. It is characterized by being.

As described above, the joined body of the present invention comprises the ceramic base material and the metal base material, or the ceramic base material and the ceramic base material, the first metal element (at least one selected from Ti, Zr and Hf). Me (1)), a second metal element (Me (2)) consisting of at least one selected from Cu, Ni, Co, Fe and Mn, and a compound containing oxygen as a main constituent element, It is bonded through a bonding layer with a thickness of 2 μm or less.

The ceramic base material used for the above-mentioned bonded body is mainly composed of an oxide-based ceramics sintered body containing aluminum oxide, beryllium oxide, magnesium oxide, silicon oxide, etc., and aluminum nitride, silicon nitride, silicon carbide, etc. It is possible to apply various ceramics sintered bodies up to the non-oxide type ceramics sintered body. Further, as the metal base material, steel material, Fe-Ni-based alloy,
Various metallic materials such as Mo alloy and W alloy can be applied according to the application.

The bonding layer in the bonded body of the present invention is Me (1)
And Me (2) and oxygen as main constituent elements, in other words, a compound containing 70 at% or more in composition ratio. This means that some impurity elements may be included. The above compound includes a space group Fd containing Me (1), Me (2) and oxygen in an atomic ratio of 3: 3: 1 to 4: 2: 1.
Those having a 3 m diamond structure are preferred. In addition,
The combination of elements in the above compound is not particularly limited, but examples thereof include a compound in which Me (1) is Ti and Me (2) is Cu, and in this case, Ti ₃ Cu ₃ O ~ Ti. ₄ Cu ₂ O
The atomic ratio changes within the range. Further, the above compound needs to be present at least in the vicinity of the bonding interface with the ceramic substrate, and specifically, it is present in a layered form or dispersed.

The compound having a diamond structure of the space group Fd3m as described above forms an interface having a large chemical bonding force with the ceramic base material, and has a thermal expansion coefficient of itself between that of the ceramic base material and that of the metal base material. Since it has an appropriate value, it plays a role of reducing the stress generated on the ceramic base material side. That is, it has a function as a stress relaxation material. From the above, it is possible to obtain a bonded body in which the mechanical strength of the bonded portion is less deteriorated as compared with the strength of the ceramic base material.

The thickness of the bonding layer containing the above-mentioned Me (1) -Me (2) -O compound is 2 μm or less. When the thickness of the bonding layer exceeds 2 μm, the mechanical strength of the bonded portion is greatly reduced. That is, when the thickness of the bonding layer is 2 μm or less, the decrease in mechanical bonding strength as compared with the ceramic base material can be minimized.

The bonding layer in the present invention is substantially the above M.
e (1) -Me (2) -O-based compound may be used alone,
Alternatively, it may be a mixed layer of the above compound and its constituent metal elements. In these forms, although the compound also has a function as a brazing filler metal, as a substantial brazing filler metal component, the constituent metal element of the compound, specifically Me
(2) can be included separately from the above compounds. In addition to Me (1) and Me (2), a metal element that functions as a brazing material, such as Ag, can be included in the bonding layer.

The method for forming the above Me (1) -Me (2) -O compound and the bonding layer containing the same is not particularly limited, but, for example, as described below, It is preferred to form the above compounds at the same time.

That is, first, thin films of Me (1) and Me (2) are sequentially laminated on the surface of a ceramic substrate to form a multilayer film. At this time, the Me (1) thin film is formed on the ceramic substrate side. In addition, when a metal element other than Me (1) and Me (2) is included in the bonding layer, the thin film is similarly formed into multiple layers. As a method for forming the above-mentioned thin film, a physical or chemical film forming method such as a sputtering method, a vapor deposition method or a CVD method can be applied. The thickness of these thin films is set so that the Me (1) -Me (2) -O-based compound having the above composition ratio is formed. For example, Me (2) itself is made to function as a brazing filler metal. At that time, the thickness shall be set in consideration of that amount. In addition, after the joining process (heat treatment), each thickness is set so that the thickness of the joining layer is 2 μm or less.

Next, a joining partner member is arranged on the above-mentioned thin multilayer film and heated to the joining temperature. At this time, it is important to set the heating rate at a rate such that the Me (1) -Me (2) -O-based compound is sufficiently formed in the heating process. That is, since the Me (1) -Me (2) -O-based compound is formed by the solid-phase reaction between the multilayer thin films, the solid-phase reaction proceeds at a slow rate so that the solid-phase reaction can proceed sufficiently. It is preferable to warm. As described above, in the method using the thin film, the contact between the ceramic base material and the thin film is made beforehand,
Diffusion and compound formation reaction in the solid phase rapidly proceed. Specifically, it is preferably set to 15 ° C./minute or less. Oxygen in the above Me (1) -Me (2) -O-based compound is supplied from the ceramic base material side when using the oxide-based ceramic base material. Oxygen can also be supplied from within the above-mentioned multi-layered thin film or from the atmosphere.

As described above, after the Me (1) -Me (2) -O-based compound is formed in the heating process, the temperature is raised to near the melting temperature (bonding temperature) of the brazing filler metal component in the bonding layer, A ceramic base material and a metal base material, or ceramic base materials of the same composition or different compositions are bonded together. By forming a Me (1) -Me (2) -O based compound in the bonding layer, a bonding interface with a large chemical bond can be obtained as described above, and the stress generated on the ceramic substrate side can be reduced. Therefore, a joined body can be obtained in which the mechanical strength of the joined portion is less likely to decrease. Also,
Since the Me (1) -Me (2) -O compound has high wettability with respect to the brazing filler metal, the brazing filler metal component in the bonding layer spreads well on the above compound, resulting in even better bonding strength. To be

In the joining method described above, the Me (1) -Me (2) -O-based compound is simultaneously formed during the joining heat treatment.
The method for forming the Me (1) -Me (2) -O-based compound in the present invention is not limited to this, and for example, the bonding heat treatment may be performed after the above compound is formed in advance.

The above-mentioned Me (1) -Me (2) -O compound having the diamond structure of the space group Fd3m contributes not only to the joining layer of the joined body but also to the improvement of the joining strength of the metallized layer. That is, the first metallized body in the present invention is the above M
A metallized layer containing an e (1) -Me (2) -O-based compound is provided on a ceramic substrate. The specific configurations and the like of the compounds and the ceramic base material are the same as those of the above-mentioned joined body. Similarly, its thickness is preferably 2 μm or less.

The metallized layer does not necessarily have to be composed of only the above compound, and may be present near the interface with the ceramic substrate from the viewpoint of improving the bonding strength. Further, when utilizing the high wettability of the Me (1) -Me (2) -O-based compound with respect to the brazing filler metal, it is sufficient that the compound appears, for example, in spots on the surface of the metallized layer. It is more preferable that they are present in layers.

The metallized body is produced, for example, as follows. First, in the same manner as in the production of the bonded body described above, thin films of Me (1) and Me (2) are sequentially formed on the ceramic base material to produce a multilayer film. The thickness of these thin films is not particularly limited, but the atomic ratio Me (1): Me
(2) = It is preferable to set it in the range of 1: 1 to 3: 1. This is because, in this composition range, the compound having the diamond structure of the space group Fd3m described above is likely to be formed.

Next, in the ceramic substrate on which the above-mentioned thin film multilayer film is formed, a temperature range below the melting point of each thin film and above the temperature at which the solid phase reaction between the multilayer thin films and between the thin film and the ceramic substrate can proceed. Heat treatment is performed. As a specific heat treatment temperature, when Ti is used as Me (1) and Cu is used as Me (2), a temperature range of 600 ° C. to 800 ° C. is preferable. Even if the heat treatment temperature is too low or higher than the melting point,
The desired Me (1) -Me (2) -O compound cannot be formed sufficiently. The heat treatment atmosphere may be a vacuum, an inert atmosphere, or an oxygen-containing atmosphere.

By the heat treatment at such a temperature, the solid phase reaction proceeds at the interface and between the multi-layer thin films, and Me (1) -Me (2)
-O compounds are formed. The progress of the solid-phase reaction is, for example, when a thin film of Ti and Cu is sequentially formed on an alumina-based substrate,
Ti reduces alumina to generate oxygen, and this oxygen and Ti
A compound having a diamond structure in the space group Fd3m is formed by Cu. Oxygen in the above Me (1) -Me (2) -O-based compound is supplied from the ceramic base material side when using the oxide-based ceramic base material. Oxygen can also be supplied from within the above-mentioned multi-layered thin film or from the atmosphere.
At this time, oxygen is supplied from the ceramic substrate side to the ceramic base material side of the metallized layer, and oxygen is supplied from the atmosphere to the surface side of the metallized layer, so that the Me (1) -Me (2) -O-based compound is metalized layer. It is also possible to form them in a separate manner or to form them in a partially continuous state.

As described above, by forming the Me (1) -Me (2) -O type compound in the metallized layer, a metallized layer having a large chemical bond can be obtained. When the above compound is present on the surface of the metallized layer, a metallized layer excellent in wettability with respect to the brazing material can be obtained. Where Me (1) -M
The ratio of the e (2) -O-based compound in the metallized layer is not particularly specified, but Me (1)
-Me (2) -O-based compound, the film thickness in the step of forming a thin film is set according to the atomic ratio of the compound, or the heat treatment time is set so that the compound is sufficiently formed. It is important to set.

Next, another metallized body of the present invention will be described. As described above, the second, third, and fourth metallized bodies according to the present invention have at least 1 selected from Ti, Zr, and Hf on the alumina-based ceramic substrate.
A metallized body provided with at least an active metal layer of seeds, wherein when the metallized layer is formed while reducing the alumina-based ceramic substrate with the active metal, the reduction reaction of alumina is performed under solid-state heat treatment, and It has a structure that prevents Al generated by the reduction of Al from remaining at the bonding interface, thereby activating the interfacial reaction.

Specific means for preventing Al from remaining at the bonding interface due to the reduction of alumina is as follows:
When Cu is metallized on an alumina-based substrate, Al produced by reduction of alumina, active metal, and compound particles containing Cu as constituent elements are dispersed at the interface between the active metal layer and the alumina-based substrate. The formed structure. That is, a thin film of active metal and a thin film of Cu are sequentially formed on an alumina-based substrate, and this thin film body is subjected to solid phase heat treatment without melting.
Thereby, the active metal thin film becomes a reaction layer composed of active metal particles (including active metal oxide particles) firmly adhered to the interface with the alumina-based substrate. At this time, alumina is reduced by the active metal to form Al having metal binding property,
Compound particles containing Al and active metal and Cu as constituent elements are dispersedly formed at the interface between the active metal layer and the alumina-based substrate, that is, at the interface between the active metal particle and the alumina-based substrate, and produced. The Al thus formed is taken in as a constituent element of the compound particles formed on the interface, and is prevented from remaining in the bonded interface as it is. On the other hand, since the active metal segregates at the bonding interface, the Cu layer maintains high purity.

(B) In the case of metallizing an active metal on an alumina-based base material, the active metal thin film formed on the alumina-based base material is bonded to Al in advance or on the surface or on the interface with the alumina-based base material. An easy substance (hereinafter referred to as an Al absorbing substance) is arranged as a dispersion layer, particles, or a thin film, and a solid phase heat treatment is performed without melting the thin film of the active metal. As a result, the active metal thin film reacts with alumina to form an active metal layer firmly adhered to the interface with the alumina-based substrate. At this time, the alumina is reduced by the active metal and has a metal-binding property.
Diffuses to the active metal layer side as Al. This Al binds to the dispersion layer, particles, or thin film of the above Al absorbing substance and is prevented from remaining at the bonding interface.

(C) When metallizing an active metal on an alumina-based substrate, the active-metal thin film formed on the alumina-based substrate is subjected to solid-phase heat treatment without melting to form an alumina-based substrate surface. The orientation film is mainly composed of active metal crystal grains in which the c-axis of the crystal is oriented within a range of ± 30 degrees with respect to the vertical direction. The active metal thin film reacts with alumina by the above solid-phase heat treatment to form an active metal layer firmly adhered to the interface with the alumina-based substrate. At this time, alumina is reduced by the active metal and diffuses to the active metal layer side as metal-binding Al. This Al diffuses in the alignment film of the active metal, which has a film structure that accelerates the diffusion of Al, and is prevented from remaining at the bonding interface.

The metallized body having the above structures (a) to (c) is produced, for example, as follows.

First, the alumina base material used in the present invention is preferably one having high surface smoothness and high cleanliness so as to enhance reactivity and diffusion at the interface. It is preferable to polish the surface of the alumina-based substrate in advance to improve smoothness, and to perform degreasing treatment before forming the metal thin film. In particular, it is preferable to carry out the reverse sputtering treatment from the viewpoint of increasing the surface cleaning degree.

An active metal thin film is formed on the alumina base material as described above. As a method of forming the active metal thin film, a PVD method such as a sputtering method or an evaporation method, or a CVD method
Although the method can be applied, PVD can be used to improve the purification of membrane components.
Method is preferred. In addition, a Cu thin film or the like is formed on the active metal thin film as needed. In the above (a), formation of a Cu thin film is essential. Further, in (b) and (c), formation of a Cu thin film on the active metal film and further formation of another metal thin film can be applied. By using the thin film forming method as described above, it is possible to achieve a processing accuracy that cannot be obtained with a conventionally used paste or the like by using masking, and also improve the adhesion. Furthermore, by using the thin film forming method, it becomes possible to cause a solid phase reaction from a low temperature which has not occurred in the pastes and foils used conventionally.

As the active metal thin film, a metal film made of one selected from Ti, Zr, and Hf, a laminated film of these metal elements, an alloy film, or the like can be used. The thickness of the active metal thin film in (a) and (b) can be about 1 nm to 5 μm, and preferably 10 nm to 1 μm. Further, in (c), about 10 nm to 5 μm can be used, and preferably 50 nm to 1 μm. The thickness of another metal thin film such as a Cu thin film may be about 1 nm to 10 μm, preferably 100 nm to 5 μm.

Here, in the above (b), a substance that easily binds to Al in the process of forming the active metal thin film (Al absorbing substance)
A dispersed layer or dispersed particles made of Al is formed in the active metal thin film, or after forming the active metal thin film, Al is formed on it.
Form a thin film of absorbent material. As the substance that is easily bonded to Al, one selected from 3A group element, 4A group element, 5A group element, 8A group element and 1B group element, or an alloy, compound, laminated film or the like composed of several kinds of them Is mentioned.

As a specific method for forming the Al absorbing substance, for example, before forming the active metal thin film, the Al absorbing substance is formed on the alumina base material while being masked. The film thickness is preferably 0.1 nm to 100 nm,
nm to 50 nm is desirable. Further, the area of the Al absorbing material is preferably 50% or less of the total metallized area, and preferably 30% or less. It is desirable to disperse as finely as possible. An active metal thin film is continuously formed on the Al absorbing material layer.

When forming a dispersion layer of an Al absorbing substance inside the active metal thin film, the film formation of the active metal thin film is interrupted and the Al absorbing substance is masked while forming the film. This process is repeated several times. Do not overlap in the same position,
It is desirable to change the masking position. The film thickness is preferably 0.1 nm to 50 nm, and more preferably 0.1 nm to 20 nm. Area of Al absorbing material is 30% of total metallized area
It is preferably not more than 15%, more preferably not more than 15%. Similarly, it is desirable to disperse as finely as possible.
Further, when a thin film of an Al absorbing material is formed on the active metal thin film, a film thickness of about 1 nm to 3 μm can be used, preferably about 1 nm to 0.5 μm.

Next, an active metal thin film and, if necessary, Cu
Heat treatment is applied to the alumina-based substrate on which the thin film and the like are formed. In order to maintain the cleanliness of the alumina surface and the metal thin film, the heat treatment atmosphere should be performed in a vacuum or in a high-purity inert gas. In practice, a vacuum of 10 ^-4 Torr or more or Ar gas of 5N or more is used. It is preferable to carry out in.

Further, the heat treatment temperature is the same as in the above (a) and (b).
Is above 500 ° C and below the melting point of the metal thin film, and in (c) above it is above 700 ° C and below the melting point of the metal thin film. In (a) and (b), heat treatment temperature is 500 ℃
If it is less than the above range, the interfacial reaction of the present invention becomes difficult to occur, and if it exceeds the melting point, the metal film is dissolved and the effect of the present invention cannot be obtained. In addition, in (c), the heat treatment temperature is 700
This is because if the temperature is lower than ° C, the orientation of the active metal film, the interfacial reaction, and the rapid diffusion of Al become difficult to occur. A more preferable heat treatment temperature is in the range of 700 ° C to 900 ° C in (a) and (b), and 700 ° C to 1000 ° C in (c). If an oxide film is formed on the surface of the metal thin film, it may be removed by etching or the like.

By carrying out the heat treatment as described above, the active metal firmly adheres to the surface of the alumina base material while reducing the alumina. Heat treatment time is 30 minutes for (a)
The time is preferably about 5 hours, and 1 to 3 hours is desirable in order to create the target tissue. Also, in (b)
It is preferably about 3 minutes to 5 hours, and more preferably 30 minutes to 1 hour. In (c), it is preferably about 5 minutes to 1 hour, and more preferably 10 minutes to 30 minutes.

Next, for each of the above (a), (b) and (c), a concrete solid phase reaction in the heat treatment process will be described. First, in (a), the structure of the active metal film at the time of film formation is an aggregate of amorphous-like ultrafine particles, but recrystallization is performed by heat treatment to make the structure of the active metal 200 nm to 500 nm wide. The height is about 150 nm to 300 nm, and the active metal particles form a layer near the interface. With such a structure, the recrystallized crystal grains and the layered structure of the crystal grains can alleviate the stress generated by heat treatment or the like due to the grain boundary movement. Further, by performing heat treatment at a temperature higher than 500 ° C. and lower than the melting point of the metal thin film, the active metal particles react with alumina and the interface becomes uneven, so that the adhesion between the alumina and the active metal film can be improved. .

The Al produced as a result of the reaction is diffused into the active metal particles to form a compound phase containing the active metal, Al and Cu as constituent elements at the interface between the alumina and the active metal particles. To form. With this active metal
The size of the compound particles consisting of Al and Cu is about 100 nm or less, and since both the components of alumina and active metal are contained and they are strongly bonded to both phases, this compound particle is formed at the interface. By doing so, higher adhesion can be obtained. Further, by incorporating Al into the compound particles, the generated Al does not hinder the interfacial reaction. Furthermore, since the particles are dispersed in the interface in the form of particles, the stress at the interface can be relaxed.

On the other hand, in the Cu thin film layer, the active metal adheres to the interface and segregates, so that mutual diffusion is suppressed and it is possible to maintain a high purity. Further, by the heat treatment for a long time of 30 minutes or more, recrystallization of Cu proceeds more than that of the active metal phase, and a film having good grain orientation and containing almost no grain boundaries can be obtained.

In addition, in (b) and (c), the active metal reduces alumina by performing heat treatment.
As long as the active metal layer and the alumina are in direct contact with each other, the alumina is reduced, which enables good metallization. Although the metal-binding Al is produced along with the reduction reaction, if it stays at the interface, it prevents the active metal layer from coming into direct contact with the alumina, and consequently the reduction of the alumina.

Therefore, in (b), Al is absorbed in a dispersion layer, particles or a thin film made of a substance that easily bonds with Al to form a bonding reaction phase. The binding reaction phase may contain an active metal. As a result, the active metal layer and the alumina are always in direct contact with each other so that the reduction reaction can always occur. This enables strong metallization.

In (c), the diffusion rate of Al of the active metal such as Ti in the c-axis direction is remarkably higher than that of the other orientations, and at 1100K, it diffuses faster than O, C and N. Therefore, by solid-phase heat treatment, the active metal thin film is formed into an alignment film in which the c-axis is aligned within a range of ± 30 degrees with respect to the direction perpendicular to the surface of the alumina-based substrate. If the c-axis of the crystal exceeds the range of ± 30 degrees with respect to the direction perpendicular to the surface of the alumina-based substrate, the Al high-speed diffusion effect cannot be sufficiently obtained.
In addition, the proportion of crystal grains whose c-axis is within ± 30 degrees with respect to the direction perpendicular to the surface of the alumina-based substrate is 5
If it is 0% or more, the high-speed diffusion effect of Al is clearly obtained.
It is more desirable to contain 0% or more. When the active metal film is an alignment film as described above, Al that interferes with the reaction
Can be diffused into the active metal film at high speed. As a result, the active metal and the alumina-based substrate are always in direct contact with each other, and the reduction reaction can be activated. Further, a metallized layer having excellent adhesion can be obtained by heat treatment for a shorter time than in the past.

In the above metallized body,
Although (a), (b) and (c) have been described individually, a structure in which these are combined is also possible.

In the metallized body of the present invention, the decrease in bonding strength due to stress concentration due to the difference in thermal expansion is suppressed, and since the active metal thin film or the like is not in a molten state, wraparound does not occur. It is possible to obtain a metallized layer having a precise pattern. The metallized body of the present invention can be used, for example, in the following applications.
That is, when obtaining a circuit board material or the like by metallization, masking should be performed according to the wiring or circuit pattern, and an active metal thin film and, if necessary, a Cu thin film should be formed, and then heat treatment should be performed in vacuum. Thus, it is possible to easily obtain a substrate material having a precise wiring or circuit pattern. Also, when joining lead pins and the like, the I / O pins can be easily brazed onto the metallized layer of the present invention or onto the Cu layer formed thereon.

[0057]

EXAMPLES Examples of the present invention will be described below.

Example 1 Thin films of Ti, Cu, and Ag were laminated in this order on the bonding surface of an alumina base material having a purity of 96% by the sputtering method. The thickness of each thin film was 360 nm, 1225 nm, and 2700 nm, respectively. Then, the Fe-42% Ni alloy base material was brought into contact with the above-mentioned thin film laminate, and heated to 800 ° C at a heating rate of 5 ° C / minute in a vacuum of 8 × 10 ^-6 Torr, thereby The alumina base material and the Fe-42% Ni alloy base material were bonded together while forming a Cu-Ti-O based compound having a diamond structure of space group Fd3m.

When a tensile test was conducted on the bonded body thus obtained, the bonding strength was 5 kg / mm ² . In addition, a Cu-Ti-O-based compound layer having a diamond structure with a space group Fd3m and a thickness of about 1 μm was detected in the bonding layer.

On the other hand, a paste-like Ti-Cu-Ag brazing material is applied on the bonding surface of an alumina base material having a purity of 96%, and the brazing material layer is melted to bond the Fe-42% Ni alloy base material. did. When a tensile test was performed on this bonded body, the bonding strength was 2 kg / mm ² , and no Cu-Ti-O based compound having a diamond structure with a space group Fd of 3 m was detected in the bonded layer. Example 2 Thin films of Ti and Cu were laminated in this order on the bonding surface of an alumina base material having a purity of 96% by the sputtering method. The thickness of each thin film was 400 nm and 800 nm, respectively. Then, contact the Fe-42% Ni alloy substrate on the laminate of the thin film, 7 ×
By heating in a vacuum of 10 ^-6 Torr to 950 ° C at a heating rate of 10 ° C / min, while forming a Cu-Ti-O compound having a diamond structure of space group Fd3m at the interface, an alumina base material And Fe-42% Ni alloy base material were joined.

When a tensile test was conducted on the thus obtained joint, the joint strength was 4 kg / mm ² . In addition, a Cu-Ti-O-based compound layer having a diamond structure with a space group Fd of 3 m and a thickness of about 0.3 μm was detected from inside the bonding layer.

On the other hand, a paste-like Ti-Cu brazing material was applied on the bonding surface of an alumina base material having a purity of 96%, and the brazing material layer was melted to bond the Fe-42% Ni alloy base material. . When a tensile test was performed on this bonded body, the bonding strength was 1 kg / mm ² , and no Cu-Ti-O-based compound having a diamond structure in the space group Fd3m was detected in the bonded layer. Example 3 Thin films of Ti and Ni were laminated in this order on the joint surface of an aluminum nitride base material having a purity of 96% by the sputtering method. The thickness of each thin film was 200 nm and 400 nm, respectively.
Then, contact the Mo alloy substrate on the laminate of the thin film,
By heating in a vacuum of 5 × 10 ^-6 Torr to 1000 ° C at a heating rate of 8 ° C / min, while forming a Ni-Ti-O-based compound having a diamond structure of space group Fd3m at the interface, nitriding is performed. The aluminum base material and the Mo alloy base material were joined.

When a tensile test was conducted on the thus obtained joint, the joint strength was 3.5 kg / mm ² . Also,
A Ni-Ti-O-based compound layer having a diamond structure with a space group Fd3m and a thickness of about 0.1 μm was detected in the bonding layer.

On the other hand, a foil-shaped Ti-Ni brazing material was placed on the bonding surface of an aluminum nitride base material having a purity of 96%, and the brazing material was melted to bond the Mo alloy base material. When a tensile test was performed on this bonded body, the bonding strength was 2 kg / mm ² ,
No Ni-Ti-O based compound having a diamond structure with space group Fd3m was detected in the bonding layer.

Example 4 Thin films of Zr, Ag, and Cu were laminated in this order on the joint surface of an aluminum nitride base material having a purity of 96% by the sputtering method. The thickness of each thin film is 70nm, 540nm and 250nm respectively.
And Then, a Fe-42% Ni alloy base material was brought into contact with the above-mentioned thin film laminate, and the temperature was raised in an Ar atmosphere at a temperature rising rate of 10 ° C./min.
By heating to ℃, while forming a Cu-Zr-O-based compound having a diamond structure of space group Fd3m at the interface,
The aluminum nitride base material and the Fe-42% Ni alloy base material were joined.

When the tensile test of the bonded body thus obtained was conducted, the bonding strength was 2 kg / mm ² . A Cu-Zr-O-based compound layer having a diamond structure with a space group Fd3m and a thickness of about 0.1 μm was detected in the bonding layer.

On the other hand, a paste Zr-Cu-Ag brazing material is placed on the joining surface of a 96% pure aluminum nitride substrate, and the brazing material is melted to form a Fe-42% Ni alloy substrate. Joined.
When a tensile test was performed on this bonded body, the bonding strength was 0.
It was 8 kg / mm ² , and no Cu-Zr-O-based compound having a diamond structure of space group Fd3m was detected in the bonding layer.

Example 5 A thin film of Ti, Cu, and Ag was laminated in this order on the bonding surface of a single crystal alumina substrate having a purity of 99% by the sputtering method. The thickness of each thin film was 72 nm, 245 nm, and 540 nm, respectively. Next, in a vacuum of 5 × 10 ^-6 Torr, the heating rate is 5 ° C /
Heat treatment was performed by heating to 700 ° C. for 7 minutes to form a layer containing a Cu—Ti—O-based compound having a diamond structure of space group Fd3m on the single crystal alumina substrate. After this, Fe-4
Pins made of 2% Ni alloy were brought into contact with each other and heated to 800 ° C to join them.

After the joining, a tensile test of the pin was conducted, and it was found that the joining strength was 6 kg / mm ² , and from the inside of the joining layer,
Has a diamond structure with a space group Fd of 3 μm and a thickness of 0.2 μm
A Cu-Ti-O based compound layer was detected.

On the other hand, a pin made of Fe-42% Ni alloy was placed in contact with the bonding surface of a single crystal alumina base material having a purity of 99% via a foil-like Ti-Cu-Ag brazing material, The brazing material was melted and the pins were joined. After the bonding, a tensile test of the pin was performed, and the bonding strength was 2 kg / mm ² , and no Cu-Ti-O-based compound having a diamond structure in the space group Fd3m was detected in the bonding layer.

Example 6 On the bonding surface of an alumina base material having a purity of 96%, a thin film of Ti and Cu was deposited in this order by a sputtering method, and the atomic ratio of Ti: Cu was
The layers were formed so as to be 3: 2. The thickness of the thin film stack is
It was set to 200 nm. Next, the alumina base material on which the above thin film laminate is formed is placed in a vacuum furnace and the atmosphere is set to 5 × 10 5.
^After setting the vacuum degree to ⁻⁶ Torr, the temperature was raised to 700 ° C. at 5 ° C./minute and kept for 2 hours, and then the heating power was turned off and the furnace was cooled. When the sample was taken out of the furnace when it reached room temperature, it had a space group Fd3m diamond structure on the alumina substrate.
A Cu-Ti-O-based compound (atomic ratio Cu: Ti: O = 2: 4: 1) layer was formed.

The wetting angle of silver solder (BAg-8) with respect to the surface on which the above compound layer was formed was measured.
It was 10 degrees smaller than the metallized layer by the o-Mn method.
Further, a Kovar alloy was brought into contact with the above compound layer, and heat bonding was performed using the above silver braze. A tensile test of this bonded body showed that the bonding strength was 5 kg / mm ² , and
-Compared with the case of joining to the metallized layer by the -Mn method,
The strength was 4 kg / mm ² .

Example 7 On the bonding surface of an alumina base material having a purity of 96%, a thin film of Ti and Cu was deposited in this order by a sputtering method, and the atomic ratio of Ti: Cu was
The layers were formed in a ratio of 1: 1. The thickness of the thin film stack is
It was set to 500 nm. Next, the alumina base material on which the above thin film laminate is formed is placed in a vacuum furnace and the atmosphere is set to 5 × 10 5.
^After setting the vacuum degree to ⁻⁶ Torr, the temperature was raised to 700 ° C. at 5 ° C./minute and kept for 2 hours, and then the heating power was turned off and the furnace was cooled. When the sample was taken out of the furnace when it reached room temperature, it had a space group Fd3m diamond structure on the alumina substrate.
A Cu-Ti-O-based compound (atomic ratio Cu: Ti: O = 3: 3: 1) layer was formed.

The wetting angle of silver solder (BAg-8) with respect to the surface on which the compound layer was formed was measured.
It was 10 degrees smaller than the metallized layer by the o-Mn method.
Further, a Kovar alloy was brought into contact with the above compound layer, and heat bonding was performed using the above silver braze. A tensile test of this bonded body showed that the bonding strength was 6 kg / mm ² , and
-Compared with the case of joining to the metallized layer by the -Mn method,
The strength was 5 kg / mm ² .

Example 8 On the bonding surface of an alumina base material having a purity of 99%, thin films of Ti and Ni were deposited in this order by a sputtering method, and the atomic ratio of Ti: Ni was
The layers were formed in a ratio of 1: 1. The thickness of the thin film stack is
It was set to 300 nm. Next, the alumina base material on which the above thin film laminate is formed is placed in a vacuum furnace and the atmosphere is set to 5 × 10 5.
After the vacuum degree was set to ^-6 Torr, the temperature was raised to 800 ° C at 5 ° C / min and kept for 1 hour, and then the heating power was turned off and the furnace was cooled. When the sample was taken out of the furnace when it reached room temperature, it had a space group Fd3m diamond structure on the alumina substrate.
A Ni-Ti-O-based compound (atomic ratio of Ni: Ti: O = 3: 3: 1) layer was formed.

The wetting angle of silver solder (BAg-8) with respect to the surface on which the above compound layer was formed was measured.
It was 5 degrees smaller than the metallized layer by the o-Mn method.
Further, a Mo material was brought into contact with the compound layer, and heat bonding was performed using the silver brazing material. A tensile test of this bonded body showed a bonding strength of 4 kg / mm ^2, which is 3 kg / mm ² compared to the case of bonding to a metallized layer by the conventional Mo-Mn method.
The strength was great.

Example 9 On the bonding surface of an alumina base material having a purity of 99%, thin films of Zr and Cu were formed in this order by a sputtering method, and the atomic ratio of Zr: Cu was
The layers were formed in a ratio of 1: 1. The thickness of the thin film stack is
It was 400 nm. Next, the alumina base material on which the above thin film laminate is formed is placed in a vacuum furnace and the atmosphere is set to 5 × 10 5.
After the vacuum degree was set to ^-6 Torr, the temperature was raised to 800 ° C at 5 ° C / min and kept for 1 hour, and then the heating power was turned off and the furnace was cooled. When the sample was taken out of the furnace when it reached room temperature, it had a space group Fd3m diamond structure on the alumina substrate.
A Cu-Zr-O-based compound (atomic ratio Cu: Zr: O = 2: 4: 1) layer was formed.

The wetting angle of silver solder (BAg-8) with respect to the surface on which the above compound layer was formed was measured.
It was 3 degrees smaller than the metallized layer by the o-Mn method.
Further, a Mo material was brought into contact with the compound layer, and heat bonding was performed using the silver brazing material. A tensile test of this bonded body showed a bonding strength of 4 kg / mm ^2, which is 3 kg / mm ² compared to the case of bonding to a metallized layer by the conventional Mo-Mn method.
The strength was great.

Example 10 On the bonding surface of an alumina base material having a purity of 99%, a thin film of Ti and Cu was formed in this order by a sputtering method, and the atomic ratio of Ti: Cu was
The layers were formed in a ratio of 1: 1. The thickness of the thin film stack is
It was 400 nm. Next, the alumina base material on which the above thin film laminate is formed is placed in a vacuum furnace and the atmosphere is set to 5 × 10 5.
After the vacuum degree was set to ^-4 Torr, the temperature was raised to 800 ° C at 5 ° C / minute, held for 1 hour, and then the heating power was turned off to cool the furnace. When the sample was taken out of the furnace when it reached room temperature, it had a space group Fd3m diamond structure on the alumina substrate.
A Cu-Ti-O-based compound (atomic ratio Cu: Ti: O = 2: 4: 1) layer was formed.

The wetting angle of silver solder (BAg-8) with respect to the surface on which the above compound layer was formed was measured.
It was 3 degrees smaller than the metallized layer by the o-Mn method.
Further, a Mo material was brought into contact with the compound layer, and heat bonding was performed using the silver brazing material. A tensile test of this bonded body showed a bonding strength of 4 kg / mm ^2, which is 3 kg / mm ² compared to the case of bonding to a metallized layer by the conventional Mo-Mn method.
The strength was great.

Example 11 First, the surface of an alumina substrate used as a circuit board material was polished to a mirror surface. Next, after degreasing with acetone to remove dirt on the surface of the alumina substrate, surface cleaning was performed by reverse sputtering. After masking the surface of this alumina substrate according to the wiring pattern, a Ti thin film with a thickness of 200 nm and a thickness of 600 nm above it were formed by sputtering.
Cu thin film was continuously formed. Then, heat treatment was performed in vacuum. The degree of vacuum was 5 × 10 ⁻⁶ Torr and the temperature was 900 ° C. for 3 hours. As a result, a precise Cu wiring pattern having good adhesion was formed on the alumina surface.

FIG. 1 is a diagram schematically showing a film structure as a result of TEM observation of the cross section of the alumina substrate and the metallized layer produced through such steps. It was confirmed that there was no free portion between the alumina substrate 1 and the Ti segregation layer 2 as the active metal thin film and the compound particles 3, and the adhesion was good.
In addition, as a result of the EDX qualitative analysis,
Al, Cu, Ti and O were detected, and Ti and O were detected from the Ti segregation layer 2, and it was confirmed that the intended structure was formed.
Further, when EDX quantitative analysis was performed on the Cu metallized layer 4, a value of 97% was obtained, and it was confirmed that the intended Cu metallized was formed.

Example 12 The surface of an alumina substrate used as a circuit board material was polished to a mirror surface. Then, degrease with ethanol to remove dirt on the surface of the alumina substrate, mask the alumina substrate surface with the wiring pattern, and then use the sputtering method to deposit a Ti thin film with a thickness of 100 nm and a Zr thin film with a thickness of 150 nm. Then, a Cu thin film having a thickness of 800 nm was sequentially formed.
Then, after putting in a chamber and evacuating to 7 × 10 ⁻⁶ Torr, heat treatment was performed in high-purity Ar gas (6N) at 800 ° C. for 1.5 hours. As a result, a precise Cu wiring pattern having an active metal reaction layer at the interface with the alumina substrate and good adhesion was formed.

FIG. 2 is a sectional view of an alumina substrate manufactured through such steps. The Cu metallization layer 4 was formed on the alumina substrate 1 via the active metal reaction layer 5. Since a thin oxide film was formed on the surface of the Cu metallized layer 4, this oxide film was removed by dry polishing.

Example 13 The surface of an alumina substrate used as a circuit board material was polished to a mirror surface. Next, after degreasing with acetone to remove dirt on the surface of the alumina substrate, surface cleaning was performed by reverse sputtering. A mask (mask A) was applied to the surface of the alumina substrate in accordance with the wiring pattern, and then a mask (mask B) having holes of 1 μm in diameter arranged at intervals of 50 μm was applied.
After forming a Cu thin film with a thickness of 40 nm by the sputtering method, remove the mask B and a Ti thin film with a thickness of 200 nm on top of this.
It was formed into a film. Then, heat treatment was performed in vacuum. The degree of vacuum was 5 × 10 ⁻⁶ Torr, and the heat treatment condition was 900 ° C. × 50 minutes. As a result, a precise wiring pattern with good adhesion was formed on the surface of the alumina substrate.

FIG. 3 is a diagram schematically showing a film structure as a result of TEM observation of the cross section of the alumina substrate and the metallized layer produced through such steps. Alumina substrate 1
It was confirmed that there was no free portion between 1 and the Ti layer 12 as the active metal layer, and the adhesion was good. It was also confirmed that the compound 13 was formed between the alumina substrate 11 and the Ti layer 12. Furthermore, as a result of EDX qualitative analysis, from the compound 13, Al, Cu, Ti and O were found to be in the Ti layer 1
Ti and O were detected from 2 and it was confirmed that the desired structure was formed.

Example 14 The surface of an alumina substrate was polished to a mirror surface. Then, degrease with ethanol to remove dirt on the surface of the alumina substrate, then form a Zr thin film with a thickness of 100 nm on the surface of the alumina substrate by a sputtering method, and then apply a mask.
A Ni thin film was formed to a thickness of 25 nm. The mask has holes with a diameter of 1 μm arranged at intervals of 70 μm. This process was repeated 5 times. The position of the mask was moved by 300 μm. Then, after putting in a chamber and evacuating to 7 × 10 ⁻⁶ Torr, heat treatment was performed at 800 ° C. for 50 minutes in high-purity Ar gas (6N).
As a result, a metallized layer having good adhesion was formed on the alumina substrate.

FIG. 4 is a diagram schematically showing a cross-sectional structure of an alumina metallized body produced through such steps. In the Zr layer 14 formed on the alumina substrate 11,
The Zr-Al-Ni-based compound 15 was formed according to the Ni film formation pattern. In addition, a Zr metallized body (using a Zr-Ni paste) produced by an ordinary metallization method was subjected to a scratch test to compare the adhesion. When tested at 7 kg / mm ² , peeling was observed in the Zr metallized layer produced by the usual metallizing method, but peeling was not observed in the metallized layer according to the above-mentioned example.

Example 15 The surface of an alumina substrate was polished to a mirror surface. Then, degrease with ethanol to remove dirt on the surface of the alumina substrate, and then deposit a Ti thin film with a thickness of 500 nm on the surface of this alumina substrate by a sputtering method, and then a Co thin film.
The film was formed at 100 nm. After this, put it in the chamber 4 × 10 ^-6
After evacuating to Torr, in high purity Ar gas (6N), 900
Heat treatment was performed at ℃ for 1 hour. As a result, a metallized layer having good adhesion was formed on the alumina substrate.

FIG. 5 is a diagram schematically showing a film structure as a result of TEM observation of an alumina metallized body produced through such steps. It was confirmed that there was no peeling portion between the alumina substrate 11 and the Ti layer 16, and that the adhesion was good. In addition, as a result of EDX qualitative analysis, Ti layer 16 and Co
It was confirmed that Al was detected from the layer 17 and that the Co layer 17 had a particularly high Al concentration and a target cross-sectional structure that promotes the diffusion of Al was formed.

Example 16 The surface of an alumina substrate used as a circuit board material was polished to a mirror surface. Next, after degreasing with acetone to remove dirt on the surface of the alumina substrate, surface cleaning was performed by reverse sputtering. After masking the surface of this alumina substrate according to the wiring pattern, by sputtering method,
A Ti thin film was formed to a thickness of 200 nm. After this, vacuum degree 5 × 10
Heat treatment was performed at 900 ° C for 50 minutes in an atmosphere of ^-6 Torr. As a result, a precise wiring pattern with good adhesion was formed on the surface of the alumina substrate.

FIG. 6 is a diagram schematically showing a film structure as a result of TEM observation of a cross section of the alumina substrate and the metallized layer produced through such steps. Alumina substrate 2
In the Ti layer 22 provided on the 1 layer, the electron beam diffraction patterns of the two Ti crystal grains A and B were examined at the place where the TEM observation was performed.
2 (bar) 0], and the (0002) direction is the first alumina substrate 2
With respect to the surface of No. 1, the crystal grain A was 15 degrees and the crystal grain B was 8 degrees. Further, it was confirmed that there was no free portion between the alumina substrate 21 and the Ti layer 22 and that the adhesion was good. Further, as a result of EDX qualitative analysis, Al was detected from the Ti layer 22 and it was confirmed that Al diffusion occurred.

Example 17 The surface of an alumina substrate was polished to a mirror surface. Then, degreasing was performed with ethanol to remove dirt on the surface of the alumina substrate, the alumina substrate surface was masked in accordance with the wiring pattern, and then a Ti thin film was formed to a thickness of 2 μm by a sputtering method. After this, put it in the chamber 7 ×
After vacuuming to 10 ⁻⁶ Torr, heat treatment was performed in high-purity Ar gas (6N) at 800 ° C. for 20 minutes. FIG. 7 is a schematic view of an alumina substrate manufactured through such steps. The Ti layer 22 having excellent adhesion was formed on the alumina substrate 21.

Further, under the same film forming conditions and heat treatment, TE
A sample for M observation was prepared, and TEM observation was performed from a direction perpendicular to the surface of the alumina substrate. When the electron beam diffraction pattern of the observed crystal grains was examined, 75% of the crystal grains obtained an electron beam diffraction pattern in which the incident direction of the electron beam was (0001) within an inclination angle of ± 30 degrees.

Next, the metallized body of the above-described embodiment and the ordinary
A scratch test was conducted to compare the adhesion with the Ti metallized body obtained by applying and firing the Ti paste.As a result, a Ti metallized body using a normal Ti paste showed a peel strength comparable to that of the Ti metallized body according to the above example. In order to obtain the above, heat treatment time of 10 to 15 times was required. In addition, when the composition analysis of the produced Ti metallized layer was performed, impurities such as C and N were detected in the Ti metallized body using the ordinary Ti paste, but from the Ti metallized body according to the example,
Impurities such as C and N were not detected.

[0096]

As described above, according to the bonded body of the present invention, the concentration of stress on the ceramics side can be suppressed while improving the chemical bonding force at the interface, so that the ceramic base material can be suppressed. It is possible to stably provide a joined body in which the mechanical strength of the joined portion is less deteriorated as compared with the strength of 1. Further, according to the metallized product of the present invention, it is possible to stably provide a metallized product having a sufficient adhesion strength and a metallized layer having excellent shape reproducibility such as a fine pattern.

[Brief description of drawings]

FIG. 1 is a diagram schematically showing a result of TEM observation of a cross section of a metallized body according to an example of the present invention.

FIG. 2 is a diagram schematically showing a sectional structure of a metallized body according to another embodiment of the present invention.

FIG. 3 is a diagram schematically showing a result of TEM observation of a cross section of a metallized body according to still another example of the present invention.

FIG. 4 is a diagram schematically showing a cross-sectional structure of a metallized body according to an example of the present invention.

FIG. 5 is a diagram schematically showing a cross-sectional structure of a metallized body according to an example of the present invention.

FIG. 6 is a diagram schematically showing a result of TEM observation of a cross section of a metallized body according to another example of the present invention.

FIG. 7 is a perspective view showing a structure of a metallized body according to an embodiment of the present invention.

[Explanation of symbols]

 1, 11, 21 ... Alumina substrate 2, 5, 12, 22, 16 ... Ti layer 3 ... Ti-Cu-Al compound particles 4 ... Cu metallization layer 13 Ti-Cu-Al system Compound 14 …… Zr layer 15 …… Zr-Al-Ni-based compound 17 …… Co layer

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masako Nakahashi, No. 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Inside the Toshiba Research Institute Co., Ltd. (72) Inventor Shinichi Nakamura Toshiba, Komukai-shi, Kawasaki-shi, Kanagawa Town No. 1 Toshiba Corporation Research Institute

Claims (6)

[Claims] 1. A ceramic base material and a metal base material, or a joined body of ceramic base materials, wherein the first metal element is at least one selected from Ti, Zr and Hf, and Cu, Ni, A second metal element consisting of at least one selected from Co, Fe and Mn, and oxygen,
Contains a compound with a composition ratio of 70 at% or more, and has a thickness of
A bonded body characterized in that the ceramic base material and the metal base material or the ceramic base materials are bonded to each other through a bonding layer of 2 μm or less. 2. A ceramic base material, a first metal element provided on the ceramic base material and comprising at least one selected from Ti, Zr, and Hf, and Cu, Ni, Co, Fe, and Mn. A metallized body comprising a metallized layer containing a compound containing at least one selected second metal element and oxygen in a composition ratio of 70 at% or more. 3. Ti, Zr and Hf on a ceramic substrate.
A step of sequentially forming a thin film of a first metal element consisting of at least one selected from the following, and a thin film of a second metal element consisting of at least one selected from Cu, Ni, Co, Fe and Mn, The ceramic substrate on which the thin film is formed is heat-treated at a temperature equal to or lower than the melting point of the thin film, and the composition ratio of the first metal element, the second metal element and oxygen is 70 at% or more on the ceramic substrate. And a step of forming a metallized layer containing the compound contained therein. 4. Alumina-based ceramic substrate, Ti, Zr
And a layer of the active metal in which compound particles containing at least one active metal selected from Hf and Cu and Al as constituent elements are dispersed and formed in the vicinity of the interface with the alumina ceramic substrate, Cu on the metal layer
A metallized body comprising a layer. 5. An alumina-based ceramic base material, and Ti, Zr and
At least one of the interface between the active metal layer and the alumina-based ceramic substrate, the inside of the active metal layer, and the surface of the active metal layer. In the above, a metallized body is characterized in that a substance that easily binds to Al is arranged in advance, and the substance that easily binds to Al is present as a bond with Al by solid-state heat treatment. 6. An alumina-based ceramic substrate, and Ti, Zr and
An active metal layer comprising at least one selected from Hf, wherein the active metal layer has a crystal c-axis within a range of ± 30 degrees with respect to a direction perpendicular to the surface of the alumina-based ceramic substrate. A metallized body, which is an oriented film mainly composed of oriented crystalline particles of the active metal.