JPH0826841A - Production of bonded ceramics and the bonded ceramics - Google Patents

Abstract

PURPOSE:To provide a production process for bonded ceramics with improved reliability of bonding, for example, increased bonding strength and strength at an elevated temperature. CONSTITUTION:A ceramic layer 1 and a metal layer 3 of which the layer near the surface to be bonded is composed of a layer containing a hexagonal active metal capable decomposing the ceramic are laminated having a non-hexagonal structure-stabilizing element 2 partially in the bonding interface. The laminate is heat-treated in solid phase in vacuum or an inert gas atmosphere to bond the ceramic layer 1 to the metal layer 3'. Or a ceramic layer and a metal layer or two ceramic layers are laminated through a soldering material and at least a part of the soldering material is molten and solidified to effect bonding. Following the bonding process, the soldering material after solidification is heat- treated in solid state to allow the elements constituting the soldering layer to react with the melting point-increasing elements to raise the melting point of the soldering layer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a ceramics joined body such as metal / ceramics and ceramics / ceramics, and a ceramics joined body to which the method is applied.

[0002]

2. Description of the Related Art As a metallizing method for a ceramics substrate surface (metallizing method) or a method for joining a ceramics substrate to a metal substrate or ceramics substrates, a Mo-Mn method,
The DBC method and the active metal method are known. Mo-Mn method and D
The BC method has a problem that it is not possible to impart sufficient strength and fatigue resistance to the bonded body because the chemical bond strength at the interface is low. In addition, the active metal method utilizes the reduction effect of active metals such as Ti on the ceramics, so that chemical bondability at the interface can be obtained, and the strength and fatigue resistance are better than those described above. Is obtained.

In the above-mentioned conventional active metal method, the joining process is easy, but on the other hand, the brazing material containing the active metal is melted and the liquid phase state of this brazing material is used to form a metallized layer or a ceramic substrate. Since this is a method of joining a brazing material and a metal substrate, the melting point of the brazing material needs to be equal to or lower than the melting point of the members to be joined, and the high temperature strength of the joined body (including the metallized body) is governed by the melting point of the brazing material. However, it has a defect that it is not suitable for use at high temperatures, and also has a defect that it is difficult to form a fine pattern due to the protrusion of the brazing filler metal on the side surface.

On the other hand, attempts have been made to form a metallized layer on a ceramic substrate by a thin film forming method such as a sputtering method or a vapor deposition method. For example, forming an active metal film of Ti or the like on a ceramic substrate by a thin film forming method has been studied. As described above, by applying the thin film forming method, it is possible to form a fine pattern with good reproducibility, but the bonding strength of the metallized layer to the ceramic substrate is weak and the sufficient strength and resistance can be obtained. There is a problem that fatigue and the like cannot be obtained. Further, it is also considered that after forming an active metal film on a ceramic substrate, solid-phase heat treatment is performed in a vacuum or the like to cause an interfacial reaction to achieve a chemical bond at the interface and enhance adhesion. This method utilizes the reduction reaction of ceramics at the interface. However, simply performing solid-phase heat treatment does not provide sufficient bond strength because the interface shape is relatively flat, and the reliability of bonding is improved. I can't improve my sex enough. Further, when the heat treatment for bonding is performed at a high temperature for a long time, stress strain and the like due to the difference in thermal expansion between the ceramic substrate and the metallized layer or the metal substrate increase, and the reliability of the bonded body is reduced.

[0005]

As described above, the conventional bonding method utilizing the solid-phase heat treatment reaction is excellent in shape reproducibility of fine patterns and the like, but the shape of the bonding interface is relatively flat. In addition, there is a problem that it is difficult to sufficiently increase the bonding force between the ceramic substrate and the metallized layer or the metal substrate, and a bonded body (including a metallized body) having sufficient reliability cannot be obtained. Further, the brazing method using the brazing filler metal containing the active metal can obtain a joined body by an easy joining process, but on the other hand, the high temperature strength is dominated by the brazing filler metal, so that the high temperature strength is inferior and the brazing material also has sufficient reliability There was a problem that a bonded body could not be obtained.

The present invention has been made to address such a problem, and the main object of the present invention is to provide a method for manufacturing a ceramics joined body and a ceramics joined body with improved reliability of the joined portion. To provide. Specifically, a ceramic bonded body manufacturing method and a ceramic bonded body, which are excellent in shape reproducibility of a fine pattern or the like and are capable of improving reliability by increasing a bonding force, are further provided. It is an object of the present invention to provide a method for manufacturing a ceramics joined body and a ceramics joined body which can facilitate the joining process and can improve reliability by increasing high temperature strength.

[0007]

A first method for producing a ceramic joined body according to the present invention is a ceramic layer and a layer containing at least a layer near a joining surface containing a hexagonal active metal capable of decomposing the ceramic. When joining the metal layer constituted by, a step of laminating the ceramic layer and the metal layer with a non-hexagonal structure stabilizing element partially intervening at the joining interface, and vacuuming the laminate. And a step of joining the ceramic layer and the metal layer by solid phase heat treatment in an atmosphere or an inert gas atmosphere.

The first ceramics joined body is a ceramics joined body comprising a ceramics layer and a metal layer joined on the ceramics layer and containing at least an active metal as a constituent element of a layer near the joining surface. , A reduction reaction inert phase having a crystal structure other than a hexagonal system containing a non-hexagonal structure stabilizing element is partially interposed at the bonding interface between the ceramic layer and the metal layer, and the reduction reaction is performed. It is characterized in that a portion other than the inactive phase has a structure in which it is relatively projected to the ceramic layer side.

In the second method for manufacturing a ceramics joined body according to the present invention, when the ceramics layer and the metal layer or the ceramics layer are joined together, the ceramics layer and the metal layer or the ceramics layer are laminated via a brazing material,
A step of melting and solidifying at least a part of the brazing material to join the ceramic layer and the metal layer or the ceramic layers together, and subsequently to the joining step, solid-state heat treatment is performed on the solidified brazing material layer. And a step of reacting the brazing material layer-constituting element with a melting point improving element to raise the melting point of the brazing material layer above the melting temperature of the brazing material.

The second ceramics joined body is a ceramics joined body comprising a ceramics layer and a metal layer or a ceramics layer joined onto the ceramics layer via a brazing material layer, wherein the brazing material is The layer is characterized by having a composition and / or compound with a melting point above the melting temperature of the brazing material.

First, a method for manufacturing the first ceramics bonded body will be described in detail. Examples of the ceramic layer used in the first manufacturing method include a general ceramic sintered body substrate. As this ceramic substrate, it is possible to use one containing an additive such as a usual sintering aid, but since a solid phase diffusion reaction is used as described later,
It is preferable to use the one having the highest density and purity as much as possible. Alumina, mullite, titania, zirconia, calcia, Zn are used as ceramics that can actively cause interfacial reactions (decomposition / reduction reaction of ceramics, etc.).
It is desirable to use an oxide-based ceramic substrate such as O or STO, or a nitride-based ceramic substrate such as silicon nitride, aluminum nitride, TiN, BN, or FeN. The ceramic substrate used is preferably one having high surface smoothness and high cleanliness. Therefore, it is preferable to previously polish the surface of the ceramic substrate to improve smoothness, and to perform degreasing treatment before joining. In addition, reverse sputtering is also effective from the viewpoint of enhancing the surface cleanliness.

The metal layer used in the first manufacturing method is
While being able to decompose the ceramic that is the joining partner member,
Any layer may be used as long as at least the layer near the bonding surface is composed of a layer containing a hexagonal active metal that is dominant in diffusion of the element generated by this decomposition. As the active metal
Ti, Zr, etc. are exemplified, and these active metals may be used as a simple metal, or may be used as an alloy thereof, an alloy containing Hf, an alloy with Ag, or a laminated film thereof. Is. When using such an alloy, the content of the active metal is preferably 70% by weight or more. That is, as the layer containing the active metal (hereinafter referred to as the active metal-containing layer) that constitutes the layer near the bonding surface, it is preferable to use a layer in which the content of the active metal is at least 70% by weight or more.

Specific examples of the structure of the metal layer used in the first manufacturing method include, for example, a metal layer composed of an active metal-containing layer alone, or an active metal-containing layer and another metal material layer to be a layer near the bonding surface. An example is a metal layer consisting of In addition,
The active metal-containing layer serving as the bonding surface vicinity layer may be formed on the ceramic layer in the manufacturing process as described later, and may be the bonding surface vicinity layer of the metal layer at the time of bonding.

As a concrete form of the metal layer, one formed by a thin film forming method such as a vapor deposition method or a sputtering method,
Alternatively, it may be either a bulk metal substrate. That is, the metal layer composed of the active metal-containing layer alone may be, for example, an active metal-containing layer formed on a ceramic layer by a thin film forming method or a bulk metal substrate containing an active metal. Further, in the case of a metal layer composed of an active metal-containing layer and another metal material layer, those in which the active metal-containing layer and the other metal material layer are sequentially formed on the ceramic layer by a thin film forming method, another metal Examples thereof include those in which an active metal-containing layer is formed on a bulk substrate made of a material by a thin film forming method (including those formed on a ceramic layer in the manufacturing process). Examples of the other metal material layer include a Cu layer that can be used as a wiring material and the like, and various metal bases that are materials to be joined with the ceramic base.

When a thin film forming method is applied as a method of forming an active metal-containing layer, it is possible to obtain processing accuracy which cannot be obtained with a brazing filler metal foil or paste, and good adhesion and reactivity from a low temperature range. . Since the above-mentioned active metal-containing layer has enhanced adhesion by controlling the crystal structure described in detail later, it can be made thinner than the conventional active metal layer simply using the thin film forming method, and has a thickness of, for example, about 1 nm to 1 μm. can do. Further, when another metal material layer such as a Cu layer that can be used as a wiring material or the like is previously formed on such an active metal-containing layer, it contributes to the interfacial reaction up to the lower active metal-containing layer. The film thickness is preferably such that oxygen can sufficiently diffuse, and for example, it is preferably 500 μm or less. When a metal substrate is used as the other metal material layer, oxygen contributing to the above interface reaction can be supplied from the ceramic substrate or the atmosphere.

As described above, the first method for producing a ceramic joined body can be applied to both a metallized body in which a metallized layer is formed on a ceramic base and a joined body of a metal base and a ceramic base. . Thus, the ceramic bonded body according to the first invention is
It includes both a metallized body and a metal / ceramic bonding body. In particular, it is suitable for the production of a metallized body because it is excellent in shape reproducibility such as a fine pattern.

In the first manufacturing method, first, the ceramic layer and the metal layer as described above are laminated with the non-hexagonal structure stabilizing element partially interposed at the bonding interface. The non-hexagonal structure-stabilizing element is an element that forms a solid solution in the active metal-containing layer and stabilizes the region to a crystal structure other than hexagonal, and is a region having a crystal structure other than the hexagonal ( In the following description, referred to as a non-hexagonal region), the diffusion of the interfacial reaction product from the interface is significantly suppressed. As the non-hexagonal structure stabilizing element, for example, an element such as Mo, V, Nb, or Ta that forms a solid solution in an active metal such as Ti, or causes a eutectoid reaction.
Elements such as Fe, Cr, Mn, Co, and Ni are listed.

Such non-hexagonal structure stabilizing element is
It suffices to intervene partially at the bonding interface between the ceramics layer and the metal layer. For example, a film may be partially formed in advance on the ceramics layer or the metal layer using masking or the like to form a non-hexagonal structure stabilizing element. Form a dispersed phase. Specifically, a dispersed phase of a non-hexagonal structure stabilizing element on the ceramic layer,
Further, if necessary, an active metal-containing layer or another metal material layer is sequentially formed by a thin film forming method, or an active metal-containing layer (active metal-containing metal layer) is formed on a metal substrate or an active metal-containing metal substrate made of another metal material. (Not necessary in the case of a substrate) and a method of sequentially forming a dispersed phase of a non-hexagonal structure stabilizing element by a thin film forming method. As a method of laminating the ceramics layer and the metal layer, thin film lamination, base material lamination, or the like may be selected according to the material used.

The shape of the dispersed phase of the non-hexagonal structure stabilizing element is preferably 100 nm or less in thickness and 5 nm to 10 μm in width, and the occupied area ratio of the dispersed phase at the bonding interface is 2 to 10 μm. It is preferably in the range of 10%. When the size of the dispersed phase of the non-hexagonal structure stabilizing element is too large,
Since a thermal stress due to the difference in thermal expansion is exerted on the ceramics layer, the possibility of causing defects such as cracks increases.

Next, solid-state heat treatment is performed on the laminate of the ceramic layer and the metal layer in which the dispersed phase of the non-hexagonal structure stabilizing element is interposed. In the temperature rising process of the solid phase heat treatment, first, the non-hexagonal structure stabilizing element is diffused and solid-solved in the metal layer, particularly the active metal-containing layer, and the active metal in the active metal-containing layer is interfacial reaction product. Phase change to an oxide that promotes diffusion from the interface.

At this time, by preliminarily performing heat treatment at a temperature at which a reaction does not occur at the interface between the active metal-containing layer and the ceramic layer, the non-hexagonal structure stabilizing element diffuses into the active metal-containing layer to form a solid solution. And a preliminary heat treatment step of forming an oxide that promotes diffusion of the interfacial reaction product may be added. Further, in particular, when a eutectoid non-hexagonal structure stabilizing element is used, the eutectoid reaction occurs in advance in the active metal-containing layer, and the non-hexagonal structure stabilizing element is an active metal-containing layer. By heat-treating at a temperature not lower than the temperature at which the reaction does not occur at the interface, the eutectoid non-hexagonal structure-stabilizing element diffuses into the hexagonal active-metal-containing layer and is solidified. It is preferable to add a step of dissolving. The region where the non-hexagonal structure stabilizing element diffuses and forms a solid solution undergoes a phase change to a crystal structure other than the hexagonal system, and this non-hexagonal region becomes the reduction reaction inactive phase.

For example, when Ti is used as the active metal and total solid solution type Mo is used as the non-hexagonal structure stabilizing element, the partially formed Mo is only 1 wt% in Ti.
By its existence, β-Ti having a body-centered cubic crystal structure can be present in Ti even in a low temperature range. Other V, N
Similarly, for non-hexagonal structural stabilizing elements such as b and Ta, if 2% by weight of V, 6% by weight of Nb, and 10% by weight of Ta are solid-solved in Ti, β-Ti Can exist.

Considering the case of using eutectoid Fe as a non-hexagonal structure stabilizing element, it was partially intercalated.
0.05% by weight of Fe in Ti in the temperature range where Fe causes the eutectoid reaction
The presence of β-Ti with a body-centered cubic crystal structure in Ti
Can exist. The temperature at which the eutectoid reaction occurs is clear from the phase diagram for each non-hexagonal structure stabilizing element, but when a thin film is used, the eutectoid temperature can be lower than the temperature shown in the equilibrium phase diagram. Reaction may occur. Therefore, the temperature of the preliminary heat treatment for diffusing and solid-dissolving the above-described eutectoid non-hexagonal structure stabilizing element is based on the phase diagram to some extent, and the state of the dispersed phase of the non-hexagonal structure stabilizing element ( It is preferable to set the temperature above the temperature at which the eutectoid reaction occurs depending on the conditions such as the film quality of the thin film) and β-Ti 3 having a body-centered cubic structure is generated. The same applies to other non-hexagonal structure stabilizing elements such as Cr, Mn, Co and Ni.
%, Mn 1%, Co 1%, Ni 0.5%
If a solid solution is formed in Ti, the eutectoid reaction will occur and β-Ti can exist.

Ti ₂ having the same hexagonal crystal structure as Ti
Ti oxygen compounds with a small number of oxygen bonds, such as O and TiO, have the function of accelerating the decomposition / reduction reaction of ceramics and the function of diffusing the metal elements generated by the decomposition / reduction reaction at high speed. There is. On the other hand, the oxide formed by solid solution of oxygen in β-Ti does not have the function of promoting the reaction as much as the hexagonal oxide. As a result, in the subsequent solid phase heat treatment, the activity (reaction rate) of the reduction reaction is relatively different in both phases.

As described above, the non-hexagonal structure stabilizing element is dispersed and intervened at the interface between the ceramic layer and the metal layer to form a reduction reaction inactive phase based on the non-hexagonal region. It can be present at the bonding interface, which makes it possible to make a significant difference in the reactivity at the bonding interface.

The above-mentioned structure can be formed by satisfying the following conditions in the temperature rising process up to the solid phase heat treatment temperature. The treatment atmosphere needs to contain a small amount of oxygen in order to oxidize the active metal, and an atmosphere in which a vacuum of 0.1 Pa or less or an inert gas such as Ar contains 5% or less of oxygen is preferable. However, it is necessary to set the conditions such that oxides or compounds that cannot reduce ceramics such as TiO ₂ are not formed. Alternatively, an active metal oxide layer having a similar function can be formed by using a reactive sputtering method or the like in which oxygen is mixed in an atmosphere when forming a film. In addition, when another metal material layer is formed on the active metal-containing layer, it is preferable to perform heat treatment at a temperature and for a time that allows oxygen to sufficiently diffuse into the lower active metal-containing layer. At this time, it is also preferable that the structure of the other metal material layer is a structure that promotes diffusion of oxygen by forming grain boundaries perpendicular to the plane direction.

The solid-phase heat treatment for causing an interfacial reaction (ceramic decomposition / reduction reaction, etc.) that strongly bonds the active metal-containing layer and the ceramics layer requires heat treatment at a higher temperature. The solid phase heat treatment temperature is preferably 600 ° C. or higher and lower than the melting point of the metal layer. Heat treatment temperature is 6
If it is less than 00 ° C, the reaction between the active metal-containing layer and the ceramic layer does not sufficiently occur. In order to reduce the thermal shock to the ceramic layer, it is preferable that the treatment is performed at a temperature as low as possible, and specifically, it is preferable that the temperature is in the range of 650 to 900 ° C. Further, the solid phase heat treatment time is preferably a short time heat treatment within a range where a sufficient interfacial reaction is obtained, and specifically, it is preferably 30 minutes or less.

In the above solid-state heat treatment, the active metal having a hexagonal crystal structure is converted into an oxide which promotes the decomposition / reduction reaction of the ceramics in the temperature rising process. In the metal phase, the decomposition / reduction reaction of ceramics is activated. On the other hand, the active metal phase having a crystal structure other than the hexagonal system (non-hexagonal system region) has a lower ability to diffuse reaction products than the hexagonal system active metal phase, so that decomposition of ceramics The rate of the reduction reaction is
It is relatively low compared to the hexagonal active metal phase. As described above, since the interfacial reaction activity is different between the two phases, the hexagonal active metal phase portion, that is, the non-hexagonal region containing the non-hexagonal structure stabilizing element (reduction reaction inactive phase A structure is obtained in which the parts other than) relatively project to the ceramic layer side.

By forming the interface structure having such irregularities, the reaction area itself is increased and the anchor effect is also generated, so that the bonding strength between the ceramic layer and the metal layer, especially the active metal-containing layer is significantly increased. It is possible to improve the reliability and the reliability. The hexagonal oxide phase is
The reduction reaction actively proceeds from a relatively low temperature. Further, although the reaction rate is relatively slow in the phases having a crystal structure other than the above-mentioned hexagonal system, a reduction reaction occurs, so that sufficient adhesion with the ceramic layer can be obtained.

The first ceramics joined body obtained by the above-mentioned manufacturing method has a crystal structure other than the hexagonal system containing a non-hexagonal structure stabilizing element at the joining interface between the ceramics layer and the metal layer. The reduction reaction inactive phase is partially interposed. Then, based on this reduction reaction inactive phase, the portion other than the reduction reaction inactive phase has a structure in which it is relatively projected to the ceramic layer side, and as described above, excellent bonding strength is obtained.

The metal layer in the first ceramics bonded body contains at least the solid phase heat treatment layer of the active metal-containing layer as a layer near the bonding interface, and for example, a metallized layer of the solid phase heat treatment layer of the active metal-containing layer alone, Alternatively, when another metal material layer such as a Cu layer is previously formed thereon, the metallized layer has a laminated structure. Further, if the active metal-containing layer is formed on a base made of another metal material, or if a metal base containing at least an active metal is used, a metal base-like metal layer bonded to the ceramics layer is obtained.

When any other metal material layer such as a Cu layer is formed on the active metal-containing layer, heat treatment causes mutual reaction and diffusion, so that good adhesion between layers can be obtained. Such a reaction behavior makes it possible to form a metal layer having high adhesion, such as a metallized layer or a bonded metal base, on the ceramic layer.

The first ceramics joined body in the present invention is suitable for the following uses, for example. That is,
When obtaining a circuit board material, etc., masking is performed according to the wiring or circuit pattern, and after forming the dispersed phase of the structural stabilizing element, the active metal-containing layer and, if necessary, the Cu layer, etc., solid phase heat treatment. By carrying out, it is possible to easily obtain a circuit board having precise wiring or a circuit pattern such as Cu. Also, when joining lead pins or the like, I / O pins can be easily brazed onto the metal layer of the present invention.

Next, the method for manufacturing the second ceramics bonded body will be described in detail. As the ceramics layer used in the second manufacturing method, a general ceramics sintered body substrate can be used as in the first manufacturing method described above. The metal layer is not particularly limited, and various metal substrates can be used.

As the brazing material, it is preferable to use a brazing material containing an active metal element such as Ti, Zr or Hf.
Further, the brazing material containing active metal elements is preferably used as an alloy brazing material. This is because the melting point of the active metal element is generally high, and by using it as an alloy, the melting point can be lowered as compared with the case of the active metal element alone.

Among the brazing filler metals containing active metal elements as described above, particularly brazing filler metals utilizing eutectic reaction of Ag-Cu-Ti, Cu-Ti, Ni-Ti, etc., Au-Cu-Ti, Cu- It is preferable to use a brazing filler metal obtained by adding an active metal to a total solid solution alloy such as Ti-Ni. This is because these eutectic brazing filler metals and total solid solution type brazing filler metals can melt the active metal-containing brazing filler metal at a relatively low temperature in the joining process.

In the second manufacturing method, first, the ceramic layer and the metal layer as described above, or the ceramic layers are laminated with the brazing material as described above interposed therebetween. As a method of interposing the brazing material, it is preferable to apply a method of depositing the brazing material on the bonding surface of the ceramic layer or the metal layer by a thin film forming method. Examples of such a thin-film brazing material include an alloy film of an active metal and another metal component, a laminated film of these, and the like. By using the thin-film brazing material, the melting point improving element described below can be melted and diffused in the brazing material layer after solidification in a short time.

As a method of forming the thin film brazing material, it is preferable to apply a sputtering method, an ion plating method, an electron beam evaporation method or the like, which can easily control the thickness and can form a good layer. The formation site of the thin film brazing material is not particularly limited, but it is preferably formed on the bonding surface of the ceramic layer. The thickness of the thin-film brazing material is not particularly limited, but is preferably about 1 μm or less. With such a thickness, diffusion of the melting point improving element can be facilitated. When using a thin film brazing material in the form of a laminated film, it is preferable to form an active metal layer on the side of the bonding material and then form another metal layer on the active metal layer. Adhesion with can be improved.

Next, the ceramic layer and the metal layer, or the laminated body of the ceramic layers, which are laminated via the brazing material as described above, is heat-treated at a temperature corresponding to the melting temperature of the brazing material used to form the brazing material. At least a part is melted and solidified. The ceramic layer and the metal layer or the ceramic layers are bonded to each other by the solidified brazing material layer. For this joining, the active action of the active metal element on the ceramic surface is utilized as in the first manufacturing method described above. That is, the active metal diffuses and adsorbs toward the surface of the ceramic, and then reduces and decomposes the ceramic.
This forms a strong bond between the ceramic layer and the metal layer. This joining step is preferably performed in a vacuum or in an inert gas atmosphere, which can prevent unnecessary reaction between the joining material and the atmosphere. The brazing material layer referred to here is a portion formed after the brazing material is melted and solidified, which is added in addition to the ceramic layer or the metal layer for the purpose of joining.

In the second manufacturing method, subsequent to the joining step, the solidified brazing material layer is subjected to solid phase heat treatment,
The melting point improving element is diffused and reacted with the brazing material layer constituent elements to raise the melting point of the brazing material layer. This process is shown in FIG.
The case where a eutectic brazing material is used will be described as an example using the -B phase diagram.

Generally, the eutectic brazing filler metal has its brazing filler metal composition adjusted so as to have the composition at X point (melting point: T ₁ ) shown in FIG. Here, when the AB element ratio is changed and the composition of the brazing material layer deviates from the eutectic composition in the arrow x direction or the arrow y direction after the brazing material layer is produced, the brazing material layer is completely melted. The temperature (the reaction temperature of θ ₁ + L → L or θ ₂ + L → L) rises. Now, when the composition of the brazing material layer is completely deviated from the a composition or the b composition, the melting point of the brazing material layer is T
It can be raised to ₂ or above T ₃ . In the second manufacturing method, by reacting at least one of the brazing filler metal layer constituent elements with a melting point improving element described later in the solid phase heat treatment step, the deviation from the eutectic composition or the like due to the mechanism described above is utilized, It raises the melting point of the brazing material layer. In the solid phase heat treatment step, the composition of the brazing filler metal layer may deviate from the original eutectic composition or the like, but it is particularly preferable to shift the composition until it is outside the a composition or the b composition in FIG. That is, it is preferable to shift the composition outside the eutectic reaction of the brazing material used. By doing so, the temperature at which the liquid phase occurs can be completely raised.

The eutectic reaction described above may be a ternary or higher ternary system including a melting point improving element. That is,
The melting point may be increased by utilizing the deviation from the multi-component eutectic composition due to the addition of the melting point improving element to the brazing filler metal layer constituent elements. For example, in the case of Ni-Ti binary brazing filler metal, oxygen is used as a melting point improving element to cause a reaction in the Ni-Ti-O ternary system, resulting in a deviation from the eutectic reaction in the ternary phase diagram. Can be used to raise the melting point. Even in the case of the solid solution type brazing material, the melting point of the brazing material layer can be increased by shifting the composition of the brazing material layer in a predetermined direction from the initial brazing material composition.

The melting point improving element in the second manufacturing method may be an element capable of reacting with the brazing material layer constituent elements to raise the melting point of the brazing material layer more than before the solid-state heat treatment, but particularly oxygen. , Nitrogen, carbon and the like are preferable. This is because these elements easily diffuse in the brazing material layer and easily form a brazing material layer constituent element such as an active metal and a high melting point compound such as an oxide, a nitride or a carbide. Therefore, the melting point of the brazing filler metal layer can be further increased by causing a deviation from the eutectic composition of the brazing filler metal itself and generating the high melting point compound as described above.

The brazing filler metal layer constituent elements which react with the melting point improving elements such as oxygen, nitrogen and carbon may be two or more elements. For example, when using Ag-Cu-Ti ternary brazing material, oxygen and Ti
The Cu and Ti may be reacted with each other to form a Cu ₃ Ti ₃ O (space group Fd3m) compound or the like to cause a deviation from the initial brazing material composition to raise the melting temperature of the brazing material layer. Further, the melting point improving element may be two or more elements, and the supply method thereof may be different.

Examples of the method of supplying the melting point improving element include a method of utilizing a ceramic constituent element or a method of supplying it from the atmosphere. When the ceramics are joined to each other by the active metal method, the active metal element reduces the ceramics. As a result, when the ceramics are oxides, oxygen is used, when nitrides are used, nitrogen is used, and when carbides, carbons are used. Diffuse into the brazing material. In other words, as long as the reduction / decomposition reaction of the ceramics at the interface continues, oxygen, nitrogen, carbon, etc. will continue to diffuse into the brazing material. Also continues. As a result, the brazing filler metal layer constituent elements produce an oxygen-containing compound, a nitrogen-containing compound, a carbon-containing compound, and the like. The melting point of the brazing material layer rises due to the formation of such a high melting point compound and the deviation from the original brazing material composition.

Further, the melting point improving element can be supplied from the atmosphere as described above. In this case, the melting point improving elements such as oxygen, nitrogen and carbon can be diffused in the brazing material layer by adjusting the partial pressure of oxygen, nitrogen and carbon in the atmosphere during the solid phase heat treatment.

The temperature of the solid phase heat treatment for raising the melting temperature of the brazing filler metal layer is not particularly limited as long as it is the temperature at which the above-mentioned reaction occurs in the solid phase reaction, but the melting of the brazing filler metal itself is not limited. It is preferable that the temperature is 30 K lower than the temperature and 873 K or higher. 3 from the original melting temperature of the brazing material
If the temperature is lower than 0K, the brazing filler metal layer may be remelted, and if the temperature is lower than 873K, a sufficient reaction rate cannot be obtained.

The second ceramic joined body obtained by the above-described manufacturing method has a high melting point composition in which the brazing material layer existing between the ceramics layer and the metal layer has a melting point exceeding the melting temperature of the original brazing material. It has a high melting point compound. By thus increasing the melting point of the brazing filler metal layer, the high temperature strength of the bonded body can be improved.

[0049]

Embodiments of the present invention will be described below.

Example 1 First, as shown in FIG. 1A, a thickness of 10 nm was formed on a single crystal alumina substrate 1 having a purity of 99.99% by a sputtering method.
Mo having a diameter of 1 μm was dispersed and a film was partially formed to form a Mo dispersed phase 2. The area of the Mo dispersed phase 2 was about 5% of the substrate area. Then, a Ti film 3 having a film thickness of 100 nm was formed on the entire surface of the single crystal alumina substrate 1 including the Mo dispersed phase 2 (FIG. 1B). After this, in an Ar gas stream with a purity of 98%, 1
A heat treatment was performed at 073K for 20 minutes to obtain a target metallized body 4 (Fig. 1 (c)).

Further, as a comparative example with the present invention, a metallized body was produced under the same conditions as in the above example except that the Mo dispersed phase was not formed.

When the cross-sectional TEM observation and EDX composition analysis of each metallized body according to these Examples and Comparative Examples were carried out, the metallized body 4 according to the Example was found to contain Mo as shown schematically in FIG. 1 (c). The Ti-O phase 5 (reduction reaction inactive phase), which is solid-solved and stabilized in the body-centered cubic structure, exists at the bonding interface, and the hexagonal Ti-O phase in the other parts is present.
It was confirmed that a structure in which the phase 3'protruded on the single crystal alumina substrate 1 side was formed.

First, in the temperature rising process of the solid phase heat treatment, Ti
While the film 3 is being oxidized, Mo 2 diffuses into the hexagonal Ti film 3 to form a solid solution, and the solid solution region contains Mo in a body-centered cubic structure.
-O phase 5 is assumed and the other parts are hexagonal Ti
-O phase 3 ', and during the holding process by 1073K, at the interface between the hexagonal Ti-O phase 3'and the single crystal alumina substrate 1,
This is because the decomposition / reduction reaction of the single crystal alumina substrate 1 occurs preferentially. As a result of the decomposition / reduction reaction preferentially occurring, unevenness is generated at the interface between the single crystal alumina substrate 1 and the hexagonal Ti—O phase 3 ′.

On the other hand, the metallized body according to the comparative example is shown in FIG.
As shown schematically in Fig. 3, no remarkable unevenness was observed at the interface between the hexagonal Ti-O phase 3'and the single crystal alumina substrate 1. Further, a scratch test was conducted to confirm the adhesion of the metallized layers of the metallized bodies according to the examples and comparative examples.
While the strength of f / mm ² was obtained, the metallized body according to the comparative example obtained only strength of about 10 kgf / mm ² .

Example 2 A V film having a thickness of 20 nm and a diameter of 4 μm was dispersed and partially formed on a polycrystalline alumina substrate having a purity of 85% by a vapor deposition method. The deposition area of the V film was set to about 3% of the substrate area. Next, on the entire surface of the polycrystalline alumina substrate including the above V film,
A 10 wt% Ti-Zr alloy film with a film thickness of 300 nm was formed. After this,
Heat treatment was carried out at 1073K for 20 minutes in a vacuum of 1.3 × 10 ^-2 Pa to obtain the desired metallized body.

The cross section T of the metallized body thus obtained
As a result of EM observation and EDX composition analysis, as shown schematically in FIG. 3, V was found to form a solid solution at the bonding interface between the polycrystalline alumina substrate 11 and the hexagonal Zr-Ti-O film 12. The Zr-Ti-O phase 13 (reduction reaction inactive phase) stabilized in the body-centered cubic structure is present, and the hexagonal Zr-Ti-O film 12 in the other part is polycrystalline alumina. It was confirmed that a protruding structure was formed on the substrate 11 side.

Example 3 After disposing a mask according to a circuit pattern on a single crystal aluminum nitride substrate having a purity of 99%, an Fe film having a thickness of 15 nm and a diameter of 500 nm was dispersed and partially formed by a sputtering method. did. The Fe film formation area was set to about 7% of the circuit pattern area. Then, with the mask still in place, a film thickness of 500 is formed on the single crystal aluminum nitride substrate including the Fe film.
A Ti film of nm was formed. Then, heat treatment was performed at 1173 K for 20 minutes in a vacuum of 1.3 × 10 ⁻⁵ Pa to obtain a desired metallized body.

Further, as a comparative example with the present invention, a metallized body was produced under the same conditions as in the above example except that the Fe film was not formed.

A scratch test was conducted to confirm the adhesion of the metallized layers of the metallized bodies according to these Examples and Comparative Examples. The metallized bodies according to the Examples did not peel off in the test of 15 kgf / mm ² . On the other hand, the metallized body according to the comparative example was peeled off under the same conditions. Further, when the reaction product was examined by X-ray diffraction, it was confirmed that β-Ti was produced in the metallized body according to the example.
Formation of β-Ti was not confirmed in the metallized body according to the comparative example.

Example 4 An Nb film having a thickness of 10 nm and a diameter of 2 μm was dispersed and partially formed on a polycrystalline aluminum nitride substrate having a purity of 98% by a sputtering method. Nb film deposition area is 3% of substrate area
It was about degree. Next, a 200 nm-thickness Ti film was formed over the entire surface of the polycrystalline aluminum nitride substrate including the above Nb film, and a 2.5 μm-thick Cu layer was further formed by sputtering. After that, heat treatment was performed at 973K for 25 minutes in a vacuum of 0.1 Pa to obtain a target metallized body.

The cross section T of the metallized body thus obtained
When EM observation and EDX composition analysis were performed, it was confirmed that a structure in which the Ti—O phase portion other than the Nb solid solution region was projected to the polycrystalline aluminum nitride substrate side was formed. Further, it was confirmed that no defect was found between the metal layers and that good adhesion was obtained.

When the electric resistance of the metallized layer (substantially Cu layer) in the metallized body was measured by the 4-terminal method, a good value of 1.7 μΩ · cm, which was close to that of a Cu bulk, was obtained. Furthermore, when the thermal conductivity of the metallized layer was measured, a good value of 350 W / m K was obtained for the laminated metal film itself. When brazing I / O pins to the metallized layer of such a metallized body, it was possible to braze by only applying Ag to the I / O pins.

Example 5 A laminated film of Ti and Cu was formed in this order on the bonding surface of an alumina substrate having a purity of 99% by a sputtering method. This thin-film brazing material has a total film thickness of 1000 nm of Ti 400 nm and Cu 600 nm.
Was deposited so that the atomic ratio was about Cu: Ti = 75: 25. Then, a Fe-42 wt% Ni alloy substrate was brought into contact with the thin-film brazing material, and the laminated body was set in a vacuum furnace.
^In a vacuum of ^-4 Pa, heating was performed at 1163 K at a temperature rising rate of 20 K / min, and this temperature was maintained for 5 minutes to sufficiently melt the brazing material.

Next, by lowering the temperature to 973K and solidifying the brazing material to form a brazing material layer, the alumina base material is formed.
The Fe-42wt% Ni alloy substrate was joined. Continue to above 97
By holding the brazing filler metal layer at a temperature of 3 K for 20 minutes, the brazing filler metal layer after solidification was subjected to solid phase heat treatment to react Ti and alumina in the brazing filler metal layer to form a compound containing oxygen. After this,
By cooling in a furnace, a target metal / ceramic bonding body was obtained.

When the composition of the brazing material layer of the metal / ceramic bonding body thus obtained was analyzed, the ratio of oxygen to unreacted Cu and Ti in the brazing material layer changed from the state at the time of film formation. The atomic ratio was Cu: Ti = 95: 5. Further, a Ti solid solution of Cu was formed in the brazing material layer. By these,
The melting point of the brazing material layer had risen above 1173K. In addition, when a tensile test of this joined body was performed at 673K, it was found to be 5 kgf / mm.
A bond strength of ² was obtained.

On the other hand, as a comparison with the present invention, a metal / ceramic bonding article was produced under the same conditions as in the above-mentioned example, except that the solid phase heat treatment at 973 K after solidification of the brazing material was not performed. When the brazing material layer of this joined body was investigated, no difference from the initial melting point of the brazing material was found. Also, when a tensile test of this joined body was similarly conducted at 673 K, the joining strength was 1 kgf / mm ² .

Example 6 A laminated film of Ti and Cu was formed in this order on the bonding surface of an alumina substrate having a purity of 99% by a sputtering method. This thin-film brazing filler metal has a total film thickness of 750 nm, including Ti 300 nm and Cu 450 nm.
Was deposited so that the atomic ratio was about Cu: Ti = 75: 25. Then, contact the SUS 304 substrate on the thin film brazing material,
After setting this laminated body in a vacuum furnace, it was heated in a vacuum of 6.7 × 10 ^-4 Pa at a heating rate of 20 K / min for 1163 K, and at this temperature.
Hold for 5 minutes to fully melt the brazing material.

Next, the temperature is lowered to 973 K, and the brazing material is solidified to form a brazing material layer, thereby forming an alumina substrate.
Bonded to a SUS 304 substrate. Then, the degree of vacuum in the furnace
After changing to 6.7 × 10 ^-3 Pa, the solidified brazing material layer is subjected to solid-state heat treatment by holding it at 873K for 25 minutes to react Ti in the brazing material layer with oxygen in the atmosphere. Let me
A compound containing oxygen was formed. After that, by cooling in a furnace, a desired metal / ceramic bonding body was obtained.

When the composition of the brazing material layer of the metal / ceramic bonding body thus obtained was investigated, the ratio of oxygen to unreacted Cu and Ti in the brazing material layer changed from the state at the time of film formation. The atomic ratio was Cu: Ti = 98: 2. Further, a Ti solid solution of Cu was formed in the brazing material layer. By these,
The melting point of the brazing material layer had risen above 1183K. In addition, when the tensile test of this joined body was performed at 673K, it was 6 kgf / mm.
A bond strength of ² was obtained.

On the other hand, as a comparison with the present invention, a metal / ceramic bonding article was produced under the same conditions as in the above-mentioned example except that the solid-phase heat treatment at 873K after solidification of the brazing material was not performed. When the brazing material layer of this joined body was investigated, no difference from the initial melting point of the brazing material was found. Further, when a tensile test of this joined body was carried out at 673K as well, the joining strength was 1.5 kgf / mm ² .

Example 7 A laminated film of Ti and Ni was formed in this order on the bonding surface of an alumina substrate having a purity of 99% by a sputtering method. This thin-film brazing material has a total film thickness of 700 nm including Ti 600 nm and Ni 100 nm,
Was deposited so that the atomic ratio was about Ni: Ti = 25: 75. Next, a Mo substrate was brought into contact with the thin-film brazing material, and this laminate was set in a vacuum furnace, and then heated to 1273K at a heating rate of 20K / min in a vacuum of 6.7 × 10 ^-4 Pa. , At this temperature 3
Hold for a minute to fully melt the brazing material.

Next, the temperature was lowered to 1073 K and the brazing material was solidified to form a brazing material layer, thereby joining the alumina base and the Mo base. Subsequently, by holding the temperature at 1073K for 20 minutes, the brazing material layer after solidification was subjected to solid-state heat treatment, and Ti in the brazing material layer was reacted with alumina to form a compound containing oxygen. After that, by cooling in a furnace, a desired metal / ceramic bonding body was obtained.

When the composition of the brazing material layer of the metal / ceramic bonding body thus obtained was investigated, the ratio of unreacted Ni and Ti in the brazing material layer changed from the state during film formation, and The ratio was Ni: Ti = 50: 50. N in the brazing material layer
An intermetallic compound of iTi was formed. By these,
The melting point of the brazing material layer had risen above 1473K. Also, when the tensile test of this joined body was conducted at 873K, it was found to be 7 kgf / mm.
A bond strength of ² was obtained.

On the other hand, as a comparison with the present invention, a metal / ceramic bonding article was produced under the same conditions as in the above-mentioned example except that the solid phase heat treatment at 1073K after solidification of the brazing material was not performed. When the brazing material layer of this joined body was investigated, no difference from the initial melting point of the brazing material was found. Further, when a tensile test of this joined body was similarly conducted at 873K, the joining strength was 2 kgf / mm ² .

Example 8 A laminated film of Ti, Cu, and Ag was formed in this order on the bonding surface of an alumina substrate having a purity of 99% by a sputtering method. This thin film brazing material was formed to have a total film thickness of 830 nm of Ti 90 nm, Cu 240 nm, and Ag 540 nm, and Ti, Cu, and Ag had an atomic ratio of Ti: Cu: Ag = 5: 26: 69. Then, contact the Mo substrate on the thin film brazing material, after setting the laminate in a vacuum furnace,
It was heated to 1073K at a temperature rising rate of 20K / min in a vacuum of 6.7 × 10 ^-4 Pa and kept at this temperature for 3 minutes to sufficiently melt the brazing material.

Next, by lowering the temperature to 873 K and solidifying the brazing filler metal to form a brazing filler metal layer, an alumina substrate is formed.
Bonded with a Mo substrate. Then, at the temperature of 873K above, 20
By holding for a minute, the brazing material layer after solidification was subjected to solid phase heat treatment to react Ti and Cu in the brazing material layer with alumina to form a compound containing oxygen. After that, by cooling in a furnace, a desired metal / ceramic bonding body was obtained.

When the composition of the brazing material layer of the metal / ceramic bonding body thus obtained was investigated, the ratio of oxygen and unreacted Ag and Cu in the brazing material layer changed from the state at the time of film formation. The atomic ratio was Ag: Cu = 95: 5. Further, a Cu solid solution of Ag was formed in the brazing material layer. By these,
The melting point of the brazing material layer had risen above 1123K. In addition, when the tensile test of this joined body was conducted at 573K, it was found to be 5kgf / mm.
A bond strength of ² was obtained.

On the other hand, as a comparison with the present invention, a metal / ceramic bonding article was produced under the same conditions as in the above-mentioned example except that solid-phase heat treatment at 873K after solidification of the brazing material was not performed. When the brazing material layer of this joined body was investigated, no difference from the initial melting point of the brazing material was found. Further, when a tensile test of this joined body was carried out at 573 K as well, the joining strength was 0.5 kgf / mm ² .

Example 9 A laminated film of Ti and Cu was formed in this order on the bonding surface of an alumina substrate having a purity of 99% by a sputtering method. The thin film brazing material had a total film thickness of 500 nm including Ti 200 nm and Cu 300 nm, and was formed such that Cu and Ti had an atomic ratio of Cu: Ti = 75: 25. Next, the Fe-42wt% Ni alloy substrate was brought into contact with the thin-film brazing material, and this laminate was set in a vacuum furnace, and then 1.1 × 10 ^-3
It was heated to 1173K in a Pa vacuum at a heating rate of 25K / min and kept at this temperature for 8 minutes to melt the brazing material sufficiently.

After the end of the holding time, the brazing material was isothermally solidified, whereby the alumina base and the Fe-42 wt% Ni alloy base were joined. Subsequently, by holding the temperature at 1173K for 10 minutes, the brazing material layer after solidification was subjected to solid-state heat treatment, and Ti in the brazing material layer was reacted with alumina to form a compound containing oxygen. After that, by cooling in a furnace, a desired metal / ceramic bonding body was obtained.

When the composition of the brazing material layer of the metal / ceramic bonding body thus obtained was investigated, the ratio of oxygen and unreacted Cu and Ti in the brazing material layer was changed from the state during film formation. The atomic ratio was Cu: Ti = 97: 3. Further, a Ti solid solution of Cu was formed in the brazing material layer. By these,
The melting point of the brazing material layer had risen above 1183K. In addition, when a tensile test of this joined body was performed at 673K, it was found to be 5.3 kgf /
A bond strength of mm ² was obtained.

On the other hand, as a comparison with the present invention, a metal / ceramic bonding article was produced under the same conditions as in the above-mentioned example except that the solid phase heat treatment at 1173K after solidification of the brazing material was not performed. When the brazing material layer of this joined body was investigated, no difference from the initial melting point of the brazing material was found. Also, when a tensile test of this joined body was similarly conducted at 873 K, the joined strength was 1.2 kgf / mm ² .

Example 10 A laminated film of Ti and Cu was formed in this order on the bonding surface of a silicon nitride substrate having a purity of 99% by a sputtering method. This thin-film brazing material has a total film thickness of 1000 nm, which is 400 nm for Ti and 600 nm for Cu.
The film was formed so that the atomic ratio of Ti was Cu: Ti = 75: 25.
Then, the Fe-42wt% Ni alloy substrate was brought into contact with the thin-film brazing material, and the laminated body was set in a vacuum furnace.
It was heated to 1163K at a temperature rising rate of 20K / min in a vacuum of 10 ^-4 Pa and kept at this temperature for 5 minutes to sufficiently melt the brazing material.

Next, by lowering the temperature to 973 K and solidifying the brazing material to form a brazing material layer, the brazing material is formed into an alumina substrate.
The Fe-42wt% Ni alloy substrate was joined. Continue to above 97
By holding at a temperature of 3 K for 20 minutes, the brazing material layer after solidification was subjected to solid-state heat treatment, Ti in the brazing material layer was reacted with silicon nitride, and a compound containing nitrogen was produced. After that, by cooling in a furnace, a desired metal / ceramic bonding body was obtained. When the composition of the brazing material layer of the metal / ceramic bonding body thus obtained was investigated,
The ratio of nitrogen and unreacted Cu and Ti in the brazing material layer changed from the state at the time of film formation, and the atomic ratio was Cu: Ti = 95: 5. Also,
A Ti solid solution of Cu was formed in the brazing material layer. As a result, the melting point of the brazing material layer was raised to 1173K or higher.
Also, when the tensile test of this joined body was performed at 673K,
A joint strength of 5 kgf / mm ² was obtained.

On the other hand, as a comparison with the present invention, a metal / ceramic bonding article was produced under the same conditions as in the above-mentioned example except that the solid phase heat treatment at 973 K after solidification of the brazing material was not performed. When the brazing material layer of this joined body was investigated, no difference from the initial melting point of the brazing material was found. Also, when a tensile test of this joined body was similarly conducted at 673 K, the joining strength was 1 kgf / mm ² .

[0086]

As described above, according to the first method for manufacturing a ceramic joined body of the present invention, unevenness is formed at the joining interface between the ceramic layer and the metal layer based on the difference in the activity of the reduction reaction. Therefore, a high joining force can be obtained. Further, since the interfacial reaction is realized by the solid phase heat treatment, the shape reproducibility of a fine pattern or the like can be improved. As a result, it is possible to provide a ceramics joined body having excellent shape reproducibility and reliability of fine patterns and the like.

Further, according to the second method for manufacturing a ceramic joined body, since the melting point of the brazing material layer is raised to be higher than the melting temperature of the initial brazing material, the temperature is higher than that of the joined body simply brazed. The strength can be improved. Therefore,
It is possible to provide a highly reliable ceramic joined body with an easy joining process.

[Brief description of drawings]

FIG. 1 is a sectional view schematically showing a manufacturing process of a metallized body according to an embodiment of the present invention.

FIG. 2 is a cross-sectional view schematically showing the structure of a metallized body which is provided for comparison with the present invention.

FIG. 3 is a sectional view schematically showing a structure of a metallized body according to another embodiment of the present invention.

FIG. 4 is a diagram for explaining a melting point improving mechanism of a brazing material layer in the second method for manufacturing a ceramic joined body of the present invention.

[Explanation of symbols]

 1 ... Single crystal alumina substrate 2 ... Mo dispersed phase 3 ... Ti film 3 '... Hexagonal Ti-O phase 4 ... Metallized body 5 ... Ti-O phase of body-centered cubic structure containing Mo 11 ... Polycrystalline alumina substrate 12 ... Hexagonal Zr-Ti-O film 13 ... Zr-Ti-O film with V-containing body-centered cubic structure

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Shinichi Nakamura 1 Komukai Toshiba-cho, Sachi-ku, Kawasaki-shi, Kanagawa Incorporated Toshiba Research and Development Center

Claims (4)

[Claims] 1. When joining a ceramics layer and a metal layer, at least a layer near the bonding surface, comprising a layer containing a hexagonal active metal capable of decomposing the ceramics, the ceramics layer and the metal layer are joined together. A step of laminating with a non-hexagonal structure stabilizing element partially interposed at the bonding interface; And a step of joining the ceramics with each other. 2. A ceramics bonded body comprising a ceramics layer and a metal layer bonded on the ceramics layer and containing at least an active metal as a constituent element of a layer near the bonding surface, the ceramics layer and the metal layer. At the bonding interface of, a reduction reaction inert phase having a crystal structure other than the hexagonal system containing a non-hexagonal structure stabilizing element is partially interposed,
A ceramics joined body having a structure in which a portion other than the reduction reaction inactive phase is relatively projected toward the ceramics layer side. 3. When joining the ceramic layer and the metal layer or the ceramic layers together, the ceramic layer and the metal layer or the ceramic layers are laminated via a brazing material, and at least a part of the brazing material is melted and solidified. A step of joining the ceramics layer and the metal layer or the ceramics layers together, and subsequently to the joining step, solid-state heat treatment is performed on the solidified brazing material layer, and the brazing material layer constituent element and the melting point improving element are added. To raise the melting point of the brazing material layer above the melting temperature of the brazing material, the method for producing a ceramic joined body. 4. A ceramics joined body comprising a ceramics layer and a metal layer or a ceramics layer joined to the ceramics layer via a brazing filler metal layer, wherein the brazing filler metal layer is a melt as a brazing filler metal. A ceramics joined body having a composition and / or a compound having a melting point exceeding a temperature.