JP2003048785A - Joined structure of metallic member and ceramic member and method of joining metallic member and ceramic member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problems with components of electronic parts and structural parts that the joining areas of metallic members and ceramic members using glass joining materials are made smaller from the downsizing and thickness reduction of these components, the joining strength of joint parts is made insufficient, cracking and peeling are brought about in manufactured steps by the thermal stress in the manufacturing stages and the externals tress during use and the breaking of the hermeticity in the joint parts is resulted. SOLUTION: The ceramic member 2 and the metallic member 3 are joined across a joining layer formed with a metallic layer 6 which consists essentially of a metallic component of <=1,100 deg.C in liquids line temperature and contains at least one kind among titanium, zirconium and hafnium as active metals, an oxidation layer 5 of an active metal and a glass layer 4, successively from the metallic member 3 side.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a joining structure between a metal member and a ceramic member, and particularly to a joining structure suitable for joining the metal member and the ceramic member in electronic parts, structural parts, etc. Regarding the joining method.

[0002]

2. Description of the Related Art Conventionally, ceramics have been excellent in properties such as electric insulation, strength at high temperature, and wear resistance. Therefore, ceramics have been used in various industrial fields as constituent members of electronic parts and structural parts by utilizing such characteristics. It has been used a lot.

However, although ceramic members as constituent members of electronic parts and structural parts have excellent characteristics as described above, ceramics themselves are brittle materials,
Due to the high hardness, it is difficult to process the ceramic member into various complicated shapes, and the manufacturing cost becomes high. Therefore, by combining such a ceramic member with a metal member having excellent workability to form a composite,
It has been variously applied to various applications utilizing the excellent characteristics of ceramics.

In general, various methods such as a shrink fitting method, a press fitting method, a brazing method, a solid phase diffusion bonding method, a glass bonding method and the like have been used to combine a ceramic member and a metal member into a composite. . Among these joining methods, the brazing method, in particular, has been widely adopted because it does not require highly precise processing of the joined portion and a relatively high joining strength can be obtained.

When such a brazing method is applied to the joining of the metal member and the ceramic member, the desired joining strength can be obtained relatively easily. However, for example, when a brazing material mainly composed of silver (Ag) that can obtain high bonding strength is used as the bonding material, the bonding temperature is as high as about 800 ° C., and bubbles are removed to keep the bonding portion dense, which is high. In order to maintain the bonding strength and prevent the metal member from being oxidized at the bonding portion, a vacuum furnace must be used to control the atmosphere. Moreover, under such conditions, it is necessary to heat the brazing filler metal to a high temperature of 800 ° C. or higher to melt and join the brazing filler metal. As a result, residual stress is likely to occur at the joint interface between the metal member and the ceramic member, and warpage due to the difference in thermal expansion between the ceramic member and the metal member or cracks or peeling of the joint portion may cause a decrease in the joint strength during use. There is a risk that the joint portion between the metal member and the ceramic member may be broken. Therefore, there are drawbacks that the use is limited and the manufacturing cost is high.

On the other hand, in the case of a joining structure of a metal member and a ceramic member which is used under a temperature condition of 500 ° C. or less and which requires airtightness, a glass joining method using glass which melts at a low joining temperature is used for comparison. It is possible to easily join the ceramic member and the metal member, and to obtain a composite member that secures high airtightness at the joint.

This glass bonding method is generally performed as follows. First, for example, alumina (Al ₂
O _3), mullite _{(3Al 2 O 3 · 2SiO 2} ), oxide ceramics such as borosilicate glass, aluminum nitride (AlN), a ceramic member non-oxide ceramics such as silicon nitride (Si ₃ N ₄₎ , Iron-nickel-cobalt (Fe-Ni-Co) alloy, iron-nickel (Fe-N)
i) An alloy is used as the metal member.

Further, lead oxide (PbO) is 56 to 66% by weight, boron oxide (B ₂ O ₃ ) is 4 to 14% by weight, silicon oxide (SiO ₂ ) is 1 to 6% by weight, zinc oxide (ZnO). 0.5 to 3 wt% and bismuth oxide (Bi ₂ O ₃ ) 0.5.
A lead oxide glass obtained by adding 10 to 20 wt% of a cordierite compound to a glass component containing 5 wt% is used as a bonding material.

Then, the metal member is heated in a batch furnace or a muffle furnace in an oxidizing atmosphere at a temperature of 500 to 600 ° C. for 5 to 15
Then, an oxidation treatment is performed for a minute to form an iron-nickel-cobalt-based oxide (FeO-NiO-CoO) or iron-nickel-based oxide (FeO-NiO) oxide layer on the surface of the metal member to a maximum thickness of about 5 μm. This oxide layer acts to enhance the bondability between the metal member and the glass of the bonding material by diffusing into the bonding material.

After that, a bonding material is applied onto the oxide layer on the surface of the metal member, heated and melted, and directly bonded to the ceramic member through the bonding material. Alternatively, in order to alleviate the difference in thermal characteristics, for example, SiO ₂ , B ₂ O ₃ , sodium oxide (Na ₂ O), or the like is formed between the oxide layer on the surface of the metal member and the bonding material of the lead oxide glass. Bonding of a metal member and a ceramic member by heating and melting through a borosilicate glass containing Al ₂ O ₃ , potassium oxide (K ₂ O), lithium oxide (Li ₂ O), barium oxide (BaO), etc. Was being done.

[0011]

[Problems to be Solved by the Invention] However, recently,
Electronic parts and structural parts used in various industrial fields are required to be further reduced in size and weight. Along with this, the constituent members of electronic parts and structural parts are further miniaturized and made thinner, which makes it difficult to secure a sufficient bonding area at the bonding portion between the metal member and the ceramic member.

As a result, as shown in FIG. 3, a lead oxide-based glass bonding material 15 is interposed between the ceramic member 12 and the oxide layer 14 of the metal member 13, or as shown in FIG. Oxide layer 14 and lead oxide-based glass bonding material 15
Ceramic member 1 with borosilicate glass 16 interposed between
In the joining structure 11 in which 2 and the metal member 13 are joined, the joining area becomes smaller as the constituent members are made smaller and thinner, so that joining is performed against the stress applied to the joining portion between the ceramic member 12 and the metal member 13. Since the shear strength per unit area in a part is about 0.2 N / mm ² , the breaking strength is small.

Therefore, due to thermal stress caused by seam welding or the like in the subsequent step of joining the ceramic member 12 and the metal member 13 or external stress applied to the joint portion during use, cracks or peeling occur at the joint portion, and the joint portion There was a problem of breaking the airtightness of.

Therefore, the present invention has been completed in view of the above problems, and an object of the present invention is to provide a thermal stress in a manufacturing process and an external stress at the time of use in a joint portion between a ceramic member and a metal member which are miniaturized and thinned. Even if added, a highly reliable joining structure between a metal member and a ceramic member and a joining method capable of preventing the occurrence of cracks or peeling of the joining portion and maintaining the airtightness of the joining portion for a long time are provided. To do.

[0015]

In the joining structure of a metal member and a ceramic member according to the present invention, the metal member and the ceramic member are mainly composed of a metal component having a liquidus temperature of 1100 ° C. or less from the metal member side. And is bonded through a bonding layer formed by forming a metal layer containing at least one of titanium, zirconium and hafnium as an active metal, an oxide layer of the active metal, and a glass layer.

According to the present invention, since the glass layer is adhered and formed on the ceramic member side by the above-mentioned constitution, SiO ₂ or magnesia (Mg) contained in the ceramic member is included.
O) and other glass components diffuse into the glass layer,
The ceramic member and the glass layer are firmly bonded. On the other hand, since a metal layer containing at least one of Ti, Zr and Hf as an active metal is deposited on the metal member side, the active metal diffuses into the metal grain boundaries of the metal member and And the metal layer are firmly bonded.

Further, since the active metal oxide layer is formed on the surface of the metal layer, this oxide layer reacts with the oxide component of the glass layer deposited on the bonding surface of the ceramic member to form a dense layer. Since the oxide layer of the active metal is generated, the metal layer and the glass layer are firmly bonded.

As a result of the above, the ceramic member and the metal member are mainly composed of a metal component having a liquidus temperature of 1100 ° C. or less from the metal member side, and contain at least one of titanium, zirconium and hafnium as an active metal. The metal layer, the oxide layer of the active metal, and the glass layer are bonded to each other through the bonding layer, so that strong bonding is achieved.

According to the method for joining a metal member and a ceramic member of the present invention, the liquidus temperature is 1100 at the joining surface of the metal member.
A metal paste containing a metal component below ℃ as a main component and containing at least one of titanium, zirconium and hafnium as an active metal is applied and heated in a reducing atmosphere to form a hydride layer of the active metal on the surface. A step of forming a metal layer formed by applying a glass paste to the surface of the hydride layer and heating the hydride layer in an oxidizing atmosphere to form the hydride layer as an oxide layer of the active metal and on the surface of the oxide layer. A step of forming a glass layer, and bringing the glass layer into contact with a bonding surface of a ceramic member and heating the glass member to bond the metal member and the ceramic member through the metal layer, the oxide layer and the glass layer. And a process.

According to the present invention, since the dense oxide layer of the active metal is formed at the interface between the metal layer and the glass layer by the above-mentioned structure, the ceramic member is formed through the glass layer, the oxide layer and the metal layer. It is possible to firmly bond to, and good airtightness can be obtained.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The joining structure of a metal member and a ceramic member of the present invention will be described in detail below. FIG. 1 is a sectional view showing an example of an embodiment of a joint structure of the present invention. In the figure, 1 is a ceramic member 2 and a metal member 3.
And the ceramic member 2 and the metal member 3 are mainly composed of a metal component having a liquidus temperature of 1100 ° C. or less from the metal member 3 side and activate at least one of titanium, zirconium and hafnium. This is a bonding structure in which a metal layer 6 contained as a metal, an active metal oxide layer 5, and a glass layer 4 are bonded together via a bonding layer.

The active metal oxide layer 5 in the present invention is obtained by heating an active metal hydride layer produced by heating the active metal-containing metal layer 6 in a heat treatment furnace in a reducing atmosphere in an oxidizing atmosphere. It is formed by oxidation, and is densely formed by baking a glass material on the surface and depositing the glass layer 4.

That is, when a brazing material containing an active metal is heat-treated in a vacuum, a hydride layer of the active metal is not formed. Therefore, even if a glass material is baked, a dense oxide layer 5 of the active metal cannot be obtained. . In addition, even if the active metal oxide layer 5 is formed by directly performing heat treatment in an oxidizing atmosphere, a thick and brittle oxide layer is formed on the surface of the metal layer 6, airtightness is not maintained, and bonding strength is low. Is not practical.

This active metal oxide layer 5 is formed by first heat treating the metal layer 6 containing the active metal in a reducing atmosphere.
Hydrogen in the atmosphere and the active metal preferentially react on the surface of the metal layer 6 to form a hydride layer of the active metal. Next, this hydride layer reacts with oxygen to become the oxide layer 5 of the active metal by heat treatment in an oxidizing atmosphere when the glass layer 4 is baked.

Therefore, the oxide layer 5 is formed, for example, by a wavelength dispersive X-ray analysis method (EPMA: ElectronProbe Microanalysi).
A cross-sectional analysis is performed by s), and the layer in which only the active metal and oxygen are detected can be specified as the active metal oxide layer 5.

The thickness of the oxide layer 5 is such that the reaction between the oxide of the active metal and the oxide in the glass layer 4 at the interface between the oxide layer 5 and the glass layer 4 is sufficient to stabilize the bonding strength. From the standpoint that it is possible, 1 μm or more is preferable. Further, the thickness of 3 μm or less is preferable from the viewpoint of making the oxide layer 5 dense and strong and preventing a decrease in bonding strength. Therefore, in particular, the metal layer 6 containing the active metal is strengthened from the viewpoint of strengthening the bonding with the glass layer 4 and obtaining the dense oxide layer 5 of the active metal.
The thickness of the active metal oxide layer 5 formed on the surface of the
μm is preferred.

The thickness of the oxide layer 5 can be controlled by the thickness of the metal layer 6, the heat treatment temperature and holding time in a reducing atmosphere, and the baking temperature condition of the glass layer 4.

In the present invention, the oxide layer 5 reacts with the oxide component of the glass layer 4 deposited on the surface of the ceramic member 2 to form a dense oxide of various active metals such as TiO ₂ , ZrO ₂ and HfO ₂ . By generating, the metal layer 6 and the glass layer 4 function so as to be firmly bonded to each other. Therefore, almost all the active metals in the oxide layer 5 are TiO ₂ , ZrO ₂ ,
It becomes an oxide such as HfO ₂ . The active metal in the oxide layer 5 has various heat treatment temperatures and extremely short heat treatment time. Therefore, when the active metal is added alone, the form of TiO ₂ , ZrO ₂ , and HfO ₂ is changed. so,
Even when two or more kinds are added, they do not form a solid solution with each other, and each surface layer exists in a state of being diffusion-bonded at the interface of oxides.

Further, in the metal layer 6 having the oxide layer 5 on the surface, the active metal is dispersed and present in a metal state in which the concentration thereof is low.

However, the diffusion or segregation of the active metal is caused when the metal layer 6 is heat-treated in a reducing atmosphere.
Hydrogen in the reducing atmosphere and the active metal preferentially react with each other on the surface of to form a hydride layer of the active metal. Therefore, since the active metal diffuses from the inside of the metal layer 6 just below the surface, the concentration of the active metal tends to be high on the surface side and decrease toward the metal member side. Moreover, the active metal may cause a non-uniform portion in the metal layer 6 due to local segregation. Therefore, in the present invention, the content of the active metal contained in the oxide layer 5 and the metal layer 6 is the average concentration of the active metal component throughout the oxide layer 5 and the metal layer 6.

Therefore, when the average concentration of the active metal in the active metal oxide layer 5 and the active metal-containing metal layer 6 is 2% by weight or more, the active metal oxide layer 5 has a sufficient thickness. It is preferable because it can be easily formed and the bonding strength with the glass layer 4 is stable. Further, if the average concentration is 4% by weight or less, it is easy to obtain a dense and strong oxide layer 5 of the active metal, and it is possible to effectively prevent a decrease in the bonding strength of the bonded portion.

Therefore, the content of the active metal in the oxide layer 5 and the metal layer 6 in the present invention is 2 to 4% by weight as an average concentration, particularly in the point of forming a dense oxide layer firmly adhered to the glass layer 4. Is preferred.

The composition of the oxide layer 5 and the metal layer 6 is
For example, a wavelength dispersive X-ray analysis method (EPMA), an X-ray analysis method (XMA: X-ray Microanalysis), an energy dispersive X-ray analysis method (EDX: Energy Dispersive X-ray Micro).
analysis), wavelength dispersive spectroscopy (WDS: Wave Leng)
th Dispersive Spectroscopy) and Auger Electron Spectroscopy (AES).

Further, for example, Ni and Fe components of the metal member 3 are diffused into the metal layer 6 so that the metal member 3 and the metal layer 6 are firmly bonded.

In the metal layer 6 of the present invention, the metal component having a liquidus temperature of 1100 ° C. or less as a main component contains silver (Ag) -copper (Cu), which is generally used as a brazing material, as a main component. Ag-Cu alloy brazing material, phosphorus (P) -Cu alloy brazing material, gold (Au) -Cu alloy brazing material, palladium (P
d) A brazing material or the like, in which a metal having a reaction activity with the components of the glass layer 4, that is, at least one of Ti, Zr, and Hf is contained as an active metal. Also,
From the viewpoint of the bonding strength between the metal layer 6 and the glass layer 4 and the denseness, the metal component is more preferably an Ag—Cu alloy brazing material. Further, in addition to the active metal, Mo may be added to the metal component as a filler from the viewpoint of adjusting the coefficient of thermal expansion and improving the flowability of the metal paste.

The metal paste for forming the metal layer 6 is a metal powder such as an Ag—Cu alloy brazing material, an active metal powder, an organic binder such as an acrylic resin, a plastic material, a solvent such as toluene or acetone, and the like. It contains.

As the metal member 3 to which such a metal layer 6 can be applied, a Fe—Ni—Co alloy or a Fe—Ni alloy typified by 42 alloy is a thermal expansion of the ceramic member 2 and the glass layer 4. It is preferable in terms of matching of coefficients.

Examples of the glass constituting the glass layer 4 of the present invention include soft glass such as silver-phosphoric acid type, lead oxide type, tin-phosphoric acid type, and borosilicate type hard glass.
Above all, from the viewpoint of the preservation of the global environment and the fact that the bonding temperature of the glass can be lowered, the tin-phosphate glass not containing lead is more preferable.

As the tin-phosphate glass, 35 to 55% by weight of phosphorus pentoxide, 20 to 40% by weight of tin monoxide, 10 to 20% by weight of zinc oxide, and 2 to 4% by weight of aluminum oxide are used. And a glass component containing silicon oxide in a range of 1 to 3% by weight, a cordierite compound as a filler, and 1 when the glass component is 100 parts by weight.
It is preferable to add 6 to 45 parts by weight. This cordierite compound has the effects of adjusting the coefficient of thermal expansion of the glass material of the glass layer 4 and improving the strength of the glass itself. If the addition amount of the cordierite compound is less than 16 parts by weight, the strength of the glass itself tends to decrease, and the bonding strength of the bonded structure 1 tends to decrease. On the other hand, when the addition amount exceeds 45 parts by weight, the fluidity of the glass decreases and the thermal expansion coefficient of the glass material decreases, so that the ceramic member 2
Also, the thermal expansion coefficient of the metal member 3 is greatly different from that of the metal member 3, and the bonding strength tends to be lowered.

Further, the glass layer 4 is 5 in terms of ensuring a sufficient glass amount for bonding and reducing variations in bonding strength.
The thickness is preferably 0 μm or more. On the other hand, from the viewpoint of controlling the flowability so as to suppress the protrusion of the glass from the bonded portion at the time of bonding, it is preferable that the thickness thereof does not exceed 200 μm. Therefore, the thickness of the glass layer 4 is taken into consideration in consideration of ensuring that the amount of glass is just enough for bonding and stable bonding strength is obtained, and that the flowability is controlled so as to prevent the glass from protruding from the bonding portion. Saha is 50-200
About μm is preferable.

The glass layer 4 reacts with the oxide layer 5 of the active metal formed on the surface of the metal layer 6 to form a dense oxide layer 5 of the active metal. Therefore, the airtightness at the interface between the ceramic member 2 and the metal member 3 is ensured, and the bonding with the metal layer 6 containing the active metal is strengthened.

The glass layer 4 is prepared, for example, by adding a predetermined organic binder to glass material powder to prepare a paste, and depositing it on the hydride layer of the active metal of the metal layer 6 deposited on the metal member 3. Apply by screen printing or calendar roll method. After that, about 500 in an oxidizing atmosphere
It is formed by heat treatment at a temperature of ° C for 10 minutes. At this time, the active metal hydride layer formed on the surface of the metal layer 6 is oxidized to form a dense and strong active metal oxide layer 5.
Becomes

The ceramic member 2 of the present invention is made of alumina,
Examples include oxides such as mullite and various glasses, and non-oxides such as silicon nitride and aluminum nitride. Of these, alumina ceramics is preferable, and the joint structure 1 with various metal members 3 becomes more preferable in terms of airtightness and joint strength reliability. Further, in order to firmly bond the ceramic member 2 to the glass layer 4 without impairing the strength of the ceramic member 2 itself, the surface roughness thereof is set to 0.2 to 1 μm in terms of average surface roughness Ra as a pretreatment. Is more preferable.

The metal member 3 of the present invention includes carbon steel, its alloy steel, stainless steel, Fe-Ni-Co alloy, F alloy.
e-Ni alloys and other low-thermal-expansion-coefficient alloys and heat-resistant alloys containing iron as a main component, heat-resistant alloys containing Ni as a main component, W, Mo and their alloys, cemented carbide, and various metal materials such as cermets. can do.

Furthermore, it is also possible to join a metal member having a different thermal expansion coefficient or a metal member having a large plastic deformation to the metal member 3 to form a composite. By doing so, the bonded structure 1 of the ceramic member 2 and the metal member 3 which is excellent in strength and relaxes the thermal stress and the plastic deformation amount applied to the bonded portion and maintains the airtightness is obtained.

Even if the bonding surface area of the bonding structure 1 of the present invention is small, sufficient bonding strength can be obtained.
Specifically, the area of the bonding surface is preferably 9～52Mm ^2, the 9 mm ^2, liable strength and airtightness of the joint portion is lowered, when it exceeds 52 mm ^2, smaller and thinner junction increases Is not realized and the practicality is reduced.

Next, an example of an embodiment of a method for joining the ceramic member 2 and the metal member 3 of the present invention will be described with reference to FIG.
It will be described in detail by the following steps [1] to [5] based on (a) to (d).

[1] First, on the joint surface of the metal member 3 with the ceramic member 2, an active metal composed of at least one of Ti, Zr and Hf and a metal component having a liquidus temperature of 1100 ° C. or less as a main component. Containing metal paste 7
Is applied by screen printing or calendar roll method to a thickness of about 70 μm (a).

[2] Next, after the printed and coated metal paste 7 is dried, it is heated to about 800 in a reducing atmosphere in a heat treatment furnace.
It was heated at a temperature of 60 ° C. for 60 minutes to deposit and form a metal layer 6 having a thickness of about 55 μm. At the same time, an active metal hydride layer 8 having a thickness of about 3 μm is formed on the surface of the metal layer 6 (b).

The thickness of the surface layer 8 can be controlled by the thickness of the metal paste 7 which is first applied by printing and the heat treatment conditions in the heat treatment furnace.

[3] After that, on the surface layer 8 of the metal layer 6 deposited on the surface of the metal member 3, a glass paste prepared by mixing tin-phosphate glass powder with a binder made of an organic resin was used. In the same manner as described above, printing is applied by a screen printing method or a calendar roll method.

Examples of the tin-phosphate type glass include:
35 to 55% by weight of phosphorus pentoxide and 20 to 4 of tin monoxide
Glass composition containing 0% by weight, 10 to 20% by weight of zinc oxide, 2 to 4% by weight of aluminum oxide and 1 to 3% by weight of silicon oxide, and 16 to 45% by weight of a cordierite compound as a filler. Partly added is preferable.

[4] Next, the glass material applied by printing is dried and then heated at a temperature of about 500 ° C. for 10 minutes in an oxidizing atmosphere to bake the glass paste to form the glass layer 4. As a result, the active metal hydride layer 8 becomes a strong and dense active metal oxide layer 5 (c).

[5] Thereafter, the ceramic member 2 is brought into contact with the glass layer 4 of the metal member 3 on which the metal layer 6, the oxide layer 5 and the glass layer 4 are formed, and heated at a temperature of about 500 ° C. for 10 minutes. The ceramic member 2 and the metal member 3 are joined. As a result, it is possible to obtain the joint structure 1 of the metal member 3 and the ceramic member 2 which have a high joint strength with a dense joint and a high airtightness (d).

Therefore, according to the joining structure 1 of the present invention, the ceramic member 2 is provided with the metal layer 6 containing the active metal having a high joining temperature.
Since it is not directly bonded to the metal member 3, residual stress is less likely to occur at the bonding interface between the ceramic member 2 and the metal member 3. As a result, the warp due to the difference in thermal expansion between the ceramic member 2 and the metal member 3 and the cracks and peeling at the joint are eliminated.

Then, the junction structure 1 was actually produced according to the above steps [1] to [5]. At this time, an alumina ceramic column having a diameter of 12 mm was used as the ceramic member 2, a 42 alloy column (42 wt% Ni-58 wt% Fe) having a diameter of 5 mm was used as the metal member 3, and 3 parts by weight of Ti (mainly as an active metal) was used. The metal component of the main component is 72 wt% Ag.
-Cu 28 wt% Ag-Cu alloy metal layer 6
And the glass layer 4 made of tin-phosphate glass as a joining layer, the joining structure 1 was produced under the same conditions as the joining method in the above steps [1] to [5].

In addition, as a comparative example, a bonding structure using the same ceramic member 2 and metal member 3 as the above, in which only the glass layer 4 made of the tin-phosphate glass was used as a bonding layer, was separately prepared.

Then, a helium gas leak test was conducted on the joint structure 1 of the present invention and the joint structure of the comparative example in order to evaluate the airtightness of the joint. As a result, a leak of helium gas was found in all 10 of the comparative examples. In contrast, the product of the present invention did not leak helium gas at all.

Next, when a shear test was performed on these joint structures, the breaking load of the comparative example was 21.
In contrast to 56 N (Newton), the breaking strength of the product of the present invention was 63.7 N on average, significantly increasing the joint strength. Therefore, it was confirmed that the airtightness can be secured and the bonding strength is extremely high in the product of the present invention.

In the above embodiment, the joining structure 1 of the cylindrical ceramic member 2 and the metal member 3 has been described, but the present invention is not limited thereto and is applied to electronic parts, structural parts and the like. 1. A joint structure 1 of a ceramic member 2 and a metal member 3, for example, a joint structure of a ceramic semiconductor element housing package and various metal airtight terminals, a joint structure of a glass lens and a metal frame component (lens holder), and a ceramic member. The present invention can be applied to a joint structure between a semiconductor element housing package and various metal heat sink parts.

[0061]

According to the joining structure of the ceramic member and the metal member of the present invention, the metal member and the ceramic member are mainly composed of a metal component having a liquidus temperature of 1100 ° C. or less from the metal member side, titanium, zirconium and The glass layer is adhered to the ceramic member side by being bonded through a bonding layer formed by forming a metal layer containing at least one of hafnium as an active metal, an oxide layer of the active metal, and a glass layer. Therefore, the glass component such as SiO ₂ or magnesia (MgO) contained in the ceramic member diffuses into the glass layer, so that the ceramic member and the glass layer are firmly bonded. On the other hand, on the metal member side, a metal component having a liquidus temperature of 1100 ° C. or lower is a main component,
Since the metal layer containing at least one of Ti, Zr, and Hf as the active metal is deposited and formed, the active metal diffuses into the metal grain boundaries of the metal member, and the metal member and the metal layer are solidified. To be joined.

Further, since the active metal oxide layer is formed on the surface of the metal layer, the oxide layer reacts with the oxide component of the glass layer adhered to the bonding surface of the ceramic member to form a dense active layer. Since the metal oxide layer is generated, the metal layer and the glass layer are strongly bonded.

Therefore, the metal member and the ceramic member are
A metal layer containing a metal component having a liquidus temperature of 1100 ° C. or less as a main component and containing at least one of titanium, zirconium, and hafnium as an active metal, an active metal oxide layer, and a glass layer are formed from the metal member side. By being joined via the joining layer formed as described above, it is possible to firmly join.

According to the method for joining a metal member and a ceramic member of the present invention, the liquidus temperature is 1100 at the joining surface of the metal member.
A metal paste containing a metal component below ℃ as a main component and containing at least one of titanium, zirconium and hafnium as an active metal is applied and heated in a reducing atmosphere to form a hydride layer of the active metal on the surface. Forming a metal layer and applying a glass paste to the surface of the hydride layer and heating it in an oxidizing atmosphere to turn the hydride layer into an active metal oxide layer and form a glass layer on the surface of the oxide layer. The step of contacting the glass layer with the bonding surface of the ceramic member and heating to bond the metal member and the ceramic member through the metal layer, the oxide layer, and the glass layer Since the oxide layer of is formed at the interface between the metal layer and the glass layer, the ceramic member can be firmly bonded to the metal member via the glass layer and the metal layer, It can be obtained a good tightness.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of an embodiment of a joint structure between a metal member and a ceramic member of the present invention.

2 (a) to 2 (d) are cross-sectional views showing the periphery of the joint in each step, showing an example of the embodiment of the method for joining the metal member and the ceramic member of the present invention.

FIG. 3 is a cross-sectional view showing a conventional joining structure of a metal member and a ceramic member.

FIG. 4 is a cross-sectional view of another example showing a conventional joining structure of a metal member and a ceramic member.

[Explanation of symbols]

1: Joining structure of metal member and ceramic member 2: Ceramic member 3: Metal member 4: Glass layer 5: Active metal oxide layer 6: Metal layer 7: Metal paste 8: hydride layer of active metal

Claims (2)

[Claims] 1. A metal member and a ceramic member mainly contain a metal component having a liquidus temperature of 1100 ° C. or less from the metal member side, and contain at least one of titanium, zirconium and hafnium as an active metal. A joining structure of a metal member and a ceramic member, wherein the metal member and the ceramic member are joined together through a joining layer formed by forming a metal layer, an oxide layer of the active metal, and a glass layer. 2. The liquidus temperature is 11 at the joint surface of the metal member.
A metal paste containing a metal component of 00 ° C. or lower as a main component and containing at least one of titanium, zirconium, and hafnium as an active metal was applied and heated in a reducing atmosphere to form a hydride layer of the active metal on the surface. A step of forming the formed metal layer, applying a glass paste to the surface of the hydride layer, and heating in an oxidizing atmosphere to make the hydride layer an oxide layer of the active metal and the surface of the oxide layer And forming a glass layer on the bonding surface of the ceramic member, and heating the glass member to bond the metal member and the ceramic member through the metal layer, the oxide layer and the glass layer. A method for joining a metal member and a ceramic member, the method comprising: