JP2000154081A - Ceramic parts and their production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance with good reproducibility the adhesion and uniformity of a 2nd metallizing layer to a 1st metallizing layer comprising a layer fired simultaneously with a substrate in the production of ceramic parts having metallizing layers, e.g. a ceramic circuit board. SOLUTION: The ceramic circuit board 4 has a ceramic substrate 1 with a 1st metallizing layer 2 and a 2nd metallizing layer 3 formed on the 1st metallizing layer 2. The 2nd metallizing layer 3 is formed by melting a metallic material having a lower melting point than the 1st metallizing layer 2 by heating on the layer 2 and solidifying the resultant melt while infiltrating it into the layer 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a ceramic component having a metallized layer and a method for manufacturing the same.

[0002]

2. Description of the Related Art In recent years, high integration and high speed of semiconductor devices have been realized.
The demand for ceramic substrates is increasing with the increase in power consumption and the size of chips. For example, aluminum (AlN) substrate nitride has a high thermal conductivity, excellent in heat dissipation, and the like to have a linear thermal expansion coefficient close to Si, a circuit board or a semiconductor in place of alumina (Al ₂ O ₃₎ substrate It is expected as a substrate for a package.

When the above-mentioned ceramic substrate is used as a circuit board for mounting electronic components or a package base, W, Mo, Ni,
A metal layer made of Cr, Pd, Ag, or the like is formed as an electrode, a wiring layer, or the like. Such a metal layer (metallized layer) is formed by simultaneous firing with the substrate, or by applying and firing a conductive paste after firing the substrate. When forming a metallized layer by simultaneous firing,
A paste of a high-melting point metal such as W or Mo containing ceramic fine powder is used in consideration of the bonding property with the ceramic base material.

[0004] On the metallized layer formed in this manner, usually, in order to impart bonding property with solder, etc.,
An electroless plating layer made of Ni, Au, Cu, or a combination thereof is formed. When an electroless plating layer is formed on a metallized layer, it is general that wet etching is performed in advance with an acid solution or an alkali solution as a pretreatment.

[0005]

However, the conventional method for manufacturing a ceramic wiring board as described above lacks consideration of the following points.

That is, when electroless plating is performed on a metallized layer provided on a ceramic substrate, the adhesion strength to the metallized layer changes depending on the type of electroless plating and the type of bath, and a plated layer adhered with sufficient strength is formed. May not be obtained. Furthermore, if the surface pretreatment is not appropriate, plating does not deposit uniformly, and for example, there is a problem that a plating film does not deposit in the concave portion.

As described above, according to the conventional method of forming a metal layer (second metalized layer) by electroless plating, the adhesion strength and the mechanical strength of the metal layer are insufficient, and the deposition form is not uniform. There was such a problem. In addition, there is a problem that the wettability of the solder is reduced due to the non-uniform deposition form or the like, and furthermore, the solder is easily broken in a tensile test or a reliability test. In addition, in electroless plating, it is difficult to form the second metallized layer sufficiently thick, and for example, there is a problem that solder erosion is likely to occur.

[0008] Ceramic parts having a metallized layer are not limited to ceramic substrates for electronic parts, but are also used when ceramic parts are used as structural parts. For example, when a ceramic member is joined to a metal member, a metallized layer is formed on the surface of the ceramic substrate as a joining layer. A similar problem occurs in such ceramic parts as structural parts.

The present invention has been made to address such a problem, and has improved the adhesion and uniformity of the second metallized layer to the first metallized layer by simultaneous firing with a ceramic substrate. To provide a ceramic part capable of ensuring a sufficient thickness of the second metallized layer, and a method of manufacturing the ceramic part capable of producing such a ceramic part with good reproducibility. And

[0010]

According to a first aspect of the present invention, there is provided a ceramic component, comprising: a ceramic base; a first metallized layer formed on a surface of the ceramic base; and a first metallized layer. And a second metallized layer formed of a molten and solidified layer of a metal material having a lower melting point than the first metallized layer.

In the ceramic part of the present invention, the first
As described in claim 2, the metallized layer is made of a refractory metal containing ceramic fine particles in a range of 5 to 15% by volume and has pores in a volume ratio of 5 to 25%. A co-firing layer with the substrate is applied.

The second metallized layer is formed so as to partially penetrate into the holes of the first metallized layer as described above. More specifically, as described in claim 4, the second metallized layer is formed of the first metallized layer.
A low-melting metal material is melted and solidified on the metallized layer, thereby causing a portion of the low-melting metal material to penetrate into the pores of the first metallized layer and be fixed. It is.

The method for manufacturing a ceramic part according to the present invention comprises:
As described in claim 8, in forming a second metallized layer on the first metallized layer provided on the surface of the ceramic base to produce a ceramic component, the second metallized layer is formed on the first metallized layer. By heating and melting a metal material having a lower melting point than the one metallized layer to fix it,
The method is characterized in that the second metallized layer is formed.

[0014] The method for manufacturing a ceramic part according to the present invention comprises:
As described in claim 9, the first metallized layer is made of a high melting point metal containing ceramic fine particles in a range of 5 to 15% by volume, and has pores in a volume ratio of 5 to 25%. It is particularly effective when it is a co-fired layer with a substrate. When the low melting point metal material is melted, a part of the first metallized layer is penetrated into the pores and solidified in this state to form the second metallized layer.

In the method for manufacturing a ceramic part according to the present invention, when the first metallized layer is a co-fired layer of a high-melting metal containing ceramic fine particles, the first metallized layer may be made of a metal. It is preferable to form fine concave portions having a depth of 0.5 to 100 nm at intervals of 0.5 to 150 nm on the surface of the high melting point metal particles located on the surface of the first metallized layer by plasma etching the surface.

In the present invention, a metal material having a lower melting point than the first metallized layer is heated and melted and solidified on the first metallized layer, and the low-melting metal material is fixed to the first metallized layer. A second metallization layer is formed. The second metallized layer made of such a melted / solidified layer partially penetrates (infiltrates) sufficiently into the pores of the first metallized layer, so that it does not depend on the material of the first metallized layer. In addition, the adhesion strength of the second metallized layer to the first metallized layer can be sufficiently increased easily and easily.

Further, the uniformity of the second metallized layer can be easily increased regardless of the surface condition of the first metallized layer, and the thickness of the second metallized layer can be sufficiently ensured. it can. Therefore, for example, the solder wettability can be improved, the occurrence of solder erosion can be suppressed, and peeling, deterioration, and the like hardly occur in various reliability tests such as a TCT test (thermal cycle test). It is possible to obtain a metallized layer.

[0018]

Embodiments of the present invention will be described below.

FIG. 1 is a cross-sectional view showing an essential structure of an embodiment in which the ceramic component of the present invention is applied to a ceramic wiring board. In FIG. 1, reference numeral 1 denotes a ceramic substrate made of a sintered body containing, for example, aluminum nitride (AlN) as a main component. The constituent material of the ceramic substrate (ceramic substrate) is not limited to AlN. For example, silicon nitride (Si ₃ N ₄ ) or alumina (Al
It is also possible to use a sintered body mainly containing ₂ O ₃ ).

On the surface 1a of the ceramic substrate 1, a first metallized layer 2 is formed. The first metallized layer 2 functions as, for example, an electrode, an input / output terminal, a surface wiring layer, an element mounting portion, and the like. Such first
The thickness of the metallized layer 2 is preferably in the range of 5 to 25 μm. If the thickness of the first metallized layer 2 is less than 5 μm, the amount of vacancies will be insufficient, and as a result, the components of the second metallized layer 2 will not easily penetrate into the first metallized layer, and the surface of the ceramic substrate 1 And it becomes difficult to form a continuous film. On the other hand, if the thickness exceeds 25 μm, distortion occurs in the metallized layer due to heat during brazing or the like, and warpage or the like occurs due to a difference in shrinkage ratio with respect to the ceramic substrate 1, and as a result, the flatness of the metallized layer is impaired, and When brazing, for example, sufficient adhesiveness may not be obtained.

The first metallized layer 2 can be formed by any of various methods, and is not particularly limited in its formation method. As the first metallized layer 2, a co-fired layer with the ceramic substrate 1 of a high melting point metal;
Alternatively, a coating and baking layer of a metal paste is applied.

The co-fired layer of the refractory metal is made of, for example, W or M
A coating layer of a high-melting-point metal paste containing a high-melting-point metal such as o as a main component is formed by simultaneous firing with the ceramic substrate 1. The applied and baked layer of the metal paste is Ni,
The paste is formed by applying a paste of a metal composition containing at least one selected from Cr, Pd, Ag, Cu, Al, Mn, etc. onto the ceramic substrate 1 and firing the paste. It is based on a method called

Of these, the first metallized layer 2 composed of a co-fired layer of a high melting point metal is, for example, 5 to 2 in volume ratio.
It is a porous layer containing 5% vacancies, and it is difficult to form a metallized layer uniformly by electroless plating. For this reason, the present invention is particularly effective for a ceramic wiring substrate (ceramic component) having the first metallized layer 2 formed by the simultaneous firing method.

As the high melting point metal paste when the simultaneous firing method is applied, a high melting point metal such as W or Mo as a main component, to which a ceramic fine powder such as AlN or Y ₂ O ₃ is added is used. Is preferred. The ceramic fine powder suppresses formation failure and peeling of the metallized layer 2 during simultaneous firing, and contributes to improvement of the adhesion strength between the metallized layer 2 and the ceramic substrate 1. It is practical to mix the ceramic fine powder in the range of 5 to 15% by volume with respect to the high melting point metal. Ni, Cr, Pd, Ag,
Al, Mn, etc. may be blended.

Although FIG. 1 shows a state in which the first metallized layer 2 is formed only on the surface 1a of the ceramic substrate 1, a metal layer (for example, an internal wiring layer) is formed inside the ceramic substrate 1 by a simultaneous firing method. May be formed. Therefore, the ceramic substrate 1 may be either a single-plate substrate or a multilayer substrate.

On the first metallized layer 2, there is formed a second metallized layer 3 made of a molten and solidified layer of a metal material having a lower melting point, for example, Cu, Ni, or an alloy containing them. By these, the ceramic wiring board 4
Is configured. The second metallized layer 3 has a function of securing electrical and mechanical reliability at the time of soldering, for example, and is appropriately selected and used depending on the application.

The second metallized layer 3 is formed by heating and melting a low melting point metal material such as Cu, Ni or an alloy containing these on the first metallized layer 2 and solidifying it by cooling and solidifying it. -It is made of solidified material. At this time, when the first metallized layer 2 is a porous layer such as a co-fired layer of a high melting point metal, as shown in FIG. 2, the first metallized layer 2 is melted in the holes 2a of the first metallized layer 2. The low melting point metal material permeates (infiltrates). Further, when the surface of the ceramic substrate 1 is relatively porous, the molten low melting point metal material penetrates into such a portion.

In the case of the conventional plating method, even if the metal material penetrates, it is only in the vicinity of the very surface of the first metallized layer. Although it depends on the thickness of the first metallized layer 2,
A low-melting-point metal material can be penetrated (infiltrated) into almost all the holes 2a of the first metallized layer 2.

The first metallized layer 2 after the second metallized layer 3 is formed by a method of melting and solidifying a low melting metal material.
Although it depends on the initial amount (volume ratio) of the holes 2a, the hole amount decreases to, for example, about 0 to 5% by volume ratio, and shows a value close to zero. As described above, the second metallized layer 3 is formed by the melting and solidifying method of the low melting point metal material, and a part thereof is formed in the first metallized layer.
By infiltrating (infiltrating) the pores 2a of the metallized layer 2, the anchor effect can be obtained, so that the adhesion strength of the second metallized layer 3 to the first metallized layer 2 can be increased. Becomes

Further, according to the melting and solidifying method of the low melting point metal material, the second metallized layer 3 can be formed sufficiently thick. Specifically, the thickness of the second metallized layer 3 can be in the range of 1 to 10 μm. By setting the thickness of the second metallized layer 3 to 1 μm or more, uniformity and adhesion can be improved, and solder wettability and solder erosion can be improved. If the thickness of the second metallized layer 3 exceeds 10 μm, blisters and the like are likely to be generated, and the adhesion to a semiconductor element mounted thereon is reduced, which may cause poor brazing or the like. There is. More preferably, the thickness of the second metallized layer 3 is in the range of 5 to 10 μm.

The constituent material of the second metallized layer 3 is
The metal material having a lower melting point than the metallized layer 2 is not limited to the above-described simple metals such as Cu and Ni, and may be an alloy containing these metals. In particular, the second
The material of the metallized layer 3 is the first metallized layer 2
In particular, when the first metallized layer 2 is a co-fired layer, it is desirable to use a metal material having a lower melting point than the firing temperature. Thereby, it is possible to prevent a decrease in the bonding strength of the first metallized layer 2 after the second metallized layer 3 is formed by melting and solidifying.

As described above, by forming a second metallized layer 3 by melting and solidifying a metal material having a lower melting point than the first metallized layer 2, wet electroless plating is applied as in the prior art. Without this, the second metallized layer 3 excellent in uniformity, adhesion, solder wettability and the like can be easily obtained.

That is, the second metallized layer 3 is formed by melting and solidifying a metal material having a lower melting point than the first metallized layer 2.
According to the forming process, the adhesion strength of the second metallized layer 3 can be easily increased regardless of the material of the first metallized layer 2 and the uniformity of the first metallized layer 2 can be improved. It can be easily increased regardless of the surface condition. Further, since the thickness of the second metallized layer 3 can be sufficiently ensured, for example, the occurrence of solder erosion can be suppressed, and the TCT test (thermal cycle test)
And the like, a metallized layer that is unlikely to peel or deteriorate in various reliability tests can be obtained.

Here, on the surface of the first metallized layer 2, before forming the second metallized layer 3 by melting and solidifying the above-mentioned low melting point metal material, an etching process is performed to form fine irregularities. It is preferable to keep it. Thereby, the adhesion strength, the film thickness and the uniformity of the second metallized layer 3 can be further improved. The etching process for the first metallized layer 2 is appropriately selected according to its constituent materials and the like. In particular, in the case of the metallized layer 2 formed by the simultaneous firing method, the following etching process should be applied. Is preferred.

FIG. 3 is a diagram schematically showing the structure of the first metallized layer 2 by the simultaneous firing method. As shown in FIG. 3, the first metallized layer 2 composed of a co-fired layer is composed of a high melting point metal particle 5 which is a main component of the high melting point metal paste, and a ceramic based on ceramic fine powder mixed in the high melting point metal paste. It is mainly composed of fine particles 6. For such a first metallized layer 2, it is preferable to apply a plasma etching process, and it is further preferable to use an etching process using an alkali solution in combination.

According to the plasma etching process, the entire surface of the refractory metal particles 5 located on the surface of the first metallized layer 2 is coated with 0.5 to Fine recesses 5a having a depth of 0.5 to 100 nm can be formed at intervals of 150 nm. The dimples based on the fine concave portions 5a can be uniformly formed on the entire surface of the first metallized layer 2 without any directionality.

According to the etching treatment using the alkaline solution, the fine metal particles 6 located on the surface of the first metallized layer 2 can be formed without causing deterioration or deterioration of the high melting point metal particles 5 such as W and Mo. On the surface, selectively 10 ~
Asperities 6a having a depth of 5 to 20 μm can be formed at intervals of 150 μm. Such a concave portion 6a can also be formed uniformly on the entire surface of the first metallized layer 2 without any directionality.

As described above, the dimples based on the fine recesses 5a are formed in advance on the surface of the high melting point metal particles 5 located on the surface of the first metallized layer 2, so that the dimples have a low melting point. An anchor effect is provided for the second metallized layer 3 by melting and solidifying the material. Therefore, the adhesion strength of the second metallized layer 3 can be further improved, and the thickness and uniformity of the second metallized layer 3 can be increased. The same effect is also obtained for the unevenness 6a provided on the surface of the ceramic fine particles 6.

The fine recesses 5a on the surface of the refractory metal particles 5
Preferably, the depth is 0.5 to 100 nm and the interval is 0.5 to 150 nm. The irregularities 6a on the surface of the ceramic fine particles 6 are as follows.
As described above, the depth is preferably 5 to 20 μm, and the interval is preferably 10 to 150 μm. Fine concave portion 5 having such a shape
The anchor effect on the second metallized layer 3 can be more favorably obtained by utilizing the “a” and the unevenness 6 a. As shown in FIG. 4, the shapes of the fine concave portions 5a and the concave and convex portions 6a indicate the depth d of each dimple 7 and the interval p based on them.

The dimples based on the fine concave portions 5a and the concave and convex portions 6a are preferably formed on the surfaces of the refractory metal particles 5 and the ceramic fine particles 6 without any direction and uniformly over the entire surface. Such dimples can be confirmed by observation with an SEM (scanning electron microscope) or an AFM (atomic force microscope) or the like, and their dimples are determined by their regularity (repeatability / interval) and size (depth). It can be distinguished from other irregularities on the surface of the one metallized layer 2.

Specific examples of use of the ceramic wiring board 4 of this embodiment include a circuit board and a package base. For example, when the ceramic wiring substrate 4 is used as a package base, a ceramic substrate 1 having a multilayer structure having an internal wiring layer is used. A laminated film of the first metallized layer 2 and the second metallized layer 3 electrically connected to the internal wiring layer forms a connection electrode with a semiconductor element and a conductor for an external input / output terminal, specifically, an input / output terminal. Functions as a solder joint for terminals.

Specific examples of the soldering of the input / output terminals include solder bumps in a BGA package and soldering of input / output pins in a PGA package. The same applies to the case where semiconductor elements are flip-chip connected. In particular, the ceramic wiring substrate of the present invention is applied to a conductor for electrodes and terminals, that is, a package base in which the area of the first metallized layer 2 is miniaturized in order to achieve a finer input / output pattern and a higher density. 4 is valid.

Next, a method of manufacturing the above-described ceramic wiring board 4 will be described.

First, a ceramic substrate 1 having a first metallized layer 2 on at least the surface is prepared. This substrate manufacturing step is performed by combining the ceramic substrate 1 and the first substrate as described above.
May be carried out by simultaneously firing the metallized layer 2 and the first metallized layer 2.
May be formed. In this way,
First metallized layer 2 on surface 1a of ceramic substrate 1
To form

Next, wet etching using an alkaline solution and dry etching using plasma are sequentially performed on the ceramic substrate 1 having the first metallized layer 2 on the surface. These etching processes are performed as needed. According to the alkali etching treatment, W or M
The surface of the ceramic fine particles 6 located on the surface portion of the first metallized layer 2 is selectively formed on the surface of the ceramic fine particles 6 at an interval of 10 to 150 μm and a depth of 5 to 20 μm without causing deterioration or deterioration of the high melting point metal particles 5 such as o Is formed.

In such an alkaline etching treatment, an aqueous solution of NaOH or KOH is used as an etching solution. Concentration of etchant is 400 ~ 900g / L
(Liter), and the temperature is 10
Preferably, the temperature is set to 5050 ° C. After being immersed in such a concentrated solution of alkali for, for example, 10 minutes or more and dried,
By performing the heat treatment at a temperature of about 300 ° C., irregularities 6 a are generated on the surface of the ceramic fine particles 6 located on the surface of the first metallized layer 2. At this time, since the reactant generated by the alkali etching adheres to the surface, it is preferable to remove the reactant using an ultrasonic cleaning device or the like, whereby good adhesion and good appearance can be obtained.

According to the plasma etching treatment, as described above, the quality of the surface of the first metallized layer 2 can be reduced without deteriorating or deteriorating the ceramic substrate 1 made of a sintered body mainly composed of AlN. At a distance of 0.5 to 150 nm and a depth of 0.5 to 100
A minute concave portion 5a having a thickness of nm can be formed.

As an etching gas used in the plasma etching step, SF ₆ type, Ar type, BrCl ₃ type, H
Br system, SiCl ₄ system, CCl ₄ system, CHCl ₃ system, C
An FCl ₃ type or the like can be used, and an SF ₆ type is particularly preferable. These may be used alone,
In order to enhance the uniformity of a and the like, it is preferable to use a mixed system of Cl ₂ gas and O ₂ gas. In particular, SF
_Six- system etching gas, specifically SF ₆ + Cl ₂ + O
The mixed gas of No. ₂ can be said to be a preferable etching gas because dimples having a good and uniform shape are easily obtained with good reproducibility. This SF ₆ + Cl ₂ + O ₂
The composition of the gas mixture is as follows: SF ₆ is 40 to 98% by volume, and Cl ₂ is
0.2 to 50 vol%, it is preferable that the O ₂ and 0.01 to 40% by volume.

The plasma etching using the etching gas as described above is performed using, for example, an apparatus as shown in FIG. In the plasma etching apparatus shown in FIG. 5, an anode electrode 12 and a cathode electrode 13 are arranged in a reaction chamber 11 so as to face each other. For example, a ceramic wiring substrate 4 to be processed is arranged on the cathode electrode 13. An RF power source 14 is connected to the anode electrode 12, and plasma is formed between the anode electrode 12 and the cathode electrode 13. The reaction chamber 11 is connected to an etching gas supply system 15 and an exhaust system (not shown). Etching gas supply system 1
5 has, for example, an SF ₆ gas cylinder 16, a Cl ₂ gas cylinder 17, and an O ₂ gas cylinder 18, all of which are controlled by a gas flow controller 19.

In the plasma etching apparatus shown in FIG. 5, a ceramic wiring substrate 4 as an object to be processed is arranged on a cathode electrode 13 and the inside of a reaction chamber 11 is, for example, 1 ×.
After evacuating to about 10 ^-4 Pa or less, each gas cylinder 16, 1
While introducing a predetermined flow rate of gas from 7 and 18, the RF power supply 1
The plasma etching is performed on the surface of the first metallized layer 2 by generating the plasma by applying the RF power from 4. The etching conditions at this time, that is, the flow rate, pressure, RF output, etching time, and the like of each gas are appropriately set. For example, it is effective to set conditions by observation using a dummy sample.

After performing the above-described alkali etching and plasma etching, a second metallized layer 3 is formed on the first metallized layer 2. In the step of forming the second metallized layer 3, first, for example, a foil or powder of, for example, Cu or Ni having a lower melting point than the first metallized layer 2 is arranged on the first metallized layer 2, And heat to melt. Thereafter, the second metallized layer 3 fixed to the first metallized layer 2 is obtained by solidifying the metal that has been cooled and melted. The molten low melting point metal material permeates into the first metallized layer 2 and solidifies in this state.

The thickness of the metal foil used for forming the second metallized layer 3 is appropriately set according to the intended thickness of the second metallized layer 3, and is preferably, for example, 10 to 100 μm. In some cases, metal powder or the like can be used. The heat treatment for melting the metal foil
For example, it is preferably carried out for 1 to 2 hours.

According to the step of forming the second metallized layer 3, the second metallized layer having excellent uniformity, adhesion, solder wettability and the like can be obtained without applying wet electroless plating as in the prior art. Layer 3 can be obtained easily and easily. The low melting point metal material is the first metallized layer 2.
Even if the first metallized layer 2 is patterned because it spreads depending on the surface shape of
The second metallized layer 3 can be formed according to the shape of the first metallized layer 2. As a result, the electrical characteristics, mechanical characteristics, reliability, and the like of the second metallized layer 3 can be improved.

Although the above embodiment is an example in which the ceramic component of the present invention is applied to a ceramic circuit board, the ceramic component of the present invention is not limited to electronic materials.
The same applies to structural materials. That is, when the first and second metallized layers are formed on the surface of the structural ceramic sintered body, for example, as a bonding layer with a metal component, a molten / solidified layer of a low melting point metal material is formed on the second metallized layer. By applying the same, effects similar to those of the above-described embodiment can be obtained.

The basic structure of the electronic material and the structural material is the same except that the shape, the constituent material of the ceramic base, and the like differ depending on the application, and will be described with reference to the ceramic circuit board of the above-described embodiment. The configuration described above can be applied. When applied to a structural material or the like, the first and second metallized layers function as, for example, a bonding layer with a metal member or another ceramic member, and the second metallized layer is formed of Ag-Cu. A brazing material or the like is used.

[0056]

Next, specific examples of the present invention and evaluation results thereof will be described.

Example 1 First, a W paste containing 20% by volume of AlN powder was prepared.
This is applied to the surface of the AlN molded body, and then fired at 1790 ± 10 ° C. to produce an AlN substrate having a W metallized layer (first metallized layer / simultaneously fired layer) containing AlN fine particles formed on the surface. did. The thickness of the obtained W metallized layer was about 10 μm, and had pores of 20% by volume.

After a Cu foil having a thickness adjusted so as to have a thickness of 3 μm after infiltration is arranged on the W metallized layer, a heat treatment is performed for 1 hour in a reducing atmosphere of dry hydrogen at 1230 ° C. To form Cu on the W metallized layer.
A metallized layer (second metallized layer) was formed.

The bonding strength of the metallized layer thus obtained was measured by a peel test. As a result, the joint strength
It was 1.0 kg / cm. The porosity of the W metallized layer after the formation of the Cu metallized layer was reduced to 3% by volume.

Examples 2 to 5 In the same manner as in Example 1, an AlN substrate having a W metallized layer (first metallized layer) containing AlN fine particles formed on the surface by simultaneous firing was produced. This W metallized layer had a thickness of about 15 μm, further contained 20% by volume of AlN fine particles, and had pores of 10% by volume.

After arranging Cu foils each having an appropriate thickness or the like such that the thickness after infiltration becomes the thickness shown in Table 1 on the W metallized layer, reduction of dry hydrogen at 1230 ° C. By performing a heat treatment for 1 to 2 hours in an atmosphere, a Cu metallized layer (second
Metallized layer).

The bonding strength of each metallized layer thus obtained was measured by a peel test. Table 1 shows the results of the peel test (joining strength) together with the thickness of the Cu metallized layer. In Comparative Example 1 in Table 1, the Cu layer was formed by electroless plating.

[0063]

[Table 1] As is clear from Table 1, it can be seen that the Cu metallized layers according to the examples have excellent bonding strength. In addition, each C
The u-metallized layers were formed uniformly, and when a solder layer was formed on them, the solder wettability was excellent.

Examples 6 to 8 An AlN substrate having a W metallized layer manufactured in the same manner as in Example 1 was subjected to etching using a concentrated aqueous solution of NaOH. The concentration of the etchant was 400 to 900 g / L, immersed in such a NaOH solution for 10 minutes or more, dried, and then heat-treated at a temperature of 200 to 300 ° C. Then
Plasma etching was performed under the following conditions.

The plasma etching was performed using the plasma etching apparatus shown in FIG. As an etching gas, a mixed gas of SF ₆ + Cl ₂ + O ₂ is used, and the flow rate of each gas is SF ₆ = 180 SCCM, Cl ₂ = 10 SCCM,
O ₂ = 10 SCCM. The pressure in the reaction chamber 11 is 1P
a, RF power generated plasma at 600W. Plasma etching was performed under such conditions.

By the above alkaline etching, W
It was confirmed that unevenness having a depth of 5 to 20 μm was formed at intervals of 10 to 150 μm on the surface of the AlN fine particles located on the surface of the metallized layer. In addition, for the plasma etching, by changing the processing time within a range of 1 to 2 minutes, a fine concave portion having a depth of about 5 nm at an interval of about 10 nm (Example 6) and a fine concave portion having a depth of about 10 nm at an interval of about 100 nm (Example 6) Example 7), and fine recesses (Example 8) having an interval of about 150 nm and a depth of about 20 nm were formed.

Next, a Cu foil having a thickness of 50 to 100 μm is arranged on each of the W metallized layers after the etching treatment, and
Heat treatment was performed for 1 to 2 hours in a reducing atmosphere of dry hydrogen at 30 ° C. The bonding strength of each metallized layer thus obtained was measured by a peel test. Table 2 shows the results of the peel test (joining strength).

[0068]

[Table 2] Example 9 After applying the Mo paste to the surface of the alumina molded body, 15
By baking at 50 ± 10 ° C., an alumina member having a Mo metallized layer (first metallized layer / co-fired layer) formed on the surface was produced. The thickness of the obtained Mo metallized layer was about 10 μm, and had 5% by volume of pores.

After a Cu foil having a thickness adjusted to 3 μm after infiltration is arranged on the Mo metallized layer, a heat treatment is performed for 1 hour in a reducing atmosphere of dry hydrogen at 1230 ° C. By applying C on the W metallized layer
A u-metallized layer (second metallized layer) was formed.

The bonding strength of the metallized layer thus obtained was measured by a peel test. As a result, the joint strength
It was 15 kg / cm 2. The porosity of the Mo metallized layer after the formation of the Cu metallized layer was reduced to almost 0% by volume.

Example 10 After W paste was applied to the surface of a Si ₃ N ₄ molded product,
Si formed by sintering at 60 ± 10 ° C. to form a W metallized layer (first metallized layer / co-fired layer) on the surface
The ₃ N ₄ member was produced. The thickness of the obtained W metallized layer was about 10 μm, and had pores of 7% by volume.

After a Cu foil having a thickness adjusted so as to have a thickness of 3 μm after infiltration is arranged on the W metallized layer, a heat treatment is performed for 1 hour in a reducing atmosphere of dry hydrogen at 1230 ° C. To form Cu on the W metallized layer.
A metallized layer (second metallized layer) was formed.

The bonding strength of the metallized layer thus obtained was measured by a peel test. As a result, the joint strength
It was 1.0 kg / cm. The porosity of the W metallized layer after the formation of the Cu metallized layer was reduced to 3% by volume.

[0074]

As described above, according to the ceramic part of the present invention, the first part formed on the ceramic base
A second metallized layer having excellent adhesion strength and a sufficient and uniform film thickness can be easily formed on the metallized layer. Therefore, it is possible to provide a ceramic part with greatly improved practicality and reliability with good reproducibility.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a main structure of a ceramic wiring board as one embodiment of a ceramic component of the present invention.

FIG. 2 is a cross-sectional view schematically showing a structure of a metallized layer portion of the ceramic wiring board shown in FIG.

FIG. 3 is an enlarged schematic cross-sectional view showing a first metallized layer portion of the ceramic wiring board shown in FIG. 1;

FIG. 4 is a diagram for explaining a surface uneven shape of a first metallized layer in the present invention.

FIG. 5 is a view showing an example of a configuration of a plasma etching apparatus used in a process of manufacturing a ceramic part according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Ceramic substrate 2 ... 1st metallization layer 2a ... Void 3 ... 2nd metallization layer 4 ... Ceramic wiring board

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kiyoto Hamamura 8 Shinsugita-cho, Isogo-ku, Yokohama-shi, Kanagawa Pref. F-term in Toshiba Yanagimachi Plant (reference)

Claims (12)

[Claims] 1. A ceramic base, a first metallized layer formed on the surface of the ceramic base, and melting and melting of a metal material formed on the first metallized layer and having a lower melting point than the first metallized layer. A ceramic component, comprising: a second metallized layer made of a solidified layer. 2. The ceramic part according to claim 1, wherein the first metallized layer contains 5 to 50% ceramic fine particles.
A ceramic component, which is a co-fired layer with the ceramic substrate, comprising a high melting point metal contained in a range of 15% by volume and containing pores in a volume ratio of 5 to 25%. 3. The ceramic part according to claim 2, wherein a part of said second metallized layer penetrates into pores of said first metallized layer. 4. The ceramic part according to claim 2, wherein the second metallized layer is formed by melting and solidifying the low melting point metal material on the first metallized layer. Is a fused / solidified layer in which a part of the ceramic component is fixed while penetrating into pores of the first metallized layer. 5. The ceramic part according to claim 1, wherein said first metallized layer has a thickness in the range of 5 to 25 μm, and said second metallized layer has a thickness in the range of 1 to 10 μm. Ceramic parts characterized by having. 6. The ceramic part according to claim 1, wherein said second metallized layer is made of a metal material having a melting point lower than a forming temperature of said first metallized layer. 7. The ceramic part according to claim 1, wherein at least a part of the interface between the first metallized layer and the second metallized layer has a depth of 0.5 to 150 nm at intervals of 0.5 to 150 nm.
A ceramic component having a fine concave portion of 100 nm. 8. A first substrate provided on a surface of a ceramic substrate.
In forming a second metallized layer on the metallized layer and manufacturing a ceramic component, a metal material having a lower melting point than the first metallized layer is fixed on the first metallized layer by heating and melting. Thereby forming the second metallized layer. 9. The method for manufacturing a ceramic component according to claim 8, wherein the first metallized layer includes ceramic fine particles of 5 to 10.
A method for producing a ceramic component, comprising a co-fired layer with the ceramic base, comprising a high melting point metal contained in a range of 15% by volume and containing pores in a volume ratio of 5 to 25%. . 10. The method for manufacturing a ceramic part according to claim 9, wherein when the low melting point metal material is melted, a part of the metal material is permeated into pores of the first metallized layer. Forming the second metallized layer by solidifying the ceramic component with the method described above. 11. The method for manufacturing a ceramic component according to claim 9, wherein the surface of the first metallized layer is subjected to plasma etching to thereby form particles of the high melting point metal located on the surface of the first metallized layer. A method for manufacturing a ceramic component, comprising forming fine recesses having a depth of 0.5 to 100 nm at intervals of 0.5 to 150 nm on the surface. 12. The method for manufacturing a ceramic part according to claim 11, wherein the second metallized layer is made of a metal material having a melting point lower than a temperature at which the first metallized layer is formed.