JPH09283657A - Circuit board and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve durability against heat shock and heat cycle without damaging thermal conductivity, by performing junction in a state that a layer containing silicon nitride as a principal component is formed at least on a part of the surface of a ceramic board and thus reinforcing the origin of breakage. SOLUTION: A metal circuit 1a and a ceramic board 2 are joined with each other in a state that a layer 3 containing silicon nitride as a principal component is formed at least on a part of the surface of the ceramic board 2. Therefore, the layer 3 containing silicon nitride as a principal component is formed near the origin of breakage which is at least a part of the surface of the ceramic board, thereby improving tenacity of this part. Thus, durability against heat shock and heat cycle may be further improved without damaging thermal conductivity of a circuit board.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a circuit board formed by forming a metal circuit on a ceramic substrate suitable for use in semiconductor power modules and the like, which require high reliability and heat dissipation, and a method for manufacturing the same. .

[0002]

2. Description of the Related Art In recent years, with the advancement of the performance of industrial equipment such as robots and motors, the transition of high-power modules such as high-power and high-efficiency inverters has been progressing, and the heat generated from semiconductor elements has been steadily increasing. ing. In order to efficiently dissipate this heat, various methods have been conventionally used for high power module substrates. In particular, recently, a structure in which a metal circuit such as copper is formed on an aluminum nitride substrate and then a semiconductor element is mounted as it is or after being subjected to a treatment such as plating is being adopted. In this case, there is also a structure in which a metal heat dissipation plate is provided on the opposite surface of the aluminum nitride substrate on which the metal circuit is formed.

Such a module was initially used for a simple machine tool, but has been used for a few years in a welding machine, a train drive part, an electric vehicle, and more stringent requirements such as a current density. In order to increase the thickness, it has been required to increase the circuit copper thickness, improve the durability against thermal shock, and further reduce the size.

For joining a copper plate and an aluminum nitride substrate, an active metal brazing method in which a brazing material containing an active metal is interposed between them and heat treatment is carried out to form a joined body (for example, Japanese Patent Laid-Open No. Sho 60).
No. 177634) or a DBC method in which an aluminum nitride substrate whose surface is subjected to an oxidation treatment and a copper plate are heat-bonded at a temperature lower than the melting point of copper and higher than the eutectic temperature of Cu—O (for example, Japanese Patent Laid-Open No.
Publication).

The active metal brazing method has the following features as compared with the DBC method. (1) Since the processing temperature for obtaining the bonded body is low, the residual stress caused by the difference in thermal expansion between the ceramic substrate and the copper plate is small. (2) Since the brazing material is a ductile metal, it is highly durable against heat shock and heat cycles.

[0006]

However, even with the active metal brazing method, the durability of the obtained circuit board against heat shock and heat cycle cannot be said to be sufficient, and a new technique has been awaited. Therefore, the volume of the metal circuit board (usually provided on the upper surface of the ceramic substrate) is adjusted to be 50 to 90% of the volume of the metal heat dissipation plate on the opposite surface (Japanese Patent Laid-Open No. 63-24815). There is a proposal that the thickness of the heat radiation side copper plate is 50% or less of the thickness of the circuit side copper plate (Japanese Patent Laid-Open No. 5-170564), but these alone are not sufficient to meet the above strict requirements.

Therefore, it is essential to improve ceramics such as aluminum nitride substrates. There are an atmospheric pressure sintering method and a hot pressing method for producing ceramics. The atmospheric pressure sintering method is simpler and more mass-producible than the hot pressing method, but defects such as pores are likely to occur in the sintered body, and the second method, which is generated by the reaction between the sintering aid component and the ceramic component, Third
Since the phase has a relatively high vapor pressure, segregation tends to occur, and the thermal shock resistance tends to be weaker than that of the sintered body produced by the hot pressing method.

On the other hand, silicon nitride has a structure in which needle-like particles are entangled with each other, and is in the stage of practical application as a high-temperature structural material as high-strength and high-toughness ceramics. Silicon nitride is characterized by not only improving brittleness but also by being an insulating nitride, but since it has lower thermal conductivity than aluminum nitride, it has not been applied as an insulating substrate requiring high thermal conductivity.

An object of the present invention is to provide a circuit board utilizing the toughness of silicon nitride and further improving durability against heat shock and heat cycle without impairing thermal conductivity, and a method for manufacturing the same. .

[0010]

That is, the present invention provides the following. (Claim 1) A circuit board, wherein a metal circuit and a ceramics substrate are joined together with at least a part of the surface of the ceramics substrate having a layer containing silicon nitride as a main component formed thereon. (Claim 2) A circuit board according to claim 1, wherein a metal heat dissipation plate is provided on the opposite surface of the metal circuit. (Claim 3) The circuit according to claim 1 or 2, wherein the layer containing silicon nitride as a main component is formed on at least a part of the surface of the ceramic substrate which is in contact with the metal circuit. substrate. (Claim 4) At least a part of the surface of the ceramic green sheet is coated with silicon nitride powder or a precursor of silicon nitride.
After sintering to form a layer containing silicon nitride as a main component on at least a part of the surface of the ceramic substrate, this is joined to a metal plate and then etched to form a metal circuit, or A method of manufacturing a circuit board, which comprises forming a metal circuit by bonding this and a metal circuit pattern.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

A feature of the present invention is that in a circuit board in which a metal circuit is formed on a ceramics substrate, or a circuit board in which a metal circuit and a metal heat dissipation plate are formed on a ceramics substrate, at least a part of the surface of the ceramics substrate. To
The reason for this is that the layers having silicon nitride as a main component were bonded to each other in the state of being formed to strengthen the starting point of destruction. This makes it possible to further improve the durability against heat shock and heat cycle without impairing the thermal conductivity of the circuit board.

Today, the circuit board most desired to be improved in terms of reliability is a copper-thickened circuit board used in power modules and the like, and usually has a thickness of 0.15 to 0.5 m.
Although a copper circuit of m is formed on a ceramics substrate (mainly an aluminum nitride substrate is practically used), when a thermal history is applied, a stress is generated due to a difference in thermal expansion between copper and ceramics. Small stresses are mainly absorbed by the elastic and plastic deformation of the copper circuit or the heat dissipation copper plate on the opposite surface, but the stress accumulated during repeated thermal history and the stress generated by large temperature changes are Be released by destroying. That is, when the ceramic substrate is damaged by thermal stress, the interface where the metal circuits are joined, particularly the edge surface of the metal circuit, becomes the starting point of the destruction. Therefore, by forming a layer containing silicon nitride as a main component on at least a part of the surface of the ceramic substrate, that is, near the starting point of the above-mentioned destruction, the toughness of that part can be enhanced. in this case,
Since the heat dissipation path where the metal circuit and the ceramics substrate are in contact with each other can have a structure in which a layer containing silicon nitride as a main component is not formed, heat shock or heat shock can be prevented without significantly sacrificing the thermal conductivity of the ceramics substrate. The durability against heat cycle can be improved.

1 to 15 show an embodiment of a circuit board of the present invention, FIG. 1 is a perspective view of the circuit board, and FIGS. 2 to 15 are a part of the XX cross section of FIG. It is a cutaway sectional view. Each of these figures shows that the metal circuit 1 and the ceramic substrate 2 are joined together with the layer 3 containing silicon nitride as a main component formed on at least a part of the surface of the ceramic substrate. . 2 to 10, the metal circuit 1 and the ceramic substrate 2 are bonded by the bonding layer 4, and in the examples of FIGS. 11 to 15, the metal circuit 1 and the ceramic substrate 2 are bonded without the bonding layer 4. It was done. 1 to 15 show the structure in which the metal heat sink is not provided, but the structure may be such that the metal heat sink is provided on the opposite ceramic substrate surface on which the metal circuit is formed.

Next, a layer containing silicon nitride as a main component (hereinafter, referred to as
It may be simply referred to as a "silicon nitride layer". The positional relationship for forming 3) on at least a part of the surface of the ceramic substrate 2 will be described. Normally, a plurality of metal circuits 1 (1a, 1b ...) Are provided, but the following description will be made by taking the metal circuit 1a as a representative. Regarding the metal circuits 1b and the like other than the metal circuit 1a, the silicon nitride layer 3 includes the metal circuit 1a.
It may be formed in the same positional relationship as that of, or may be formed in a different positional relationship.

As shown in FIGS. 8 to 10 and 13 to 15, the advantage of forming the silicon nitride layer 3 on the entire surface of the ceramic substrate 2 in contact with the metal circuit 1a is that the upper surface of the metal circuit 1a is formed. It is possible to reduce damage to the ceramic substrate when attaching the electrode to the.

The advantage of forming the silicon nitride layer 3 only on a part of the surface of the ceramic substrate 2 which is in contact with the metal circuit 1a is that the silicon nitride layer 3 has a smaller thermal conductivity than the ceramic substrate. In that case, the adverse effect can be reduced. As described above, when the ceramic substrate is damaged by the thermal stress, the edge surface of the metal circuit is often the starting point of the destruction, so that FIGS.
It is particularly preferable to form the silicon nitride layer 3 on the edge surface without forming it near the center of the lower surface of the metal circuit, particularly near the center of the bare chip mounting pattern, as shown in FIG.

The joining layer 4 in the examples of FIGS. 2 to 10 is generally made of a brazing material, but the metal circuit 1 and the ceramic substrate 2 may be joined together without the joining layer 4 as shown in FIGS. it can. The method is, for example, to preliminarily form a silicon nitride layer 3 on the surface of a ceramics substrate, and to perform surface treatment as it is or by a method of forming an oxide layer as needed, and then performing a surface treatment on the copper plate or copper. A circuit pattern is directly arranged and heat bonding is performed at a Cu-O eutectic temperature or higher.

As for the thickness of the ceramic substrate used in the present invention, if it is too thick, the thermal resistance becomes large, and if it is too thin, the durability and withstand voltage decrease, so it is 0.15 to 1.0.
It is preferably about mm. Further, the ceramic substrate used in the present invention is preferably manufactured by forming a silicon nitride layer on a part of the surface of the ceramic green sheet during the firing process in terms of production efficiency. Is preferably insulative, has a small difference in coefficient of thermal expansion from silicon nitride, and is a nitride.
In particular, aluminum nitride and silicon nitride are preferable.

Copper, aluminum, tungsten, molybdenum and the like are used as the material of the metal circuit, but copper is generally used. The thickness of the metal circuit is preferably thicker than 0.3 mm because the current density tends to increase in recent years. In addition, the metal circuit on the surface of the ceramic substrate,
In addition, the above-mentioned materials are used for the material of the metal heat sink in the structure where the metal heat sink is formed on the back surface, and its thickness is balanced with the thickness of the metal circuit in consideration of the warpage of the circuit board. It is decided as appropriate.

In the present invention, the presence of the silicon nitride layer is X
It can be easily known by the identification of the crystal phase by line diffraction or a usual texture analysis method such as an X-ray microanalyzer. When performing the analysis, the ceramic substrate can be separated from the circuit substrate by dissolving and removing the metal circuit and the bonding layer with an acid such as nitric acid or hydrofluoric acid.
The thermal conductivity of the ceramic substrate can be measured by the laser flash method.

In the present invention, the thickness of the silicon nitride layer is 5 μm.
It is preferably m or more. When the silicon nitride layer is formed on the entire circuit surface of the ceramics substrate, if the thickness is too thick, the thermal resistance of the element mounting portion increases, so the thickness is adjusted in consideration of this point. On the other hand, when the silicon nitride layer is formed not only on the entire surface of the circuit surface of the ceramic substrate but only in the vicinity of the end of the contact surface that is the starting point of the destruction of the metal circuit, the thickness does not need much consideration. When the silicon nitride layer is formed so as to project from the surface of the ceramic substrate as shown in FIG. 2 and the like, the thickness of the silicon nitride layer is set in a range capable of absorbing the difference in the projecting height in the step of joining the metal circuits. It is preferable to adjust.

Further, since a layer having sufficiently high toughness can be obtained even with generally known silicon nitride, the conditions such as the type and amount of the silicon nitride raw material and the sintering aid used for forming the silicon nitride layer are particularly important. Although not limited, it goes without saying that a silicon nitride layer having a high thermal conductivity and a high toughness is preferable. These characteristics differ depending on the structure and impurities of the silicon nitride layer, and can be adjusted by the silicon nitride raw material, the type and amount of the sintering aid, the heat treatment conditions, and the like. When a silicon nitride substrate is used as the ceramic substrate, the silicon nitride of the ceramic substrate has thermal conductivity,
The silicon nitride layer preferably has a structure that plays a role of toughness and heat cycle resistance.

As an impurity that lowers the thermal conductivity of the silicon nitride layer, for example, Al ₂ O ₃ is used. On the other hand, this component is used as a sintering aid for high toughness silicon nitride ceramics for high temperature structural materials and various rare earth elements. Is used with. Therefore, when a silicon nitride layer having high thermal conductivity is required, it is preferable not to use Al ₂ O _{3 but} to use MgO in combination with various rare earth elements.

Next, a method of manufacturing the circuit board of the present invention will be described.

Since the circuit board of the present invention is formed by bonding at least a part of the surface of the ceramics substrate with a layer containing silicon nitride as a main component being formed, such a structure is realized. There is no particular limitation on the method of manufacturing the circuit board as long as it can be performed. For example, it is possible to manufacture a ceramic substrate by a conventional method and form a silicon nitride layer on the surface of the ceramic substrate. As a method for forming the silicon nitride layer, there are, for example, a thin film forming method such as a CVD method and a sputtering method, and a method such as screen printing and coating of a paste. These methods require a ceramic substrate manufacturing step and a silicon nitride layer forming step. However, in the circuit board manufacturing method of the present invention described below, the ceramic substrate and the silicon nitride layer are simultaneously manufactured. This is a highly productive method.

The method of manufacturing a circuit board of the present invention will be described by using an aluminum nitride substrate as a ceramic substrate.

A green aluminum nitride sheet containing yttria as a sintering aid is produced. As the method, for example, a usual sheet forming method such as a doctor blade method or an extrusion forming method can be adopted. At least a part of the surface of the ceramic green sheet is coated with silicon nitride powder or a precursor of silicon nitride. The term "silicon nitride precursor" as used in the present invention means a silicon nitride powder composition containing a sintering aid or an organic aid, or a material such as silicon polyimide which produces a layer containing silicon nitride as a main component by heat treatment. A composition containing a substance. The silicon nitride powder or the precursor of silicon nitride is preferably in paste form for the convenience of coating. The silicon nitride powder may be any of α type, β type and amorphous, and the coating method may be any of a screen printing method, a roll coater method and the like.

The paste-form silicon nitride powder or the precursor of silicon nitride is prepared by adding an organic binder to the silicon nitride powder, the sintering aid, and the organic solvent, if necessary, and using a roll, a kneader, a universal mixer, or a ladle machine. And the like. Methylcellosolve, terpineol, isophorone, toluene, etc. are used as the organic solvent, and ethylcellulose, methylcellulose, polymethacrylate, etc. are used as the organic binder. The proportion is preferably 2 to 20% by weight with respect to the powder of silicon nitride and the sintering aid.

Next, the ceramic green sheet to which the silicon nitride powder or the precursor of silicon nitride is applied has its surface smoothened by passing it between rolls, if necessary. This is because when the silicon nitride powder or the precursor of silicon nitride is partially applied, unevenness on the surface of the obtained sintered body is reduced, the smoothness of the ceramic substrate is improved, and the bonding at the time of forming a metal circuit is performed. This is a process performed to reduce problems such as defects.

Sintering is performed at a temperature at which the ceramic substrate is sufficiently densified, and under the condition that the silicon nitride layer is also densified to form a structure having high toughness. Specifically, first, the ceramic raw sheet is heated at a temperature of 300 to 800 ° C. to sufficiently remove and degrease organic assistant components such as a binder contained in the ceramic raw sheet, but the atmosphere at that time is organic. Depending on the type of system auxiliary agent, etc., an oxidizing atmosphere such as air or nitrogen, argon, hydrogen, carbon dioxide,
A non-oxidizing atmosphere such as hydrocarbon or vacuum is applied. Next, the degreased sheet is sintered at a temperature of 1600 to 2000 ° C. for a predetermined time in an atmosphere of an inert gas such as nitrogen gas or argon gas. 160 for pressureless sintering
A sintering temperature of about 0 to 1800 ° C. is preferable.

Next, a metal plate is bonded to the ceramic substrate on which the silicon nitride layer is formed as described above and then etched to form a metal circuit, or a metal circuit pattern is bonded to form a metal circuit. .

In the present invention, the method of joining the metal plates is not particularly limited, and the DBC method or the brazing method with or without addition of active metal can be adopted. For example, when the metal circuit is formed of aluminum, an aluminum alloy such as Ai-Si system or Ai-Ge system is used, and when the metal circuit is formed of copper, the active metal brazing method is suitable. The metal component of the active metal brazing material in the active metal brazing method is silver,
It contains copper, silver-copper, zinc, indium, cadmium, tin, etc. as a main component, and an active metal as a sub-component for ensuring wettability with an aluminum nitride substrate during melting. The active metal reacts with the aluminum nitride substrate to generate an oxide or a nitride, and these products strengthen the bond between the brazing material and the aluminum nitride substrate.

Specific examples of the active metal include titanium, zirconium, hafnium, niobium, tantalum, vanadium and compounds thereof. Among these components, preferred active metal components are zirconium or its compound and titanium or its compound. As an example of these ratios, the total amount of active metal is 0.5 to 15 per 100 parts by weight of the total amount of 69 to 100 parts by weight of silver and 0 to 31 parts by weight of copper.
Parts by weight, especially 1 to 10 parts by weight. The silver component is an important component that mainly reacts with the copper component to form a low melting point compound, promotes melting of the active metal bonding material, and plays a role of wetting the bonding surface. In the case where the metal circuit is copper or a copper alloy, the copper component may be used, and therefore it may not be necessary to previously include copper in the brazing material paste. If the amount of the active metal component is small, the bonding becomes poor, and if it is large, the heat cycle resistance is deteriorated, which is not preferable.

The brazing material is usually used in a paste, which is prepared by adding an organic solvent and, if necessary, an organic binder to the metal components of the above brazing material and mixing them with a roll, a kneader, a universal mixer, a raider or the like. Can be prepared by
As the organic solvent, methyl cellosolve, terpineol,
Isophorone, toluene, etc. are used, and as the organic binder, ethyl cellulose, methyl cellulose, polymethacrylate, etc. are used.

The joining condition between the aluminum nitride substrate and the metal plate or the pattern of the metal circuit is 10 −7 to 10 −5 Torr.
In a vacuum of about 700 to 900 ° C., preferably 7
It is about 50 to 850 ° C. This condition is the same for the silicon nitride substrate.

On one surface of the ceramic substrate, a metal circuit,
As a method of forming a metal heat sink on the other surface, a method of etching a bonded body of a ceramic substrate and a metal plate,
This can be performed by a method of joining a metal circuit pattern and / or a metal heat sink plate pattern punched from a metal plate to a ceramic substrate.

[0038]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples.

Examples 1 to 8 96 parts by weight of aluminum nitride powder, average particle size 0.8 μm
Yttria (Y_TwoO _Three Powder 4 parts by weight, oleic acid double
After preliminarily mixing the parts with a vibrating mill,
8 parts by weight, glycerin trioleate 3 parts by weight and water 12
Parts by weight were blended and mixed with a mixer. Molding this mixture
Speed 1.0 m / min, molding pressure 55-70 kg / cm^Twoso
Extruded and dried with far infrared rays at 120 ° C for 5 minutes
After that, leave at room temperature for 1 day to obtain a ceramic green sheet
Was. Screen the surface of this sheet with silicon nitride paste.
The circuit board shown in FIG. 7 can be obtained by the screen printing method.
1mm between the circuit patterns, the edge and the edge of the circuit board
After applying the pattern to the area up to
-By passing it through, the surface irregularities were removed. The coating amount is 1.7-
20 mg / cm^TwoWas changed within the range.

The silicon nitride paste has an oxygen content of 1.5.
%, 90 parts by weight of silicon nitride powder having an average particle size of 0.7 μm, 3 parts by weight of magnesia (MgO) powder having an average particle size of 1.0 μm, and 7 parts by weight of yttria (Y ₂ O ₃ ) powder having an average particle size of 0.8 μm. And 16 parts by weight of terpineol and 7 parts by weight of a solid solution of a toluene solution of polyisoptyl methacrylate were added, and the mixture was kneaded with a raker machine.

The ceramic green sheet coated with the silicon nitride paste is then degreased in air at 500 ° C.
Sintering was performed at 1800 ° C. for 4 hours under a nitrogen gas pressure of 0.9 MPa. The size of the obtained sintered body was 60 mm × 36 mm and the thickness was 0.65 mm. In addition, as a result of analyzing this sintered body by X-ray diffraction and an X-ray microanalyzer,
It was found that a layer containing a β-type silicon nitride crystal phase as a main component was formed on the surface of the aluminum nitride sintered body on which the silicon nitride paste was applied.

Metal powders were blended in the proportions shown in Table 1, 14 parts by weight of terpineol and 7 parts by weight of a solid solution of polyisoptylmethacrylate in a solid content were added to 100 parts by weight of the metal components, and the resulting mixture was kneaded by a kneader. To prepare an active metal brazing paste. This brazing paste was applied to the circuit surface (front surface) of the aluminum nitride substrate manufactured as described above by screen printing to form an L-shaped pattern having a pattern ratio of 0.20, and the entire surface of the heat dissipation surface (back surface) was applied. The coating amount (after drying) at that time was 9 mg / cm ² .

[0043]

[Table 1]

Next, the size of the surface is 60 mm × 36 m.
m, 0.3 mm thick copper plate, size 60 on the back
10 × ⁶ Torr Torr 10 mm × 36 mm, 0.2 mm thick copper plates are stacked and the whole is housed in a heating furnace with the weight still loaded.
A heat treatment was performed for 30 minutes at the temperature shown in Table 1 in the following vacuum, followed by cooling at a temperature decrease rate of 2 ° C./minute to produce a joined body.

Then, a UV curing type etching resist is applied by screen printing on the copper plate of this joined body,
Unnecessary portions of the copper plate were dissolved and removed by performing an etching treatment using a cupric chloride solution, and the etching resist was peeled off with a 5% sodium hydroxide solution. In the joined body after this etching treatment, there is a residual unnecessary brazing material or an active metal component between the copper circuit patterns, so it was removed by immersing it in a 10% ammonium fluoride solution at a temperature of 60 ° C. for 10 minutes. Then, a 2 μm-thick Ni plating was performed on the copper surface to manufacture a circuit board in which a copper circuit and a heat dissipation copper plate were formed on an aluminum nitride board.

The circuit board manufactured in this manner was kept at -40 ° C for 30 minutes in the atmosphere, then left at 25 ° C for 10 minutes, further held at 125 ° C for 30 minutes, and then kept at 25 ° C for 10 minutes.
1 heat cycle resistance test with 1 minute of standing for 1 minute
The number of heat cycles at which cracks or peeling started to be observed was measured by evaluating the presence of cracks between circuits and edge surfaces by a fluorescent flaw detection test and the presence or absence of peeling of the heat dissipation copper plate or the copper circuit by performing a fluorescent test.

Further, when the cross section of the circuit board was analyzed using a scanning electron microscope and an X-ray microanalyzer,
It was found that the same structure as in FIG. 7 was formed. In addition, the thickness of the silicon nitride layer was analyzed by X-ray diffraction and an X-ray microanalyzer on the remaining aluminum nitride substrate after removing the heat dissipation copper plate, the copper circuit and the bonding layer of the circuit board. It was confirmed that a layer containing a β-type silicon nitride crystal phase as a main component was formed in the portion coated with the silicon nitride paste. The results of these evaluations are summarized in Table 2.

Comparative Examples 1 to 4 Circuit boards were manufactured in the same manner as in Examples 1 to 4 except that the surface of the ceramic green sheet was not coated with the silicon nitride paste. The results are shown in Table 2.

[0049]

[Table 2]

Examples 9 to 13 Comparative Example 5 In Examples 4 to 8, except that a silicon nitride paste was applied on the entire surface of the ceramic green sheet by a roll coater so that the circuit board shown in FIG. 8 was obtained. Is
Circuit boards were manufactured according to Examples 4 to 8. With respect to the obtained circuit board, the thickness of the silicon nitride layer, the heat cycle resistance test, and the thermal conductivity by the laser flash method were measured. For comparison, a circuit board was manufactured without applying a silicon nitride paste. Table 3 shows the results. Furthermore, when the structure of the circuit boards of Examples 9 to 13 was analyzed according to the above method, it was the same as that shown in FIG.

[0051]

[Table 3]

Examples 14 to 18 Comparative Example 6 90 parts by weight of a silicon nitride powder having an oxygen content of 1.5% by weight and an average particle size of 0.7 μm, and 3 parts by weight of magnesia (MgO) powder having an average particle size of 1.0 μm. 7 parts by weight of yttria (Y ₂ O ₃ ) powder having an average particle size of 0.8 μm was added, and further 9 parts by weight of polyvinyl butyral, 4 parts by weight of butyl phthalate, 1 part by weight of glycerin trioleate, 45 parts by weight of toluene,
15 parts by weight of isopropyl alcohol was added, and the slurry was mixed using a ball mill. The slurry was defoamed and the viscosity was adjusted to 20,000 cps, and then a ceramic green sheet was formed by the doctor blade method. A silicon nitride paste is screen-printed on the surface of this sheet so that the circuit board shown in FIG. 7 can be obtained by patterning between the circuit patterns and on the edge surface and the portion up to a distance of 1 mm from the end of the circuit board. After applying to, the product was passed between rollers to remove surface irregularities. Coating amount is 1.7 to 20 m
It was changed within the range of g / cm ² .

The silicon nitride paste has an oxygen content of 1.5.
% By weight, 90 parts by weight of silicon nitride powder having an average particle size of 0.7 μm and ₂ parts of alumina (Al ₂ O ₃ ) powder having an average particle size of 1.0 μm
3 parts by weight of magnesia (MgO) powder having an average particle size of 1.0 μm and yttria (Y ₂ O) having an average particle size of 0.8 μm
₃ ) 5 parts by weight of powder was added, and 16 parts by weight of terpineol and 7 parts by weight of a solid solution of a toluene solution of polyisoputyl methacrylate were added, and the mixture was kneaded in a raker machine to prepare.

The ceramic green sheet coated with the silicon nitride paste was then degreased in air at 500 ° C.,
Sintering was performed at 1850 ° C. for 4 hours under a nitrogen gas pressure of 0.9 MPa. The size of the obtained sintered body was 60 mm × 36 mm and the thickness was 0.5 mm. In order to know the thermal conductivity of the silicon nitride substrate portion and the silicon nitride layer portion of the obtained sintered body, another sintered body was prepared under the above conditions and measured with the same composition, and the substrate portion was 80 W / mK. , The silicon nitride layer is 30 W / m
It was K.

Metal powders were mixed in the proportion of E in Table 1, and a paste was prepared and applied in the same manner as in Example 1. next,
A copper plate having a size of 60 mm × 36 mm and a thickness of 0.5 mm was bonded to the front surface, and a copper plate having a size of 60 mm × 36 mm and a thickness of 0.3 mm was bonded to the back surface, and thereafter, a circuit board was manufactured according to Example 1. .

The circuit board manufactured in this manner was subjected to a thermal shock test in order to evaluate its durability. The thermal shock test employs a method in which the circuit board is held at 380 ° C. for 10 minutes and then rapidly cooled to room temperature. After the thermal shock cycle is performed 10 times, the circuit board is subjected to a fluorescent flaw detection test to detect the inter-circuit and edge surfaces. The presence or absence of cracks and the presence or absence of peeling of the heat dissipation copper plate or the copper circuit were evaluated, and the defect occurrence rate was measured.
A circuit board manufactured without applying a silicon nitride paste was used as Comparative Example 6. The results are shown in Table 4.

Further, when the structures of the circuit boards obtained in Examples 14 to 18 were analyzed by the same method as in Example 1, it was found that the same structure as in FIG. 7 was formed.

[0058]

[Table 4]

Examples 19 to 23 Circuit boards were prepared in the same manner as in Examples 14 to 18 except that a silicon nitride paste was applied to the entire surface of the ceramic green sheets produced in Examples 14 to 18 by a roll coater. Manufactured. As a result, good results similar to those in Examples 14 to 18 were obtained. Further, when the structure of the circuit board was analyzed, it was found that the same structure as in FIG. 8 was formed.

[0060]

According to the present invention, it is possible to provide a circuit board in which a metal circuit is formed on a ceramics substrate, which is further improved in durability against heat cycles.

[Brief description of drawings]

FIG. 1 is a perspective view of a circuit board of the present invention.

FIG. 2 is a partially cutaway cross-sectional view taken along the line XX in FIG.

FIG. 3 is a partially cutaway sectional view taken along line XX of FIG.

FIG. 4 is a partially cutaway sectional view taken along line XX of FIG.

5 is a partially cutaway cross-sectional view taken along the line XX of FIG.

6 is a partially cutaway sectional view taken along line XX of FIG.

7 is a partially cutaway cross-sectional view taken along line XX of FIG.

8 is a partially cutaway cross-sectional view taken along line XX of FIG.

9 is a partially cutaway cross-sectional view taken along the line XX of FIG.

10 is a partially cutaway cross-sectional view taken along the line XX of FIG.

11 is a partially cutaway cross-sectional view taken along the line XX of FIG.

FIG. 12 is a partially cutaway sectional view taken along line XX of FIG.

13 is a partially cutaway cross-sectional view taken along the line XX of FIG.

14 is a partially cutaway cross-sectional view taken along the line XX in FIG.

FIG. 15 is a partially cutaway sectional view taken along line XX of FIG.

[Explanation of symbols]

 1a metal circuit 1b metal circuit 2 ceramics substrate 3 layer containing silicon nitride as a main component 4 bonding layer

Continuation of the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical display location H05K 3/20 7511-4E H05K 3/20 Z 3/38 7511-4E 3/38 A (72) Inventor Nakajima Seiko 3-5-1, Asahimachi, Machida, Tokyo Denka Kagaku Kogyo Co., Ltd.

Claims (4)

[Claims] 1. A circuit board, comprising: a metal circuit and a ceramics substrate, which are bonded to each other with at least a part of the surface of the ceramics substrate having a layer containing silicon nitride as a main component formed thereon. 2. The circuit board according to claim 1, further comprising a metal heat dissipation plate on a surface opposite to the metal circuit. 3. The circuit according to claim 1, wherein the layer containing silicon nitride as a main component is formed on at least a part of the surface of the ceramic substrate which is in contact with the metal circuit. substrate. 4. A silicon nitride powder or a precursor of silicon nitride is applied to and sintered on at least a part of the surface of the ceramic green sheet, and silicon nitride is contained as a main component on at least a part of the surface of the ceramic substrate. After forming a layer to be formed, the metal plate is joined to the metal plate and then etched to form a metal circuit, or this and the metal circuit pattern are joined to form a metal circuit. Substrate manufacturing method.