JP2021197411A - Plate and radiation material - Google Patents

Abstract

To provide a plate capable of achieving long service life of a radiation material when used as a component for the radiation material.SOLUTION: A plate includes a first base material containing at least one type of first compound selected from a group comprised of silicon carbide, silicon nitride and aluminum nitride, and a conductive oxide coating arranged on the first base material.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a plate material and a heat radiating material.

As a base material for a heat radiating material used for heat dissipation of a semiconductor element, a ceramic base material such as aluminum nitride or silicon nitride, or a metal in which a filler material such as silicon carbide or diamond is dispersed in a metal such as copper, aluminum or silver- A ceramic composite substrate is used.

Generally, in order to solder the heat radiating material and the semiconductor element, a nickel-based or copper-based metal layer is formed on the surface of the base material of the heat radiating material.

Examples of the method for forming a metal layer on a ceramic base material include metallizing treatment (for example, Japanese Patent Application Laid-Open No. 5-221759 (Patent Document 1)). In the metallizing treatment, a paste containing metal particles and an organic substance is applied onto a ceramic substrate and then heated at a high temperature to form a metal layer on the ceramic substrate.

As a method for forming a metal layer on a metal-ceramic composite base material, it is common to form an electroless plating layer on the base material and then perform electrolytic plating (for example, JP-A-11-130568). Publication No. (Patent Document 2)).

Japanese Unexamined Patent Publication No. 5-221759 Japanese Unexamined Patent Publication No. 11-130568

In recent years, in the semiconductor field, high power devices are known as a kind of semiconductor element. In high power devices, heat generation tends to increase due to an increase in power consumption and the like. In order to suppress the decrease in the life of the semiconductor element due to the increase in heat generation, it is also required to extend the life of the heat radiating material.

Therefore, an object of the present invention is to provide a plate material capable of extending the life of the heat radiating material when used as a component of the heat radiating material, and a heat radiating material using the plate material.

The plate material of the present disclosure is
A first substrate containing at least one first compound selected from the group consisting of silicon carbide, silicon nitride and aluminum nitride.
It is a plate material provided with a conductive oxide film arranged on the first base material.

The plate material of the present disclosure is
At least one second compound selected from the group consisting of aluminum oxide, magnesium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium nitride, silicon nitride and aluminum nitride, and at least selected from the group consisting of aluminum, magnesium and copper. A second substrate containing one metal, and
It is a plate material provided with a conductive oxide film arranged on the second base material.

The heat radiating material of the present disclosure is a heat radiating material including the above-mentioned plate material.

The plate material of the present disclosure enables a long life of the heat radiating material when used as a component of the heat radiating material.

FIG. 1 is a diagram illustrating a typical configuration example of the plate material according to the first embodiment. FIG. 2 is a diagram illustrating a typical configuration example of the film forming apparatus. FIG. 3 is a diagram illustrating a typical configuration example of the plate material according to the second embodiment.

[Explanation of Embodiments of the present disclosure]
First, embodiments of the present disclosure will be listed and described.
(1) The plate material of this disclosure is
A first substrate containing at least one first compound selected from the group consisting of silicon carbide, silicon nitride and aluminum nitride.
It is a plate material provided with a conductive oxide film arranged on the first base material.

The plate material of the present disclosure enables a long life of the heat radiating material when used as a component of the heat radiating material.

(2) The plate material of this disclosure is
At least one second compound selected from the group consisting of aluminum oxide, magnesium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium nitride, silicon nitride and aluminum nitride, and at least selected from the group consisting of aluminum, magnesium and copper. A second substrate containing one metal, and
It is a plate material provided with a conductive oxide film arranged on the second base material.

The plate material of the present disclosure enables a long life of the heat radiating material when used as a component of the heat radiating material.

(3) The conductive oxide film preferably contains at least one element selected from the group consisting of tin, indium and zinc.

Tin, indium and zinc have high conductivity. Therefore, when the conductive oxide film contains these elements, the amount of current can be increased when the plating layer is formed on the conductive compound film, and the plating speed becomes high.

(4) It is preferable to provide a plating layer arranged on the conductive oxide film. According to this, it becomes possible to solder the plate material and the semiconductor element.

(5) The first base material preferably contains aluminum nitride. Aluminum nitride has high thermal conductivity, is chemically stable, and has excellent heat dissipation.

(6) The second base material preferably contains silicon carbide. Silicon carbide has high thermal conductivity, is chemically stable, and has excellent heat dissipation.

(7) The plating layer preferably contains at least one metal selected from the group consisting of nickel and copper, or nickel phosphate. According to this, the adhesive force between the plate material and the semiconductor element can be enhanced.

(8) The heat radiating material of the present disclosure is a heat radiating material including the above-mentioned plate material. The heat radiating material of the present disclosure has a long life.

[Details of Embodiments of the present disclosure]
Specific examples of the plate material and the heat radiating material of the present disclosure will be described below with reference to the drawings. In the drawings of the present disclosure, the same reference numerals represent the same or equivalent parts. Further, the dimensional relations such as length, width, thickness, and depth are appropriately changed for the purpose of clarifying and simplifying the drawings, and do not necessarily represent the actual dimensional relations.

In the present specification, the notation of the form "A to B" means the upper and lower limits of the range (that is, A or more and B or less), and when there is no description of the unit in A and the unit is described only in B, A. The unit of and the unit of B are the same.

In the present specification, when a compound or the like is represented by a chemical formula, it shall include all conventionally known atomic ratios when the atomic ratio is not particularly limited, and is not necessarily limited to those in the stoichiometric range. For example, when described as "AlN", the ratio of the number of atoms of the aluminum element and the nitrogen element constituting AlN includes any conventionally known atomic ratio.

[Embodiment 1: Plate material]

In developing a heat-dissipating material having a long life, the present inventors first investigated the cause of shortening the life of a heat-dissipating material in which a metal layer was formed on a conventional ceramic base material. As a result, the following findings were obtained as the cause of shortening the life of the heat radiating material.

Conventionally, in order to solder a heat radiating material and a semiconductor element, a metal layer (hereinafter, also referred to as “metallized layer”) has been formed on a ceramic base material by a metallizing process. Since the coefficients of thermal expansion of the metal layer and the ceramic base material are different during heating in the metallization treatment, thermal stress is generated at the interface between the metal layer and the ceramic base material, and peeling occurs. Further, when the temperature changes due to the use of the heat radiating material, thermal stress is generated at the interface between the metal layer and the ceramic base material, and the metal layer is peeled off from the ceramic base material. Therefore, it is presumed that the electric resistance derived from the metal layer increases and the life of the heat radiating material is shortened.

As a result of diligent studies based on the above findings, the present inventors have obtained a plate material in which the electric resistance is unlikely to increase even when the heat radiating material is used, and the life of the heat radiating material can be extended. The plate material will be described with reference to FIG.

FIG. 1 is a diagram illustrating a typical configuration example of the plate material according to the first embodiment. As shown in FIG. 1, the plate material 10 is arranged on a first base material 11 containing at least one first compound selected from the group consisting of silicon carbide, silicon nitride, and aluminum nitride, and on the first base material 11. The conductive oxide coating 12 (hereinafter, also referred to as “coating”) is provided. The plate material of the first embodiment can include a plating layer 13 arranged on the conductive oxide film 12.

When the plate material of the first embodiment is used as a component of the heat radiating material, the life of the heat radiating material can be extended. The reason is presumed to be as follows (i) and (ii).

(I) In the plate material of the first embodiment, a conductive oxide film is formed on a first base material containing at least one first compound selected from the group consisting of silicon carbide, silicon nitride and aluminum nitride. Both the first base material and the conductive oxide film are ceramics. Therefore, when the heat radiating material containing the plate material is used, the thermal stress generated at the interface between the first base material and the conductive oxide film is smaller than the thermal stress generated at the interface between the conventional base material and the metallized layer. Become. Therefore, peeling due to thermal stress and the accompanying increase in electrical resistance are unlikely to occur, and the life of the heat radiating material is extended.

(Ii) When the plate material of the first embodiment is used as the heat radiating material, the plating layer is arranged on the conductive oxide film. The adhesive force between the conductive oxide film and the plating layer is larger than the adhesive force between the conventional base material and the metallized layer. Therefore, even when the heat radiating material is used, peeling at the interface between the conductive oxide film and the plating layer and the accompanying increase in electrical resistance are unlikely to occur, and the life of the heat radiating material is extended.

<First base material>
The first substrate 11 contains at least one first compound selected from the group consisting of silicon carbide, silicon nitride and aluminum nitride. The first substrate can contain one type of first compound. Further, the first base material can contain two or more kinds of first compounds. The first base material is a polycrystal containing particles made of the first compound, and is a ceramic sintered body.

The lower limit of the content of the first compound in the first substrate can be 70% by volume or more, 90% by volume or more and 95% by volume or more. The upper limit of the content of the first compound in the first substrate can be 100% by volume or less, 95% by volume or less, and 90% by volume or less. The content of the first compound in the first substrate can be 70% by volume or more and 100% by volume or less, 90% by volume or more and 100% by volume or less, and 95% by volume or more and 100% by volume or less. When two or more kinds of first compounds are contained in the first base material, the content of the above first compound is the total content of two or more kinds of first compounds.

The content of each first compound in the first substrate is measured by an X-ray diffraction method (measuring device: "SmartLab" (trademark) manufactured by Rigaku Corporation). From the peak intensity of each of the obtained first compounds, the volume content of each first compound can be determined by the RIR (reference intensity ratio) method.

The first substrate preferably contains aluminum nitride. Since aluminum nitride has high thermal conductivity and is chemically stable, the plate material can have excellent heat dissipation when the first base material contains aluminum nitride. Aluminum nitride is also advantageous in terms of price. The content of aluminum nitride in the first base material can be 70% by volume or more and 100% by volume or less, 90% by volume or more and 100% by volume or less, and 95% by volume or more and 100% by volume or less.

The average particle size of the first compound is preferably 0.5 μm or more and 300 μm or less. According to this, the surface roughness of the first base material can be reduced, and the thermal conductivity of the plate material can be improved.

The lower limit of the average particle size of the first compound can be 0.5 μm or more, 1 μm or more, and 3 μm or more. The upper limit of the average particle size of the first compound can be 300 μm or less, 200 μm or less, and 100 μm or less. The average particle size of the first compound can be 0.5 μm or more and 300 μm or less, 1 μm or more and 200 μm or less, and 3 μm or more and 100 μm or less.

The method for measuring the average particle size of the first compound is as follows. The cross section of the first substrate is observed with a secondary electron microscope at an arbitrary magnification between 500 and 3000 times, and the particles are observed in 4 fields of view at the selected magnification, and 30 or more particles are not cut in the field of view. Identify the particles. Find the area of each particle. Assuming that the obtained area = πr ² , 2r is calculated and used as the particle diameter. Of the obtained particle diameters (2r), the average of the remaining particle diameters obtained by subtracting the maximum and second largest particle diameters and the minimum and second smallest particle diameters is defined as the average particle diameter of the first compound.

The first substrate may contain a sintering aid in addition to the first compound. The sintering aid, for example, yttrium oxide _{(Y 2 O} 3), and calcium oxide (CaO) is. The lower limit of the content of the sintering aid in the first substrate can be 0.01% by volume or more, 0.1% by volume or more, and 1% by volume or more. The upper limit of the content of the sintering aid in the first substrate can be 15% by volume or less, 10% by volume or less, and 5% by volume or less. The content of each sintering aid in the first substrate is measured by an X-ray diffraction method (measuring device: "SmartLab" (trademark) manufactured by Rigaku Corporation). From the peak intensity of each obtained sintering aid, the volume content of each sintering aid can be determined by the RIR (reference strength ratio) method.

The lower limit of the thickness of the first base material can be 0.05 mm or more, 0.08 mm or more, and 0.1 mm or more. The upper limit of the thickness of the first base material can be 5 mm or less, 4 mm or less, and 2 mm or less. The thickness of the first base material can be 0.05 mm or more and 5 mm or less, 0.08 mm or more and 4 mm or less, and 0.1 mm or more and 2 mm or less. The thickness of the first base material is measured at five points on the plane of the substrate with a micrometer and used as the average value.

<Conductive oxide film>
The conductive oxide film 12 is arranged on the first base material 11. The conductive oxide film can be arranged so as to cover the entire substrate. Further, it can be arranged so as to cover a part of the base material.

The conductive oxide film 12 preferably contains at least one element selected from the group consisting of tin, indium and zinc. Oxides containing tin, indium and zinc have high conductivity. Therefore, when the conductive oxide film contains an oxide containing these elements, the amount of current can be increased when the plating layer is formed on the conductive compound film, and the plating speed becomes high.

The conductive oxide film preferably contains a conductive oxide such as tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), and zinc oxide (Zn O). These conductive oxides may be used in a single phase, may be phase-separated and mixed, or may be used in the form of a composite material. The composite material is, for example, various solid solutions in which Sn is dissolved in _{In 2} O _{3 or Al is dissolved in Zn O.} The composite material may also be used by being mixed with each other or with a single phase separated from each other. These mixed materials and composite materials can enhance the conductivity of the coating.

The lower limit of the content of the conductive oxide in the conductive oxide film can be 30 atomic% or more, 50 atomic% or more, and 70 atomic% or more. The upper limit of the content of the conductive oxide in the conductive oxide film can be 100 atomic% or less, 95 atomic% or less, and 90 atomic% or less. The content of the conductive oxide in the conductive oxide film is 30 atomic% or more and 100 atomic% or less, 30 atomic% or more and 95 atomic% or less, 30 atomic% or more and 70 atomic% or less, and 50 atomic% or more and 100 atomic% or less. Hereinafter, it can be 50 atomic% or more and 95 atomic% or less, 50 atomic% or more and 70 atomic% or less, 70 atomic% or more and 100 atomic% or less, and 70 atomic% or more and 95 atomic% or less. When two or more kinds of conductive oxides are contained in the conductive oxide film, the content of the conductive oxides is the total content of two or more kinds of conductive oxides.

In the present specification, the content of the conductive oxide in the conductive oxide film is defined as a value calculated by the following procedure. A secondary electron microscope (SEM) with an energy dispersive X-ray (EDX) attached to the cross section of the conductive oxide film (measuring device: "SU3800" (trademark) manufactured by Hitachi High-Tech) or energy dispersive fluorescence. Elements are identified by observation with a transmission electron microscope (TEM) (measuring device: "HF-3300" (trademark) manufactured by Shimadzu Corporation) accompanied by X-ray (EDX). A region in which oxygen above impurities and a metal element that can become a conductive oxide by combining with oxygen is mixed is identified, and the coating is specified as a conductive oxide coating. The number of atoms of the metal element constituting the conductive oxide contained in the conductive oxide film and the number of atoms of the metal element constituting all the compounds constituting the conductive oxide film are measured. The "content of the metal element constituting the conductive oxide in the conductive oxide film" is calculated by the following formula (3).
Content of metal elements constituting the conductive oxide in the conductive oxide film = (Number of atoms of the metal elements constituting the conductive oxide / Metal elements constituting all the compounds constituting the conductive oxide film) Number of atoms) x 100
The above-mentioned "content of a metal element constituting a conductive oxide in a conductive oxide film" is defined to correspond to "a content of a conductive oxide in a conductive oxide film".

The lower limit of the film thickness of the conductive oxide film is preferably thicker from the viewpoint of suppressing the exposure of the base material, and is, for example, 0.005 μm or more, 0.01 μm or more, 0.5 μm or more, and 1 μm or more. Can be done. On the other hand, the conductive oxide film inhibits heat conduction. Therefore, the upper limit of the film thickness of the conductive oxide film is preferably thin from the viewpoint of maintaining high thermal conductivity, and can be, for example, 30 μm or less, 20 μm or less, and 10 μm or less. The film thickness of the conductive oxide film is 0.005 μm or more and 30 μm or less, 0.005 μm or more and 20 μm or less, 0.005 μm or more and 10 μm or less, 0.01 μm or more and 30 μm or less, 0.01 μm or more and 20 μm or less, 0.01 μm or more and 10 μm. Hereinafter, it can be 0.5 μm or more and 30 μm or less, 0.5 μm or more and 20 μm or less, and 0.5 μm or more and 10 μm or less.

The film thickness of the conductive oxide film is measured by the following procedure. In the plate material in which the conductive oxide film is formed on the base material, a sample is obtained by cutting out an arbitrary place having a length of 3 mm or more and 10 mm or less in the in-plane direction. Prepare 4 samples. Polish the cross section of each sample. Elements are identified by observing the cross section of each sample with a secondary electron microscope (SEM) accompanied by energy dispersive X-ray fluorescence (EDX). EDX identifies a region in which oxygen above impurities and a metal element that can become a conductive oxide by combining with oxygen are mixed, and the coating is specified as a conductive oxide coating. The film thickness of the specified conductive oxide film is measured from the SEM image.

For each sample cut out, the film thickness of the conductive oxide film is measured at 5 points, and the average value of the film thickness at 3 points excluding the maximum and minimum values (hereinafter referred to as "average value A") is taken. calculate. The average value of the average value A of the four samples is taken as the film thickness of the conductive oxide film.

<Plating layer>
It is preferable that the plate member 107 of the first embodiment includes a plating layer 13 arranged on the conductive oxide film 12. According to this, it becomes possible to solder the plate material and the semiconductor element.

The plating layer can be arranged so as to cover the entire conductive oxide film. Further, it can be arranged so as to cover a part of the conductive oxide film.

The plating layer preferably contains at least one metal selected from the group consisting of nickel and copper, or nickel phosphate. When the plating layer contains these nickel, copper or nickel phosphate, the adhesive strength between the plate material and the semiconductor element can be enhanced.

Specifically, the plating layer can be a nickel plating layer, a copper plating layer, or a nickel phosphorus plating layer. The nickel plating layer, the copper plating layer, and the nickel phosphorus plating layer can enhance the adhesive force between the plate material and the semiconductor element. In addition to these plating layers, a gold plating layer can be used. These different plating layers may be formed in layers to be used in a laminated or multi-layered manner.

The lower limit of the film thickness of the plating layer can be 1 μm or more, 2 μm or more, and 3 μm or more. The upper limit of the film thickness of the plating layer can be 20 μm or less, 10 μm or less, and 8 μm or less. The film thickness of the plating layer is 1 μm or more and 20 μm or less, 1 μm or more and 10 μm or less, 1 μm or more and 8 μm or less, 2 μm or more and 20 μm or less, 2 μm or more and 10 μm or less, 2 μm or more and 8 μm or less, 3 μm or more and 20 μm or less, 3 μm or more and 10 μm or less, 3 μm or more and 8 μm. It can be as follows.

The film thickness of the plating layer is measured by the following procedure. A sample is prepared by the same procedure as the above-mentioned measurement of the film thickness of the conductive oxide film, and the conductive oxide film is specified by observing the cross section with SEM. The layer on the identified conductive oxide film is identified as a plating layer. The thickness of the identified plating layer is measured from the SEM image.

The film thickness of the plating layer is measured at 5 points for each sample cut out, and the average value of the film thicknesses at 3 points excluding the maximum value and the minimum value (hereinafter referred to as "average value B") is calculated. The average value of the average value B of the four samples is taken as the film thickness of the plating layer.

<Other layers>
The plate material of the first embodiment may be provided with another layer on the plating layer. Examples of other layers include various solder layers and various metal brazing layers.

<Manufacturing method of plate material of Embodiment 1>
The plate material of the first embodiment can be manufactured, for example, by the following method.

(Preparation of base material)
A first substrate containing at least one first compound selected from the group consisting of silicon carbide, silicon nitride and aluminum nitride is prepared. Since the details of the first base material are as described above, the description thereof will not be repeated.

(Formation of conductive oxide film)
A conductive oxide film is formed on the first substrate. Examples of the method for forming the conductive oxide film include a spray pyrolysis method, a mist CVD method, and a physical vapor deposition method.

Above all, it is preferable to use the spray pyrolysis method from the viewpoint that the film thickness of the conductive oxide can be easily increased. In the spray pyrolysis method, the stress remaining in the conductive oxide film can be reduced as compared with the physical vapor deposition method. Therefore, according to the spray pyrolysis method, even if the film thickness is increased, the film is less likely to peel off from the substrate or the film itself is less likely to be destroyed by its own stress.

The spray pyrolysis method will be described with reference to FIG. FIG. 2 is a diagram illustrating a typical configuration example of a film forming apparatus used in the spray decomposition method. The film forming apparatus includes a mist generation mechanism including a glass bottle 3 containing a raw material solution 2, an ultrasonic vibrator 5 attached to the bottom surface of a container 4 containing water, and a mist generating mechanism. The mist transfer mechanism includes a gas flow meter 6 for adjusting the supply amount of the carrier gas (Ar, N ₂ ), a flow path 7 for flowing the mist and the carrier gas, and a supply port 8 for spraying the mist on the base material. .. The film forming mechanism includes a jig (base material holder) 9 for setting the film forming chamber and the base material 1, and a hot plate 15 arranged so as to be in contact with the jig and the base material holder. A thermocouple 16 is set in the base material holder so that the base material temperature can be measured. In addition to this, a configuration necessary for carrying out the film formation may be appropriately installed.

For example, the carrier gas flow rate can be 3 L / min and the substrate temperature can be 450 ° C.

_{When tin oxide (SnO 2} ) is synthesized as a conductive oxide film, tin _{chloride (SnCl 2} ) dissolved in pure water at a concentration of 0.3 mol / L is used as a raw material solution.

When synthesizing zinc oxide (ZnO) as a conductive oxide film, zinc acetylacetonate (Zn (acac) 2, C ₁₀ H ₁₄ O ₄ Zn) is dissolved in methanol at a concentration of 0.1 mol / L. Use the zinc oxide as the raw material solution.

When synthesizing the indium oxide _(In 2 _{O 3)} as the conductive oxide film, the concentration of 0.1 mol / L indium acetylacetonate and _{(In (acac) 3, C} 15 H 21 O 6 In) in methanol The raw material solution is the one dissolved in.

The ultrasonic transducer is vibrated at a frequency of, for example, 2.4 MHz to mist the raw material solution. The mist generated by the mist generation mechanism is conveyed by the carrier gas and reaches the base material whose temperature has been raised by the hot plate. The mist that has reached the base material is heated by the heat of the hot plate on the base material, the solute in the mist is precipitated as an oxide, a conductive oxide film is formed on the base material, and a plate material is obtained.

(Formation of plating layer)
A plating layer can be formed on the above-mentioned conductive oxide film. Examples of the plating layer include a nickel plating layer, a copper plating layer, and a nickel phosphorus plating layer.

The plating layer can be formed on the conductive oxide film by a plating treatment instead of a metallizing treatment. The plating process can be performed by a conventionally known method.

The temperature of the plating treatment can be lower than the temperature of the metallization treatment, and the thermal stress generated during the formation of the plating layer can also be reduced. If the thermal stress can be reduced, peeling of the plating layer can be suppressed, and non-uniform film thickness of the plating layer can be suppressed. This makes it possible to reduce the electrical resistance value derived from the plating layer.

[Embodiment 2: Plate material]
In developing a heat-dissipating material having a long life, the present inventors first first form a heat-dissipating material in which a metal layer is formed on a conventional metal-ceramics composite base material (hereinafter, also referred to as “composite base material”). In, the cause of the shortened life was investigated. As a result, the following findings were obtained as the cause of shortening the life of the heat radiating material.

Conventionally, a nickel plating layer, a copper plating layer, or a nickel phosphorus plating layer has been formed on a metal-ceramic composite base material in order to solder a heat radiating material and a semiconductor element.

The nickel plating layer and the copper plating layer are formed by electrolytic plating. The electrolytic plating process is an electrochemical method, and the smaller the electric resistance value of the base material, the faster the precipitation rate of nickel plating or copper plating. When the nickel plating layer and the copper plating layer are directly formed on the metal-ceramic composite substrate, the electric resistance value of the metal is smaller than that of the ceramics, so that the plating layer on the metal region becomes thicker and the plating layer on the ceramics region becomes thicker. The plating layer tends to be thin, and the thickness of the plating layer is distributed. As a result, the plating layer is not formed on a part of the composite base material, and the part is exposed to the atmosphere. Therefore, it is presumed that corrosion progresses with the use of the heat radiating material, and the life of the heat radiating material is shortened.

In addition, electroless plating has also been performed after forming an electroless plating layer on a metal-ceramic composite substrate. Even in this case, since the surface energies of the metal and the ceramics are different, the film thickness of the electroless plating layer becomes non-uniform, and the film thickness of the electroless plating layer formed on the electroless plating layer is also non-uniform. Tends to be uniform. Therefore, it is presumed that the use of the heat radiating material causes corrosion of the metal in the composite base material in the vicinity of the thin portion of the metal layer, and the life of the heat radiating material is shortened.

When the nickel phosphorus plating layer is formed on the base material, the catalyst particles are first deposited on the base material, but the formation density of the catalyst particles differs between the metal region and the ceramic region. Therefore, when the nickel phosphorus plating layer is formed on the metal-ceramic composite, the film thickness of the nickel phosphorus plating layer becomes non-uniform, and the metal in the composite base material in the vicinity of the thin portion is corroded. It is presumed that the life of the heat radiating material will be shortened.

As a result of diligent studies based on the above findings, the present inventors have obtained a plate material that is less likely to cause corrosion of the metal in the composite base material even when the heat radiating material is used, and enables the life of the heat radiating material to be extended. .. The plate material will be described with reference to FIG.

FIG. 3 is a diagram illustrating a typical configuration example of the plate material according to the second embodiment. As shown in FIG. 3, the plate material 20 includes at least one second compound selected from the group consisting of aluminum oxide, magnesium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium nitride, silicon nitride and aluminum nitride. A second base material 21 containing at least one metal selected from the group consisting of aluminum, magnesium and copper, and a conductive oxide film 22 arranged on the second base material 21 are provided. The plate material of the second embodiment can include a plating layer 23 arranged on the conductive oxide film 22.

When the plate material of the second embodiment is used as a component of the heat radiating material, the life of the heat radiating material can be extended. The reason is presumed to be as follows (iii) and (iv).

(Iii) In the plate material of the second embodiment, at least one second compound selected from the group consisting of aluminum oxide, magnesium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium nitride, silicon nitride and aluminum nitride, and aluminum. A conductive oxide film is formed on a second substrate containing at least one metal selected from the group consisting of magnesium and copper. The ease of forming the conductive oxide film does not differ between the second compound and the metal region. Therefore, the film thickness of the conductive oxide film becomes uniform, and the exposure of the second base material is unlikely to occur. Therefore, corrosion of the metal in the composite base material from the exposed portion is unlikely to occur, and the life of the heat radiating material is extended.

(Iv) When the plate material of the second embodiment is used as the heat radiating material, the plating layer is arranged on the conductive oxide film. As described above, since the film thickness of the conductive oxide film is uniform, the film thickness of the plating layer formed on the conductive oxide film is also uniform, and the exposure of the second base material is unlikely to occur. Therefore, corrosion of the metal in the composite base material from the exposed portion is unlikely to occur, and the life of the heat radiating material is extended.

<Second base material>
The second base material is made of at least one second compound selected from the group consisting of aluminum oxide, magnesium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium nitride, silicon nitride and aluminum nitride, and aluminum, magnesium and copper. Includes at least one metal selected from the group. The second base material is a metal-ceramic composite composed of particles made of the second compound and a metal existing between the particles and joining the particles to each other.

Aluminum, magnesium and copper have high thermal conductivity, but their linear expansion coefficient is larger than that of semiconductor devices such as silicon (Si), silicon carbide (SiC) and gallium nitride (GaN) and the ceramic packages used around them. .. When aluminum, magnesium and copper are used as heat dissipation materials for semiconductor devices, thermal stress is generated in the semiconductor devices and ceramics packages due to the difference in linear expansion coefficient between aluminum, magnesium and copper and the semiconductor devices and ceramics packages. Damage to semiconductor devices and ceramic packages may occur. Alternatively, cracks may occur at the interface between the heat radiating material and the semiconductor element or the ceramic package, and the heat of the semiconductor element cannot be dissipated and damage may occur.

In the second base material, these metals and ceramic particles having a small coefficient of linear expansion are mixed to bring the coefficient of linear expansion of the base material close to the coefficient of linear expansion of the semiconductor element, so that the generation of thermal stress is suppressed. , The occurrence of the above damage is prevented.

The second substrate can contain one type of second compound. Further, the second base material can contain two or more kinds of second compounds.

The second substrate can contain one type of metal. Further, the second base material can contain two or more kinds of metals.

As the material of the second base material, for example, a composite containing magnesium and silicon carbide (hereinafter, also referred to as “Mg-SiC”) and a composite containing aluminum and silicon carbide (hereinafter, also referred to as “Al-SiC”). ), A composite containing aluminum and aluminum nitride (hereinafter also referred to as "Al-AlN"), a composite containing aluminum and aluminum oxide (hereinafter also referred to as "Al-Al ₂ O ₃ "), and aluminum. A composite containing titanium carbide (hereinafter also referred to as "Al-TiC"), a composite containing aluminum and magnesium oxide (hereinafter also referred to as "Al-MgO"), and a composite containing aluminum and tungsten carbide (hereinafter also referred to as "Al-MgO"). Hereinafter, it is also referred to as "Al-WC"), a composite containing aluminum and titanium nitride (hereinafter also referred to as "Al-TiN"), and a composite containing aluminum and silicon nitride (hereinafter referred to as "Al-Si ₃ N _4"). ”), And a composite containing copper and titanium nitride (hereinafter, also referred to as“ Cu—TiN ”). The material of the second base material is generally described as Al-SiC, Mg-SiC and the like, and may be the same as that commercially available.

The lower limit of the content of the second compound in the second substrate can be 20% by volume or more, 30% by volume or more, and 40% by volume or more. The upper limit of the content of the second compound in the second substrate can be 95% by volume or less, 90% by volume or less, and 85% by volume or less. The content of the second compound in the second substrate is 20% by volume or more and 95% by volume or less, 20% by volume or more and 90% by volume or less, 20% by volume or more and 85% by volume or less, 30% by volume or more and 95% by volume or less. It can be 30% by volume or more and 90% by volume or less, 30% by volume or more and 85% by volume or less, 40% by volume or more and 95% by volume or less, 20% by volume or more and 90% by volume or less, and 20% by volume or more and 85% by volume or less. When two or more kinds of the second compound are contained in the second base material, the content of the second compound is the total content of the two or more kinds of the second compound. The content of the second compound in the second substrate is measured by an X-ray diffraction method (measuring device: "SmartLab" (trademark) manufactured by Rigaku Corporation). The volume content is determined by the RIR (reference intensity ratio) method from the peak intensities of the second compound and each metal.

The second substrate preferably contains silicon carbide. Since silicon carbide has high thermal conductivity and is chemically stable, the plate material can have excellent heat dissipation when the second base material contains silicon carbide. Silicon carbide is also advantageous in terms of price. The content of silicon carbide in the second base material can be 20% by volume or more, 30% by volume or more, and 40% by volume or more. The upper limit of the content of the second compound in the second substrate can be 95% by volume or less, 90% by volume or less, and 85% by volume or less. The content of the second compound in the second substrate is 20% by volume or more and 95% by volume or less, 20% by volume or more and 90% by volume or less, 20% by volume or more and 85% by volume or less, 30% by volume or more and 95% by volume or less. It can be 30% by volume or more and 90% by volume or less, 30% by volume or more and 85% by volume or less, 40% by volume or more and 95% by volume or less, 20% by volume or more and 90% by volume or less, and 20% by volume or more and 85% by volume or less. The content of silicon carbide in the second substrate is measured by an X-ray diffraction method (measuring device: "SmartLab" (trademark) manufactured by Rigaku Corporation). The volume content is determined by the RIR (reference intensity ratio) method from the obtained second compound containing silicon carbide and the peak intensity of each metal.

The average particle size of the second compound is preferably 0.5 μm or more and 300 μm or less. According to this, the surface roughness of the second base material can be reduced, and the thermal conductivity of the plate material can be improved.

The lower limit of the average particle size of the second compound can be 0.5 μm or more, 1 μm or more, and 3 μm or more. The upper limit of the average particle size of the second compound can be 300 μm or less, 200 μm or less, and 100 μm or less. The average particle size of the second compound can be 0.5 μm or more and 300 μm or less, 1 μm or more and 200 μm or less, and 3 μm or more and 100 μm or less.

The method for measuring the average particle size of the second compound is as follows. The cross section of the second substrate is observed with a secondary electron microscope at an arbitrary magnification between 500 and 3000 times, and the particles are observed in 4 fields of view at the selected magnification, and 30 or more particles are not cut in the field of view. Identify the particles. Find the area of each particle. Assuming that the obtained area = πr ² , 2r is calculated and used as the particle diameter. Of the obtained particle diameters (2r), the average of the remaining particle diameters obtained by subtracting the maximum and second largest particle diameters and the minimum and second smallest particle diameters is defined as the average particle diameter of the second compound.

The metal in the second base material may consist of pure Al, pure Mg, and pure Cu, or pure Al, pure Mg, and pure Cu (hereinafter, pure Al, pure Mg, and pure Cu are collectively referred to as "pure metal". It is also described.) At least one kind of metal and another metal may be phase-separated and mixed. "Pure" means that it does not contain any elements other than unavoidable elements. Examples of unavoidable impurities include oxygen, nitrogen, hydrogen, titanium (Ti), silicon (Si), various aluminum alloys, various Mg alloys, and various Cu alloys.

The lower limit of the metal content in the second base material can be 5% by volume or more, 10% by volume or more, and 15% by volume or more. The upper limit of the content of the second compound in the second substrate can be 80% by volume or less, 70% by volume or less, and 60% by volume or less. The content of the second compound in the second substrate is 5% by volume or more and 80% by volume or less, 5% by volume or more and 70% by volume or less, 5% by volume or more and 60% by volume or less, 10% by volume or more and 80% by volume or less, It can be 10% by volume or more and 70% by volume or less, 10% by volume or more and 60% by volume or less, 15% by volume or more and 80% by volume or less, 15% by volume or more and 70% by volume or less, and 15% by volume or more and 60% by volume or less. When two or more kinds of metals are contained in the second base material, the metal content is the total content of two or more kinds of metals. The content of each metal in the second base material is measured by an X-ray diffraction method (measuring device: "SmartLab" (trademark) manufactured by Rigaku Corporation). The volume content is determined by the RIR (reference intensity ratio) method from the peak intensities of each of the obtained metals and the second compound.

The lower limit of the content of pure Al, pure Mg and pure Cu in the metal in the second base material is preferably 50% by volume or more, and 75% by volume or more, 90 volumes from the viewpoint of increasing the thermal conductivity of the second base material. % Or more is preferable, and 100% by volume is most preferable. When two or more kinds of pure metals are contained in the second base material, the content of pure metals shall be the total content of two or more kinds of pure metals.

The lower limit of the thickness of the second base material can be 0.5 mm or more, 1.0 mm or more, and 1.5 mm or more. The upper limit of the thickness of the second base material can be 6.0 mm or less, 5.0 mm or less, 4.0 mm or less. The thickness of the second base material is 0.5 mm or more and 6.0 mm or less, 0.5 mm or more and 5.0 mm or less, 0.5 mm or more and 4.0 mm or less, 1.0 mm or more and 6.0 mm or less, 1.0 mm or more and 5 It can be 0.0 mm or less, 1.0 mm or more and 4.0 mm or less, 1.5 mm or more and 6.0 mm or less, 1.5 mm or more and 5.0 mm or less, and 1.5 mm or more and 4.0 mm or less. The thickness of the second base material is measured at five points on the plane of the substrate with a micrometer and used as the average value.

<Conductive oxide film>
In the plate material 20 of the second embodiment, the conductive oxide film 22 can be the same as the conductive oxide film 12 described in the first embodiment, and therefore the description thereof will not be repeated.

The ease of forming the conductive oxide film does not differ between the second compound and the metal region. Therefore, in the plate material of the second embodiment, the film thickness of the conductive oxide film becomes uniform, and the exposure of the second base material is unlikely to occur. Therefore, corrosion of the metal in the composite base material from the exposed portion is unlikely to occur, and the life of the heat radiating material is extended.

<Plating layer>
In the plate material 20 of the second embodiment, the plating layer 23 can be the same as the plating layer 13 described in the first embodiment, and therefore the description thereof will not be repeated.

In the plate material of the second embodiment, since the film thickness of the conductive oxide film is uniform, the film thickness of the plating layer formed on the conductive oxide film is also uniform, and the second base material is exposed. Hateful. Therefore, corrosion of the metal in the composite base material from the exposed portion is unlikely to occur, and the life of the heat radiating material is extended.

<Other layers>
The plate material of the second embodiment may be provided with another layer on the plating layer. Examples of other layers include various solder layers and various metal brazing layers.

<Manufacturing method of plate material of Embodiment 2>
The plate material of the second embodiment can be manufactured, for example, by the following method.

(Preparation of base material)
At least one second compound selected from the group consisting of aluminum oxide, magnesium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium nitride, silicon nitride and aluminum nitride, and at least selected from the group consisting of aluminum, magnesium and copper. Prepare a second substrate containing one type of metal. Since the details of the second base material are as described above, the description thereof will not be repeated.

(Formation of conductive oxide film)
A conductive oxide film is formed on the above-mentioned second base material. Since the method for forming the conductive oxide film can be the same as the method for forming the conductive oxide film in the method for producing the plate material of the first embodiment, the description thereof will not be repeated.

(Formation of plating layer)
A plating layer can be formed on the above-mentioned conductive oxide film. Examples of the plating layer include a nickel plating layer, a copper plating layer, and a nickel phosphorus plating layer.

When the nickel plating layer and the copper plating layer are directly formed on the metal-ceramic composite base material as in the conventional case, the electric resistance value of the metal is smaller than that of the ceramics, so that the plating layer on the metal region becomes thicker. , The plating layer on the ceramics area tends to be thin.

On the other hand, in the second embodiment, the nickel plating layer and the copper plating layer are formed on the conductive oxide film having a uniform film thickness. The conductive oxide film has a more uniform distribution of electrical resistance values in the plane than the metal-ceramic composite substrate. Therefore, the film thickness of the plating layer formed on the conductive oxide film is also uniform.

When the nickel phosphorus plating layer is formed on the metal-ceramic composite substrate, the catalyst particles are first deposited on the substrate, but the formation density of the catalyst particles differs between the metal region and the ceramic region. Therefore, when the nickel phosphorus plating layer is formed on the metal-ceramics composite, the film thickness of the nickel phosphorus plating layer becomes non-uniform.

On the other hand, in the second embodiment, the nickel phosphorus plating layer is formed on the conductive oxide film having a uniform film thickness. Since the in-plane of the conductive oxide film is homogeneous, the formation density of the catalyst particles is uniform, and the film thickness of the nickel phosphorus plating layer is uniform.

[Embodiment 3: Heat Dissipating Material]
The heat radiating material of the third embodiment is a heat radiating material including the plate material of the above-mentioned first embodiment or the second embodiment. When the heat radiating material of the present disclosure includes the plate material of the first embodiment, the electric resistance is unlikely to increase during use, and the life can be long. When the heat-dissipating material of the present disclosure includes the plate material of the second embodiment, the metal in the composite base material is less likely to be corroded during use, and can have a long life.

The present embodiment will be described more specifically by way of examples. However, these embodiments do not limit the present embodiment.

[Example 1]
In Example 1, the relationship between the presence or absence of the conductive oxide film on the substrate and the life of the plate material was investigated. More specifically, the relationship between the presence or absence of a conductive oxide film on the substrate and the electrical resistance of the plate material after the thermal cycle test was investigated.

<Sample 1-1, Sample 1-2>
(Preparation of base material)
An aluminum nitride plate (“AlN170W” manufactured by Allied Material, size 30 mm × 30 mm × thickness 3 mm) was prepared as a base material.

(Formation of conductive oxide film)
A conductive oxide film was produced on the substrate by the method described in the first embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C. Tin chloride (SnCl ₂ ) was dissolved in pure water at a concentration of 0.3 mol / L to prepare a mist raw material solution. As a result, _{a film made of tin oxide (SnO 2} ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 1.

(Formation of plating layer)
In Sample 1-1, a nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material. In Sample 1-2, a copper (Cu) plating layer was formed on the conductive oxide film to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 1.

<Sample 1-3, Sample 1-4>
(Preparation of base material)
An aluminum nitride plate (“AlN170W” manufactured by Allied Material, size 30 mm × 30 mm × 3 mm) was prepared as a base material.

(Formation of conductive oxide film)
A conductive oxide film was produced on the substrate by the method described in the first embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C. Zinc acetylacetonate (Zn (acac) 2, C ₁₀ H ₁₄ O ₄ Zn) was dissolved in methanol at a concentration of 0.1 mol / L to prepare a mist raw material solution. As a result, a film made of zinc oxide (ZnO) was formed on the base material. The thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 1.

(Formation of plating layer)
In Samples 1-3, a nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material. In Samples 1-4, a copper (Cu) plating layer was formed on the conductive oxide film to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 1.

<Sample 1-5>
(Preparation of base material)
An aluminum nitride plate (“AlN170W” manufactured by Allied Material, size 30 mm × 30 mm × thickness 3 mm) was prepared as a base material.

(Formation of conductive oxide film)
A conductive oxide film was produced on the substrate by the method described in the first embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C. Indium acetylacetonate (In (acac) ₃ , C ₁₅ H ₂₁ O ₆ In) was dissolved in methanol at a concentration of 0.1 mol / L to prepare a mist raw material solution. As a result, _{a film made of indium oxide (In 2} O ₃ ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 1.

(Formation of plating layer)
A nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 1.

<Sample 1-6>
(Preparation of base material)
A silicon carbide plate (manufactured by Hitachi Chemical Co., Ltd., 30 mm × 30 mm × 3 mm) was prepared as a base material.

A film made of _{tin oxide (SnO 2} ) was formed on the base material in the same manner as in Sample 1-1. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 1.

(Formation of plating layer)
A nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 1.

<Sample 1-7>
(Preparation of base material)
A silicon nitride plate (“SN-90” manufactured by MARUWA, 30 mm × 30 mm × 3 mm) was prepared as a base material.

A film made of _{tin oxide (SnO 2} ) was formed on the base material in the same manner as in Sample 1-1. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 1.

(Formation of plating layer)
A nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 1.

<Sample 1-8, Sample 1-9>
(Preparation of base material)
An aluminum nitride plate (“AlN170W” manufactured by Allied Material, size 30 mm × 30 mm × 3 mm) was prepared as a base material.

(Formation of plating layer)
In Samples 1-8, a nickel layer was formed on the above-mentioned substrate by a thin-film deposition method to obtain a plate material. In Sample 1-9, a copper layer was formed on the above-mentioned substrate by a thin-film deposition method to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 1.

<Sample 1-10, Sample 1-11>
(Preparation of base material)
For Sample 1-10, a silicon carbide plate (manufactured by Hitachi Chemical Co., Ltd., 30 mm × 30 mm × 3 mm) was prepared as a base material. For Sample 1-11, a silicon nitride plate (“SN-90” manufactured by MARUWA, 30 mm × 30 mm × 3 mm) was prepared as a base material.

(Formation of plating layer)
A nickel layer was formed on the above-mentioned substrate by a vapor deposition method to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 1.

<Evaluation>
(Measurement of electrical resistance of plate material after thermal cycle test)
The obtained plate material was subjected to a thermodynamic cycle test between −50 ° C. and 185 ° C. The cycle pattern was maintained at −50 ° C. for 30 minutes, raised to 185 ° C. over 1 hour, held at 185 ° C. for 30 minutes, and lowered to −50 ° C. over 1 hour, and 1000 cycles were repeated.

The electric resistance values on the outermost surface of the plating layer were measured between the two pairs of opposite corners of the plate material after the thermal cycle test, and the average value of the two electric resistance values was obtained. The closer the ratio of the electrical resistance values before and after the thermal cycle test (= electrical resistance value before the thermal cycle test / electrical resistance value after the thermal cycle test) is to 1, the more the increase in electrical resistance due to the use of the plate material is suppressed. , Indicates that the life of the plate material is long. In the "Electrical resistance measurement" column of Table 1, if the ratio of the electric resistance value before and after the thermal cycle test is smaller than 0.8, it is indicated as B, and the ratio of the electric resistance value before and after the thermal cycle test is 0. The case of 8 or more and 1 or less is shown as A.

＜考察＞
試料１−１〜試料１−７は実施例に該当する。試料１−８〜試料１−１１は比較例に該当する。

<Discussion>
Samples 1-1 to 1-7 correspond to Examples. Samples 1-8 to 1-11 correspond to Comparative Examples.

Samples 1-1 to 1-7 have a ratio of electrical resistance values before and after the thermal cycle test (= electrical resistance value before the thermal cycle test / electrical resistance value after the thermal cycle test) of 0.8 or more and 1 or less. There is little change. In Samples 1-1 to 1-7, the plating layer was hardly peeled off even after the thermal cycle test. Therefore, it is presumed that the increase in electrical resistance hardly occurred.

It was confirmed that in Samples 1-8 to 1-11, the ratio of the electrical resistance values before and after the thermal cycle test was smaller than 0.8, the electrical resistance was high after the thermal cycle test, and the life of the plate material was short. .. In Samples 1-8 to 1-11, a part of the plating layer on the substrate was peeled off after the thermal cycle test. Therefore, it is presumed that the electrical resistance has increased.

[Example 2]
In Example 2, the relationship between the presence or absence of the conductive oxide film on the substrate and the life of the plate material was investigated. More specifically, the relationship between the presence or absence of the conductive oxide film on the substrate and the weight change of the plate material after the salt spray test was investigated.

<Sample 2-1 to Sample 2-7>
(Preparation of base material)
As a base material, a base material (Mg-SiC) containing magnesium and silicon carbide (“Mg-SiC” manufactured by Allied Material, size 30 mm × 30 mm × 5 mm) was prepared.

(Formation of conductive oxide film)
A conductive oxide film was produced on the substrate by the method described in the second embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C.

In Samples 2-1 to Sample 2-3, tin chloride (SnCl ₂ ) was dissolved in pure water at a concentration of 0.3 mol / L to prepare a mist raw material solution. As a result, _{a film made of tin oxide (SnO 2} ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

In Samples 2-4 to 2-6, zinc acetylacetonate (Zn (acac) 2, C ₁₀ H ₁₄ O ₄ Zn) was dissolved in methanol at a concentration of 0.1 mol / L to prepare a mist raw material solution. did. As a result, a film made of zinc oxide (ZnO) was formed on the base material. The thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

In Sample 2-7, the indium acetylacetonate _{(In (acac) 3, C} 15 H 21 O 6 In) was dissolved at a concentration of 0.1 mol / L in methanol, as a raw material solution of the mist. As a result, _{a film made of indium oxide (In 2} O ₃ ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

(Formation of plating layer)
In Sample 2-1 and Sample 2-4 and Sample 2-7, a nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material.

In Sample 2-2 and Sample 2-5, a copper (Cu) plating layer was formed on the conductive oxide film to obtain a plate material.

In Samples 2-3 and 2-6, a nickel phosphorus (NiP) plating layer was formed on the conductive oxide film to obtain a plate material.

The film thickness of the plating layer of each sample is as shown in the "film thickness (μm)" column of the "plating layer" in Table 2.

<Sample 2-8 to Sample 2-14>
As a base material, a base material containing aluminum and silicon carbide (hereinafter, also referred to as “Al-SiC”) (“β8” manufactured by Allied Material, size 30 mm × 30 mm × t5 mm) was prepared.

(Formation of conductive oxide film)
A conductive oxide film was produced on the substrate by the method described in the second embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C.

In Samples 2-8 to 2-10, tin chloride (SnCl ₂ ) was dissolved in pure water at a concentration of 0.3 mol / L to prepare a mist raw material solution. As a result, _{a film made of tin oxide (SnO 2} ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

In Samples 21 to 2-13, zinc acetylacetonate (Zn (acac) 2, C ₁₀ H ₁₄ O ₄ Zn) is dissolved in pure water at a concentration of 0.1 mol / L to provide a mist raw material solution. And said. As a result, a film made of zinc oxide (ZnO) was formed on the base material. The thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

Sample 2-14, indium acetylacetonate _{(In (acac) 3, C} 15 H 21 O 6 In) was dissolved at a concentration of 0.1 mol / L in methanol, as a raw material solution of the mist. As a result, _{a film made of indium oxide (In 2} O ₃ ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

(Formation of plating layer)
In Sample 2-8, Sample 2-11 and Sample 2-14, a nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material.

In Sample 2-9 and Sample 2-12, a copper (Cu) plating layer was formed on the conductive oxide film to obtain a plate material.

In Samples 2-10 and 2-13, a nickel phosphorus (NiP) plating layer was formed on the conductive oxide film to obtain a plate material.

The film thickness of the plating layer of each sample is as shown in the "film thickness (μm)" column of the "plating layer" in Table 2.

<Sample 2-15>
(Preparation of base material)
Aluminum (Al) and aluminum nitride (AlN) powder (D50: 30 μm) are composited by a penetration method to form a base material (Al-AlN) containing aluminum and aluminum nitride (size 30 mm × 30 mm × 5 mm). Prepared.

A conductive oxide film was produced on the substrate by the method described in the second embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C. Tin chloride (SnCl ₂ ) was dissolved in pure water at a concentration of 0.3 mol / L to prepare a mist raw material solution. As a result, _{a film made of tin oxide (SnO 2} ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

(Formation of plating layer)
A copper (Cu) plating layer was formed on the above-mentioned conductive oxide film to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 2.

<Sample 2-16>
(Preparation of base material)
Aluminum (Al) and aluminum oxide (Al ₂ O ₃ ) powder (D50: 30 μm) are composited by a dipping method, and a base material (Al-Al ₂ O ₃ ) containing aluminum and aluminum oxide (size). 30 mm × 30 mm × 5 mm) was prepared.

A conductive oxide film was produced on the substrate by the method described in the second embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C. Tin chloride (SnCl ₂ ) was dissolved in pure water at a concentration of 0.3 mol / L to prepare a mist raw material solution. As a result, _{a film made of tin oxide (SnO 2} ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

(Formation of plating layer)
A copper (Cu) plating layer was formed on the above-mentioned conductive oxide film to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 2.

<Sample 2-17 to Sample 2-22>
(Preparation of base material)
Sample 2-17 is a substrate (Al-TiC) (size) containing aluminum and titanium carbide by compounding aluminum (Al) and titanium carbide (TiC) powder (D50: 30 μm) by a dipping method. 30 mm × 30 mm × 5 mm) was prepared.

In sample 2-18, aluminum (Al) and magnesium oxide (MgO) powder (D50: 30 μm) are composited by a dipping method, and a base material (Al-MgO) containing aluminum and magnesium oxide (size). 30 mm × 30 mm × 5 mm) was prepared.

In sample 2-19, aluminum (Al) and tungsten carbide (WC) powder (D50: 30 μm) are composited by a dipping method, and a base material (Al-WC) containing aluminum and tungsten carbide (size) is prepared. 30 mm × 30 mm × 5 mm) was prepared.

Sample 2-20 is a base material (Al-TiN) (size) containing aluminum and titanium nitride by compounding aluminum (Al) and titanium nitride (TiN) powder (D50: 30 μm) by a penetration method. 30 mm × 30 mm × 5 mm) was prepared.

Samples 2-21, an aluminum (Al), silicon nitride _(Si 3 _{N 4)} powder (D50: 30 [mu] m) and a complexed by infiltration method, substrates comprising aluminum and silicon nitride (Al-Si ₃ N ₄ ) (size 30 mm × 30 mm × 5 mm) was prepared.

Sample 2-22 is a base material (Cu-TiN) (size) containing copper and titanium nitride by compounding copper (Cu) and titanium nitride (TiN) powder (D50: 30 μm) by a dipping method. 30 mm × 30 mm × 5 mm) was prepared.

(Formation of conductive oxide film)
A conductive oxide film was produced on the substrate by the method described in the second embodiment using the film forming apparatus of FIG. The carrier gas flow rate was 3 L / min and the substrate temperature was 450 ° C. Tin chloride (SnCl ₂ ) was dissolved in pure water at a concentration of 0.3 mol / L to prepare a mist raw material solution. As a result, _{a film made of tin oxide (SnO 2} ) was formed on the substrate. The film thickness of the coating film is as shown in the “Film thickness (μm)” column of the “Conductive oxide coating film” in Table 2.

(Formation of plating layer)
A nickel (Ni) plating layer was formed on the conductive oxide film to obtain a plate material.

<Sample 2-23, Sample 2-24>
(Preparation of base material)
As a base material, a base material containing magnesium and silicon carbide (hereinafter, also referred to as “Mg-SiC plate”) (“Mg-SiC” manufactured by Allied Material, size 30 mm × 30 mm × 5 mm) was prepared.

(Formation of plating layer)
In Sample 2-23, a NiP electroless plating layer of 1 μm was formed on the substrate, and then a nickel layer was formed by electrolytic plating to obtain a plate material. In Sample 2-24, a NiP electroless plating layer of 1 μm was formed on the substrate, and then a copper layer was formed by electrolytic plating to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 2.

<Sample 2-25, Sample 2-26>
(Preparation of base material)
As a base material, a base material (Al-SiC plate) containing aluminum and silicon carbide (“β8” manufactured by Allied Material, size 30 mm × 30 mm × t5 mm) was prepared.

(Formation of plating layer)
In Sample 2-25, a NiP electroless plating layer of 1 μm was formed on the substrate, and then a nickel layer was formed by electroplating to obtain a plate material. In Sample 2-26, a NiP electroless plating layer of 1 μm was formed on the substrate, and then a copper layer was formed by electrolytic plating to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 2.

<Sample 2-27 to Sample 2-32>
(Preparation of base material)
For sample 2-27, a substrate (Al-TiC) was prepared in the same manner as for sample 2-17. For Sample 2-28, a substrate (Al-MgO) was prepared in the same manner as for Sample 2-18. For Sample 2-29, a substrate (Al-WC) was prepared in the same manner as for Sample 2-19. For Sample 2-30, a base material (Al-TiN) was prepared in the same manner as for Sample 2-20. Samples 2-31 were prepared base material _(Al-Si 3 _{N 4)} in the same manner as Sample 2-21. For Sample 2-32, a base material (Cu-TiN) was prepared in the same manner as for Sample 2-22.

(Formation of plating layer)
In each sample, a NiP electroless plating layer of 1 μm was formed on the substrate, and then a nickel layer was formed by electrolytic plating to obtain a plate material. The film thickness of the plating layer is as shown in the "film thickness (μm)" column of the "plating layer" in Table 2.

<Evaluation>
(Measurement of weight change of plate material after salt spray test)
The obtained plate material was subjected to a salt spray test specified in JIS Z 2371: 2000. The test time was 200 hours. In the salt spray test, when corrosion occurs, the sample is oxidized or hydroxide, and the weight of the sample increases. Therefore, it is shown that the larger the increase in the sample weight, the larger the degree of corrosion and the shorter the life of the plate material. The change in weight of the plate material before and after the salt spray test was measured, and the case where an increase of 1% or more was observed was designated as B, and the case where the increase was less than 1% was designated as A. The results are shown in the "Salt spray test" column of Table 2.

<Discussion>
Samples 2-1 to 2-22 correspond to Examples. Samples 2-23 to 2-32 correspond to Comparative Examples.

Samples 2-1 to 2-22 had a weight increase of less than 1%. That is, it was confirmed that the samples 2-1 to 2-22 are less likely to be corroded even in the salt spray test and have a long life of the plate material. It is presumed that this is because it was difficult for the samples to be oxidized or hydroxide in Samples 2-1 to 2-22.

Samples 2-23 to 2-32 had a weight increase of 1% or more. That is, it was confirmed that the life of the plate material of Samples 2-23 to 2-32 was shorter than that of the examples. It is presumed that this is because in Samples 2-23 to 2-32, corrosion occurred in the salt spray test, and the samples were oxidized or hydroxideed.

Although the embodiments and examples of the present disclosure have been described as described above, it is planned from the beginning that the configurations of the above-described embodiments and examples may be appropriately combined or variously modified.
The embodiments and examples disclosed this time should be considered to be exemplary in all respects and not restrictive. The scope of the present invention is shown by the scope of claims rather than the embodiments and examples described above, and is intended to include the meaning equivalent to the scope of claims and all modifications within the scope.

1 Base material 2 Raw material solution 3 Glass bottle 4 Container 5 Ultrasonic oscillator 6 Gas flow meter 7 Flow path 8 Supply port 9 Jig 10, 20 Plate material 11 First base material 12, 22 Conductive product coating 13, 23 Plating layer 15 Hot plate 16 Thermocouple 21 2nd base material

Claims (8)

A first substrate containing at least one first compound selected from the group consisting of silicon carbide, silicon nitride and aluminum nitride.
A plate material comprising a conductive oxide film arranged on the first substrate. At least one second compound selected from the group consisting of aluminum oxide, magnesium oxide, silicon carbide, titanium carbide, tungsten carbide, titanium nitride, silicon nitride and aluminum nitride, and at least selected from the group consisting of aluminum, magnesium and copper. A second substrate containing one metal, and
A plate material comprising a conductive oxide film arranged on the second base material. The plate material according to claim 1 or 2, wherein the conductive oxide film contains at least one element selected from the group consisting of tin, indium and zinc. The plate material according to any one of claims 1 to 3, further comprising a plating layer arranged on the conductive oxide film. The plate material according to claim 1, wherein the first base material contains aluminum nitride. The plate material according to claim 2, wherein the second base material contains silicon carbide. The plate material according to claim 4, wherein the plating layer contains at least one metal selected from the group consisting of nickel and copper, or nickel phosphate. A heat radiating material containing the plate material according to any one of claims 1 to 7.

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