JP2003277929A - Heat- and oxidation resistant material and method for manufacturing the same, and heating element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a heat- and oxidation resistant material which has an excellent oxidation resistance even under a high-temperature oxidative atmosphere and has an electroconductivity in combination and a method for manufacturing the same, and a heating element using the same. <P>SOLUTION: The heat- and oxidation resistant material has a base material consisting of a heat resistant material, such as a sintered silicon carbide compact and a film coating at least a portion of the base material with the film and containing one or ≥2 kinds selected from a diamond single crystal, diamond polycrystals, diamond-like carbon, graphite, and amorphous carbon. The film is formed as a carbon film in which the carbon of a portion of the carbon used as an essential component has a C-X bond (where X is one or ≥2 kinds selected from F, Cl and I). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heat and oxidation resistant material having excellent oxidation resistance even in a high temperature oxidizing atmosphere and also having electrical conductivity, a method for producing the same and heat generation using the same. It is about the body.

[0002]

2. Description of the Related Art Conventionally, in a heater such as a resistance heating furnace or a heat treatment apparatus which is used in a temperature range of 1000 ° C. or less, a heat resistant metal such as molybdenum (Mo) or tungsten (W), graphite, or amorphous. A carbon (C) material such as carbon is used. Further, for example, as a material used in a high-temperature oxidizing atmosphere exceeding 1000 ° C., aluminum oxide (Al ₂ O ₃ ), aluminum nitride (AlN), yttrium aluminum garnet (YAG), magnesium oxide (MgO), etc. Ceramics with excellent properties are often used. Since these ceramics are excellent in insulation and heat resistance, they are used as furnace body materials for the above-mentioned various devices, boats and setters for samples, insulating substrates, electrically insulating materials and the like.

[0003]

By the way, the above-mentioned M
Since the conductive materials such as o, W, and C are not always sufficiently resistant to oxidation particularly in a high temperature oxidizing atmosphere, they can be used only in a limited, ie, not so high temperature oxidizing atmosphere. There was a problem. In addition, although the above-mentioned ceramics have excellent heat resistance, they have a low electric conductivity and cannot be used for parts requiring conductivity such as a heater of a high temperature heating device. was there.

The present invention has been made in order to solve the above-mentioned problems, and has a heat-resistant and oxidation-resistant material which has excellent oxidation resistance even in a high temperature oxidizing atmosphere and further has electrical conductivity. And a manufacturing method thereof and a heating element using the same.

[0005]

Means for Solving the Problems The inventors of the present invention have made earnest studies to solve the problems of the above-mentioned conventional techniques, and as a result, if the surface of the heat resistant material is coated with a special carbon-based coating, It was clarified that the problem can be solved efficiently. That is, the heat-resistant and oxidation-resistant material of the present invention comprises a base material made of a heat-resistant material and a coating film that covers at least a part of the base material, and the coating film is a part of carbon as a main component. Carbon is a C-X bond (where X is F, C
1 or 2 or more selected from l and I).

In this heat and oxidation resistant material, the coating is
A part of carbon among the main component carbon has a C-X bond (where X is one or more selected from F, Cl and I), so that this carbon is The system coating becomes chemically very stable and has excellent oxidation resistance even in a high temperature oxidizing atmosphere.

The inventors of the present invention have found that if any one of conductive ceramics, heat-resistant metal and carbon is used as the heat resistant material, an inexpensive material can be used as a base material in a high temperature oxidizing atmosphere. In addition to exhibiting excellent heat resistance and oxidation resistance, it has also been proved that excellent heat conductivity and oxidation resistance can be provided, and that the heat resistance and oxidation resistance material can be provided at a low price. That is, the heat resistant material is preferably any one of conductive ceramics, heat resistant metal, and carbon.

An interlayer film is preferably formed between the base material and the carbon-based coating. By forming this interlayer film, when the carbon-based coating is formed, the influence from the surface of the base material that is the underlayer is prevented, and the formed carbon-based coating has a disordered crystal structure or defects. It does not have the desired crystal structure.

The interlayer film is preferably a carbon diffusion prevention film. By forming this carbon diffusion prevention film,
A part of carbon constituting the carbon-based coating is prevented from diffusing into the base material and forming an intervening layer at the interface between the base material and the carbon-based coating. This improves the adhesion between the base material and the carbon-based coating.

Further, the present inventors have carried out a fluorination treatment, a chlorination treatment or an iodination treatment on a carbon-based coating film by a chemical vapor phase method, so that a part of carbon as a main component is carbon-carbonized. It has been clarified that a heat-resistant and oxidation-resistant material having a special carbon-based coating having an X bond (where X is one or more selected from F, Cl and I) can be provided at a low price. .

That is, the carbon-based coating is subjected to a fluorination treatment, a chlorination treatment or an iodination treatment by a chemical vapor phase method so that a part of the carbon of the carbon-based coating is converted into C--X.
It is preferably a carbon having a bond (where X is one or more selected from F, Cl and I).

Further, the present inventors have found that the carbon-based coating is
As long as it contains one or more of any one of diamond single crystal, diamond polycrystal, diamond-like carbon, graphite and amorphous carbon, its surface can be easily fluorinated by chemical vapor deposition. It has been clarified that oxidization resistance can be further improved by performing chlorination treatment or iodination treatment. That is, it is preferable that the carbon-based coating contains one kind or two or more kinds selected from a diamond single crystal body, a diamond polycrystal body, diamond-like carbon, graphite, and amorphous carbon.

The present inventors have also found that at least a part of the base material has a C--X bond (where X is selected from F, Cl and I) to a part of the carbons as the main component. When forming a special carbon-based coating containing one or two or more), the carbon-based coating is fluorinated, chlorinated or iodinated by a chemical vapor phase method, so that it is inexpensive and efficient. It was found that they can be formed selectively.

That is, the method for producing a heat-resistant and oxidation-resistant material according to the present invention comprises a heat-resistant and oxidation-resistant material comprising a base material made of a heat-resistant material and a carbon-based coating covering at least a part of the base material. In the method for producing, the carbon-based coating is subjected to a fluorination treatment, a chlorination treatment, or an iodination treatment by a chemical vapor phase method, and a part of carbon in the carbon-based coating is converted into C-X.
It is characterized in that it is a carbon having a bond (however, X is one or more selected from F, Cl and I).

In this manufacturing method, the carbon-based coating is subjected to a fluorination treatment, a chlorination treatment or an iodination treatment by a chemical vapor phase method, so that a part of carbon in the carbon-based coating is C-
By introducing an X bond (where X is one or more selected from F, Cl, and I), it is chemically very stable and high-temperature oxidation is at least part of the substrate. A carbon-based coating having excellent oxidation resistance even under a strong atmosphere can be formed inexpensively and efficiently.

Further, the inventors of the present invention have excellent oxidation resistance even in a high temperature oxidizing atmosphere if the main body of the heating element is made of the heat and oxidation resistant material of the present invention. It has been clarified that the heat generating element having excellent heat resistance and oxidation resistance can be provided at a low price by having the conductivity as well. That is, the heating element of the present invention is characterized in that at least the main body is made of the heat and oxidation resistant material of the present invention.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of a heat and oxidation resistant material of the present invention, a method for producing the same, and a heating element using the same will be described. It should be noted that the present embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.

[First Embodiment] The heat and oxidation resistant material of this embodiment will be described below. The heat-resistant and oxidation-resistant material according to the present embodiment includes a base material made of a heat-resistant material and a coating film that covers at least a part of the base material. Some carbon is C-
A carbon-based coating having an X bond (where X is one or more selected from F, Cl and I) (hereinafter, simply C-
It is composed of an X bond-introduced carbon-based coating). Hereinafter, the base material and the C-X bond-introduced carbon-based coating will be further described in terms of items.

"Substrate" The heat-resistant material constituting this substrate is not particularly limited, but for example, conductive ceramics such as silicon carbide, tantalum carbide, molybdenum carbide, and metal-ceramic composite sintering. A conductive metal composite ceramic such as a body, a heat resistant metal such as tungsten, molybdenum, or iridium, or a carbon material such as graphite or amorphous carbon is appropriately used.

Among these heat resistant materials, conductive ceramics such as a silicon carbide sintered body, a tantalum carbide sintered body and a molybdenum carbide sintered body are materials excellent in heat resistance, oxidation resistance and conductivity. Is. In particular, a highly pure and dense silicon carbide sintered body can be obtained by any of the following manufacturing methods.

(Production method 1) The average particle size is 0.1 to 10
Introducing a raw material gas consisting of silane compound or silicon halide and silicon carbide into plasma of a silicon carbide powder of μm (first silicon carbide powder: β type is preferable) and plasma of a non-oxidizing atmosphere such as Ar, The reaction system pressure is 1.01 × 10 ⁵ P
less than a (1 atm) to 1.33 × 10 Pa (0.1 to
rr) and a silicon carbide fine powder having an average particle diameter of 0.1 μm or less (second silicon carbide powder: β type is preferable) synthesized by performing a gas phase reaction with a predetermined compounding ratio. A method in which the mixture is weighed and mixed so that the mixture is formed into a predetermined shape, and the formed body is fired at a predetermined temperature to obtain a silicon carbide sintered body.

(Manufacturing Method 2) The silicon carbide fine powder (second silicon carbide powder) in Manufacturing Method 1 is molded into a predetermined shape, and this molded body is fired at a predetermined temperature to obtain a silicon carbide sintered body. Method. Regarding these manufacturing methods, see Patent No. 27.
It is disclosed in Japanese Patent No. 26694 and Japanese Patent No. 2732408, and can be easily manufactured.

The silicon carbide sintered body obtained by these manufacturing methods has a resistance of 1 Ωcm or less, for example, 1 × 10 ^-2 to 1 × 1.
Since it has both excellent conductivity of about 0 ⁻¹ Ω · cm and heat resistance, it is suitable as a base material for the heat and oxidation resistant material of the present embodiment. When applied to the body part, it becomes a heating element having excellent heat resistance and oxidation resistance.

The base material made of these silicon carbide sintered bodies is
After processing into a desired shape, excess free carbon on the surface of the base material is burned and removed by applying a heat treatment in the atmosphere, and thereafter, SiO ₂ formed on the surface of the base material by dipping treatment with hydrofluoric acid or the like. It is preferable to dissolve and remove impurities such as. The heat treatment temperature is 400 to 1500 ° C., especially 600 to 1
000 ° C is preferred. The reason is that below 400 ° C,
The free carbon on the surface of the substrate is not sufficiently removed, and
This is because if the temperature exceeds 0 ° C., the surface of the base material is oxidized and part or all of the surface becomes an oxide, and the purity of the silicon carbide sintered body decreases.

The heat treatment time is not particularly limited, but is usually 1 to 40 hours. Where 1 ~
The reason why 40 hours is preferable is that when the heat treatment time is less than 1 hour, the removal efficiency of the free carbon on the surface of the substrate is low, while even when the heat treatment time exceeds 40 hours, the removal of the free carbon on the surface of the substrate is removed. This is because it does not improve efficiency but is meaningless.

Further, as the conductive metal composite ceramics constituting the base material, Pt-Al ₂ O ₃ and Ag-Si-Ni-
A metal-ceramic composite sintered body such as SiO ₂ or Mo-ZrO ₂ is also preferably used. Further, as the heat-resistant material forming the base material, heat-resistant metal materials such as tungsten, molybdenum, and iridium are also preferably used. When these heat-resistant metal materials are used as the base material, when the "carbon-based coating film" described later is formed on the surface of the base material, carbon diffuses inside the base material, and the interface between the base material and the carbon-based coating film. There is a possibility that an intervening layer is formed on the surface and the adhesion is reduced. In order to prevent this, it is preferable to previously form a carbon diffusion preventive film on the surface of this base material.

Examples of the carbon diffusion preventive film include a titanium film and a carbide film of a metal component of the above-mentioned heat-resistant metal material. The film thickness is usually 0.01
About 1 μm is sufficient. The film thickness is 0.01 μm
If it is less than the above range, the effect of preventing carbon diffusion becomes insufficient, while if the film thickness exceeds 1 μm, the adhesion between the base material and the carbon-based coating may be deteriorated. The film forming method is not particularly limited, but for example, a sputtering method, a vapor deposition method or the like is preferably used.

As the heat-resistant material constituting the base material,
Carbon materials such as graphite and amorphous carbon are also preferably used. The carbon material as the base material is advantageous in that it has excellent workability as compared with conductive ceramics and heat resistant metals.

By the way, the carbon material constituting the base material is not sufficiently resistant to plasma used in forming a carbon-based coating film described later and is easily worn. Therefore,
Until the surface of the base material is sufficiently covered with the carbon-based coating, the surface condition, shape, dimensions, etc. of the base material may change. In addition, when the carbon-based coating is formed, the carbon component excited by the plasma easily takes the same crystal structure as the crystal structure of the base material when deposited on the base material surface. When forming a carbon-based coating such as a diamond polycrystal, there is a possibility that a diamond structure will not be formed. Therefore, it is preferable to form an intermediate film (interlayer film) such as a titanium film in advance on the surface of the base material as in the case of using a heat resistant metal as the base material.

"C-X bond-introduced carbon-based coating" The C-X bond-introduced carbon-based coating covering at least a part of the substrate, for example, the surface, is, for example, a carbon-based coating formed by fluorine gas, chlorine gas or iodine. When exposed to halogen-based corrosive gases other than bromine, such as gas, or its plasma gas, it is fluorinated, chlorinated, or iodinated, and this carbon-based coating has a C—X bond (where X is selected from F, Cl, and I). One or two or more of the above mentioned) have been introduced.

The above-mentioned carbon-based coating is not particularly limited, but may be one or more selected from a diamond single crystal body, a diamond polycrystal body, diamond-like carbon, graphite and amorphous carbon. It is preferable to contain, for example, any one of diamond single crystal, diamond polycrystal, diamond-like carbon, graphite and amorphous carbon, or diamond polycrystal containing diamond-like carbon and / or carbon is suitable. Used for. These materials are
It is preferable because a film can be easily formed on the surface of the substrate by using a plasma CVD method, an ion plating method, or the like. Above all, a diamond single crystal body and a diamond polycrystal body are preferable because they have not only conductivity but also excellent abrasion resistance.

The diamond-like carbon and / or the diamond polycrystal containing carbon is as follows.
The diamond-like carbon and / or carbon is segregated between the diamond crystal grains or between the base material and the diamond crystal grains (grain boundaries).

The thickness of the above-mentioned carbon-based coating is not particularly limited, but is usually preferably in the range of 1 to 100 μm. The reason is that if the thickness is less than 1 μm, the surface of the base material is not completely covered and the oxidation resistance becomes insufficient, while if it exceeds 100 μm, the surface shape of the base material changes. However, there is a risk that defects may occur, for example, irregularities and grooves formed on the surface of the base material may be buried by the coating film. This is because it is not economical.

The method for forming such a carbon-based coating on the surface of the above-mentioned substrate is not particularly limited, but, for example, a chemical vapor deposition method such as a plasma vapor deposition method is used to form a dense film. Can be formed, and a carbon-based coating composed of a diamond single crystal body or a diamond polycrystal body can be formed. Examples of the raw material used for forming the carbon-based film include methane, ethane, propane, butane, carbon monoxide, carbon dioxide, alcohols, etc., which contain carbon atoms in the structure and are easily converted into vapor phase species. A carbon compound that can be used is used. As a plasma excitation source, microwave, DC glow discharge, DC arc discharge, high frequency,
A hot filament or the like is preferably used.

As the above chemical vapor deposition method, a microwave plasma CVD method is particularly preferably used. This microwave plasma CVD method is a known method that has already been disclosed, in which a substrate is placed in a plasma reaction chamber and microwaves are applied to the plasma reaction chamber,
In this method, a standing wave is formed in this chamber, and a source gas containing carbon atoms is decomposed and plasmatized on the surface of the substrate that has been heated in advance, and a carbon-based coating film is formed on the surface of the substrate. is there.

As the above-mentioned source gas containing carbon atoms,
Any compound containing a carbon atom and capable of easily forming a gas phase species may be used, and for example, a mixed gas of methane and hydrogen is preferable, and a mixture ratio of methane and hydrogen is preferably CH ₄ : 0.1. ˜10.0 v / v%, H ₂ : 99.9-9
A mixed gas of 0.0 v / v% is preferable because it can form a carbon-based coating film composed of a diamond single crystal body or a diamond polycrystal body, and an excess carbon component does not adhere to the inner wall of the reaction chamber.

The flow rate of the source gas is usually 1 to 500 scc
m, preferably 10 to 200 sccm. The reason is that if the flow rate of the raw material gas is less than 1 sccm, the reaction efficiency decreases, and the rate at the time of film formation decreases. On the other hand, if it exceeds 500 sccm, forced convection of gas occurs in the plasma reaction chamber, This is because the plasma cannot be kept stable. The reaction pressure is usually 7.5 × 10.
^-4 Pa to ⁴ Pa, preferably 7.5 x 10 ^-3 Pa to 1.
It is 5 Pa. When the reaction pressure is less than 7.5 × 10 ⁻⁴ Pa, for example, the film forming rate of a diamond single crystal body or a diamond polycrystalline body becomes slow, while when it exceeds ⁴ Pa, plasma disappears. is there.

Then, a C--F bond is introduced into the carbon-based coating. The carbon-based coating has C- on the outermost carbon atom.
Oxidation resistance can be imparted by introducing an X (where X is one or more selected from F, Cl and I) bond. As a method of introducing such a C—X bond, a base material coated with a carbon-based film is prepared by using nitrogen fluoride, carbon fluoride, fluorine gas, carbon tetrachloride, hydrogen chloride, hydrogen iodide, etc. other than bromine. The method of exposing to plasma containing a halogen element other than bromine, which is excited at a constant pressure in the presence of a gaseous substance containing a halogen element, can be exemplified.

Such surface modification of the carbon-based coating may be carried out by replacing the gas in the chamber with a fluorine-based gas immediately after the carbon-based coating is formed and generating plasma again. The base material coated with the system coating may be taken out of the system once, inspected and confirmed, and then separately performed.

As a method for generating a plasma excitation source used for this surface modification, any method such as microwave, direct current glow discharge, direct current arc discharge, and high frequency can be used, but the method is not limited to these methods. Any method may be used as long as plasma can be generated by electric discharge and the surface of the carbon-based coating can be modified. The reaction pressure is usually 7.5 × 10 ⁻⁴ Pa to ⁴ Pa, preferably 7.
It is 5 × 10 ⁻³ Pa to 1.5 Pa. Reaction pressure is 7.5
If it is less than × 10 ^-4 Pa, the effect of surface modification of the carbon-based coating is low, while if it exceeds ⁴ Pa, plasma becomes unstable. The reaction temperature is preferably 300 to 500 ° C. This is because when the reaction temperature is out of this range, the efficiency of surface modification is reduced.

The C—X bond-introduced carbon-based coating film thus formed has a volume resistivity value of about 10 ² Ωm to 10 ³ Ωm and is excellent in conductivity. Therefore, this C-
Even if the surface of the conductive base material is covered with the X-bond-introduced carbon-based coating, the conductivity of the base material is not significantly impaired. Therefore, when a material having good conductivity is used for the base material, the obtained coating-type heat-resistant and oxidation-resistant material becomes a material having conductivity, and this heat-resistant and oxidation-resistant material is applied to, for example, the body portion of the heating element. When applied, it is suitable as a heater material used under a high temperature oxidizing atmosphere.

[Second Embodiment] FIG. 1 shows a second embodiment of the present invention.
2 is a plan view showing the silicon carbide heater of the embodiment of FIG. 2, and FIG. 2 is a cross-sectional view taken along the line AA of FIG. 1. The silicon carbide heater (heating element) 1 is arranged in six directions from the center outward in the plane. Protruding substantially disk-shaped heater element (main body of heating element) 2
And electrodes 3 made of molybdenum provided on the respective tip portions of a pair of protrusions which are symmetrical with respect to the center of the heater element 2. This heater element 2 is manufactured using the heat and oxidation resistant material of the first embodiment, and the surface of the base material made of a silicon carbide sintered body is covered with a C—X bond-introduced carbon-based film. There is.

According to the silicon carbide heater 1 of this embodiment, since the heat resistant and oxidation resistant material of the first embodiment is used for the heater element 2 which is the main body portion of the heating element, this heater element 2 is chemically It becomes very stable and has excellent oxidation resistance even in a high temperature oxidizing atmosphere. Therefore, it is possible to provide the silicon carbide heater 1 having excellent heat resistance and oxidation resistance.

[Third Embodiment] FIG. 3 shows the third embodiment of the present invention.
FIG. 11 is a sectional view showing a pulse heater for manufacturing a semiconductor chip mounting board of the embodiment of FIG.
Includes a heating element 12, a base material 13 for insulating heat from the heating element 12, and an electrode 14 for energizing the heating element 12 to raise the heating element 12 to a predetermined temperature. . The heating element 12 is manufactured using the heat and oxidation resistant material of the first embodiment, and the surface of the base material made of a silicon carbide sintered body is covered with a C—X bond-introduced carbon-based coating. There is.

Adsorption holes 15 for adsorbing the semiconductor chips and adsorption holes 16 for adsorbing the heat transfer plate are formed on the heating element 12 and the base material 13 so as to penetrate them. The base material 13 is further formed with a plurality of cooling holes 17 for forcibly cooling the heating element 12 to lower the temperature. Lead wires 18 are connected to the electrodes 14 and 14, respectively.

In order to manufacture a semiconductor chip mounting board using this pulse heater 11, as shown in FIG.
First, a pulse heater in which the heat transfer plate 21 is fixed to the heating element 12 of the pulse heater 11 is prepared, and this pulse heater is arranged on the semiconductor chip 24 arranged on the substrate 22 via the conductive bonding material 23. While pressing the pulse heater against the pressure receiving plate 25, the substrate 22, the conductive bonding material 23, and the semiconductor chip 24 are heated by the heating element 12 via the heat transfer plate 21, and the conductive bonding material 23 is melted. .

Next, cooling air is sent to the cooling holes 17 to cool the heating element 12 and the heat transfer plate 21 to a predetermined temperature, for example, to the solidification temperature of the conductive bonding material 23 or less, and the conductive bonding material 23 is removed. After being solidified, the semiconductor chip 24 and the substrate 22 are bonded by the conductive bonding material 23.

According to the pulse heater of the present embodiment, the heat-resistant and oxidation-resistant material of the first embodiment is used for the heating element 12, so that the heating element 12 becomes chemically very stable and high temperature. It has excellent oxidation resistance even in an oxidizing atmosphere. Therefore, it is possible to provide a pulse heater having excellent heat resistance and oxidation resistance.

[0049]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 Commercially available average particle size is 1.1 μm.
An average particle diameter of 0.02μ obtained by vapor-phase synthesis of 95 parts by weight of β-type silicon carbide powder of m (first silicon carbide powder) using monosilane and methane as raw material gases by a plasma CVD method.
5 parts by weight of β-type silicon carbide fine powder of m (second silicon carbide powder) was added, dispersed in methanol, and further mixed by a ball mill for 12 hours, and this mixture was dried.

The dried mixture is then heated to an inner diameter of 210
mm graphite mold and filled with a hot press machine under an argon atmosphere at a pressing pressure of 400 Kg / cm ² ,
Pressure sintering was performed for 90 minutes under a sintering temperature of 2200 ° C. to obtain a disc-shaped silicon carbide sintered body. The density of the obtained silicon carbide sintered body was 3.22 g / cm ³ , and the volume specific resistance value was measured using a resistance measuring device equipped with a guard electrode. Specific resistance value is 8 × 1
It was 0 ^-2 Ωcm.

Next, the above-mentioned silicon carbide sintered body was placed in the atmosphere 8
After heat treatment at 00 ° C. for 15 hours to remove the carbon content on the surface, hydrofluoric acid treatment at 45 ° C. for 5 hours was performed on the hydrofluoric acid,
The SiO ₂ portion of the surface layer was dissolved to obtain a silicon carbide substrate. This silicon carbide substrate was placed in a plasma reaction chamber, and H ₂ gas containing 2 mol% CH ₄ was introduced into this chamber under the conditions of a substrate temperature of 900 ° C. and a reaction pressure of 0.6 Pa for 5 hours. While forming plasma with a microwave output of 600 W, a carbon-based coating film was formed on the silicon carbide substrate.

When the thickness of this carbon-based coating was observed with a scanning electron microscope (SEM), the thickness was uniform at 2 μm in both the central portion and the outer peripheral portion. Furthermore, analysis of the composition and structure of the carbon-based coating film in Raman spectroscopy, the half width of the Raman shift of diamond appearing at 1333 cm ^-1 (half-width) is 6 cm ^-1, 1550 cm
^-1 is a carbon-based coating composed of a high-quality diamond polycrystal having a Raman shift of diamond-like carbon centered at ^-1 and a Raman shift of diamond centered at 1333 cm ^-1 I _{sp 2 / sp3} of 0.1. It was

Next, the silicon carbide sintered body coated with the carbon-based coating composed of this diamond polycrystal is placed in the plasma reaction chamber, and 100% NF ₃ gas is added thereto for 20 minutes.
Atmospheric pressure of 7.6 while flowing at a flow rate of sccm
× and 10 ^-4 Pa, a high frequency power RF in this state 500
By treatment with plasma generated by applying W for 10 minutes (reaction temperature: 400 ° C.), a C—F bond is formed in the surface layer of the carbon-based coating composed of diamond polycrystal, and the heat-resistant and oxidation-resistant property of Example 1 is obtained. I obtained the material.

The coating structure of this carbon-based coating is ESCA (el
ectron spectroscopy for chemical analysis), the atomic ratio F / C of fluorine and carbon was 0.9.
It was confirmed that a C—F bond was formed on the surface layer of the coating. When the volume resistivity value was measured using the resistance measuring device equipped with the guard electrode, the volume resistivity value of this carbon-based coating was 4 × 10 ² Ωcm.

[Example 2] The β-type silicon carbide fine powder (second silicon carbide powder) used in Example 1 was pressure-fired under the same conditions as in Example 1 to obtain a disc-shaped carbonized material. A silicon sintered body was obtained. When the density of the obtained silicon carbide sintered body was measured,
3.2 g / cm ³ , and the volume resistivity value is 2 ×
It was 10 ^-2 Ωcm. Then, a carbon-based coating having a C—F bond was formed on the surface of this silicon carbide sintered body according to Example 1 to obtain the heat-resistant and oxidation-resistant material of Example 2.

Example 3 On the surface of a commercially available molybdenum metal plate, a titanium film (film thickness: 0.
1 μm), and this molybdenum metal plate coated with titanium was used as a base material. This titanium film is a carbon diffusion preventing film for suppressing the diffusion of carbon into the molybdenum metal plate. Then, according to Example 1, a carbon-based coating film having a C—F bond was formed on the titanium film to obtain a heat and oxidation resistant material of Example 3.

Example 4 The surface of a commercially available carbon material (amorphous carbon) was coated with a titanium film (film thickness: 0.1 μm) by the sputtering method, and this carbon material with a titanium film was used as a base material. Others were the same as in Example 1, and the heat-resistant and oxidation-resistant material of Example 4 was obtained.

"Evaluation" The heat resistance and oxidation resistance of Examples 1 to 4 were evaluated for the oxidation resistance and the surface condition after heat treatment on the surface on which the carbon-based coating was formed. As comparative examples, molybdenum (Comparative Example 1), high-density carbon (graphite: Comparative Example 2),
Using the aluminum nitride sintered body (Comparative Example 3) and the diamond-coated silicon carbide sintered body before the fluorination treatment in Example 1 (Comparative Example 4), the oxidation resistance and the surface state after the heat treatment were also obtained. It was evaluated together.

The evaluation methods of the oxidation resistance and the surface condition after the heat treatment are as follows. "Oxidation resistance" Place the sample in an infrared concentrator and set the pressure to 1.
In a 33 × 10 Pa, oxygen (100%) atmosphere, the temperature was raised to 600 ° C. at a temperature rising rate of 5 ° C./sec, and the sample was held at this temperature for 30 minutes for heat treatment.
The oxidation resistance (wear rate) was calculated by calculating the wear film thickness from the weight reduction amount of the sample, the density of the carbon-based coating, and the surface area of the sample, and dividing this wear film thickness by the heat treatment time. It should be noted that in Table 1, it is shown by "consumption rate".

"Surface condition after heat treatment" The surface condition after heat treatment was visually observed and the presence or absence of oxide phase formation was confirmed by X-ray diffraction. The evaluation results are shown in Table 1.

[0062]

[Table 1]

According to Table 1, in Examples 1 to 4, no consumption of the carbon-based coating film was observed, and no change was observed in the surface condition after the heat treatment. Was also found to have excellent oxidation resistance. On the other hand, in Comparative Examples 1 to 4, consumption of the carbon-based coating film was observed, and regarding the surface state after the heat treatment, generation of an oxide phase, peeling of the oxide film, generation of CO ₂ gas, etc. were observed. It became clear that the film quality was deteriorated. Therefore, it was found that the oxidation resistance in a high temperature oxidizing atmosphere was extremely poor.

[Embodiment 5] A heater element 2 as shown in FIGS. 1 and 2 is manufactured using the heat and oxidation resistant material of Embodiment 1, and further an electrode 3 made of molybdenum is attached to the silicon carbide heater 1. And This silicon carbide heater 1 was attached to an oxidation heating furnace and the applied voltage was kept constant at 5 A.
When the current was applied, the temperature of the surface of the silicon carbide heater 1 was raised at a rate of about 10 ° C./min, and after 80 minutes, it reached the set temperature of 800 ° C. Next, when this heating was continued for 10 hours, the silicon carbide heater 1 was not consumed at all, and no abnormality was recognized even after repeating this heating test 10 times.

[Embodiment 6] A heating element 12 as shown in FIG.
Was produced using the heat and oxidation resistant material of Example 1, and the pulse heater 11 was produced using this heating element 12. Next, as shown in FIG. 4, the heat transfer plate 21 is provided on the upper surface (lower surface in FIG. 4) of the heating element 12, and the semiconductor chip 24, the conductive bonding material 23, and the substrate 22 are interposed via the heat transfer plate 21. The semiconductor chip 24 and the substrate 22 are electrically conductively bonded to each other by heating and pressurizing the semiconductor chip 24 and the substrate 22 in the atmosphere by the heating element 12.
Bonded by.

The heating pattern is from room temperature to 450 ° C.
The temperature was raised in 2 seconds and the temperature was kept at 450 ° C. for 10 seconds to heat and melt the conductive bonding material 23, and then cooling air was blown from the cooling holes 17 to lower the temperature to room temperature. As the temperature dropped, the molten conductive bonding material 23 solidified and the bonding was completed. When the production of such a semiconductor mounting board was repeated 10,000 times in succession, the heating element 12 was not consumed at all.

[0067]

As described above, according to the heat-resistant and oxidation-resistant material of the present invention, a coating for covering at least a part of a base material made of a heat-resistant material is used as a main component of a part of carbon. Since the carbon is a carbon-based coating having a C—X bond (where X is one selected from F, Cl, and I), it has excellent acid resistance not only in heat resistance but also in a high temperature oxidizing atmosphere. It is possible to achieve chemical conversion.

Further, if any one of conductive ceramics, heat-resistant metal and carbon is used as the heat-resistant material, it goes without saying that excellent heat-oxidation resistance is exhibited even in a high temperature oxidizing atmosphere. It can also have excellent conductivity and can provide a heat resistant and oxidation resistant material at a low price.

According to the method for producing a heat-resistant and oxidation-resistant material of the present invention, a carbon-based coating is fluorinated by a chemical vapor phase method,
Chlorination treatment or iodination treatment is performed, and a part of carbon of the carbon-based coating is converted into C—X bond (where X is F, Cl,
Since carbon having one or more selected from I) is used, a carbon-based coating film having heat resistance and excellent oxidation resistance even in a high temperature oxidizing atmosphere can be formed inexpensively and efficiently. be able to.

According to the heating element of the present invention, at least the main body is made of the heat and oxidation resistant material of the present invention.
It is possible to provide at low cost a heating element which has excellent conductivity as well as heat and oxidation resistance in a high temperature oxidizing atmosphere.

[Brief description of drawings]

FIG. 1 is a plan view showing a silicon carbide heater according to a second embodiment of the present invention.

FIG. 2 is a cross-sectional view taken along the line AA of FIG.

FIG. 3 is a sectional view showing a pulse heater for manufacturing a semiconductor chip mounting board according to a third embodiment of the present invention.

FIG. 4 is a side view showing how a mounting board for a semiconductor chip is manufactured using a pulse heater according to a third embodiment of the present invention.

[Explanation of symbols]

1 Silicon carbide heater (heating element) 2 Heater element (main body of heating element) 3 electrodes 11 pulse heater 12 heating element 13 Base material 14 electrodes 18 lead wire 21 heat transfer plate 22 Substrate 23 Conductive bonding material 24 semiconductor chips 25 Pressure plate

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Mikio Konishi             28 Sumitomo Osaka, 6-6 Rokubancho, Chiyoda-ku, Tokyo             Inside Cement Co., Ltd. F-term (reference) 4K030 AA09 AA17 BA24 BA27 BA28                       CA02 CA05 DA02 FA01 HA04                       LA11                 4K044 AA01 AA13 AB10 BA18 BA20                       BB03 BC11 CA13 CA14

Claims (8)

[Claims] 1. A base material made of a heat-resistant material, and a coating film covering at least a part of the base material, wherein the coating film contains a part of carbon as a main component of carbon.
-X bond (where X is 1 selected from F, Cl and I)
A heat-resistant and oxidation-resistant material, characterized in that it comprises a carbon-based coating having one or more kinds. 2. The heat and oxidation resistant material according to claim 1, wherein the heat resistant material is any one of conductive ceramics, heat resistant metal, and carbon. 3. The interlayer film is formed between the base material and the carbon-based coating film.
The heat resistant and oxidation resistant material described. 4. The heat and oxidation resistant material according to claim 3, wherein the interlayer film is a carbon diffusion preventive film. 5. The carbon-based coating is subjected to a fluorination treatment, a chlorination treatment or an iodination treatment by a chemical vapor phase method so that a part of the carbon of the carbon-based coating is converted to C—X bond (however, , X is a carbon having one or more selected from F, Cl and I). The heat and oxidation resistant material according to any one of claims 1 to 4, wherein 6. The carbon-based coating comprises a diamond single crystal body, a diamond polycrystal body, diamond-like carbon,
The heat and oxidation resistant material according to claim 5, which contains one or more selected from graphite and amorphous carbon. 7. A method for producing a heat-resistant and oxidation-resistant material, comprising: a base material made of a heat-resistant material; and a carbon-based coating film covering at least a part of the base material. Fluorination treatment, chlorination treatment, or iodination treatment is performed by the phase method, and a part of carbon of the carbon-based coating is converted into C—X bond (where X is F, Cl, I).
1. A method for producing a heat-resistant and oxidation-resistant material, comprising: carbon having one or more selected from 8. A heating element, characterized in that at least a main body is made of the heat-resistant and oxidation-resistant material according to any one of claims 1 to 6.