JPH09227234A - Crucible for vapor depositing metal nickel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crucible used for forming a vapor-deposited film of metal Ni, etc., and having such superior characteristics as high corrosion resistance and high electric conductivity. SOLUTION: This crucible is made of composite ceramics contg. 80-95wt.% TiB2 , 2.5-17.5wt.% CrB and 2.5-17.5wt.% TiC and having 1×10<-5> -8×10<-5> Ω.cm specific resistance. The ceramics preferably has <=5% open pore volume and 5-15% closed pore volume. This crucible is produced by compacting prescribed starting materials constituting the ceramics in a crucible shape and sintering the resultant compact under atmospheric pressure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crucible for vapor-depositing Ni (nickel) metal, and more particularly to a vapor-deposited film of a high-quality Ni metal simple substance or a Ni alloy containing Ni as a main component, which is used in the electronics and optical industries. The present invention relates to a crucible for vapor deposition of Ni metal, which is used for an electron beam vapor deposition apparatus, a plasma vapor deposition apparatus, and the like, and has high corrosion resistance and high conductivity.

[0002]

2. Description of the Related Art Various thin films are widely used in the fields of electronic industry and optical industry. However, since the final characteristics of the product obtained are greatly affected by the properties of the thin film to be formed, thin film formation is currently underway. Technology is being actively developed. As a typical thin film forming method by chemical vapor deposition, there are an electron beam vapor deposition method and a plasma vapor deposition method. The electron beam evaporation method is a method in which an evaporation material is heated and evaporated by an electron beam in a vacuum and condensed on a substrate. The plasma vapor deposition method is a method in which an electric field is applied in a vacuum to cause discharge to form plasma, and ions or radicals are generated from a vapor deposition material to deposit a product on a substrate. N by these methods
In order to form a thin film of an i metal alone or a Ni alloy containing Ni as a main component, it is necessary to heat and melt the Ni metal or Ni alloy as a raw material by electron beam or plasma irradiation to evaporate the molten metal. A holding crucible for vapor deposition is used.

The vapor deposition crucible used for the above-mentioned electron beam or plasma irradiation is required to have excellent conductivity. This is because if it is non-conductive or low-conductivity, the molten metal for vapor deposition held in the crucible is charged by the electron beam or plasma irradiation and cannot be evaporated smoothly. In order to prevent electrification of the molten metal in the crucible, it is said that it is desirable to manufacture the crucible using a material having a specific resistance of several hundreds μΩ · cm or less. Generally, for the crucible material for Ni metal vapor deposition, A metal material having a high melting point and a conductive metal such as graphite, W (tungsten), Mo (molybdenum), or Ta (tantalum) is used. However, these metal materials have a problem because they have low corrosion resistance to molten Ni. For example, when a graphite crucible is used, Ni metal alone or Ni which is melted and held in the crucible is used.
A large amount of carbon is eluted from the crucible into a Ni alloy containing Ni as a main component (hereinafter, simply referred to as Ni metal or the like), and impurities such as Cr, Mo, Fe, Cu, and Ti contained in the Ni metal or the like (hereinafter, simply There is a possibility that metal carbides may be generated by reacting with impurities such as Cr) to reduce the purity, while the graphite crucible conversely infiltrates impurities such as Cr contained in Ni metal, etc., and the composition changes. Therefore, the crucible may be cracked during heating or cooling. Even in a crucible containing W, Mo, Ta or the like as a main component, impurities such as Cr contained in Ni metal or the like and the constituent materials W, Mo, Ta or the like of the crucible easily react with each other to easily form an alloy, and the crucible is made of graphite. As with the crucible, there was a problem with corrosion resistance.

Due to these problems as described above, various materials for the Ni vapor deposition crucible have been conventionally studied and proposed in order to improve the corrosion resistance and the like. For example, JP
Japanese Patent Publication No. 157181 proposes a crucible in which a graphite crucible is coated with a diboride such as TiB ₂ which is a corrosion resistant material. However, when the vapor deposition test is repeatedly performed by electron beam vapor deposition or plasma vapor deposition using this diboride-coated graphite crucible, the heating or cooling rate in the vapor deposition apparatus is very fast, and therefore the coating layer diboride is caused by the difference in thermal expansion. May peel off. Also, Al
_The crucible mainly composed of ₂ O ₃ , BN, Si ₃ N ₄ and MgO proposed in Japanese Patent Publication No. 57-3627 is compared with the above-mentioned high melting point metals such as graphite, W, Mo or Ta. Although it is excellent in corrosion resistance, it is not practical for mass production because it is necessary to ground the vapor-deposited metal in the crucible and the vapor-deposition apparatus because it is insulating. In addition, Al ₂ O ₃ and MgO
The crucible containing as a main component has a low thermal shock resistance, and the crucible is easily cracked during the vapor deposition operation, which has been a problem. Furthermore, as a material for a metal vapor deposition container, Japanese Examined Patent Publication No. 52-969.
The 0 JP manufacturing method of a three-component material BN-TiB ₂ -TiN is proposed, the material and the manufacturing method mainly composed of BN-TiB ₂ -AlN is proposed in JP-B-58-2260 ing. These improve corrosion resistance by combining a conductive material such as TiB ₂ or TiN with an insulating material such as BN or AlN. However, BN-TiB ₂ -T
The ternary material of iN and BN—TiB ₂ —AlN generally has a specific resistance of several thousand μΩ · cm, and is made of Ni metal or Ni by electron beam evaporation method or plasma evaporation method.
When the alloy is vapor-deposited, the alloy is likely to be charged and the vapor deposition may not be stable. Further, since these three-component materials are formed of the conductive material and the insulating material as described above, the specific resistance varies so much that the electron beam and plasma discharge are not stable. Therefore, there is a problem that vapor deposition cannot be performed stably, and that local heating is likely to occur and cracking is likely to occur.

[0005]

As described above, various studies have been made on the crucible for vapor deposition of metals from the viewpoint of the material, but none of them can satisfy both the corrosion resistance and the electrical conductivity. There is a problem for practical application. Further, when a crucible is manufactured using the above-mentioned various materials, since sintering generally needs to be performed using a hot pressing method, only a simple shape such as a cylindrical shape can be produced, and a diamond grindstone or the like after sintering. Since it is necessary to process the sintered body using the above method, not only the cost is increased, but also residual stress and microcracks during processing are likely to remain in the obtained vapor deposition crucible, which also causes the crucible to crack during use. On the other hand, the applicant proposed a refractory for molten metal containing TiB ₂ as a main component in JP-A-6-221768 and JP-A-1-278956. The inventors diligently studied to apply this refractory, particularly the latter refractory for molten metal composed of TiB ₂ -metal boride-titanium carbide to a crucible for vapor deposition of Ni. As a result, by specifying the blending ratio of the above three components, the specific resistance can be made to be a predetermined value, the problems of the above Ni vapor deposition crucible can be solved, and it is highly industrially practical, in particular, corrosion resistance and conductivity. It is possible to obtain a material that satisfies both properties, and unlike conventional materials, there is no need for hot press sintering, and since the crucible shape can be formed by the atmospheric pressure sintering method, residual stress and micro cracks can be formed. The present invention has been completed by finding that the problem of can be solved.

[0006]

According to the present invention, 80 to 95% by weight of titanium diboride (TiB ₂ ), 2.5 to 17.5% by weight of chromium boride (CrB) and titanium carbide (Ti) are used.
C) A crucible for vapor deposition of Ni metal, characterized in that the crucible contains 2.5 to 17.5% by weight and is formed of a composite ceramic having a specific resistance of 1 to 8 × 10 ⁻⁵ Ω · cm. Will be provided. In the crucible for vapor deposition of Ni of the present invention,
It is preferable that the ceramic has an open porosity of 5% or less and a closed porosity of 5 to 15%. Further, the crucible of the present invention can be obtained by forming a predetermined raw material constituting the ceramics into a crucible shape and sintering it under normal pressure.

The present invention is constructed as described above, and the crucible for vapor deposition of Ni contains TiB ₂ as a main component and CrB and TiC.
Is formed of a composite ceramic containing each predetermined amount of
TiB ₂ , CrB and TiC of each component are non-reactive with Ni metal and impurities such as Cr and Mo in Ni metal, and TiB _{2 of} the main component has high conductivity, Since these three components coexist uniformly in a predetermined ratio, it is possible to sufficiently have both corrosion resistance and conductivity, which cannot be obtained by the conventional vapor deposition molten metal material, and to stably provide the Ni melt in the crucible. And has a predetermined specific resistance evenly, the electron beam and plasma discharge are stable, and a uniform vapor deposition process can be performed. Further, since the above three-component-containing composite ceramics constituting the crucible has predetermined open and closed pores, in combination with the non-reactivity of each component, the corrosion resistance is significantly excellent, and the thermal shock resistance is also excellent. A stable vapor deposition process can be performed without fear of damage or cracking.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The composite ceramics constituting the Ni vapor deposition crucible of the present invention are TiB ₂ , CrB and TiC.
Containing the following three components: TiB ₂ 80-95% by weight, CrB
It is adjusted in the range of 2.5 to 17.5 wt% and TiC 2.5 to 17.5 wt%. The content of TiB ₂ is 80% by weight
This is because if it is below, the specific resistance increases, the predetermined specific resistance cannot be maintained, and the corrosion resistance also decreases. On the other hand, when the content is 95% by weight or more, sufficient properties, particularly sufficient strength as a crucible cannot be obtained by the atmospheric pressure sintering method. This is because if the CrB content is 2.5% by weight or less, the corrosion resistance decreases due to CrB, and if it is 17.5% by weight or more, the specific resistance increases and the conductivity decreases. Further, when the content of TiC is 2.5% by weight or less, excellent properties of corrosion resistance and high melting point due to TiC are deteriorated, and when it is 17.5% by weight or more, specific resistance is increased and conductivity is decreased. This is because.

Each component of the composite ceramics of the present invention is non-reactive with Ni metal, and is contained in a Ni metal simple substance or a Ni alloy containing Ni as a main component (hereinafter, simply referred to as Ni metal or the like). It is also non-reactive with impurities such as Cr contained therein, and in particular, TiB ₂ is completely inactive with respect to the above impurities. Therefore, the crucible formed of ceramics containing TiB ₂ as a main component is excellent in corrosion resistance, is free from contamination of Ni metal or the like melted and held in the crucible, is stably vapor-deposited, and has a predetermined homogeneity. A vapor-deposited film such as a Ni metal is formed. The melting points of the three components of the above composite ceramics are 2790 ° C. for TiB _{2 and} 210 for CrB, respectively.
0 ° C., TiC is 3257 ° C., and the ceramic of the present invention formed from these three components has a melting point of metallic Ni of 145
It has a higher melting point than 5 ° C. and has sufficient heat resistance to hold a molten liquid such as Ni metal. Further, TiB ₂ which is the main component of the ceramics of the present invention has a room temperature resistivity of 9 × 10 5.
^-6 Ω · cm, which is remarkably excellent in conductivity, while CrB and TiC are 4.6 × 10 ⁻⁵ Ω · cm and 1 × 1 respectively.
It is 0 ⁻⁴ Ω · cm, and the composite ceramic formed of TiB ₂ , CrB and TiC has lower conductivity than TiB ₂ alone. However, as compared with the case where an insulating material is used as in the prior art, each component is a conductive substance as described above and forms a homogeneous composite ceramics, so that the specific resistance is about 1 to 8 × in the entire crucible. 10 ^-5 Ω · cm
Therefore, it is excellent in conductivity and can prevent electrification of molten Ni, has stable discharge property with respect to electron beam and plasma, and can perform Ni deposition treatment stably.

The composite ceramics of the present invention can be formed in the same manner as the titanium diboride ceramics proposed in the above-mentioned Japanese Patent Application Laid-Open No. 1-278956. The main component is TiB ₂ powder and Cr (chromium). It is a sintered body obtained by mixing powder and C (carbon) powder in a predetermined manner and sintering, and TiB ₂ reacts with Cr and C at the time of sintering to form C at the grain boundary.
rB and TiC are formed and deposited to bond the TiB ₂ particles and densify. Therefore, the composite ceramic of the present invention is homogeneous and has high strength. Further, the composite ceramic of the present invention,
A predetermined amount of Cr powder and C powder was added to the main component TiB ₂ powder, and finally, TiB ₂ was 80 to 95% by weight, CrB was 2.5 to 17.5% by weight, and TiC was 2.
C to obtain a composition ratio in the range of 5 to 17.5% by weight.
It can also be obtained by adding the required amounts of rB powder and TiC powder and sintering. Conventionally, in order to obtain a molded product with sufficient mechanical strength from a composite ceramic composed of multiple components, hot press molding had to be performed. However, in the present invention, the Ni vapor deposition crucible formed of the above-mentioned composite ceramics is subjected to mold molding or CIP molding, and if necessary, the obtained molded body is processed, and thereafter sintered under normal pressure to obtain a desired shape. A shaped and high-strength sintered molded body can be manufactured. Therefore, it is not necessary to process the sintered body, and there is no influence of microcracks, residual stress, etc. due to the mechanical processing after the conventional hot press sintering. Therefore, the Ni metal vapor deposition crucible of the present invention is not only excellent in performance but also industrially practical in terms of manufacturing cost. The reason why a sufficiently high strength can be achieved as a crucible by pressureless sintering is that the Cr powder and C powder as raw materials react with TiB ₂ during sintering as described above, and the sintered body is densified.

The composite ceramic forming the crucible for vapor deposition of Ni of the present invention has the characteristics of corrosion resistance and conductivity due to the above-mentioned constituents, and at the same time, has an open porosity of 5% or less and a closed porosity of 5 or less. It is preferably about 15%. By setting the open porosity to 5% or less, Ni metal or the like hardly infiltrates into the pores even if heating and cooling are repeated, so that the composite ceramics constituting the crucible of the present invention and the Ni metal or the like having a large coefficient of thermal expansion are formed. It does not crack due to the difference in thermal expansion and has excellent impact resistance. When the open porosity exceeds 5%, Ni metal or the like gradually infiltrates into the pores by repeating heating and cooling, and the crucible may crack due to the difference in thermal expansion between the composite ceramics and Ni metal or the like. . On the other hand, the closed porosity is difficult to be less than 5% at the present time in normal pressure sintering used for preparing the composite ceramic of the present invention, and if the closed porosity is 5 to 15%. The crucible has sufficient strength, is excellent in thermal shock resistance, and is not damaged even when the temperature rises or falls rapidly, so that the Ni vapor deposition treatment can be stably performed. When the closed porosity exceeds 15%, the strength becomes particularly low, and it becomes difficult to use it as a crucible. In the present invention,
The open pores refer to portions of the ceramic voids that communicate with the outside air, and the closed pores refer to portions of the ceramic voids that do not communicate with the outside air.

The porosity of the composite ceramics of the present invention is determined by the above-mentioned densification at the time of sintering as TiB ₂ powder, C
It can be adjusted by controlling the purity and average particle size of the r powder and the C powder, and the CrB powder and the TiC powder that are added as necessary, and the sintering temperature. In order to prepare the composite ceramics of the present invention, TiB ₂ powder, Cr powder, CrB powder and TiC powder as raw material powders each having a purity of 98% or more and an average particle size of 1 to 15 μm, preferably 1 to 12 μm, and a maximum particle size. Diameter 30 μm, preferably 2
It is preferable to use one having a thickness of 5 μm. Further, as the carbon powder, for example, carbon black can be used, the purity is 99% or more, and the average particle size is 10 to 100 n.
m, preferably 10 to 50 nm, maximum particle size 150 nm,
It is preferable to use one having a thickness of 100 nm.
TiB ₂ powder, Cr powder, to the 1~15μm an average particle size of CrB powder and TiC powder, the average particle size, respectively is less than 1 [mu] m, TiB ₂ particles, Cr particles, Cr
This is because the surface oxidation and aggregation of the B powder and the TiC powder become remarkable and the sinterability decreases. Also, TiB ₂ powder, C
This is because if the average particle size of the rB powder and the TiC powder exceeds 15 μm, the driving force for sintering becomes small and the sinterability deteriorates. This is because if the average particle size of the Cr powder exceeds 15 μm, coarse particles of CrB having many cracks in the particles are generated in the sintered body, and the strength of the sintered body is reduced. Further, C
The average particle size of the powder is set to 10 to 100 nm. When the average particle size is less than 10 nm, the surface oxidation and aggregation of the carbon particles become remarkable and the sinterability decreases, while the average particle size is 100 nm.
This is because if the thickness exceeds nm, the driving force for sintering becomes small and the sinterability deteriorates. The above raw material TiB ₂ powder, Cr powder,
The maximum particle size of CrB powder and TiC powder is set to 30 μm. When the maximum particle size exceeds 30 μm, the driving force for sintering becomes small and the sinterability decreases, and the particles remain in the sintered body as coarse particles. This is because, as a result, the strength of the sintered body is reduced. The maximum particle size of C powder is 15
The reason for setting the thickness to 0 nm is that the driving force for sintering becomes small, the sinterability decreases, and the coarse C powder remains in the sintered body, resulting in a decrease in the strength of the sintered body. .

TiB having the average particle size adjusted as described above
₂ , Cr and C and, if necessary, CrB and TiC raw material powders are mixed so as to have a component ratio of the composite ceramic of the target sintered body. If necessary, a mixed powder prepared by mixing the raw material powders and the like is wet pulverized by a ball mill or the like, and then a commonly used binder or dispersant is added as necessary for granulation. Then, the desired crucible shape, usually 20 to
After die molding or CIP molding at a pressure of 150 MPa and further processing if necessary, pressureless sintering is carried out in an inert atmosphere such as argon gas or in a non-oxidizing atmosphere such as hydrogen gas. Sintering is 1700-2100 ° C, preferably 1800
It is preferable to carry out at ˜2000 ° C. Sintering temperature is 170
When the temperature is lower than 0 ° C, the porosity is out of the above range, so that the crucible strength is lowered. Further, when the temperature exceeds 2100 ° C., the generated CrB and the CrB added as necessary are thermally decomposed and a predetermined composite ceramic cannot be obtained.
The Ni vapor deposition crucible of the present invention is a crucible formed for the purpose of melting and vapor depositing a Ni metal simple substance or a Ni alloy containing Ni as a main component, but a reaction gas such as oxygen or nitrogen in the vapor deposition apparatus. , Ni metal alone or Ni
It can also be used as a crucible for vapor-depositing a Ni alloy containing as a main component by changing it to an oxide or a nitride. Further, naturally, it can also be used for vapor deposition of a metal containing a component other than Ni as a main component. The composite ceramic forming the crucible of the present invention has excellent thermal shock resistance and can prevent the crucible from cracking due to a rapid change in temperature during electron beam vapor deposition or plasma vapor deposition. The life of the crucible can also be improved by using it as a floor plate for installing a vapor deposition crucible in a copper hearth of an apparatus or the like.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in more detail with reference to embodiments. However, the present invention is not limited by the following examples. (Preparation of crucibles) Examples 1-2 TiB ₂ powder (purity 98% or more, average particle size 8.0 μm,
Maximum particle size 25 μm), Cr powder (purity 99% or more, average particle size 6.0 μm, maximum particle size 20 μm), carbon powder (purity 99.5% or more, average particle size 30 nm, maximum particle size 120 n
m), CrB powder (purity 98.5% or more, average particle size 6.
5 μm, maximum particle size 20 μm) and TiC powder (purity 9
8.5% or more, average particle diameter 5.5 μm, maximum particle diameter 18 μ
m) is a reaction that proceeds according to the following reaction formula (1),
The obtained sintered body was TiB ₂ , CrB and T shown in Table 1.
The respective blending amounts were calculated and blended to obtain a mixed powder so that the composition ratio of iC was obtained. In Example 1, only the raw material powders of TiB ₂ , Cr and C were blended to prepare a mixed powder, and in Example 2, the same Ti powder was used.
B _2, were mixed Cr and C, further, was added a predetermined amount of CrB and TiC powders for component adjustment. TiB ₂ + Cr + C (+ CrB + TiC) ➝TiB ₂ + CrB + TiC (1) The mixed powder was wet pulverized using a ball mill, a binder and a dispersant in a predetermined amount were added, and the mixture was granulated using a spray dryer. The granulated powder was used to fill a crucible molding die and pressure-molded at 50 MPa. Next, the obtained molded product is degreased to remove the binder, the dispersant, the lubricant and the like by heating, and then 190 in a pressureless state in an argon gas atmosphere.
Hold at 0 ° C. for 2 hours, and have the shape shown in FIG. 1 containing TiB ₂ as a main component, outer diameter (D) 30 mmφ, inner diameter (d) 24 mm
φ, outer bottom radius of curvature (R) 7 mm, inner bottom radius of curvature (r) 5.5 mm 3 crucibles for Ni metal deposition respectively
Each was produced.

Comparative Example 1 Three crucibles having the component compositions shown in Table 1 were prepared in exactly the same manner as in Example 1 except that TiB ₂ powder having an average particle size of 18 μm and a maximum particle size of 42 μm was used.

Comparative Example 2 Components shown in Table 1 in the same manner as in Comparative Example 1 except that Cr powder having an average particle size of 22 μm and maximum particle size of 45 μm and C powder having an average particle size of 50 nm and maximum particle size of 200 nm were used. Three crucibles having the composition were prepared.

Comparative Examples 3 to 7 Crucibles 3 were prepared in the same manner as in Example 2 except that the raw material powders were adjusted so as to have the composition shown in Table 1.
Each was produced.

(Characteristics of Crucibles Made of Composite Ceramics) As a result of crushing a part of one crucible having each composition obtained in the above-mentioned Examples and Comparative Examples and identifying the crystal phase by powder X-ray diffraction method, Cr powder and C powder of raw material powder were not recognized, and T powder
Only iB ₂ , CrB and TiC were identified. Also, I
Elemental quantitative analysis was carried out by the CP (Argon Plasma Emission Spectroscopy) method and the atomic absorption spectrometry, and the results are shown in Table 1. Furthermore, the open porosity is measured by the Archimedes method,
After measuring the true specific gravity using an auto pycnometer, the closed porosity was calculated by the following formula (2) and shown in Table 1. Closed porosity (%) = 100−bulk specific gravity / true specific gravity × 100 (2) About 20 mmφ × 3 mm in diameter from the bottom of the obtained crucible.
Four-probe method resistivity meter (Mitsubishi Yuka Co., Ltd.)
The specific resistance Ω · cm was measured by using a product, manufactured by Loresta AP. The results are shown in Table 1.

[0019]

[Table 1]

(Crucible evaluation by Ni deposition test)
Each of the remaining crucibles was placed in a water-cooled copper hearth of an electron beam vapor deposition apparatus as shown in the schematic cross-sectional explanatory view of FIG. 3, and Ni metal (purity 99.99 was obtained under the conditions of a voltage of 10 kV and an output of 18 kW. %) Was repeatedly deposited on the glass substrate. With respect to each crucible after the vapor deposition test, the following evaluation items were measured as follows. The results are shown in Table 2. Corrosion resistance: Regarding the reaction between the inner surface of the crucible and the interface with Ni, the presence or absence of reaction products, the amount of erosion and the amount of infiltration were confirmed by a reflection microscope. Impurity amount: The amount of impurities in Ni remaining in the crucible after completion of vapor deposition was measured by atomic absorption spectrometry after acid dissolution. Life: Repeated vapor deposition process under the above vapor deposition conditions,
The life end is defined as the time when vapor deposition cannot be performed under the same conditions due to cracking of the crucible or reaction between the crucible material and Ni, and the number of tests up to that point is shown. In this case, the crucible obtained in Comparative Example 2 could be vapor-deposited twice, but the specific resistance was high and vapor deposition was difficult to stabilize. Ni vapor deposition film thickness distribution: The distribution of the Ni vapor deposition film thickness on the glass substrate immediately before the life end was measured using an ultrasonic flaw detector, and the thickness variation was shown in%.

(Durability Test) Further, each crucible obtained in Example 1 was placed in a Cu hearth of an electron beam vapor deposition apparatus similar to that used in the vapor deposition test, and Ni metal was not placed in the crucible. The operation of irradiating the electron beam for 20 seconds under the same condition, and leaving it as it is for 10 minutes after the irradiation was repeated until the crucible was damaged (broken).
As a result, it withstood repeated vapor deposition conditions up to eight times.

Comparative Examples 8 to 9 The outer diameter of the shape shown in FIG.
A crucible of an upper opening cylindrical container having a height of 25 mm and a bottom thickness of 5 mm was made of Mo and graphite as in the conventional method. The open porosity, the closed porosity and the specific resistance were measured in the same manner as in Example 1 and shown in Table 1. Further, each evaluation item was confirmed and measured in the same manner as in Example 1, and the results are shown in Table 2.

[0023]

[Table 2]

After the vapor deposition test, the crucibles of Example 1, Comparative Example 8 and Comparative Example 9 were each cut in the vicinity of the center and then polished and lapped. The enlarged cross-sectional views obtained by observing the cross-section with a microscope (× 5) are shown in FIG. 4 (a), FIG. 4 (b) and FIG. 4 (c), respectively. As a result, in FIG. 4, the crucible of Example 1 of the present invention hardly erodes, the crucible wall 1 retains the original shape, the Ni metal 2 does not infiltrate, and the deposition of Ni on the inner surface does not occur. It can be seen that it is observed. On the other hand, in the Mo crucible and the graphite crucible, it can be seen that Ni is infiltrated into the thickness of the crucible at the same time as the bottom is eroded.

Comparative Examples 10 to 12 Al ₂ O ₃ having a high purity of 99% or more and a theoretical density ratio of 98% or more, and a high purity product of 99% or more and a theoretical density ratio in the same shape as in Example 1. 98% or more of MgO and BN-TiB ₂ -proposed in Japanese Patent Publication No. 58-2260.
AlN material (BN (boron nitride) 45% by weight, TiB ₂ 4
Crucibles were prepared by a hot pressing method so as to have 5% by weight and 10% by weight of AlN (aluminum nitride), and were tested for durability in the same manner as the durability test of the crucible of Example 1 above. The results are shown in Table 2.
In addition, between these three types of crucibles and the Cu hearth, grounding was performed using a thin wire made of W and having a diameter of 1 mmφ.

As is clear from the above Examples and Comparative Examples, the crucible for vapor deposition of Ni containing TiB ₂ as a main component of the present invention has good conductivity, excellent thermal shock resistance and corrosion resistance and is suitable for vapor deposition of Ni. It can be seen that the Ni vapor deposition film having no variation can be obtained in the case. It is also found that it has high durability and can be repeatedly used even under severe conditions such as electron beam. On the other hand, even if it is a TiB ₂ -based ceramic, if it is different from the composite ceramic composition of the present invention,
It can be seen that the strength is insufficient, the specific resistance is increased and the life is shortened, and the life is shortened due to uneven film thickness distribution or infiltration. Further, it can be seen that in the crucible prepared by the conventional method, the Ni vapor deposition film obtained has low uniformity and is eroded and has low durability.

[0027]

EFFECT OF THE INVENTION The crucible for vapor deposition of Ni formed of the composite ceramics containing TiB ₂ as a main component of the present invention has excellent conductivity, and therefore Ni or Ni alloy containing Ni as a main component is melted and held in the crucible. Is not charged, has excellent corrosion resistance to molten Ni metal, etc., and has high thermal shock resistance, and can perform stable Ni vapor deposition treatment, and the formed Ni vapor deposition film is uniform and good. Become.
In addition, the Ni vapor deposition crucible of the present invention can be manufactured at a low cost in a desired shape by an atmospheric pressure sintering method, and has a longer life than conventional ones, and can provide an excellent vapor deposition film. Extremely useful.

[Brief description of drawings]

FIG. 1 is an explanatory cross-sectional view of a Ni vapor deposition crucible used in an example of the present invention.

FIG. 2 is an explanatory sectional view of a crucible used in a comparative example of the present invention.

FIG. 3 is a schematic cross-sectional explanatory view of a water-cooled copper hearth electron beam apparatus of an electron beam vapor deposition apparatus used in an embodiment of the present invention.

FIG. 4 is an enlarged cross-sectional view of each crucible after being used for crucible evaluation by Ni vapor deposition test in Examples and Comparative Examples of the present invention (×
5), (a) is an enlarged view of the cross section of the composite ceramic crucible of the present invention (b) is an enlarged view of the Mo cross section of the crucible (c) is an enlarged view of the cross section of the graphite crucible

[Explanation of symbols]

 1 Crucible wall 2 Ni metal

Front Page Continuation (72) Inventor Taiji Okiyama No. 1 Ogakie Nanto Fuji, Kariya City, Aichi Toshiba Cera Mix Co., Ltd. Kariya Factory

Claims (3)

[Claims] 1. Titanium diboride (TiB ₂ ) 80-95
% By weight, chromium boride (CrB) 2.5 to 17.5% by weight, titanium carbide (TiC) 2.5 to 17.5% by weight, and specific resistance is 1 to 8 × 10 ^{−. A} crucible for vapor deposition of Ni metal, which is formed of a composite ceramic having a resistance of ⁵ Ω · cm. 2. The crucible for vapor deposition of Ni metal according to claim 1, wherein the ceramic has an open porosity of 5% or less and a closed porosity of 5 to 15%. 3. The crucible for vapor deposition of Ni metal according to claim 1, wherein a predetermined raw material forming the ceramics is formed into a crucible shape and is sintered under normal pressure.