KR100997068B1 - Magnesium oxide for vapor deposition - Google Patents

Abstract

(Problem) Provided is a magnesium oxide vapor deposition material which can be advantageously used for forming a magnesium oxide film useful as a protective film for a dielectric layer of an alternating current plasma display panel by an electron beam vapor deposition method.

(Solution means) The magnesium oxide vapor deposition material containing the metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent in 0.01-6 mol%. Alternatively, the alkaline earth metal oxides other than magnesium oxide and the metal oxides having any valence of trivalent, tetravalent or pentavalent of the metal elements are respectively 0.005 mol% or more in terms of the amount of metal elements, and the total amount thereof is a metal source. Magnesium oxide vapor deposition material containing so that it may become 6 mol% or less in conversion in small quantity.

Description

Magnesium Oxide Evaporation Material {MAGNESIUM OXIDE FOR VAPOR DEPOSITION}

TECHNICAL FIELD This invention relates especially to the vapor deposition material for magnesium oxide film formation useful as a protective film of the dielectric layer of an AC plasma display panel.

In an AC plasma display panel (AC type PDP), it is common to form a protective film on the dielectric layer surface in order to protect the dielectric layer on the electrode surface from ion bombardment (sputtering) by plasma. Magnesium oxide films are widely used as protective films for dielectric layers. The electron beam vapor deposition method which is a method of evaporating a vapor deposition material by irradiation of an electron beam and depositing on a gas is widely used for formation of this magnesium oxide film. As a vapor deposition material, a magnesium oxide sintered body (polycrystalline magnesium oxide) obtained by sintering a single crystal of magnesium oxide (electrolytic magnesium oxide) or magnesium oxide powder is used.

In order to lower the drive voltage of the AC type PDP, the protective film (magnesium oxide film) of the dielectric layer preferably has a high emission efficiency of secondary electrons, that is, a low work function (minimum energy for one electron to be emitted to the outside). Do.

As a means for solving this problem, the method of introducing a specific metal oxide into a magnesium oxide film is examined.

Patent Literature 1 discloses a metal oxide formed by using a magnesium oxide sintered body containing a metal oxide having a valence of a metal element of any one of trivalent, tetravalent or pentavalent (hereinafter may be simply referred to as a metal oxide). It is described to use a magnesium oxide film containing 0.1 to 20 mol% as a dielectric layer protective film for AC type PDP. And as an example of the metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent, aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel , Oxides of cerium, neodymium, samarium, europium, gadolinium, and dysprosium.

According to the description of the Patent Document 1, the secondary electron emission efficiency of the magnesium oxide film in which the valence of the metal element is 3 to 5 valent metal oxide is improved is a metal element substituted with magnesium element (ion). This is because (ion) forms a donor level between the energy gaps of magnesium oxide. In addition, Patent Document 1 discloses that a basic magnesium carbonate pentahydrate and iron oxide are mixed at a predetermined ratio, put into a mold, and press-molded, and then pellets formed by sintering pellets formed by firing in the air into small lumps are used as evaporation materials. Although the magnesium oxide protective film in which the iron oxide was solid-dissolved by the vapor deposition method was described, it does not mention the iron oxide concentration in a pellet (small lump).

Patent Literature 2 includes a magnesium oxide sintered body in which 0.5 to 50% by volume of alkaline earth metal oxides other than magnesium oxide (hereinafter may be simply referred to as alkaline earth metal oxides) or alkaline earth metal oxides and rare earth metal oxides are contained. It is described to use a magnesium oxide film containing an alkaline earth metal oxide formed by using a magnesium oxide sintered body as a dielectric layer protective film of an AC type PDP. And as examples of alkaline earth metal oxides, calcium oxide, strontium oxide and barium oxide are described.

(Patent Document 1) Japanese Patent Application Laid-Open No. 11-339665

(Patent Document 2) Japanese Unexamined Patent Publication No. 2000-290062

Although the magnesium oxide protective film which melt | dissolved the metal oxide whose valence of the metal element as disclosed in patent document 1 is 3-5 mol in the concentration range of 0.1-20 mol% is excellent from a viewpoint of secondary electron emission efficiency, According to the review, there are the following problems.

When basic magnesium carbonate pentahydrate is used as a raw material of magnesium oxide of a vapor deposition material, since carbon dioxide gas is generated at the time of baking, there exists a problem that a bubble is likely to generate | occur | produce inside a vapor deposition material. If bubbles are present inside the vapor deposition material, splashes are likely to occur due to thermal shock during electron beam irradiation.

In addition, the metal oxide concentration of the magnesium oxide film formed by vapor deposition tends to be lower than the metal oxide concentration of the vapor deposition material (particularly, in metal oxides having a higher boiling point than magnesium oxide, such as zirconium oxide, the tendency is increased). The higher the metal oxide concentration of the evaporation material, the more difficult it is to disperse the metal oxide uniformly in the evaporation material. When electron beam deposition is carried out using a deposition material in which metal oxides are not uniformly dispersed, not only partial deviations are observed in the secondary electron emission efficiency of the obtained magnesium oxide film, but also the film density (refractive index) decreases, that is, This will cause a decrease in ion bombardment.

On the other hand, since calcium oxide, strontium oxide and barium oxide described in Patent Document 2 exhibit lower work functions than magnesium oxide, magnesium oxide films containing these alkaline earth metal oxides are useful as protective films for AC-type PDPs. However, according to the investigation by the present inventor, the magnesium oxide sintered body containing a large amount of alkaline earth metal oxide has a problem of high hygroscopicity. When the magnesium oxide sintered body containing water is used as the evaporation material, the state (vacuum degree) in the chamber of the evaporation apparatus becomes unstable, which causes problems such as lengthy time for forming the magnesium oxide film or deterioration of homogeneity of the magnesium oxide film. It becomes a factor.

Accordingly, an object of the present invention is to provide a vapor deposition material containing magnesium oxide as a main component which enables the formation of a magnesium oxide film having a high secondary electron emission efficiency and a high film density by an electron beam vapor deposition method. It is also an object of the present invention to provide a magnesium oxide film having a high secondary electron emission efficiency and a high film density.

MEANS TO SOLVE THE PROBLEM This inventor manufactures the sintered compact pellet of magnesium oxide and a metal oxide containing in the various concentration range which can disperse | distribute the metal oxide whose valence of a metal element is 3-5, and uses the sintered compact pellet A magnesium oxide film was formed by the beam vapor deposition method. As a result, when the content of the metal oxide in the sintered pellets was in the range of 0.01 to 6 mol%, it was found that a magnesium oxide film having a sufficiently high secondary electron emission efficiency and a high film density was obtained, thereby reaching the present invention.

Accordingly, the present invention is a pellet obtained by sintering a metal oxide having a valence of magnesium oxide and a metal element of any one of trivalent, tetravalent, or pentavalent, wherein the content of the metal oxide is in the range of 0.01 to 6 mol%. It is in the vapor deposition material characterized by the above-mentioned.

The preferable aspect of the vapor deposition material of the said invention is shown below.

(1) The metal oxide is selected from the group consisting of aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, cerium, neodymium, samarium, europium, gadolinium and dysprosium It consists of oxide of 1 type, or 2 or more types of metal elements.

(2) The metal oxide is zirconium oxide.

(3) Magnesium oxide is 99.9 mass% or more in purity.

(4) Magnesium oxide is comprised from the cube-shaped primary particle.

(5) The relative density is 95% or more.

(6) A metal oxide having any valence of trivalent, tetravalent or pentavalent of magnesium oxide and a metal element is formed by dispersing in an aqueous dispersion medium containing a binder in a molar ratio of 99.99: 0.01 to 94: 6. The resulting slurry is spray-dried by a spray dryer to obtain a mixed granulated product of magnesium oxide and the metal oxide, and the obtained granulated product is molded into pellets, followed by sintering pellet shaped moldings.

This invention is also a magnesium oxide film formed by the electron beam vapor deposition method using the vapor deposition material of the said invention.

The preferable aspect of the said magnesium oxide film of this invention is shown below.

(1) Content of the metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent is in the range of 0.0001-0.06 mol%.

(2) The refractive index is in the range of 1.70 to 1.74.

The present inventors further provide hygroscopic properties of the magnesium oxide sintered body by adding a small amount of alkaline earth metal oxides other than magnesium oxide and metal oxides having any valence of trivalent, tetravalent, or pentavalent to the magnesium oxide sintered body. When the magnesium oxide sintered compact was used for the evaporation material, it was confirmed that the magnesium oxide film with high emission efficiency of secondary electrons can be stably formed, and the present invention was reached.

Therefore, this invention is a sintered compact which consists of magnesium oxide, alkali earth metal oxides other than magnesium oxide, and metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent, and it is alkaline earth metal oxides other than magnesium oxide. The content of and the metal oxide having any valence of trivalent, tetravalent or pentavalent of the metal element are each 0.005 mol% or more in terms of the amount of metal elements, and the total amount thereof is 6 mol in terms of the amount of metal elements. It is also a deposition material that is less than or equal to%.

The preferable aspect of the vapor deposition material of the said invention is as follows.                     

(1) Content of the metal oxide whose alkaline valence oxide other than magnesium oxide and the valence of a metal element are either trivalent, tetravalent, or pentavalent is 2: 1-1: 2 in the molar ratio converted into metal element amount. Is in range.

(2) Content of alkaline earth metal oxides other than magnesium oxide is in the range of 0.005-3.5 mol% in conversion of the amount of metal elements.

(3) Alkaline earth metal oxides other than magnesium oxide are oxides of one or two or more alkaline earth metal elements selected from the group consisting of calcium, strontium and barium.

(4) The metal oxide having a valence of trivalent, tetravalent or pentavalent of a metal element is aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, An oxide of one or two or more metal elements selected from the group consisting of cerium, neodymium, samarium, europium, gadolinium and dysprosium.

(5) Magnesium oxide or magnesium compound which produces magnesium oxide by heating, alkaline-earth metal oxides other than magnesium oxide, or alkaline earth metal compound which produces | generates the alkaline earth metal oxide by heating, and valence of a metal element is trivalent, 4 It is obtained by heating and sintering the mixture which consists of a metal oxide which is the value of either hexavalent or pentavalent, or the metal compound which produces this metal oxide by heating.

(6) Magnesium oxide or a composite oxide or heating of a magnesium compound which forms magnesium oxide by heating, and a metal oxide having an valence of an alkaline earth metal oxide other than magnesium oxide and a metal element of any one of trivalent, tetravalent, or pentavalent. Obtained by heating and sintering a mixture made of a compound that produces the complex oxide.

(7) The dielectric protective film is formed for an AC plasma display panel.

Best Mode for Carrying Out the Invention

The vapor deposition material of the present invention has a diameter of 3.0 to 20 mm, more preferably a diameter of 5.0 to 10 mm, a thickness of 1.0 to 5.0 mm, more preferably a thickness of 1.0 to 2.5 mm, and particularly preferably a thickness of 1.0. It is preferable that it is a disc shaped pellet of -1.8 mm. The thinner one improves the deposition rate while maintaining the quality (secondary electron emission coefficient) of the magnesium oxide film obtained by the electron beam evaporation method. It is preferable that an aspect ratio (thickness / diameter) is 1.0 or less. If a large vapor deposition material whose diameter and thickness exceeds the above range is supplied to the hearth of the vapor deposition apparatus by using an automatic supply device, the side of the vapor deposition material may be loaded to face upward. It tends to be difficult to continuously supply the apparatus with the direction of the vapor deposition material. On the other hand, in the small vapor deposition material whose diameter and thickness are less than the said range, there exists a tendency for a splash to occur easily at the time of vapor deposition.

It is preferable that the relative density of a vapor deposition material is 95% or more. If the relative density is less than 95%, splashing tends to occur.

[Evaporation Material Containing Metal Oxide of Any of Trivalent, Tetravalent, or Pentavalent]                     

In the vapor deposition material of this invention which consists of a pellet obtained by sintering the metal oxide whose magnesium oxide and the valence of a metal element are any of trivalent, tetravalent, or pentavalent, the content of metal oxide is 0.01-6 mol%, Preferably it is in the range of 0.1 to 0.5 mol%. If the content of the metal oxide is less than 0.01 mol%, the effect of addition is not sufficiently recognized. If the content of the metal oxide is more than 6 mol%, it is difficult to uniformly disperse the metal oxide.

It is preferable that purity is 99.9 mass% or more, as for magnesium oxide, it is more preferable that it is 99.95 mass% or more, and it is especially preferable that it is higher than 99.98 mass%. Moreover, it is preferable that the shape of the primary particle of magnesium oxide is a cube. It is preferable that the average particle diameter of the primary particle of magnesium oxide exists in the range of 0.05-0.2 micrometer.

As magnesium oxide whose purity is higher than 99.98 mass% and the shape of a primary particle is a cube, the magnesium oxide obtained by gas-phase oxidation reaction of high purity metal magnesium and oxygen can be used preferably.

Metal oxides having a valence of 3 to 5 valences of metal elements include aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, cerium, neodymium, samarium, europium, gadolinium, and dysprosium It is preferable that it is an oxide of the metal element chosen from the group which consists of these.

Preferred among these metal oxides are metal oxides whose boiling point is higher than the boiling point of magnesium oxide (3600 ° C), specifically, an oxide of zirconium (zirconium oxide). The metal oxide whose boiling point is higher than the boiling point of magnesium oxide has the effect of suppressing crystal growth of magnesium oxide in the vapor deposition material heated by the irradiation of the electron beam when forming the magnesium oxide film by the electron beam vapor deposition method.

It is preferable that the said metal oxide is 99.9 mass% or more in purity. Moreover, it is preferable that the average particle diameter of a primary particle exists in the range of 0.01-3 micrometers.

The vapor deposition material includes, for example, an aqueous dispersion containing a metal oxide having a valence of magnesium oxide and a valence of a metal element in any one of trivalent, tetravalent or pentavalent in a range of 99.99: 0.01 to 94: 6 in molar ratio. The slurry formed by dispersing in a medium can be spray-dried with a spray dryer to obtain a mixed granulated product of magnesium oxide and a metal oxide, and then the obtained granulated product is molded into pellets and then pellet-shaped molded products can be produced by sintering.

It is preferable to make the density | concentration of magnesium oxide in a slurry into the range of 30-75 mass%.

As an aqueous dispersion medium, the mixture of water and the organic solvent which is compatible with water, or water can be used. In particular, it is preferable to use water. As an example of an organic solvent, ketones, such as alcohol, such as ethanol, and acetone, are mentioned. In the mixture of water and an organic solvent, it is preferable that content of an organic solvent is less than 50 mass%.

As a binder, water-soluble polymers, such as polyethyleneglycol, polyvinyl alcohol, polyvinyl butyral, or water-soluble acrylic copolymer, can be used. It is preferable that the binder concentration in an aqueous dispersion medium exists in the range of 0.1-10 mass%. In addition, a dispersant may be added to the aqueous dispersion medium. As a dispersing agent, the ammonium salt of polycarboxylic acid can be used preferably. It is preferable that the dispersing agent concentration in an aqueous dispersion medium exists in the range of 0.1-6 mass%.

A portion of the surface of the magnesium oxide may be hydrated until a slurry of the mixed powder is prepared and then the slurry is spray-dried by a spray dryer, thereby producing magnesium hydroxide. For this reason, it is preferable to make the hydration rate (magnesium hydroxide amount in a granulated material) of magnesium oxide in the mixed granule obtained from a slurry to be 50 mass% or less (especially 30 mass%, More preferably, 5 mass% or less). . In order to obtain a granulated product having a hydration rate of 50% by mass or less, it is a simple and effective method to shorten the time from preparing the slurry to spray drying with a spray dryer. Specifically, it is preferable to spray-dry the slurry with a spray dryer within 2 hours after preparing the slurry. In addition, it is preferable to maintain the temperature of a slurry at 30 degrees C or less (especially 10-30 degreeC) between preparation of magnesium oxide and spray drying with a spray dryer.

It is preferable that the heating temperature at the time of spray-drying a slurry with a spray dryer exists in the range of 200-280 degreeC.

Conventional press molding methods can be used for molding the mixed granules. Molding pressure is in the range of 0.3 to 3 tons / cm 2.

It is preferable to perform baking of a pellet shaped molding at the temperature of 1400-2300 degreeC. The firing time cannot be determined uniformly because it varies depending on the requirements of the size (particularly, thickness) of the formed product, the firing temperature and the like, but is generally 1 to 5 hours.

When the magnesium oxide film is formed by the electron beam evaporation method using the vapor deposition material of the present invention, a magnesium oxide film in which a metal oxide is homogeneously dissolved in the film can be formed. It is preferable that content of the metal oxide in this magnesium oxide film exists in the range of 0.0001-0.06 mol%.

It is preferable that the said magnesium oxide film exists in the range of the refractive index 1.70-1.74 which is one of the indexes which show density.

[Deposition Material Containing Alkaline Earth Metal Oxides Other Than Magnesium Oxide and Metal Oxides with Any of Trivalent, Tetra, or Pentavalent of Metal Elements]

In the vapor deposition material of this invention which consists of a magnesium oxide, alkaline-earth metal oxides other than magnesium oxide, and the metal oxide whose metal number and the number of valences are either trivalent, tetravalent, or pentavalent, the vapor deposition material of this invention WHEREIN: Content and the content of the metal oxide whose valence of a metal element is either trivalent, tetravalent, or pentavalent are 0.005 mol% or more in conversion of the amount of metal elements, respectively, and the total amount is 6 mol% in conversion of the amount of metal elements, respectively. It is as follows. Alkaline earth metal oxides other than magnesium oxide and the metal oxide whose valence of a metal element is either trivalent, tetravalent, or pentavalent may form the complex oxide. The content of the alkaline earth metal oxide and the metal oxide whose valence of the metal element is any one of trivalent, tetravalent, or pentavalent is preferably in the range of 2: 1 to 1: 2 in molar ratio in terms of the amount of metal elements. It is preferable to exist in the range of 1.5: 1-1: 1.5.                     

The alkaline earth metal oxide is preferably calcium oxide, strontium oxide and barium oxide. These can also use 2 or more types together. The content of alkaline earth metal oxides other than magnesium oxide is preferably in the range of 0.005 to 3.5 mol%, more preferably in the range of 0.01 to 3.0 mol%, in terms of the amount of metal elements.

Metal oxides having a valence of trivalent, tetravalent or pentavalent of a metal element include aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, cerium and neodymium. , An oxide of a metal element selected from the group consisting of samarium, europium, gadolinium and dysprosium. These can also use 2 or more types together.

Preferred among the metal oxides are oxides of aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt and nickel. Particularly preferred are metal oxides whose boiling point is equal to or higher than that of magnesium oxide (3600 ° C.), specifically aluminum oxide and zirconium oxide. When the metal oxide of high boiling point forms a magnesium oxide film by the electron beam vapor deposition method, there exists an effect which suppresses the crystal growth of magnesium oxide in the vapor deposition material heated by the electron beam irradiation.

In the vapor deposition material, magnesium oxide or a magnesium compound that generates magnesium oxide by heating can be used as a raw material of magnesium oxide as the main component. The magnesium oxide and magnesium compounds preferably have a purity of 99.9% by mass or more, more preferably 99.95% by mass or more, and particularly preferably higher than 99.98% by mass. Examples of the magnesium compound which produces magnesium oxide by heating include magnesium hydroxide and magnesium carbonate. It is more preferable to use magnesium oxide than a magnesium compound.

As for magnesium oxide, it is preferable that the shape of a primary particle is a cube. Moreover, it is preferable that the average particle diameter of the primary particle exists in the range of 0.05-0.2 micrometer. As magnesium oxide whose high purity and primary particle shape is a cube, the magnesium oxide obtained by gas-phase oxidation of high-purity metal magnesium and oxygen can be used preferably.

As a raw material of alkaline earth metal oxide, alkaline earth metal oxide or alkaline earth metal compound which produces | generates alkaline earth metal oxide by heating can be used. Examples of alkaline earth metal oxides include carbonates, hydroxides and oxalates of alkaline earth metal elements. It is preferable to use an alkaline earth metal compound rather than an alkaline earth metal oxide, and it is particularly preferable to use a carbonate of an alkaline earth metal element.

As a raw material of the metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent, the metal oxide or the metal compound which produces this metal oxide by heating can be used. Examples of the metal compound include carbonates, hydroxides and oxalates of metal elements. It is more preferable to use a metal oxide than a metal compound.

Alkali earth metal oxide and the metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent, The metal oxide whose valence of an alkaline earth metal oxide and a metal element is any of trivalent, tetravalent, or pentavalent. Complex oxide or a compound which produces the complex oxide by heating. The compound which produces | generates a metal oxide by heating may be any of carbonate, hydroxide, and oxalate. It is more preferable to use a metal oxide than a metal compound.

An alkaline earth metal compound for producing an alkaline earth metal oxide by heating the alkaline earth metal oxide and heating, a metal oxide having any valence of trivalent, tetravalent or pentavalent of a metal element, and a metal compound for producing the metal oxide by heating, And the complex oxide of the metal oxide having any one of trivalent, tetravalent, or pentavalent valences of the alkaline earth metal oxide and the metal element, and the compound producing the composite oxide by heating, are all preferably 99% by mass or more. It is more preferable that it is 99.9 mass% or more. Moreover, it is preferable to exist in the range of 0.01-3 micrometers, and, as for the average particle diameter of the primary particle, it is more preferable to exist in the range which is 0.1-2 micrometers.

The vapor deposition material may be, for example, magnesium oxide or magnesium compound that generates magnesium oxide by heating, alkaline earth metal oxide or alkaline earth metal compound that generates alkaline earth metal oxide by heating, and valence of metal element is trivalent, Metal oxides, either tetravalent or pentavalent, or mixtures with metal compounds that produce the metal oxides by heating, or magnesium oxides or magnesium earth, magnesium earth compounds that form magnesium oxide by heating, and valences of metal elements The complex oxide of a metal oxide of any one of trivalent, tetravalent, or pentavalent or a mixture with a compound that forms the complex oxide by heating can be molded into pellets, and then the molded product can be produced by heating and sintering. have.

For the preparation of the mixture, a normal wet mixing method can be used. Specifically, a method of dispersing and mixing the raw materials in an aqueous dispersion medium containing a binder, respectively, to prepare a mixture slurry, and a method of spray drying the mixture slurry using a spray dryer can be used.

As an aqueous dispersion medium, the mixture of the above-mentioned water and the organic solvent which is compatible with water, or water can be used. In addition, a dispersant may be added to the aqueous dispersion medium. As a dispersing agent, the ammonium salt of polycarboxylic acid mentioned above can be used preferably. It is preferable that the dispersing agent concentration in an aqueous dispersion medium exists in the range of 0.1-6 mass%.

As a binder, the water-soluble polymer mentioned above can be used. It is preferable that the binder concentration in an aqueous dispersion medium exists in the range of 0.1-10 mass%.

The conventional press molding method can be used for molding the mixture. It is preferable that molding pressure exists in the range of 0.3-3 ton / cm <2>.

It is preferable to perform baking of a pellet shaped molding at the temperature of 1400-2300 degreeC. The firing time cannot be determined uniformly because it varies depending on the requirements of the size (particularly, thickness) of the formed product, the firing temperature and the like, but is generally 1 to 5 hours.

When the magnesium oxide film is formed by the electron beam evaporation method using the vapor deposition material of the present invention, a magnesium oxide film in which a metal oxide having an alkali earth metal oxide and a metal oxide of any one of trivalent, tetravalent, or pentavalent is homogeneously dissolved is formed. Can be formed. The content of the alkaline earth metal oxide in the magnesium oxide film is in the range of 0.005 to 3.5 mol%, particularly in the range of 0.01 to 3.0 mol%, in terms of the metal element content. In addition, content of the metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent is in the range of 0.0005 to 0.1 mol% in conversion with metal element content.

Example

(1) Sintered body composed of magnesium oxide and zirconium oxide

Example 1-1

Magnesium oxide (MgO) powder (purity: 99.985 mass%, average particle diameter of primary particles: 0.2 µm, shape of primary particles: cube) and zirconium oxide (ZrO ₂ ) powder (purity) prepared by a gas phase oxidation reaction method. : 99.9% by mass, average particle diameter of primary particles: 0.2㎛) mixed powder _{[MgO / ZrO 2 = 99.967 /} 0.033 ( molar ratio)] 50 parts by weight, polyethylene glycol concentration 6% by weight and a polycarboxylic acid ammonium salt concentration of 1 mass It mixed and dispersed in 50 mass parts of aqueous solution of%, and prepared the slurry (temperature: 25 degreeC). After preparation, the slurry was spray dried (heating temperature: 230 ° C.) using a spray dryer rapidly (within about 15 minutes after slurry preparation) while maintaining the slurry temperature at 25 ° C. to obtain a granulated product. The obtained granulated product was molded at a molding pressure of 2 ton / cm 2, into a pellet (diameter: 6.0 mm, height: 2.5 mm, molded body density: 2.50 g / cm 3). Subsequently, the molded product was baked and sintered at a temperature of 1650 ° C. for 4 hours using an electric furnace. The relative density of the obtained sintered compact pellets was 98.3%.

Using the sintered compact pellets as a deposition material, a magnesium oxide film was formed on the silicon wafer substrate and the stainless steel substrate by the electron beam evaporation method, respectively, and the zirconium oxide content, secondary electron emission coefficient and refractive index of the magnesium oxide film were measured. Conditions of vapor deposition were voltage: 8 KV, current: 40 mA, oxygen partial pressure of the deposition chamber: 2x10 ^-2 Pa, and substrate temperature: 200 deg. The zirconium oxide content uses a magnesium oxide film having a thickness of 100 nm formed on a silicon wafer substrate, the secondary electron emission coefficient uses a magnesium oxide film having a thickness of 100 nm formed on a stainless steel substrate, and the refractive index is on the silicon wafer substrate. It measured by the following method, respectively using the formed magnesium oxide film of thickness 100nm. The results are shown in Table 1.

[Measurement Method of Zirconium Oxide Content]

Zirconium content was measured by the fluorescent X-ray method, and the value was converted into zirconium oxide content.

[Measurement Method of Secondary Electron Emission Coefficient]

The amount of secondary electrons generated by irradiation of Ne ions was measured. Irradiation conditions of Ne ion were made into the degree of vacuum of 3x10 <^-5> Pa, the acceleration voltage of Ne ion: 300 eV, and the substrate temperature: 300 degreeC.

[Measurement Method of Refractive Index]

The refractive index of the light of wavelength 633nm was measured using the ellipsometer.                     

[Example 1-2]

Sintered compact pellets were manufactured on the same conditions as in Example 1-1 except that the composition ratio of the mixed powder was MgO / ZrO ₂ = 99.84 / 0.16 (molar ratio). The relative density of the obtained sintered compact pellets was 99.0%.

Using this sintered compact pellet as a vapor deposition material, a magnesium oxide film was formed by an electron beam vapor deposition method in the same manner as in Example 1-1. Table 1 shows the zirconium content, secondary electron emission coefficient and refractive index of the obtained magnesium oxide film.

[Example 1-3]

Sintered compact pellets were manufactured on the same conditions as in Example 1-1 except that the composition ratio of the mixed powder was MgO / ZrO ₂ = 99.67 / 0.33 (molar ratio). The relative density of the obtained sintered compact pellets was 99.0%.

Using this sintered compact pellet as a vapor deposition material, a magnesium oxide film was formed by an electron beam vapor deposition method in the same manner as in Example 1-1. Table 1 shows the zirconium content, secondary electron emission coefficient and refractive index of the obtained magnesium oxide film.

Example 1-4

Sintered compact pellets were manufactured on the same conditions as in Example 1-1 except that the composition ratio of the mixed powder was MgO / ZrO ₂ = 99.00 / 1.00 (molar ratio). The relative density of the obtained sintered compact pellets was 98.9%.

Using this sintered compact pellet as a vapor deposition material, a magnesium oxide film was formed by an electron beam vapor deposition method in the same manner as in Example 1-1. Table 1 shows the zirconium content, secondary electron emission coefficient and refractive index of the obtained magnesium oxide film.

[Example 1-5]

Sintered compact pellets were manufactured on the same conditions as in Example 1-1 except that the composition ratio of the mixed powder was MgO / ZrO ₂ = 98.31 / 1.69 (molar ratio). The relative density of the obtained sintered compact pellets was 98.8%.

Using this sintered compact pellet as a vapor deposition material, a magnesium oxide film was formed by an electron beam vapor deposition method in the same manner as in Example 1-1. Table 1 shows the zirconium content, secondary electron emission coefficient and refractive index of the obtained magnesium oxide film.

Example 1-6

Sintered compact pellets were manufactured on the same conditions as in Example 1-1 except that the composition ratio of the mixed powder was MgO / ZrO ₂ = 96.49 / 3.51 (molar ratio). The relative density of the obtained sintered compact pellets was 98.8%.

Using this sintered compact pellet as a vapor deposition material, a magnesium oxide film was formed by an electron beam vapor deposition method in the same manner as in Example 1-1. Table 1 shows the zirconium content, secondary electron emission coefficient and refractive index of the obtained magnesium oxide film.

Example 1-7

Sintered compact pellets were manufactured on the same conditions as in Example 1-1 except that the composition ratio of the mixed powder was MgO / ZrO ₂ = 94.54 / 5.46 (molar ratio). The relative density of the obtained sintered compact pellets was 98.7%.

Using this sintered compact pellet as a vapor deposition material, a magnesium oxide film was formed by an electron beam vapor deposition method in the same manner as in Example 1-1. Table 1 shows the zirconium content, secondary electron emission coefficient and refractive index of the obtained magnesium oxide film.

[Comparative Example 1-1]

Sintered compact pellets were prepared under the same conditions as in Example 1-1 except that no zirconium oxide powder was added. The relative density of the obtained sintered compact pellets was 97.0%.

Using this sintered compact pellet as a vapor deposition material, a magnesium oxide film was formed by an electron beam vapor deposition method in the same manner as in Example 1-1. Table 1 shows the zirconium content, secondary electron emission coefficient and refractive index of the obtained magnesium oxide film.

Sintered pellet Magnesium oxide film ZrO ₂ content
(mole%) ZrO ₂ content
(mole%) Secondary electron emission coefficient (*)
(-) Refractive index
(-) Example 1-1 0.033 0.00016 1.10 1.702 Example 1-2 0.16 0.00033 1.30 1.705 Example 1-3 0.33 0.0049 1.35 1.708 Example 1-4 1.00 0.013 1.32 1.723 Examples 1-5 1.69 0.016 1.29 1.735 Example 1-6 3.51 0.033 1.20 1.729 Example 1-7 5.46 0.049 1.15 1.722 Comparative Example 1-1 ZrO _{2 not} added Not detected 1.00 1.693 (*) The secondary electron emission coefficients of Examples 1-1 to 1-7 are relative ratios when the secondary electron emission coefficient of Comparative Example 1-1 is set to 1.00.

From the results in Table 1, all of the magnesium oxide films (Examples 1-1 to 1-7) formed from sintered pellets having a content of zirconium oxide in the range of 0.01 to 6 mol% were sintered pellets containing no zirconium oxide. It can be seen that the secondary electron emission efficiency and the refractive index are improved as compared with the formed magnesium oxide film (Comparative Example 1-1).

(2) A sintered body composed of magnesium oxide, calcium oxide, strontium oxide or barium oxide, and zirconium oxide

Example 2-1

Magnesium oxide (MgO) powder (purity: 99.985 mass%, average particle diameter of primary particles: 0.2 µm, primary particle shape: cube) prepared by vapor phase oxidation reaction, and calcium carbonate (CaCO ₃ ) powder (purity) : 99.9 mass%, average primary particle diameter of the particles: 0.2㎛) and zirconium (ZrO ₂₎ powder (purity oxide: 99.9 mass%, average particle diameter of primary particles: 0.2㎛) the respective MgO: CaCO ₃ : ZrO ₂ = 99.892: 0.054: were mixed in a ratio of 0.054 (mol ratio). 50 mass parts of this mixed powder was dispersed in 50 mass parts of water of 6 mass% of polyethyleneglycol concentration, and 1 mass% of ammonium polycarboxylate salt concentration, and the slurry (liquid temperature: 25 degreeC) was prepared.

The prepared slurry was spray-dried quickly using a spray dryer (within about 15 minutes), maintaining the liquid temperature at 25 degreeC, and the granulated material was obtained.

The granulated material thus obtained was filled into a mold and molded into pellets (diameter: 6.0 mm, thickness: 2.5 mm, molded body density: 2.50 g / cm 3) at a molding pressure of 2 ton / cm 2.

And finally, the pellet-shaped molded object was baked and sintered at the temperature of 1650 degreeC for 4 hours using an electric furnace.

Metal element content (calcium content, zirconium content), relative density, and moisture absorption rate of the said sintered compact pellet were measured by the following method, respectively. The results are shown in Table 2 below.

[Measurement Method of Metal Element Content]

The metal element content was measured by the ICP emission spectrometer.

[Measurement method of relative density]

It measured by the Archimedes method.

[Measuring method of moisture absorption rate]

30 g of sintered compact pellets were weighed correctly, and it was left still for 300 hours in the environment of the temperature of 60 degreeC, and 85% RH of relative humidity. The weight of the sintered compact pellet after standing was measured, and the weight increase rate calculated | required by the following formula was made into the moisture absorption rate. It is preferable that a moisture absorption is 0.1% or less.

Moisture absorption% = {weight of sintered compact pellet after politics-weight of sintered compact pellet before politics} / weight (30g) of sintered compact pellet before politics

Example 2-2

A sintered pellet was prepared in the same manner as in Example 2-1 except that the mixing ratio of magnesium oxide powder, calcium carbonate powder and zirconium oxide powder was MgO: CaCO ₃ : ZrO ₂ = 99.642: 0.179: 0.179 (molar ratio), respectively. Prepared. The metal element content (calcium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-3

A sintered pellet was prepared in the same manner as in Example 2-1 except that the mixing ratio of magnesium oxide powder, calcium carbonate powder and zirconium oxide powder was MgO: CaCO ₃ : ZrO ₂ = 98.214: 0.893: 0.893 (molar ratio), respectively. Prepared. The metal element content (calcium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-4

A sintered pellet was prepared in the same manner as in Example 2-1 except that the mixing ratio of magnesium oxide powder, calcium carbonate powder and zirconium oxide powder was MgO: CaCO ₃ : ZrO ₂ = 94.642: 2.679: 2.679 (molar ratio), respectively. Prepared. The metal element content (calcium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-5

Mixing ratio of magnesium oxide powder and calcium zirconate powder, using calcium zirconate (CaZrO ₃ ) powder (purity: 99.5% by mass, average particle diameter of primary particles: 0.4 μm) instead of calcium carbonate powder and zirconium oxide powder A sintered compact pellet was produced in the same manner as in Example 2-1, except that Mg0: CaZrO ₃ = 99.821: 0.179 (molar ratio). The metal element content (calcium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-6

A sintered compact pellet was produced in the same manner as in Example 2-5, except that the mixing ratio of the magnesium oxide powder and the calcium zirconate powder was MgO: CaZrO ₃ = 99.107: 0.893 (molar ratio). The metal element content (calcium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-7

A sintered compact pellet was produced in the same manner as in Example 2-5 except that the mixing ratio of magnesium oxide powder and calcium zirconate powder was Mg0: CaZrO ₃ = 97.321: 2.679 (molar ratio). The metal element content (calcium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-8

Instead of calcium carbonate powder, the mixture ratio of magnesium oxide powder, strontium carbonate powder and zirconium oxide powder was determined using strontium carbonate (SrCO ₃ ) powder (purity: 99.9 mass%, average particle diameter of primary particles: 0.3 µm), Sintered compact pellets were prepared in the same manner as in Example 2-1, except that MgO: SrCO ₃ : ZrO ₂ = 99.034: 0.483: 0.483 (molar ratio), respectively. The metal element content (strontium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-9

Mixing ratio of magnesium oxide powder and strontium zirconate powder using strontium zirconate (SrZrO ₃ ) powder (purity: 99.2% by mass, average particle diameter of primary particles: 0.8 μm) instead of strontium carbonate powder and zirconium oxide powder Sintered compact pellets were manufactured in the same manner as in Example 2-8 except that MgO: SrZrO ₃ = 99.517: 0.483 (molar ratio). The metal element content (strontium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-10

Instead of calcium carbonate powder, using a barium carbonate (BaCO ₃ ) powder (purity: 99.9% by mass, average particle diameter of the primary particles: 0.5 μm), the mixing ratio of magnesium oxide powder, barium carbonate powder, and zirconium oxide powder was determined. Sintered compact pellets were prepared in the same manner as in Example 2-1, except that MgO: BaCO ₃ : ZrO ₂ = 99.348: 0.326: 0.326 (molar ratio), respectively. The metal element content (barium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Example 2-11

Mixing ratio of magnesium oxide powder and barium zirconate powder using barium zirconate (BaZrO ₃ ) powder (purity: 99.2% by mass, average particle diameter of primary particles: 1.0 μm) instead of barium carbonate powder and zirconium oxide powder Sintered compact pellets were prepared in the same manner as in Example 2-10 except that MgO: BaZrO ₃ = 99.674: 0.326 (molar ratio). The metal element content (barium content, zirconium content), the relative density, and the moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Comparative Example 2-1

A sintered compact pellet was produced in the same manner as in Example 2-1, except that the mixing ratio of the magnesium oxide powder and the calcium carbonate powder was MgO: CaCO ₃ = 99.821: 0.179 (molar ratio) without using a zirconium oxide powder. The metal element content (calcium content), relative density, and moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Comparative Example 2-2

A sintered pellet was produced in the same manner as in Example 2-1, except that the mixture ratio of magnesium oxide powder and calcium carbonate powder was MgO: CaCO ₃ = 99.107: 0.893 (molar ratio) without using a zirconium oxide powder. The metal element content (calcium content), relative density, and moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Comparative Example 2-3

A sintered pellet was prepared in the same manner as in Example 2-8, except that the mixing ratio of the magnesium oxide powder and the strontium carbonate powder was MgO: SrCO ₃ = 99.517: 0.483 (molar ratio) without using a zirconium oxide powder. . The metal element content (strontium content), relative density, and moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Comparative Example 2-4

A sintered compact pellet was produced in the same manner as in Example 2-10, except that the mixing ratio of the magnesium oxide powder and the lithium carbonate powder was MgO: BaCO ₃ = 99.674: 0.326 (molar ratio) without using a zirconium oxide powder. The metal element content (barium content), relative density, and moisture absorption rate of this sintered compact pellet were measured by the above-mentioned method, respectively. The results are shown in Table 2.

Ca
(mole%) Sr
(mole%) Ba
(mole%) Zr
(mole%) Relative density
(%) Moisture absorption rate
(%) Example 2-1 0.054 - - 0.054 97.9 0.05 Example 2-2 0.179 - - 0.179 98.9 0.01 or less Example 2-3 0.893 - - 0.893 98.7 0.01 or less Examples 2-4 2.679 - - 2.679 98.2 0.01 or less Example 2-5 0.179 - - 0.179 99.0 0.03 Example 2-6 0.893 - - 0.893 98.7 0.01 or less Example 2-7 2.679 - - 2.679 98.4 0.01 or less Example 2-8 - 0.483 - 0.483 97.5 0.03 Example 2-9 - 0.483 - 0.483 97.8 0.02 Example 2-10 - - 0.326 0.326 97.0 0.03 Example 2-11 - - 0.326 0.326 97.4 0.02 Comparative Example 2-1 0.179 - - - 91.7 4.7 Comparative Example 2-2 0.893 - - - 90.2 6.9 Comparative Example 2-3 - 0.483 - - 94.5 2.6 Comparative Example 2-4 - - 0.326 - 93.2 3.4

As shown in Table 2, sintered compacts (Examples 2-1 to 2-11) containing alkaline earth metal oxides (except magnesium oxide) and zirconium oxide are sintered bodies containing only alkaline earth metal oxides (except magnesium oxide). Compared with pellets (Comparative Examples 2-1 to 2-4), it turns out that the relative density is high and the moisture absorption rate is falling.

[Evaluation as evaporation material for magnesium oxide film formation]

A magnesium oxide film was formed by the electron beam evaporation method using the sintered compact pellets manufactured in Examples 2-1 to 2-11 and Comparative Examples 2-1 to 2-4. The deposition rate at that time, the secondary electron emission coefficient and the metal oxide content of the formed magnesium oxide film were measured by the following method, respectively. The results are shown in Table 3 below. In addition, the vapor deposition rate and secondary electron emission coefficient of Table 3 are relative values at the time of making the value of the sintered compact pellet of the comparative example 2-1 into 1.

[Measurement method of deposition rate]

The film thickness of the magnesium oxide film formed on the stainless steel substrate on the following film forming conditions was recorded for every time passed from the start of film forming, and the film forming speed per unit time (minute) was calculated. This film forming speed was made into the deposition rate.

(Film forming condition)

Voltage: 8kV

Current: 40 mA

Oxygen partial pressure in the deposition chamber: 2 × 10 ^-5 Pa

Substrate Temperature: 200 ℃                     

[Measurement Method of Secondary Electron Emission Coefficient]

A 100 nm magnesium oxide film was formed on the stainless substrate by the same film forming conditions as those of the above-described deposition rate measurement method. The amount of secondary electrons generated when the magnesium oxide film was irradiated with Ne ions under the following conditions was measured.

(Irradiation conditions of Ne ions)

Vacuum degree: 3 × 10 ^-5 Pa

Acceleration voltage of Ne ion: 300eV

Substrate temperature: 300 ℃

[Measurement Method of Metal Element Content]

A magnesium oxide film having a thickness of 1000 nm was formed on the silicon wafer substrate under the same film forming conditions as those for measuring the deposition rate. The metal element content of this magnesium oxide film was measured by the fluorescent X-ray method.

Deposition rate
(-) Secondary electron emission coefficient
(-) CaO
(mole%) SrO
(mole%) BaO
(mole%) ZrO ₂
(mole%) Example 2-1 1.2 1.30 0.0464 - - 0.0016 Example 2-2 1.3 1.32 0.1464 - - 0.0041 Example 2-3 1.2 1.25 0.6071 - - 0.0097 Examples 2-4 1.1 1.12 1.5179 - - 0.0235 Example 2-5 1.3 1.35 0.1071 - - 0.0032 Example 2-6 1.2 1.20 0.5000 - - 0.0089 Example 2-7 1.1 1.10 1.4643 - - 0.0244 Example 2-8 1.2 1.21 - 0.3475 - 0.0057 Example 2-9 1.2 1.25 - 0.32819 - 0.0049 Example 2-10 1.2 1.18 - - 0.2609 0.0041 Example 2-11 1.2 1.22 - - 0.2479 0.0032 Comparative Example 2-1 1.0 1.00 0.1643 - - - Comparative Example 2-2 0.8 0.90 0.7161 - - - Comparative Example 2-3 0.9 0.95 - 0.3089 - - Comparative Example 2-4 0.9 0.92 - - 0.2461 -

As shown in Table 3, magnesium oxide sintered pellets (Examples 2-1 to 2-11) containing alkaline earth metal oxides (except magnesium oxide) and zirconium oxide only contain alkaline earth metal oxides (except magnesium oxide). As compared with the magnesium oxide sintered pellet (Comparative Examples 2-1 to 2-4), it can be seen that the deposition rate and the secondary electron emission coefficient are high.

Example 2-12

In Example 2-1, the obtained granulated product was formed in a pellet form (diameter: 6 mm, height 1.5 mm, molded body density 2.50 g / cm 3) at a molding pressure of 2 ton / cm 2, and was obtained in Example 2-1. In the same manner, sintered pellets were prepared.

As a result of measuring the relative density and the moisture absorption rate of the obtained sintered compact pellets by the above-mentioned method, the relative density was 98.8% and the moisture absorption rate was 0.01% or less. And using this sintered compact pellet, the magnesium oxide film was formed by the electron beam vapor deposition method, and the deposition rate, the secondary electron emission coefficient, and metal element content of the formed magnesium oxide film were measured by the above-mentioned method, respectively. As a result, the deposition rate was 1.9, the secondary electron emission coefficient was 1.32 (relative value when the sintered pellet of Comparative Example 2-1 was set to 1.0, respectively), the content of calcium oxide was 0.1490 mol%, and zirconium oxide. The content of was 0.0048 mol%, and the deposition rate was faster than that of the sintered compact pellets prepared in Example 2-1.

The vapor deposition material containing a metal oxide having a valence of trivalent, tetravalent, or pentavalent of the metal element of the present invention can easily disperse the metal oxide uniformly in the content of the metal oxide having a valence of the metal element of 3-5. Since it is in the range of 0.01-6 mol%, the magnesium oxide film in which the metal oxide was uniformly dispersed can be formed by the electron beam vapor deposition method by using this vapor deposition material. Further, in the magnesium oxide film formed by the electron beam evaporation method using the vapor deposition material of the present invention, the secondary electron emission efficiency is increased because the metal oxide dispersed in the film forms a donor level between the energy gaps of magnesium oxide. In addition, since the metal oxide in the magnesium oxide film is uniformly dispersed, the film density also increases. Therefore, the magnesium oxide film of the present invention can be advantageously used as a protective film for the dielectric of the AC plasma display panel.

Next, the evaporation material containing alkaline earth metal oxides other than magnesium oxide of the present invention and metal oxides having any valence of trivalent, tetravalent or pentavalent of metal elements is low in hygroscopicity and therefore homogeneous even after long-term storage. Magnesium oxide film can be formed stably. In addition, the magnesium oxide film obtained by using this vapor deposition material contains alkaline earth metal oxides (calcium oxide, strontium oxide or barium oxide) other than magnesium oxide, so that secondary electrons have high emission efficiency. Therefore, the vapor deposition material of the present invention can be advantageously used in forming a magnesium oxide film useful as a protective film of a dielectric layer of an alternating-current plasma display panel.

Claims (18)

A pellet obtained by sintering a metal oxide having a valence of magnesium oxide and a metal element of any one of trivalent, tetravalent or pentavalent, wherein the content of the metal oxide is in the range of 0.01 to 6 mol%. . The group according to claim 1, wherein the metal oxide is composed of aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel, cerium, neodymium, samarium, europium, gadolinium, and dysprosium. Evaporation material that is an oxide of one or two or more metal elements selected from The vapor deposition material of Claim 1 whose metal oxide is zirconium oxide. The vapor deposition material of Claim 1 whose magnesium oxide is purity 99.9 mass% or more. The vapor deposition material of Claim 1 in which magnesium oxide is comprised from the cube-shaped primary particle. The vapor deposition material of claim 1 wherein the relative density is at least 95%. A slurry formed by dispersing a metal oxide having a valence of trivalent, tetravalent or pentavalent of magnesium oxide and a metal element in an aqueous dispersion medium containing a binder in a molar ratio of 99.99: 0.01 to 94: 6 in a molar ratio. The manufacturing method of the vapor deposition material of Claim 1 which spray-drys with a spray dryer, obtains the mixed granulated material of magnesium oxide and the said metal oxide, shape | molds the obtained granulated material to pellet shape, and then sinters the pellet shaped molding. Magnesium oxide film formed by the electron beam vapor deposition method using the vapor deposition material of Claim 1. The magnesium oxide film according to claim 8, wherein the valence of the metal element is any of trivalent, tetravalent, or pentavalent. The magnesium oxide film has a content of 0.0001 to 0.06 mol%. The magnesium oxide film according to claim 8, wherein the magnesium oxide film has a refractive index in the range of 1.70 to 1.74. A sintered body composed of magnesium oxide, alkaline earth metal oxides other than magnesium oxide, and metal oxides having any valence of trivalent, tetravalent, or pentavalent of a metal element, wherein the content of alkali earth metal oxides other than magnesium oxide and The vapor deposition material whose content of the metal oxide of valence trivalent, tetravalent, or pentavalent is 0.005 mol% or more in conversion of the amount of metal elements, respectively, and its total amount is 6 mol% or less in conversion of the amount of metal elements. The content of alkaline earth metal oxides other than magnesium oxide and the metal oxide whose valence of a metal element is any of trivalent, tetravalent, or pentavalent are 2: 1 in molar ratio converted into the amount of metal elements. The vapor deposition material in the range of -1: 2. The vapor deposition material of Claim 11 whose content of alkaline-earth metal oxides other than magnesium oxide is 0.005-3.5 mol% in conversion of the amount of metal elements. The vapor deposition material of Claim 11 whose alkaline earth metal oxides other than magnesium oxide are oxide of 1 type, or 2 or more types of alkaline earth metal elements chosen from the group which consists of calcium, strontium, and barium. The metal oxide of claim 11, wherein the valence of the metal element is any one of trivalent, tetravalent, or pentavalent, aluminum, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, iron, and cobalt. A vapor deposition material which is an oxide of one or two or more metal elements selected from the group consisting of nickel, cerium, neodymium, samarium, europium, gadolinium and dysprosium. The vapor deposition material of Claim 11 for formation of the dielectric protective film of an AC plasma display panel. Magnesium oxide or magnesium compound which produces magnesium oxide by heating, alkaline earth metal oxide other than magnesium oxide, or alkaline earth metal compound which produces | generates the alkaline earth metal oxide by heating, and valence of a metal element is trivalent, tetravalent, or 5 The manufacturing method of the vapor deposition material of Claim 11 which heats and sinters the mixture which consists of a metal oxide which is any of the addition, or the metal compound which produces this metal oxide by heating. Magnesium oxide or a magnesium compound that produces magnesium oxide by heating, an alkaline earth metal oxide other than magnesium oxide, and a metal oxide having a valence of trivalent, tetravalent, or pentavalent of a metal element, or by heating The manufacturing method of the vapor deposition material of Claim 11 which heats and sinters the mixture which consists of a compound which produces a complex oxide.