JP2000290062A - MgO VAPOR-DEPOSITED MATERIAL AND ITS PRODUCTION - Google Patents
MgO VAPOR-DEPOSITED MATERIAL AND ITS PRODUCTIONInfo
- Publication number
- JP2000290062A JP2000290062A JP11097342A JP9734299A JP2000290062A JP 2000290062 A JP2000290062 A JP 2000290062A JP 11097342 A JP11097342 A JP 11097342A JP 9734299 A JP9734299 A JP 9734299A JP 2000290062 A JP2000290062 A JP 2000290062A
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- Prior art keywords
- mgo
- powder
- earth metal
- alkaline earth
- metal oxide
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ＭｇＯマトリック
ス中に、アルカリ土類金属酸化物粒子又はアルカリ土類
金属酸化物粒子及び希土類酸化物粒子を含む複合セラミ
ックからなるＭｇＯ系蒸着材及びその製造方法に関す
る。更に詳しくは、ＡＣ型ＰＤＰ（Plasma Display Pan
el）の誘電体層を保護するＭｇＯ膜を成膜するのに好適
なＭｇＯ系蒸着材及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a MgO-based vapor deposition material comprising a composite ceramic containing alkaline earth metal oxide particles or alkaline earth metal oxide particles and rare earth oxide particles in a MgO matrix, and a method for producing the same. About. More specifically, an AC type PDP (Plasma Display Pan)
The present invention relates to an MgO-based vapor deposition material suitable for forming an MgO film for protecting a dielectric layer of el) and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】ここ数年、平面ディスプレイ、なかでも
プラズマ発光を用いた大型ディスプレイパネルの研究開
発と実用化はめざましく、その生産も急増している。カ
ラープラズマディスプレイパネル（以下、ＰＤＰとい
う）は、その開発と実用化の動きが活発化しており、ハ
イビジョン用大画面壁掛けテレビの最短距離にあり、対
角４０インチクラス以上のＰＤＰの試作が進められてい
る。ＰＤＰは、電極構造の点で放電空間に金属電極が露
出しているＤＣ型と、金属電極が誘電体層で覆われてい
るＡＣ型とに分類される。このＡＣ型ＰＤＰの開発の当
初は、ガラス誘電体層が放電空間に露出していたため、
直接放電にさらされ、イオン衝撃のスパッタリングによ
り誘電体層表面が変化して放電開始電圧が上昇し、パネ
ル寿命等に安定性が得られなかった。2. Description of the Related Art In recent years, research and development and commercialization of flat panel displays, especially large display panels using plasma emission have been remarkable, and their production has been rapidly increasing. Color plasma display panels (hereinafter referred to as PDPs) have been actively developed and put into practical use, and trial production of PDPs with a diagonal size of 40 inches or more, which are the shortest distance from large screen TVs for high-definition televisions, is underway. ing. PDPs are classified into a DC type in which a metal electrode is exposed in a discharge space in terms of an electrode structure, and an AC type in which a metal electrode is covered with a dielectric layer. At the beginning of the development of this AC type PDP, the glass dielectric layer was exposed to the discharge space,
When exposed to direct discharge, the surface of the dielectric layer was changed by ion bombardment and the discharge start voltage was increased, and stability in panel life and the like could not be obtained.
【０００３】そのため、上記イオン衝撃のスパッタリン
グで変化しないという、重要な役割を担う種々の酸化物
を誘電体層の保護膜とする試みがなされている。即ち、
保護膜に求められる特性は、低い放電電圧、耐スパ
ッタ性、速い放電の応答性、絶縁性、である。これ
らの条件を満たす材料として、ＭｇＯが挙げられる。こ
のＭｇＯからなる保護膜は、誘電体層表面をスパッタリ
ングから守り、ＰＤＰの長寿命化に重要な働きをする。
またＭｇＯは材料としての仕事関数が小さく、二次電子
を放出し易いため、放電時の駆動電圧が低くなるという
利点を有する。For this reason, attempts have been made to use various oxides, which do not change by the ion bombardment sputtering and play an important role, as protective films for the dielectric layer. That is,
The characteristics required for the protective film are low discharge voltage, spatter resistance, fast discharge response, and insulation. MgO is a material that satisfies these conditions. This protective film made of MgO protects the surface of the dielectric layer from sputtering and plays an important role in extending the life of the PDP.
In addition, MgO has the advantage that the work function as a material is small and secondary electrons are easily emitted, so that the driving voltage at the time of discharge is reduced.
【０００４】現在、ＡＣ型ＰＤＰの上記保護膜として、
単結晶ＭｇＯの破砕品を蒸着材とする電子ビーム蒸着法
により成膜されたＭｇＯ膜が一般的である。なお、単結
晶ＭｇＯの破砕品は純度が９８％以上のＭｇＯクリンカ
や軽焼ＭｇＯ（１０００℃以下で焼結されたＭｇＯ）を
電弧炉（アーク炉）で溶融することにより、即ち電融に
よりインゴットとした後、このインゴットから単結晶部
を取り出して破砕することにより製造される。この電子
ビーム蒸着法によるＭｇＯ膜は１０００Å／分程度の速
度で成膜されている。また、成膜されたＭｇＯ膜は、低
い維持電圧で駆動でき、更に膜中に存在する（１１１）
面の量が増えるほど、二次電子放出比は増大し、駆動電
圧も減少すると言われている。At present, as the above protective film of AC type PDP,
An MgO film formed by an electron beam evaporation method using a crushed single crystal MgO as an evaporation material is generally used. The crushed single-crystal MgO is obtained by melting an MgO clinker having a purity of 98% or more or lightly burned MgO (MgO sintered at 1000 ° C. or less) in an electric arc furnace (ie, an arc furnace). Then, the single crystal portion is taken out of the ingot and crushed to produce the ingot. The MgO film formed by the electron beam evaporation method is formed at a speed of about 1000 ° / min. Further, the formed MgO film can be driven at a low sustaining voltage, and further exists in the film (111).
It is said that as the surface area increases, the secondary electron emission ratio increases and the driving voltage also decreases.
【０００５】[0005]
【発明が解決しようとする課題】しかし、上記従来の単
結晶ＭｇＯの破砕品を蒸着材として用いた電子ビーム蒸
着法では、成膜速度が速い利点がある反面、破砕品であ
るため、形状が均一でなく、スプラッシュが発生し易い
不具合があった。また、上記従来の単結晶ＭｇＯの破砕
品を蒸着材として用いた電子ビーム蒸着法では、単一の
組成からなるため、異種原料を混合した成膜には適さ
ず、また成膜面積が広いときには、膜厚及び膜組成を均
一にすることが難しい問題点があった。However, the conventional electron beam evaporation method using a crushed single-crystal MgO product as a vapor deposition material has the advantage of a high film forming rate, but is a crushed product. There was a problem that it was not uniform and splash was easily generated. In addition, the conventional electron beam evaporation method using a crushed single crystal MgO as an evaporation material has a single composition, and thus is not suitable for film formation in which different kinds of raw materials are mixed. It is difficult to make the film thickness and film composition uniform.
【０００６】本発明の目的は、電子ビーム蒸着法による
成膜時にスプラッシュが発生せず、成膜面積が広くて
も、膜厚及び膜組成が均一なＭｇＯ膜を得ることができ
る、ＭｇＯ蒸着材及びその製造方法を提供することにあ
る。本発明の別の目的は、電子ビーム蒸着法による成膜
後、低い電圧でプラズマを生成しかつ維持することがで
き、放電時の耐スパッタ性，速い放電の応答性及び高い
絶縁性を有するＭｇＯ膜を得ることができる、ＭｇＯ蒸
着材及びその製造方法を提供することにある。本発明の
更に別の目的は、ＭｇＯ焼結体のＭｇＯマトリックス粒
界の欠陥を低減することができ、かつ強度も向上するこ
とができ、またＭｇＯ焼結体のＭｇＯマトリックスを均
一な組織にすることができる、ＭｇＯ蒸着材及びその製
造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a MgO vapor deposition material which does not generate a splash during film formation by an electron beam vapor deposition method and can provide an MgO film having a uniform film thickness and film composition even if the film formation area is large. And a method for manufacturing the same. Another object of the present invention is to provide a plasma processing apparatus which can generate and maintain plasma at a low voltage after film formation by electron beam evaporation, and has a sputter resistance at the time of discharge, a fast discharge response and a high insulating property. An object of the present invention is to provide a MgO vapor deposition material capable of obtaining a film and a method for producing the same. Still another object of the present invention is to reduce the defects at the MgO matrix grain boundaries of the MgO sintered body, improve the strength, and make the MgO matrix of the MgO sintered body a uniform structure. It is an object of the present invention to provide an MgO vapor deposition material and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】請求項１に係る発明は、
相対密度が９５％以上のＭｇＯ焼結体であって、平均結
晶粒径が０．３〜１００μｍの結晶粒子を有するＭｇＯ
マトリックス中に、アルカリ土類金属酸化物粒子が０．
５〜５０体積％分散されたＭｇＯ蒸着材である。請求項
２に係る発明は、請求項１に係る発明であって、更にア
ルカリ土類金属酸化物粒子中のアルカリ土類金属元素が
Ｃａ，Ｓｒ及びＢａからなる群より選ばれた１種又は２
種以上の元素であることを特徴とする。これらの請求項
１又は２に記載されたＭｇＯ蒸着材では、異方性のない
ＭｇＯマトリックス中に、アルカリ土類金属酸化物粒子
を分散して複合化を行うことにより、ＭｇＯ焼結体の物
理的性質を改善できる。The invention according to claim 1 is
MgO sintered body having a relative density of 95% or more and having crystal grains having an average crystal grain size of 0.3 to 100 μm
Alkaline earth metal oxide particles are contained in the matrix at a concentration of 0.1%.
It is a MgO vapor deposition material dispersed in 5 to 50% by volume. The invention according to claim 2 is the invention according to claim 1, wherein the alkaline earth metal element in the alkaline earth metal oxide particles is one or more selected from the group consisting of Ca, Sr and Ba.
It is characterized by being at least one kind of element. In the MgO vapor deposition material according to claim 1 or 2, the physical properties of the MgO sintered body are obtained by dispersing the alkaline earth metal oxide particles in an MgO matrix having no anisotropy and performing complexation. Properties can be improved.
【０００８】例えば、Ａｌ2Ｏ3マトリックスにＳｉＣ粒
子を分散させた場合には、分散粒子の熱膨張係数がＡｌ
2Ｏ3マトリックスより２倍以上小さいため、焼結時にこ
の熱膨張係数の差に起因して焼結過程で分散粒子の周囲
や内部に応力が発生する。この応力は１０００ＭＰａ〜
１５００ＭＰａに達する程大きいため、Ａｌ2Ｏ3マトリ
ックスと分散粒子の界面に亀裂が走る場合がある。従っ
て、これを防ぐには、非常に細かいＳｉＣ粒子を分散さ
せなければならない問題点がある。これに対して本発明
では、アルカリ土類金属酸化物粒子が高温で軟化し、そ
の熱膨張係数が高温でＭｇＯマトリックスの熱膨張係数
（約１４×１０-6／℃）の約０．７〜０．９倍になる。
ＭｇＯマトリックスに対するアルカリ土類金属酸化物粒
子の高温時の熱挙動から、焼結時にＭｇＯマトリックス
と分散粒子はその界面で強く結合する。この界面での強
い結合により、蒸着材として用いた場合に、数千オング
ストローム／分以上の成膜速度が得られる。For example, when SiC particles are dispersed in an Al 2 O 3 matrix, the thermal expansion coefficient of the dispersed particles is Al.
Since it is smaller than the 2 O 3 matrix by a factor of two or more, stress is generated around and inside the dispersed particles during the sintering process due to the difference in the coefficient of thermal expansion during sintering. This stress is 1000MPa ~
Since it is so large as to reach 1500 MPa, cracks may run at the interface between the Al 2 O 3 matrix and the dispersed particles. Therefore, in order to prevent this, there is a problem that very fine SiC particles must be dispersed. On the other hand, in the present invention, the alkaline earth metal oxide particles soften at a high temperature and have a thermal expansion coefficient of about 0.7 to about the thermal expansion coefficient of the MgO matrix (about 14 × 10 −6 / ° C.) at a high temperature. 0.9 times.
From the thermal behavior of the alkaline earth metal oxide particles with respect to the MgO matrix at a high temperature, the MgO matrix and the dispersed particles are strongly bonded at the interface during sintering. Due to the strong bonding at the interface, a film forming speed of several thousand angstroms / min or more can be obtained when used as a vapor deposition material.
【０００９】上述のように分散粒子であるアルカリ土類
金属酸化物粒子は、高温で軟らかくなるために、高温で
はマトリックスと分散粒子との熱膨張係数の差は、小さ
くなる。従って、界面に亀裂を発生させない範囲で大き
なアルカリ土類金属酸化物粒子を分散させることが可能
で、そのためにマトリックス粒界を締め付けるトータル
の領域が大きくなり、粒界の欠陥も少なく、かつ強度も
向上する。更にアルカリ土類金属酸化物粒子を添加する
ことにより、ＭｇＯ焼結体のＭｇＯマトリックスが均一
な組織となる。As described above, the alkaline earth metal oxide particles, which are dispersed particles, become soft at high temperatures, so that at high temperatures, the difference in the coefficient of thermal expansion between the matrix and the dispersed particles becomes small. Therefore, it is possible to disperse the large alkaline earth metal oxide particles within a range that does not cause cracks at the interface, thereby increasing the total area for tightening the matrix grain boundaries, reducing the number of defects at the grain boundaries, and improving the strength. improves. Further, by adding the alkaline earth metal oxide particles, the MgO matrix of the MgO sintered body has a uniform structure.
【００１０】請求項３に係る発明は、相対密度が９５％
以上のＭｇＯ焼結体であって、平均結晶粒径が０．３〜
１００μｍの結晶粒子を有するＭｇＯマトリックス中
に、アルカリ土類金属酸化物粒子及び希土類酸化物粒子
が合計０．５〜５０体積％分散されたＭｇＯ蒸着材であ
る。請求項４に係る発明は、請求項３に係る発明であっ
て、更にアルカリ土類金属酸化物粒子中のアルカリ土類
金属元素がＣａ，Ｓｒ及びＢａからなる群より選ばれた
１種の元素であり、希土類酸化物粒子中の希土類元素が
Ｓｃ，Ｙ，Ｌａ，Ｃｅ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｙｂ
及びＤｙからなる群より選ばれた１種の元素であること
を特徴とする。[0010] The invention according to claim 3 has a relative density of 95%.
In the above MgO sintered body, the average crystal grain size is 0.3 to
This is an MgO vapor deposition material in which alkaline earth metal oxide particles and rare earth oxide particles are dispersed in a total of 0.5 to 50% by volume in an MgO matrix having crystal particles of 100 μm. The invention according to claim 4 is the invention according to claim 3, wherein the alkaline earth metal element in the alkaline earth metal oxide particles is one element selected from the group consisting of Ca, Sr and Ba. And the rare earth elements in the rare earth oxide particles are Sc, Y, La, Ce, Nd, Sm, Gd, Tb, and Yb.
And Dy is one kind of element selected from the group consisting of:
【００１１】これらの請求項３又は４に記載されたＭｇ
Ｏ蒸着材では、希土類酸化物粒子がアルカリ土類金属酸
化物粒子と同様に、高温で軟化し、その熱膨張係数が高
温でＭｇＯマトリックスの熱膨張係数（約１４×１０-6
／℃）の約０．７〜０．９倍になる。この結果、ＭｇＯ
マトリックスに対するアルカリ土類金属酸化物粒子及び
希土類酸化物粒子の高温時の熱挙動から、焼結時にＭｇ
Ｏマトリックスと分散粒子はその界面で強く結合する。
また分散粒子であるアルカリ土類金属酸化物粒子及び希
土類酸化物粒子は、高温で軟らかくなるために、請求項
１に記載されたＭｇＯ蒸着材と同様に、高温ではマトリ
ックスと分散粒子との熱膨張係数の差が小さくなり、界
面に亀裂を発生させない範囲で大きなアルカリ土類金属
酸化物粒子及び希土類酸化物粒子を分散させることが可
能となる。そのためにマトリックス粒界を締め付けるト
ータルの領域が大きくなり、粒界の欠陥も少なく、かつ
強度も向上する、即ちＭｇＯ焼結体の物理的性質を改善
できる。またアルカリ土類金属酸化物粒子及び希土類酸
化物粒子を添加することにより、ＭｇＯ焼結体のＭｇＯ
マトリックスが均一な組織となる。[0011] The Mg according to claim 3 or 4
In the O-deposited material, the rare-earth oxide particles soften at a high temperature similarly to the alkaline-earth metal oxide particles, and the thermal expansion coefficient of the rare-earth oxide particles at the high temperature is about 14 × 10 −6 of the MgO matrix.
/ ° C) about 0.7 to 0.9 times. As a result, MgO
From the thermal behavior of the alkaline earth metal oxide particles and rare earth oxide particles at high temperature with respect to the matrix,
The O matrix and the dispersed particles are strongly bonded at the interface.
Also, the alkaline earth metal oxide particles and the rare earth oxide particles, which are dispersed particles, become soft at a high temperature, so that the thermal expansion of the matrix and the dispersed particles at a high temperature is the same as the MgO vapor deposition material according to claim 1. The difference in coefficient becomes small, and large alkaline earth metal oxide particles and rare earth oxide particles can be dispersed within a range that does not cause cracks at the interface. Therefore, the total area for tightening the matrix grain boundaries is increased, the number of defects at the grain boundaries is reduced, and the strength is improved, that is, the physical properties of the MgO sintered body can be improved. In addition, by adding alkaline earth metal oxide particles and rare earth oxide particles, MgO
The matrix has a uniform structure.
【００１２】上記請求項１又は２に係るＭｇＯ蒸着材
は、ＭｇＯ粉末とアルカリ土類金属の酸化物粉末又は炭
酸塩粉末とバインダと有機溶媒とを混合して所定濃度の
混合スラリーを調製する工程と、このスラリーを噴霧乾
燥して所定粒径の造粒粉末を得る工程と、この造粒粉末
を所定の型に入れて所定の圧力で成形する工程と、この
成形体を脱脂した後に１４５０〜１７００℃の温度で焼
結する工程とを含む製造方法で製造されることが好まし
い。また上記請求項３又は４に係るＭｇＯ蒸着材は、Ｍ
ｇＯ粉末とアルカリ土類金属の酸化物粉末又は炭酸塩粉
末と希土類酸化物粉末とバインダと有機溶媒とを混合し
て所定濃度の混合スラリーを調製する工程と、このスラ
リーを噴霧乾燥して所定粒径の造粒粉末を得る工程と、
この造粒粉末を所定の型に入れて所定の圧力で成形する
工程と、この成形体を脱脂した後に１４５０〜１７００
℃の温度で焼結する工程とを含む製造方法で製造される
ことが好ましい。The MgO vapor deposition material according to claim 1 or 2 is a step of mixing MgO powder and alkaline earth metal oxide powder or carbonate powder, a binder and an organic solvent to prepare a mixed slurry having a predetermined concentration. And a step of spray-drying the slurry to obtain a granulated powder having a predetermined particle size; a step of placing the granulated powder in a predetermined mold and molding at a predetermined pressure; And sintering at a temperature of 1700 ° C. Further, the MgO vapor deposition material according to claim 3 or 4 is characterized in that:
a step of mixing a gO powder and an alkaline earth metal oxide powder or a carbonate powder, a rare earth oxide powder, a binder and an organic solvent to prepare a mixed slurry having a predetermined concentration; A step of obtaining granulated powder having a diameter,
A step of placing the granulated powder in a predetermined mold and molding at a predetermined pressure, and 1450 to 1700 after degreasing the molded body.
And sintering at a temperature of ° C.
【００１３】なお、上記アルカリ土類金属酸化物粉末は
アルカリ土類金属元素の水酸化物，炭酸塩，蓚酸塩又は
有機金属化合物のアルコキシドを熱分解することにより
作製され、希土類酸化物粉末は希土類元素の水酸化物，
炭酸塩，蓚酸塩又は有機金属化合物のアルコキシドを熱
分解することにより作製されることが好ましい。上記製
造方法で製造されたＭｇＯ蒸着材では、焼結工程で緻密
に焼結され、この蒸着材のＭｇＯマトリックス内に分散
相であるアルカリ土類金属酸化物粒子又はアルカリ土類
金属酸化物粒子及び希土類酸化物粒子が均一に分散され
る。The alkaline earth metal oxide powder is prepared by thermally decomposing a hydroxide, a carbonate, an oxalate of an alkaline earth metal element or an alkoxide of an organometallic compound, and the rare earth oxide powder is rare earth. Elemental hydroxide,
It is preferably produced by thermally decomposing an alkoxide of a carbonate, an oxalate or an organometallic compound. In the MgO vapor-deposited material manufactured by the above-described manufacturing method, the sintered body is densely sintered in the sintering step, and the alkaline-earth metal oxide particles or the alkaline-earth metal oxide particles that are dispersed phases in the MgO matrix of the vapor-deposited material; The rare earth oxide particles are uniformly dispersed.
【００１４】上記請求項１ないし４いずれか記載のＭｇ
Ｏ蒸着材を用いて電子ビーム蒸着法によりＭｇＯ膜を成
膜すると、二相共存、即ちＭｇＯマトリックスと分散粒
子とが固溶体や反応物を形成しない状態で蒸発するの
で、高速で安定な成膜が可能となり、またスプラッシュ
が発生せず、成膜面積が広くても、膜厚及び膜組成が均
一なＭｇＯ膜を得ることができる。またこのＭｇＯ膜は
ＭｇＯ中にアルカリ土類金属酸化物粒子又はアルカリ土
類金属酸化物粒子及び希土類酸化物粒子をドーピングし
た構造、即ちＭｇＯ中に上記アルカリ土類金属酸化物粒
子等を固溶した構造、或いはスピネル構造であるので、
ＭｇＯ膜の配向性は向上する。この結果、このＭｇＯ膜
を成膜した基板をＰＤＰに組込むと、低い電圧でプラズ
マを生成しかつ維持することができ、放電時の耐スパッ
タ性を向上でき、速い放電の応答性及び高い絶縁性を得
ることができる。またＭｇＯ膜が蛍光体に悪影響を及ぼ
すことはなく、青色に関係する輝度も向上することがで
きる。即ち、ＡＣ型ＰＤＰの誘電体層の保護膜に好適な
ものとなる。The Mg according to any one of claims 1 to 4,
When an MgO film is formed by an electron beam evaporation method using an O vapor deposition material, the two phases coexist, that is, the MgO matrix and the dispersed particles evaporate without forming a solid solution or a reactant. This makes it possible to obtain an MgO film having a uniform film thickness and a uniform film composition, even if the film formation area is large without splash. The MgO film has a structure in which alkaline earth metal oxide particles or alkaline earth metal oxide particles and rare earth oxide particles are doped in MgO, that is, the above alkaline earth metal oxide particles and the like are dissolved in MgO. Structure or spinel structure,
The orientation of the MgO film is improved. As a result, when the substrate on which the MgO film is formed is incorporated into a PDP, plasma can be generated and maintained at a low voltage, spatter resistance during discharge can be improved, and fast discharge response and high insulation properties can be achieved. Can be obtained. Also, the MgO film does not adversely affect the phosphor, and the luminance related to blue can be improved. That is, it is suitable as a protective film for the dielectric layer of the AC PDP.
【００１５】[0015]
【発明の実施の形態】以下に本発明の第１の実施の形態
を説明する。本発明のＭｇＯ蒸着材は、相対密度が９５
％以上のＭｇＯ焼結体であって、平均結晶粒径が０．３
〜１００μｍ、好ましくは２〜５０μｍの結晶粒子を有
するＭｇＯマトリックス中に、アルカリ土類金属酸化物
粒子が０．５〜５０体積％、好ましくは１〜３０体積
％、更に好ましくは５〜２５体積％分散されたものであ
る。この蒸着材はマトリックスとしてＭｇＯを用い、か
つ分散相（分散粒子）としてアルカリ土類金属酸化物粒
子を用いたセラミック焼結体である。上記アルカリ土類
金属酸化物粒子中のアルカリ土類金属元素としては、Ｃ
ａ，Ｓｒ及びＢａからなる群より選ばれた１種又は２種
以上の元素が用いられることが好ましい。また分散粒子
の平均粒径は３．０μｍ以下であることが好ましく、分
散粒子の含有割合はＭｇＯマトリックス及び分散粒子の
合計に対する内割の割合である。DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS A first embodiment of the present invention will be described below. The MgO vapor deposition material of the present invention has a relative density of 95.
% Of MgO sintered body having an average crystal grain size of 0.3
0.5 to 50% by volume, preferably 1 to 30% by volume, more preferably 5 to 25% by volume of alkaline earth metal oxide particles in a MgO matrix having crystal particles of from 100 to 100 [mu] m, preferably from 2 to 50 [mu] m. It is distributed. This vapor deposition material is a ceramic sintered body using MgO as a matrix and alkaline earth metal oxide particles as a dispersed phase (dispersed particles). Examples of the alkaline earth metal element in the alkaline earth metal oxide particles include C
It is preferable to use one or more elements selected from the group consisting of a, Sr and Ba. Further, the average particle size of the dispersed particles is preferably 3.0 μm or less, and the content ratio of the dispersed particles is a ratio of the inner part to the total of the MgO matrix and the dispersed particles.
【００１６】上記ＭｇＯマトリックスの平均結晶粒径を
０．３〜１００μｍの範囲に限定したのは、この範囲に
おいてＭｇＯマトリックスの組織制御が可能なためであ
る。また分散粒子の平均粒径を３．０μｍ以下に限定し
たのは、ＭｇＯマトリックスの組織構造を制御し易く、
また残留応力がある限度以上になってもマイクロクラッ
クが発生しないためである。なお、分散粒子の平均粒径
が３．０μｍを越えるとマイクロクラックが発生し易く
なる。The reason why the average crystal grain size of the MgO matrix is limited to the range of 0.3 to 100 μm is that the structure of the MgO matrix can be controlled in this range. The reason why the average particle size of the dispersed particles is limited to 3.0 μm or less is that the structure of the MgO matrix can be easily controlled,
Also, microcracks do not occur even when the residual stress exceeds a certain limit. When the average particle size of the dispersed particles exceeds 3.0 μm, micro cracks are easily generated.
【００１７】このように構成された本発明のＭｇＯ蒸着
材の製造方法を説明する。平均粒径が０．１〜５μｍ、
好ましくは０．２〜２μｍのＭｇＯ粉末に、平均粒径が
０．２〜３．０μｍのアルカリ土類金属酸化物粉末とバ
インダとを合計０．２〜２．５重量％添加し、更にエタ
ノールやプロパノール等を分散媒として湿式混合して濃
度が４０〜７０重量％の混合スラリーに調製する。上記
アルカリ土類金属酸化物粉末はこのアルカリ土類金属酸
化物粉末とＭｇＯ粉末との合計体積に対してアルカリ土
類金属酸化物粉末が０．５〜５０体積％となるように秤
量してＭｇＯ粉末に加えられる。また上記湿式混合はボ
ールミル又は撹拌ミルにより行われる。上記ＭｇＯ粉末
の粒径を０．１〜５μｍの範囲に限定したのは、焼結し
易くするためである。また分散粒子の添加量、即ちアル
カリ土類金属酸化物粉末の添加量を０．５〜５０体積％
の範囲に限定したのは、０．５体積％未満ではアルカリ
土類金属酸化物粉末を添加した効果が乏しく、５０体積
％を越えると、材料組織の制御が困難となり、耐スパッ
タ性や絶縁性にバラツキが生じ、材料の信頼性がなくな
るからである。分散粒子の添加量が上記範囲内であれ
ば、ＭｇＯマトリックス中に分散粒子が均一に取り込ま
れかつＭｇＯマトリックスの組織を制御でき、成膜した
膜特性も向上する。A method for manufacturing the MgO vapor deposition material of the present invention having the above-described structure will be described. Average particle size of 0.1 to 5 μm,
Preferably, a total of 0.2 to 2.5% by weight of an alkaline earth metal oxide powder having an average particle diameter of 0.2 to 3.0 μm and a binder is added to 0.2 to 2 μm of MgO powder, and ethanol is further added. And a mixed slurry having a concentration of 40 to 70% by weight by wet mixing with a dispersion medium such as ethanol or propanol. The alkaline earth metal oxide powder is weighed such that the alkaline earth metal oxide powder is 0.5 to 50% by volume based on the total volume of the alkaline earth metal oxide powder and the MgO powder. Added to powder. The wet mixing is performed by a ball mill or a stirring mill. The reason for limiting the particle size of the MgO powder to the range of 0.1 to 5 μm is to facilitate sintering. Further, the addition amount of the dispersed particles, that is, the addition amount of the alkaline earth metal oxide powder is 0.5 to 50% by volume.
If the content is less than 0.5% by volume, the effect of adding the alkaline earth metal oxide powder is poor, and if it exceeds 50% by volume, it is difficult to control the material structure, and the This causes variations in the reliability of the material. When the amount of the dispersed particles is within the above range, the dispersed particles are uniformly taken into the MgO matrix, the structure of the MgO matrix can be controlled, and the characteristics of the formed film can be improved.
【００１８】上記アルカリ土類金属酸化物粉末はアルカ
リ土類金属元素の水酸化物又は炭酸塩を熱分解すること
により作製されることが好ましい。例えば、アルカリ土
類金属元素の水酸化物としては水酸化カルシウム、炭酸
塩としては炭酸カルシウムが用いられる。また上記混合
スラリーの濃度を４０〜７０重量％に限定したのは、こ
の範囲内であれば混合スラリーの粘度が２００ｐｐｍ以
下であり、スプレードライ造粒しても安定して製造でき
ること、更には後述する成形体の密度が高くなり、緻密
な焼結体の製造が可能になるためである。混合スラリー
の濃度が７０重量％を越えると、非水系スラリーである
ために、安定した造粒が難しく、４０重量％未満では、
均一な組織を有した緻密なＭｇＯ焼結体が得られない。The alkaline earth metal oxide powder is preferably produced by thermally decomposing a hydroxide or carbonate of an alkaline earth metal element. For example, calcium hydroxide is used as the hydroxide of the alkaline earth metal element, and calcium carbonate is used as the carbonate. The reason why the concentration of the mixed slurry is limited to 40 to 70% by weight is that the viscosity of the mixed slurry is 200 ppm or less within this range, and that the slurry can be manufactured stably even by spray-dry granulation. This is because the density of the compact to be formed increases and a dense sintered body can be manufactured. When the concentration of the mixed slurry exceeds 70% by weight, stable granulation is difficult due to the non-aqueous slurry.
A dense MgO sintered body having a uniform structure cannot be obtained.
【００１９】次に上記混合スラリーを噴霧乾燥して平均
粒径が５０〜２００μｍの造粒粉末を得た後、この造粒
粉末を所定の型に入れて所定の圧力で成形する。上記噴
霧乾燥はスプレードライヤを用いて行われることが好ま
しく、ペレットの成形には、メカニカルプレス法、タブ
レットマシン法又はブリケットマシン法のいずれかの金
型プレス法を用いて行われることが好ましい。Next, the mixed slurry is spray-dried to obtain a granulated powder having an average particle diameter of 50 to 200 μm, and then the granulated powder is placed in a predetermined mold and molded at a predetermined pressure. The spray drying is preferably performed using a spray dryer, and the pellets are preferably formed using a mold pressing method such as a mechanical press method, a tablet machine method, or a briquette machine method.
【００２０】更に上記成形体を１４５０℃〜１７００℃
で焼結する。焼結する前に成形体を３５０〜６２０℃の
温度で脱脂処理することが好ましい。この脱脂処理は、
成形体の焼結後の色むらと反りを防止するために行わ
れ、時間をかけて十分に行うことが好ましい。上記成形
体の焼結温度を１４５０℃〜１７００℃に限定したの
は、１４５０℃未満では緻密な焼結体が得られず、１７
００℃を越えると粒成長が著しく速く、特性が低下する
からである。また、成形体を不活性ガス雰囲気中で焼結
する場合には、不活性ガスとしてアルゴンガスを用いる
ことが好ましい。このようにして相対密度が９５％以上
の緻密なＭｇＯ蒸着材が得られる。Further, the above-mentioned molded product is heated at 1450 ° C. to 1700 ° C.
And sinter. Before sintering, it is preferable that the molded body is subjected to a degreasing treatment at a temperature of 350 to 620 ° C. This degreasing process
It is performed in order to prevent color unevenness and warpage after sintering of the molded body, and it is preferable to sufficiently perform the process over time. The reason why the sintering temperature of the compact was limited to 1450 ° C. to 1700 ° C. is that a compact sintered body cannot be obtained below 1450 ° C.
If the temperature exceeds 00 ° C., the grain growth is remarkably fast, and the characteristics deteriorate. When the compact is sintered in an inert gas atmosphere, it is preferable to use argon gas as the inert gas. In this way, a dense MgO vapor deposition material having a relative density of 95% or more can be obtained.
【００２１】上記ＭｇＯ蒸着材を用いて電子ビーム蒸着
法によりＭｇＯ膜を基板等に成膜すれば、高速で安定な
成膜が可能となり、またスプラッシュが発生せず、成膜
面積が広くても、膜厚及び膜組成が均一なＭｇＯ膜を得
ることができる。またこのＭｇＯ膜はＭｇＯ中にアルカ
リ土類金属酸化物粒子をドーピングした構造、即ちＭｇ
Ｏ中に上記アルカリ土類金属酸化物粒子を固溶した構
造、或いはスピネル構造であるので、ＭｇＯ膜の配向性
は向上する。この結果、このＭｇＯ膜を成膜した基板を
ＰＤＰに組込むと、低い電圧でプラズマを生成しかつ維
持することができ、放電時の耐スパッタ性を向上でき、
速い放電の応答性及び高い絶縁性を得ることができる。
またＭｇＯ膜が蛍光体に悪影響を及ぼすことはなく、青
色に関係する輝度も向上することができる。従って、Ａ
Ｃ型ＰＤＰの誘電体層の保護膜に好適であり、また高機
能セラミック材料の保護膜などにも適用できる。If an MgO film is formed on a substrate or the like by the electron beam evaporation method using the above-described MgO evaporation material, a high-speed and stable film formation becomes possible. It is possible to obtain an MgO film having a uniform thickness, thickness and composition. The MgO film has a structure in which alkaline earth metal oxide particles are doped in MgO, that is, MgO.
Because of the structure in which the alkaline earth metal oxide particles are dissolved in O or the spinel structure, the orientation of the MgO film is improved. As a result, when the substrate on which the MgO film is formed is incorporated in a PDP, plasma can be generated and maintained at a low voltage, and the spatter resistance during discharge can be improved.
Fast discharge response and high insulation can be obtained.
Also, the MgO film does not adversely affect the phosphor, and the luminance related to blue can be improved. Therefore, A
It is suitable as a protective film for a dielectric layer of a C-type PDP, and is also applicable to a protective film of a high-performance ceramic material.
【００２２】次に本発明の第２の実施の形態を説明す
る。本発明のＭｇＯ蒸着材は、相対密度が９５％以上の
ＭｇＯ焼結体であって、平均結晶粒径が０．３〜１００
μｍ、好ましくは２〜５０μｍの結晶粒子を有するＭｇ
Ｏマトリックス中に、アルカリ土類金属酸化物粒子及び
希土類酸化物粒子が合計で０．５〜５０体積％、好まし
くは１〜３０体積％、更に好ましくは５〜２５体積％分
散されたものである。この蒸着材はマトリックスとして
ＭｇＯを用い、かつ分散相（分散粒子）としてアルカリ
土類金属酸化物粒子及び希土類酸化物粒子を用いたセラ
ミック焼結体である。上記アルカリ土類金属酸化物粒子
中のアルカリ土類金属元素としては、Ｃａ，Ｓｒ及びＢ
ａからなる群より選ばれた１種の元素が用いられ、希土
類酸化物粒子中の希土類元素としては、Ｓｃ，Ｙ，Ｌ
ａ，Ｃｅ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔｂ，Ｙｂ及びＤｙから
なる群より選ばれた１種の元素が用いられることが好ま
しい。上記以外は第１の実施の形態と同一に構成され
る。Next, a second embodiment of the present invention will be described. The MgO vapor deposition material of the present invention is a MgO sintered body having a relative density of 95% or more, and has an average crystal grain size of 0.3 to 100.
Mg having crystal grains of μm, preferably 2 to 50 μm
In the O matrix, the alkaline earth metal oxide particles and the rare earth oxide particles are dispersed in a total of 0.5 to 50% by volume, preferably 1 to 30% by volume, and more preferably 5 to 25% by volume. . This vapor deposition material is a ceramic sintered body using MgO as a matrix and alkaline earth metal oxide particles and rare earth oxide particles as a dispersed phase (dispersed particles). The alkaline earth metal elements in the alkaline earth metal oxide particles include Ca, Sr and B
a selected from the group consisting of Sc, Y, and L as rare earth elements in the rare earth oxide particles.
Preferably, one element selected from the group consisting of a, Ce, Nd, Sm, Gd, Tb, Yb and Dy is used. Except for the above, the configuration is the same as that of the first embodiment.
【００２３】このように構成された本発明のＭｇＯ蒸着
材の製造方法を説明する。平均粒径が０．１〜５μｍ、
好ましくは０．２〜２μｍのＭｇＯ粉末に、平均粒径が
０．２〜３．０μｍのアルカリ土類金属酸化物粉末及び
希土類酸化物粉末と、バインダとを合計０．２〜２．５
重量％添加し、更にエタノールやプロパノール等を分散
媒として湿式混合して濃度が４５〜７０重量％の混合ス
ラリーに調製する。上記アルカリ土類金属酸化物粉末及
び希土類酸化物粉末はアルカリ土類金属酸化物粉末と希
土類酸化物粉末とＭｇＯ粉末との合計体積に対してアル
カリ土類金属酸化物粉末及び希土類酸化物粉末が０．５
〜５０体積％となるように秤量してＭｇＯ粉末に加えら
れる。分散粒子の添加量、即ちアルカリ土類金属酸化物
粉末及び希土類酸化物粉末の合計添加量を０．５〜５０
体積％の範囲に限定したのは、０．５体積％未満ではア
ルカリ土類金属酸化物及び希土類酸化物を添加した効果
が乏しく、５０体積％を越えると、材料組織の制御が困
難となり、耐スパッタ性や絶縁性にバラツキが生じ、材
料の信頼性がなくなるからである。A method for manufacturing the MgO vapor deposition material of the present invention having the above-described structure will be described. Average particle size of 0.1 to 5 μm,
Preferably, a total of 0.2 to 2.5 μm of an alkaline earth metal oxide powder and a rare earth oxide powder having an average particle size of 0.2 to 3.0 μm and a binder is added to a 0.2 to 2 μm MgO powder.
% By weight and further wet-mixed with ethanol or propanol as a dispersion medium to prepare a mixed slurry having a concentration of 45 to 70% by weight. The alkaline earth metal oxide powder and the rare earth oxide powder are such that the amount of the alkaline earth metal oxide powder and the rare earth oxide powder is 0 with respect to the total volume of the alkaline earth metal oxide powder, the rare earth oxide powder and the MgO powder. .5
It is weighed to be と 50% by volume and added to the MgO powder. The added amount of the dispersed particles, that is, the total added amount of the alkaline earth metal oxide powder and the rare earth oxide powder is 0.5 to 50.
When the content is limited to the range of 0.5% by volume, the effect of adding an alkaline earth metal oxide and a rare earth oxide is poor when the content is less than 0.5% by volume. This is because the sputtering properties and the insulation properties vary, and the reliability of the material is lost.
【００２４】上記希土類酸化物粉末は希土類元素の水酸
化物，炭酸塩，蓚酸塩又は有機金属化合物のアルコキシ
ドを熱分解することにより作製されることが好ましい。
例えば、希土類元素の水酸化物としては水酸化ランタン
［Ｌａ（ＯＨ）3］、炭酸塩としては炭酸ランタン［Ｌ
ａ2（ＣＯ3）3］、蓚酸塩としては蓚酸ランタン［Ｌａ2
（Ｃ2Ｏ4）3・１０Ｈ2Ｏ］、有機金属化合物としてはＬ
ａ（Ｃ5Ｈ8Ｏ2）3が用いられる。上記以外のＭｇＯ蒸着
材の製造方法は第１の実施の形態と略同様であるので、
繰返しの説明を省略する。The rare earth oxide powder is preferably prepared by thermally decomposing a hydroxide, carbonate, oxalate or alkoxide of an organometallic compound of a rare earth element.
For example, lanthanum hydroxide [La (OH) 3 ] is used as a hydroxide of a rare earth element, and lanthanum carbonate [L is used as a carbonate.
a 2 (CO 3 ) 3 ], lanthanum oxalate [La 2
(C 2 O 4 ) 3 · 10H 2 O], and the organometallic compound is L
a (C 5 H 8 O 2 ) 3 is used. Since the manufacturing method of the MgO vapor deposition material other than the above is substantially the same as that of the first embodiment,
The description of the repetition is omitted.
【００２５】上記ＭｇＯ蒸着材を用いて電子ビーム蒸着
法によりＭｇＯ膜を基板等に成膜すれば、第１の実施の
形態と同様に、高速で安定な成膜が可能となり、またス
プラッシュが発生せず、成膜面積が広くても、膜厚及び
膜組成が均一なＭｇＯ膜を得ることができる。またこの
ＭｇＯ膜はＭｇＯ中にアルカリ土類金属酸化物粒子及び
希土類酸化物粒子をドーピングした構造、即ちＭｇＯ中
に上記アルカリ土類金属酸化物粒子及び希土類酸化物粒
子を固溶した構造、或いはスピネル構造であるので、Ｍ
ｇＯ膜の配向性は向上する。この結果、このＭｇＯ膜を
成膜した基板をＰＤＰに組込むと、低い電圧でプラズマ
を生成しかつ維持することができ、放電時の耐スパッタ
性を向上でき、速い放電の応答性及び高い絶縁性を得る
ことができる。またＭｇＯ膜が蛍光体に悪影響を及ぼす
ことはなく、青色に関係する輝度も向上することができ
る。従って、ＡＣ型ＰＤＰの誘電体層の保護膜に好適で
あり、また高機能セラミック材料の保護膜などにも適用
できる。If an MgO film is formed on a substrate or the like by an electron beam evaporation method using the above-described MgO evaporation material, a high-speed and stable film formation can be achieved as in the first embodiment, and a splash is generated. Without this, an MgO film having a uniform film thickness and film composition can be obtained even if the film formation area is large. Further, the MgO film has a structure in which alkaline earth metal oxide particles and rare earth oxide particles are doped in MgO, that is, a structure in which the above alkaline earth metal oxide particles and rare earth oxide particles are dissolved in MgO, or a spinel structure. M
The orientation of the gO film is improved. As a result, when the substrate on which the MgO film is formed is incorporated into a PDP, plasma can be generated and maintained at a low voltage, spatter resistance during discharge can be improved, and fast discharge response and high insulation properties can be achieved. Can be obtained. Also, the MgO film does not adversely affect the phosphor, and the luminance related to blue can be improved. Therefore, it is suitable as a protective film for a dielectric layer of an AC type PDP, and is also applicable to a protective film of a high-performance ceramic material.
【００２６】なお、上記第１及び第２の実施の形態で
は、混合スラリーを噴霧乾燥して所定粒径の造粒粉末を
得た後に所定の型に入れて所定の圧力で成形したが、転
動造粒機を用いて成形体を成形してもよい。即ち、先ず
ＭｇＯ粉末とアルカリ土類金属酸化物粉末等とバインダ
とを混練し、この混練物を転動造粒機の回転皿に入れた
後に、スプレー機でエタノールやプロパノール等の有機
溶媒を噴霧することにより上記混練物を造粒して球状の
成形体を成形し、回転皿に更に上記混練物を入れかつ有
機溶媒を噴霧する作業を繰返すことにより、所定の大き
さの球状の成形体を成形してもよい。また、上記第１及
び第２の実施の形態では、成形体を脱脂した後に１４５
０〜１７００℃の温度で焼結したが、ホットプレス焼結
してもよい。即ち、ＭｇＯ粉末とアルカリ土類金属酸化
物粉末等とを湿式混合し、この混合物を減圧加熱して乾
燥した後に乾式解砕し、更にこの乾式解砕した混合粉末
を所定の型に入れて所定の圧力をかけた状態で不活性ガ
ス雰囲気中で１４５０〜１６５０℃に昇温して焼結して
もよい。In the first and second embodiments, the mixed slurry is spray-dried to obtain a granulated powder having a predetermined particle size, and then placed in a predetermined mold and molded at a predetermined pressure. The compact may be formed using a dynamic granulator. That is, first, MgO powder, alkaline earth metal oxide powder, etc., and a binder are kneaded, and the kneaded material is put in a rotating plate of a tumbling granulator, and then an organic solvent such as ethanol or propanol is sprayed with a sprayer. The kneaded product is granulated to form a spherical molded product, and the operation of further adding the kneaded product to a rotating dish and spraying an organic solvent is repeated to obtain a spherical molded product of a predetermined size. It may be molded. In the first and second embodiments, after the molded body is degreased, 145
Although sintering was performed at a temperature of 0 to 1700 ° C., hot press sintering may be performed. That is, the MgO powder and the alkaline earth metal oxide powder are wet-mixed, the mixture is heated under reduced pressure, dried, and then subjected to dry pulverization, and the dry pulverized mixed powder is put into a prescribed mold and placed in a prescribed mold. The pressure may be raised to 1450 to 1650 ° C. in an inert gas atmosphere while sintering.
【００２７】[0027]
【実施例】以下に実施例及び比較例を挙げて、本発明を
より具体的に説明するが、本発明はその要旨を超えない
限り、以下の実施例に限定されるものではない。 ＜実施例１＞ＭｇＯ粉末（岩谷化学社製、平均粒径０．
１μｍ）とＣａＣＯ3粉末（関東化学社製、平均粒径
１．０〜１．５μｍ）とを加え、更にバインダ（ポリビ
ニールブチラール）を添加し、エタノールを分散媒とし
て、撹拌ミルで１時間湿式混合し、濃度が５５％の混合
スラリーに調製した。ここで、ＣａＣＯ3粉末はＣａＯ
に換算してＭｇＯとＣａＯとの合計体積に対しＣａＯが
１０体積％になるように秤量した。この混合スラリーを
スプレードライヤで噴霧乾燥して造粒することにより造
粒粉末を得た。この造粒粉末を金型（内径が１００ｍｍ
で深さが８ｍｍの金型）に充填し、メカニカルプレスで
成形して成形体を作製した。この成形体を大気雰囲気
中、１６５０℃に昇温し、焼結炉（広築社製）で３時間
焼結することにより直径が約８０ｍｍのＭｇＯ焼結体を
得た。このＭｇＯ焼結体を実施例１とした。EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to the following examples unless it exceeds the gist. <Example 1> MgO powder (manufactured by Iwatani Chemical Co., Ltd .;
1 μm) and CaCO 3 powder (manufactured by Kanto Chemical Co., Inc., average particle size: 1.0 to 1.5 μm), and a binder (polyvinyl butyral) is further added. The mixture was mixed to prepare a mixed slurry having a concentration of 55%. Here, CaCO 3 powder is CaO
And weighed so that CaO was 10% by volume with respect to the total volume of MgO and CaO. The mixed slurry was spray-dried with a spray dryer and granulated to obtain a granulated powder. This granulated powder is placed in a mold (with an inner diameter of 100 mm
To a mold having a depth of 8 mm) and molded by a mechanical press to produce a molded body. This molded body was heated to 1650 ° C. in the air atmosphere and sintered in a sintering furnace (manufactured by Hiroki Corporation) for 3 hours to obtain a MgO sintered body having a diameter of about 80 mm. This MgO sintered body was used as Example 1.
【００２８】＜実施例２＞ＣａＣＯ3粉末をＣａＯに換
算してＭｇＯとＣａＯとの合計体積に対しＣａＯが２０
体積％になるように秤量して、ＭｇＯ粉末に加え、実施
例１と同様にして混合スラリーを調製した後に造粒粉末
を得た。この造粒粉末を２つの金型（内径が１００ｍｍ
で深さが８ｍｍの金型、内径が６ｍｍで深さが３ｍｍの
金型）にそれぞれ充填し、メカニカルプレスで成形して
成形体をそれぞれ作製し、更にこれらの成形体を実施例
１と同様に焼結することにより直径が約８０ｍｍ及び５
ｍｍのＭｇＯ焼結体をそれぞれ得た。上記直径が約８０
ｍｍ及び５ｍｍのＭｇＯ焼結体を実施例２とした。 ＜実施例３＞ＣａＣＯ3粉末をＣａＯに換算してＭｇＯ
とＣａＯとの合計体積に対しＣａＯが３０体積％になる
ように秤量して、ＭｇＯ粉末に加えたことを除いて、実
施例１と同様にして直径が約８０ｍｍのＭｇＯ焼結体を
得た。このＭｇＯ焼結体を実施例３とした。Example 2 CaCO 3 powder was converted to CaO, and CaO was 20 to the total volume of MgO and CaO.
The mixture was weighed so as to be a volume%, added to the MgO powder, and a mixed slurry was prepared in the same manner as in Example 1 to obtain a granulated powder. This granulated powder is placed in two molds (with an inner diameter of 100 mm
, A mold having a depth of 8 mm, and a mold having an inner diameter of 6 mm and a depth of 3 mm), and molding by a mechanical press to produce molded bodies. Further, these molded bodies are the same as in Example 1. About 80mm and 5
mm MgO sintered bodies were obtained. The above diameter is about 80
Examples 2 mm and 5 mm MgO sintered bodies were used. Example 3 CaCO 3 powder was converted to CaO and MgO
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1, except that CaO was weighed so as to be 30% by volume with respect to the total volume of CaO and CaO, and was added to the MgO powder. . This MgO sintered body was used as Example 3.
【００２９】＜実施例４＞ＳｒＣＯ3粉末（堺化学社
製、平均粒径０．３〜０．５μｍ）をＳｒＯに換算して
ＭｇＯとＳｒＯとの合計体積に対しＳｒＯが１０体積％
になるように秤量して、ＭｇＯ粉末に加えたことを除い
て、実施例１と同様にして直径が約８０ｍｍのＭｇＯ焼
結体を得た。このＭｇＯ焼結体を実施例４とした。 ＜実施例５＞ＳｒＣＯ3粉末をＳｒＯに換算してＭｇＯ
とＳｒＯとの合計体積に対しＳｒＯが２０体積％になる
ように秤量して、ＭｇＯ粉末に加えたことを除いて、実
施例２と同様にして直径が約８０ｍｍ及び５ｍｍのＭｇ
Ｏ焼結体を得た。これらのＭｇＯ焼結体を実施例５とし
た。 ＜実施例６＞ＳｒＣＯ3粉末をＳｒＯに換算してＭｇＯ
とＳｒＯとの合計体積に対しＳｒＯが３０体積％になる
ように秤量して、ＭｇＯ粉末に加えたことを除いて、実
施例１と同様にして直径が約８０ｍｍのＭｇＯ焼結体を
得た。このＭｇＯ焼結体を実施例６とした。Example 4 SrCO 3 powder (manufactured by Sakai Chemical Co., average particle size 0.3 to 0.5 μm) was converted to SrO, and SrO was 10% by volume with respect to the total volume of MgO and SrO.
, And a MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO powder was added to the MgO powder. This MgO sintered body was used as Example 4. <Example 5> SrCO 3 powder was converted to SrO to obtain MgO
In the same manner as in Example 2 except that the SrO was weighed so that SrO became 20% by volume with respect to the total volume of
An O-sinter was obtained. These MgO sintered bodies were designated as Example 5. <Example 6> SrCO 3 powder was converted to SrO and MgO
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that SrO was weighed so as to be 30% by volume with respect to the total volume of SrO and SrO, and was added to the MgO powder. . This MgO sintered body was used as Example 6.
【００３０】＜実施例７＞ＢａＣＯ3粉末（関東化学社
製、平均粒径１．０〜１．５μｍ）をＢａＯに換算して
ＭｇＯとＢａＯとの合計体積に対しＢａＯが１０体積％
になるように秤量して、ＭｇＯ粉末に加えたことを除い
て、実施例１と同様にして直径が約８０ｍｍのＭｇＯ焼
結体を得た。このＭｇＯ焼結体を実施例７とした。 ＜実施例８＞ＢａＣＯ3粉末をＢａＯに換算してＭｇＯ
とＢａＯとの合計体積に対しＢａＯが２０体積％になる
ように秤量して、ＭｇＯ粉末に加えたことを除いて、実
施例２と同様にして直径が約８０ｍｍ及び５ｍｍのＭｇ
Ｏ焼結体を得た。これらのＭｇＯ焼結体を実施例８とし
た。 ＜実施例９＞ＢａＣＯ3粉末をＢａＯに換算してＭｇＯ
とＢａＯとの合計体積に対しＢａＯが３０体積％になる
ように秤量して、ＭｇＯ粉末に加えたことを除いて、実
施例１と同様にして直径が約８０ｍｍのＭｇＯ焼結体を
得た。このＭｇＯ焼結体を実施例９とした。Example 7 BaCO 3 powder (manufactured by Kanto Kagaku Co., average particle size 1.0-1.5 μm) was converted to BaO, and BaO was 10% by volume with respect to the total volume of MgO and BaO.
, And a MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO powder was added to the MgO powder. This MgO sintered body was used as Example 7. <Example 8> BaCO 3 powder was converted to BaO and MgO
And BaO were weighed so as to be 20% by volume with respect to the total volume of BaO and added to the MgO powder in the same manner as in Example 2 except that MgO having a diameter of about 80 mm and 5 mm was used.
An O-sinter was obtained. These MgO sintered bodies were used as Example 8. <Example 9> BaCO 3 powder was converted to BaO and MgO
A BaO having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that BaO was weighed such that BaO became 30% by volume with respect to the total volume of BaO and added to the MgO powder. . This MgO sintered body was used as Example 9.
【００３１】＜実施例１０＞ＣａＣＯ3粉末（関東化学
社製、平均粒径１．０〜１．５μｍ）及びＳｃ2Ｏ3粉末
（三菱マテリアル社製、平均粒径１〜３μｍ）を、Ｃａ
ＣＯ3粉末をＣａＯに換算して、ＭｇＯとＣａＯとＳｃ2
Ｏ3の合計体積に対し、ＣａＯ及びＳｃ2Ｏ3がそれぞれ
１０体積％及び５体積％になるように秤量して、ＭｇＯ
粉末に加えたことを除いて、実施例１と同様にして直径
が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結体
を実施例１０とした。 ＜実施例１１＞ＣａＣＯ3粉末及びＳｃ2Ｏ3粉末を、Ｃ
ａＣＯ3粉末をＣａＯに換算して、ＭｇＯとＣａＯとＳ
ｃ2Ｏ3の合計体積に対し、ＣａＯ及びＳｃ2Ｏ3がそれぞ
れ２０体積％及び１０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例２と同様にして
直径が約８０ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。こ
のＭｇＯ焼結体を実施例１１とした。 ＜実施例１２＞ＣａＣＯ3粉末及びＳｃ2Ｏ3粉末を、Ｃ
ａＣＯ3粉末をＣａＯに換算して、ＭｇＯとＣａＯとＳ
ｃ2Ｏ3の合計体積に対し、ＣａＯ及びＳｃ2Ｏ3がそれぞ
れ３０体積％及び２０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例１と同様にして
直径が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼
結体を実施例１２とした。Example 10 CaCO 3 powder (manufactured by Kanto Chemical Co., average particle size: 1.0 to 1.5 μm) and Sc 2 O 3 powder (manufactured by Mitsubishi Materials Corporation, average particle size: 1 to 3 μm) were mixed with Ca
Converting CO 3 powder into CaO, MgO, CaO and Sc 2
The total volume of O 3 to, were weighed so as CaO and Sc 2 O 3 is 10% by volume and 5% by volume, respectively, MgO
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the powder was added to the powder. This MgO sintered body was used as Example 10. Example 11 CaCO 3 powder and Sc 2 O 3 powder were
aCO 3 powder is converted into CaO, and MgO, CaO and S
CaO and Sc 2 O 3 were weighed so as to be 20% by volume and 10% by volume, respectively, based on the total volume of c 2 O 3 , and M
Except for adding to the gO powder, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2. This MgO sintered body was used as Example 11. <Example 12> CaCO 3 powder and Sc 2 O 3 powder were mixed with C
aCO 3 powder is converted into CaO, and MgO, CaO and S
CaO and Sc 2 O 3 were weighed so as to be 30% by volume and 20% by volume, respectively, based on the total volume of c 2 O 3 , and M
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO powder was added to the gO powder. This MgO sintered body was used as Example 12.
【００３２】＜実施例１３＞ＣａＣＯ3粉末（関東化学
社製、平均粒径１．０〜１．５μｍ）及びＹ2Ｏ3粉末
（信越化学社製、平均粒径０．６〜１．０μｍ）を、Ｃ
ａＣＯ3粉末をＣａＯに換算して、ＭｇＯとＣａＯとＹ2
Ｏ3の合計体積に対し、ＣａＯ及びＹ2Ｏ3がそれぞれ１
０体積％及び５体積％になるように秤量して、ＭｇＯ粉
末に加えたことを除いて、実施例１と同様にして直径が
約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結体を
実施例１３とした。 ＜実施例１４＞ＣａＣＯ3粉末及びＹ2Ｏ3粉末を、Ｃａ
ＣＯ3粉末をＣａＯに換算して、ＭｇＯとＣａＯとＹ2Ｏ
3の合計体積に対し、ＣａＯ及びＹ2Ｏ3がそれぞれ２０
体積％及び１０体積％になるように秤量して、ＭｇＯ粉
末に加えたことを除いて、実施例２と同様にして直径が
約８０ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。このＭｇ
Ｏ焼結体を実施例１４とした。 ＜実施例１５＞ＣａＣＯ3粉末及びＹ2Ｏ3粉末を、Ｃａ
ＣＯ3粉末をＣａＯに換算して、ＭｇＯとＣａＯとＹ2Ｏ
3の合計体積に対し、ＣａＯ及びＹ2Ｏ3がそれぞれ３０
体積％及び２０体積％になるように秤量して、ＭｇＯ粉
末に加えたことを除いて、実施例１と同様にして直径が
約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結体を
実施例１５とした。Example 13 CaCO 3 powder (manufactured by Kanto Chemical Co., average particle size 1.0-1.5 μm) and Y 2 O 3 powder (manufactured by Shin-Etsu Chemical Co., average particle size 0.6-1.0 μm) ) To C
aCO 3 powder is converted to CaO, and MgO, CaO and Y 2
The total volume of O 3 with respect to, CaO and Y 2 O 3 are each 1
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1, except that the mixture was weighed to be 0% by volume and 5% by volume and added to the MgO powder. This MgO sintered body was used as Example 13. <Example 14> CaCO 3 powder and Y 2 O 3 powder were mixed with Ca
Converting CO 3 powder into CaO, MgO, CaO and Y 2 O
3, the total volume of CaO and Y 2 O 3 was 20
MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2, except that they were weighed so as to be 10% by volume and 10% by volume, respectively, and were added to the MgO powder. This Mg
An O-sintered body was used as Example 14. Example 15 CaCO 3 powder and Y 2 O 3 powder were
Converting CO 3 powder into CaO, MgO, CaO and Y 2 O
3, the total volume of CaO and Y 2 O 3 was 30
A MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1, except that the mixture was weighed so as to be 20% by volume and added to the MgO powder. This MgO sintered body was used as Example 15.
【００３３】＜実施例１６＞ＳｒＣＯ3粉末（堺化学社
製、平均粒径０．３〜０．５μｍ）及びＬａ2Ｏ3粉末
（信越化学社製、平均粒径０．１〜０．２μｍ）を、Ｓ
ｒＣＯ3粉末をＳｒＯに換算して、ＭｇＯとＳｒＯとＹ2
Ｏ3の合計体積に対し、ＳｒＯ及びＹ2Ｏ3がそれぞれ１
０体積％及び５体積％になるように秤量して、ＭｇＯ粉
末に加えたことを除いて、実施例１と同様にして直径が
約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結体を
実施例１６とした。 ＜実施例１７＞ＳｒＣＯ3粉末及びＬａ2Ｏ3粉末を、Ｓ
ｒＣＯ3粉末をＳｒＯに換算して、ＭｇＯとＳｒＯとＹ2
Ｏ3の合計体積に対し、ＳｒＯ及びＹ2Ｏ3がそれぞれ２
０体積％及び１０体積％になるように秤量して、ＭｇＯ
粉末に加えたことを除いて、実施例２と同様にして直径
が約８０ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。このＭ
ｇＯ焼結体を実施例１７とした。 ＜実施例１８＞ＳｒＣＯ3粉末及びＬａ2Ｏ3粉末を、Ｓ
ｒＣＯ3粉末をＳｒＯに換算して、ＭｇＯとＳｒＯとＹ2
Ｏ3の合計体積に対し、ＳｒＯ及びＹ2Ｏ3がそれぞれ３
０体積％及び２０体積％になるように秤量して、ＭｇＯ
粉末に加えたことを除いて、実施例１と同様にして直径
が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結体
を実施例１８とした。Example 16 SrCO 3 powder (manufactured by Sakai Chemical Co., average particle size: 0.3 to 0.5 μm) and La 2 O 3 powder (manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 0.1 to 0.2 μm) ) To S
The rCO 3 powder was converted to SrO, and MgO, SrO and Y 2
The total volume of O 3 with respect to, SrO and Y 2 O 3 are each 1
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1, except that the mixture was weighed to be 0% by volume and 5% by volume and added to the MgO powder. This MgO sintered body was used as Example 16. <Example 17> SrCO 3 powder and La 2 O 3 powder were
The rCO 3 powder was converted to SrO, and MgO, SrO and Y 2
The total volume of O 3 with respect to, SrO and Y 2 O 3, respectively 2
0% by volume and 10% by volume,
Except for adding the powder, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2. This M
The gO sintered body was used as Example 17. Example 18 SrCO 3 powder and La 2 O 3 powder were
The rCO 3 powder was converted to SrO, and MgO, SrO and Y 2
The total volume of O 3 with respect to, SrO and Y 2 O 3, respectively 3
0% by volume and 20% by volume,
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the powder was added to the powder. This MgO sintered body was used as Example 18.
【００３４】＜実施例１９＞ＳｒＣＯ3粉末（堺化学社
製、平均粒径０．３〜０．５μｍ）及びＣｅ2Ｏ3粉末
（信越化学社製、平均粒径０．６〜１．０μｍ）を、Ｓ
ｒＣＯ3粉末をＳｒＯに換算して、ＭｇＯとＳｒＯとＣ
ｅ2Ｏ3の合計体積に対し、ＳｒＯ及びＣｅ2Ｏ3がそれぞ
れ１０体積％及び５体積％になるように秤量して、Ｍｇ
Ｏ粉末に加えたことを除いて、実施例１と同様にして直
径が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結
体を実施例１９とした。 ＜実施例２０＞ＳｒＣＯ3粉末及びＣｅ2Ｏ3粉末を、Ｓ
ｒＣＯ3粉末をＳｒＯに換算して、ＭｇＯとＳｒＯとＣ
ｅ2Ｏ3の合計体積に対し、ＳｒＯ及びＣｅ2Ｏ3がそれぞ
れ２０体積％及び１０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例２と同様にして
直径が約８０ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。こ
のＭｇＯ焼結体を実施例２０とした。 ＜実施例２１＞ＳｒＣＯ3粉末及びＣｅ2Ｏ3粉末を、Ｓ
ｒＣＯ3粉末をＳｒＯに換算して、ＭｇＯとＳｒＯとＣ
ｅ2Ｏ3の合計体積に対し、ＳｒＯ及びＣｅ2Ｏ3がそれぞ
れ３０体積％及び２０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例１と同様にして
直径が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼
結体を実施例２１とした。<Example 19> SrCO 3 powder (manufactured by Sakai Chemical Co., average particle size 0.3 to 0.5 μm) and Ce 2 O 3 powder (manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 0.6 to 1.0 μm) ) To S
The rCO 3 powder was converted to SrO, and MgO, SrO and C
the total volume of e 2 O 3, were weighed so as SrO and Ce 2 O 3 is 10% by volume and 5% by volume, respectively, Mg
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO sintered body was added to the O powder. This MgO sintered body was used as Example 19. <Example 20> SrCO 3 powder and Ce 2 O 3 powder were
The rCO 3 powder was converted to SrO, and MgO, SrO and C
SrO and Ce 2 O 3 were weighed to 20% by volume and 10% by volume, respectively, based on the total volume of e 2 O 3 , and M
Except for adding to the gO powder, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2. This MgO sintered body was used as Example 20. <Example 21> SrCO 3 powder and Ce 2 O 3 powder were
The rCO 3 powder was converted to SrO, and MgO, SrO and C
SrO and Ce 2 O 3 were weighed so as to be 30% by volume and 20% by volume, respectively, based on the total volume of e 2 O 3 , and M
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO powder was added to the gO powder. This MgO sintered body was used as Example 21.
【００３５】＜実施例２２＞ＢａＣＯ3粉末（関東化学
社製、平均粒径１．０〜２．０μｍ）及びＮｄ2Ｏ3粉末
（信越化学社製、平均粒径０．７〜１．５μｍ）を、Ｂ
ａＣＯ3粉末をＢａＯに換算して、ＭｇＯとＢａＯとＣ
ｅ2Ｏ3の合計体積に対し、ＢａＯ及びＣｅ2Ｏ3がそれぞ
れ１０体積％及び５体積％になるように秤量して、Ｍｇ
Ｏ粉末に加えたことを除いて、実施例１と同様にして直
径が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結
体を実施例２２とした。 ＜実施例２３＞ＢａＣＯ3粉末及びＮｄ2Ｏ3粉末を、Ｂ
ａＣＯ3粉末をＢａＯに換算して、ＭｇＯとＢａＯとＣ
ｅ2Ｏ3の合計体積に対し、ＢａＯ及びＣｅ2Ｏ3がそれぞ
れ２０体積％及び１０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例２と同様にして
直径が約８０ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。こ
のＭｇＯ焼結体を実施例２３とした。 ＜実施例２４＞ＢａＣＯ3粉末及びＮｄ2Ｏ3粉末を、Ｂ
ａＣＯ3粉末をＢａＯに換算して、ＭｇＯとＢａＯとＣ
ｅ2Ｏ3の合計体積に対し、ＢａＯ及びＣｅ2Ｏ3がそれぞ
れ３０体積％及び２０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例１と同様にして
直径が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼
結体を実施例２４とした。Example 22 BaCO 3 powder (manufactured by Kanto Chemical Co., average particle size 1.0-2.0 μm) and Nd 2 O 3 powder (Shin-Etsu Chemical Co., Ltd., average particle size 0.7-1.5 μm) ) To B
aCO 3 powder is converted to BaO, and MgO, BaO and C
the total volume of e 2 O 3, were weighed so that BaO and Ce 2 O 3 becomes 10 vol% and 5 vol%, respectively, Mg
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO sintered body was added to the O powder. This MgO sintered body was used as Example 22. <Example 23> BaCO 3 powder and Nd 2 O 3 powder were mixed with B
aCO 3 powder is converted to BaO, and MgO, BaO and C
BaO and Ce 2 O 3 were weighed to 20% by volume and 10% by volume, respectively, based on the total volume of e 2 O 3 , and M
Except for adding to the gO powder, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2. This MgO sintered body was used as Example 23. <Example 24> BaCO 3 powder and Nd 2 O 3 powder were mixed with B
aCO 3 powder is converted to BaO, and MgO, BaO and C
Based on the total volume of e 2 O 3 , BaO and Ce 2 O 3 were weighed so as to be 30% by volume and 20% by volume, respectively, and M
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO powder was added to the gO powder. This MgO sintered body was used as Example 24.
【００３６】＜実施例２５＞ＢａＣＯ3粉末（関東化学
社製、平均粒径１．０〜２．０μｍ）及びＳｍ2Ｏ3粉末
（信越化学社製、平均粒径１．０〜１．５μｍ）を、Ｂ
ａＣＯ3粉末をＢａＯに換算して、ＭｇＯとＢａＯとＳ
ｍ2Ｏ3の合計体積に対し、ＢａＯ及びＳｍ2Ｏ3がそれぞ
れ１０体積％及び５体積％になるように秤量して、Ｍｇ
Ｏ粉末に加えたことを除いて、実施例１と同様にして直
径が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結
体を実施例２５とした。 ＜実施例２６＞ＢａＣＯ3粉末及びＳｍ2Ｏ3粉末を、Ｂ
ａＣＯ3粉末をＢａＯに換算して、ＭｇＯとＢａＯとＳ
ｍ2Ｏ3の合計体積に対し、ＢａＯ及びＳｍ2Ｏ3がそれぞ
れ２０体積％及び１０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例２と同様にして
直径が約８０ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。こ
のＭｇＯ焼結体を実施例２６とした。 ＜実施例２７＞ＢａＣＯ3粉末及びＳｍ2Ｏ3粉末を、Ｂ
ａＣＯ3粉末をＢａＯに換算して、ＭｇＯとＢａＯとＳ
ｍ2Ｏ3の合計体積に対し、ＢａＯ及びＳｍ2Ｏ3がそれぞ
れ３０体積％及び２０体積％になるように秤量して、Ｍ
ｇＯ粉末に加えたことを除いて、実施例１と同様にして
直径が約８０ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼
結体を実施例２７とした。Example 25 BaCO 3 powder (manufactured by Kanto Chemical Co., average particle size 1.0-2.0 μm) and Sm 2 O 3 powder (Shin-Etsu Chemical Co., Ltd., average particle size 1.0-1.5 μm) ) To B
aCO 3 powder is converted to BaO, and MgO, BaO and S
BaO and Sm 2 O 3 were weighed so as to be 10% by volume and 5% by volume, respectively, based on the total volume of m 2 O 3 , and Mg was added.
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO sintered body was added to the O powder. This MgO sintered body was designated as Example 25. <Example 26> BaCO 3 powder and Sm 2 O 3 powder were mixed with B
aCO 3 powder is converted to BaO, and MgO, BaO and S
Based on the total volume of m 2 O 3 , BaO and Sm 2 O 3 were weighed so as to be 20% by volume and 10% by volume, respectively.
Except for adding to the gO powder, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2. This MgO sintered body was used as Example 26. <Example 27> BaCO 3 powder and Sm 2 O 3 powder were mixed with B
aCO 3 powder is converted to BaO, and MgO, BaO and S
BaO and Sm 2 O 3 were weighed so as to be 30% by volume and 20% by volume, respectively, based on the total volume of m 2 O 3 , and M
An MgO sintered body having a diameter of about 80 mm was obtained in the same manner as in Example 1 except that the MgO powder was added to the gO powder. This MgO sintered body was used as Example 27.
【００３７】＜比較例１＞市販のＭｇＯ焼結体（直径が
約８０ｍｍ）を比較例１とした。 ＜比較例２＞ＣａＣＯ3粉末（関東化学社製、平均粒径
１．０〜１．５μｍ）をＣａＯに換算してＭｇＯとＣａ
Ｏの合計体積に対しＣａＯが０．３体積％になるように
秤量して、ＭｇＯ粉末に加えたことを除いて、実施例１
と同様にして直径が約８０ｍｍのＭｇＯ焼結体を得た。
このＭｇＯ焼結体を比較例２とした。 ＜比較例３＞ＳｒＣＯ3粉末（堺化学社製、平均粒径
０．３〜０．５μｍ）をＳｒＯに換算してＭｇＯとＳｒ
Ｏの合計体積に対しＳｒＯが０．２体積％になるように
秤量して、ＭｇＯ粉末に加えたことを除いて、実施例１
と同様にして直径が約８０ｍｍのＭｇＯ焼結体を得た。
このＭｇＯ焼結体を比較例３とした。 ＜比較例４＞ＢａＣＯ3粉末（関東化学社製、平均粒径
１．０〜１．５μｍ）をＢａＯに換算してＭｇＯとＢａ
ＯとＳｍ2Ｏ3の合計体積に対しＢａＯが６０体積％にな
るように秤量して、ＭｇＯ粉末に加えたことを除いて、
実施例２と同様にして直径が約８０ｍｍ及び５ｍｍのＭ
ｇＯ焼結体を得た。これらのＭｇＯ焼結体を比較例４と
した。Comparative Example 1 A commercially available MgO sintered body (about 80 mm in diameter) was used as Comparative Example 1. <Comparative Example 2> CaCO 3 powder (manufactured by Kanto Chemical Co., Ltd., average particle size: 1.0 to 1.5 μm) was converted into CaO, and MgO and Ca were converted.
Example 1 was repeated except that CaO was weighed to 0.3% by volume with respect to the total volume of O and added to MgO powder.
In the same manner as in the above, an MgO sintered body having a diameter of about 80 mm was obtained.
This MgO sintered body was used as Comparative Example 2. <Comparative Example 3> SrCO 3 powder (manufactured by Sakai Chemical Co., average particle size: 0.3 to 0.5 μm) was converted to SrO, and MgO and Sr were converted.
Example 1 was repeated except that SrO was weighed to 0.2% by volume with respect to the total volume of O and added to the MgO powder.
In the same manner as in the above, an MgO sintered body having a diameter of about 80 mm was obtained.
This MgO sintered body was used as Comparative Example 3. <Comparative Example 4> BaCO 3 powder (manufactured by Kanto Chemical Co., Ltd., average particle size 1.0 to 1.5 μm) was converted into BaO, and MgO and Ba were converted.
Except that BaO was weighed to be 60% by volume with respect to the total volume of O and Sm 2 O 3 and added to MgO powder,
M having diameters of about 80 mm and 5 mm in the same manner as in Example 2.
A gO sintered body was obtained. These MgO sintered bodies were designated as Comparative Example 4.
【００３８】＜比較例５＞ＣａＣＯ3粉末（関東化学社
製、平均粒径１．０〜１．５μｍ）及びＳｃ2Ｏ3粉末
（三菱マテリアル社製、平均粒径１〜３μｍ）を、Ｃａ
ＣＯ3粉末をＣａＯに換算して、ＭｇＯとＣａＯとＳｃ2
Ｏ3の合計体積に対し、ＣａＯ及びＳｃ2Ｏ3がそれぞれ
１０体積％及び４５体積％になるように秤量して、Ｍｇ
Ｏ粉末に加えたことを除いて、実施例２と同様にして直
径が約８０ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。これ
らのＭｇＯ焼結体を比較例５とした。 ＜比較例６＞ＳｒＣＯ3粉末（堺化学社製、平均粒径
０．３〜０．５μｍ）及びＬａ2Ｏ3粉末（信越化学社
製、平均粒径０．１〜０．２μｍ）を、ＳｒＣＯ3粉末
をＳｒＯに換算して、ＭｇＯとＳｒＯとＬａ2Ｏ3の合計
体積に対し、ＳｒＯ及びＬａ2Ｏ3がそれぞれ２０体積％
及び５０体積％になるように秤量して、ＭｇＯ粉末に加
えたことを除いて、実施例２と同様にして直径が約８０
ｍｍ及び５ｍｍのＭｇＯ焼結体を得た。これらのＭｇＯ
焼結体を比較例６とした。 ＜比較例７＞ＢａＣＯ3粉末（関東化学社製、平均粒径
１．０〜１．５μｍ）及びＮｄ2Ｏ3粉末（信越化学社
製、平均粒径０．７〜１．５μｍ）を、ＢａＣＯ3粉末
をＢａＯに換算して、ＭｇＯとＢａＯとＮｄ2Ｏ3の合計
体積に対し、ＢａＯ及びＮｄ2O3がそれぞれ４０体積％
及び２０体積％になるように秤量して、ＭｇＯ粉末に加
えたことを除いて、実施例１と同様にして直径が約８０
ｍｍのＭｇＯ焼結体を得た。このＭｇＯ焼結体を比較例
７とした。<Comparative Example 5> CaCO 3 powder (manufactured by Kanto Chemical Co., average particle size 1.0 to 1.5 μm) and Sc 2 O 3 powder (manufactured by Mitsubishi Materials Corporation, average particle size 1 to 3 μm) were mixed with Ca
Converting CO 3 powder into CaO, MgO, CaO and Sc 2
The total volume of O 3 to, were weighed so as CaO and Sc 2 O 3 is 10 vol% and 45 vol% respectively, Mg
Except for adding to the O powder, a MgO sintered body having a diameter of about 80 mm and 5 mm was obtained in the same manner as in Example 2. These MgO sintered bodies were used as Comparative Example 5. <Comparative Example 6> SrCO 3 powder (manufactured by Sakai Chemical Co., average particle size 0.3 to 0.5 μm) and La 2 O 3 powder (manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 0.1 to 0.2 μm) SrCO 3 powder was converted to SrO, and SrO and La 2 O 3 were each 20% by volume based on the total volume of MgO, SrO, and La 2 O 3.
And 50% by volume and weighed to about 80% by volume in the same manner as in Example 2 except that it was added to the MgO powder.
mm and 5 mm MgO sintered bodies were obtained. These MgO
The sintered body was designated as Comparative Example 6. <Comparative Example 7> BaCO 3 powder (manufactured by Kanto Chemical Co., average particle size 1.0 to 1.5 μm) and Nd 2 O 3 powder (Shin-Etsu Chemical Co., Ltd., average particle size 0.7 to 1.5 μm) BaCO 3 powder is converted into BaO, and BaO and Nd 2 O 3 are each 40% by volume based on the total volume of MgO, BaO and Nd 2 O 3.
And 20% by volume and weighed to about 80% by volume in the same manner as in Example 1 except that it was added to the MgO powder.
mm MgO sintered body was obtained. This MgO sintered body was used as Comparative Example 7.
【００３９】＜比較試験と評価＞ (a) 相対密度と強度試験 実施例１〜２７及び比較例１〜７で得られたＭｇＯ焼結
体（直径８０ｍｍのＭｇＯ焼結体）を切り出し、研削・
研磨加工して、ＪＩＳ Ｒ１６０１に準じた３×４×４
０ｍｍの３点曲げ試験片の大きさとし、相対密度、曲げ
強度を測定した。これらの結果を表１に示す。なお、相
対密度はトルエン中、アルキメデス法で測定した。破壊
強度は３点曲げ試験により測定した。<Comparative Test and Evaluation> (a) Relative Density and Strength Test The MgO sintered bodies (MgO sintered bodies having a diameter of 80 mm) obtained in Examples 1 to 27 and Comparative Examples 1 to 7 were cut out and ground.
Polished, 3 × 4 × 4 according to JIS R1601
The size of a 0 mm three-point bending test piece was measured, and the relative density and bending strength were measured. Table 1 shows the results. The relative density was measured in toluene by Archimedes' method. The breaking strength was measured by a three-point bending test.
【００４０】[0040]
【表１】 [Table 1]
【００４１】表１から明らかなように、比較例１の市販
のＭｇＯ焼結体の相対密度９６％であるのに対して、実
施例１〜２７のＭｇＯ焼結体の相対密度は９６％以上と
緻密になっている。また実施例１〜２７のＭｇＯ焼結体
の曲げ強度は比較例１〜７の２倍以上の高強度を示し
た。これは、実施例１〜２７では結晶粒界面に亀裂を発
生させない範囲内でアルカリ土類金属酸化物粒子又はア
ルカリ土類金属酸化物粒子及び希土類酸化物粒子を分散
でき、結晶粒界の欠陥も少なく強度が改善できるためで
あり、比較例２〜７では分散粒子の添加割合の過多によ
り、結晶粒界に欠陥が生じたためであると考えられる。As is clear from Table 1, the relative density of the commercially available MgO sintered body of Comparative Example 1 was 96%, whereas the relative density of the MgO sintered bodies of Examples 1 to 27 was 96% or more. It has become dense. Further, the bending strength of the MgO sintered bodies of Examples 1 to 27 was twice or more as high as those of Comparative Examples 1 to 7. This is because, in Examples 1 to 27, the alkaline earth metal oxide particles or the alkaline earth metal oxide particles and the rare earth oxide particles can be dispersed within a range that does not cause cracking at the crystal grain interface, and defects at the crystal grain boundaries are also present. This is considered to be because the strength can be improved to a small extent, and in Comparative Examples 2 to 7, defects were generated in the crystal grain boundaries due to an excessive addition ratio of the dispersed particles.
【００４２】(b) ＭｇＯ膜の特性試験 実施例２，５，８，１１，１４，１７，２０，２３及び
２６と比較例１及び４〜６の直径５ｍｍのＭｇＯ焼結体
を電子ビーム蒸着法によりガラス基板に成膜して１０種
類のＴＥＧ（Test Element Group）基板を作製した。な
お、上記比較例１の直径５ｍｍのＭｇＯ焼結体は直径が
約８０ｍｍのものを直径が５ｍｍで厚さが２．５ｍｍに
機械加工することにより作製した。図１に示すようにＴ
ＥＧ基板１０は、厚さ１ｍｍのガラス基板（コーニング
＃７０５９ガラス）１１上にフォトリソグラフィにより
ＩｎＳｎ複合酸化膜からなる下地電極１２を１００μｍ
の間隔で厚さ０．２μｍ、幅１００μｍに形成し、これ
らの下地電極１２を覆うようにＳｉの反応性ＤＣスパッ
タリングで厚さ２μｍのガラス層１３を形成した後、上
記電子ビーム蒸着法により同一の成膜条件で厚さ０．５
μｍのＭｇＯ膜１４を成膜することにより作られた。な
お、ＭｇＯ膜の成膜条件は、到達圧力が４×１０-4Ｐ
ａ、酸素分圧が１×１０-2Ｐａ、基板温度が２００℃で
あった。(B) Characteristic test of MgO film The MgO sintered bodies having a diameter of 5 mm of Examples 2, 5, 8, 11, 14, 17, 20, 23 and 26 and Comparative Examples 1 and 4 to 6 were subjected to electron beam evaporation. Ten types of TEG (Test Element Group) substrates were prepared by forming a film on a glass substrate by the method. The 5 mm diameter MgO sintered body of Comparative Example 1 was manufactured by machining a material having a diameter of about 80 mm to a diameter of 5 mm and a thickness of 2.5 mm. As shown in FIG.
The EG substrate 10 has a base electrode 12 made of an InSn composite oxide film formed on a 1 mm-thick glass substrate (Corning # 7059 glass) 11 by photolithography at 100 μm.
After forming a glass layer 13 having a thickness of 0.2 μm and a width of 100 μm at a distance of 2 μm by reactive DC sputtering of Si so as to cover these underlying electrodes 12, the same electron beam evaporation method was used. Thickness of 0.5
It was formed by forming a μm MgO film 14. The conditions for forming the MgO film are such that the ultimate pressure is 4 × 10 −4 P
a, the oxygen partial pressure was 1 × 10 −2 Pa, and the substrate temperature was 200 ° C.
【００４３】先ず上記ＭｇＯ膜１４の屈折率及び吸収係
数を測定した。ＭｇＯ膜の屈折率と吸収係数は、Ｈｅ−
Ｎｅレーザ（波長６２３８オングストローム）により、
膜に対し１波長、２入射角（５５°、７０°）のエリプ
ソ測定を行い、解析ソフトを用いて求めた。次に上記Ｍ
ｇＯ膜の放電開始電圧を以下の方法で測定した。上記１
３種類のＴＥＧ基板をＴＥＧ基板毎に図２に示す装置の
Ｎｅ−５％Ｘｅで５００Ｔｏｒｒの真空ベルジャー１５
内に配置した加熱サンプル台１６に載せ、下地電極１９
（図１）をパルス電源１７に接続し、ＴＥＧ基板１０を
熱電対１８で測定しながら一定の温度に制御して、電源
電圧を上昇して行き、放電を開始する電圧を測定した。
パルス電源１７は０〜３００Ｖの範囲で電圧可変であっ
て、周波数３０ｋＨｚでパルス幅１０μsecのパルスを
発生するようになっている。上記方法で求めたＭｇＯ膜
の屈折率、吸収係数及び放電開始電圧を表２に示す。First, the refractive index and the absorption coefficient of the MgO film 14 were measured. The refractive index and absorption coefficient of the MgO film are He-
By Ne laser (wavelength 6238 angstroms)
Ellipsometry was performed on the film at one wavelength and two incident angles (55 ° and 70 °), and the film was determined using analysis software. Next, the above M
The firing voltage of the gO film was measured by the following method. 1 above
A vacuum bell jar 15 of 500 Torr with Ne-5% Xe of the apparatus shown in FIG.
Placed on the heating sample table 16 arranged in the
(FIG. 1) was connected to a pulse power source 17, and the temperature of the TEG substrate 10 was controlled at a constant temperature while being measured by a thermocouple 18, the power source voltage was increased, and the voltage at which discharge started was measured.
The pulse power supply 17 is variable in a voltage range of 0 to 300 V, and generates a pulse having a frequency of 30 kHz and a pulse width of 10 μsec. Table 2 shows the refractive index, absorption coefficient, and firing voltage of the MgO film obtained by the above method.
【００４４】[0044]
【表２】 [Table 2]
【００４５】表２から明らかなように、比較例１及び比
較例４〜６のＭｇＯ焼結体を用いて成膜されたＭｇＯ膜
の屈折率は１．６５以下で吸収係数は０．００８以上
（但し、比較例１の吸収係数は０．００２）であったの
に対して、実施例２，５，８，１１，１４，１７，２
０，２３及び２６のＭｇＯ焼結体を用いて成膜されたＭ
ｇＯ膜の屈折率は１．７０以上で吸収係数は０．００５
以下であった。これらのことから、実施例のＭｇＯ焼結
体を用いれば、結晶性と透過性に優れたＭｇＯ膜が得ら
れることが分かった。また上記実施例の放電開始電圧は
上記比較例の放電開始電圧と比べて、いずれも２０〜５
０Ｖ程度低いことから、実施例のＭｇＯ焼結体を用いて
成膜されたＭｇＯ膜は低い電圧でのプラズマの生成と維
持が可能なことが分かった。As is apparent from Table 2, the refractive index of the MgO film formed using the MgO sintered bodies of Comparative Example 1 and Comparative Examples 4 to 6 was 1.65 or less and the absorption coefficient was 0.008 or more. (However, while the absorption coefficient of Comparative Example 1 was 0.002), Examples 2, 5, 8, 11, 14, 17, and 2 were used.
M formed using MgO sintered bodies of 0, 23 and 26
The refractive index of the gO film is 1.70 or more and the absorption coefficient is 0.005.
It was below. From these facts, it was found that the use of the MgO sintered body of the example can provide an MgO film having excellent crystallinity and transparency. In addition, the discharge starting voltage of the above example was 20 to 5 compared with the discharge starting voltage of the comparative example.
Since the voltage was low by about 0 V, it was found that the MgO film formed using the MgO sintered body of the example can generate and maintain plasma at a low voltage.
【００４６】[0046]
【発明の効果】以上述べたように、本発明によれば、相
対密度が９５％以上のＭｇＯ焼結体であって、平均結晶
粒径が０．３〜１００μｍの結晶粒子を有するＭｇＯマ
トリックス中に、アルカリ土類金属酸化物粒子を０．５
〜５０体積％分散することにより、ＭｇＯ蒸着材を構成
したので、ＭｇＯ焼結体の物理的性質を改善できる。即
ち、ＭｇＯ焼結体におけるＭｇＯマトリックスと分散粒
子であるアルカリ土類金属酸化物粒子はその界面で強く
結合するので、蒸着材として用いた場合に、数千オング
ストローム／分以上の成膜速度が得られる。また分散粒
子であるアルカリ土類金属酸化物粒子とＭｇＯマトリッ
クスの熱膨張係数の差は小さいので、界面に亀裂を発生
させない範囲で大きなアルカリ土類金属酸化物粒子を分
散させることが可能となる。この結果、マトリックス粒
界を締め付けるトータルの領域が大きくなり、粒界の欠
陥も少なく、かつ強度も向上でき、ＭｇＯマトリックス
の組織を均一にすることができる。また上記ＭｇＯマト
リックス中に、アルカリ土類金属酸化物粒子及び希土類
酸化物粒子を合計０．５〜５０体積％分散しても、上記
と同様の効果が得られる。As described above, according to the present invention, a MgO sintered body having a relative density of not less than 95% and having crystal grains having an average crystal grain size of 0.3 to 100 μm. And 0.5 parts of alkaline earth metal oxide particles
Since the MgO vapor deposition material was formed by dispersing by about 50% by volume, the physical properties of the MgO sintered body can be improved. That is, since the MgO matrix in the MgO sintered body and the alkaline earth metal oxide particles as dispersed particles are strongly bonded at the interface, when used as a vapor deposition material, a film formation rate of several thousand angstroms / minute or more can be obtained. Can be Further, since the difference between the thermal expansion coefficients of the alkaline earth metal oxide particles, which are the dispersed particles, and the MgO matrix is small, large alkaline earth metal oxide particles can be dispersed within a range that does not cause cracks at the interface. As a result, the total area for tightening the matrix grain boundaries increases, the number of defects at the grain boundaries can be reduced, the strength can be improved, and the structure of the MgO matrix can be made uniform. The same effect as described above can be obtained even when the alkaline earth metal oxide particles and the rare earth oxide particles are dispersed in the MgO matrix in a total amount of 0.5 to 50% by volume.
【００４７】またＭｇＯ粉末と，アルカリ土類金属の酸
化物粉末等又はアルカリ土類金属の酸化物粉末等及び希
土類酸化物粉末と，バインダと，有機溶媒とを混合して
所定濃度の混合スラリーを調製し、このスラリーを噴霧
乾燥して所定粒径の造粒粉末を作製し、この造粒粉末を
所定の型に入れて所定の圧力で成形し、更にこの成形体
を脱脂した後に１４５０〜１７００℃の温度で焼結する
ことが好ましい。上記アルカリ土類金属酸化物粉末をア
ルカリ土類金属元素の水酸化物，炭酸塩，蓚酸塩又は有
機金属化合物のアルコキシドを熱分解することにより作
製し、上記希土類酸化物粉末を希土類元素の水酸化物，
炭酸塩，蓚酸塩又は有機金属化合物のアルコキシドを熱
分解することにより作製することが更に好ましい。これ
らの方法で製造された蒸着材は、焼結工程で緻密に焼結
され、この蒸着材のＭｇＯマトリックスの粒子内に分散
相のアルカリ土類金属酸化物粉末や希土類酸化物粉末が
均一に分散される。この結果、上記方法で製造されたＭ
ｇＯ蒸着材は、高純度で緻密なＭｇＯ焼結体となる。Further, a MgO powder, an alkaline earth metal oxide powder or the like or an alkaline earth metal oxide powder or the like, a rare earth oxide powder, a binder and an organic solvent are mixed to form a mixed slurry having a predetermined concentration. The slurry is spray-dried to produce a granulated powder having a predetermined particle size, the granulated powder is placed in a predetermined mold, molded at a predetermined pressure, and the molded body is degreased. Sintering at a temperature of ° C. is preferred. The alkaline earth metal oxide powder is prepared by thermally decomposing a hydroxide, a carbonate, an oxalate of an alkaline earth metal element or an alkoxide of an organometallic compound, and the rare earth oxide powder is subjected to hydroxylation of the rare earth element. object,
It is more preferable that the alkoxide is prepared by thermally decomposing an alkoxide of a carbonate, an oxalate or an organic metal compound. The vapor deposition material manufactured by these methods is densely sintered in the sintering step, and the dispersed phase alkaline earth metal oxide powder or the rare earth oxide powder is uniformly dispersed in the MgO matrix particles of the vapor deposition material. Is done. As a result, the M
The gO vapor deposition material is a dense and dense MgO sintered body.
【００４８】また上記ＭｇＯ蒸着材を用いて電子ビーム
蒸着法によりＭｇＯ膜を成膜すれば、二相共存、即ちＭ
ｇＯマトリックスと分散粒子とが固溶体や反応物を形成
しない状態で蒸発するので、高速で安定な成膜が可能と
なり、またスプラッシュが発生せず、成膜面積が広くて
も、膜厚及び膜組成が均一なＭｇＯ膜を得ることができ
る。更にこのＭｇＯ膜はＭｇＯ中にアルカリ土類金属酸
化物粒子又はアルカリ土類金属酸化物粒子及び希土類酸
化物粒子をドーピングした構造、即ちＭｇＯ中に上記ア
ルカリ土類金属酸化物粒子等を固溶した構造、或いはス
ピネル構造であるので、ＭｇＯ膜の配向性は向上する。
この結果、このＭｇＯ膜を成膜した基板をＰＤＰに組込
むと、低い電圧でプラズマを生成しかつ維持することが
でき、放電時の耐スパッタ性を向上でき、速い放電の応
答性及び高い絶縁性を得ることができる。またＭｇＯ膜
が蛍光体に悪影響を及ぼすことはなく、青色に関係する
輝度も向上することができる。従って、ＡＣ型ＰＤＰの
誘電体層の保護膜に好適なものとなる。When an MgO film is formed by electron beam evaporation using the above-mentioned MgO evaporation material, two phases coexist, that is, M
Since the gO matrix and the dispersed particles evaporate without forming a solid solution or a reactant, high-speed and stable film formation is possible, and no splash occurs. Can obtain a uniform MgO film. Further, the MgO film has a structure in which alkaline earth metal oxide particles or alkaline earth metal oxide particles and rare earth oxide particles are doped in MgO, that is, the above alkaline earth metal oxide particles and the like are dissolved in MgO. Because of the structure or the spinel structure, the orientation of the MgO film is improved.
As a result, when the substrate on which the MgO film is formed is incorporated into a PDP, plasma can be generated and maintained at a low voltage, spatter resistance during discharge can be improved, and fast discharge response and high insulation properties can be achieved. Can be obtained. Also, the MgO film does not adversely affect the phosphor, and the luminance related to blue can be improved. Therefore, it is suitable as a protective film for the dielectric layer of the AC type PDP.
【図面の簡単な説明】[Brief description of the drawings]
【図１】本発明のＭｇＯ蒸着材を用いて電子ビーム蒸着
法で成膜したＭｇＯ膜を有するＴＥＧ基板の断面図。FIG. 1 is a cross-sectional view of a TEG substrate having an MgO film formed by an electron beam evaporation method using the MgO evaporation material of the present invention.
【図２】図１に示すＴＥＧ基板の放電開始電圧を測定す
る装置の構成図。FIG. 2 is a configuration diagram of an apparatus for measuring a discharge starting voltage of the TEG substrate shown in FIG.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4G030 AA05 AA08 AA09 AA10 AA11 AA13 AA14 BA12 CA01 CA02 CA04 GA05 GA27 4G076 AA01 AA02 AA10 AA16 AA26 AC07 BA38 BC08 CA11 CA30 4K029 BA50 BB07 CA01 DB05 DB07 DB21 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G030 AA05 AA08 AA09 AA10 AA11 AA13 AA14 BA12 CA01 CA02 CA04 GA05 GA27 4G076 AA01 AA02 AA10 AA16 AA26 AC07 BA38 BC08 CA11 CA30 4K029 BA50 BB07 CA01 DB05 DB07 DB21
Claims (9)
あって、平均結晶粒径が０．３〜１００μｍの結晶粒子
を有するＭｇＯマトリックス中に、アルカリ土類金属酸
化物粒子が０．５〜５０体積％分散されたＭｇＯ蒸着
材。1. An MgO sintered body having a relative density of 95% or more, wherein an MgO matrix having crystal grains having an average crystal grain size of 0.3 to 100 μm contains alkaline earth metal oxide particles in an amount of 0.1%. MgO vapor deposition material dispersed in 5 to 50% by volume.
リ土類金属元素がＣａ，Ｓｒ及びＢａからなる群より選
ばれた１種又は２種以上の元素である請求項１記載のＭ
ｇＯ蒸着材。2. The M according to claim 1, wherein the alkaline earth metal element in the alkaline earth metal oxide particles is one or more elements selected from the group consisting of Ca, Sr and Ba.
gO vapor deposition material.
あって、平均結晶粒径が０．３〜１００μｍの結晶粒子
を有するＭｇＯマトリックス中に、アルカリ土類金属酸
化物粒子及び希土類酸化物粒子が合計０．５〜５０体積
％分散されたＭｇＯ蒸着材。3. An MgO sintered body having a relative density of 95% or more and having an average crystal grain size of 0.3 to 100 μm in a MgO matrix having alkaline earth metal oxide particles and rare earth oxides. MgO vapor deposition material in which material particles are dispersed in a total of 0.5 to 50% by volume.
リ土類金属元素がＣａ，Ｓｒ及びＢａからなる群より選
ばれた１種の元素であり、希土類酸化物粒子中の希土類
元素がＳｃ，Ｙ，Ｌａ，Ｃｅ，Ｎｄ，Ｓｍ，Ｇｄ，Ｔ
ｂ，Ｙｂ及びＤｙからなる群より選ばれた１種の元素で
ある請求項３記載のＭｇＯ蒸着材。4. The alkaline earth metal element in the alkaline earth metal oxide particles is one element selected from the group consisting of Ca, Sr and Ba, and the rare earth element in the rare earth oxide particles is Sc, Y, La, Ce, Nd, Sm, Gd, T
The MgO vapor deposition material according to claim 3, wherein the material is one element selected from the group consisting of b, Yb, and Dy.
粉末又は炭酸塩粉末とバインダと有機溶媒とを混合して
所定濃度の混合スラリーを調製する工程と、 前記スラリーを噴霧乾燥して所定粒径の造粒粉末を得る
工程と、 前記造粒粉末を所定の型に入れて所定の圧力で成形する
工程と、 前記成形体を脱脂した後に１４５０〜１７００℃の温度
で焼結する工程とを含むＭｇＯ蒸着材の製造方法。5. A step of mixing a MgO powder and an alkaline earth metal oxide powder or a carbonate powder, a binder and an organic solvent to prepare a mixed slurry having a predetermined concentration, and spray-drying the slurry to obtain a predetermined slurry. A step of obtaining a granulated powder having a diameter; a step of placing the granulated powder in a predetermined mold and molding at a predetermined pressure; and a step of sintering at a temperature of 1450 to 1700 ° C. after degreasing the molded body. A method for producing an MgO vapor-deposited material.
粉末又は炭酸塩粉末と希土類酸化物粉末とバインダと有
機溶媒とを混合して所定濃度の混合スラリーを調製する
工程と、 前記スラリーを噴霧乾燥して所定粒径の造粒粉末を得る
工程と、 前記造粒粉末を所定の型に入れて所定の圧力で成形する
工程と、 前記成形体を脱脂した後に１４５０〜１７００℃の温度
で焼結する工程とを含むＭｇＯ蒸着材の製造方法。6. A step of mixing a MgO powder and an alkaline earth metal oxide powder or a carbonate powder, a rare earth oxide powder, a binder, and an organic solvent to prepare a mixed slurry having a predetermined concentration, and spraying the slurry. Drying to obtain a granulated powder having a predetermined particle size; placing the granulated powder in a predetermined mold and molding at a predetermined pressure; and degreased the molded body, followed by firing at a temperature of 1450 to 1700 ° C. And a sintering step.
土類金属元素の水酸化物，炭酸塩，蓚酸塩又は有機金属
化合物のアルコキシドを熱分解することにより作製され
た請求項５又は６記載のＭｇＯ蒸着材の製造方法。7. The method according to claim 5, wherein the alkaline earth metal oxide powder is produced by thermally decomposing a hydroxide, carbonate, oxalate or alkoxide of an organic metal compound of an alkaline earth metal element. Manufacturing method of MgO vapor deposition material.
物，炭酸塩，蓚酸塩又は有機金属化合物のアルコキシド
を熱分解することにより作製された請求項６記載のＭｇ
Ｏ蒸着材の製造方法。8. The Mg according to claim 6, wherein the rare earth oxide powder is prepared by thermally decomposing a hydroxide, carbonate, oxalate or alkoxide of an organometallic compound of a rare earth element.
Manufacturing method of O vapor deposition material.
蒸着材を用いて電子ビーム蒸着法により成膜するＭｇＯ
膜の製造方法。9. The MgO according to claim 1, wherein
MgO deposited by electron beam evaporation using evaporation material
Manufacturing method of membrane.
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|---|---|---|---|
| JP09734299A JP3893793B2 (en) | 1999-04-05 | 1999-04-05 | MgO vapor deposition material and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09734299A JP3893793B2 (en) | 1999-04-05 | 1999-04-05 | MgO vapor deposition material and method for producing the same |
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| Publication Number | Publication Date |
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ID=14189817
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005264272A (en) * | 2004-03-19 | 2005-09-29 | Technology Seed Incubation Co Ltd | Material of magnesium oxide thin film |
| JP2005330574A (en) * | 2003-10-21 | 2005-12-02 | Ube Material Industries Ltd | Magnesium oxide vapor-deposition material |
| JP2005330589A (en) * | 2003-10-21 | 2005-12-02 | Ube Material Industries Ltd | Method for producing magnesium oxide vapor-deposition material |
| WO2006006633A1 (en) * | 2004-07-14 | 2006-01-19 | Mitsubishi Materials Corporation | MgO DEPOSITION MATERIAL |
| WO2007126061A1 (en) * | 2006-04-28 | 2007-11-08 | Panasonic Corporation | Plasma display panel and its manufacturing method |
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