JPH11323533A - Vapor deposition material comprising mgo as major component and its production - Google Patents
Vapor deposition material comprising mgo as major component and its productionInfo
- Publication number
- JPH11323533A JPH11323533A JP11058144A JP5814499A JPH11323533A JP H11323533 A JPH11323533 A JP H11323533A JP 11058144 A JP11058144 A JP 11058144A JP 5814499 A JP5814499 A JP 5814499A JP H11323533 A JPH11323533 A JP H11323533A
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- JP
- Japan
- Prior art keywords
- mgo
- powder
- sintered body
- sintering
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Compositions Of Oxide Ceramics (AREA)
- Physical Vapour Deposition (AREA)
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、希土類元素を含む複合セラミックスからなるＭ
ｇＯ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 Panel）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。[0001] The present invention relates to a composite ceramic comprising a rare earth element in an MgO matrix.
The present invention relates to a gO-based deposition material and a method for producing the same. More specifically, the present invention relates to a MgO-based vapor deposition material suitable for forming an MgO film for protecting a dielectric layer of an AC type PDP (Plasma Display Panel), and a method of manufacturing the same.
【０００２】[0002]
【従来の技術】ここ数年、液晶（Liquid Crystal Displ
y：以下、ＬＣＤという）をはじめとして、各種の平面
ディスプレイ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）についても、その開発と実用化
の動きが最近活発になっている。ＰＤＰは大型化し易
く、ハイビジョン用大画面壁掛けテレビの最短距離にあ
り、既に対角４０インチクラスのＰＤＰの試作が進めら
れている。ＰＤＰは、電極構造の点で金属電極が誘電体
材料で覆われているＡＣ型と、放電空間に金属電極が露
出しているＤＣ型とに分類される。2. Description of the Related Art In recent years, liquid crystal (Liquid Crystal Displ.)
The research and development and commercialization of various flat displays, including LCDs, are remarkable, and their production is also increasing rapidly. The development and commercialization of color plasma display panels (PDPs) has recently been active. PDPs are easy to increase in size, are at the shortest distance from large-screen TVs for high-definition televisions, and trial production of a 40-inch diagonal PDP is already underway. PDPs are classified into an AC type in which a metal electrode is covered with a dielectric material in terms of an electrode structure, and a DC type in which a metal electrode is exposed in a discharge space.
【０００３】上記ＡＣ型ＰＤＰ開発の当初は、ガラス誘
電体層が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
昇していた。そのため、高い昇華熱を持つ種々の酸化物
を保護膜とする試みがなされた。この保護膜は直接ガス
と接しているため、重要な役割を担っている。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が保護膜に用いられ
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
している。At the beginning of the development of the AC type PDP, the glass dielectric layer was directly exposed to discharge, and the surface of the dielectric layer was changed by sputtering by ion bombardment, so that the firing voltage was increased. For this reason, attempts have been made to use various oxides having high sublimation heat as protective films. Since this protective film is in direct contact with the gas, it plays an important role. That is, the characteristics required for the protective film are a low discharge voltage, spatter resistance, fast discharge response, and insulation. MgO is used for the protective film as a material satisfying these conditions. The 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.
【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膜が知られている。この電子ビ
ーム蒸着法によるＭｇＯ膜は、数千オングストローム／
分の高速で成膜することができる。また、成膜されたＭ
ｇＯ膜の結晶方位は、（１１１）面に配向した膜が最も
低い維持電圧で駆動でき、更に膜中に存在する（１１
１）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。なお、上記単結晶Ｍ
ｇＯ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、このインゴットの中から純度の高い部分を
取り出して、破砕することにより製造される。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 known. The MgO film formed by this electron beam evaporation method has a thickness of several thousand angstroms /
It is possible to form a film at a high speed. In addition, the deposited M
The crystal orientation of the gO film is such that a film oriented in the (111) plane can be driven at the lowest sustaining voltage and further exists in the film (11
1) It is said that as the amount of the surface increases, the secondary electron emission ratio increases and the driving voltage also decreases. The single crystal M
The crushed product of gO 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 arc furnace, that is, into an ingot by electrofusion. It is manufactured by taking out a high-purity part from the inside and crushing it.
【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、蒸着材に局所的に高いエネルギを与えるた
め、蒸着材のスプラッシュが発生したり、蒸着材のサイ
ズが一定でないため、供給系での搬送トラブルで成膜の
効率が低下する不具合があった。このスプラッシュの発
生の防止や供給系のトラブル防止には、蒸着材の粗粒化
が有効であると考えれているが、単結晶ＭｇＯの粉砕品
では現行の粒径１〜５ｍｍより大きくかつ大きさの揃っ
た粒子を、歩留り良く安定して確保することが困難であ
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、大面積のガラス誘
電体層に対してＭｇＯ膜を均一に成膜することが難し
く、膜厚分布に問題がある。この結果、ＭｇＯを成膜し
たガラス誘電体層をＰＤＰに組み込んだ場合に、電気的
特性、例えば放電開始電圧や駆動電圧が高くなったり或
いは変化したりする問題点があった。However, in the above-mentioned conventional electron beam evaporation method using a crushed single-crystal MgO product as a deposition material, a high energy is locally applied to the deposition material, so that a splash of the deposition material occurs. In addition, there was a problem that the efficiency of film formation was reduced due to transport trouble in the supply system because the size of the vapor deposition material was not constant. In order to prevent the generation of the splash and the trouble of the supply system, it is considered that the coarsening of the vapor deposition material is effective. However, in the case of the pulverized single crystal MgO, the particle size is larger than the current particle size of 1 to 5 mm. It was difficult to stably obtain particles having a uniform particle size with good yield. Further, in the conventional electron beam evaporation method using a crushed product of single crystal MgO as an evaporation material, it is difficult to uniformly form an MgO film on a large-area glass dielectric layer, and there is a problem in film thickness distribution. There is. As a result, when a glass dielectric layer formed of MgO is incorporated in a PDP, there is a problem that electric characteristics, for example, a discharge starting voltage and a driving voltage are increased or changed.
【０００６】一方、ＭｇＯクリンカや軽焼ＭｇＯは、海
水から得られるＭｇＣｌ2を原料としていることが多
く、このＭｇＣｌ2には比較的多くのＣａ、Ｓｉ、Ｆ
ｅ、Ｎａ、Ｋなどの不純物が含まれるため、これらの不
純物が単結晶ＭｇＯ中に残留する。また、単結晶ＭｇＯ
の製造過程におけるインゴットでは、このインゴットの
中心から表面部に向かって連続的に不純物量が増加して
おり、このため単結晶部の取り出し方によって製品の純
度が極めて容易に変動してしまい、単結晶ＭｇＯの純度
の安定性や信頼性を欠く問題点があった。On the other hand, MgO clinker and lightly burned MgO often use MgCl 2 obtained from seawater as a raw material, and this MgCl 2 contains a relatively large amount of Ca, Si, F
Since impurities such as e, Na, and K are contained, these impurities remain in the single-crystal MgO. In addition, single crystal MgO
In the manufacturing process of the ingot, the amount of impurities continuously increases from the center of the ingot toward the surface portion. Therefore, the purity of the product fluctuates extremely easily depending on how the single crystal portion is taken out. There was a problem that the stability and reliability of the purity of crystalline MgO were lacking.
【０００７】これらの点を解消するために、単結晶Ｍｇ
Ｏに代えて多結晶ＭｇＯを用いる方法も考えられる。し
かし、種々の焼結助剤の添加により緻密化した高密度の
多結晶ＭｇＯでは、組織的には粒界に欠陥が存在する問
題点があり、また純度を高くすると密度が低くなる問題
点があった。この結果、これらの多結晶ＭｇＯ蒸着材を
用いて電子ビーム蒸着法で成膜したＭｇＯ膜は配向性に
劣るため、またＰＤＰに組み込んだときの電気的特性が
低下するために、使用できなかった。更に保護膜の絶縁
性には、ＭｇＯ焼結体の純度・結晶粒界・膜の物性が大
きく影響する問題点があった。In order to solve these problems, a single crystal Mg
A method using polycrystalline MgO instead of O is also conceivable. However, high-density polycrystalline MgO densified by the addition of various sintering aids has a problem that defects are present at grain boundaries in terms of structure, and a problem that the density decreases when the purity is increased. there were. As a result, an MgO film formed by an electron beam evaporation method using these polycrystalline MgO evaporation materials could not be used because of poor orientation and electrical characteristics when incorporated into a PDP deteriorated. . Further, there is a problem that the insulating property of the protective film is greatly affected by the purity of the MgO sintered body, crystal grain boundaries, and physical properties of the film.
【０００８】本発明の目的は、電子ビーム蒸着法で成膜
しても、ＭｇＯ焼結体の供給系のトラブルがなく、スプ
ラッシュを発生させず、安定した均一な成膜ができるＭ
ｇＯを主成分とする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、成膜されたＭｇＯの
膜特性を向上できるＭｇＯを主成分とする蒸着材及びそ
の製造方法を提供することにある。An object of the present invention is to provide a stable and uniform film without causing a trouble in the supply system of the MgO sintered body even when the film is formed by the electron beam evaporation method, without generating a splash.
An object of the present invention is to provide a deposition material containing gO as a main component and a method for producing the same. Another object of the present invention is to provide a deposition material containing MgO as a main component and a method for producing the same, which can improve the film characteristics of the formed MgO.
【０００９】[0009]
【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０．５〜１００μｍの結晶粒子を有するＭｇＯ
マトリックス中に、希土類酸化物粒子が０．５〜５０体
積％分散されたＭｇＯを主成分とする蒸着材である。こ
の請求項１に記載されたＭｇＯを主成分とする蒸着材で
は、異方性のないＭｇＯマトリックス中に、希土類酸化
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 0.5 to 100 μm
This is a vapor deposition material containing MgO as a main component, in which rare earth oxide particles are dispersed in a matrix in an amount of 0.5 to 50% by volume. In the vapor deposition material containing MgO as a main component according to the first aspect of the present invention, the rare-earth oxide particles are dispersed in an MgO matrix having no anisotropy to form a composite, whereby the physical properties of the MgO sintered body are reduced. Properties can be improved.
【００１０】例えば、Ａｌ2Ｏ3マトリックスにＳｉＣ粒
子を分散させた場合には、Ａｌ2Ｏ3マトリックスの熱膨
張係数が、分散したＳｉＣ粒子の熱膨張係数より２倍以
上大きいため、焼結体には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残留応力が発生す
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
面に亀裂が走り易い。これに対して本発明では、希土類
酸化物粒子が高温で軟化し易く、またその熱膨張係数が
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倍になり、残留応力が非常
に小さい。このためＭｇＯマトリックスに対する希土類
酸化物粒子の高温時の熱挙動は、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しており、急激
な熱変化に対して安定である。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。この蒸着材を用いて
成膜されたＭｇＯ膜は、パネルに組み込んだ場合、低い
放電電圧、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。この結果、ＡＣ型ＰＤＰの誘電
体層の保護膜に好適なものとなる。上述のように分散粒
子である希土類酸化物粒子は、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
範囲で大きな希土類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。[0010] For example, when dispersed SiC particles to Al 2 O 3 matrix, the coefficient of thermal expansion of Al 2 O 3 matrix, larger than 2 times greater than the thermal expansion coefficient of the dispersed SiC particles, the sintered body During the sintering process, residual stress is generated around and inside the dispersed particles due to the difference in thermal expansion coefficient. Since this stress is so large as to reach 1000 MPa to 1500 MPa, cracks easily run at the interface between the Al 2 O 3 matrix and the dispersed particles. On the other hand, in the present invention, the rare-earth oxide particles tend to soften at a high temperature, and the thermal expansion coefficient of the rare-earth oxide particles is high at a high temperature.
−6 / ° C.), and the residual stress is very small. Therefore, the thermal behavior of the rare-earth oxide particles with respect to the MgO matrix at a high temperature is such that the MgO matrix and the dispersed particles are strongly bonded at the interface during sintering, and are stable against a rapid thermal change. 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. When the MgO film formed using this vapor deposition material is incorporated in a panel, it has a low discharge voltage, spatter resistance during discharge, fast discharge response, and high insulation. As a result, it becomes suitable as a protective film for the dielectric layer of the AC type PDP. As described above, the rare-earth oxide particles that are dispersed particles become soft at high temperatures, so that the difference in the coefficient of thermal expansion between the matrix and the dispersed particles becomes small at high temperatures. Therefore, it is possible to disperse large rare earth 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 defects at the grain boundaries, and improving the strength.
【００１１】請求項２に係る発明は、請求項１に係る発
明であって、更に希土類酸化物粒子中の希土類元素がＳ
ｃ，Ｙ，Ｌａ，Ｃｅ，Ｇｄ，Ｙｂ，Ｎｄ，Ｓｍ，Ｔｂ及
びＤｙ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。この請求項２に記載されたＭ
ｇＯを主成分とする蒸着材では、希土類元素を添加する
ことにより、ＭｇＯマトリックスも均一な組織となり、
パネルに組み込んだときの蛍光体への悪影響はなく、青
色に関係する輝度も向上する。The invention according to claim 2 is the invention according to claim 1, wherein the rare earth element in the rare earth oxide particles is S
It is one or more elements selected from the group consisting of c, Y, La, Ce, Gd, Yb, Nd, Sm, Tb and Dy. M according to claim 2
In a deposition material containing gO as a main component, the MgO matrix also has a uniform structure by adding a rare earth element,
There is no adverse effect on the phosphor when incorporated into the panel, and the luminance associated with blue is also improved.
【００１２】上記請求項１又は２に記載されたＭｇＯを
主成分とする蒸着材は、ＭｇＯ粉末と、希土類元素の酸
化物粉末，炭酸塩粉末，水酸化物粉末又は硝酸塩粉末
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、成形体を
脱脂した後に１５００〜１７００℃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
ＭｇＯ粉末と、希土類元素の酸化物粉末，炭酸塩粉末，
水酸化物粉末又は硝酸塩粉末と、バインダとを混練する
工程と、この混練物を転動造粒機の回転皿に入れた後に
有機溶媒を噴霧することにより混練物を造粒して球状の
成形体を成形する工程と、上記回転皿に更に混練物を入
れかつ有機溶媒を噴霧する作業を繰返すことにより球状
の成形体を所定の大きさに成長させる工程と、成長した
成形体を脱脂した後に１５００〜１７００℃の温度で焼
結する工程とを含む製造方法により製造してもよい。更
にＭｇＯ粉末と、希土類元素の酸化物粉末，炭酸塩粉
末，水酸化物粉末又は硝酸塩粉末とを湿式混合する工程
と、この混合物を減圧加熱して乾燥した後に乾式解砕す
る工程と、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１４
５０〜１７５０℃に昇温して焼結する工程とを含む製造
方法により製造してもよい。上記製造方法で製造された
ＭｇＯを主成分とする蒸着材では、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の
希土類酸化物粒子が均一に分散される。ここで希土類元
素の炭酸塩粉末，水酸化物粉末又は硝酸塩粉末は焼結時
に希土類酸化物粒子となってＭｇＯマトリックス内に均
一に分散される。[0012] The vapor deposition material containing MgO as a main component according to claim 1 or 2 comprises a MgO powder, an oxide powder, a carbonate powder, a hydroxide powder or a nitrate powder of a rare earth element, a binder, A step of preparing a mixed slurry having a predetermined concentration by mixing with an organic solvent; a step of spray-drying the slurry to obtain a granulated powder having a predetermined particle size; It is preferable to be manufactured by a manufacturing method including a step of forming under pressure and a step of sintering at a temperature of 1500 to 1700 ° C. after degreasing the formed body. MgO powder, rare earth element oxide powder, carbonate powder,
A step of kneading the hydroxide powder or nitrate powder and a binder, and granulating the kneaded material by spraying an organic solvent after putting the kneaded material in a rotating plate of a tumbling granulator to form a spherical shape. A step of forming the body, a step of growing the spherical shaped body to a predetermined size by repeating the operation of further kneading the mixture in the rotating dish and spraying the organic solvent, and after degreased the grown shaped body And sintering at a temperature of 1500 to 1700 ° C. A step of wet-mixing the MgO powder and a powder of an oxide of a rare earth element, a powder of a carbonate, a powder of a hydroxide or a powder of a nitrate; The crushed mixed powder is placed in a predetermined mold and subjected to a predetermined pressure in an inert gas atmosphere.
And sintering by raising the temperature to 50 to 1750 ° C. The vapor deposition material containing MgO as a main component produced by the above production method is densely sintered in the sintering step, and the rare earth oxide particles of the dispersed phase are uniformly dispersed in the MgO matrix of the vapor deposition material. Here, the rare earth element carbonate powder, hydroxide powder or nitrate powder becomes rare earth oxide particles during sintering and is uniformly dispersed in the MgO matrix.
【００１３】なお、上記請求項１又は２記載のＭｇＯを
主成分とする蒸着材を用いてＭｇＯ膜を成膜すると、例
えば蒸着材を電子ビーム蒸着法で成膜すると、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、高速安定性膜が
可能となり、得られたＭｇＯ膜は完全固溶し、かつＭｇ
Ｏ膜の配向性は向上し、このＭｇＯ膜を成膜した基板を
ＰＤＰに組み込んだとき、放電電圧を低くでき、放電時
の耐スパッタ性を向上でき、更にこのＭｇＯ膜は高い絶
縁性を有する。When an MgO film is formed by using an evaporation material containing MgO as a main component according to claim 1 or 2, for example, when the evaporation material is formed by an electron beam evaporation method, two phases coexist, that is, MgO is formed. Since the matrix and the dispersed particles evaporate without forming a solid solution or a reactant, a high-speed stable film becomes possible, and the obtained MgO film completely dissolves
The orientation of the O film is improved. When the substrate on which the MgO film is formed is incorporated into a PDP, the discharge voltage can be reduced, the spatter resistance during discharge can be improved, and the MgO film has high insulation properties. .
【００１４】[0014]
【発明の実施の形態】以下に本発明の実施の形態を説明
する。本発明のＭｇＯを主成分とする蒸着材は、相対密
度が９５％以上のＭｇＯ焼結体であって、平均結晶粒径
が０．５〜１００μｍ、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、希土類酸化物粒
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。上記希土類酸化物粒子中の希土類
元素としては、Ｓｃ，Ｙ，Ｌａ，Ｃｅ，Ｇｄ，Ｙｂ，Ｎ
ｄ，Ｓｍ，Ｔｂ及びＤｙ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。Embodiments of the present invention will be described below. The vapor deposition material containing MgO as a main component of the present invention is a sintered body of MgO having a relative density of 95% or more, and has an average crystal grain size of 0.5 to 100 μm, preferably 2 to 50 μm. In the matrix, the rare earth oxide particles contain 0.5 to 50% by volume, preferably 1 to 30% by volume,
More preferably, 5 to 25% by volume is dispersed.
This vapor deposition material is a ceramic sintered body using MgO as a matrix and rare earth oxide particles as a dispersed phase (dispersed particles). The rare earth elements in the rare earth oxide particles include Sc, Y, La, Ce, Gd, Yb, and N.
It is preferable to use one or more elements selected from the group consisting of d, Sm, Tb and Dy. 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.
【００１５】上記ＭｇＯマトリックスの平均結晶粒径を
０．５〜１００μｍ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、
また材料中での欠陥を生じさせないためである。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 0.5 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,
In addition, this is because a defect in the material is not caused. In addition,
If the average particle size of the dispersed particles exceeds 3.0 μm, microcracks are likely to occur.
【００１６】このように構成された本発明のＭｇＯを主
成分とする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の希土類元素の酸
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。上記希土類元素の酸化物粉末はこの希土類元素
の酸化物粉末とＭｇＯ粉末との合計体積に対して希土類
元素の酸化物が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、即ち希土類元
素の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％未満では希土類元素の酸化
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。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 vapor deposition material having MgO as a main component according to the present invention thus configured will be described. MgO powder having an average particle diameter of 0.1 to 5 μm, preferably 0.2 to 2 μm, and a rare earth element oxide powder having an average particle diameter of 0.2 to 3.0 μm and a binder in total of 0.2 to 2 μm And then wet-mixed with ethanol or propanol as a dispersion medium to prepare a mixed slurry having a concentration of 40 to 70% by weight. The oxide powder of the rare earth element is weighed so that the oxide of the rare earth element is 0.5 to 50% by volume with respect to the total volume of the oxide powder of the rare earth element and the MgO powder, and is added to the MgO 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 oxide powder of the rare earth element is limited to the range of 0.5 to 50% by volume. The effect of adding the oxide of the rare earth element is less than 0.5% by volume. If the content is less than 50% by volume, it is difficult to control the material structure, the spatter resistance and the insulating property vary, and the reliability of the material is lost. When the amount of the dispersed particles is within the above range, the dispersed particles can be 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.
【００１７】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２００ｃＰ（センチポアズ）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。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。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 not more than 200 cP (centipoise) within this range, and the mixed slurry can be produced stably even when spray-dried. This is because the density of the compact, which will be described later, increases, and a dense sintered body can be manufactured. If the concentration of the mixed slurry exceeds 70% by weight, stable granulation is difficult because the slurry is a non-aqueous slurry. If the concentration is less than 40% by weight, a dense MgO sintered body having a uniform structure cannot be obtained. 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 put into 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.
【００１８】更に上記成形体を１５００℃〜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１５００℃〜１７００℃に限定したの
は、１５００℃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を主成分とする蒸着材が得られる。Further, the above molded product is heated at 1500 ° 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 1500 ° C. to 1700 ° C. is that a compact sintered body cannot be obtained below 1500 ° 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 vapor-deposited material mainly composed of dense MgO having a relative density of 95% or more can be obtained.
【００１９】上記ＭｇＯを主成分とする蒸着材を電子ビ
ーム蒸着法、プラズマイオンプレーティング法等を用い
てＭｇＯ膜を基板等に成膜すれば、二相共存、即ちＭｇ
Ｏ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、高速安定性膜が可能となり、
得られたＭｇＯ膜は完全固溶し、かつＭｇＯ膜の配向性
は向上する。また上記蒸着材を用いてＭｇＯ膜を成膜し
た基板をＰＤＰに組み込んだとき、放電電圧を低くで
き、放電時の耐スパッタ性を向上でき、更にこのＭｇＯ
膜は高い絶縁性を有する。従って、上記ＭｇＯ膜はＡＣ
型ＰＤＰの保護膜の成膜に好適であり、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 using the above-described evaporation material containing MgO as a main component by using an electron beam evaporation method, a plasma ion plating method, or the like, two phases coexist, that is, MgO
Since the O matrix and the dispersed particles evaporate without forming a solid solution or a reactant, a high-speed stable film becomes possible,
The obtained MgO film is completely dissolved, and the orientation of the MgO film is improved. Further, when a substrate on which an MgO film is formed using the above-described vapor deposition material is incorporated into a PDP, the discharge voltage can be lowered, the spatter resistance during discharge can be improved, and
The film has high insulating properties. Therefore, the above MgO film is AC
It is suitable for forming a protective film of a type PDP, and is also applicable to a protective film of a high-performance ceramic material.
【００２０】なお、上記実施の形態では、ＭｇＯ粉末に
希土類元素の酸化物粉末を添加したが、ＭｇＯ粉末に希
土類元素の炭酸塩粉末，水酸化物粉末又は硝酸塩粉末を
添加してもよい。この場合、希土類元素の炭酸塩粉末，
水酸化物粉末又は硝酸塩粉末は焼結時に希土類酸化物粒
子となってＭｇＯマトリックス内に均一に分散される。
また、上記実施の形態では、ＭｇＯ粉末と希土類元素の
酸化物粉末等とバインダと有機溶媒とを混合して混合ス
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粉末と希土類元素の酸化物粉末等
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、回転皿に更に前記混練物を
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。更に、
上記実施の形態では、ＭｇＯ粉末と希土類元素の酸化物
粉末等とバインダと有機溶媒とを混合して混合スラリー
を調製し、このスラリーを噴霧乾燥して所定粒径の造粒
粉末を得た後に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１５００〜１７００℃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粉末と希土類元素の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１４５
０〜１６５０℃に昇温して焼結してもよい。In the above embodiment, the rare earth element oxide powder is added to the MgO powder, but the rare earth element carbonate powder, hydroxide powder or nitrate powder may be added to the MgO powder. In this case, rare earth carbonate powder,
The hydroxide powder or the nitrate powder becomes rare earth oxide particles during sintering and is uniformly dispersed in the MgO matrix.
Further, in the above embodiment, a mixed slurry is prepared by mixing MgO powder, rare earth element oxide powder and the like, a binder and an organic solvent, and this slurry is spray-dried to obtain a granulated powder having a predetermined particle size. After that, it was placed in a predetermined mold and molded at a predetermined pressure, but the molded body may be molded using a rolling granulator. That is, first, MgO powder, rare earth element oxide powder and the like are kneaded with a binder, 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. By granulating the kneaded material to form a spherical molded body by repeating the operation of further adding the kneaded material to a rotating dish and spraying an organic solvent,
A spherical molded body having a predetermined size may be formed. Furthermore,
In the above embodiment, a mixed slurry is prepared by mixing MgO powder, rare earth element oxide powder or the like, a binder, and an organic solvent, and the slurry is spray-dried to obtain a granulated powder having a predetermined particle size. Put it in a given mold and mold it with a given pressure,
Furthermore, although the molded body was degreased and sintered at a temperature of 1500 to 1700 ° C., hot press sintering may be performed. That is, the MgO powder and the oxide powder of a rare earth element are wet-mixed, the mixture is heated under reduced pressure, dried, and then subjected to dry pulverization. 145 in an inert gas atmosphere under pressure
The temperature may be raised to 0 to 1650 ° C. for sintering.
【００２１】[0021]
【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Ｓｃ2Ｏ3（三菱マテリアル社製、平均粒径
１．５〜２．５μｍ）粉末との合計体積に対してＳｃ2
Ｏ3粉末が１体積％となるように秤量し、このＳｃ2Ｏ3
粉末を上記ＭｇＯ粉末に加え、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８
ｍｍ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（以下、
常圧焼結という）。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 [mu] m) and Sc 2 O 3 (manufactured by Mitsubishi Materials Corporation, Sc 2 with respect to the total volume of the average particle diameter 1.5 to 2.5 [mu] m) powder
O 3 powder was weighed so as to be 1% by volume, and this Sc 2 O 3
The powder was added to the above MgO powder, a binder (polyvinyl butyral) was further added, and the mixture was wet-mixed for 1 hour with a stirring mill using ethanol as a dispersion medium to prepare a mixed slurry having a concentration of 55%. 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 and a depth of 8 mm).
mm) and molded by a mechanical press to produce a molded body. The molded body is placed in an air atmosphere at 1650.
C., and sintered for 3 hours in a sintering furnace (manufactured by Hirotsuki Co., Ltd.) to obtain a MgO sintered body having a diameter of about 80 mm (hereinafter, referred to as “MgO sintered body”)
Normal pressure sintering). This MgO sintered body was used as Example 1.
【００２２】＜実施例２＞ＭｇＯ粉末にＳｃ2Ｏ3粉末を
１０体積％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６
ｍｍ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と同様に常圧焼結することによ
り直径が約８０ｍｍ及び５ｍｍのＭｇＯ焼結体をそれぞ
れ得た。上記直径８０ｍｍ及び５ｍｍのＭｇＯ焼結体を
実施例２とした。 ＜実施例３＞ＭｇＯ粉末にＳｃ2Ｏ3粉末を２０体積％加
えたことを除いて、実施例１（常圧焼結）と同様にして
ＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例３とし
た。<Example 2> 10% by volume of Sc 2 O 3 powder was added to 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 (a mold having an inner diameter of 100 mm and a depth of 8 mm, and an inner diameter of 6).
mm and a depth of 3 mm), and molded by a mechanical press to produce molded bodies. These molded bodies were sintered under normal pressure in the same manner as in Example 1 to reduce the diameter to about 80 mm and 5 mm MgO sintered bodies were obtained, respectively. Example 2 was a MgO sintered body having a diameter of 80 mm and a diameter of 5 mm. Except that the addition 20% by volume of Sc 2 O 3 powder <Example 3> MgO powder, in the same manner as in Example 1 (pressureless sintering) to obtain a sintered MgO. This MgO sintered body was used as Example 3.
【００２３】＜実施例４＞ＭｇＯ粉末（岩谷化学社製、
平均粒径０．２μｍ）にＳｃ2Ｏ3粉末を１５体積％加
え、エタノールを分散媒として、撹拌ミルで１時間湿式
混合した。これをロータリーエバポレータを用いて減圧
加熱して乾燥した後、乾式ボールミルで乾式解砕して混
合した。この混合粉末を黒鉛ダイス（内径φ８０ｍｍ）
に充填して混合粉末に１５ＭＰａのプレス圧をかけた状
態で焼結炉（富士電波工業社製）に収容し、かつこの焼
結炉内をアルゴン雰囲気にして１５００℃に昇温し、こ
の温度で１時間保持してホットプレス焼結して（以下、
ＨＰ焼結という）直径が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＞ＭｇＯ粉末にＳｃ2Ｏ3粉末を２５体積％加
えたことを除いて、実施例４（ＨＰ焼結）と同様にして
ＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例５とし
た。<Example 4> MgO powder (manufactured by Iwatani Chemical Co., Ltd.)
15% by volume of Sc 2 O 3 powder was added to an average particle size of 0.2 μm), and the mixture was wet-mixed for 1 hour with a stirring mill using ethanol as a dispersion medium. This was dried by heating under reduced pressure using a rotary evaporator, and then dry-crushed by a dry ball mill and mixed. This mixed powder is graphite die (inner diameter φ80mm)
And the mixed powder was housed in a sintering furnace (manufactured by Fuji Denki Kogyo Co., Ltd.) while applying a pressure of 15 MPa to the mixed powder, and the inside of the sintering furnace was heated to 1500 ° C. under an argon atmosphere. For 1 hour and hot-press sintering.
An MgO sintered body having a diameter of 80 mm (referred to as HP sintering) was obtained. This MgO sintered body was used as Example 4. Except that the addition 25% by volume Sc 2 O 3 powder <Example 5> MgO powder, in the same manner as in Example 4 (HP sintering) to obtain a sintered MgO. This MgO sintered body was used as Example 5.
【００２４】＜実施例６＞ＭｇＯ粉末にＹ2Ｏ3（第一希
元素社製、平均粒径０．８〜１．２μｍ）粉末を２体積
％加えたことを除いて、実施例１（常圧焼結）と同様に
してＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例６
とした。 ＜実施例７＞ＭｇＯ粉末にＹ2Ｏ3粉末を１０体積％加え
たことを除いて、実施例２（常圧焼結）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焼結体を実施例７とした。 ＜実施例８＞ＭｇＯ粉末にＹ2Ｏ3粉末を２０体積％加え
たことを除いて、実施例１（常圧焼結）と同様にしてＭ
ｇＯ焼結体を得た。このＭｇＯ焼結体を実施例８とし
た。 ＜実施例９＞ＭｇＯ粉末にＹ2Ｏ3粉末を１０体積％加え
たことを除いて、実施例４（ＨＰ焼結）と同様にしてＭ
ｇＯ焼結体を得た。このＭｇＯ焼結体を実施例９とし
た。 ＜実施例１０＞ＭｇＯ粉末にＹ2Ｏ3粉末を２５体積％加
えたことを除いて、実施例４（ＨＰ焼結）と同様にして
ＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例１０と
した。Example 6 The procedure of Example 1 was repeated except that 2% by volume of Y 2 O 3 (manufactured by Daiichi Rare Element Co., average particle size 0.8-1.2 μm) powder was added to MgO powder. MgO sintered body was obtained in the same manner as described above. This MgO sintered body was used in Example 6
And Example 7 An MgO sintered body having a diameter of about 80 mm and 5 mm was obtained in the same manner as in Example 2 (normal pressure sintering), except that 10% by volume of Y 2 O 3 powder was added to MgO powder. Was. These MgO sintered bodies were designated as Example 7. Example 8 The procedure of Example 1 (normal pressure sintering) was repeated except that 20% by volume of Y 2 O 3 powder was added to MgO powder.
A gO sintered body was obtained. This MgO sintered body was used as Example 8. Example 9 The procedure of Example 4 (HP sintering) was repeated except for adding 10% by volume of Y 2 O 3 powder to MgO powder.
A gO sintered body was obtained. This MgO sintered body was used as Example 9. <Example 10> An MgO sintered body was obtained in the same manner as in Example 4 (HP sintering), except that 25% by volume of Y 2 O 3 powder was added to MgO powder. This MgO sintered body was used as Example 10.
【００２５】＜実施例１１＞ＭｇＯ粉末にＬａ2Ｏ3（信
越化学社製、平均粒径０．７〜１．５μｍ）粉末を５体
積％加えたことを除いて、実施例１（常圧焼結）と同様
にして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＞ＭｇＯ粉末にＬａ2Ｏ3粉末を１５体積％
加えたことを除いて、実施例２（常圧焼結）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焼結体を実施例１２とした。 ＜実施例１３＞ＭｇＯ粉末にＬａ2Ｏ3粉末を２５体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
て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＞ＭｇＯ粉末にＬａ2Ｏ3粉末を１０体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例１４
とした。Example 11 Example 1 (normal pressure) except that 5% by volume of La 2 O 3 (Shin-Etsu Chemical Co., Ltd., average particle size 0.7-1.5 μm) powder was added to MgO powder. Sintered) to obtain a MgO sintered body. This MgO sintered body was used as Example 11. <Example 12> 15% by volume of La 2 O 3 powder in MgO powder
Except for the addition, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2 (normal pressure sintering).
These MgO sintered bodies were designated as Example 12. Example 13 25% by volume of La 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 13
And <Example 14> 10% by volume of La 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 14
And
【００２６】＜実施例１５＞ＭｇＯ粉末にＣｅ2Ｏ3（信
越化学社製、平均粒径１．０〜１．４μｍ）粉末を３体
積％加えたことを除いて、実施例２（常圧焼結）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焼結体を実施例１５とした。 ＜実施例１６＞ＭｇＯ粉末にＣｅ2Ｏ3粉末を１５体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
て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＞ＭｇＯ粉末にＣｅ2Ｏ3粉末を２５体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例１７
とした。 ＜実施例１８＞ＭｇＯ粉末にＣｅ2Ｏ3粉末を１０体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例１８
とした。 ＜実施例１９＞ＭｇＯ粉末にＣｅ2Ｏ3粉末を２０体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例１９
とした。Example 15 The procedure of Example 2 (normal pressure) was repeated except that 3% by volume of Ce 2 O 3 (Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 to 1.4 μm) powder was added to MgO powder. In the same manner as in (Sintering), MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained. These MgO sintered bodies were used as Example 15. Example 16 15% by volume of Ce 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 16
And Example 17 25% by volume of Ce 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 17
And Example 18 10% by volume of Ce 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 18
And <Example 19> MgO powder Ce 2 O 3 powder of 20 vol%
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 19
And
【００２７】＜実施例２０＞ＭｇＯ粉末にＧｄ2Ｏ3（信
越化学社製、平均粒径１．０〜１．４μｍ）粉末を２体
積％加えたことを除いて、実施例１（常圧焼結）と同様
にして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＞ＭｇＯ粉末にＧｄ2Ｏ3粉末を１０体積％
加えたことを除いて、実施例２（常圧焼結）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焼結体を実施例２１とした。 ＜実施例２２＞ＭｇＯ粉末にＧｄ2Ｏ3粉末を２０体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
て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＞ＭｇＯ粉末にＧｄ2Ｏ3粉末を１５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
て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＞ＭｇＯ粉末にＧｄ2Ｏ3粉末を２５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例２４
とした。Example 20 The procedure of Example 1 (normal pressure) was performed except that 2% by volume of Gd 2 O 3 (manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 to 1.4 μm) powder was added to MgO powder. Sintered) to obtain a MgO sintered body. This MgO sintered body was used as Example 20. Example 21 10% by volume of Gd 2 O 3 powder in MgO powder
Except for the addition, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2 (normal pressure sintering).
These MgO sintered bodies were used as Example 21. <Example 22> MgO powder Gd 2 O 3 powder of 20 vol%
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 22.
And Example 23 15% by volume of Gd 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 23
And Example 24 25% by volume of Gd 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was prepared in Example 24.
And
【００２８】＜実施例２５＞ＭｇＯ粉末にＹｂ2Ｏ3（信
越化学社製、平均粒径１．５μｍ）粉末を２体積％加え
たことを除いて、実施例１（常圧焼結）と同様にしてＭ
ｇＯ焼結体を得た。このＭｇＯ焼結体を実施例２５とし
た。 ＜実施例２６＞ＭｇＯ粉末にＹｂ2Ｏ3粉末を１０体積％
加えたことを除いて、実施例２（常圧焼結）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焼結体を実施例２６とした。 ＜実施例２７＞ＭｇＯ粉末にＹｂ2Ｏ3粉末を２５体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例２７
とした。 ＜実施例２８＞ＭｇＯ粉末にＹｂ2Ｏ3粉末を１５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例２８
とした。Example 25 Example 1 (normal pressure sintering) was repeated except that 2% by volume of Yb 2 O 3 (Shin-Etsu Chemical Co., Ltd., average particle size: 1.5 μm) powder was added to MgO powder. Similarly, M
A gO sintered body was obtained. This MgO sintered body was designated as Example 25. Example 26 10% by volume of Yb 2 O 3 powder in MgO powder
Except for the addition, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2 (normal pressure sintering).
These MgO sintered bodies were used as Example 26. <Example 27> 25 volume% of Yb 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 27.
And Example 28 15% by volume of Yb 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 28
And
【００２９】＜実施例２９＞ＭｇＯ粉末にＳｍ2Ｏ3（信
越化学社製、平均粒径０．３〜０．６μｍ）粉末を２０
体積％加えたことを除いて、実施例１（常圧焼結）と同
様にしてＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施
例２９とした。 ＜実施例３０＞ＭｇＯ粉末にＳｍ2Ｏ3粉末を１０体積％
加えたことを除いて、実施例２（常圧焼結）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焼結体を実施例３０とした。 ＜実施例３１＞ＭｇＯ粉末にＳｍ2Ｏ3粉末を１５体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例３１
とした。 ＜実施例３２＞ＭｇＯ粉末にＳｍ2Ｏ3粉末を２５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例３２
とした。 ＜実施例３３＞ＭｇＯ粉末にＳｍ2Ｏ3粉末を３０体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例３３
とした。<Example 29> Sm 2 O 3 powder (manufactured by Shin-Etsu Chemical Co., Ltd., average particle size 0.3 to 0.6 μm) was added to MgO powder for 20 times.
An MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering), except that the volume% was added. This MgO sintered body was used as Example 29. <Example 30> 10% by volume of Sm 2 O 3 powder in MgO powder
Except for the addition, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2 (normal pressure sintering).
These MgO sintered bodies were designated as Example 30. <Example 31> 15% by volume of Sm 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 31
And Example 32 25% by volume of Sm 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 32
And Example 33 30% by volume of Sm 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 33
And
【００３０】＜実施例３４＞ＭｇＯ粉末にＴｂ4Ｏ7（信
越化学社製、平均粒径０．３〜０．６μｍ）粉末を１０
体積％加えたことを除いて、実施例１（常圧焼結）と同
様にしてＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施
例３４とした。 ＜実施例３５＞ＭｇＯ粉末にＴｂ4Ｏ7粉末を２０体積％
加えたことを除いて、実施例２（常圧焼結）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焼結体を実施例３５とした。 ＜実施例３６＞ＭｇＯ粉末にＴｂ4Ｏ7粉末を３０体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例３６
とした。 ＜実施例３７＞ＭｇＯ粉末にＴｂ4Ｏ7粉末を１５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例３７
とした。 ＜実施例３８＞ＭｇＯ粉末にＴｂ4Ｏ7粉末を２５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例３８
とした。<Example 34> Tb 4 O 7 (manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 0.3 to 0.6 μm) powder was added to MgO powder by 10
An MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering), except that the volume% was added. This MgO sintered body was designated as Example 34. Example 35 20% by volume of Tb 4 O 7 powder in MgO powder
Except for the addition, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2 (normal pressure sintering).
These MgO sintered bodies were designated as Example 35. Example 36 30% by volume of Tb 4 O 7 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 36
And Example 37 15% by volume of Tb 4 O 7 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 37.
And Example 38 25% by volume of Tb 4 O 7 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 38.
And
【００３１】＜実施例３９＞ＭｇＯ粉末にＤｙ2Ｏ3（信
越化学社製、平均粒径０．５〜１．０μｍ）粉末を１０
体積％加えたことを除いて、実施例１（常圧焼結）と同
様にしてＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施
例３９とした。 ＜実施例４０＞ＭｇＯ粉末にＤｙ2Ｏ3粉末を２０体積％
加えたことを除いて、実施例２（常圧焼結）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焼結体を実施例４０とした。 ＜実施例４１＞ＭｇＯ粉末にＤｙ2Ｏ3粉末を３０体積％
加えたことを除いて、実施例１（常圧焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例４１
とした。 ＜実施例４２＞ＭｇＯ粉末にＤｙ2Ｏ3粉末を２５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例４２
とした。 ＜実施例４３＞ＭｇＯ粉末にＤｙ2Ｏ3粉末を１５体積％
加えたことを除いて、実施例４（ＨＰ焼結）と同様にし
てＭｇＯ焼結体を得た。このＭｇＯ焼結体を実施例４３
とした。Example 39 Dy 2 O 3 (Shin-Etsu Chemical Co., Ltd., average particle size: 0.5 to 1.0 μm) powder was added to MgO powder in 10
An MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering), except that the volume% was added. This MgO sintered body was used as Example 39. Example 40 20% by volume of Dy 2 O 3 powder in MgO powder
Except for the addition, MgO sintered bodies having diameters of about 80 mm and 5 mm were obtained in the same manner as in Example 2 (normal pressure sintering).
These MgO sintered bodies were designated as Example 40. Example 41 30% by volume of Dy 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering). This MgO sintered body was used in Example 41.
And Example 42 25% by volume of Dy 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 42.
And Example 43 15% by volume of Dy 2 O 3 powder in MgO powder
Except for the addition, a MgO sintered body was obtained in the same manner as in Example 4 (HP sintering). This MgO sintered body was used in Example 43.
And
【００３２】＜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＞ＭｇＯ粉末にＳｃ2Ｏ3粉末を３５体積％加
えたことを除いて、実施例１（常圧焼結）と同様にして
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＞ＭｇＯ粉末にＹ2Ｏ3粉末を３５体積％加え
たことを除いて、実施例１（常圧焼結）と同様にしてＭ
ｇＯ焼結体を得た。このＭｇＯ焼結体を比較例３とし
た。 ＜比較例４＞ＭｇＯ粉末にＬａ2Ｏ3粉末を３５体積％加
えたことを除いて、実施例２（常圧焼結）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４とした。 ＜比較例５＞ＭｇＯ粉末にＣｅ2Ｏ3粉末を３５体積％加
えたことを除いて、実施例２（常圧焼結）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＞ＭｇＯ粉末にＧｄ2Ｏ3粉末を３５体積％加
えたことを除いて、実施例２（常圧焼結）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６とした。 ＜比較例７＞ＭｇＯ粉末にＹｂ2Ｏ3粉末を３５体積％加
えたことを除いて、実施例１（常圧焼結）と同様にして
ＭｇＯ焼結体を得た。このＭｇＯ焼結体を比較例７とし
た。Comparative Example 1 A commercially available MgO sintered body (about 80 mm in diameter) was used as Comparative Example 1. Except that the addition 35% by volume of Sc 2 O 3 powder in <Comparative Example 2> MgO powder to obtain a sintered MgO in the same manner as in Example 1 (pressureless sintering). This MgO sintered body was used as Comparative Example 2. <Comparative Example 3> M was prepared in the same manner as in Example 1 (normal pressure sintering) except that 35 vol% of Y 2 O 3 powder was added to MgO powder.
A gO sintered body was obtained. This MgO sintered body was used as Comparative Example 3. <Comparative Example 4> An MgO sintered body having a diameter of about 80 mm and 5 mm was obtained in the same manner as in Example 2 (normal pressure sintering) except that 35 vol% of La 2 O 3 powder was added to MgO powder. Was. These MgO sintered bodies were designated as Comparative Example 4. <Comparative Example 5> An MgO sintered body having a diameter of about 80 mm and 5 mm was obtained in the same manner as in Example 2 (normal pressure sintering), except that 35% by volume of Ce 2 O 3 powder was added to MgO powder. Was. These MgO sintered bodies were used as Comparative Example 5. <Comparative Example 6> An MgO sintered body having a diameter of about 80 mm and 5 mm was obtained in the same manner as in Example 2 (normal pressure sintering), except that 35 vol% of Gd 2 O 3 powder was added to MgO powder. Was. These MgO sintered bodies were used as Comparative Example 6. <Comparative Example 7> A MgO sintered body was obtained in the same manner as in Example 1 (normal pressure sintering), except that 35% by volume of Yb 2 O 3 powder was added to MgO powder. This MgO sintered body was used as Comparative Example 7.
【００３３】＜比較試験と評価＞ (a) 相対密度と強度試験 実施例１〜４３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及び表２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 1-43 and Comparative Examples 1-7 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. Tables 1 and 2 show these results.
The relative density was measured in toluene by Archimedes' method. The breaking strength was measured by a three-point bending test.
【００３４】[0034]
【表１】 [Table 1]
【００３５】[0035]
【表２】 [Table 2]
【００３６】表１及び表２から明らかなように、比較例
１の市販のＭｇＯ焼結体の相対密度が９５％であるのに
対して、実施例１〜４３のＭｇＯ焼結体の相対密度は９
７％以上と緻密になっている。また実施例１〜４３のＭ
ｇＯ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１〜４３では結晶粒界面に
亀裂を発生させない範囲内で希土類元素の酸化物を分散
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 Tables 1 and 2, the relative density of the commercially available MgO sintered bodies of Comparative Example 1 is 95%, while the relative densities of the MgO sintered bodies of Examples 1 to 43 are 95%. Is 9
It is as dense as 7% or more. M of Examples 1-43
The bending strength of the gO sintered body was twice as high as that of Comparative Examples 1 to 7. This is because in Examples 1 to 43, the oxide of the rare earth element can be dispersed within a range in which no crack is generated at the crystal grain interface, and the defect at the crystal grain boundary can be reduced and the strength can be improved. In Comparative Examples 2 to 7, This is considered to be because defects were generated in the crystal grain boundaries due to the excessive addition ratio of the dispersed particles.
【００３７】(b) ＭｇＯ膜の特性試験 実施例２，７，１２，１５，２１，２６，３０，３５及
び４０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１３
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
ＴＥＧ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１００μ
ｍ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．
５μｍ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, 7, 12, 15, 21, 26, 30, 35 and 40 and Comparative Examples 1 and 4 to 6 were subjected to electron beam evaporation. 13 on a glass substrate
Various kinds of TEG (Test Element Group) substrates were produced.
The MgO sintered body having a diameter of 5 mm in Comparative Example 1 had a diameter of about 80 mm and a diameter of 5 mm and a thickness of 2.5 mm.
It was manufactured by machining. As shown in FIG. 1, a TEG substrate 10 has a base electrode 12 made of an InSn composite oxide film formed on a glass substrate (Corning # 7059 glass) 11 having a thickness of 1 mm by photolithography.
After forming a glass layer 13 having a thickness of 0.2 μm and a width of 100 μm at intervals of m by reactive DC sputtering of Si so as to cover these base electrodes 12,
With the same film forming conditions, a thickness of 0.
It was formed by forming a 5 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.
【００３８】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
０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３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 3 shows the refractive index, absorption coefficient, and firing voltage of the MgO film obtained by the above method.
【００３９】[0039]
【表３】 [Table 3]
【００４０】表３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０．０１以上であ
ったのに対して、実施例２，７，１２，１５，２１，２
６，３０，３５及び４０のＭｇＯ焼結体を用いて成膜さ
れたＭｇＯ膜の屈折率は１．７２以上で吸収係数は０．
００１以下であった。これらのことから、実施例のＭｇ
Ｏ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１
２〜２３Ｖ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 clear from Table 3, 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 0.01 or more. In contrast to Examples 2, 7, 12, 15, 21, 21
The MgO films formed using the 6, 30, 35 and 40 MgO sintered bodies have a refractive index of 1.72 or more and an absorption coefficient of 0.5.
001 or less. From these facts, the Mg of the example
It was found that the use of an O sintered body provided an MgO film having excellent crystallinity and permeability. In addition, the firing voltage of the above example was 1 unit compared to the firing voltage of the comparative example.
Since the voltage was low by about 2 to 23 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.
【００４１】[0041]
【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０．５〜１００μｍの結晶粒子を有するＭｇＯマ
トリックス中に、希土類酸化物粒子を０．５〜５０体積
％分散することにより、ＭｇＯを主成分とする蒸着材を
構成したので、強度と耐熱衝撃性を向上できる。また上
記希土類酸化物粒子中の希土類元素としてＳｃ，Ｙ，Ｌ
ａ，Ｃｅ，Ｇｄ，Ｙｂ，Ｎｄ，Ｓｍ，Ｔｂ及びＤｙから
なる群より選ばれた１種又は２種以上の元素を用いれ
ば、ＭｇＯマトリックスが均一な組織となり、パネルに
組み込んだときの蛍光体への悪影響はなく、青色に関係
する輝度も向上する。As described above, according to the present invention, an MgO sintered body having a relative density of 95% or more and having an average crystal grain size of 0.5 to 100 μm in the MgO matrix. By dispersing the rare earth oxide particles in an amount of 0.5 to 50% by volume, a vapor deposition material containing MgO as a main component is formed, so that strength and thermal shock resistance can be improved. Sc, Y, and L are rare earth elements in the rare earth oxide particles.
If one or more elements selected from the group consisting of a, Ce, Gd, Yb, Nd, Sm, Tb and Dy are used, the MgO matrix has a uniform structure, and the phosphor when incorporated into the panel There is no adverse effect on the brightness, and the luminance related to blue is also improved.
【００４２】また上記蒸着材は、ＭｇＯ粉末及び希土類
元素の酸化物粉末等を含む混合スラリーを造粒して得ら
れた造粒粉末をプレス成形した後に常圧焼結したり、転
動造粒機を用いて成形された球状の成形体を焼結した
り、或いはＭｇＯ粉末と希土類元素の酸化物粉末等の混
合粉末をホットプレス焼結したりすることにより製造さ
れることが好ましい。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希土類元素の酸化物粉末
等が均一に分散される。この結果、上記方法で製造され
たＭｇＯ蒸着材は、高純度で緻密なＭｇＯ焼結体とな
る。The above-mentioned vapor deposition material is obtained by granulating a mixed slurry containing an MgO powder, a rare earth element oxide powder, and the like, and then press-molding the granulated powder and then sintering under normal pressure or rolling granulation. It is preferably manufactured by sintering a spherical compact formed by using a machine, or hot-press sintering a mixed powder of an MgO powder and an oxide powder of a rare earth element. The vapor deposition material manufactured by these methods is densely sintered in the sintering step, and the oxide powder of the rare earth element of the dispersed phase and the like are uniformly dispersed in the MgO matrix particles of the vapor deposition material. As a result, the MgO vapor-deposited material manufactured by the above method becomes a dense and dense MgO sintered body.
【００４３】また上記ＭｇＯを主成分とする蒸着材を用
いてＭｇＯ膜を成膜すれば、例えば蒸着材を電子ビーム
蒸着法で成膜すれば、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、高速安定性膜が可能となり、得られたＭｇ
Ｏ膜は完全固溶し、かつＭｇＯ膜の配向性は向上し、こ
のＭｇＯ膜を成膜した基板をＰＤＰに組み込んだとき、
放電電圧を低くでき、放電時の耐スパッタ性を向上で
き、更にこのＭｇＯ膜は高い絶縁性を有する。即ちスプ
ラッシュの発生も少なく、得られた膜特性も良好で、Ｐ
ＤＰに組み込んだときの耐スパッタ性も良好で駆動電圧
も低下し、安定した成膜が可能であり、ＰＤＰの保護膜
に有用な特性の膜を得ることができる。If an MgO film is formed using the above-described deposition material containing MgO as a main component, for example, if the deposition material is formed by an electron beam deposition method, two phases coexist, that is, the MgO matrix and the dispersed particles are formed. Since evaporation takes place without forming a solid solution or a reactant, a high-speed stable film becomes possible, and the obtained Mg
The O film completely dissolves, and the orientation of the MgO film is improved. When the substrate on which the MgO film is formed is incorporated into a PDP,
The discharge voltage can be lowered, the spatter resistance during discharge can be improved, and the MgO film has high insulating properties. That is, the occurrence of splash is small, the obtained film properties are good, and P
When incorporated into the DP, the sputter resistance is good, the driving voltage is lowered, stable film formation is possible, and a film having characteristics useful as a protective film for a PDP can be obtained.
【図１】本発明のＭｇＯを主成分とする蒸着材を用いて
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 an evaporation material containing MgO as a main component 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.
Claims (6)
あって、平均結晶粒径が０．５〜１００μｍの結晶粒子
を有するＭｇＯマトリックス中に、希土類酸化物粒子が
０．５〜５０体積％分散されたＭｇＯを主成分とする蒸
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 0.5 to 100 μm contains 0.5 to 50 rare earth oxide particles. A deposition material containing MgO dispersed as a main component by volume%.
ｃ，Ｙ，Ｌａ，Ｃｅ，Ｇｄ，Ｙｂ，Ｎｄ，Ｓｍ，Ｔｂ及
びＤｙ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ＭｇＯを主成分とする蒸着材。2. The rare-earth element in the rare-earth oxide particles is S
The MgO-based deposition material according to claim 1, wherein the deposition material is one or more elements selected from the group consisting of c, Y, La, Ce, Gd, Yb, Nd, Sm, Tb, and Dy.
末，炭酸塩粉末，水酸化物粉末又は硝酸塩粉末と、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１５００〜１７００℃の温度
で焼結する工程とを含むＭｇＯを主成分とする蒸着材の
製造方法。3. A step of mixing a MgO powder, a rare earth oxide powder, a carbonate powder, a hydroxide powder or a nitrate powder, a binder, and an organic solvent to prepare a mixed slurry having a predetermined concentration; 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 1500 to 1700 ° C. after degreasing the molded body And a step of sintering at a temperature of 0.1 mm.
末，炭酸塩粉末，水酸化物粉末又は硝酸塩粉末と、バイ
ンダとを混練する工程と、 前記混練物を転動造粒機の回転皿に入れた後に有機溶媒
を噴霧することにより前記混練物を造粒して球状の成形
体を成形する工程と、 前記回転皿に更に前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前記球状の成形体を所定の
大きさに成長させる工程と、 前記成長した成形体を脱脂した後に１５００〜１７００
℃の温度で焼結する工程とを含むＭｇＯを主成分とする
蒸着材の製造方法。4. A step of kneading an MgO powder, an oxide powder of a rare earth element, a carbonate powder, a hydroxide powder or a nitrate powder, and a binder, and placing the kneaded product on a rotating plate of a tumbling granulator. A step of granulating the kneaded material by spraying an organic solvent after the addition to form a spherical molded body, and repeating the operation of further adding the kneaded material to the rotating dish and spraying the organic solvent. A step of growing a spherical molded body to a predetermined size; and 1500 to 1700 after degreasing the grown molded body.
And sintering at a temperature of ° C.
末，炭酸塩粉末，水酸化物粉末又は硝酸塩粉末とを湿式
混合する工程と、 前記混合物を減圧加熱して乾燥した後に乾式解砕する工
程と、 前記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１４５０〜１７
５０℃に昇温して焼結する工程とを含むＭｇＯを主成分
とする蒸着材の製造方法。5. A step of wet-mixing the MgO powder with an oxide powder, a carbonate powder, a hydroxide powder or a nitrate powder of a rare-earth element, a step of heating the mixture under reduced pressure, drying it and then dry-crushing it. And placing the dry-crushed mixed powder in a predetermined mold under a predetermined pressure in an inert gas atmosphere at 1450-17.
A method of producing a vapor-deposited material containing MgO as a main component, comprising a step of heating to 50 ° C. and sintering.
する蒸着材を用いて成膜するＭｇＯ膜の製造方法。6. A method for producing an MgO film using the vapor deposition material containing MgO as a main component according to claim 1 or 2.
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| JP05814499A JP3470633B2 (en) | 1998-03-16 | 1999-03-05 | Deposition material containing MgO as a main component and method for producing the same |
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| JP10-64979 | 1998-03-16 | ||
| JP6497998 | 1998-03-16 | ||
| JP05814499A JP3470633B2 (en) | 1998-03-16 | 1999-03-05 | Deposition material containing MgO as a main component and method for producing the same |
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| Publication Number | Publication Date |
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| JPH11323533A true JPH11323533A (en) | 1999-11-26 |
| JP3470633B2 JP3470633B2 (en) | 2003-11-25 |
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| JP2005019391A (en) * | 2003-05-30 | 2005-01-20 | Pioneer Plasma Display Corp | Vapor deposition material, manufacturing method of plasma display panel using the same, and manufacturing method of plasma display device |
| JP2005264272A (en) * | 2004-03-19 | 2005-09-29 | Technology Seed Incubation Co Ltd | Material of magnesium oxide thin film |
| JP2005330589A (en) * | 2003-10-21 | 2005-12-02 | Ube Material Industries Ltd | Method for producing magnesium oxide vapor-deposition material |
| JP2005330574A (en) * | 2003-10-21 | 2005-12-02 | Ube Material Industries Ltd | Magnesium oxide vapor-deposition material |
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| CN111848133A (en) * | 2020-06-09 | 2020-10-30 | 西昌学院 | Preparation method of high-thermal-shock-resistance magnesium oxide ceramic |
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