JP4575035B2 - Single crystal magnesium oxide sintered body, method for producing the same, and protective film for plasma display panel - Google Patents
Single crystal magnesium oxide sintered body, method for producing the same, and protective film for plasma display panel Download PDFInfo
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本発明は、例えばプラズマディスプレイパネル（以下、「ＰＤＰ」という）用保護膜を真空蒸着法により製造する際に、蒸着源として使用される単結晶酸化マグネシウム（ＭｇＯ）焼結体及びその製造方法、並びにこの単結晶酸化マグネシウム焼結体をターゲット材として得られるプラズマディスプレイパネル保護膜に関する。 The present invention provides, for example, a single crystal magnesium oxide (MgO) sintered body used as a vapor deposition source when a protective film for a plasma display panel (hereinafter referred to as “PDP”) is produced by a vacuum vapor deposition method, and a method for producing the same. The present invention also relates to a protective film for a plasma display panel obtained using the single crystal magnesium oxide sintered body as a target material.
放電発光現象を利用したＰＤＰは、大型化しやすい平面ディスプレイとしてその開発が進められている。ＰＤＰは、その電極構造の違いから、放電空間に金属電極が露出している直流型（ＤＣ型）と、金属電極が誘電体で覆われている交流型（ＡＣ型）とに大別される。 Development of a PDP using the discharge light emission phenomenon is being promoted as a flat display which is easily increased in size. PDPs are roughly classified into a direct current type (DC type) in which a metal electrode is exposed in a discharge space and an alternating current type (AC type) in which the metal electrode is covered with a dielectric material, depending on the difference in electrode structure. .
ＡＣ型のＰＤＰでは、イオン衝撃のスパッタリングにより誘電体層表面が変質して放電電圧が上昇することを防止するために、一般的にこの誘電体上に保護膜が形成されている。この保護膜は、低い放電電圧を有し、耐スパッタリング性に優れていることが要求される。 In the AC type PDP, a protective film is generally formed on the dielectric material in order to prevent the surface of the dielectric layer from being altered by ion bombardment sputtering to increase the discharge voltage. This protective film is required to have a low discharge voltage and excellent sputtering resistance.
かかる要求を満足する保護膜として、従来から、酸化マグネシウム（ＭｇＯ）膜が使用されている。ＭｇＯ膜は耐スパッタリング性に優れ、かつ、２次電子の放出係数が大きい絶縁物であるため、放電開始電圧を下げることができ，ＰＤＰの長寿命化に寄与する。 Conventionally, a magnesium oxide (MgO) film has been used as a protective film that satisfies this requirement. Since the MgO film is an insulator having excellent sputtering resistance and a large secondary electron emission coefficient, the discharge start voltage can be lowered, contributing to the extension of the life of the PDP.
現在、ＭｇＯ保護膜は、ＭｇＯ焼結体をターゲット材とする電子ビーム蒸着法により誘電体上に形成されることが一般的である。一例として、ＭｇＯ純度が９９．０％以上、相対密度が９０％以上の多結晶ＭｇＯの焼結体ペレットからなり、かつ、この焼結体ペレットの平均結晶粒径が３〜１００μｍである多結晶ＭｇＯターゲット材が提案されている（特許文献１） At present, the MgO protective film is generally formed on a dielectric by an electron beam evaporation method using an MgO sintered body as a target material. As an example, a polycrystal composed of a sintered pellet of polycrystalline MgO having a MgO purity of 99.0% or more and a relative density of 90% or more, and having an average crystal grain size of 3 to 100 μm. An MgO target material has been proposed (Patent Document 1).
しかしながら、この多結晶ＭｇＯをターゲット材として電子ビーム蒸着法を使用して成膜した場合、以下のような問題がある。
第一に、大面積のガラス誘電体層に対してＭｇＯ膜を均一に生成させることが困難であり、膜厚分布が均一とならない。このように均一性が十分でないＭｇＯ膜を成膜したガラス誘電体層をＰＤＰに組み込んだ場合は、電気的特性、例えば放電開始電圧や駆動電圧が上昇したり、変動するなどの問題が生じる。一方、膜厚分布を均一にするためには、成膜速度を小さく制御する必要があり、生産性が著しく低下するという問題もある。
However, when the polycrystalline MgO is used as a target material to form a film using the electron beam evaporation method, there are the following problems.
First, it is difficult to uniformly form a MgO film on a large-area glass dielectric layer, and the film thickness distribution is not uniform. When a glass dielectric layer formed with an MgO film with insufficient uniformity is incorporated into a PDP, problems such as an increase in electric characteristics, for example, a discharge start voltage and a drive voltage, and the like arise. On the other hand, in order to make the film thickness distribution uniform, it is necessary to control the film forming speed to be small, and there is a problem that the productivity is remarkably lowered.
第二に、保護膜の原料である多結晶ＭｇＯは、微細粒子であるため、それに吸蔵されている気体や水分の量が多く、ターゲット材であるＭｇＯや、基板を装置内に設置して減圧を開始してから蒸着可能な真空度に到達するまでに長時間を要するという問題がある。さらに、電子ビーム蒸着等による加熱時に、ＭｇＯ中に吸蔵された気体の離脱が生じ、蒸着操作条件を不安定にするとともに、減圧下で離脱する気体により基板が汚染され、その結果、清浄なＭｇＯ膜を成膜することができないという問題がある。 Secondly, since polycrystalline MgO, which is a raw material for the protective film, is a fine particle, it has a large amount of gas and moisture occluded therein, and the target material MgO and the substrate are placed in the apparatus to reduce the pressure. There is a problem that it takes a long time from the start of the process until the degree of vacuum is reached. Further, during heating by electron beam evaporation or the like, the gas occluded in MgO occurs, destabilizing the vapor deposition operation conditions, and the substrate is contaminated by the gas desorbed under reduced pressure. As a result, clean MgO There is a problem that a film cannot be formed.
第三に、ＭｇＯ膜は炭酸ガスや水との反応性が高く、化学的に活性であるため、水や炭酸ガスを吸着し、経時的に水酸化マグネシウム又は炭酸マグネシウムに変化する。したがって、製造工程で、大気中にさらされる工程時間を厳密に管理する必要があるなど取り扱いが煩雑である。 Third, since the MgO film has high reactivity with carbon dioxide gas and water and is chemically active, it adsorbs water and carbon dioxide gas, and changes to magnesium hydroxide or magnesium carbonate over time. Therefore, handling is complicated, for example, in the manufacturing process, it is necessary to strictly control the process time exposed to the atmosphere.
第四に、多結晶ＭｇＯターゲット材は、出発原料となるＭｇＯ粉末に含まれる不純物量により、最終的に得られるＭｇＯ保護膜の純度が決定されてしまうため、ＭｇＯ粉末原料により純度のばらつきがあるという問題がある。 Fourthly, the purity of the polycrystalline MgO target material varies depending on the MgO powder raw material because the purity of the MgO protective film finally obtained is determined by the amount of impurities contained in the starting MgO powder. There is a problem.
第五に、多結晶ＭｇＯ焼結体は、密度が高いため、蒸着速度が遅く、生産性に欠けるなどの問題もある。 Fifth, since the polycrystalline MgO sintered body has a high density, there are also problems such as a low deposition rate and a lack of productivity.
かかる問題を解決するために、粒度分布の異なる２種類以上の粉末を混合して焼結することにより、多結晶ＭｇＯ焼結体の相対密度を低減し、結果として、蒸着速度を改善したものが提案されている（特許文献２）。 In order to solve such a problem, by mixing and sintering two or more kinds of powders having different particle size distributions, the relative density of the polycrystalline MgO sintered body is reduced, and as a result, the deposition rate is improved. It has been proposed (Patent Document 2).
しかしながら、ＰＤＰの開発が進められる中で、さらに消費電力を低減することが求められており、そのためには、ＰＤＰの発光効率を高めることが必要となっている。そのための有効な手段の一つとして、ＭｇＯ保護膜を生成するターゲット材であるＭｇＯ焼結体の特性を改善することがあげられる。上記の多結晶ＭｇＯ焼結体では、特性の向上に限界があり、ＭｇＯ焼結体のさらなる改良が望まれている。 However, further development of PDP is required, and further reduction of power consumption is required. For this purpose, it is necessary to increase the luminous efficiency of PDP. One effective means for that purpose is to improve the properties of the MgO sintered body, which is a target material for producing the MgO protective film. In the above-mentioned polycrystalline MgO sintered body, there is a limit to improvement in characteristics, and further improvement of the MgO sintered body is desired.
本発明の目的は、上記の課題を解消し、例えば、電子ビーム蒸着法を使用して基板上にＭｇＯ膜を成膜するためにターゲット材として使用する単結晶ＭｇＯ焼結体であって、得られたＭｇＯ膜の密度及び耐スパッタ性を低下させることなく、優れた膜特性、例えばＰＤＰ用保護膜として使用した場合の放電特性などを向上させることが可能な単結晶ＭｇＯ焼結体及びその製造方法、並びにこの単結晶ＭｇＯ焼結体をターゲット材として得られたＰＤＰ用保護膜を提供することである。 An object of the present invention is to solve the above-mentioned problems, for example, a single crystal MgO sintered body used as a target material for forming an MgO film on a substrate using an electron beam evaporation method, Single-crystal MgO sintered body capable of improving excellent film characteristics, for example, discharge characteristics when used as a protective film for PDP, and the like without reducing the density and sputtering resistance of the obtained MgO film The present invention provides a method and a protective film for PDP obtained using this single crystal MgO sintered body as a target material.
本発明者らは、上記目的を達成すべく、まず、電子ビーム蒸着法のターゲット材として使用されるＭｇＯ焼結体の出発原料として、従来の多結晶ＭｇＯに替えて、表面の反応性が低い単結晶ＭｇＯの粉砕品を使用することとした。
単結晶ＭｇＯは、従来、含有される不純物量が多いと考えられていたが、本発明者らが検討を重ねた結果、不純物成分の全てが最終的に得られるＭｇＯ膜の特性を低下させるのではなく、その中にはＭｇＯ膜の特性を改善する成分も含まれていることを見出した。
In order to achieve the above object, the present inventors first have a low surface reactivity in place of conventional polycrystalline MgO as a starting material for an MgO sintered body used as a target material for an electron beam evaporation method. A pulverized product of single crystal MgO was used.
Single crystal MgO has been conventionally considered to contain a large amount of impurities, but as a result of repeated studies by the present inventors, the properties of the MgO film in which all of the impurity components are finally obtained are deteriorated. Instead, it has been found that a component for improving the properties of the MgO film is also contained therein.
つまり、全ての不純物の含有量を低減して徒にコストを上昇させるよりも、むしろ、ＭｇＯ膜の特性を向上させる不純物成分と、特性を低下させる不純物成分との含有量のバランスを考慮することが必要である。単結晶ＭｇＯの不純物レベルは高純度多結晶ＭｇＯに比べて幾分高いものの、不純物である各元素の存在比率については理想的な状態にある。言うなれば、特性を低下させる成分の悪影響が、特性を改善する成分により相殺されると考えられる。 In other words, rather than reducing the content of all impurities and increasing the cost, the balance between the content of impurities that improve the properties of the MgO film and the content of impurities that degrade the properties should be considered. is required. Although the impurity level of single-crystal MgO is somewhat higher than that of high-purity polycrystalline MgO, the abundance ratio of each element as an impurity is in an ideal state. In other words, it is considered that the adverse effect of the component that lowers the characteristic is offset by the component that improves the characteristic.
このような不純物成分を含有する単結晶ＭｇＯを使用し、上述したＭｇＯ膜の特性を改善する不純物成分を積極的に添加すれば、ＭｇＯ膜の特性の改善効果が顕著に発現することが明らかになった。 It is clear that if single crystal MgO containing such an impurity component is used and the impurity component that improves the characteristics of the MgO film described above is positively added, the effect of improving the characteristics of the MgO film is remarkably exhibited. became.
さらに、従来の単結晶ＭｇＯ焼結体を用いるターゲット材は密度が高く、例えば電子ビーム蒸着する場合、蒸着速度が遅く生産性が低かった。これらの課題を解消するために、単結晶ＭｇＯを粉砕した比較的粒径の大きな粒子を焼結体に含有させることにより、蒸着速度を改善しうる点でより好ましいことを確認した。 Furthermore, the target material using a conventional single crystal MgO sintered body has a high density. For example, when electron beam evaporation is performed, the evaporation rate is low and the productivity is low. In order to solve these problems, it was confirmed that it is more preferable in that the deposition rate can be improved by adding particles having a relatively large particle size obtained by pulverizing single crystal MgO to the sintered body.
すなわち、本発明によれば、ＭｇＯ膜の特性を改善するＳｉ、Ａｌ、Ｆｅ及びＹのうちの少なくとも１種の元素を、ＭｇＯ中のＭｇ元素に対して０．０３〜３．５ｍｏｌ％含む単結晶ＭｇＯ焼結体が提供される。 That is, according to the present invention, at least one element of Si, Al, Fe, and Y that improves the characteristics of the MgO film is simply contained in an amount of 0.03 to 3.5 mol% with respect to the Mg element in MgO. A crystalline MgO sintered body is provided.
上記の単結晶ＭｇＯ焼結体は、相対密度が５０％以上９０％未満であり、ＭｇＯ純度が９７質量％以上であり、かつ、粒径２００μｍ以上の粗大粒子を全体の２０〜８０質量％含むことが好ましい。 The single crystal MgO sintered body has a relative density of 50% or more and less than 90%, an MgO purity of 97% by mass or more, and 20 to 80% by mass of coarse particles having a particle size of 200 μm or more. It is preferable.
さらに、上記の単結晶ＭｇＯ焼結体は、ＭｇＯ膜の特性を低下させるＢの含有量が２００ｐｐｍ以下であることがより好ましい。また、上記の単結晶ＭｇＯ焼結体は、電子ビーム蒸着法をはじめとする真空蒸着法を用いてプラズマディスプレイパネル用保護膜を成膜するためのターゲット材として好適に使用される。 Furthermore, it is more preferable that the single crystal MgO sintered body has a B content of 200 ppm or less that lowers the properties of the MgO film. The single crystal MgO sintered body is suitably used as a target material for forming a protective film for a plasma display panel using a vacuum vapor deposition method such as an electron beam vapor deposition method.
さらに、本発明によれば、上記のいずれかの単結晶酸化マグネシウム焼結体をターゲット材として使用し、電子ビーム蒸着法、イオン照射蒸着法、又はスパッタリング法等の真空蒸着法により製造したプラズマディスプレイパネル用保護膜も提供される。 Furthermore, according to the present invention, a plasma display produced by a vacuum vapor deposition method such as an electron beam vapor deposition method, an ion irradiation vapor deposition method, or a sputtering method using any of the above-mentioned single crystal magnesium oxide sintered bodies as a target material. A protective film for a panel is also provided.
また、本発明によれば、平均粒径２００〜１０００μｍの単結晶酸化マグネシウム粒子に、平均粒径１０μｍ以下の単結晶酸化マグネシウム粒子を全体の５〜６０質量％になるように混合したのち、単結晶酸化マグネシウムのマグネシウムに対して、Ｓｉ、Ａｌ、Ｆｅ及びＹのうちの少なくとも１種を０．０３〜３．５ｍｏｌ％含むように添加して得られる、平均粒径１００〜５００μｍの単結晶酸化マグネシウム粒子混合体を成型したのち焼結する、単結晶酸化マグネシウム焼結体の製造方法が提供される。 In addition, according to the present invention, single crystal magnesium oxide particles having an average particle size of 200 to 1000 μm are mixed with single crystal magnesium oxide particles having an average particle size of 10 μm or less so as to be 5 to 60% by mass of the total. Single crystal oxidation with an average particle size of 100 to 500 μm obtained by adding 0.03 to 3.5 mol% of at least one of Si, Al, Fe and Y to magnesium of crystalline magnesium oxide Provided is a method for producing a single crystal magnesium oxide sintered body, which is sintered after molding the magnesium particle mixture.
本発明の単結晶酸化マグネシウム（ＭｇＯ）焼結体は、不純物成分として、Ｓｉ、Ａｌ、Ｆｅ及びＹから選ばれる少なくとも１種を、ＭｇＯ中のＭｇ元素に対して、０．０３〜３．５ｍｏｌ％含有する。これらの元素の含有量は、好ましくは、０．０３〜２．０ｍｏｌ％であり、さらに好ましくは、０．０５〜１．０ｍｏｌ％であり、より好ましくは、０．１〜０．５ｍｏｌ％である。 In the single crystal magnesium oxide (MgO) sintered body of the present invention, at least one selected from Si, Al, Fe and Y as an impurity component is 0.03 to 3.5 mol with respect to Mg element in MgO. %contains. The content of these elements is preferably 0.03 to 2.0 mol%, more preferably 0.05 to 1.0 mol%, more preferably 0.1 to 0.5 mol%. is there.
これらの各成分は、最終的に得られるＭｇＯ保護膜の特性、具体的には、ＰＤＰ用保護膜として使用した場合の消費電力の低減に資する成分である。これらの成分のうち、Ｓｉ、Ａｌ及びＦｅは、本来ＭｇＯ粉末に不純物として不可避的に含有されているものであるため、当初の不純物としての含有量と、添加剤としての含有量の合計が上記の範囲の数値となるように添加量を決定する。一方で、Ｙを添加成分とする場合、ＹはＭｇＯに本来不純物として含有される成分ではないため、上記所定量をそのまま添加する。 Each of these components is a component that contributes to reducing the properties of the finally obtained MgO protective film, specifically, power consumption when used as a protective film for PDP. Among these components, Si, Al and Fe are originally inevitably contained as impurities in the MgO powder, so the total content as an additive and the content as an additive is the above The addition amount is determined so as to be a numerical value in the range. On the other hand, when Y is used as an additive component, Y is not a component that is originally contained in MgO as an impurity, so the predetermined amount is added as it is.
これらの成分元素は、単独でも２種以上を同時に含有していてもよいが、これらの成分元素の合計の含有量が、ＭｇＯ中のＭｇ元素に対して０．０５〜５．０ｍｏｌ％の範囲になるようにすることが好ましく、さらに好ましくは、０．１〜４．０ｍｏｌ％とする。
２種以上の元素を複合添加することにより、得られるＭｇＯ膜の特性、例えば、二次電子放出係数を高めて、消費電力を低減する効果がより顕著となる。
These component elements may be contained alone or in combination of two or more, but the total content of these component elements is in the range of 0.05 to 5.0 mol% with respect to the Mg element in MgO. It is preferable to set it to be 0.1 to 4.0 mol%.
By adding two or more kinds of elements in combination, the effect of reducing the power consumption by increasing the characteristics of the obtained MgO film, for example, the secondary electron emission coefficient, becomes more remarkable.
このように、本来の単結晶ＭｇＯの特徴である不純物量のバランスに加えて、最終的に得られるＭｇＯ膜の特性を向上しうる成分を積極的に添加することにより、ＭｇＯ膜の特性をさらに改善することが可能となる。 In this way, in addition to the balance of the amount of impurities, which is a characteristic of the original single crystal MgO, by actively adding components that can improve the properties of the finally obtained MgO film, the properties of the MgO film can be further improved. It becomes possible to improve.
成膜後のＭｇＯ膜の密度を低下させず、かつ、蒸着速度を向上させるためには、上記の単結晶ＭｇＯ焼結体の相対密度は、５０％以上９０％未満であることが好ましい。また、ＭｇＯ純度が９７質量％以上であり、かつ、粒径２００μｍ以上、さらに、粒径が２００〜１０００μｍの粗大粒子を全体の２０〜８０質量％の範囲で含むことが好ましい。 In order to improve the deposition rate without reducing the density of the MgO film after film formation, the relative density of the single crystal MgO sintered body is preferably 50% or more and less than 90%. Moreover, it is preferable that MgO purity is 97 mass% or more, and the coarse particle which has a particle size of 200 micrometers or more and 200-1000 micrometers is further included in 20-80 mass% of the whole.
単結晶ＭｇＯ焼結体の相対密度を上記の範囲とすることによって、蒸着速度を増大し、生産性を改善することができる。また、単結晶ＭｇＯ焼結体の相対密度を従来の単結晶ＭｇＯ焼結体の相対密度に比べて小さくすることにより、例えば、電子ビームによる蒸着工程を実施した際、低出力の電子ビームで蒸着することができるという利点もある。 By setting the relative density of the single crystal MgO sintered body within the above range, the deposition rate can be increased and the productivity can be improved. Further, by reducing the relative density of the single crystal MgO sintered body compared to the relative density of the conventional single crystal MgO sintered body, for example, when performing an evaporation process by an electron beam, it is deposited by a low output electron beam. There is also an advantage that it can be done.
この単結晶ＭｇＯ焼結体の相対密度は、より好ましくは、６０％以上９０％未満であり、さらに好ましくは、７５％以上９０％未満である。 The relative density of the single crystal MgO sintered body is more preferably 60% or more and less than 90%, and still more preferably 75% or more and less than 90%.
また、蒸着後に得られるＭｇＯ膜の特性を低下させないためには、単結晶ＭｇＯ焼結体中のＭｇＯ純度は９７質量％以上であることが好ましい。このＭｇＯ純度は、より好ましくは、９８質量％以上であり、さらに好ましくは、９９質量％以上である。 Moreover, in order not to deteriorate the properties of the MgO film obtained after vapor deposition, the MgO purity in the single crystal MgO sintered body is preferably 97% by mass or more. This MgO purity is more preferably 98% by mass or more, and still more preferably 99% by mass or more.
一般的に単結晶ＭｇＯ粉末は非常に微細であり、この単結晶ＭｇＯ粉末から得られる焼結体の密度は必然的に高くなるため、ターゲット材として使用したときに得られるＭｇＯ膜の特性を低下させない粒度の範囲内で、かつ、できる限り粒度の大きいＭｇＯ粒子を含むことが好ましい。具体的には、粒径が２００μｍ以上、より好ましくは、２００〜１０００μｍの単結晶ＭｇＯの粗大粒子を含むことが好ましい。この粗大粒子の含有率は、例えば、焼結体中に、２０〜８０質量％の範囲に設定することが好ましく、さらに好ましくは、３０〜７０質量％の範囲である。 In general, single crystal MgO powder is very fine, and the density of the sintered body obtained from this single crystal MgO powder inevitably increases, so the characteristics of the MgO film obtained when used as a target material are reduced. It is preferable to include MgO particles having a particle size as large as possible within the range of the particle size that is not allowed. Specifically, it is preferable to include single crystal MgO coarse particles having a particle diameter of 200 μm or more, more preferably 200 to 1000 μm. For example, the content of the coarse particles is preferably set in the range of 20 to 80% by mass in the sintered body, and more preferably in the range of 30 to 70% by mass.
また、本発明の単結晶ＭｇＯ焼結体中のホウ素（Ｂ）の含有量は、２００ｐｐｍ以下にすることが好ましい。これは、単結晶ＭｇＯ粒子粉末を成型したのち、焼結して焼結体を製造する際、ホウ素のような低融点化合物が多量に存在すると、焼結中に液相が生じ、その液相が焼結を促進する焼結助剤として作用するため、過度に焼結が進行してしまい、所望の焼結密度を得られない場合があるからである。ホウ素の含有量は、さらに好ましくは、１００ｐｐｍ以下、より好ましくは、１０ｐｐｍ以下である。 Further, the content of boron (B) in the single crystal MgO sintered body of the present invention is preferably 200 ppm or less. This is because when a single crystal MgO particle powder is molded and then sintered to produce a sintered body, if a low melting point compound such as boron is present in a large amount, a liquid phase is generated during the sintering. This is because, since it acts as a sintering aid for promoting the sintering, the sintering proceeds excessively and a desired sintered density may not be obtained. The boron content is more preferably 100 ppm or less, and more preferably 10 ppm or less.
上述した本発明の単結晶ＭｇＯ焼結体は、以下のようにして製造することができる。まず、平均粒径２００〜１０００μｍ、好ましくは、平均粒径２００〜８００μｍのＭｇＯ粉末に対し、平均粒径１０μｍ以下のＭｇＯ粉末を混合する。この時の混合比率は、平均粒径１０μｍ以下のＭｇＯ粉末が、全体の５〜６０質量％になるようにする。このように異なる平均粒径のＭｇＯ粒子粉末を所定割合で混合することにより、平均粒径が１００〜５００μｍのＭｇＯ混合粒子粉末を得る。 The single crystal MgO sintered body of the present invention described above can be manufactured as follows. First, MgO powder having an average particle size of 10 μm or less is mixed with MgO powder having an average particle size of 200 to 1000 μm, preferably 200 to 800 μm. The mixing ratio at this time is such that the MgO powder having an average particle size of 10 μm or less is 5 to 60 mass% of the whole. Thus, MgO mixed particle powder with an average particle diameter of 100-500 micrometers is obtained by mixing MgO particle powder with a different average particle diameter in a predetermined ratio.
このような異種粒径のＭｇＯ粉末を用意するにあたり、平均粒径２００〜１０００μｍの粉末は、１種でもよいが、２種以上を混合することもできる。例えば、平均粒径３００μｍのＭｇＯ粉末と、平均粒径６００μｍのＭｇＯ粉末とを合計で全ＭｇＯ粉末の４０〜９５質量％となるように混合してもよい。この混合粉末を焼結することにより、粒径２００μｍ以上のＭｇＯ粒子を上記の範囲、すなわち全体の２０〜８０質量％の範囲で含むＭｇＯ焼結体を得ることができる。 In preparing such MgO powders with different particle diameters, one kind of powder having an average particle diameter of 200 to 1000 μm may be used, or two or more kinds may be mixed. For example, you may mix MgO powder with an average particle diameter of 300 micrometers, and MgO powder with an average particle diameter of 600 micrometers so that it may become 40-95 mass% of total MgO powder in total. By sintering this mixed powder, a MgO sintered body containing MgO particles having a particle diameter of 200 μm or more in the above range, that is, in the range of 20 to 80% by mass as a whole can be obtained.
上記のように、平均粒径が異なる、すなわち、異なる粒度分布を有する２種以上のＭｇＯ粉末を混合することにより、同じ平均粒径を有していても単一の粒度分布を有する粉末を１種単独で使用した場合に比べて、焼結体の相対密度の制御をより正確に行うことができる。 As described above, by mixing two or more kinds of MgO powders having different average particle sizes, that is, having different particle size distributions, a powder having a single particle size distribution can be obtained even if they have the same average particle size. The relative density of the sintered body can be controlled more accurately than when the seed is used alone.
また、このような粒子径に調整した単結晶ＭｇＯ粉末は、本来の粒子径が小さな単結晶ＭｇＯ粉末に比べ、表面が不活性で、大気との反応性が低いので、貯蔵時に水分や炭酸ガスの付着を防ぐことができ、高真空下でも離脱ガスの少ない高純度のＭｇＯターゲット材を得ることが可能となる。このようなターゲット材は電子ビーム蒸着法により蒸着した際にもガス化成分を低減することができる。 In addition, the single crystal MgO powder adjusted to such a particle size has an inert surface and low reactivity with the atmosphere compared to a single crystal MgO powder with a small original particle size. Can be prevented, and it is possible to obtain a high-purity MgO target material with little detached gas even under high vacuum. Such a target material can reduce gasification components even when it is deposited by an electron beam deposition method.
上記のＭｇＯ混合粒子粉末を製造する際に、添加元素すなわちＳｉ、Ａｌ、Ｆｅ及びＹから選択された少なくとも１種を同時に混合する。この場合、各添加元素は、酸化物、硝酸塩、炭酸塩、硫酸塩、水酸化物、亜硫酸塩及びハロゲン化物などの化合物の形態で添加することが好ましい。しかるのち、この混合粒子粉末を成型、焼成することにより、本発明の単結晶ＭｇＯ焼結体を得る。 When manufacturing the above MgO mixed particle powder, at least one selected from additive elements, that is, Si, Al, Fe, and Y is mixed at the same time. In this case, each additive element is preferably added in the form of a compound such as oxide, nitrate, carbonate, sulfate, hydroxide, sulfite and halide. Thereafter, the mixed particle powder is molded and fired to obtain the single crystal MgO sintered body of the present invention.
具体的には、添加物元素化合物を混合した混合粉末に、バインダーを混合する。この混合工程は、例えば、パワーニーダー、撹拌ミルなどを使用して実施される。バインダーとしては、特に限定されるものではないが、例えば、ポリエチレングリコール、ＣＭＣ、ＰＶＡ、ポリビニルブチラールなどが使用される。バインダーの添加量は、混合粉末の総量に対して、３〜１０質量％とすることが好ましい。 Specifically, the binder is mixed with the mixed powder in which the additive element compound is mixed. This mixing process is implemented using a power kneader, a stirring mill, etc., for example. Although it does not specifically limit as a binder, For example, polyethyleneglycol, CMC, PVA, polyvinyl butyral, etc. are used. The addition amount of the binder is preferably 3 to 10% by mass with respect to the total amount of the mixed powder.
次いで、バインダーを添加混合したＭｇＯ粉末粒子を成型する。すなわち、まず、平均粒径を調整して添加元素及びバインダーを添加混合したＭｇＯ粉末を乾燥させ、例えば、解砕機を用いて粉砕することにより造粒し、顆粒粉末を得る。顆粒粉末は流動性に優れるため、続く成型工程における金型への充填性が向上する。この顆粒粉末の平均粒径は、０．８ｍｍ以下とすることが好ましい。 Subsequently, the MgO powder particle which added and mixed the binder is shape | molded. That is, first, the average particle diameter is adjusted, and the MgO powder added and mixed with the additive element and the binder is dried and granulated by, for example, pulverization using a crusher to obtain a granular powder. Since granular powder is excellent in fluidity | liquidity, the filling property to the metal mold | die in the subsequent shaping | molding process improves. The average particle size of the granular powder is preferably 0.8 mm or less.
このようにして造粒された顆粒粉末を所定の金型に投入して成型する。成型には例えば一軸プレス装置などを使用することができる。成型圧は、得られる成型体の相対密度を調整するために、例えば、１００〜３００ＭＰａに設定することが好ましい。さらに好ましい成型圧は、１５０〜２００ＭＰａである。 The granulated powder thus granulated is put into a predetermined mold and molded. For example, a uniaxial press machine or the like can be used for molding. The molding pressure is preferably set to 100 to 300 MPa, for example, in order to adjust the relative density of the obtained molded body. A more preferable molding pressure is 150 to 200 MPa.
しかるのち、この成型体を焼成し、本発明の単結晶ＭｇＯ焼結体を得る。焼成雰囲気は、大気中、ガス炉で、焼成温度は、１５００〜１７００℃、焼成時間は、３〜５時間にそれぞれ設定することが好ましい。 Thereafter, this molded body is fired to obtain a single crystal MgO sintered body of the present invention. The firing atmosphere is preferably a gas furnace in the air, the firing temperature is set to 1500 to 1700 ° C., and the firing time is preferably set to 3 to 5 hours.
このようにして得られた単結晶ＭｇＯ焼結体は、ＰＤＰ用保護膜を成膜するためのターゲット材として使用することができる。この単結晶ＭｇＯ焼結体をターゲット材として使用した成膜法としては、電子ビーム蒸着法、イオン照射蒸着法、又はスパッタリング法などの真空蒸着法をあげることができ、特に電子ビーム蒸着法は好適である。 The single crystal MgO sintered body thus obtained can be used as a target material for forming a protective film for PDP. As a film forming method using this single crystal MgO sintered body as a target material, an electron beam vapor deposition method, an ion irradiation vapor deposition method, or a vacuum vapor deposition method such as a sputtering method can be exemplified, and the electron beam vapor deposition method is particularly preferable. It is.
本発明を実施例により具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES The present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples.
実施例１
焼結体製造用単結晶ＭｇＯ粉末の調製
出発原料粉末として、純度９９．０質量％以上の単結晶ＭｇＯ粉末（商品名ＳＳＰ、タテホ化学工業株式会社製、Ｂ含有量１ｐｐｍ以下）を使用した。この原料粉末を粉砕して平均粒径１０μｍ以下にしたＭｇО粉末Ａと、平均粒径６００μｍのＭｇО粉末Ｂの、平均粒径分布の異なる２種類のＭｇО粉末Ａ，Ｂを、質量比で１：１で混合し、平均粒径３００μｍの混合ＭｇО粉末を得た。このとき、添加元素としてＳｉを混合するため、シリカコロイドを上記混合ＭｇО粉末の総重量に対してＳｉＯ２換算で１７００ｐｐｍとなるように添加した。表１から分かるように、実施例１では、ＳｉＯ２を１７００ｐｐｍ添加したことにより、焼結体中のＳｉＯ２含有量は１８００ｐｐｍとなり、これはＭｇに対するＳｉの含有量としては、０．１２ｍｏｌ％に相当する。また、焼結体中の粒径２００μｍ以上の粒子の含有量は、５０質量％であった。
Example 1
Preparation of Single Crystal MgO Powder for Sintered Body Production As a starting material powder, a single crystal MgO powder having a purity of 99.0% by mass or more (trade name SSP, manufactured by Tateho Chemical Industry Co., Ltd., B content: 1 ppm or less) was used. Two types of MgO powders A and B having different average particle size distributions, ie, MgO powder A having an average particle size of 10 μm or less by pulverizing this raw material powder and MgO powder B having an average particle size of 600 μm, have a mass ratio of 1: 1 to obtain a mixed MgO powder having an average particle size of 300 μm. At this time, in order to mix Si as an additive element, the silica colloid was added to 1700 ppm in terms of SiO 2 with respect to the total weight of the mixed MgO powder. As can be seen from Table 1, in Example 1, by which the SiO 2 was added 1700 ppm, SiO 2 content in the sintered body 1800ppm, and the Is this the content of Si to Mg, the 0.12 mol% Equivalent to. The content of particles having a particle size of 200 μm or more in the sintered body was 50% by mass.
ターゲット用単結晶ＭｇО焼結体の製造
上記により得られた混合ＭｇО粉末にバインダー（商品名メトローズ９０ＳＨ−４００、信越化学株式会社製）を６質量％になるように混合した。この混合工程は、パワーニーダー（ＤＡＬＴＯＮ ＰＫ型）を使用し、回転数２５０ｒｐｍで５分間運転することにより実施した。
Manufacture of single-crystal MgO sintered compact for target The binder (trade name Metrolose 90SH-400, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed with the mixed MgO powder obtained as described above so as to be 6% by mass. This mixing step was performed by using a power kneader (DALTON PK type) and operating at a rotational speed of 250 rpm for 5 minutes.
続いて、この粉末を乾燥させ、目開き１．０ｍｍスクリーンを取り付けた解砕機（商品名Ｐ−３、ダルトン社製）を使用し、回転数２０００ｒｐｍで運転することにより造粒し、平均粒径０．８ｍｍ以下の顆粒粉末を得た。この顆粒粉末を直径６．５ｍｍ、厚さ２ｍｍの金型に入れて成型した。成型には一軸プレス装置（商品名ＳＲ１００−１Ｐ−９Ｈ、菅原精機株式会社製）を使用し、成型圧は１００〜３００ＭＰａに設定した。 Subsequently, this powder was dried, granulated by operating at a rotational speed of 2000 rpm using a crusher (trade name P-3, manufactured by Dalton Co., Ltd.) equipped with a screen having an opening of 1.0 mm, and the average particle diameter Granule powder of 0.8 mm or less was obtained. This granule powder was put into a mold having a diameter of 6.5 mm and a thickness of 2 mm and molded. A uniaxial press device (trade name SR100-1P-9H, manufactured by Ebara Seiki Co., Ltd.) was used for molding, and the molding pressure was set to 100 to 300 MPa.
このようにして得られた成型体を大気中、焼成炉（炉床昇降式、丸祥電器株式会社製）を使用し、１６２０℃で４時間焼成することにより、直径約６．５ｍｍ、厚さ２ｍｍの単結晶ＭｇО焼結体を得た。この単結晶ＭｇＯ焼結体の組成を表１に示す。 The molded body thus obtained is fired at 1620 ° C. for 4 hours in the atmosphere using a firing furnace (furnace raising / lowering type, manufactured by Marusho Denki Co., Ltd.). A 2 mm single crystal MgO sintered body was obtained. The composition of this single crystal MgO sintered body is shown in Table 1.
物性値測定
上記の単結晶ＭｇＯ粉末、および単結晶ＭｇＯ焼結体の物性値を下記のように測定し、結果を表１に示す。
Measurement of Physical Property Values Physical property values of the single crystal MgO powder and the single crystal MgO sintered body were measured as follows, and the results are shown in Table 1.
ｉ）ＭｇＯ純度
下記の微量不純物量を測定し、９９．９９％から差し引いた値として算出した。
i) MgO purity The following trace amount of impurities was measured and calculated as a value subtracted from 99.99%.
ii）不純物量
ＣａＯ、ＳｉＯ２、Ａｌ２Ｏ３、Ｆｅ２Ｏ３、Ｙ２Ｏ３及びＢの含有量は、ＩＣＰ発光分光分析装置（商品名ＳＰＳ−１７００ＶＲ、セイコーインスツルメンツ株式会社製）を使用し、試料を酸溶解したのち測定した。なお、表１には、Ｍｇに対するＣａ、Ｓｉ、Ａｌ、Ｆｅ及びＹのｍｏｌ％も併せて示した。
ii) Impurity amount For the contents of CaO, SiO 2 , Al 2 O 3 , Fe 2 O 3 , Y 2 O 3 and B, an ICP emission spectrometer (trade name SPS-1700VR, manufactured by Seiko Instruments Inc.) is used. The sample was dissolved in acid and measured. Table 1 also shows mol% of Ca, Si, Al, Fe, and Y with respect to Mg.
iii）平均粒径
焼成前のＭｇＯ粉末の平均粒径は、レーザー回折式粒度測定装置（商品名ＨＲＡ、日機装株式会社製）により測定した。
iii) Average particle size The average particle size of the MgO powder before firing was measured with a laser diffraction particle size measuring device (trade name HRA, manufactured by Nikkiso Co., Ltd.).
iv）ペリクレース径
焼結体のペリクレース径は、電子顕微鏡（商品名ＪＳＭ−５４１０、ＪＥＯＬ製）を使用してＳＥＭ組成像を撮影し、結晶粒の大きさを測定した。
iv) Periclase diameter As for the periclase diameter of the sintered body, an SEM composition image was taken using an electron microscope (trade name: JSM-5410, manufactured by JEOL), and the size of the crystal grains was measured.
v）密度
焼結体の嵩密度の測定は、アルキメデス法により求めた。焼結体の相対密度は、ＭｇＯ単結晶の密度を３．５８とし、相対密度を計算上求めた。
v) Density The bulk density of the sintered body was determined by the Archimedes method. The relative density of the sintered body was calculated by setting the density of the MgO single crystal to 3.58 and calculating the relative density.
vi）粒径２００μｍ以上の粒子の含有率
ＪＩＳ標準篩、７４ｍｅｓｈ（篩目の開き２００μｍ）を使用して一定質量の粉末を分級し、この標準篩上に残留した粒子の質量を測定し、粉末全体に対するこの残留粒子の質量の割合を算出し、２００μｍ以上の粒子の含有量とした。
vi) Content of particles having a particle size of 200 μm or more A JIS standard sieve, 74 mesh (a sieve opening of 200 μm) is used to classify a certain mass of powder, and the mass of particles remaining on the standard sieve is measured to obtain a powder. The ratio of the mass of the residual particles to the whole was calculated, and the content of particles of 200 μm or more was taken.
４．単結晶ＭｇＯ焼結体をターゲット材として作製されたＰＤＰ用保護膜の特性評価試験
上記により得られた単結晶ＭｇＯ焼結体をターゲット材として、ステンレス基板に電子ビーム蒸着装置を使用して１００ｎｍの厚さに成膜することにより測定試料を作製した。
4). Characteristic evaluation test of protective film for PDP prepared using single crystal MgO sintered body as target material Using single crystal MgO sintered body obtained as above as target material, using electron beam evaporation apparatus on stainless steel substrate, 100 nm A measurement sample was prepared by forming a film to a thickness.
このようにして得られた測定試料を二次電子測定装置のターゲット位置に設置した後、高真空中で活性化処理を行った後、二次電子放出係数を測定した。その結果を図１のグラフに示す。なお、二次電子放出係数測定時の試料温度は３００℃、イオン加速電圧は３００Ｖとした。 After the measurement sample thus obtained was placed at the target position of the secondary electron measuring device, the activation treatment was performed in a high vacuum, and then the secondary electron emission coefficient was measured. The result is shown in the graph of FIG. The sample temperature at the time of measuring the secondary electron emission coefficient was 300 ° C., and the ion acceleration voltage was 300V.
実施例２
１．焼結体製造用単結晶ＭｇＯ粉末の調製
出発原料粉末として、純度９９．０％以上の単結晶ＭｇＯ粉末［商品名ＳＳＰ、４０−２００ｍｅｓｈ（平均粒径３００μｍの粉末Ａ）、−３３０ｍｅｓｈ（平均粒径７μｍの粉末Ｂ）、１００−２００ｍｅｓｈ（平均粒径１００μｍの粉末Ｃ）の３種類、タテホ化学工業株式会社製、Ｂ含有量１ｐｐｍ以下］を使用した。この３種の原料粉末のうち、粉末Ｃを粉砕して、平均粒径２μｍ（最大粒子径１０μｍ）のＭｇＯ粉末Ｄを製造した。
Example 2
1. Preparation of Single-Crystal MgO Powder for Manufacturing Sintered Body As starting raw material powder, single-crystal MgO powder having a purity of 99.0% or more [trade name SSP, 40-200 mesh (powder A having an average particle size of 300 μm), -330 mesh (average particle) Three types of powder B) having a diameter of 7 μm and 100-200 mesh (powder C having an average particle diameter of 100 μm, manufactured by Tateho Chemical Co., Ltd., B content of 1 ppm or less) were used. Of these three kinds of raw material powders, powder C was pulverized to produce MgO powder D having an average particle size of 2 μm (maximum particle size of 10 μm).
平均粒径が異なる３種類のＭｇＯ粉末、すなわち、粉末Ａ、粉末Ｂ及び粉末Ｄを混合して（混合重量比Ａ：Ｂ：Ｄ＝７０：２５：５）、平均粒径が２００μｍの混合ＭｇО粉末を得た。このとき、添加元素としてＡｌを混合するため、Ａｌ２Ｏ３（商品名Ａ−１６ＳＧ、アルコア株式会社製）を上記混合ＭｇО粉末の総重量に対してＡｌ２０３換算で１０００ｐｐｍ配合した。表１に示すように、得られた焼結体中のＡｌ２Ｏ３含有量は、１２００ｐｐｍであり、Ｍｇに対するＡｌの含有量は０．１０ｍｏｌ％であった。 Three kinds of MgO powders having different average particle diameters, that is, powder A, powder B and powder D are mixed (mixing weight ratio A: B: D = 70: 25: 5), and mixed MgO having an average particle diameter of 200 μm. A powder was obtained. At this time, in order to mix Al as an additive element, Al 2 O 3 (trade name A-16SG, manufactured by Alcoa Corporation) was blended at 1000 ppm in terms of Al 2 O 3 with respect to the total weight of the mixed MgO powder. As shown in Table 1, the content of Al 2 O 3 in the obtained sintered body was 1200 ppm, and the content of Al with respect to Mg was 0.10 mol%.
ターゲット用単結晶ＭｇО焼結体の製造
上記により得られた混合ＭｇО粉末を使用し、上記実施例１と同様にしてターゲット用単結晶ＭｇＯ焼結体を得た。
以下、上記実施例と同様にして、物性値測定ならびにＰＤＰ用保護膜の特性評価試験を実施し、得られた結果を表１及び図１に示す。
Production of single-crystal MgO sintered body for target Using the mixed MgO powder obtained as described above, a single-crystal MgO sintered body for target was obtained in the same manner as in Example 1 above.
Hereinafter, in the same manner as in the above examples, physical property value measurement and characteristic evaluation test of the protective film for PDP were carried out, and the obtained results are shown in Table 1 and FIG.
実施例３
酸化鉄（Ｆｅ２０３）を添加したことを除いては、実施例１と同様にして単結晶ＭｇＯ焼結体を製造した。焼結体中に含有されるＦｅは、ＭｇＯに対するＦｅ２Ｏ３換算で２０００ｐｐｍ（Ｍｇに対してＦｅが０．１０ｍｏｌ％）であった。この焼結体をターゲット材として成膜したＭｇＯ膜を得て、同様の特性評価を行い、その結果を表１及び図１に示した。
Example 3
A single crystal MgO sintered body was produced in the same manner as in Example 1 except that iron oxide (Fe 2 O 3 ) was added. Fe contained in the sintered body was 2000 ppm in terms of Fe 2 O 3 with respect to MgO (Fe was 0.10 mol% with respect to Mg). An MgO film formed using this sintered body as a target material was obtained, and the same characteristic evaluation was performed. The results are shown in Table 1 and FIG.
実施例４
イットリア（Ｙ２０３）を添加したことを除いては、実施例１と同様にして単結晶ＭｇＯ焼結体を製造した。焼結体中に含有されるＹは、ＭｇＯに対するＹ２０３換算で２０００ｐｐｍ（Ｍｇに対してＹが０．０７ｍｏｌ％）であった。この焼結体をターゲット材として成膜したＭｇＯ膜を得て、同様の特性評価を行い、その結果を表１及び図１に示した。
Example 4
A single crystal MgO sintered body was produced in the same manner as in Example 1 except that yttria (Y 2 0 3 ) was added. Y contained in the sintered body was 2000 ppm in terms of Y 2 O 3 with respect to MgO (Y is 0.07 mol% with respect to Mg). An MgO film formed using this sintered body as a target material was obtained, and the same characteristic evaluation was performed. The results are shown in Table 1 and FIG.
実施例５〜７
Ａｌ、Ｓｉ及びＦｅを複合添加したことを除いては、実施例１と同様にして単結晶ＭｇＯ焼結体、及びその焼結体をターゲット材として成膜したＭｇＯ膜を得て、同様の特性評価を行い、その結果を表１及び図１に示した。
Examples 5-7
A single crystal MgO sintered body and a MgO film formed using the sintered body as a target material were obtained in the same manner as in Example 1 except that Al, Si, and Fe were added together, and the same characteristics were obtained. Evaluation was performed and the results are shown in Table 1 and FIG.
実施例８
Ｂの含有量が２００ｐｐｍを超える混合粉末を得るために、酸化ホウ素（Ｂ２０３）をＭｇＯ混合粉末に対して２３０ｐｐｍとなるように添加したことを除いては、実施例１と同様にして単結晶ＭｇＯ焼結体、及びその焼結体をターゲット材として成膜したＭｇＯ膜を得て、同様の特性評価を行い、その結果を表１及び図１に示した。
Example 8
In order to obtain a mixed powder having a B content exceeding 200 ppm, boron oxide (B 2 O 3 ) was added in an amount of 230 ppm with respect to the MgO mixed powder in the same manner as in Example 1. A single crystal MgO sintered body and an MgO film formed using the sintered body as a target material were obtained, and the same characteristics were evaluated. The results are shown in Table 1 and FIG.
比較例１
出発原料として純度９９．０以上の高純度多結晶ＭｇＯ粉末（平均粒径２〜８μｍ）を用意する。このＭｇＯ粉末に対し、バインダーとしてＰＶＡを２質量％添加し、さらにエタノールを分散媒としてスラリー濃度５０％となるように調整し、２４時間ボールミルにて混合撹拌してスラリーを得た。
次に、このスラリーをスプレードライヤーにて噴霧し、平均粒径２００μｍの造粒粉末を得た。
Comparative Example 1
A high-purity polycrystalline MgO powder (average particle diameter of 2 to 8 μm) having a purity of 99.0 or more is prepared as a starting material. To this MgO powder, 2% by mass of PVA as a binder was added, and further adjusted to a slurry concentration of 50% using ethanol as a dispersion medium, and mixed and stirred in a ball mill for 24 hours to obtain a slurry.
Next, this slurry was sprayed with a spray dryer to obtain a granulated powder having an average particle size of 200 μm.
以下、上記実施例１と同様にして、成型体を作製した後、焼結することにより多結晶ＭｇＯ焼結体、さらには、焼結体をターゲットとしてＰＤＰ用保護膜を得る。その物性値及びＰＤＰ用保護膜特性評価試験を実施し、得られた結果を表１及び図１に示した。 Thereafter, in the same manner as in Example 1, a molded body is prepared and then sintered to obtain a polycrystalline MgO sintered body, and further, a protective film for PDP is obtained using the sintered body as a target. The physical property value and the protective film property evaluation test for PDP were carried out, and the obtained results are shown in Table 1 and FIG.
比較例２〜４
ＭｇＯ粉末に添加する成分の配合量を表１に示すように、種々に替えたことを除いては、実施例１と同様にして単結晶ＭｇＯ焼結体、及びこれらの焼結体をターゲット材として成膜したＭｇＯ膜を得て、同様の特性評価を行い、その結果を表１及び図１に示した。
Comparative Examples 2-4
As shown in Table 1, the amount of the component added to the MgO powder is changed to various values as in Example 1 except that the single crystal MgO sintered body, and these sintered bodies are used as target materials. The obtained MgO film was obtained, and the same characteristics were evaluated. The results are shown in Table 1 and FIG.
比較例５
出発原料粉末として、純度９９．０質量％以上の単結晶ＭｇＯ粉末（商品名ＳＳＰ１００−２００ｍｅｓｈ、タテホ化学工業株式会社製）を粉砕した平均粒径２μｍ（最大粒子径１０μｍ）のＭｇＯ粉末を使用し、他の成分を添加しないことを除いては、実施例１と同様にして単結晶ＭｇＯ焼結体、及びその焼結体をターゲット材として成膜したＭｇＯ膜を得て、同様の特性評価を行い、その結果を表１及び図１に示した
Comparative Example 5
As the starting material powder, an MgO powder having an average particle diameter of 2 μm (maximum particle diameter of 10 μm) obtained by pulverizing a single crystal MgO powder having a purity of 99.0% by mass or more (trade name SSP100-200 mesh, manufactured by Tateho Chemical Co., Ltd.) is used. A single crystal MgO sintered body and a MgO film formed using the sintered body as a target material were obtained in the same manner as in Example 1 except that no other components were added. The results are shown in Table 1 and FIG.
表１の結果から明らかなように、本発明の単結晶ＭｇＯ焼結体は、従来の高純度多結晶ＭｇＯ焼結体と比べて、相対密度が比較的小さいため、蒸着速度が大きく生産性が向上する。 As is clear from the results in Table 1, the single crystal MgO sintered body of the present invention has a relatively low relative density compared to the conventional high-purity polycrystalline MgO sintered body. improves.
さらに、ＰＤＰの放電維持電極に電圧が印加されるとセル内のガスに含まれるイオン、電子が加速され、加速されたイオンはＭｇＯ保護膜に衝突する。高い二次電子放出係数（γｉ）を持つＭｇＯ保護膜を用いると、放電開始電圧が低下することが確かめられている。放電開始電圧が低下すると、駆動電圧が引き下げられ、その結果、発光効率を向上することができるため、消費電力が低下するという利点がある。 Further, when a voltage is applied to the discharge sustaining electrode of the PDP, ions and electrons contained in the gas in the cell are accelerated, and the accelerated ions collide with the MgO protective film. It has been confirmed that when an MgO protective film having a high secondary electron emission coefficient (γi) is used, the discharge start voltage decreases. When the discharge start voltage is lowered, the drive voltage is lowered. As a result, the light emission efficiency can be improved, so that there is an advantage that power consumption is reduced.
図１から明らかなように、本発明の単結晶ＭｇＯ焼結体をターゲット材として得られたＰＤＰ用保護膜（実施例１〜８）は、単結晶ＭｇＯに本来含有される不純物のバランスを生かしつつ、さらに、保護膜特性を改善しうる不純物成分を見出し、それを添加物として所定の範囲で増量したので、不純物の微量化のみに焦点を絞った従来の多結晶ＭｇＯ焼結体から得られた保護膜（比較例１）、及び、含有不純物量を全く調整していない単結晶ＭｇＯ粉末を原料とする単結晶ＭｇＯ焼結体から得られた保護膜（比較例５）に比べて、二次電子放出係数を増加させることが可能となった。 As is apparent from FIG. 1, the protective films for PDPs (Examples 1 to 8) obtained using the single crystal MgO sintered body of the present invention as a target material make use of the balance of impurities originally contained in the single crystal MgO. In addition, since an impurity component that can improve the protective film characteristics was found and added as an additive in a predetermined range, it was obtained from a conventional polycrystalline MgO sintered body focused only on a small amount of impurities. Compared to a protective film (Comparative Example 1) and a protective film (Comparative Example 5) obtained from a single-crystal MgO sintered body using a single-crystal MgO powder whose raw material content is not adjusted at all. The secondary electron emission coefficient can be increased.
また、Ａｌ、Ｓｉ、Ｆｅ及びＹのようなＭｇＯ膜特性の向上に資する添加成分は、各々を単独で添加した場合（実施例１〜４）よりも、複数種を複合添加した場合（実施例５〜７）の方が、ＭｇＯ膜特性の向上効果が大きいことが確認された。これは、複合添加した方が、単結晶ＭｇＯに含有される本来の不純物成分のバランスを大きく崩すことなく、特性向上に有効な成分を添加することができるためではないかと考えられる。 Moreover, the additive component which contributes to the improvement of MgO film | membrane characteristics like Al, Si, Fe, and Y is a case where multiple types are added together (Examples 1-4) rather than the case where each is added independently (Examples 1-4). It was confirmed that the effect of improving the MgO film characteristics was larger in 5-7). This is probably because the compound addition can add an effective component for improving the characteristics without greatly degrading the balance of the original impurity component contained in the single crystal MgO.
さらに、Ｂの含有量を２００ｐｐｍ以下に抑えたもの（実施例１〜７）は、Ｂの含有量が２００ｐｐｍを超えるもの（実施例８）よりも、ＭｇＯ膜の放電特性がさらに向上することが確認された。 Furthermore, the discharge characteristics of the MgO film can be further improved in the case where the B content is suppressed to 200 ppm or less (Examples 1 to 7) than in the case where the B content exceeds 200 ppm (Example 8). confirmed.
以上詳細に説明したように、本発明の単結晶ＭｇＯ焼結体は、例えば、電子ビーム蒸着法を使用して基板上にＭｇＯ膜を成膜するためのターゲット材として使用した際、得られたＭｇＯ膜の密度及び耐スパッタ性を低下させることなく、優れた膜特性、例えばＰＤＰ用保護膜の放電特性などを向上させることが可能である。 As described above in detail, the single crystal MgO sintered body of the present invention was obtained when used as a target material for forming an MgO film on a substrate using, for example, an electron beam evaporation method. It is possible to improve excellent film characteristics such as the discharge characteristic of the protective film for PDP without reducing the density and sputtering resistance of the MgO film.
また、この単結晶ＭｇＯ焼結体は、異なる平均粒径を有する２種以上のＭｇＯ粉末を混合することにより容易に製造することができる。さらには、この単結晶ＭｇＯ焼結体をターゲット材として使用して製造されたＰＤＰ用保護膜は、二次電子放出係数が高く、放電開始電圧が低くくなる。その結果、発光効率が高くなるため消費電力を低下させることが可能となり、その工業的価値は極めて大である。 The single crystal MgO sintered body can be easily manufactured by mixing two or more kinds of MgO powders having different average particle diameters. Furthermore, a protective film for PDP manufactured using this single crystal MgO sintered body as a target material has a high secondary electron emission coefficient and a low discharge start voltage. As a result, the luminous efficiency is increased, so that the power consumption can be reduced, and its industrial value is extremely large.
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| JP2004167055A JP4575035B2 (en) | 2004-06-04 | 2004-06-04 | Single crystal magnesium oxide sintered body, method for producing the same, and protective film for plasma display panel |
| TW094117776A TW200613235A (en) | 2004-06-04 | 2005-05-31 | Monocrystal oxide magnesium sintered body and fabricating method thereof and plasma display panel |
| CN 200580018097 CN1964932A (en) | 2004-06-04 | 2005-06-03 | Single-crystal magnesium oxide sinter, process for producing the same, and protective film for plasma display panel |
| PCT/JP2005/010226 WO2005118504A1 (en) | 2004-06-04 | 2005-06-03 | Single-crystal magnesium oxide sinter, process for producing the same, and protective film for plasma display panel |
| KR1020067023656A KR20070041440A (en) | 2004-06-04 | 2005-06-03 | Single-ctystal magnesium oxide sinter, process for produsing the same, and protective film for plasma display panel |
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| JP2006002208A (en) * | 2004-06-17 | 2006-01-05 | Tateho Chem Ind Co Ltd | Single crystal magnesium oxide sintered compact, its production method and protective film for plasma display panel |
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| US8072143B2 (en) | 2007-03-19 | 2011-12-06 | Panasonic Corporation | Plasma display panel and its manufacturing method |
| KR101103175B1 (en) * | 2007-08-10 | 2012-01-04 | 가부시키가이샤 히타치세이사쿠쇼 | Plasma display panel |
| JP2009140617A (en) * | 2007-12-03 | 2009-06-25 | Tateho Chem Ind Co Ltd | Magnesium oxide deposition material of plasma display panel and protection film |
| JP5425457B2 (en) * | 2008-12-19 | 2014-02-26 | タテホ化学工業株式会社 | Deposition material for protective film of plasma display panel |
| CN102191455A (en) * | 2010-03-15 | 2011-09-21 | 三菱综合材料株式会社 | Vapour deposition material for forming film, film sheet and laminated sheet having the same |
| US9824868B2 (en) | 2011-11-04 | 2017-11-21 | Ferrotec Ceramics Corporation | Sputtering target and method for producing the same |
| US10704139B2 (en) * | 2017-04-07 | 2020-07-07 | Applied Materials, Inc. | Plasma chamber target for reducing defects in workpiece during dielectric sputtering |
| CN112805403B (en) * | 2018-10-10 | 2023-06-16 | 捷客斯金属株式会社 | Magnesium oxide sputtering target |
| US11227751B1 (en) * | 2020-07-01 | 2022-01-18 | Applied Materials, Inc. | Plasma chamber target for reducing defects in workpiece during dielectric sputtering |
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| JPH1192212A (en) * | 1997-09-10 | 1999-04-06 | Oputoron:Kk | Magnesium oxide sintered compact, its production and magnesium oxide thin film |
| JP2003027221A (en) * | 2001-07-19 | 2003-01-29 | Nec Corp | Material for vapor deposition for protective film of plasma display panel and method for manufacturing the same |
| JP2003109511A (en) * | 2001-09-27 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Plasma display panel |
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|---|---|---|---|---|
| JPH1192212A (en) * | 1997-09-10 | 1999-04-06 | Oputoron:Kk | Magnesium oxide sintered compact, its production and magnesium oxide thin film |
| JP2003027221A (en) * | 2001-07-19 | 2003-01-29 | Nec Corp | Material for vapor deposition for protective film of plasma display panel and method for manufacturing the same |
| JP2003109511A (en) * | 2001-09-27 | 2003-04-11 | Matsushita Electric Ind Co Ltd | Plasma display panel |
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| JP2006002208A (en) * | 2004-06-17 | 2006-01-05 | Tateho Chem Ind Co Ltd | Single crystal magnesium oxide sintered compact, its production method and protective film for plasma display panel |
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