WO2010001796A1 - Rare-erath-element boride member and process for producing the same - Google Patents

Rare-erath-element boride member and process for producing the same Download PDF

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WO2010001796A1
WO2010001796A1 PCT/JP2009/061572 JP2009061572W WO2010001796A1 WO 2010001796 A1 WO2010001796 A1 WO 2010001796A1 JP 2009061572 W JP2009061572 W JP 2009061572W WO 2010001796 A1 WO2010001796 A1 WO 2010001796A1
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present
temperature
boride
rare earth
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忠弘 大見
哲也 後藤
幹郎 小西
和人 安藤
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国立大学法人東北大学
住友大阪セメント株式会社
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
    • C04B35/5805—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on borides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B35/00—Boron; Compounds thereof
    • C01B35/02—Boron; Borides
    • C01B35/04—Metal borides
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C04B35/6455—Hot isostatic pressing
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/04—Electrodes; Screens; Shields
    • H01J61/06—Main electrodes
    • H01J61/067—Main electrodes for low-pressure discharge lamps
    • H01J61/0675—Main electrodes for low-pressure discharge lamps characterised by the material of the electrode

Abstract

Sintered compacts of rare-earth-element borides, in particular, LaB6, were proved unsuitable for use as a sputtering member or the like because a pollutant is present therein in a large amount.  Based on a new view that the contamination by conventional sintered compacts of LaB6 is attributed to the existence of a large amount of pores, an LaB6 compact is pressed in a hot-press furnace and then subjected to HIP.  Pores are thus diminished to attain a porosity of 7 vol.% or lower, preferably 1 vol.% or lower.  Thus, a member reduced in pollutant content can be formed.

Description

希土類元素ホウ化物部材およびその製造方法Rare earth element boride member and manufacturing method thereof
　本発明は、希土類元素ホウ化物によって形成された部材およびその製造方法に関し、特に、ＬａＢ６部材およびその製造方法に関する。 The present invention relates to a member formed of a rare earth element boride and a manufacturing method thereof, and more particularly to a LaB 6 member and a manufacturing method thereof.
　一般に、ＬａＢ６，ＹＢ６，ＧｄＢ６，ＣｅＢ６等の希土類元素ホウ化物によって形成された部材は、耐久性が高く且つ低電流動作で長期間に亘って高い発光効率を有しているため、特許文献１に示されているように、液晶バックライト光源を構成する冷陰極蛍光ランプのエミッタとして利用されている。また、特許文献１では、上記希土類ホウ化物からなるエミッタを円筒状カップに流し塗り、乾燥、焼結することによって形成している。即ち、希土類元素ホウ化物部材は、通常、焼結によって形成するのが普通である。 In general, members formed of rare earth element borides such as LaB 6 , YB 6 , GdB 6 , and CeB 6 have high emission efficiency over a long period of time with high durability and low current operation. As shown in Patent Document 1, it is used as an emitter of a cold cathode fluorescent lamp constituting a liquid crystal backlight light source. In Patent Document 1, the emitter made of the rare earth boride is formed by pouring, drying, and sintering a cylindrical cup. That is, the rare earth element boride member is usually formed by sintering.
　一方、本発明者等は、先に、特許文献２において、希土類ホウ化物膜、特に、ＬａＢ６膜を電極部材上にスパッタリングによって形成することにより、高輝度、高効率、及び長寿命の希土類ホウ化物部材として陰極体が得られることを提案した。このように、希土類ホウ化物部材をスパッタリングする場合、スパッタリング用ターゲット部材が必要である。 On the other hand, the inventors previously disclosed a rare-earth boride film having high brightness, high efficiency, and long life in Patent Document 2 by forming a rare-earth boride film, particularly a LaB 6 film, on an electrode member by sputtering. It was proposed that a cathode body could be obtained as a chemical member. Thus, when sputtering a rare earth boride member, a sputtering target member is required.
　いずれにしても、仕事関数が低いという特徴のためにターゲット部材、陰極体部材、電極部材その他の部材に使われる希土類ホウ化物部材、特に、ＬａＢ６部材は、一般に、高純度粉末を焼結して作られている。 In any case, due to the low work function, rare earth boride members used for target members, cathode body members, electrode members and other members, particularly LaB 6 members, generally sinter high-purity powder. It is made.
　しかしながら、本発明者等の実験によれば、純度９９体積％の希土類ホウ化物粉末をターゲットとして使用して、スパッタリングを行った場合、良好なスパッタ膜が得られないことが判明した。即ち、スパッタされた膜に有機物、水分等の汚染物が大量に含まれていることが判った。 However, according to experiments by the present inventors, it has been found that when sputtering is performed using a rare earth boride powder having a purity of 99% by volume as a target, a good sputtered film cannot be obtained. That is, it was found that the sputtered film contained a large amount of contaminants such as organic matter and moisture.
特開平１０－１４４２５５号公報JP-A-10-144255 特願２００７－２３９２１９号Japanese Patent Application No. 2007-239219
　本発明者等の研究によれば、希土類ホウ化物、特に、ＬａＢ６粉末の純度が９９体積％であっても、焼結部材には多数の孔が開いていて、体積で密度は８０％程度（即ち、空隙率が２０％程度）であり、空気や水分起因の酸素や、孔に取り込まれた有機物起因の炭素が大量に含まれていることを見出した。 According to the study by the present inventors, even if the purity of the rare earth boride, especially LaB 6 powder is 99% by volume, the sintered member has a large number of pores and the density is about 80% by volume. (That is, the porosity is about 20%), and it has been found that a large amount of oxygen derived from air and moisture and carbon derived from organic matter taken into the pores are contained.
　このようなＬａＢ６部材をスパッタのターゲットに使うと、スパッタされた膜に大量の汚染物（有機物や水分）が含まれることになる。スパッタ成膜の際に基板を高温にし、且つ、スパッタされた膜を高純度Ａｒガス中で６００～８００℃の高温アニールすることにより、スパッタされた膜中の汚染物を除去することができ、これによって、抵抗および仕事関数が低いＬａＢ６膜を得ることができた。 When such a LaB 6 member is used as a sputtering target, the sputtered film contains a large amount of contaminants (organic matter and moisture). By raising the temperature of the substrate during sputter deposition and annealing the sputtered film at a high temperature of 600 to 800 ° C. in high-purity Ar gas, contaminants in the sputtered film can be removed. As a result, a LaB 6 film having a low resistance and work function could be obtained.
　換言すれば、ＬａＢ６ターゲット部材は、使用前に８００℃の熱処理を行って、水分や有機物を除去しなければ、スパッタ膜中の汚染物を低減できない。このように、熱処理されたターゲット部材を使用しても、Ｘ線光電子分光法で評価した結果、内部には酸素・カーボンが５％程度存在し、一度大気に触れると再汚染されてしまうと云う現象が見出された。 In other words, the LaB 6 target member cannot reduce contaminants in the sputtered film unless it is subjected to heat treatment at 800 ° C. before use to remove moisture and organic matter. As described above, even when the heat-treated target member is used, as a result of evaluation by X-ray photoelectron spectroscopy, about 5% of oxygen and carbon are present inside, and once it is exposed to the atmosphere, it is said that it is recontaminated. A phenomenon was found.
　これは、ターゲット部材表面は酸化されているので、空孔の表面にも酸化物が形成されているためであると考えられる。具体的に説明すると、表面が酸化されたターゲット部材がスパッタされると、最初の空スパッタでターゲット部材表面の酸化物は除去できても、スパッタが進行して空孔表面の酸化物からの酸素や付着有機物がスパッタ膜にとりこまれて、結局は酸素や炭素で汚染されてしまうことになる。したがって、ターゲット部材を使用前に熱処理したとしても、基板を高温にしてスパッタし、且つ、スパッタ膜を高温でアニールしなければ、低い仕事関数は得られない。 This is presumably because the surface of the target member is oxidized, and oxide is also formed on the surface of the pores. More specifically, when a target member having an oxidized surface is sputtered, even if the oxide on the surface of the target member can be removed by the first void sputtering, the sputtering proceeds and oxygen from the oxide on the void surface Or adhering organic substances are taken into the sputtered film and eventually contaminated with oxygen or carbon. Therefore, even if the target member is heat-treated before use, a low work function cannot be obtained unless the substrate is sputtered at a high temperature and the sputtered film is annealed at a high temperature.
　このような余分な工程はコスト高を招くし、有機ＥＬのように基板を高温にすることが出来ない場合もある。 Such an extra process leads to high costs, and there are cases where the substrate cannot be heated to a high temperature like organic EL.
　このような従来の問題は、希土類ホウ化物部材、特に、ＬａＢ６部材の内部に空孔が多いことが原因であることを見出し、本発明はこのような問題を解決することを目的とする。 Such a conventional problem has been found to be caused by a large number of pores inside the rare earth boride member, in particular, the LaB 6 member, and the present invention aims to solve such a problem.
　本発明の第１の態様によれば、実質的に希土類元素のホウ化物からなり、空隙率が８体積％以下、好ましくは７体積％以下であることを特徴とする部材が得られる。 According to the first aspect of the present invention, there can be obtained a member which is substantially composed of a boride of a rare earth element and has a porosity of 8% by volume or less, preferably 7% by volume or less.
　本発明の第２の態様によれば、第１の態様に記載された部材において、前記希土類元素のホウ化物がＬａＢ６を含むことを特徴とする部材が得られる。 According to the second aspect of the present invention, there is obtained the member described in the first aspect, wherein the rare earth element boride contains LaB 6 .
　本発明の第３の態様によれば、第1又は２の態様に記載された部材において、空隙率が１体積％以下であることを特徴とする部材が得られる。 According to the third aspect of the present invention, in the member described in the first or second aspect, a member having a porosity of 1% by volume or less is obtained.
　本発明の第４の態様によれば、第1乃至第３のいずれか一の態様に記載された部材において、表面および内部に孔が実質的に無いことを特徴とする部材が得られる。 According to the fourth aspect of the present invention, in the member described in any one of the first to third aspects, a member characterized in that there is substantially no hole on the surface and inside is obtained.
　本発明の第５の態様によれば、スパッタリング用ターゲット部材、陰極体用部材、及び電極用部材のいずれか一つの部材であることを特徴とする第１乃至４の態様のいずれかに記載の部材が得られる。 According to a fifth aspect of the present invention, in any one of the first to fourth aspects, the member is any one of a sputtering target member, a cathode body member, and an electrode member. A member is obtained.
　本発明の第６の態様によれば、実質的にＬａＢ６からなる粉末を成形する工程と、該工程で生じた成形体をホットプレスにて加熱しつつ圧縮する工程とを有し、ＬａＢ６部材を得ることを特徴とするＬａＢ６部材の製造方法が得られる。 According to a sixth aspect of the present invention, comprises the steps of molding a powder consisting essentially of LaB 6, and a step of compressing while heating the molded body produced in about該工at hot pressing, LaB 6 LaB 6 member manufacturing method characterized by obtaining a member is obtained.
　本発明の第７の態様によれば、前記加熱しつつ圧縮する工程は、温度が１８００℃以上、圧力が３０ＭＰａ以上で行われることを特徴とする第６の態様に記載のＬａＢ６部材の製造方法が得られる。 According to a seventh aspect of the present invention, in the production of the LaB 6 member according to the sixth aspect, the step of compressing while heating is performed at a temperature of 1800 ° C. or higher and a pressure of 30 MPa or higher. A method is obtained.
　本発明の第８の態様によれば、前記加熱しつつ圧縮する工程の後に、加熱しつつ高圧気体にて等方性の圧縮を行う工程を有することを特徴とする第６又は第７の態様に記載のＬａＢ６部材の製造方法が得られる。 According to an eighth aspect of the present invention, the method according to the sixth or seventh aspect, further comprising a step of performing isotropic compression with a high-pressure gas while heating after the step of compressing while heating. method of manufacturing a LaB 6 member according to obtain.
　本発明の第９の態様によれば、前記等方性の圧縮を行う工程は、温度が１８５０℃以上、圧力が１５０ＭＰａ以上で行われることを特徴とする第８の態様に記載のＬａＢ６部材の製造方法が得られる。 According to a ninth aspect of the present invention, in the LaB 6 member according to the eighth aspect, the step of performing isotropic compression is performed at a temperature of 1850 ° C. or higher and a pressure of 150 MPa or higher. The manufacturing method is obtained.
　本発明の第１０の態様によれば、前記ＬａＢ６部材は、スパッタリング用ターゲット部材、陰極体用部材、及び電極用部材のいずれか一つの部材であることを特徴とする第６乃至９の態様のいずれか一つに記載のＬａＢ６部材の製造方法が得られる。 According to a tenth aspect of the present invention, in the sixth to ninth aspects, the LaB 6 member is any one of a sputtering target member, a cathode member, and an electrode member. method of manufacturing a LaB 6 member according to any one of is obtained.
　本発明では、ターゲットとして用いてスパッタリングを行った場合、有機物、酸素、及び炭素等の不純物の少ない部材を得ることができる。 In the present invention, when sputtering is performed using as a target, a member with less impurities such as organic matter, oxygen, and carbon can be obtained.
従来のＬａＢ６部材のＳＥＭ画像を示す図である。It is a figure which shows the SEM image of the conventional LaB 6 member. 従来のＬａＢ６焼結体を熱処理した場合の昇温プロファイルを示すグラフである。It is a graph showing a Atsushi Nobori profile when heat treated conventional LaB 6 sintered body. 従来のＬａＢ６焼結体を４００℃まで加熱処理した場合のマススペクトルを示す図である。Conventional LaB 6 sintered body is a diagram showing a mass spectrum when subjected to heat treatment up to 400 ° C.. 従来のＬａＢ６焼結体を８００℃まで加熱処理した場合のマススペクトルを示す図である。Conventional LaB 6 sintered body is a diagram showing a mass spectrum when subjected to heat treatment up to 800 ° C.. 熱処理された従来のＬａＢ６焼結体を再度大気に曝露して４００℃まで加熱した場合におけるマススペクトルを示す図である。It is a diagram showing a mass spectrum in case of heating the heat-treated conventional LaB 6 sintered body to exposure to 400 ° C. again air. 熱処理された従来のＬａＢ６焼結体を再度大気に曝露して８００℃まで加熱した場合におけるマススペクトルを示す図である。It is a figure which shows the mass spectrum at the time of exposing the heat-treated conventional LaB6 sintered compact to air | atmosphere again, and heating to 800 degreeC. 本発明の実施例において、ＬａＢ６成形体をプレスするホットプレス炉の一例を示す図である。In an embodiment of the present invention, it is a diagram illustrating an example of a hot press furnace for pressing the LaB 6 moldings. （ａ）はホットプレス炉でＬａＢ６成形体を１８００℃の温度、４０ＭＰａの圧力で１時間プレスした場合のＳＥＭ画像を示す図、（ｂ）はホットプレス炉でＬａＢ６成形体を１８００℃の温度、３０ＭＰａの圧力で１時間プレスした場合のＳＥＭ画像を示す図である。(A) a temperature of 1800 ° C. The LaB 6 moldings by hot pressing furnace, shows an SEM image when the 1 hour pressed at a pressure of 40 MPa, (b) is a 1800 ° C. the LaB 6 moldings by hot press furnace It is a figure which shows the SEM image at the time of pressing at temperature and the pressure of 30 Mpa for 1 hour. 図７のホットプレス炉を使用した場合におけるホットプレス体の相対密度を示すグラフである。It is a graph which shows the relative density of the hot press body at the time of using the hot press furnace of FIG. 本発明の実施例によるＬａＢ６ホットプレス体を４００℃まで加熱した場合のマススペクトルを示す図である。The LaB 6 hot-pressed body according to an embodiment of the present invention shows a mass spectrum when heated to 400 ° C.. 本発明の実施例によるＬａＢ６ホットプレス体を８００℃まで加熱した場合のマススペクトルを示す図である。The LaB 6 hot-pressed body according to an embodiment of the present invention shows a mass spectrum when heated to 800 ° C.. 本発明の実施例によるＬａＢ６ホットプレス体のＳＥＭ画像を示す図である。Is a diagram showing an SEM image of the LaB 6 hot-pressed body according to an embodiment of the present invention. 本発明の実施例により、ＬａＢ６ホットプレス体を更に１８００℃の温度、１５０ＭＰａの圧力で１時間、ＨＩＰ処理した部材のＳＥＭ画像である。4 is a SEM image of a member obtained by HIP processing a LaB 6 hot press body at a temperature of 1800 ° C. and a pressure of 150 MPa for 1 hour according to an embodiment of the present invention. 本発明の実施例により、ＬａＢ６ホットプレス体を更に１８５０℃の温度、１５０ＭＰａの圧力で１時間、ＨＩＰ処理した部材のＳＥＭ画像である。4 is an SEM image of a member obtained by HIP processing a LaB 6 hot press body at a temperature of 1850 ° C. and a pressure of 150 MPa for 1 hour according to an embodiment of the present invention.
　以下、本発明の実施例について図面を参照して説明する。尚、ここでは、希土類ホウ化物として、ＬａＢ６を用いた場合についてのみ説明するが、本発明は何等これに限定されるものでは無い。 Embodiments of the present invention will be described below with reference to the drawings. Although only the case where LaB 6 is used as the rare earth boride will be described here, the present invention is not limited to this at all.
　図１は、本発明に係る処理を行なう前におけるＬａＢ６部材の状態を示すＳＥＭ写真である。この例では、純度９９体積％のＬａＢ６粉末を焼結した焼結体のＳＥＭ画像（×２０００）が示されている。図示されているように、焼結体の表面には、多数の空孔が形成されている。この焼結体を図２に示す昇温プロファイルにて昇温した。即ち、室温で１０時間保持した後、５℃／ｍｉｎの昇温速度で８００℃まで昇温し、８００℃の温度に３０分間保持した。この昇温中、高純度Ａｒガスを流してＡＰＩ－ＭＳ測定を行うと、４００℃では図３のマススペクトルで示すように大量の汚染物質が観測された。 FIG. 1 is a SEM photograph showing the state of the LaB 6 member before performing the process according to the present invention. In this example, an SEM image (× 2000) of a sintered body obtained by sintering LaB 6 powder having a purity of 99% by volume is shown. As shown in the drawing, a large number of pores are formed on the surface of the sintered body. The temperature of this sintered body was raised with the temperature rise profile shown in FIG. That is, after holding at room temperature for 10 hours, the temperature was raised to 800 ° C. at a temperature rising rate of 5 ° C./min, and kept at a temperature of 800 ° C. for 30 minutes. When API-MS measurement was performed while flowing high purity Ar gas during this temperature rise, a large amount of contaminants was observed at 400 ° C. as shown by the mass spectrum in FIG.
　一方、図４に示すように、８００℃、３０分維持で汚染は減るが、このように、熱処理された焼結体を大気暴露して４００℃まで加熱して再度測定すると、図５に示すように、また、汚染物質に伴うスペクトルが現われ、再度、汚染されていることが判る。この状態で、８００℃の温度で再高温処理を行なうと、図６のように、再高温処理で汚染物質の量を減少させることができる。 On the other hand, as shown in FIG. 4, the contamination is reduced by maintaining at 800 ° C. for 30 minutes, but when the heat-treated sintered body is exposed to the atmosphere and heated to 400 ° C. and measured again, it is shown in FIG. Thus, the spectrum accompanying the pollutant appears, and it can be seen that it is contaminated again. In this state, when the high temperature treatment is performed at a temperature of 800 ° C., the amount of contaminants can be reduced by the high temperature treatment as shown in FIG.
　本発明は、従来のＬａＢ６焼結体に内在する大量の汚染物質が従来のＬａＢ６焼結体の空孔による（相対密度が低いことによる）との新規な知見に基づき、焼結体の空孔、即ち、空隙率を減少させることならびにその手法を提案する。尚、本発明の実施例では、ＬａＢ６焼結体について説明するが、本発明は焼結されたＬａＢ６部材には限定されない。 The present invention is based on the novel finding of a large amount of contaminants inherent in conventional LaB 6 sintered body according to the holes of a conventional LaB 6 sintered body (due to the relative density is low), the sintered body We propose to reduce vacancies, i.e., porosity, and techniques. In the embodiment of the present invention will be described LaB 6 sintered body, the present invention is not limited to LaB 6 members which are sintered.
　図７を参照すると、本発明の実施例で使用したホットプレス炉が示されている。図示されたホットプレス炉は、炉壁内に、断熱材１２及びヒーター１４を配置し、当該炉内にアルゴンガスを導入するガス導入系と、ポンプによって炉内を排気できる排気系を備えている。また、炉内には、カーボンによって形成された型（ダイス）１６が設けられ、当該ダイス１６はダイス受け台１８によって支持され、ダイス１６上部にはパンチ２２が設けられている。ダイス１６内に配置されたＬａＢ６の成形体２０は、パンチ２２とダイス受け台１８とにより、油圧によりプレスされる。 Referring to FIG. 7, the hot press furnace used in the embodiment of the present invention is shown. The illustrated hot press furnace includes a heat introduction member 12 and a heater 14 in a furnace wall, a gas introduction system for introducing argon gas into the furnace, and an exhaust system capable of exhausting the inside of the furnace by a pump. . Further, a die (die) 16 made of carbon is provided in the furnace, the die 16 is supported by a die receiving base 18, and a punch 22 is provided above the die 16. The LaB 6 shaped body 20 disposed in the die 16 is pressed by a hydraulic pressure by the punch 22 and the die support 18.
　このホットプレス炉により、１，８００℃、１時間、３０または４０ＭＰａの圧力でＬａＢ６の成形体をプレスし、ホットプレス体を得た。 In this hot press furnace, a LaB 6 molded body was pressed at 1,800 ° C., 1 hour, 30 or 40 MPa, to obtain a hot pressed body.
　図８を参照すると、ホットプレス体のＳＥＭ画像が示されている。図８からも明らかな通り、ＬａＢ６ホットプレス体の表面における空孔が大幅に減少している。 Referring to FIG. 8, an SEM image of the hot press body is shown. As is clear from FIG. 8, the number of vacancies on the surface of the LaB 6 hot press body is greatly reduced.
　図９を参照すると、ホットプレス後のＬａＢ６ホットプレス体の相対密度が示されている。図の横軸は、ホットプレス時の温度（℃）、圧力（ＭＰａ）、およびホットプレス時間（ｈｏｕｒ）を示し、縦軸は相対密度を示している。図からも明らかな通り、ホットプレスの温度１，８００℃以上、圧力３０ＭＰａ以上で、相対密度が９２～９５％（空隙率８～５％）になっているのがわかる。なお、本発明において、空隙率は、好ましくは７体積％以下、より好ましくは1体積％以下である。 Referring to FIG. 9, the relative density of the LaB 6 hot press body after hot pressing is shown. The horizontal axis of the figure indicates the temperature (° C.), the pressure (MPa), and the hot press time (hour) during hot pressing, and the vertical axis indicates the relative density. As is apparent from the figure, the relative density is 92 to 95% (the porosity is 8 to 5%) at a hot press temperature of 1,800 ° C. or higher and a pressure of 30 MPa or higher. In the present invention, the porosity is preferably 7% by volume or less, more preferably 1% by volume or less.
　図１０および１１を参照すると、ホットプレス後のＬａＢ６ホットプレス体を４００℃及び８００℃で熱処理した場合におけるマススペクトルが示されており、いずれの温度においても汚染物質が大幅に減少していることが判る。ホットプレス後のＬａＢ６ホットプレス体を使用することによって、従来用いられているターゲットに比較して汚染物質の少ないＬａＢ６部材を構成できる。 Referring to FIGS. 10 and 11, mass spectra are shown when the LaB6 hot press body after hot pressing is heat-treated at 400 ° C. and 800 ° C., and the contaminants are greatly reduced at any temperature. I understand. By using a LaB 6 hot-pressed body after hot pressing, a LaB 6 member with less contaminants can be formed compared to a conventionally used target.
　本発明では、更に空孔を減少させるために、ＬａＢ６のホットプレス体をＨＩＰ（Ｈｏｔ　Ｉｓｏｓｔａｔｉｃ　Ｐｒｅｓｓｉｎｇ）処理した。ＨＩＰ処理は温度と全方向からの（等方的）圧力の相乗効果を利用して空孔を減少させることができる。 In the present invention, in order to further reduce the pores, the LaB 6 hot pressed body was subjected to HIP (Hot Isostatic Pressing) treatment. HIP treatment can reduce pores by utilizing the synergistic effect of temperature and (isotropic) pressure from all directions.
　図１２は、１，８００℃、４０ＭＰａでホットプレスしたＬａＢ６ホットプレス体（密度９３．５％）の表面拡大を示し、この状態では、未だ空孔が若干存在している。これを１５０ＭＰａで１時間、１８００℃および１８５０℃で、ＨＩＰ処理炉で処理した。加圧は高純度Ａｒガスを用いて行った。その結果を図１３および１４にそれぞれ示す。１，８００℃処理したＬａＢ６部材は若干空孔が存在しているが、１８５０℃処理のＬａＢ６部材は空孔がほとんど無くなっている。この結果、図１４に示されたＬａＢ６部材の密度は約１００％（９９％以上）であった。また、不純物成分としてはカーボンが０．１％以下、酸素は１．６％まで低減された。この酸素は、焼結材料であるＬａＢ６膜粉末に含まれている成分であり、材料粉末を高純度化することでさらに酸素を低減することが可能である。このターゲットを用いて低仕事関数（３ｅＶ以下）の薄膜を、室温で成膜して成膜後の熱処理無しで実現することができた。 FIG. 12 shows the surface enlargement of a LaB 6 hot-pressed body (density 93.5%) hot-pressed at 1,800 ° C. and 40 MPa. In this state, there are still some pores. This was processed in a HIP processing furnace at 1800 ° C. and 1850 ° C. for 1 hour at 150 MPa. Pressurization was performed using high-purity Ar gas. The results are shown in FIGS. 13 and 14, respectively. LaB 6 member treated at 1,800 ° C. has some pores, but LaB 6 member treated at 1850 ° C. has almost no voids. As a result, the density of the LaB 6 member shown in FIG. 14 was about 100% (99% or more). As impurity components, carbon was reduced to 0.1% or less, and oxygen was reduced to 1.6%. This oxygen is a component contained in the LaB 6 film powder, which is a sintered material, and it is possible to further reduce oxygen by increasing the purity of the material powder. Using this target, a thin film having a low work function (3 eV or less) was formed at room temperature and could be realized without heat treatment after film formation.
　本発明によるＬａＢ６等の希土類元素ホウ化物部材は、スパッタリングに用いられるターゲット部材に適用できるだけでなく、冷陰極蛍光ランプの陰極部材、その他の電極部材を形成するのにも適用できる。更に、本発明は、熱処理を行うことなく、低仕事関数を有するＬａＢ６薄膜を実現できる。また、本発明は、ＬａＢ６だけでなく、他の希土類ホウ化物元素（例えば、ＬａＢ４，ＹＢ６，ＧｄＢ６，ＣｅＢ６）等にも適用できる。 The rare earth element boride member such as LaB 6 according to the present invention can be applied not only to a target member used for sputtering but also to form a cathode member of a cold cathode fluorescent lamp and other electrode members. Furthermore, the present invention can realize a LaB 6 thin film having a low work function without performing heat treatment. The present invention can be applied not only to LaB 6 but also to other rare earth boride elements (eg, LaB 4, YB 6 , GdB 6 , CeB 6 ) and the like.
　１２　　　　　断熱材
　１４　　　　　ヒーター
　１６　　　　　ダイス
　１８　　　　　ダイス受け台
　２０　　　　　ＬａＢ６焼結体
　２２　　　　　パンチ 12 Heat Insulating Material 14 Heater 16 Dies 18 Die Base 20 LaB 6 Sintered Body 22 Punch

Claims (10)

  1. 　実質的に希土類元素のホウ化物からなり、空隙率が８体積％以下であることを特徴とする部材。 A member characterized by substantially consisting of a boride of a rare earth element and having a porosity of 8% by volume or less.
  2. 　請求項１に記載された部材において、前記希土類元素のホウ化物は、ＬａＢ６を含むことを特徴とする部材。 The member according to claim 1, wherein the rare earth element boride contains LaB 6 .
  3. 　請求項１又は２に記載された部材において、前記空隙率が１体積％以下であることを特徴とする部材。 The member according to claim 1 or 2, wherein the porosity is 1% by volume or less.
  4. 　請求項１乃至３の内のいずれか一項に記載された部材において、表面および内部に孔が実質的に無いことを特徴とする部材。 The member according to any one of claims 1 to 3, wherein the surface and the inside thereof are substantially free of holes.
  5. 　前記部材は、スパッタリング用ターゲット部材、陰極体用部材、及び電極用部材のいずれか一つの部材であることを特徴とする部材。 The member is one of a sputtering target member, a cathode member, and an electrode member.
  6. 　実質的にＬａＢ６からなる粉末を成形する工程と、該工程で生じた成形体をホットプレスにて加熱しつつ圧縮する工程とを有し、ＬａＢ６部材を得ることを特徴とするＬａＢ６部材の製造方法。 A LaB 6 member, characterized by having a step of forming a powder substantially consisting of LaB 6 and a step of compressing the compact formed in the step while heating with a hot press, to obtain a LaB 6 member Manufacturing method.
  7. 　前記加熱しつつ圧縮する工程は、温度が１８００℃以上、圧力が３０ＭＰａ以上で行われることを特徴とする請求項６に記載のＬａＢ６部材の製造方法。 The method for producing a LaB 6 member according to claim 6, wherein the step of compressing while heating is performed at a temperature of 1800 ° C or higher and a pressure of 30 MPa or higher.
  8. 　前記加熱しつつ圧縮する工程の後に、加熱しつつ高圧気体にて等方性の圧縮を行う工程を有することを特徴とする請求項６又は７に記載のＬａＢ６部材の製造方法。 The method for producing a LaB 6 member according to claim 6 or 7, further comprising a step of performing isotropic compression with high-pressure gas while heating after the step of compressing while heating.
  9. 　前記等方性の圧縮を行う工程は、温度が１８５０℃以上、圧力が１５０ＭＰａ以上で行われることを特徴とする請求項８に記載のＬａＢ６部材の製造方法。 The method for producing an LaB 6 member according to claim 8, wherein the isotropic compression is performed at a temperature of 1850 ° C or higher and a pressure of 150 MPa or higher.
  10. 　前記ＬａＢ６部材はスパッタリング用ターゲット部材、陰極体用部材、及び電極用部材のいずれか一つの部材に用いられることを特徴とする請求項６乃至９の内のいずれか１項に記載のＬａＢ６部材の製造方法。 The LaB 6 member sputtering target member, according to any one of claims 6 to 9, characterized by being used in any one of the members of the cathode body member, and the electrode member LaB 6 Manufacturing method of member.
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WO2011122100A1 (en) * 2010-03-29 2011-10-06 住友大阪セメント株式会社 Lanthanum hexaboride sintered body, target and lanthanum hexaboride film each comprising same, and process for production of the sintered body
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JP2012214374A (en) * 2011-03-29 2012-11-08 Sumitomo Osaka Cement Co Ltd Method for producing microparticle of lanthanum hexaboride, microparticle of lanthanum hexaboride, sintered compact of lanthanum hexaboride, film of lanthanum hexaboride, and organic semiconductor device
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JP2011063487A (en) * 2009-09-18 2011-03-31 Sumitomo Osaka Cement Co Ltd Lanthanum boride sintered compact, target using sintered compact and method for producing sintered compact
WO2011122100A1 (en) * 2010-03-29 2011-10-06 住友大阪セメント株式会社 Lanthanum hexaboride sintered body, target and lanthanum hexaboride film each comprising same, and process for production of the sintered body
JP5761178B2 (en) * 2010-03-29 2015-08-12 住友大阪セメント株式会社 Lanthanum hexaboride sintered body, target using the same, lanthanum hexaboride film, and method for producing the sintered body
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JP2012012249A (en) * 2010-06-30 2012-01-19 Sumitomo Osaka Cement Co Ltd Method for producing lanthanum hexaboride fine particle and lanthanum hexaboride fine particle
JP2012214374A (en) * 2011-03-29 2012-11-08 Sumitomo Osaka Cement Co Ltd Method for producing microparticle of lanthanum hexaboride, microparticle of lanthanum hexaboride, sintered compact of lanthanum hexaboride, film of lanthanum hexaboride, and organic semiconductor device
EP2703349A1 (en) * 2012-09-03 2014-03-05 NGK Insulators, Ltd. Lanthanum boride sintered body and method for producing the same
US9257210B2 (en) 2012-09-03 2016-02-09 Ngk Insulators, Ltd. Lanthanum boride sintered body and method for producing the same

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