WO2010050409A1 - Method for storing target comprising rare earth metal or oxide thereof - Google Patents

Method for storing target comprising rare earth metal or oxide thereof Download PDF

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Publication number
WO2010050409A1
WO2010050409A1 PCT/JP2009/068248 JP2009068248W WO2010050409A1 WO 2010050409 A1 WO2010050409 A1 WO 2010050409A1 JP 2009068248 W JP2009068248 W JP 2009068248W WO 2010050409 A1 WO2010050409 A1 WO 2010050409A1
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Prior art keywords
target
oxide
rare earth
earth metal
storing
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PCT/JP2009/068248
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French (fr)
Japanese (ja)
Inventor
和幸 佐藤
由将 小井土
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日鉱金属株式会社
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Application filed by 日鉱金属株式会社 filed Critical 日鉱金属株式会社
Priority to KR1020117006460A priority Critical patent/KR101290941B1/en
Priority to CN2009801435671A priority patent/CN102203314B/en
Priority to US13/119,377 priority patent/US20110162322A1/en
Priority to JP2010519298A priority patent/JP5032662B2/en
Publication of WO2010050409A1 publication Critical patent/WO2010050409A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
    • B65D81/24—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants
    • B65D81/26—Adaptations for preventing deterioration or decay of contents; Applications to the container or packaging material of food preservatives, fungicides, pesticides or animal repellants with provision for draining away, or absorbing, or removing by ventilation, fluids, e.g. exuded by contents; Applications of corrosion inhibitors or desiccators
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F15/00—Other methods of preventing corrosion or incrustation

Definitions

  • the present invention relates to a method for storing a target comprising a rare earth metal that is easily powdered by oxidation or hydroxylation, or an oxide thereof.
  • the rare earth metal is contained in the earth's crust as a mixed composite oxide. Since rare earth metals were separated from relatively rare (rare) minerals, they were named as such, but they are not rare when viewed from the entire crust. Recently, rare earth metals have attracted attention as electronic materials, and are being researched and developed. Among these rare earth metals, lanthanum (La) is particularly attracting attention. Briefly introducing this lanthanum, the lanthanum has an atomic number of 57 and an atomic weight of 138.9, and is a white metal with a double hexagonal close-packed structure at room temperature. The melting point is 921 ° C., the boiling point is 3500 ° C., and the density is 6.15 g / cm 3.
  • the surface is oxidized in the air and gradually dissolved in water. Soluble in hot water and acid. There is no ductility, but there is slight malleability.
  • the resistivity is 5.70 ⁇ 10 ⁇ 6 ⁇ cm. It burns at 445 ° C or higher to become oxide (La 2 O 3 ) (see Physics and Chemistry Dictionary).
  • rare earth metals compounds having an oxidation number of 3 are generally stable, but lanthanum is also trivalent. This lanthanum is a metal attracting attention as an electronic material, such as a metal gate material and a high dielectric constant material (High-k). Rare earth metals other than lanthanum have attributes similar to this lanthanum.
  • rare earth metals such as lanthanum have a problem that they are easily oxidized during purification, they are difficult materials to be highly purified. Further, when a rare earth metal such as lanthanum is left in the air, it is oxidized and discolored in a short time, so that there is a problem that handling is not easy. Recently, thinning is required as a gate insulating film in next-generation MOSFETs, but in SiO 2 that has been used as a gate insulating film so far, leakage current due to a tunnel effect increases and normal operation has become difficult. .
  • HfO 2 , ZrO 2 , Al 2 O 3 , La 2 O 3 having a high dielectric constant, high thermal stability, and a high energy barrier against holes and electrons in silicon are proposed.
  • La 2 O 3 is highly evaluated, electrical characteristics have been investigated, and research reports as a gate insulating film in next-generation MOSFETs have been made (see Non-Patent Document 1).
  • the object of research is the La 2 O 3 film, and the characteristics and behavior of La metal are not particularly mentioned.
  • the rare earth metals such as lanthanum and their oxides are still in the research stage, but when investigating the characteristics of such rare earth metals and their oxides, the rare earth metals and their oxides themselves are sputtered. If it exists as a target material, it is possible to form a thin film of rare earth metal and its oxide on the substrate, and also the behavior of the interface with the silicon substrate, and further the formation of a rare earth metal compound to form a high dielectric constant gate. It is easy to examine the characteristics of an insulating film and the like, and has a great advantage that the degree of freedom as a product is increased.
  • a lanthanum sputtering target even if a lanthanum sputtering target is produced, it is oxidized in the air in a short time as described above. In general, a stable oxide film is formed on the surface of a metal target. However, since it is usually very thin, it peels off at the initial stage of sputtering and does not significantly affect the sputtering characteristics. However, in the lanthanum sputtering target, the oxide film becomes thick, the electric conductivity is lowered, and the sputtering is defective. Also, if left in the air for a long time, it reacts with the moisture in the air and is covered with a white powder of hydroxide, eventually resulting in a powdered state, and normal sputtering is not possible Even it happens.
  • Patent Document 1 a method of covering a hollow cathode sputtering target with a resin bag
  • Patent Document 2 a method of attaching a protective film of a plastic film to a target
  • Patent Document 3 A method of packing a target using a nonexistent surface film
  • Patent Document 4 a method of producing a target storage container using a transparent acrylic resin top cover and screwing
  • Patent Document 5 a method of producing a target storage container using a transparent acrylic resin top cover and screwing
  • Patent Document 5 a method that encloses a bag-like material.
  • these enclose the target using a resin lid or a resinous film, and are not sufficient as a method for storing a target made of a rare earth metal or its oxide.
  • the present invention devised a method for storing a target made of a rare earth metal or its oxide, and suppresses oxidization of the target due to residual and intrusion of air and pulverization due to hydroxylation, so that it can be used as a sputtering target. It is an object of the present invention to provide a technique capable of storing a period.
  • the present invention 1) A method for storing a sputtering target comprising a rare earth metal or an oxide thereof, and a target comprising a rare earth metal or an oxide thereof stored in a container or film seal for storage of the target The same rare earth metal oxide is introduced as a desiccant, and the storage container or the film-like seal is sealed and stored.
  • a large rare earth metal oxide is introduced as a desiccant, and the container for storage or the film-like seal is sealed and stored.
  • Target storage method of a rare earth metal or an oxide thereof, characterized in, provides.
  • the present invention also provides: 3) In the case of a target composed of two or more kinds of rare earth metals or oxides thereof, the rare earth metal oxide having the highest hygroscopicity is used as a desiccant, or the rare earth metals or oxides thereof according to 2) above 4.
  • a method for storing a target comprising 4)
  • a method for carrying out sealing storage is vacuum sealing, wherein the target comprising a rare earth metal or oxide thereof according to any one of 1) to 3) above is characterized. 5.
  • Storage method 5) The rare earth metal or oxide thereof according to any one of 1) to 4) above, wherein the sealed storage means is a vacuum seal using a flexible film.
  • a method for storing a target In the case of a target composed of two or more kinds of rare earth metals or oxides thereof, the rare earth metal oxide having the highest hygroscopicity is used as a desiccant, or the rare earth metals or oxides thereof according to 2) above 4.
  • a method for storing a target comprising
  • the present invention provides 6) The rare earth metal according to any one of 1) to 5) above, wherein these are sealed by sealing with an inert gas having a dew point of ⁇ 80 ° C. or lower. 7. Method for storing a target made of oxide 7) Any one of 1) to 6) above, wherein the rare earth metal oxide used as a desiccant is placed or filled in a space generated during sealing. 8. A method for storing a target comprising the rare earth metal or oxide thereof according to any one of 8) to 8), wherein the rare earth metal constituting the target contains La or La. 9. A method for storing a target comprising a rare earth metal or an oxide thereof according to 9), wherein the rare earth metal oxide used as a desiccant is a La oxide.
  • Noble earth described in Metal or moisture intrusion of external moisture permeation or container flexible film storage method 10) used to seal storage target made of these oxides is the following 0.1g / m 2 ⁇ 24h
  • a method for storing a target comprising the rare earth metal or oxide thereof according to any one of 1) to 9) above is provided.
  • the la 2 O 3 target in a film is a diagram illustrating an example of a case where vacuum sealing.
  • rare earths particularly lanthanum and lanthanum oxides
  • lanthanum oxide is more hygroscopic than lanthanum, and when storing lanthanum targets, lanthanum oxide (sintered powder, plates, blocks, etc.) It is intended to prevent oxidation and hydroxylation of the lanthanum target body by applying, placing, or placing on the lantern.
  • lanthanum oxide target it is possible to absorb and remove moisture more effectively by encapsulating a powder with a larger surface area and granular lanthanum oxide. It is possible to prevent deterioration due to.
  • the method for storing a target comprising a rare earth metal or an oxide thereof according to the present invention is the same as the rare earth metal stored in a storage container or a film-like seal.
  • An oxide is introduced as a desiccant.
  • the lanthanum oxide reacts with water to be hydroxylated and powdered and adheres to the target surface, it is a compound of the same metal and is a powder, so it can be easily removed, causing contamination. Not. This is a significant advantage over the use of desiccants made of other metals.
  • a rare earth metal oxide that has higher hygroscopicity than the stored rare earth metal or its oxide target material is used as a desiccant for target storage. It can be introduced into a container or film-like seal, and the storage container or film-like seal can be sealed and stored.
  • a rare earth metal oxide having the highest hygroscopicity can also be used as a desiccant.
  • vacuum sealing can be used.
  • vacuum-sealing and storing it is desirable to replace the inside of the container or film-like seal once with an inert gas having a dew point of ⁇ 80 ° C. or lower and then vacuum-seal.
  • a flexible film can be used, and this can be vacuum-sealed as a sealed bag.
  • vacuum sealing has been described.
  • an inert gas having a dew point of ⁇ 80 ° C. or lower can be sealed and sealed. Both prevent outside air from entering.
  • the target is bonded to the backing plate.
  • the target when using a flexible film and vacuum-sealing it as a sealed bag, the target inevitably has a step between the backing plate, and the gap Is likely to occur. In such a gap, the outside air is easily stored. And it becomes easy to advance powdering of the target from there. It is desirable to fill such a step or void with a rare earth oxide serving as a desiccant.
  • the rare earth oxide serving as the desiccant is preferably a powder or granule having a large surface area in this sense.
  • simply placing a rare earth oxide blob in a place where the outside air can easily be stored is effective.
  • a general desiccant even if sealed in a moisture-permeable film, it is sufficiently effective.
  • the rare earth metal constituting the target is particularly effective for a lanthanum target or a target containing lanthanum.
  • the rare earth oxide used as the desiccant is lanthanum oxide.
  • lanthanum oxide which is most easily hydroxylated, is the most effective in suppressing the hydroxylation of a target made of rare earth metal or its oxide. It is expensive.
  • the moisture permeation amount of the flexible film used for sealed storage or the moisture intrusion amount from the outside of the container should be 0.1 g / m 2 ⁇ 24 h or less to prevent moisture from entering as much as possible.
  • Table 1 shows preferable examples of the flexible film used for sealed storage and other examples. From Table 1, those having characteristics more than GX barrier (trade name) are effective. As shown in Table 1, a GX barrier (trade name) and a bag containing Al foil are suitable. Table 1 shows typical examples, and it goes without saying that other flexible films can be used as long as the above conditions are satisfied.
  • Example 1 the La target is vacuum-packed, and La oxide powder is thinly filled on the surface and side surfaces.
  • FIG. 1 A specific example is shown in FIG.
  • the presence of the lanthanum oxide layer between the vacuum pack film and the La target allows moisture remaining inside the vacuum pack and moisture passing through the film to be lanthanum oxide powder.
  • lanthanum hydroxide which is effective in preventing the phenomenon that the surface of the La target reacts with moisture and becomes hydroxide to be pulverized.
  • Example 2 This is an example in which a La target is vacuum-packed and La oxide powder is placed in a stepped space from BP (like a silica gel bag). A specific example is shown in FIG. As shown in FIG. 2, in the vacuum pack, La oxide absorbs moisture remaining in the slightly remaining space and fixes it as lanthanum hydroxide, so that the La target reacts with moisture to become hydroxide and powder. This is effective in preventing the phenomenon that occurs.
  • Example 3 A La oxide target is placed in a metal container, and the target is filled with La oxide powder. Then, the surrounding air is temporarily replaced with argon having a dew point of ⁇ 80 ° C. or lower, and then vacuum sealed. A specific example of the stopped example is shown in FIG. As shown in FIG. 3, since lanthanum oxide absorbs moisture remaining after being evacuated and fixes it as lanthanum hydroxide, it is effective in preventing the phenomenon that La reacts with moisture to become hydroxide and powder. It is.
  • Example 4 A metal alloy target composed of La and Er is placed in a metal container, and then a sintered La oxide block is placed on the step between the target and BP, and the air in the container has a dew point of -80 ° C or less.
  • This is an example of evacuation after replacement with argon gas.
  • lanthanum oxide absorbs moisture remaining after being evacuated and is fixed as lanthanum hydroxide, which is effective in preventing the phenomenon that La reacts with moisture to form hydroxide and powder. It is.
  • the La 2 O 3 target is vacuum-sealed with a film.
  • a specific example is shown in FIG.
  • La oxide (La 2 O 3 ) absorbs moisture remaining in the slightly remaining space in the vacuum pack and fixes it as lanthanum hydroxide, so that the La 2 O 3 target reacts with moisture. It becomes a hydroxide and is pulverized.
  • the method for storing a target comprising a rare earth metal or its oxide according to the present invention does not cause such a problem.
  • the same rare earth metal oxide as the target comprising a rare earth metal or oxide stored therein is placed in a storage container or a film-like seal. Introduced as a desiccant. This effectively suppresses the state of reacting with moisture in the air and being covered with hydroxide white powder. This makes it possible to stably supply a target as an electronic material such as a metal gate material and a high dielectric constant material (High-k), which is extremely useful industrially.
  • High-k high dielectric constant material

Abstract

Disclosed is a method for storing a target comprising a rare earth metal or an oxide thereof.  The method is characterized in that an oxide of the same rare earth metal as one contained in the target to be stored is introduced, as a desiccant, into a storage container or a film-like sealing material for storing the target therein, the storage container or the film-like sealing material is sealed, and the sealed storage container or the sealed film-like sealing material is stored.  It becomes possible to provide a technique which enables the storage of a target comprising a rare earth metal or an oxide thereof for a long period by devising a method for storing the target so as to prevent the oxidation of the target upon the penetration of air or the dusting of the target caused by the hydroxylation of the target.

Description

希土類金属又はこれらの酸化物からなるターゲットの保管方法Storage method of target comprising rare earth metal or oxide thereof
　本発明は、酸化又は水酸化により粉化し易い希土類金属又はこれらの酸化物からなるターゲットの保管方法に関する。 The present invention relates to a method for storing a target comprising a rare earth metal that is easily powdered by oxidation or hydroxylation, or an oxide thereof.
希土類金属は、混合複合酸化物として地殻に含有されている。希土類金属は比較的希（まれ）に存在する鉱物から分離されたので、このような名称がついたが、地殻全体からみると決して希少ではない。最近、希土類金属が電子材料として着目されており、研究開発が進められている材料である。
この希土類金属の中では、特にランタン（Ｌａ）が注目されている。このランタンを簡単に紹介すると、ランタンの原子番号は５７、原子量１３８．９の白色の金属であり、常温で複六方最密構造を備えている。融点は９２１°Ｃ、沸点３５００°Ｃ、密度６．１５ｇ／ｃｍ３であり、空気中では表面が酸化され、水には徐々にとける。
熱水、酸に可溶である。延性はないが、展性はわずかにある。抵抗率は５．７０×１０－６Ωｃｍである。４４５°Ｃ以上で燃焼して酸化物（Ｌａ２Ｏ３）となる（理化学辞典参照）。希土類金属は、一般に酸化数３の化合物が安定であるが、ランタンも３価である。
このランタンは、メタルゲート材料、高誘電率材料（Ｈｉｇｈ－ｋ）等の、電子材料として注目されている金属である。ランタン以外の希土類金属も、このランタンに類似した属性を持っている。 The rare earth metal is contained in the earth's crust as a mixed composite oxide. Since rare earth metals were separated from relatively rare (rare) minerals, they were named as such, but they are not rare when viewed from the entire crust. Recently, rare earth metals have attracted attention as electronic materials, and are being researched and developed.
Among these rare earth metals, lanthanum (La) is particularly attracting attention. Briefly introducing this lanthanum, the lanthanum has an atomic number of 57 and an atomic weight of 138.9, and is a white metal with a double hexagonal close-packed structure at room temperature. The melting point is 921 ° C., the boiling point is 3500 ° C., and the density is 6.15 g / cm 3. The surface is oxidized in the air and gradually dissolved in water.
Soluble in hot water and acid. There is no ductility, but there is slight malleability. The resistivity is 5.70 × 10 −6 Ωcm. It burns at 445 ° C or higher to become oxide (La 2 O 3 ) (see Physics and Chemistry Dictionary). As for rare earth metals, compounds having an oxidation number of 3 are generally stable, but lanthanum is also trivalent.
This lanthanum is a metal attracting attention as an electronic material, such as a metal gate material and a high dielectric constant material (High-k). Rare earth metals other than lanthanum have attributes similar to this lanthanum.
ランタン等の希土類金属は、精製時に酸化し易いという問題があるため、高純度化が難しい材料である。また、ランタン等の希土類金属を空気中に放置した場合には短時間で酸化し変色するので、取り扱いが容易でないという問題がある。
最近、次世代のＭＯＳＦＥＴにおけるゲート絶縁膜として薄膜化が要求されているが、これまでゲート絶縁膜として使用されてきたＳｉＯ２では、トンネル効果によるリーク電流が増加し、正常動作が難しくなってきた。
このため、それに変わるものとして、高い誘電率、高い熱的安定性、シリコン中の正孔と電子に対して高いエネルギー障壁を有するＨｆＯ２、ＺｒＯ２、Ａｌ２Ｏ３、Ｌａ２Ｏ３が提案されている。特に、これらの材料の中でも、Ｌａ２Ｏ３の評価が高く、電気的特性を調査し、次世代のＭＯＳＦＥＴにおけるゲート絶縁膜としての研究報告がなされている（非特許文献１参照）。しかし、この特許文献の場合に、研究の対象となっているのは、Ｌａ２Ｏ３膜であり、Ｌａ金属の特性と挙動については、特に触れてはいない。 Since rare earth metals such as lanthanum have a problem that they are easily oxidized during purification, they are difficult materials to be highly purified. Further, when a rare earth metal such as lanthanum is left in the air, it is oxidized and discolored in a short time, so that there is a problem that handling is not easy.
Recently, thinning is required as a gate insulating film in next-generation MOSFETs, but in SiO 2 that has been used as a gate insulating film so far, leakage current due to a tunnel effect increases and normal operation has become difficult. .
For this reason, HfO 2 , ZrO 2 , Al 2 O 3 , La 2 O 3 having a high dielectric constant, high thermal stability, and a high energy barrier against holes and electrons in silicon are proposed. Has been. In particular, among these materials, La 2 O 3 is highly evaluated, electrical characteristics have been investigated, and research reports as a gate insulating film in next-generation MOSFETs have been made (see Non-Patent Document 1). However, in the case of this patent document, the object of research is the La 2 O 3 film, and the characteristics and behavior of La metal are not particularly mentioned.
このようにランタン等の希土類金属及びその酸化物については、まだ研究の段階にあると言えるが、このような希土類金属及びその酸化物の特性を調べる場合において、希土類金属及びその酸化物自体がスパッタリングターゲット材として存在すれば、基板上に希土類金属及びその酸化物の薄膜を形成することが可能であり、またシリコン基板との界面の挙動、さらには希土類金属化合物を形成して、高誘電率ゲート絶縁膜等の特性を調べることが容易であり、また製品としての自由度が増すという大きな利点を持つものである。 Thus, it can be said that the rare earth metals such as lanthanum and their oxides are still in the research stage, but when investigating the characteristics of such rare earth metals and their oxides, the rare earth metals and their oxides themselves are sputtered. If it exists as a target material, it is possible to form a thin film of rare earth metal and its oxide on the substrate, and also the behavior of the interface with the silicon substrate, and further the formation of a rare earth metal compound to form a high dielectric constant gate. It is easy to examine the characteristics of an insulating film and the like, and has a great advantage that the degree of freedom as a product is increased.
しかしながら、ランタンスパッタリングターゲットを作製しても、上記の通り、空気中で短時間に酸化してしまう。一般的に金属ターゲット表面には安定な酸化皮膜が形成されるが、通常は非常に薄いため、スパッタリング初期に剥がれ落ち、スパッタリング特性に大きな影響を与えることはない。しかし、ランタンスパッタリングターゲットでは、酸化皮膜が厚くなって、電気伝導度の低下が起き、スパッタリングの不良を招く。
また、空気中に長時間放置しておくと、空気中の水分と反応して水酸化物の白い粉で覆われ、最終的には粉化してしまう状態に至り、正常なスパッタリングができないという問題すら起こる。このために、ターゲット作製後、すぐ真空パックするか又は油脂で覆い、酸化及び水酸化防止策を講ずる必要がある。
希土類金属の保管方法としては、大気との接触を避けるために鉱物性油中での保管が一般的であるが、スパッタリングターゲットとして使用する場合、使用前に鉱物油を取り除くため洗浄する必要がある。ところが、前記のような酸素、水分、二酸化炭素との反応性から洗浄自体が難しいという問題がある。
従って、通常、真空パックによる保管・梱包することが必要となる。ところが、真空パックをした状態でも、使用するフィルムを透過するわずかな水分によっても、酸化・水酸化による粉化が進行するので、スパッタリングターゲットとして使用可能な状態での長期間の保管が困難であった。 However, even if a lanthanum sputtering target is produced, it is oxidized in the air in a short time as described above. In general, a stable oxide film is formed on the surface of a metal target. However, since it is usually very thin, it peels off at the initial stage of sputtering and does not significantly affect the sputtering characteristics. However, in the lanthanum sputtering target, the oxide film becomes thick, the electric conductivity is lowered, and the sputtering is defective.
Also, if left in the air for a long time, it reacts with the moisture in the air and is covered with a white powder of hydroxide, eventually resulting in a powdered state, and normal sputtering is not possible Even it happens. For this reason, it is necessary to vacuum-pack or cover with oils and fats immediately after producing the target, and to take measures to prevent oxidation and hydroxylation.
As a rare earth metal storage method, it is common to store in mineral oil in order to avoid contact with the atmosphere, but when used as a sputtering target, it is necessary to clean the mineral oil before use. . However, there is a problem that cleaning itself is difficult due to the reactivity with oxygen, moisture, and carbon dioxide as described above.
Therefore, it is usually necessary to store and pack with a vacuum pack. However, even in a vacuum-packed state, even with a slight amount of moisture that permeates the film to be used, pulverization due to oxidation and hydroxylation proceeds, making it difficult to store for a long time in a usable state as a sputtering target. It was.
従来の公知技術を見ると、ホローカソード型スパッタリングターゲットを樹脂の袋で覆う方法（特許文献１参照）、プラスチックスフィルムの保護膜をターゲットに貼り付ける方法（特許文献２参照）、離脱性パーティクルが存在しない表面のフィルムを用いてターゲットを梱包する方法（特許文献３参照）、透明のアクリル樹脂の上蓋を用いてターゲットの保管容器を作製し、ねじ止めする方法（特許文献４参照）、スパッタリングターゲットを袋状物に封入する方法（特許文献５参照）がある。しかし、これらは樹脂の蓋又は樹脂性のフィルムを用いてターゲットを封入するもので、希土類金属又はその酸化物からなるターゲットの保管方法としては、十分ではない。
徳光永輔、外２名著、「Ｈｉｇｈ－ｋ ゲート絶縁膜用酸化物材料の研究」電気学会電子材料研究会資料、Ｖｏｌ．６－１３、Ｐａｇｅ．３７－４１、２００１年９月２１日発行 国際公開ＷＯ２００５／０３７６４９公報 特開２００２－２１２７１８号公報 特開２００１－２４０９５９号公報 特開平８－２４６１３５号公報 特開平４－２３１４６１号公報 Looking at conventional known techniques, a method of covering a hollow cathode sputtering target with a resin bag (see Patent Document 1), a method of attaching a protective film of a plastic film to a target (see Patent Document 2), A method of packing a target using a nonexistent surface film (see Patent Document 3), a method of producing a target storage container using a transparent acrylic resin top cover and screwing (see Patent Document 4), a sputtering target There is a method (see Patent Document 5) that encloses a bag-like material. However, these enclose the target using a resin lid or a resinous film, and are not sufficient as a method for storing a target made of a rare earth metal or its oxide.
Eisuke Tokumitsu and 2 other authors, "Studies on oxide materials for high-k gate insulating films", Electrochemical Society of Japan, Materials for Electronic Materials, Vol. 6-13, Page. 37-41, issued on September 21, 2001 International Publication WO2005 / 037649 Japanese Patent Laid-Open No. 2002-212718 JP 2001-240959 A JP-A-8-246135 JP-A-4-231461
本発明は、希土類金属又はその酸化物からなるターゲットの保管方法を工夫し、空気の残留及び侵入によるターゲットの酸化及び水酸化による粉化を抑制して、スパッタリングターゲットとして使用可能な状態での長期間の保管が可能となる技術を提供することを課題とする。 The present invention devised a method for storing a target made of a rare earth metal or its oxide, and suppresses oxidization of the target due to residual and intrusion of air and pulverization due to hydroxylation, so that it can be used as a sputtering target. It is an object of the present invention to provide a technique capable of storing a period.
本発明は、
１）希土類金属又はこれらの酸化物からなるスパッタリングターゲットの保管方法であって、当該ターゲットの保管用の容器又はフィルム状のシールの中に、保管される希土類金属又はこれらの酸化物からなるターゲットと同じ希土類金属の酸化物を乾燥剤として導入し、前記保管用の容器又はフィルム状のシールを封止して保管することを特徴とする希土類金属又はその酸化物からなるターゲットの保管方法
２）希土類金属又はこれらの酸化物からなるターゲットの保管方法であって、当該ターゲットの保管用の容器又はフィルム状のシールの中に、保管される希土類金属又はこれらの酸化物ターゲット材料よりも、吸湿性が大きい希土類金属酸化物を乾燥剤として導入し、前記保管用の容器又はフィルム状のシールを封止して保管することを特徴とする希土類金属又はこれらの酸化物からなるターゲットの保管方法、を提供する。 The present invention
1) A method for storing a sputtering target comprising a rare earth metal or an oxide thereof, and a target comprising a rare earth metal or an oxide thereof stored in a container or film seal for storage of the target The same rare earth metal oxide is introduced as a desiccant, and the storage container or the film-like seal is sealed and stored. A method for storing a target comprising a metal or an oxide thereof, wherein the hygroscopic property is higher than that of a rare earth metal or an oxide target material stored in a container or film-like seal for storing the target. A large rare earth metal oxide is introduced as a desiccant, and the container for storage or the film-like seal is sealed and stored. Target storage method of a rare earth metal or an oxide thereof, characterized in, provides.
また、本発明は、
３）２種以上の希土類金属又はこれらの酸化物からなるターゲットの場合、吸湿性が最も大きい希土類金属酸化物を乾燥剤として用いることを特徴とする上記２）記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法
４）封止保管する方法が、真空封止であることを特徴とする上記１）～３）のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法
５）封止保管する手段が、可撓性フィルムを用いた真空シールであることを特徴とする上記１）～４）のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法、を提供する。 The present invention also provides:
3) In the case of a target composed of two or more kinds of rare earth metals or oxides thereof, the rare earth metal oxide having the highest hygroscopicity is used as a desiccant, or the rare earth metals or oxides thereof according to 2) above 4. A method for storing a target comprising 4) A method for carrying out sealing storage is vacuum sealing, wherein the target comprising a rare earth metal or oxide thereof according to any one of 1) to 3) above is characterized. 5. Storage method 5) The rare earth metal or oxide thereof according to any one of 1) to 4) above, wherein the sealed storage means is a vacuum seal using a flexible film. A method for storing a target.
さらに、本発明は、
６）封止保管する方法が、露点－８０°Ｃ以下の不活性ガスを封入して封止することを特徴とする上記１）～５）のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法
７）乾燥剤として用いる上記希土類金属酸化物を、封止される際に生じる空間に載置又は充填することを特徴とする上記１）～６）のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法
８）上記ターゲットを構成する希土類金属が、Ｌａ又はＬａを含有することを特徴とする上記１）～７）のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法
９）乾燥剤として用いる上記希土類金属酸化物が、Ｌａ酸化物であることを特徴とする上記１）～８）のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法
１０）封止保管に使用する可撓性フィルムの水分透過量又は容器の外部からの水分侵入量が、０．１ｇ／ｍ２・２４ｈ以下であることを特徴とする上記１）～９）のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法、を提供する。 Furthermore, the present invention provides
6) The rare earth metal according to any one of 1) to 5) above, wherein these are sealed by sealing with an inert gas having a dew point of −80 ° C. or lower. 7. Method for storing a target made of oxide 7) Any one of 1) to 6) above, wherein the rare earth metal oxide used as a desiccant is placed or filled in a space generated during sealing. 8. A method for storing a target comprising the rare earth metal or oxide thereof according to any one of 8) to 8), wherein the rare earth metal constituting the target contains La or La. 9. A method for storing a target comprising a rare earth metal or an oxide thereof according to 9), wherein the rare earth metal oxide used as a desiccant is a La oxide. Noble earth described in Metal or moisture intrusion of external moisture permeation or container flexible film storage method 10) used to seal storage target made of these oxides is the following 0.1g / m 2 · 24h A method for storing a target comprising the rare earth metal or oxide thereof according to any one of 1) to 9) above is provided.
従来の希土類金属又はこれらの酸化物からなるターゲットを密閉容器又はプラスチックス性のフィルムに封止して保管する場合に、長時間放置しておくと、酸素及び水分と反応して水酸化物の白い粉で覆われるという状態になり、正常なスパッタリングができなくなる問題が発生するが、本発明の保管用の容器又はフィルム状のシールの中に保管したターゲットは、このような問題を発生しない、という大きな効果を有する。 When storing a target made of a rare earth metal or an oxide thereof in a hermetically sealed container or a plastic film and storing it for a long time, it reacts with oxygen and moisture to form a hydroxide. It becomes a state of being covered with white powder, and there is a problem that normal sputtering cannot be performed, but the target stored in the storage container or the film-like seal of the present invention does not cause such a problem. It has a great effect.
Ｌａ酸化物粉末をＬａターゲットの表面と側面に薄く充填し、これを真空パックした場合の例を示す図である。It is a figure which shows the example at the time of carrying out thin filling with the La oxide powder on the surface and side surface of a La target, and vacuum-packing this. Ｌａ酸化物粉末をＬａターゲットとＢＰとの段差の空間に置いて真空パックした例を示す図である。It is a figure which shows the example which put La oxide powder in the space of the level | step difference of La target and BP, and was vacuum-packed. 金属製の容器内にＬａターゲットを配置し、このＬａターゲットの周囲にＬａ酸化物粉末を充填し、周囲の空気を一旦露点－８０°Ｃ以下のアルゴンで置換したのち真空封止した例を示す図である。An example is shown in which a La target is placed in a metal container, a La oxide powder is filled around the La target, the surrounding air is once replaced with argon having a dew point of −80 ° C. or lower, and then vacuum sealed. FIG. 金属製の容器内にＬａとＥｒからなる金属合金ターゲットと配置し、次に該ターゲットとＢＰとの段差に焼結したＬａ酸化物のブロックを置き、容器内の空気をアルゴンガスで置換した後、真空引きした例を示す図である。After placing a metal alloy target composed of La and Er in a metal container, and then placing a block of sintered La oxide on the step between the target and BP, and replacing the air in the container with argon gas It is a figure which shows the example evacuated. Ｌａターゲットを、フィルムで真空封止した場合の例を示す図である。It is a figure which shows the example at the time of vacuum-sealing a La target with a film. Ｌａターゲットをフィルムで真空封止し、乾燥剤として（シリカゲル）をおいた場合の例を示す図である。It is a figure which shows the example at the time of vacuum-sealing a La target with a film and putting (silica gel) as a desiccant. Ｌａ２Ｏ３ターゲットをフィルムで真空封止した場合の例を示す図である。The la 2 O 3 target in a film is a diagram illustrating an example of a case where vacuum sealing.
希土類、特にランタン及びランタンの酸化物は極めて吸湿性（水分との反応性）が強いことが知られている。そのため、これまでランタンおよびランタン酸化物を以下に吸湿させないか、水分の少ない環境で保管するかが、課題であった。
ところがランタンよりもランタン酸化物の方が、より吸湿性が高いことを逆に利用し、ランタンターゲットを保管する際に、ランタン酸化物（粉末、板・ブロックなどの焼結体）を、ターゲット表面にまぶしたり、載せたり、置いたりすることにより、ランタンターゲット本体の酸化・水酸化を防止するものである。
また、ランタン酸化物ターゲットを保管する場合には、より表面積の多い粉末、顆粒状のランタン酸化物を封入することにより、より効果的に水分を吸収、除去することが出来るため、ターゲットの水酸化による劣化を防止することが出来る。 It is known that rare earths, particularly lanthanum and lanthanum oxides, are extremely hygroscopic (reactive with moisture). Therefore, until now, it has been a problem to prevent lanthanum and lanthanum oxide from absorbing moisture below or to store them in an environment with little moisture.
However, lanthanum oxide is more hygroscopic than lanthanum, and when storing lanthanum targets, lanthanum oxide (sintered powder, plates, blocks, etc.) It is intended to prevent oxidation and hydroxylation of the lanthanum target body by applying, placing, or placing on the lantern.
In addition, when storing a lanthanum oxide target, it is possible to absorb and remove moisture more effectively by encapsulating a powder with a larger surface area and granular lanthanum oxide. It is possible to prevent deterioration due to.
すなわち、本発明の希土類金属又はこれらの酸化物からなるターゲットの保管方法は、保管用の容器又はフィルム状のシールの中に、保管される希土類金属又はこれらの酸化物ターゲットと、同一希土類金属の酸化物を乾燥剤として導入するものである。
このとき、ランタン酸化物が水分と反応して水酸化し粉末化してターゲット表面に付着したとしても、同一金属の化合物であり、かつ粉末であるため、除去が容易であることから、汚染の原因とならない。この点が他の金属から成る乾燥剤を使用する場合に比べて顕著な優位点である。 That is, the method for storing a target comprising a rare earth metal or an oxide thereof according to the present invention is the same as the rare earth metal stored in a storage container or a film-like seal. An oxide is introduced as a desiccant.
At this time, even if the lanthanum oxide reacts with water to be hydroxylated and powdered and adheres to the target surface, it is a compound of the same metal and is a powder, so it can be easily removed, causing contamination. Not. This is a significant advantage over the use of desiccants made of other metals.
また、他の希土類金属による汚染が特に問題とならない場合には、保管される希土類金属又はその酸化物ターゲット材料よりも、吸湿性が大きい希土類金属の酸化物を乾燥剤として、ターゲットの保管用の容器又はフィルム状のシールの中に導入し、前記保管用の容器又はフィルム状のシールを封止して保管することが可能である。
２種以上の希土類金属又はそれらの酸化物からなるターゲットの場合、吸湿性が最も大きい希土類金属酸化物を乾燥剤として用いることもできる。 In addition, when contamination with other rare earth metals is not particularly problematic, a rare earth metal oxide that has higher hygroscopicity than the stored rare earth metal or its oxide target material is used as a desiccant for target storage. It can be introduced into a container or film-like seal, and the storage container or film-like seal can be sealed and stored.
In the case of a target composed of two or more kinds of rare earth metals or oxides thereof, a rare earth metal oxide having the highest hygroscopicity can also be used as a desiccant.
封止・保管する方法については、極力外気が入らないようにすることがより好ましいことであり、その方法の一つとして、真空封止とすることができる。また、真空封止・保管するとき、容器又はフィルム状のシールの中を、一旦露点－８０°Ｃ以下の不活性ガスで置換した後、真空封止することが望ましい。封止保管する手段としては、可撓性フィルムを用い、これを密閉状の袋として真空シールすることができる。
上記においては、真空封止について説明したが、保管する方法として、露点－８０°Ｃ以下の不活性ガスを封入して封止することもできる。いずれも外気の侵入を防ぐものである。 About the method of sealing and storing, it is more preferable to prevent outside air from entering as much as possible, and as one of the methods, vacuum sealing can be used. Further, when vacuum-sealing and storing, it is desirable to replace the inside of the container or film-like seal once with an inert gas having a dew point of −80 ° C. or lower and then vacuum-seal. As a means for sealing and storing, a flexible film can be used, and this can be vacuum-sealed as a sealed bag.
In the above description, vacuum sealing has been described. However, as a storage method, an inert gas having a dew point of −80 ° C. or lower can be sealed and sealed. Both prevent outside air from entering.
このように、外気と遮断し、なるべく外気の湿気の侵入を抑制するが、わずかな侵入があっても、乾燥剤として用いる上記希土類酸化物を、封止される際に生じる空間に載置又は充填することによって、ターゲット本体の水酸化を抑制することが可能となる。
一般に、ターゲットはバッキングプレートに接合されるが、これを例えば、可撓性フィルムを用い、これを密閉状の袋として真空シールする場合には、どうしてもターゲットはバッキングプレートの間に段差ができ、空隙が発生し易い。このような空隙には、外気が貯留し易くなる。そして、そこからターゲットの粉状化が進み易くなる。このような段差又は空隙に、乾燥剤となる希土類酸化物を充填することが望ましい。
この乾燥剤となる希土類酸化物は、この意味で表面積が大きい粉末又は顆粒状が良いことは理解できるであろう。しかし、外気が貯留し易い場所に、希土類酸化物の小塊を置くだけでも、効果がある。
また、希土類酸化物とターゲットは直接触れるように置くのが最も効果的であるが、ターゲット表面への粉末の附着は、スパッタリング中のパーティクル発生の原因となり得る。そのような場合は、一般的な乾燥剤のように、透湿性のフィルムにパックした状態で封入しても十分効果がある。 In this way, it shuts off from the outside air and suppresses the entry of moisture in the outside air as much as possible, but even if there is a slight intrusion, the rare earth oxide used as a desiccant is placed in the space generated when sealed or By filling, it becomes possible to suppress hydroxylation of the target body.
In general, the target is bonded to the backing plate. For example, when using a flexible film and vacuum-sealing it as a sealed bag, the target inevitably has a step between the backing plate, and the gap Is likely to occur. In such a gap, the outside air is easily stored. And it becomes easy to advance powdering of the target from there. It is desirable to fill such a step or void with a rare earth oxide serving as a desiccant.
It will be understood that the rare earth oxide serving as the desiccant is preferably a powder or granule having a large surface area in this sense. However, simply placing a rare earth oxide blob in a place where the outside air can easily be stored is effective.
Moreover, it is most effective to place the rare earth oxide and the target in direct contact with each other, but the adhesion of the powder to the surface of the target may cause generation of particles during sputtering. In such a case, as with a general desiccant, even if sealed in a moisture-permeable film, it is sufficiently effective.
本願発明ターゲットの保管方法においては、ターゲットを構成する希土類金属が、ランタンターゲット又はランタンを含有するターゲットに、特に有効である。また、乾燥剤として用いる上記希土類酸化物は、ランタン酸化物である。これは皮肉な話ではあるが、希土類金属又はその酸化物からなるターゲットの保管方法として、最も水酸化され易いランタン酸化物が、最も希土類金属又はその酸化物からなるターゲットの水酸化の抑制効果が高いということである。
封止保管に使用する可撓性フィルムの水分透過量又は容器の外部からの水分侵入量を、０．１ｇ／ｍ２・２４ｈ以下とし、極力水分の浸入を防ぐことも、希土類金属又はその酸化物からなるターゲットの保管方法として、重要である。
封止保管に使用する可撓性フィルムの好適な例と、それ以外の例を表１に示す。この表１からは、ＧＸバリア（商品名）以上の特性を持つものが有効である。表１に示すように、ＧＸバリア（商品名）とＡｌフォイル入り袋が好適である。表１は代表的な例を示すものであり、上記の条件を満たすものであれば、他の可撓性フィルムを使用できることは言うまでも無い。 In the method for storing a target of the present invention target, the rare earth metal constituting the target is particularly effective for a lanthanum target or a target containing lanthanum. The rare earth oxide used as the desiccant is lanthanum oxide. Although this is an irony story, as a method of storing a target made of rare earth metal or its oxide, lanthanum oxide, which is most easily hydroxylated, is the most effective in suppressing the hydroxylation of a target made of rare earth metal or its oxide. It is expensive.
The moisture permeation amount of the flexible film used for sealed storage or the moisture intrusion amount from the outside of the container should be 0.1 g / m 2 · 24 h or less to prevent moisture from entering as much as possible. It is important as a method for storing targets made of objects.
Table 1 shows preferable examples of the flexible film used for sealed storage and other examples. From Table 1, those having characteristics more than GX barrier (trade name) are effective. As shown in Table 1, a GX barrier (trade name) and a bag containing Al foil are suitable. Table 1 shows typical examples, and it goes without saying that other flexible films can be used as long as the above conditions are satisfied.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　次に、本願発明を実施した場合の例について説明する。なお、この例は理解を容易にするためのものであり、本発明を制限するものではない。すなわち、本発明の技術思想の範囲内における、他の例及び変形は、本発明に含まれるものである。 Next, an example when the present invention is implemented will be described. Note that this example is for easy understanding, and does not limit the present invention. That is, other examples and modifications within the scope of the technical idea of the present invention are included in the present invention.
（実施例１）
Ｌａターゲットを真空パックし、Ｌａ酸化物粉末を表面と側面に薄く充填した場合の例である。この具体例を、図１に示す。
　図１に示すように、真空パックのフィルムとＬａターゲットとの間に酸化ランタンの層が存在することにより、真空パック内側に残留している水分及び、フィルムを透過してくる水分は酸化ランタン粉末に吸収され、水酸化ランタンとして固定されるため、Ｌａターゲット表面が水分と反応して水酸化物となって粉化する現象の防止に有効である。 Example 1
In this example, the La target is vacuum-packed, and La oxide powder is thinly filled on the surface and side surfaces. A specific example is shown in FIG.
As shown in FIG. 1, the presence of the lanthanum oxide layer between the vacuum pack film and the La target allows moisture remaining inside the vacuum pack and moisture passing through the film to be lanthanum oxide powder. And is fixed as lanthanum hydroxide, which is effective in preventing the phenomenon that the surface of the La target reacts with moisture and becomes hydroxide to be pulverized.
（実施例２）
Ｌａターゲットを真空パックし、Ｌａ酸化物粉末を（シリカゲルの袋のように）ＢＰとの段差の空間に置いた例である。この具体例を、図２に示す。
図２に示すように、真空パックにおいて、わずかに残る空間に残留する水分をＬａ酸化物が吸収、水酸化ランタンとして固定するため、Ｌａターゲットが水分と反応して水酸化物となって粉化する現象の防止に有効である。 (Example 2)
This is an example in which a La target is vacuum-packed and La oxide powder is placed in a stepped space from BP (like a silica gel bag). A specific example is shown in FIG.
As shown in FIG. 2, in the vacuum pack, La oxide absorbs moisture remaining in the slightly remaining space and fixes it as lanthanum hydroxide, so that the La target reacts with moisture to become hydroxide and powder. This is effective in preventing the phenomenon that occurs.
（実施例３）
金属製の容器内にＬａ酸化物ターゲットを設置し、該ターゲットの周囲にＬａ酸化物粉末で充填した後、周囲の空気をいったん露点－８０°Ｃ以下のアルゴンで置換し、さらにそれを真空封止した例の具体例を図３に示す。
図３に示すように、真空にひいた後に残留する水分を酸化ランタンが吸収し、水酸化ランタンとして固定するため、Ｌａが水分と反応し水酸化物となって粉化する現象の防止に有効である。 (Example 3)
A La oxide target is placed in a metal container, and the target is filled with La oxide powder. Then, the surrounding air is temporarily replaced with argon having a dew point of −80 ° C. or lower, and then vacuum sealed. A specific example of the stopped example is shown in FIG.
As shown in FIG. 3, since lanthanum oxide absorbs moisture remaining after being evacuated and fixes it as lanthanum hydroxide, it is effective in preventing the phenomenon that La reacts with moisture to become hydroxide and powder. It is.
（実施例４）
金属製の容器内にＬａとＥｒからなる金属合金ターゲットと配置し、次に該ターゲットとＢＰとの段差に焼結したＬａ酸化物のブロックを置き、容器内の空気を露点－８０°Ｃ以下のアルゴンガスで置換した後、真空引きした例である。
図４に示すように、真空にひいた後に残留する水分を酸化ランタンが吸収し、水酸化ランタンとして固定するため、Ｌａが水分と反応し水酸化物となって粉化する現象の防止に有効である。 Example 4
A metal alloy target composed of La and Er is placed in a metal container, and then a sintered La oxide block is placed on the step between the target and BP, and the air in the container has a dew point of -80 ° C or less. This is an example of evacuation after replacement with argon gas.
As shown in FIG. 4, lanthanum oxide absorbs moisture remaining after being evacuated and is fixed as lanthanum hydroxide, which is effective in preventing the phenomenon that La reacts with moisture to form hydroxide and powder. It is.
（比較例１）
Ｌａターゲットをフィルムで真空封止した場合である。この具体例を図５に示す。図５に示すように、真空パックフィルムとターゲットの間に出来た空間に僅かに残留している水分とＬａターゲット反応して、ランタン水酸化物になり、粉化した。 (Comparative Example 1)
This is a case where the La target is vacuum-sealed with a film. A specific example is shown in FIG. As shown in FIG. 5, the La target reacted with the water slightly remaining in the space formed between the vacuum pack film and the target to become lanthanum hydroxide and powdered.
（比較例２）
Ｌａターゲットをフィルムで真空封止し、乾燥剤として（シリカゲル）をおいた場合である。この具体例を図６に示す。
図６に示すように、シリカゲルを置いた場合は、シリカゲルのない場合よりも早く粉化した。これは、シリカゲルが吸着している水分が脱離し、真空パックフィルム中に放出されるため、水分とＬａとの反応が促進されてランタン水酸化物になったと考えられる。このことから、一般に乾燥剤として使用するシリカゲルは、希土類金属又は希土類金属酸化物の粉化現象の防止には役に立たず、むしろ好ましくないことが分かる。 (Comparative Example 2)
This is a case where the La target is vacuum-sealed with a film and (silica gel) is placed as a desiccant. A specific example is shown in FIG.
As shown in FIG. 6, when silica gel was placed, it was pulverized faster than when no silica gel was present. This is presumably because the moisture adsorbed by the silica gel was desorbed and released into the vacuum pack film, so that the reaction between moisture and La was promoted to lanthanum hydroxide. This indicates that silica gel generally used as a desiccant is not useful for preventing the rare earth metal or rare earth metal oxide powdering phenomenon, and is rather undesirable.
（比較例３）
この例は、Ｌａ２Ｏ３ターゲットをフィルムで真空封止した場合である。この具体例を図７に示す。図７に示すように、真空パック内の、わずかに残る空間に残留する水分をＬａ酸化物（Ｌａ２Ｏ３）が吸収、水酸化ランタンとして固定するため、Ｌａ２Ｏ３ターゲットが水分と反応して水酸化物となって粉化する。 (Comparative Example 3)
In this example, the La 2 O 3 target is vacuum-sealed with a film. A specific example is shown in FIG. As shown in FIG. 7, La oxide (La 2 O 3 ) absorbs moisture remaining in the slightly remaining space in the vacuum pack and fixes it as lanthanum hydroxide, so that the La 2 O 3 target reacts with moisture. It becomes a hydroxide and is pulverized.
以上の実施例と比較例から明らかなように、希土類金属又はこれらの酸化物からなるターゲットの保管に際して、密封容器又はシール内に、保管される希土類金属又はこれらの酸化物からなるターゲットと同じ希土類金属の酸化物を乾燥剤として導入することは、極めて有効であることが分かる。これによって、空気の残留及び侵入によるターゲットの酸化及び水酸化による粉化を効果的に抑制可能となる。 As is clear from the above examples and comparative examples, when storing a target made of rare earth metal or an oxide thereof, the same rare earth as the target made of the rare earth metal or an oxide stored in a sealed container or seal is stored. It can be seen that introducing a metal oxide as a desiccant is extremely effective. As a result, it is possible to effectively suppress oxidization and pulverization of the target due to air remaining and intrusion.
従来、希土類金属及び希土類金属の酸化物スパッタリングターゲットを、空気中に長時間放置しておくと、空気中の水分と反応して水酸化物の白い粉で覆われるという状態になり、正常なスパッタリングができないという問題が起きるが、本発明の希土類金属又はその酸化物からなるターゲットの保管方法は、このような問題を発生しない。
本発明の希土類金属又はその酸化物からなるターゲットの保管方法は、保管用の容器又はフィルム状のシールの中に、保管される希土類金属又はその酸化物からなるターゲットと同じ希土類金属の酸化物を乾燥剤として導入するものである。これによって、空気中の水分と反応して水酸化物の白い粉で覆われるという状態を効果的に抑制できる。
これによって、メタルゲート材料、高誘電率材料（Ｈｉｇｈ－ｋ）等の、電子材料として、ターゲットの安定供給が可能となり、産業上極めて有用である。 Conventionally, if a rare earth metal and rare earth metal oxide sputtering target is left in the air for a long time, it will react with moisture in the air and will be covered with white hydroxide powder. However, the method for storing a target comprising a rare earth metal or its oxide according to the present invention does not cause such a problem.
In the method for storing a target comprising a rare earth metal or oxide thereof according to the present invention, the same rare earth metal oxide as the target comprising a rare earth metal or oxide stored therein is placed in a storage container or a film-like seal. Introduced as a desiccant. This effectively suppresses the state of reacting with moisture in the air and being covered with hydroxide white powder.
This makes it possible to stably supply a target as an electronic material such as a metal gate material and a high dielectric constant material (High-k), which is extremely useful industrially.

Claims (10)

  1. 　希土類金属又はこれらの酸化物からなるターゲットの保管方法であって、当該ターゲットの保管用の容器又はフィルム状のシールの中に、保管される希土類金属又はこれらの酸化物からなるターゲットと同じ希土類金属の酸化物を乾燥剤として導入し、前記保管用の容器又はフィルム状のシールを封止して保管することを特徴とする希土類金属又はこれらの酸化物からなるターゲットの保管方法。 A method for storing a target comprising a rare earth metal or an oxide thereof, wherein the rare earth metal is the same as the target comprising a rare earth metal or an oxide stored in a container or film seal for storing the target. A storage method of a target comprising a rare earth metal or an oxide thereof, wherein the oxide is introduced as a desiccant and the container for storage or the film-like seal is sealed and stored.
  2. 　希土類金属又はこれらの酸化物からなるターゲットの保管方法であって、当該ターゲットの保管用の容器又はフィルム状のシールの中に、保管される希土類金属又はこれらの酸化物ターゲット材料よりも、吸湿性が大きい希土類金属酸化物を乾燥剤として導入し、前記保管用の容器又はフィルム状のシールを封止して保管することを特徴とする希土類金属又はこれらの酸化物からなるターゲットの保管方法。 A method for storing a target comprising a rare earth metal or an oxide thereof, wherein the target is stored in a container or a film-like seal, and is more hygroscopic than a rare earth metal or an oxide target material stored therein. A method for storing a target comprising a rare earth metal or an oxide thereof, wherein a rare earth metal oxide having a large particle size is introduced as a desiccant and the container or film-like seal for storage is sealed and stored.
  3. ２種以上の希土類金属又はこれらの酸化物からなるターゲットの場合、吸湿性が最も大きい希土類金属の酸化物を乾燥剤として用いることを特徴とする請求項２記載の希土類金属又はこれらの酸化物ターゲットの保管方法。 3. The rare earth metal or oxide target according to claim 2, wherein a rare earth metal oxide having the highest hygroscopicity is used as a desiccant in the case of a target composed of two or more rare earth metals or oxides thereof. Storage method.
  4. 　封止保管する方法が、真空封止であることを特徴とする請求項１～３のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法。 The method for storing a target comprising a rare earth metal or an oxide thereof according to any one of claims 1 to 3, wherein the sealed storage method is vacuum sealing.
  5. 　封止保管する手段が、可撓性フィルムを用いた真空シールであることを特徴とする請求項１～４のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法。 The method for storing a target comprising a rare earth metal or an oxide thereof according to any one of claims 1 to 4, wherein the means for sealing and storing is a vacuum seal using a flexible film.
  6. 　封止保管する方法が、露点－８０°Ｃ以下の不活性ガスを封入して封止することを特徴とする請求項１～５のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法。 The rare earth metal or oxide thereof according to any one of claims 1 to 5, wherein the sealed storage is performed by sealing with an inert gas having a dew point of -80 ° C or lower. The target storage method.
  7. 　乾燥剤として用いる上記希土類金属酸化物を、封止される際に生じる空間に載置又は充填することを特徴とする請求項１～６のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法。 7. The rare earth metal or oxide thereof according to any one of claims 1 to 6, wherein the rare earth metal oxide used as a desiccant is placed or filled in a space generated when sealed. A target storage method consisting of:
  8. 上記ターゲットを構成する希土類金属が、Ｌａ又はＬａを含有することを特徴とする請求項１～７のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法。 The method for storing a target comprising a rare earth metal or an oxide thereof according to any one of claims 1 to 7, wherein the rare earth metal constituting the target contains La or La.
  9. 乾燥剤として用いる上記希土類金属酸化物が、Ｌａ酸化物であることを特徴とする請求項１～８のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法。 The method for storing a target comprising a rare earth metal or an oxide thereof according to any one of claims 1 to 8, wherein the rare earth metal oxide used as a desiccant is La oxide.
  10. 封止保管に使用する可撓性フィルムの水分透過量又は容器の外部からの水分侵入量が、０．１ｇ／ｍ２・２４ｈ以下であることを特徴とする請求項１～９のいずれか一項に記載の希土類金属又はこれらの酸化物からなるターゲットの保管方法。 The moisture permeation amount of the flexible film used for sealed storage or the moisture penetration amount from the outside of the container is 0.1 g / m 2 · 24 h or less, characterized in that it is not more than one. A method for storing a target comprising the rare earth metal or the oxide thereof according to item 2.
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WO2012117834A1 (en) 2011-03-01 2012-09-07 Jx日鉱日石金属株式会社 Method for storing metallic lanthanum target, vacuum-sealed metallic lanthanum target, and thin film formed by sputtering using metallic lanthanum target
EP2682497A1 (en) * 2011-03-01 2014-01-08 JX Nippon Mining & Metals Corporation Method for storing metallic lanthanum target, vacuum-sealed metallic lanthanum target, and thin film formed by sputtering using metallic lanthanum target
EP2682497A4 (en) * 2011-03-01 2014-08-13 Jx Nippon Mining & Metals Corp Method for storing metallic lanthanum target, vacuum-sealed metallic lanthanum target, and thin film formed by sputtering using metallic lanthanum target
JP5583777B2 (en) * 2011-03-01 2014-09-03 Ｊｘ日鉱日石金属株式会社 Method for storing metallic lanthanum target and vacuum sealed metallic lanthanum target
JP2014167167A (en) * 2011-03-01 2014-09-11 Jx Nippon Mining & Metals Corp Storage method of metal lanthanum target, vacuum-sealed metal lanthanum target, and thin film formed by sputtering using metal lanthanum target

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JP5032662B2 (en) 2012-09-26
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KR20110047235A (en) 2011-05-06
JPWO2010050409A1 (en) 2012-03-29
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TW201016551A (en) 2010-05-01
US20110162322A1 (en) 2011-07-07

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