201016551 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種因氧化或氫氧化而容易粉末化之由 稀土金屬或稀土金屬之氧化物所構成之靶的保存方法。 【先前技術】[Technical Field] The present invention relates to a method for preserving a target composed of an oxide of a rare earth metal or a rare earth metal which is easily powdered by oxidation or hydrogenation. [Prior Art]
稀土金屬，係以混合複合氧化物之形態而含有於地殼 中。稀土金屬由於係分離自較稀有存在的礦物，故被冠以 此種名稱，但就地殼總體而言絕不稀少。最近，稀土金屬 係作為電子材料而受到矚目’為受到研究開發中的材料。 。此稀土金屬之中，鑭（La)特別受到矚目。在此對鑭進行 簡單地介紹，鑭係原子序為57、原子量為138 9之白色的 金屬，於常溫下具有六方最密堆積結構。其熔點為921它， 彿點為35〇〇C，齋庚或3 在度為6.15g/cm3，於空氣中表面會被氧 化，於水令則會緩慢溶解。 可溶解於熱水、酸中。無延性，但略有展性。其電阻 ^為5.7〇Xl0、cm。於4价以上會燃燒而形成氧化物 2 3)(參…、理化學辭典對於稀土金屬而言，通常氧化數 為3之化合物較為穩定，鑭亦為3價。 高介電常數材料（High - k)等電 鑭以外之稀土金屬亦具有與鑭 鑭係作為金屬閘材料 子材料而受到矚目之金屬 類似的屬性。 鋼等之稀土金屬，由 題，因此屬於難以高純度 於在純化時有容易發生氧化的問 化之材料。又，將鑭等之稀土金 3 201016551 屬放置於工轧中時，由於會在短時間内發 7又土孔化，因此亦 有處理不易的問題。 刀 骐係要求薄膜 !，會由於隧道 最近’對新一代MOSFET中之閘絕緣 化，但迄今為止被使用作為閘絕緣膜之Si〇 效應而導致漏電流增加，難以正常動作。 因此，作為其代替品，係提出有具有高介電常數、高 熱穩定性、對矽中之電洞及電子具有高能量障壁㈣叫: 的励2、Zr〇2、Al2〇3、La2〇3。特別是此等材料之 中，La2〇3之評價較高，研究其電特性後，而完成有將其作 為新-代MOSFET中之閘絕緣膜的研究報告（參照非專利文 獻1)。但是，於該專利文獻之情形，為研究對象者係乙4〇3 膜’並未特別提及L a金屬之特性及行為。 如此，關於鑭等之稀土金屬及其氧化物，可謂尚處於 研究階段，在對此種稀土金屬及其氧化物之特性進行研究 時，若稀土金屬及其氧化物本身係以濺鍍靶材的形態存 在，則具有如下的大優點：可於基板上形成稀土金屬及其 氧化物的薄膜，又，容易研究與矽基板之界面處的行為， 並且容易形成稀土金屬化合物而研究高介電常數閘絕緣膜 等之特性，又，作為製品之自由度增加。 然而’即使製作成鑭濺鍍靶，亦會如上述般於空氣中 在紐時間内發生氧化。一般在金屬靶表面會形成穩定的氧 化被膜，但通常非常地薄，因此在濺鍍初期會剝落，而不 會對賤錢特性造成重大影響。然而，鋼藏鑛把之氧化被膜 厚，導致導電度下降，而造成濺鍍不良。 201016551 又’若於空氣中長時間放置時，則甚至會引起與空氣 中的水分發生反應而變成為被氫氧化物之白色粉末覆蓋最 後粉末化的狀態而無法進行正常濺鍍的問題。因此，在製 作靶之後，必須立即進行真空包裝或用油脂覆蓋，採取抗 氧化及抗氫氧化的對策。 稀土金屬的保存方法，一般係為了避免與大氣接觸而 保存在礦物性油中，但是當要作為濺鍍靶使用時，在使用The rare earth metal is contained in the earth's crust in the form of a mixed composite oxide. Rare earth metals are given this name because they are separated from rarer minerals, but they are not rare in general. Recently, rare earth metals have been recognized as electronic materials as materials for research and development. . Among the rare earth metals, lanthanum (La) is particularly attracting attention. Here, a simple introduction is made to the ruthenium, which is a white metal having an atomic number of 57 and an atomic weight of 138, and has a hexagonal closest packing structure at normal temperature. It has a melting point of 921, a Buddha point of 35 〇〇C, a gamma or a degree of 6.15 g/cm3, which is oxidized in the air and slowly dissolved in water. It can be dissolved in hot water and acid. No ductility, but slightly malleable. Its resistance ^ is 5.7 〇 Xl0, cm. It will burn when it is above 4 valence to form oxide 2 3) (Reference, chemistry dictionary for rare earth metals, usually the compound with oxidation number 3 is relatively stable, and yttrium is also trivalent. High dielectric constant material (High - k) Rare earth metals other than electric iridium have properties similar to those of lanthanide as a metal material for thyristor materials. Rare earth metals such as steel are subject to the problem, so it is difficult to have high purity and easy to purify. In addition, when the rare earth gold 3 201016551 genus of yttrium and other genus is placed in the industrial rolling, it will be difficult to handle due to the fact that it will be 7 times and soiled in a short time. The film is required to be insulated from the gate of the next-generation MOSFET, but it has been used as a Si 〇 effect of the gate insulating film to increase the leakage current, making it difficult to operate normally. Therefore, as a substitute, It is proposed that there are high dielectric constants, high thermal stability, high energy barriers for the holes and electrons in the crucible (4): 2, Zr〇2, Al2〇3, La2〇3. Especially among these materials , La2〇3 has a high evaluation, and after studying its electrical characteristics, it has been reported as a gate insulating film in a new-generation MOSFET (see Non-Patent Document 1). However, in the case of the patent document, The subject of the study is B 4 〇 3 film' does not specifically mention the characteristics and behavior of L a metal. Thus, the rare earth metal and its oxides of bismuth, etc., are still in the research stage, and in this kind of rare earth metal and When the characteristics of the oxide are studied, if the rare earth metal and the oxide itself are present in the form of a sputtering target, there is a great advantage that a thin film of a rare earth metal and an oxide thereof can be formed on the substrate, and it is easy Studying the behavior at the interface with the ruthenium substrate, and easily forming a rare earth metal compound to study the characteristics of a high dielectric constant gate insulating film, etc., and increasing the degree of freedom as a product. However, even if a sputtering target is produced, Oxidation occurs in the air during the time as described above. Generally, a stable oxide film is formed on the surface of the metal target, but it is usually very thin, so it peels off at the initial stage of sputtering, instead of It has a major impact on the characteristics of the money. However, the oxidized film of the steel mine is thick, resulting in a decrease in electrical conductivity and poor sputtering. 201016551 And 'If it is placed in the air for a long time, it will even cause it in the air. The water reacts and becomes a state of being finally powdered by the white powder of the hydroxide, and the problem of normal sputtering cannot be performed. Therefore, after the target is produced, it must be vacuum-packed or covered with grease to take anti-oxidation and anti-oxidation. Measures for the oxidation of rare earth metals, generally in order to avoid contact with the atmosphere and stored in mineral oil, but when used as a sputtering target, in use
前為了要將礦物油去除而必須進行洗淨。又，由於前述之 與氧、水分、二氧化碳之反應性問題，因此亦有洗淨本身 難以進行的問題。 因此，通常必須要藉由真空包裝來加以保存、 又’儘管為真空包裝之狀態，由於透過所使用之膜的水分 即使很少，氧化、氫氧化所導致之粉末化亦會進行，因此 要在可使用作為濺鍍靶之狀態下作長時間保存並不容易。 右參見以往的公知技術，則有以樹脂製的袋子來覆蓋 空心陰極型濺鍍靶的方法（參照專利文獻υ、將塑膠膜之保 濩膜貼附在靶的方法（參照專利文獻2)、使用不存在脫離性 粒子（releasab丨e particle)之表面之膜來包裝靶的方法（參照 專利文獻3)、使用透明之丙烯酸樹脂的上蓋來製作靶的保 存容器，並加以擰緊的方法（參照專利文獻4)、將賤餘封 閉於袋狀物的方法（參照專利文獻5)。然而此等方法，由 於係使用樹脂之蓋或樹脂性臈來將靶加以封閉者，因此作 為稀土金屬或其氧化物所構成之乾的保存方法，並不够充 分0 5 201016551 非專利文獻1 .德光永辅及另外2人著，「High— k閘 絕緣膜用氧化物材料之研究」電氣學會電子材料研究會資 料，第6〜13卷，第37〜41頁，2〇〇1年9月21曰發行。 專利文獻1 .國際公開W〇2005/037649公報。 專利文獻2 專利文獻3 專利文獻4 專利文獻5 曰本特開2002 — 212718號公報。 曰本特開2001 — 240959號公報。 曰本特開平8一 246135號公報。 曰本特開平4_ 231461號公報。 【發明内容】 、本發明，係對稀土金屬或其氧化物所構成之靶的保存 方法進行改進，其課題在於提供一種抑制因空氣之殘留及 侵入所造成之起的氧化及氳氧化而導致的粉末化，而可於 可使用作為濺鍍靶之狀態下作長時間保存的技術。 本發明提供： 1) —種稀土金屬或其氧化物所構成之靶的保存方法，係 用以保存稀土金屬《稀土金屬之氧化物所構成的滅鑛， 其特徵在於： 於該靶之保存用容器或臈狀密封件中，導入與所保存 之稀土金屬或稀土金屬《氧化物所構成之把相同的稀土金 屬之氧化物作域燥劑，然後將該保存用容器或膜狀密封 件加以封閉進行保存。 2) 一種稀土金屬或稀土金屬之氧化物所構成之靶的保 存方法，係、用以保存稀土金屬或稀土金屬之氧化物所構成 201016551 之乾’其特徵在於： 於該靶之保存用容器或膜狀 於所仅六μ , 丁 Τ 导入吸濕性大 屬氧=Γ屬或稀土金屬之氧化物粗材料的稀土金 屬氧化物作為乾燥劑，然後 加以封閉進行保存。 存用4或膜狀密封件 又，本發明提供： 構成2)所記載之稀土金屬或稀土金屬之氧化物所 存方法，其中，當為2種以上之稀土金二 稀金屬之乳化物所構成之把的情# 一 的稀土金屬氧化物作為乾燥劑。/ 〃 π濕性最大 4)如上述υ〜3)中任—項所記载之稀土金屬或稀土金 屬之氧化物所構成之靶的保存 之方法係真空封閉。#方法加以封閉保存 屬々上述”〜4)令任一項所記載之稀土金屬或稀土金 2 物所構成之把的保存方法，其中，加以封閉保存 參 手奴，係使用可撓性膜之真空密封件。 ’、 並且’本發明提供： 上述1)〜5)中任一項所記載之稀土金屬或稀土金 屬之氧化物所構成之靶的保存 之方半放心# 力次其中，加以封閉保存 之方法，係封入露點-啊以下之惰性氣體加以封閉。 :)如上述υ〜6)中任一項所記載之稀土金屬或稀土金 屬之礼化物所構成之靶的保存方法，α中 、 =劍之該稀土金屬氧化物裝載或填充於封閉時所產生： 201016551 8)如上述i)〜7)中任一項 Μ ^ 5己載之稀土金屬或稀土金 属之軋化物所構成之靶的保 +么遥或r ^ 仔方法，其中，構成該靶之稀 土金屬為La或含有[a。 9)如上述1)〜8)中任—馆私 邀夕翁" 所^己載之稀土金屬或稀土金 屬之軋化物所構成之靶的保存 ^ ^ Μ 4- ^ Μ - 方法其中，使用作為乾燥 劑之β亥稀土金屬氧化物為La氧化物。 s己載之稀土金屬或稀土金 法，其中，封閉保存所使 自容器外部的水分侵入量 10)如上述1)〜9)中任—項所 屬之氧化物所構成之靶的保存方 用之可撓性膜的水分透過量或來 在 〇.lg/m2 . 24h 以下。 本發，具有下述之大效果：在將以往之稀土金屬或稀 土金屬之軋化物所構成之靶封閉在密閉容器或塑料性之膜 加以保存時’若經長時間放置，則會與氧及水分發生反應 而變成為被氫氧化物之白色粉末覆蓋的狀態，而發生無法 進行正常之濺錄的問豸，但是保存在纟發明之保存用容器 或膜狀密封件中之靶，卻不會發生此種問題。 【實施方式] 已知稀土類，尤其是鑭及鑭之氧化物的吸濕性（與水分 的反應性）極強。因此，迄今為止要如何地不使鑭及鑭氧化 物吸濕’或是要如何地在水分少的環境來加以保存，一直 是個課題。 然而’反而利用鑭氧化物的吸濕性大於鑭的特性，當 保存鑭靶時’藉由將鑭氧化物（粉末、板或塊等燒結體）塗 201016551 覆、载置或者是放置絲表面，來防 氫氧化。 糊祀I身之乳化、 又，在保存鑭氧化物靶時， 末、顆粒狀的鑭氧化物，由於 ，纟面積較多之粉 去除，, 可更有效地將水分加以吸收、 ’、此可防止靶之氫氧化所導致的劣化。 亦即，本發明之稀土金 之乾的保存方法，係於伴在稀金屬之氧化物所構成 入所_力 係、於保存用容器或膜狀密封件之中，導 烊#| A、+之稀土金屬或稀土金屬之氧化物#、與作為# 燥劑之同-稀土金相氧化^ 與作為乾 此時’即使鑭氧化物 化而附著於乾表面，由：：應而氣氧化，然後粉末 故亦可容易將;為同—金屬之化合物且為粉末， 相較於使用由其他金屬…會成為巧染的原因。此點 優勢。 、 成之乾燥劑的情形，明顯具有 又’畲由其他之稀土舍届 為問題時，可v B、 每成的污染並不會特別成 物乾材料的締土冬遥从所欲保存之稀土金屬或其氧化 存用容器或肢业饮土 乍為乾餘劑，導入於靶的保 密封件加以封閉來保存。，、、後將該保存用容器或膜狀 的情ΐ由二種以上之稀土金屬或其等之氧化物所構成之乾 劑。 使用吸濕性最大之稀土金屬氧化物作為乾燥 其方：：二保存之方法’更佳為極力不使外界氣體進入， ，可為真空封閉。又，較佳在真空封閉、保存 201016551 時’ mhwc:以下之惰性氣體對容器或膜狀密 之中進行置換後’ #進行真空封閉。封閉保存之手段，可 使用可撓性膜，將其作成密閉狀之袋來進行真空密封。 於上述中’雖對真空封閉加以説明，但是亦可封入露 點-阶以下之惰性氣體來進行封閉。任一者均是為 外界氣體侵入者。 如此，與外界氣體隔絕，盡量抑制外界氣體之濕氣的 侵入，而即使僅有些許之侵人，亦可藉由將使用作為乾燥 劑之上述稀土氧化物裝載或填充於封閉時所產生之空間，、 來抑制靶本身的氫氧化。 -般，粗係接合於支持板’然而例如當使用可撓性膜 將其作成密閉狀之袋來對接合於支持板之靶進行真*密封 時，由於乾會在支持板之間產生段差，而容易ς生六 隙。於此種空隙，容易殘留有外界氣體。因此乾之粉狀： 容易由此處進行。較佳為將作為乾燥劑之稀土氧化 於此種段差或空隙。 ' 作為此乾燥劑之稀土氧化物，其意義應可理解為表面 積大之粉末或宜為顆粒狀。《而，在容易殘留外界氣體的 地方，即使僅放置小塊的稀土氧化物，亦具有效果。 又，最有效果係放置成使稀土氧化物與乾直接接觸， 但粉末會附著於乾表面，而成為滅链中發生粒子的原因。 二該種情形，即使如一般的乾燥劑般以包裝在透濕性膜的 狀態封入，亦具有充分的效果。 本發明把之保存方本，变+ _ 子構成托之稀土金屬為鑭乾或 201016551 2有鑭之㈣別有效。又，使用作為乾燥劑之上述稀土氧 化物’係鑭氧化物。此雖為 抽窃说也 勹埋所虽然，但是作為稀土金屬 化物所構成之乾的保存方法，最容易被氫氧化之鋼 乳化物，其㈣稀土金屬或其氧㈣所構叙Μ氣氧化 的效果最高。 使封閉保存所使用之可撓性膜的水分透過量或來自容 器外部的水分侵人量在G.lg/m2.241^T，來極力防止水 分的侵人’對稀土金屬或其氧化物所構成之㈣保存方法 而言，亦為重要。 封閉保存所使用之可撓性膜的較佳例、與其他之例示 於表1。由此表丨，具有Gx巴利亞（商品名）以上之特性者 =有效。如表1所*，較佳為GX巴利亞（商品名）與裝有紹 羯之袋°纟1係顯示具代表性之例，若為滿足上述之條件 者’當然可使用其他的可撓性膜。 [表1】 透過率 水蒸氣 (g/m2 · 24h) 酸素 (cm3/m2 · 24h · atm) EVAL 4 3 NM巴利亞 0.32 0.24In order to remove the mineral oil, it must be washed. Further, due to the aforementioned problem of reactivity with oxygen, moisture, and carbon dioxide, there is a problem that washing itself is difficult to carry out. Therefore, it is usually necessary to store it by vacuum packaging, and in the state of vacuum packaging, since the moisture of the film to be used is small, the pulverization caused by oxidation and oxidation will proceed. It is not easy to store for a long time in a state where it can be used as a sputtering target. In the related art, a method of covering a hollow cathode-type sputtering target with a resin bag is known (refer to the patent document υ, a method of attaching a protective film of a plastic film to a target (refer to Patent Document 2), A method of packaging a target using a film having no surface of a releasab丨e particle (see Patent Document 3), and using a cover of a transparent acrylic resin to form a target storage container and tightening the same (refer to the patent) Document 4), a method of sealing the remainder in a bag (refer to Patent Document 5). However, since these methods use a resin cover or a resinous crucible to seal the target, it is used as a rare earth metal or oxidation thereof. The preservation method of the dry matter of the object is not sufficient. 0 5 201016551 Non-patent literature 1. Deguang Yongsuke and two others, "Research on oxide materials for high-k gate insulating film" Electronic Materials Research Association of the Institute of Electrical Engineering , pp. 6 to 13, pp. 37 to 41, issued on September 21, 2001. Patent Document 1. International Publication No. 2005/037649. Patent Document 2 Patent Document 3 Patent Document 4 Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The method for preserving a target composed of a rare earth metal or an oxide thereof is improved, and an object of the invention is to provide a powder which is inhibited by oxidation and antimony oxidation caused by residual and intrusion of air, and can be used. The present invention provides a method for preserving a target of a rare earth metal or an oxide thereof for storing a rare earth metal "oxide of a rare earth metal". Excavation, characterized in that: in the container for preservation or the seal of the target, the rare earth metal oxide formed by the rare earth metal or the rare earth metal "oxide" is introduced as a domain drying agent. Then, the storage container or the film seal is sealed and stored. 2) A method for preserving a target composed of an oxide of a rare earth metal or a rare earth metal, which is used to store a rare earth metal or an oxide of a rare earth metal, which is characterized by: a container for preservation of the target or The film is introduced into a rare earth metal oxide having a hygroscopicity of a large oxide material of oxygen = genus or a rare earth metal as a desiccant, and is then sealed and stored. In addition, the present invention provides a method for forming an oxide of a rare earth metal or a rare earth metal described in 2), which is composed of an emulsion of two or more kinds of rare earth gold diphobic metals. The rare earth metal oxide of the kind one is used as a desiccant. / 〃 π Humidity is the largest 4) The method for preserving the target composed of the rare earth metal or the rare earth metal oxide described in the above item υ~3) is vacuum-sealed. The method of storing and storing the rare earth metal or the rare earth gold 2 as described in any one of the above-mentioned "~4", wherein the method of conserving and holding the slave is to use a flexible film. The present invention provides the storage of the target of the rare earth metal or the rare earth metal oxide according to any one of the above 1) to 5). The method of preserving is a method of preserving a target composed of a rare earth metal or a rare earth metal as described in any one of the above-mentioned υ~6), in which the dew point is sealed with an inert gas. = The rare earth metal oxide of the sword is loaded or filled in a closed state: 201016551 8) A target composed of a rare earth metal or a rare earth metal rolled by any of the above i) to 7) A method of protecting the rare earth metal constituting the target as La or containing [a. 9) as in the above 1) to 8) Preservation of a target composed of a rolled metal or rare earth metal ^ ^ Μ 4- ^ Μ - Method wherein a β-e rare earth metal oxide as a desiccant is used as a La oxide. s a rare earth metal or rare earth gold method, wherein the amount of moisture intrusion from the outside of the container is closed by the storage. 10) The moisture permeation amount of the flexible film for the purpose of preserving the target composed of the oxides of the above-mentioned items 1) to 9) is 〇.lg/m2. 24h or less. The effect of the following is that when a target consisting of a conventional rare earth metal or a rare earth metal rolled product is sealed in a sealed container or a plastic film and stored for a long time, it reacts with oxygen and moisture. It becomes a state covered with a white powder of hydroxide, and there is a problem that normal sputtering cannot be performed, but the target stored in the storage container or the film-like sealing member of the invention does not cause such a problem. [Embodiment] It is known that rare earths, especially oxides of cerium and lanthanum, have extremely high hygroscopicity (reactivity with moisture). Therefore, how to prevent moisture absorption of cerium and lanthanum oxides so far or Is how to be less in water It has always been a problem to preserve the environment. However, 'the hygroscopicity of the cerium oxide is greater than that of the cerium oxide. When the cerium target is preserved', the cerium oxide (sintered body such as powder, plate or block) is coated with 201016551. The surface of the wire is placed or placed to prevent oxidation. The emulsification of the paste is in the form of a cerium, and when the cerium oxide target is stored, the cerium oxide of the granules is removed. The water can be absorbed more effectively, and this can prevent deterioration caused by the oxidation of the target. That is, the method for preserving the rare earth gold of the present invention is based on the formation of oxides of the rare metal. _ force system, in storage container or film seal, guide |#| A, + rare earth metal or rare earth metal oxide #, and as the #燥剂--Rare earth metallurgical oxidation ^ and as a dry At this time, even if the yttrium is oxidized and adhered to the dry surface, it is oxidized by the gas: then the powder can be easily removed; the same as the metal compound and the powder, compared with the use of other metals... The cause of the dye. This point has the advantage. In the case of a desiccant, it is obvious that when the other rare earths are used as a problem, v B, each of the pollution does not become a special dry material of the soil. The metal or its oxidizing container or the limb drinker is a dry residue, and the sealing member introduced into the target is sealed and stored. Then, the container for storage or the film-like condition is a dry agent composed of two or more kinds of rare earth metals or oxides thereof. The most hygroscopic rare earth metal oxide is used as the drying side: the second method of preservation is more preferably to prevent the outside air from entering, and it can be closed by vacuum. Further, it is preferable to vacuum-close and store 201016551 when mhwc: the following inert gas is replaced in a container or a film-like seal. For the purpose of closed storage, a flexible film can be used, and it can be vacuum-sealed by making it a sealed bag. In the above, although the vacuum sealing is described, the inert gas of the dew point-order or lower may be sealed for sealing. Either one is an outside gas intruder. In this way, it is isolated from the outside air, and the intrusion of moisture of the outside air is suppressed as much as possible, and even if only a little intrusive, the above-mentioned rare earth oxide used as a desiccant can be loaded or filled in the space generated by the sealing. , to suppress the oxidation of the target itself. In general, the support is thickly bonded to the support plate. However, for example, when a flexible film is used to form a sealed bag to perform true* sealing on a target bonded to the support plate, since the dryness causes a step difference between the support plates, It is easy to create six gaps. In such a space, external air is likely to remain. Therefore dry powder: easy to carry out here. It is preferred to oxidize the rare earth as a desiccant to such a step or void. The rare earth oxide as the desiccant is understood to mean a powder having a large surface area or preferably in the form of particles. "And, where a small amount of rare earth oxide is placed, it is effective in places where external gas is easily left. Further, the most effective effect is to place the rare earth oxide in direct contact with the dry, but the powder adheres to the dry surface and causes the particles to occur in the chain. In this case, even if it is packaged in a moisture permeable film like a general desiccant, it has a sufficient effect. The invention saves the square, and the + _ sub-constituting the rare earth metal is 镧 dry or 201016551 2 镧 (4) is effective. Further, the above rare earth oxide cerium oxide is used as a desiccant. Although it is buried in the sneak, although it is a dry preservation method composed of rare earth metallization, it is most easily oxidized by the oxidized steel emulsion, (4) rare earth metal or its oxygen (4). The effect is the highest. The moisture permeation amount of the flexible film used for the closed storage or the moisture intrusion from the outside of the container is at G.lg/m2.241^T to prevent the intrusion of moisture to the rare earth metal or its oxide. It is also important to have a (4) preservation method. Preferred examples of the flexible film used for the enclosed storage and other examples are shown in Table 1. From this point of view, those with the characteristics of Gx Baria (trade name) or higher = valid. As shown in Table 1, * GX Bally (trade name) and bag with Shao Shao are shown as representative examples. If the above conditions are met, of course, other flexible can be used. Sex film. [Table 1] Transmittance Water vapor (g/m2 · 24h) Acid (cm3/m2 · 24h · atm) EVAL 4 3 NM Baria 0.32 0.24
11 201016551 接著，說明實施本發明時 易理解者，並非用以限制本發 思想範圍内的其他之例及變形 (實施例1) 之例。另，此例僅是為了容 明。亦即，在本發明之技術 ’皆包含於本發明。 係對L a把進行真空肖_ 脸 埴右私“， 層薄La氧化物粉末層 填充於表面與側面之情形之例。 此*具體例顯示於圖1。 如圖1所示，係藉由在真空 升二匕展之膜與1^靶之間存在 氧化鑭層，使真空包裝内側所殘 α汊留之水分、及透過膜進來 的水分被氧化鑭粉末吸收，而 向以氧氧化鑭的形態固定下 來’因此可有效地防止La靶表面血>、^ ;衣面與水分反應變成氫氧化物 而粉末化的現象。 (實施例2) 係對La乾進行真空包裝，膝τ ^ α具匕衮將“氧化物粉末置於與（如 矽膠袋)BP之段差的空間之例。此具體例顯示於圖2。如圖 所不’於真空包裝中，La氧化物將會吸收殘留在些許殘 存之空間的水分，而以氫氧化鋼的形態固定下來，因此可 有效地防止La靶與水分反應變成氫氧化物而粉末化的現 © 象。 (實施例3) 係將La氧化物靶設置在金屬製的容器内，於該靶的周 圚填充La氧化物粉末後，暫時以露點—8(rc以下之氬對周 圍的空氣進行置換，然後再進一步對其進行真空封閉之 例。其具體例顯示於圖3。 如圖3所示，於抽成真空後，氧化鑭將會吸收所殘留 12 201016551 之水分，而以氫敦化鑭的形態固定下來，因此可有效地防 止La與水分反應變成氫氧化物而粉末化的現象。 (實施例4) 係於金屬製的容器内配置La# Er所構成之金屬合金 靶’接著在該靶與BP之段差放置經燒結之"氧化物塊， 以露點-80〇C以下之氬氣將容器内的空氣加以置換後，再 進行抽真空之例。 參 ％圖4所示，於抽成真空後，氧化鑭將會吸收所殘留 之水分，而以氫氧化鑭的形態固定下來，因此可有效地防 止La與水分反應變成氫氧化物而粉末化的現象。 (比較例1) 係以膜對Μ進行真空封閉的情形。此具體例顯示於 圖5。如圖5所示，些許殘留於真空包裝膜與靶間所形成之 空間的水分與La靶反應，形成鑭氫氧化物而粉末化。 (比較例2) 係以膜對La把進行直空, ❿ 仃具工封閉，放置矽膠作為乾燥劑的 情形。此具體例示於圖6。 如圖6料’放㈣料，較切料μ粉末化。 此被認為是由於石夕膠所吸附之水分脫離釋放於真 中，而促進水分仏之反應，變成鑭氫氧化物。因此可知 :般作為乾燥劑使用的石夕膠’在防止稀土金屬或稀土金屬 氧化物之粉末化現象上，並不起 (比較例3) 起作用倒不如說是不佳。 此例係以膜對U2〇3^進行真空封閉的情形。此具體例 13 201016551 示於圖7如圖7所不，La氧化物(以〇3)將會吸收殘留在 真空包裝内些許殘存之空間的水分…氫氧化鑭的形態 固定下來，故LhO3靶將會與水分發生反應變成氫氧化物， 而粉末化。 從以上之實施例與比較例清楚得知，在保存稀土金屬 或稀土金屬之氧化物所構成之把時’於密封容器或密封件 内導入與所保存之稀土金屬或稀土金屬之氧化物所構成 之靶相同的稀土金屬之氧化物作為乾燥劑，極為有效。藉 ，’可有效抑制因空氣之殘留及侵人所造成之㈣氧化及 氫氧化而導致的粉末化。 產業上之可利用性 以往，若將稀土金屬或稀土金屬之氧化物粗長時間放 置於空氣中時，則將會與空氣中的水分發生反應而變 被氫氧化物之白色粉末覆蓋的狀態，而發生無法進行正常 之_的問題’但是本發明之稀土金屬或其氧化物所構成 之靶的保存方法，並不會發生此類的問題。 、、本發明之稀土金屬或其氧化物所構成之粗 法，係於保存用容器或膜狀密封件之中，導入與所 稀土金屬或其氧化物所構成之乾相同的稀土金屬之 作為乾燥劑者。藉此，可有效抑制因與空氣中之水分反康 而被氫氧化物之白色粉末覆蓋的狀態。 〜 藉此，可穩定地供給乍為金屬閉極材料、高 數材料（High-k)等之電子材料，在産業上極為_。常 201016551 【圖式簡單說明】 圖1 ’係顯示將—層薄La氧化物粉末層填充於La靶之 表面與側面，對其進行真空包裝之情形之例。 圖2係顯不將La氧化物粉末放置於La靶與BP之段 差的空間’進行真空包裝之例。 W 3 ’ 係顯示膝 Τ β h B + A » .1.11 201016551 The following is a description of other examples and modifications (Example 1) within the scope of the present invention. In addition, this example is for the sake of illustration only. That is, the technology of the present invention is included in the present invention. This is an example of a case where a layer of thin La oxide powder layer is filled on the surface and the side surface, and the specific example is shown in Fig. 1. As shown in Fig. 1, There is a ruthenium oxide layer between the film of the vacuum rising film and the 1^ target, so that the moisture remaining in the inside of the vacuum package and the moisture coming in through the film are absorbed by the cerium oxide powder, and the cerium oxide is oxidized by oxyhydroxide. The morphology is fixed, so that the surface of the La target surface can be effectively prevented, and the surface of the La target is reacted with water to become a hydroxide and powdered. (Example 2) Vacuum lamination of La dry, knee τ ^ α There is an example in which the "oxide powder is placed in a space different from that of (for example, a silicone bag) BP. This specific example is shown in Figure 2. As shown in the figure, in the vacuum packaging, the La oxide will absorb the moisture remaining in the remaining space and be fixed in the form of hydroxide steel, thereby effectively preventing the La target from reacting with moisture to become a hydroxide. A powdered image. (Example 3) The La oxide target was placed in a metal container, and after the La oxide powder was filled around the target, the surrounding air was temporarily replaced by dew point-8 (argon below rc), and then Further, vacuum sealing is carried out. A specific example thereof is shown in Fig. 3. As shown in Fig. 3, after vacuuming, cerium oxide absorbs the residual water of 201016551 and is fixed in the form of hydrogen hydride. Therefore, it is possible to effectively prevent the phenomenon that La reacts with water to become a hydroxide and is powdered. (Example 4) A metal alloy target composed of La# Er is placed in a metal container, and then the target and BP are placed. The sintered portion is placed in the sintered "oxide block, and the air in the container is replaced by argon gas having a dew point of -80 〇C or less, and then vacuum is taken. As shown in Fig. 4, after vacuuming Since cerium oxide absorbs the remaining water and is fixed in the form of cerium hydroxide, it can effectively prevent the phenomenon that La reacts with water to become a hydroxide and is powdered. (Comparative Example 1) Vacuum sealing This specific example is shown in Fig. 5. As shown in Fig. 5, some of the water remaining in the space formed between the vacuum packaging film and the target reacts with the La target to form a ruthenium hydroxide and is powdered. (Comparative Example 2) The film is placed in a straight space, and the crucible is closed, and the crucible is placed as a desiccant. This specific example is shown in Fig. 6. As shown in Fig. 6, the material is placed in the material, which is considered to be due to the powdering of the material. The water adsorbed by Shixijiao is released from the scent and promotes the reaction of hydrazine and becomes a ruthenium hydroxide. Therefore, it can be seen that the diarrhea used as a desiccant prevents the granulation of rare earth metals or rare earth metal oxides. In the case of the phenomenon, it does not matter (Comparative Example 3). It is not good to act. This case is a case where the film is vacuum-sealed to U2〇3^. This specific example 13 201016551 is shown in Figure 7 as shown in Figure 7. The La oxide (〇3) will absorb the moisture remaining in the space left in the vacuum package... The shape of the barium hydroxide is fixed, so the LhO3 target will react with water to become a hydroxide and be powdered. From the above examples and comparative examples Chu knows that when the rare earth metal or the oxide of the rare earth metal is preserved, the oxidation of the rare earth metal which is the same as the target of the deposited rare earth metal or rare earth metal oxide is introduced into the sealed container or the sealing member. As a desiccant, it is extremely effective. By borrowing, it can effectively suppress the pulverization caused by (4) oxidation and oxidation caused by air residue and invading. Industrial Applicability In the past, if rare earth metals or rare earth metals were used. When the oxide is placed in the air for a long time, it will react with the moisture in the air to become covered with the white powder of the hydroxide, and the problem of being unable to perform normal is generated. However, the rare earth of the present invention A method of preserving a target composed of a metal or an oxide thereof does not cause such a problem. The crude method of the rare earth metal of the present invention or an oxide thereof is used as a drying agent or a film-like sealing member, and is introduced into a rare earth metal which is the same as the dry metal or an oxide thereof. Agent. Thereby, the state of being covered with the white powder of the hydroxide due to the reversal of moisture in the air can be effectively suppressed. ～ By this, it is possible to stably supply electronic materials such as metal-enclosed materials and high-grade materials, which are extremely industrially excellent. Normally, 201016551 [Simplified Schematic Description] Fig. 1 shows an example in which a thin layer of La oxide powder is filled on the surface and side surfaces of a La target and vacuum-packed. Fig. 2 shows an example in which the La oxide powder is not placed in a space where the La target and the BP are inferior. W 3 ' shows knee Τ β h B + A » .1.
圖5，係顯示以膜對La 圖6，係顯示以膜對La 為乾燥劑夕，法Figure 5 shows the film pair La Figure 6, showing the film pair La as a drying agent.
❹ 圖7 ’係顯示以膜對❹ Figure 7 ’ shows the film pair
La靶進行真空封閉之情形之例。 La靶進行真空封閉，放置矽膠作 【主要元件符號說明】 無 15An example of the case where the La target is vacuum-sealed. The La target is vacuum-sealed and the silicone is placed. [Main component symbol description] None 15