TW200946692A

TW200946692A - Sb-te alloy powder for sintering, process for production of the powder, and sintered target

Info

Publication number: TW200946692A
Application number: TW098105386A
Authority: TW
Inventors: Hideyuki Takahashi
Original assignee: Nippon Mining Co
Priority date: 2008-02-26
Filing date: 2009-02-20
Publication date: 2009-11-16
Also published as: WO2009107498A1; KR20130007676A; KR20090130315A; JPWO2009107498A1; TWI481725B; KR101475133B1; JP5496078B2

Abstract

An Sb-Ti alloy powder for sintering, characterized by consisting of particles having a mean particle diameter of 0.1 to 200μm and by having an oxygen content of 1000wtppm or below; and a sintered target made of an Sb-Te alloy, characterized by an oxygen content of 1000wtppm or below, a bending strength of 50MPa or above, and a relative density of 99% or above. The sintered target has a uniform and refined structure, and is inhibited from cracking and from arcing in sputtering by virtue of the structure. Further, the surface unevenness caused by sputter erosion is reduced, whereby a high-quality Sb-Te alloy sputtering target can be obtained.

Description

200946692 六、發明說明：【發明所屬之技術領域】本發明，係關於-種由燒結用Sb—Te系合金粉末，例如Ag-In-Sb-Te合金或Ge—Sb—Te合金所構成之用以形成相變化記錄層的Sb—Te系合金減鍵乾、適合用以製造該靶之燒結用Sb-Te系合金粉末及燒結用Sb — 粉末之製造方法。糸〇〇 ❹ 【先前技術】近年來，逐漸使用由Sb-Te系材料所構成之薄膜來作為相變化記錄用材料’料作為利用相變態來記錄資訊的媒體。用以形成此Sb— Te系合金材料所構成之薄膜的方法通韦係以真空蒸鍍法、減鍵法等一般稱為物理蒸鍵法之手段來進行。特別是’從操作性及被膜穩定性考量大多使用磁控管濺鍍法來形成。以滅鑛法進行臈之形成，係使Ar離子等陽離子物理性地撞擊設置於陰極之靶’藉由其撞擊能量將構成靶之材料擊出’而在對面之陽極側的基板’積層與拓材料大致相同組成之膜。以減鍍法所進行之被覆法，具有下述特徵，藉由調節理時間、供給電力等，能夠以穩定的成膜速度，形成從埃單位之薄臈至數十"m之厚膜。形成由相變化記錄膜用sb—Te系合金材料所構成之膜時，特別會發生問題的是：⑽時粒子（panieai)的產生或異常放電（微電弧）、為產生群落狀（凝固後附著）薄臈形 200946692 及在濺鍍時靶產生裂的製造步驟，吸收大成原因之結球（突起物）的發生、以痕或裂縫，更有甚者是在靶用燒結粉量的氧。係造成記錄媒體之薄膜品質此種靶或濺鍍時的問題降低的重要原因。上述之問題，已知受燒結用粉啊尽之粒徑或靶之構造及特性很大的影響。然而，以往在劁地田仕製造用以形成相變化記錄層之Sb-Te系合錢㈣時，無法製得適當之粉末且以燒結所製得之㈣未保有充分之特性，於減鍍時無法避免粒子的產生、異常放電、結球與㈣裂痕或裂缝的發生、且在乾中含有大量的氧。以往Sb-Te系合金滅鑛乾的製造方法若舉 -Te系錢鍵用把的製造方法做為例子，則揭示有一種以惰性氣體霧化法，藉由急速冷卻來製作Ge—Te合金、讥―h200946692 VI. Description of the Invention: [Technical Field] The present invention relates to a material composed of Sb—Te alloy powder for sintering, such as Ag—In—Sb—Te alloy or Ge—Sb—Te alloy. The Sb-Te-based alloy which forms the phase-change recording layer is dry-bonded, and is suitable for the Sb-Te-based alloy powder for sintering and the Sb-powder for powder production.先前〇 ❹ [Prior Art] In recent years, a film composed of a material of Sb-Te has been gradually used as a material for phase change recording as a medium for recording information by using a phase change state. The method for forming a thin film of the Sb-Te alloy material is carried out by a method generally called a physical vapor bonding method such as a vacuum vapor deposition method or a subtractive bond method. In particular, the use of magnetron sputtering is widely used in consideration of operability and film stability. The formation of ruthenium by the ore-eliminating method is such that a cation such as Ar ion physically strikes a target disposed at the cathode, and the material constituting the target is struck by the impact energy thereof, and the substrate on the opposite side of the anode is laminated and expanded. A film of approximately the same composition. The coating method by the subtractive plating method has a feature that a thick film of from tens of angstroms to several tens of "m" can be formed at a stable film formation rate by adjusting the conditioning time, supplying electric power, and the like. When a film composed of an sb—Te-based alloy material for a phase change recording film is formed, problems particularly occur in the case of (10) generation of a panieai or abnormal discharge (micro-arc), and formation of a colony (adhesion after solidification) The thin 臈 shape 200946692 and the manufacturing step of cracking the target during sputtering absorb the occurrence of the ball (protrusion) caused by the large cause, the mark or crack, and the oxygen in the amount of the sintered powder for the target. The film quality of the recording medium is an important cause of the problem of such a target or sputtering. The above problems are known to be greatly affected by the particle size of the sintering powder or the structure and characteristics of the target. However, in the past, when the Sb-Te system (4) used to form the phase change recording layer was manufactured by Shoji, it was not possible to obtain a suitable powder and it was obtained by sintering. (4) It did not retain sufficient characteristics during deplating. The generation of particles, abnormal discharge, ball formation and (4) cracks or cracks cannot be avoided, and a large amount of oxygen is contained in the dry. In the conventional manufacturing method of the Sb-Te alloy ore-killing dry, the manufacturing method of the -Te-based money-bonding method is exemplified as an example of producing a Ge-Te alloy by rapid cooling by an inert gas atomization method.讥―h

合金之各粉末’並將合金粉末均句混合後，：行加壓燒J 之Ge_sb_Te系_用托之製造方法（例如參照專利文獻1)。又’亦記載有-種Ge-Sb—Te系濺鍍靶之製造方法及藉由霧化法製造此等所使用之粉末的技術，其肖徵在於，含有Ge、Sb、Te之合金粉末中，將振實密度為50%以上的粉末注入模具中，以低溫或高溫加壓，並將低溫加壓後之密度在95%以上的成形材，在Ar或真空環境氣氛中施以熱處理，以進行燒結’藉此，使該燒結體的含氧量在以下（例如，參照專利文獻2)。 200946692 又’記載有一種Ge — Sb — Te系滅锻乾材之製造方法，係對含有Ge、Sb、Te之原料，以惰性氣體霧化法製作急速冷卻之粉末，使用該粉末中具有20 以上、且每單位重量之比表面積在300mm2/ g以下之粒度分布的粉末，以低溫或高溫加壓成形後’對成形體進行燒結（例如，參照專利文獻3) » 其他使用霧化粉來製造靶之技術，另有下述專利文獻 4、5、6。 ❹ 然而’以上之專利文獻，係直接使用霧化粉，故無法得到具有充分強度之靶，且亦難以達成靶組織之微細化及均質化。又，所容許之含氧量亦高，作為用以形成相變化記錄層之Sb—Te系濺鍍靶而言，不能說是十分成熟。因此，本案申請人先前曾提出一種Sb— Te系濺鍍靶及其所使用之粉末（參照專利文獻7、8、9)。此等係用以解決上述之問題者。〇專利文獻1 :日本特開2000— 265262號公報專利文獻2 :日本特開2001 — 98366號公報專利文獻3:日本特開2001 — 123266號公報專利文獻4 :日本特開昭丨〇 — 81962號公報專利文獻5 :日本特開2〇〇1 — 123267號公報專利文獻6 ··日本特開2〇〇〇_ 129316號公報專利文獻7 :日本特開2004 — 162109號公報專利文獻8 : W02006/ 077692號公報專利文獻9 : W02006/067937號公報 200946692 【發明内容】本發明，可使結晶化速度為最佳，目的在於提升非晶與結晶之變態的反覆耐性，並且進行成膜之比電阻的最佳化。並且，提供一種在濺鍍時，可有效抑制粒子之產生、異常放電、結球與靶之裂痕或裂縫的發生等，並減少乾中所含有之氧等雜質的靶燒結用Sb— Te系合金粉末，特別是一種適合用以製造由Ag—In-Sb-Te合金或Ge-Sb-Te 合金所構成之用以形成相變化記錄層的Sb—Te系合金減鑛把之燒結用Sb—Te系合金粉末，及一種燒結用Sb—Te系合金粉末之製造方法，以及一種藉由該製造方法所製得之燒結體把。用以解決上述問題點之技術手段，係發現穩定且均質之相變化記錄層，可藉由對粉末之性狀與靶之構造及特性下功夫來得到。基於此發現’本發明係提供： 1)—種燒結用Sb—Te系合金粉末，其特徵在於，係由平均粒徑為0.1〜200 之粉末所構成，且含氧量在 lOOOwtpprn 以下。本發明之燒結用Sb-Te系合金粉末，可使用Ag、八卜After the alloy powders are mixed and the alloy powders are uniformly mixed, the Ge_sb_Te system which is subjected to pressure-burning is used (for example, refer to Patent Document 1). Also described is a method for producing a Ge-Sb-Te sputtering target and a technique for producing such a powder by an atomization method, which is characterized by containing an alloy powder of Ge, Sb, and Te. a powder having a tap density of 50% or more is injected into a mold, pressed at a low temperature or a high temperature, and a molded material having a density of 95% or more after being pressed at a low temperature is subjected to heat treatment in Ar or a vacuum atmosphere to Sintering is performed, whereby the oxygen content of the sintered body is as follows (for example, see Patent Document 2). 200946692 Further, a method for producing a Ge-Sb-Te-based forging dry material is described, which is a powder containing Ge, Sb, and Te, which is rapidly cooled by an inert gas atomization method, and has 20 or more powders. And the powder having a particle size distribution of a specific surface area of 300 mm 2 /g or less per unit weight is sintered at a low temperature or a high temperature, and then the molded body is sintered (for example, refer to Patent Document 3) » Others use atomized powder to produce a target The technology is also the following Patent Documents 4, 5, and 6. However, in the above patent documents, the atomized powder is directly used, so that a target having sufficient strength cannot be obtained, and it is also difficult to achieve miniaturization and homogenization of the target structure. Further, the allowable oxygen content is also high, and it cannot be said that it is very mature as an Sb-Te-based sputtering target for forming a phase-change recording layer. Therefore, the applicant of the present application has previously proposed an Sb-Te sputtering target and a powder used therefor (see Patent Documents 7, 8, and 9). These are used to solve the above problems. Patent Document 1: JP-A-2000-265262 Patent Document 2: JP-A-2001-98366 Patent Document 3: JP-A-2001-123266 Patent Document 4: JP-A-No. 81962 [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. 129 316. Patent Document 9: WO2006/067937, No. 200946692 SUMMARY OF THE INVENTION The present invention can optimize the crystallization rate, and the purpose is to improve the resistance of the amorphous and crystalline metamorphism, and to perform the specific resistance of the film formation. optimization. Further, it is possible to provide Sb-Te alloy powder for target sintering which can effectively suppress generation of particles, abnormal discharge, cracking of a ball and a target, cracks, and the like, and reduce impurities such as oxygen contained in the dryness during sputtering. In particular, a Sb-Te system for sintering Sb-Te alloys for forming a phase change recording layer composed of an Ag-In-Sb-Te alloy or a Ge-Sb-Te alloy An alloy powder, a method for producing a sintered Sb—Te alloy powder, and a sintered body obtained by the production method. The technical means for solving the above problems is to find a stable and homogeneous phase change recording layer which can be obtained by working on the properties of the powder and the structure and characteristics of the target. Based on the findings, the present invention provides: 1) A Sb—Te-based alloy powder for sintering, which is composed of a powder having an average particle diameter of 0.1 to 200 and an oxygen content of 1,000,000 wt pprn or less. The Sb-Te alloy powder for sintering of the present invention can be used for Ag or Babu.

As、Au、B、c、Ga、Ge、In、p、pd pt、s、Se、si T 來作為添加it素，可含有i〜編％之選自此等之i種以上 ::素。通常’藉由此等之添加元素，可使結晶化速度為 ’且可使熔點及結晶化溫度為最佳…可提升非晶 …结晶之變態的反覆耐性，並且可進行成膜之比電阻的最 200946692 佳化。上述添加元素之選擇與添加量，必須也要根據元素所具備之特性來調整添加量，但通常若未達上述lat%的話，則無添加之效果’又’若超過為上限值之30at%時，則將會失去作為原本之相變化記錄用材料的機能，靶之強度會大幅下降’在靶製造時或使用時，靶會發生裂縫，因此，選自 Ag、Al、As、Au、B、C、Ga、Ge、In、P、Pd、Pt；、 S、Se、Si、Ti之1種以上之元素的添加量較佳為i〜3〇at %。粉末之平均粒徑在〇_ 1〜200 y m之範圍。粒徑以較小為佳’較佳之平均粒徑為1〜5〇ym，更佳為1〜2〇vm。由於難以製造粒徑統一之粉末，因此某程度之參差不一是盔可避免的，但特別是混合有超過200仁m之情形時，由於損及燒結體之均一性，因此必須藉由分級使粒度一致，以使粉末之大部分（粒度分布之3σ以内）在0.1〜200私m的範圍。並且’使含氧量在lOOOwtppm以下。若含氧量變高，則會形成燒結性差之氧化物絕緣層，導致靶之機械強度下降’產生龜裂、裂縫，且會發生絕緣層部之異常放電（電弧），成為粒子的原因’故不佳。為了防止此類缺點，故必須使其上限值為lOOOwtppm。含氧量，較佳在5〇〇wtppm以下，更佳在lOOwtppm以下。若使用比表面積（BET)為0.15〜0.25m2/g之粉末，則由於在燒結時，可製造緻密之燒結體靶，因此更佳為使用 200946692As, Au, B, c, Ga, Ge, In, p, pd pt, s, Se, and si T may be contained as an addition of an element, and may include i or more selected from the group of i or more. Generally, by adding elements such as this, the crystallization rate can be ', and the melting point and the crystallization temperature can be optimized. The reverse resistance of the amorphous state can be improved, and the specific resistance of the film can be formed. Most 200946692 Jiahua. The selection and addition amount of the above-mentioned additive elements must also be adjusted according to the characteristics of the elements. However, if the above lat% is not reached, the effect of no addition is 'yes' if it exceeds the upper limit of 30 at%. At this time, the function of the original phase change recording material will be lost, and the intensity of the target will be greatly reduced. 'The target will crack when the target is manufactured or used. Therefore, it is selected from Ag, Al, As, Au, B. The addition amount of one or more elements of C, Ga, Ge, In, P, Pd, and Pt; and S, Se, Si, and Ti is preferably i 〜3 〇 at %. The average particle size of the powder ranges from 〇 1 to 200 y m. The particle diameter is preferably small, and the preferred average particle diameter is 1 to 5 〇 ym, more preferably 1 to 2 〇 vm. Since it is difficult to manufacture a powder having a uniform particle size, a certain degree of variation is avoidable by the helmet, but especially when the mixture is more than 200 lm, since the uniformity of the sintered body is impaired, it is necessary to classify The particle size is uniform so that most of the powder (within 3σ of the particle size distribution) is in the range of 0.1 to 200 private m. And 'the oxygen content is below 1000 wtppm. When the oxygen content is high, an oxide insulating layer having poor sinterability is formed, and the mechanical strength of the target is lowered. "The cracks and cracks are generated, and the abnormal discharge (arc) of the insulating layer portion occurs, which is the cause of the particles. good. In order to prevent such disadvantages, it is necessary to set the upper limit value to 1000 wtppm. The oxygen content is preferably 5 〇〇 wt ppm or less, more preferably 100 MPa ppm or less. When a powder having a specific surface area (BET) of 0.15 to 0.25 m 2 /g is used, since a dense sintered body target can be produced at the time of sintering, it is more preferably used.

Sb—Te系合金粉末。本發明，又提供： 2)-種燒結用Sb-Te系合金粉末之製造方法，係將別 — Te系合金所構成之原料加以熔解後，對其進行加工製成粉末，然後將藉此所製得之粉末加以還原，使成為含氧量在lOOOwtppm以下，平均粒徑為〇 1〜2〇〇“111之粉末。此時’製成平均粒徑4 HO" m(進一#為平均粒徑i 〜20//m)之燒結用Sb-Te系合金粉末係較佳之條件。此可藉由粉末之加工方法的調整與分級來達成。又，於粉末之製造步驟中，還原處理，可藉由進行酸洗後之真空乾燥處理（例如，5〇%硝酸水溶液χ1〇分鐘之浸潰後，以真空度100mT〇rr(l3Pa)以下進行6小時之乾燥處理）、惰性氣體（Ar)環境氣氛中熱處理（例如，5〇〇〇Cx2小時）、氫還原處理（例如，50(TCx2小時）、混合有還原材料（Mg、Fe) 之锻燒處理，來將粉末加以還原。此等處理之選擇為任意，又，還原條件，亦只要根據粉末之量、氧化之程度來達成目標粉末之還原即可，並無特別限制。藉此，本發明亦可達成使含氧量在5〇〇wtppm以下、300wtppm以下、甚至是100wtppm以下。本發明能夠達成此等。並且’可提供一種將比表面積（BET)調整為〇_ 15〜 0.25m /g之粉末的燒結用Sb_Te系合金粉末之製造方法。此亦同樣地，可藉由粉碎之程度等、粉末之加工方法之調整，來調整比表面積。 200946692 3)藉由對以上述方式所得之粉末進行燒結，可得到一種由Sb — Te系合金所構成之燒結體靶，其含氧量在 lOOOwtppm以下，抗彎強度在5〇MPa以上，相對密度在99 %以上。並且，本發明，可提供一種由Sb—Te系合金所構成之燒、、n體乾，其特徵在於，含氧量在5〇〇wtppm以下抗彎強度在60MPa以上，相對密度在99 5%以上。可進一步使含 ^ 氧量在500wtppm以下。所燒結成之Sb—Te系合金濺鍍靶，較佳為靶濺蝕面之表面粗糙度Ra在〇_5ym以下，本發明可達成此，藉此，粒子之發生少，可進行更均一的成膜。靶之成分組成，可含有之選自Ag、A卜As、 Au、B、C、Ga、Ge、In、p、Pd、pt、s、Se、si、Ti 之 i 種以上的元素。此等之添加元素，如上述，容易使得結晶化速度為最〇佳，且容易使得熔點及結晶化溫度為最佳。又，可提升非晶與結晶之變態的反覆耐性，並且可容易進行成膜之比電阻的最佳化。如上述，能得到可進行Sb — Te系合金濺鍍靶組織之均 —與微細化、燒結靶不會發生裂痕、濺鍍時可抑制電弧之發生的效果。並且，具有濺鑛濺钮所造成之表面的凹凸減少、靶上面之再沈積膜剝離所造成之粒子發生減少的效果。如此，藉由對靶組織進行微細化及均質化，可抑制所製作之薄膜的面内及批次間的組成變動，具有使相變化上 9 200946692 之記錄層之品質穩定的效果。又，於粉末之製造步驟之中，藉由將粉末加以還原，具有可得到低氧濃度及低碳濃度之材料的效果。並且，本發明之Sb—Te系濺鍍靶燒結體，抗f強度在6〇Mpa以上，強度高，在減鍵時不會發生裂痕、裂縫，具有極為優異的特性。藉由使用本發明之Sb_Te系合金之粉末，可使結晶化速度為最佳，且可使熔點及結晶化溫度為最佳。並且，能得到可提升非晶與結晶之變態的反覆耐性、並且可進行成膜之比電阻之最佳化的優異效果。 ❹ 【實施方式】本發明，係提供一種由平均粒徑為〇〗〜2〇〇#m之粉末所構成且含氧量在l000wtppm以下之燒結用sb_Te系合金粉末、其製造方法及對該粉末進行燒結所製得之燒結= 減鑛乾。一般而言’氣體霧化粉’可得到較機械粉末更微細之粉末，並且由於可防止因使用粉碎機械所造成之污染，因此被直接作為燒結粉末來使用。然而，並不需限定於此氣〇體霧化法’只要為可得到本發明之合金粉末的條件任何公知之粉碎加工皆可採用。然而，實際上所製造之粉碎粉在粒度上會參差不齊，在燒結時，該巨大粒子會成為燒結體靶發生裂縫的起點。’，於使用此種乾材進行滅鏟時，容易成為電弧的起點。因此，為了避免發生上述情事，可藉由分級來使粒度一致。可得到具有適當之粒度分布（平均粒徑為〇 10 200946692 之霧化粉’但以上述手法將其加以還原，可進一步使細化，可調整其粒度分布。又，藉由此還原處理，可減少因氧之混入所產生的氧化物，亦即Sb或^的氧化物，：且可減少由選自 Ag、A1、As、Au、B、c、Ga Ge、in p、Sb—Te alloy powder. The present invention further provides: 2) a method for producing a Sb-Te alloy powder for sintering, which is obtained by melting a raw material composed of a Te-based alloy, and then processing the powder into a powder, and then The obtained powder is reduced to a powder having an oxygen content of less than 100 ppm by weight and an average particle diameter of 〇1 to 2 〇〇 "111. At this time, the average particle diameter of 4 HO" m is formed (into one is the average particle diameter) The Sb-Te alloy powder for sintering of i to 20//m) is preferably a condition which can be achieved by adjustment and classification of the powder processing method. Further, in the production step of the powder, the reduction treatment can be borrowed. After vacuum drying after pickling (for example, immersion in a 5 % aqueous solution of nitric acid for 1 minute, drying under a vacuum of 100 mT rr (l3 Pa) for 6 hours), inert gas (Ar) atmosphere Medium heat treatment (for example, 5 〇〇〇 C x 2 hours), hydrogen reduction treatment (for example, 50 (TC x 2 hours), calcination treatment with reduced materials (Mg, Fe) to reduce the powder. The choice of these treatments For any, and, the conditions of restoration, as long as the root The amount of the powder and the degree of oxidation are not particularly limited as long as the reduction of the target powder is achieved. Therefore, the present invention can also achieve an oxygen content of 5 〇〇 wt ppm or less, 300 wt ppm or less, or even 100 wt ppm or less. This can be achieved. Further, a method for producing a Sb_Te-based alloy powder for sintering in which a specific surface area (BET) is adjusted to a powder of 〇 15 to 0.25 m /g can be provided. Similarly, the degree of pulverization can be achieved. Etc., adjustment of the processing method of the powder to adjust the specific surface area. 200946692 3) By sintering the powder obtained in the above manner, a sintered body target composed of an Sb-Te alloy can be obtained, and the oxygen content thereof is lOOOOwtppm or less, the flexural strength is 5 〇 MPa or more, and the relative density is 99% or more. Further, the present invention provides a sintered, n-body dry composed of an Sb-Te alloy, which is characterized by oxygen content. The flexural strength below 5 〇〇 wtppm is above 60 MPa, and the relative density is above 99 5%. The oxygen content may be further less than 500 wtppm. The sintered Sb-Te alloy sputtering target, preferably the target splash The surface roughness Ra of the etched surface is 〇5 μm or less, which can be achieved by the present invention, whereby the occurrence of particles is small, and a more uniform film formation can be performed. The component composition of the target may be selected from Ag, A, and As. , more than one element of Au, B, C, Ga, Ge, In, p, Pd, pt, s, Se, si, Ti. These additional elements, as described above, tend to make the crystallization rate the most It is preferable to optimize the melting point and the crystallization temperature, and to improve the resistance of the amorphous and crystalline metamorphosis, and to optimize the specific resistance of the film formation. As described above, it is possible to obtain an effect that the Sb-Te alloy sputtering target structure can be made fine and fine, the sintered target can be prevented from cracking, and the occurrence of arc can be suppressed during sputtering. Further, there is an effect that the unevenness of the surface caused by the splashing splash button is reduced, and the particles caused by the peeling of the redeposited film on the target are reduced. By miniaturizing and homogenizing the target structure, it is possible to suppress variations in the in-plane and batch-to-batch composition of the produced film, and to stabilize the quality of the recording layer of the phase change 9 200946692. Further, in the production step of the powder, by reducing the powder, there is an effect that a material having a low oxygen concentration and a low carbon concentration can be obtained. Further, the Sb-Te sputtering target sintered body of the present invention has an anti-f strength of 6 〇Mpa or more, has high strength, and does not cause cracks or cracks at the time of key reduction, and has extremely excellent characteristics. By using the powder of the Sb_Te alloy of the present invention, the crystallization rate can be optimized, and the melting point and the crystallization temperature can be optimized. Further, it is possible to obtain an excellent effect of improving the resistance of the amorphous and crystalline metamorphosis and optimizing the specific resistance of the film formation. [Embodiment] The present invention provides a sintering sb_Te alloy powder composed of a powder having an average particle diameter of 〇〜 2 〇〇 #m and having an oxygen content of 1000 ppm by weight or less, a method for producing the same, and a powder thereof. Sintering made by sintering = reduced ore dry. In general, the "gas atomized powder" can obtain a finer powder than the mechanical powder, and is used as a sintered powder because it can prevent contamination due to the use of a pulverizing machine. However, it is not necessary to limit the gas atomization method as long as any known pulverization process can be employed as long as the alloy powder of the present invention can be obtained. However, in practice, the pulverized powder produced may vary in particle size, and at the time of sintering, the large particles may become a starting point for cracking of the sintered body target. When using this kind of dry material to remove the shovel, it is easy to become the starting point of the arc. Therefore, in order to avoid the above, the granularity can be made uniform by grading. An atomized powder having an appropriate particle size distribution (average particle diameter of 〇10 200946692) can be obtained, but it can be further reduced by the above method, and the fine particle size can be further refined, and the particle size distribution can be adjusted. Reducing oxides generated by the incorporation of oxygen, that is, oxides of Sb or ^, and can be reduced by a selected from the group consisting of Ag, A1, As, Au, B, c, Ga Ge, in p,

Pd、Pt、S、Se、Si、Ti 之 1 錄 u 士之1種M上之兀素所構成的氧化物的形成’可抑制以此等氧化物作為起點之電弧的發生。由上述，本發明mTe系合金加㈣解後〇行粉碎加工，然後進-步將其加以還原，製成合金粉末。藉此，可製造使含氧量在1000wtppm以下之平均粒徑為〜的球狀粉末，且將所製得之球狀系人金粉末^以燒結而成之乾，由於機械強度的提升，故具Μ 裂、裂縫之發生減少的效果。較权佳為使含氧量在5〇〇wtppm 以下’更佳為使含氧量在3〇〇wtppm以下更亦可使含氧量在lOOwtppm以下，藉此可得到更佳之效果。氧之降低化’可藉由氫還原處理之加熱溫度與時間、 ©於酸f真空換裝處理令調整酸濃度、處理時間或真空度、惰性氣體中進行熱處理之還原處〆行使用有還原材⑽' Fe)=:二熱時間與時間、進鍛燒溫度來達成。還原處理時調整混合處理量與此等條件，由於亦有必要根玴吾>5备少〜“ 脊根據Sb— Te系合金粉末之處量氧之存在（3有量）來進行調整，因二：:據作為目標之條件，亦即可根據作為=氧氣量來任意調整。 π曰知（乳亂 -般而言’由於外1系合金黏度較高，因此於機械 11 200946692 粉碎時會大量附著於粉碎治具，又粉末相互接觸而發生粉末粒子被壓軋之現象。因此，若長時間進行粉碎，則在扁平狀（平板狀）粒子形成的同時，亦會產生粒度未達〇1“瓜之微粉這樣的問題。 m 此種平板狀粒子，由於粒形變大，而成為粒子之不均一性的原因，因此無法使用於燒結體，造成原料產率的惡化。此意味容易得到球狀粉之霧化法為推薦之粉碎方法。本發明’最後可得到平均粒徑為的球狀粉末。Sb — Te系合金之粒子形狀，若整體觀之，係由平均〇粒徑為0.1〜200私m之球狀粉末所構成，亦可製成平均粒徑為10〜50"m之大直徑之球狀粉末、與平均粒徑為〜10/zm之小直徑之球狀粉末的混合體。又，此大直徑之球狀粉末與小直徑之球狀粉末的容積比率，分別較佳在1〇〜 90%之範圍。此可於氣體霧化等之粉碎粉的製造階段來進行調整。於燒結時，由於小直徑之粒子會進入大直徑之粒子間，因此可得到均一且緻密之燒結體，此亦是一項優點。〇容積比率為10〜90%，係表示用以達成其之最佳的條件。本發明之燒結用Sb—Te系合金粉末及將此粉末燒結所製得之燒結體濺鍍靶，可含有最大3〇at%之選自Ag、ai、The formation of an oxide composed of a halogen on the M of one of Pd, Pt, S, Se, Si, and Ti can suppress the occurrence of an arc having such an oxide as a starting point. From the above, the mTe-based alloy of the present invention is subjected to a pulverization process by addition of (4), and then it is further reduced to form an alloy powder. Thereby, a spherical powder having an average particle diameter of ~1 or less and having an oxygen content of 1000 wtppm or less can be produced, and the obtained spherical human gold powder can be sintered and dried, and the mechanical strength is improved. It has the effect of reducing cracks and cracks. Preferably, the oxygen content is 5 〇〇 wtppm or less. More preferably, the oxygen content is 3 〇〇 wt ppm or less, and the oxygen content is 100 MPa or less, whereby a better effect can be obtained. The reduction of oxygen can be achieved by the heating temperature and time of the hydrogen reduction treatment, the adjustment of the acid concentration, the treatment time or the degree of vacuum by the acid f vacuum replacement treatment, and the reduction of the heat treatment in the inert gas. (10) 'Fe) =: The second heat time and time, the temperature of the calcination is achieved. In the reduction treatment, it is necessary to adjust the amount of the mixing treatment and the above conditions. Since it is also necessary to reduce the amount of oxygen in the Sb-Te alloy powder (the amount is 3), it is necessary to adjust 2: According to the conditions as the target, it can be adjusted arbitrarily according to the amount of oxygen = π 曰 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( When the powder is adhered to the pulverizing jig and the powders are in contact with each other, the powder particles are pulverized. Therefore, if the pulverization is carried out for a long period of time, the flat (plate-like) particles are formed, and the particle size is less than 〇1. The problem of micro-powder of melon. m such a tabular particle is a cause of unevenness of particles due to the large grain size, and therefore cannot be used in a sintered body, resulting in deterioration of raw material yield. This means that spherical powder is easily obtained. The atomization method is the recommended pulverization method. The present invention 'finally obtains a spherical powder having an average particle diameter. The particle shape of the Sb-Te alloy, if viewed as a whole, is an average 〇 particle size of 0.1 〜 It is composed of 200 gram of spherical powder, and can also be a mixture of a spherical powder having a large diameter of 10 to 50 mm and a spherical powder having a small diameter of 〜10/zm. Further, the volume ratio of the large-diameter spherical powder to the small-diameter spherical powder is preferably in the range of 1 〇 to 90%, which can be adjusted at the production stage of the pulverized powder such as gas atomization. At the time of sintering, since small-diameter particles enter between large-diameter particles, a uniform and dense sintered body can be obtained, which is also an advantage. The volume ratio of 〇 is 10 to 90%, which is used to achieve The Sb-Te alloy powder for sintering of the present invention and the sintered body sputtering target obtained by sintering the powder may contain a maximum of 3 〇 at% selected from Ag, ai,

As、Au、B、C、Ga、Ge、In、p、pd、pt、s、以、si、^ 之i種以上的元素，來作為添加元素。藉此，可得到晶粒微細且強度高的Sb — Te系合金燒結體濺鍍靶。藉由此添加元素，可使結晶化速度為最佳，且可使熔 12As, Au, B, C, Ga, Ge, In, p, pd, pt, s, 、, si, ^ are more than one element, as an additive element. Thereby, an Sb-Te alloy sintered body sputtering target having fine crystal grains and high strength can be obtained. By adding elements, the crystallization rate can be optimized and the melting can be achieved.

❹ 200946692 點及結晶化溫度為蜃反覆耐性，並且可H又，可提升非晶與結晶之變態的、卫且了進仃成膜之比電阻的最佳化。上述添加元素之選擇與 ^ ^ 伴兴添加量，可根據元素所具有之特性’來對添加量進行镧棼、3分务則益調整通常’右添加量未達lat%，果又，若超過上限值時，則由於有喪失作、…、之相變化記錄用材料之機能之虞，因此選自Ag、Al、 AS、AU、B、C、Ga、Ge、In、P、Pd、Pt、S、Se、si、Ti 之1種以上之70素的添加量’較佳為1〜30at%。此種元素之選擇與添加為任意。、般’濺鍍後之濺蝕面’會成為表面粗糙度Ra為1" 、之粗糙面，會有隨著濺鑛之進行而變得越來越粗的傾向，但本發明之Sb-Te系合金錢鍵&，係一種賤鍵後之潑蝕面的表面粗糙度Ra會在〇5#m以下之極為不同之处― Te系合金踐鍍乾。如此，均一微細之結晶構造之靶，濺鍍濺蝕所造成之表面凹凸會減少，可抑制靶上面之再沈積（再附著物）膜剝離所造成之粒子發生。又’由於組織微細化’故亦可抑制減鑛膜之面内及批次間之組成變動’具有相變化記錄層之品質穩定的優點。因此’如此便可有效抑制濺鍍時粒子的發生、異常放電、結球的發生等。又’本發明之Sb — Te系濺鍍靶，使抗彎強度在60MPa 以上’此為一重點。如此藉由顯著提升機械強度，可有效地減少靶之龜裂或裂縫的發生。 13 200946692 並且，本發明之Sb—Te系濺鍍靶藉由使含氧量在 1〇〇〇wtppm以下，不僅可進一步提升機械強度，降低靶之龜裂或裂縫的發生’且可進一步減少粒子、異常放電的發生。如此，還原具有重要之角色。又，本發明，可提供一種特別添加有卜3〇at%之選自 N (：、3、？、81、3之元素之任一成分以上的燒結用外— Te系合金粉末。如上述，藉由此等之輕元素的添加，於薄膜中，上述輕元素會進入Sb—Te合金之晶格間，具有實現薄膜之比電阻之最佳化的效果。又，於靶中，由於會析出於結晶晶界，具有作為内部應力之緩衝層的機能因此具有可實現增加機械強度的效果。另，此時，雖然具有與上述說明書第12頁第24行〜第13頁第9行所記載之添加元素重複的元素，但應容易理解其選擇與調整係任意。為了保有此種添加之效果，故必須在lat%以上，但係根據需要所進行者，添加為任意。添加時係在3〇at%以下。若超過此上限值，則靶之強度會降低，於靶製造時或使用時，靶會產生裂縫，故不佳^ 結晶粒微細且強度高之本發明之Sb—Te系濺鍍靶之製造所使用的粉末，可使用具有〇.5m2/g以上（甚至〇7m2/g 以上）之比表面積（BET)的粉末。於上述，雖然敘述了主要的構成要件，但應理解附帶且附加之要件，為不一定要被納入發明之主要構成要件者。亦即，係可根據靶之視為必要之性質或用途來任意採 200946692 實施例說明本發明之實施例。另，本實施例僅為一例，而非限制於此例亦即，於本發明之技術思想的範圍内，包含實施例以外之全部態様或變形。 (實施例1) 對GeMjSbujTew.^at% )合金原料使用氣體霧化裝置製成霧化粉。此霧化粉之平均粒徑為15“m，含氧量為 11 OOwtppm 〇進一步將此氣鱧霧化粉浸潰於硝酸50%水溶液1〇分鐘，以1〇Pa於真空中乾燥6小時，藉此進行還原處理。：由此還原處理，使含氧量為550wtppm。又’平均粒徑為14 〆m 〇藉由熱壓，將以上述方式所得之粉末製成相對密度1〇〇 %之高密度靶。此靶之抗彎強度為70MPa，得到具有極高強度的燒結體（靶）。又，完全沒有發生裂痕。 Q 使用此托實施減鑛。結果，沒有發生電弧，1 〇k\V · hr 後之平均粒子發生數為30個，實施濺鍍後之濺蝕面的表面粗糙度Ra為0.4# m。將以上之結果示於表j。 (實施例2) 對上述實施例丨之氣體霧化粉，藉由在Μ環境氣氛下以500t進行2小時之熱處理，來進行還原處理。藉由此還原處理，使含氧量為29〇wtppn^又，平均粒徑為13以爪。藉此所得之粉末的SEM照片（影像）示於圖丨。圖i之比例尺如圖内所示。 15 200946692 如圖所示，得到粒徑為1〜5〇wm之範圍之完美球形的粉末。3 ’此場合’平均粒禮為⑺〜心瓜之大直經的球狀粉末，以容積率計約8〇%，平均粒徑為i〜i〇#m之小直徑的球狀粉末’以容積率計則約2〇%。另大直徑之球狀粉末大部分為15〜20/zm左右之球狀粉末。將圖2作為參考圖。此圖2，係氣艘霧化粉，為未調節粉末之粒在，亦即未經調節之粉末。此氣體霧化粉大部分之粒徑係在60〜70 之範圍，並不適於本案之目的。 ^並且，藉由熱壓，將以上述方式所得之粉末製成相對 © 密度100%之高密度靶。此靶之抗彎強度為70MPa，得到具有極高強度的燒結體（靶）。又，完全沒有發生裂痕。使用此靶實施濺鍍。結果，沒有發生電弧，i 〇kw · ^ 後之平均粒子發生數為25個，實施濺鍍後之濺蝕面的表面粗糙度Ra為0.4私m。將以上之結果示於表i。 [表1 ] 16❹ 200946692 The point and crystallization temperature are 蜃 resistance, and H can improve the amorphous and crystalline metamorphism, and optimize the specific resistance of the film. The selection of the above-mentioned additive elements and the addition amount of the ^ ^ can be added according to the characteristics of the element ', the amount of addition is 镧棼, and the 3 points are adjusted. Generally, the right addition amount is less than lat%, and if it exceeds When the upper limit value is used, it is selected from Ag, Al, AS, AU, B, C, Ga, Ge, In, P, Pd, Pt because of the function of the material for recording the phase change. The addition amount of 70 or more of one or more of S, Se, Si, and Ti is preferably 1 to 30 at%. The selection and addition of such elements is arbitrary. The 'splashing surface after sputtering' will become a rough surface with a surface roughness Ra of 1", which tends to become thicker as the splashing progresses, but the Sb-Te of the present invention The alloy surface money & is a kind of ruthenium surface, the surface roughness Ra of the ruthenium surface will be very different below 〇5#m - Te system alloy is dried. Thus, the target of the uniform fine crystal structure is reduced in surface unevenness due to sputtering spatter, and the occurrence of particles caused by the re-deposition (reattachment) film peeling on the target can be suppressed. Further, the structure variation can be suppressed in the in-plane and batch between the reduced ore films, and the quality of the phase-change recording layer is stabilized. Therefore, the occurrence of particles, abnormal discharge, and occurrence of ball formation during sputtering can be effectively suppressed. Further, the Sb-Te sputtering target of the present invention has a bending strength of 60 MPa or more. Thus, by significantly increasing the mechanical strength, the occurrence of cracks or cracks in the target can be effectively reduced. 13 200946692 Further, the Sb—Te-based sputtering target of the present invention can further improve the mechanical strength and reduce the occurrence of cracks or cracks of the target by making the oxygen content less than 1 〇〇〇 wt ppm, and further reduce the particles. The occurrence of abnormal discharge. As such, restoration has an important role. Further, according to the present invention, it is possible to provide an outer-Te alloy powder for sintering which is selected from any one of elements of N (:, 3, ?, 81, and 3). By adding such a light element, the light element enters the lattice of the Sb—Te alloy in the film, and has an effect of optimizing the specific resistance of the film. Further, in the target, precipitation occurs. In the crystal grain boundary, the function of having a buffer layer as internal stress has an effect of achieving an increase in mechanical strength. Further, at this time, it has the same as that described on page 12, line 24 to page 13, line 9 of the above specification. Add elements with repeated elements, but it should be easy to understand that the selection and adjustment are arbitrary. In order to maintain the effect of such addition, it must be above lat%, but it is added as needed according to the needs. If it exceeds the upper limit, the strength of the target will decrease, and the target will be cracked during the manufacture or use of the target, so that the Sb-Te splash of the present invention is fine and has high strength and high strength. Powder used in the manufacture of plating targets A powder having a specific surface area (BET) of 〇.5 m 2 /g or more (or even m 7 m 2 /g or more) may be used. In the above, although the main constituent elements are described, it should be understood that the incidental and additional requirements are not necessarily It is to be included in the main constituent elements of the invention. That is, the embodiment of the present invention can be arbitrarily used according to the nature or use of the target as deemed necessary. In addition, this embodiment is only an example, not a limitation. In this example, all the states or deformations other than the examples are included within the scope of the technical idea of the present invention. (Example 1) A gas atomizing device is used to form an atomized powder for a GeMjSbujTew. . The atomized powder has an average particle diameter of 15"m and an oxygen content of 11 OOwtppm. The gas atomized powder is further immersed in a 50% aqueous solution of nitric acid for 1 minute, and dried in a vacuum of 1 〇Pa for 6 hours. The reduction treatment is thereby carried out. The reduction treatment is carried out so that the oxygen content is 550 wtppm, and the average particle diameter is 14 〆m. The powder obtained in the above manner is made to have a relative density of 1% by mass by hot pressing. High-density target. The target has a flexural strength of 70 MPa, and a sintered body (target) with extremely high strength is obtained. Further, no cracks occur. Q The ore is used to perform the reduction. As a result, no arc occurs, 1 〇k\ The average number of particles generated after V · hr was 30, and the surface roughness Ra of the sputtered surface after sputtering was 0.4 # m. The above results are shown in Table j. (Example 2) For the above example The gas atomized powder was subjected to a reduction treatment by heat treatment at 500 t for 2 hours in an atmosphere of ruthenium. By this reduction treatment, the oxygen content was 29 〇wtppn^, and the average particle diameter was 13 to the claw. The SEM photograph (image) of the powder thus obtained is shown in Fig. 比例. As shown in the figure, 15 200946692, as shown in the figure, a perfectly spherical powder with a particle size of 1 to 5 〇 wm is obtained. 3 'This occasion' is an average granule (7) ~ a heart-shaped spheroid The powder, about 8% by volume ratio, and the small-diameter spherical powder having an average particle diameter of i~i〇#m is about 2% by volume. The other large-diameter spherical powder is mostly 15 Sphere powder of ~20/zm. Figure 2 is taken as a reference figure. This Figure 2 is a gas atomized powder, which is an unadjusted powder, that is, an unregulated powder. The particle size of the portion is in the range of 60 to 70, which is not suitable for the purpose of the present invention. ^ Also, the powder obtained in the above manner is made into a high-density target having a density of 100% relative to 100% by hot pressing. The bending strength was 70 MPa, and a sintered body (target) having extremely high strength was obtained. Further, no crack occurred. The sputtering was carried out using this target. As a result, no arc occurred, and the average particle number after i 〇kw · ^ was 25 The surface roughness Ra of the sputtered surface after sputtering was 0.4 m. The above results are shown in Table i. Table 1] 16

200946692 (實施例3) 以Jr上進述實Γ例1之氣⑽^ 二〇時之減理，來進行還原處理。藉由此還原處理，使含氧量Aq 藉由此還 …: 又’平均粒徑為13"- 一—，將以上述方式所得之粉末製成相對密度100 /之咼密度乾。此勒竣由& 強声…：為80Mpa，得到具有極高強度的燒結_。又，完全沒有發生裂痕。200946692 (Embodiment 3) The reduction treatment was carried out by the reduction of the gas (10) ^ 2 Γ of the example 1 of Jr. By this reduction, the oxygen content Aq is thus made to have a relative density of 100 / 咼 density by means of a further average particle size of 13 "--. This 竣 is made by & strong sound...: 80Mpa, which gives a very high strength sintering _. Again, there were no cracks at all.

/使用此乾實施踐鍍。結果，沒有發生電弧，10kw· hr 後之平均粒子發生數為19個，實施⑽後之料面的表面粗糙度Ra為0.4 " m。將以上之結果示於表i。 (實施例4) 進步將上述實施例1之氣體霧化粉與預先經過還原處理之鐵粉加以混合’以則。c進行24小時之圾燒然後將鐵粉加以去除，藉此進行還原處理。藉由此還原處理，使含氧量為600wtPpm。又，平均粒徑為14"m。藉由熱壓’將以上述方式所得之粉末製成相對密度1〇〇/ Use this dry to implement plating. As a result, no arc occurred, and the average number of occurrences of particles after 10 kw·hr was 19, and the surface roughness Ra of the surface after the implementation of (10) was 0.4 " m. The above results are shown in Table i. (Example 4) Progress The gas atomized powder of the above Example 1 was mixed with the iron powder previously subjected to the reduction treatment. c The rubbing is carried out for 24 hours and then the iron powder is removed to carry out the reduction treatment. By this reduction treatment, the oxygen content was made 600 wt Ppm. Further, the average particle diameter is 14 " m. The powder obtained in the above manner was made into a relative density by hot pressing.

%之尚密度靶。此靶之抗彎強度為60Mpa，得到具有極高強度的燒結體（起）。又，完全沒有發生裂痕。然後，使用此靶實施濺鍍。結果，沒有發生電弧，i 0kw · hr後之平均粒子發生數為35個’實施濺鍍後之濺蝕面的表面粗糙度Ra為〇.4仁將以上之結果示於表1。 (實施例5) 對上述實施例1之氣體霧化粉，藉由在Ar環境氣氛下 18 200946692 以50(TC進行5小時之熱處理，來進行還原處理。藉由此還原處理，使氧更加減少，含氧量為2〇〇wtppm。又，此還原處理後之平均粒徑為13#me其他之粉末的特性，並無特別產生變化，抗彎強度為72MPa，與實施例2 相較之下’得到具有更高強度的燒結體⑻。X，完全沒有發生裂痕。〇 ❹ 從以上，可確§忍還原處理能夠減少氧，且對抗彎強度之增加具有很大的助益。此雖然無特別顯示在實施例但並不限於Ge22 2Sb22.2Te55.6(at%)合金材料，可確認於本發明之燒結用Sb-Te系合金粉末之全部，皆具有相同之傾向。使用此乾實施減鍍。結果，沒有發生電弧，碰评士後之平均粒子發生數為15個，實施續後之賴面的表面粗糙度Ra為0.4" m。將以上之結果示於表卜 (實施例6) 將Ge22.2Sb22.2Te55.6(at%)合金原料導入機械粉碎用機 ϋ之㈣球磨機’㈣Ar惰性氣體作為環境氣氛氣體，進订機械粉碎°機械粉碎時間為20分。其結果，得到平均粒徑2〇㈣之粉末。對此粉碎粉之超過谓㈣的粉末，藉由分級加以去除。粉碎粉之含氧量為靡吻㈣。進一步將此粉碎粉浸潰於硝酸50%水溶液10分鐘，以 2於真空中乾燥6小時’藉此進行還原處理。藉由此還二處：，使含氧量為7〇一。又，此還原處理後之平均粒控為19 /z m。藉由熱Μ ’將以上述方式所得之粉末製成相對密度⑽ 200946692 %之高密度乾。此乾之抗弩強度為65 MPa，得到具有^強度的燒結體（靶”又，沒有發生裂痕。然後，使用此乾實施濺鍍。結果’沒有發生電弧’ 1 OkW · hr後之平均粒子發生數為25個’實施濺鍵後之濺姓面的表面粗輪度^^為〇9〆爪，為良好之結果。將以上之結果示於表1。 (實施例7) 將GezuSl^uTess.dat% )合金原料以喷射磨機加以粉碎，得到平均粒徑2ym之粉末。此粉碎粉之氧含有量為 © 6〇〇〇wtPpnm進一步對此粉碎粉在氫環境氣氛下以5〇〇。(：進行12小時之熱處理，藉此進行還原處理。藉由此還原處理，使含氧量為900wtppm。又，此還原處理後之平均粒徑為2 // m。藉由熱壓，將以上述方式所得之粉末製成相對密度1〇〇 %之高密度靶。此靶之抗彎強度為90MPa，得到具有高強度的燒結體（靶）。又，沒有發生裂痕。然後，使用此靶實施濺鍍。〇結果’沒有發生電弧，1 OkW · hr後之平均粒子發生數為25個，實施濺鍍後之濺蝕面的表面粗糙度Ra為〇.1 “m，為良好之結果。將以上之結果示於表1。 (比較例1) 將Ge22 2Sb22 2Te55.6(at% )合金原料導入機械粉碎用機器之振動球磨機，使用Ar惰性氣體作為環境氣氛氣體，進行機械粉碎。機械粉碎時間為2〇分。此機械粉碎後之氧含 20 200946692 有量為1500wtppm。又，最大教徑暴增至则口。其進行刀級’得到平均粒徑3 〇 "爪之粉末。又對此粉末進仃熱壓。結果，相對密度冑”％，抗彎強度為 50MPa’得到抗f強度低的燒結鱧⑻。又有發生裂痕。、，使用此乾實施賤鑛。結果，有發生電弧，】〇請· ^後之平均粒子發生數增加至14〇個。又實施錢鍵後之滅触面的表面粗糙度“為0.9^m。將以上之結果示於表卜〇如以上所示，可確認含氧量之增加，將會產生大量的粒子。 (比較例2) 對GemSbnjTe55.6^% )合金原料使用氣體霧化裝置製成霧化粉。此霧化粉之平均粒徑為15"m，含氧量為 11 OOwtppm。對此粉末進行熱壓。結果，相對密度為97%，抗彎強度為52MPa，得到抗彎強度低之燒結體（靶）。又，有發生裂 Q 痕。使用此無實施減鑛。結果，有發生電弧，1 W · hr後之平均粒子發生數為90個。又，實施濺鍍後之濺蝕面的表面粗糙度Ra為〇_5//m。將以上之結果示於表1。如以上所示，可確認含氧量之增加，將會產生大量的粒子β (比較例3) 將比較例2之氣體霧化粉加以分級，使之為平均粒徑η Mm。此時，含氧量為i500wtppm。 21 200946692 對此粉末進行熱Μ。結果，相對密度$ 97%，抗弯強度為55MPa’得到抗f強度低之燒結體（乾）。X，有發生裂痕。、使用此靶實施濺鍍。結果，有發生電弧，1〇kW ·心後之平均粒子發生數為70個。又，實施濺鍍後之濺蝕面的表面粗輪度Ra為0.4私m。將以上之結果示於表如以上所示，可確認含氧量之增加，將會產生大量的粒子。 (實施例8) 〇將上述比較例1所示之機械粉碎粉加以分級，使之為平均粒徑30//m，對其進行氫還原，使之為平均粒徑26以 m、氧濃度550ppm。藉由熱壓，將以上述方式所得之粉末製成相對密度1〇〇 %之高密度靶。此靶之抗彎強度為65Mpa，得到具有高強度的燒結體（靶）。又，沒有發生裂痕。使用此靶實施濺鍍。結果，沒有發生電弧，l〇kw · hr 後之平均粒子發生數為20個，實施濺鍍後之濺蝕面的表面粗輪度Ra為0.9 em，為良好之結果。將以上之結果示於表卜 (實施例9) 對Ag5.0In5.0Sb70 0Te2〇 0(at%)合金原料使用氣體霧化裝置製成霧化粉。此霧化粉之平均粒徑為15/ζιη，含氧量為 9〇wtppm。對此氣體霧化粉，藉由在氫環境氣氛下以500°C進行2 小時之熱處理，來進行還原處理。藉由此還原處理，使含 22 200946692 氧量為 350wtppm。τ , ΡΡ 又，平均粒徑為13ym。藉由熱壓，將以卜+ ^ 一上述方式所付之粉末製成相對密度100 %之同密度此乾之抗彎強度為8QMpa，得到強度的燒結體⑻。又，完全沒有發生裂痕，、。使用此粗實施濺錢。結果，沒有發生電狐，l〇kW · hr 後之平均粒子發生數為_，實施濺鑛後之㈣面的表面粗糙度Ra為0·4 β m。將以上之結果示於表1。 (實施例10)% of the density target. The target had a flexural strength of 60 MPa, and a sintered body having extremely high strength was obtained. Again, there were no cracks at all. Then, sputtering is performed using this target. As a result, no arc occurred, and the average number of occurrences of particles after i 0kw · hr was 35. The surface roughness Ra of the sputtered surface after sputtering was 〇.4 kernel. The above results are shown in Table 1. (Example 5) The gas atomized powder of the above-mentioned Example 1 was subjected to a reduction treatment by heat treatment at 50, TC for 5 hours in an Ar ambient atmosphere at 18 200946692. By this reduction treatment, oxygen was further reduced. The oxygen content is 2 〇〇 wt ppm. Further, the average particle diameter after the reduction treatment is 13#me, and the characteristics of the other powders are not particularly changed, and the bending strength is 72 MPa, which is compared with Example 2. 'The sintered body (8) with higher strength is obtained. X, there is no crack at all. 〇❹ From the above, it can be confirmed that the reduction treatment can reduce oxygen, and it is very helpful to increase the bending strength. In the examples, it is not limited to the Ge22 2Sb22.2Te55.6 (at%) alloy material, and it is confirmed that all of the Sb-Te alloy powders for sintering of the present invention have the same tendency. As a result, no arc occurred, and the average number of occurrences of particles after hitting the judges was 15, and the surface roughness Ra of the succeeding surface was 0.4 " m. The above results are shown in Table (Example 6). Ge22.2Sb22.2Te55.6 (at%) alloy raw materials (4) Ball mill (4) Ar inert gas is used as the ambient atmosphere gas, and the mechanical pulverization time is 20. The mechanical pulverization time is 20 minutes. As a result, a powder having an average particle diameter of 2 〇 (4) is obtained. (4) The powder is removed by classification. The oxygen content of the pulverized powder is 靡 kiss (4). The pulverized powder is further immersed in a 50% aqueous solution of nitric acid for 10 minutes, and dried in 2 hours in vacuum for 6 hours. Therefore, the oxygen content is 7 〇. Further, the average particle size after the reduction treatment is 19 /zm. The powder obtained in the above manner is made into a relative density by heat ( (10) 200946692% high density dry. The dry strength of this dry is 65 MPa, and the sintered body (target) with ^ strength is obtained, and no crack occurs. Then, the dry is used for sputtering. The result 'no arc occurs' 1 OkW · The average number of particles generated after hr is 25 'the surface roughness of the splashed surface after the splash key is ^ 〆 9 〆 claw, which is a good result. The above results are shown in Table 1. 7) Will GezuSl^uTess.dat%) alloy The material was pulverized by a jet mill to obtain a powder having an average particle diameter of 2 μm. The pulverized powder had an oxygen content of 6 〇〇〇wt Ppnm and further the pulverized powder was 5 Torr under a hydrogen atmosphere. (: 12 hours) The heat treatment is carried out, whereby the reduction treatment is carried out, whereby the oxygen content is 900 wtppm by the reduction treatment, and the average particle diameter after the reduction treatment is 2 // m. The powder obtained in the above manner is obtained by hot pressing. A high-density target having a relative density of 1% by weight was produced, and the target had a flexural strength of 90 MPa, and a sintered body (target) having high strength was obtained. Again, no cracks occurred. Then, sputtering is performed using this target. 〇Results 'There is no arc, the average particle number after 1 OkW · hr is 25, and the surface roughness Ra of the sputtered surface after sputtering is 〇.1 "m, which is a good result. The above result (Comparative Example 1) A Ge22 2Sb22 2Te55.6 (at%) alloy raw material was introduced into a vibratory ball mill of a machine for mechanical pulverization, and Ar inert gas was used as an ambient atmosphere gas to carry out mechanical pulverization. The mechanical pulverization time was 2 〇. The mechanically pulverized oxygen contains 20 200946692 and the amount is 1500wtppm. In addition, the maximum diameter is increased to the mouth. It is graded to obtain a powder with an average particle size of 3 〇" claws. Hot pressing. As a result, the relative density 胄"%, the bending strength was 50 MPa', and the sintered crucible (8) having a low anti-f strength was obtained. There are cracks. , using this dry implementation of antimony ore. As a result, there was an arc, and the average number of particles after the increase was increased to 14〇. Further, the surface roughness of the touch-off surface after the execution of the money key was "0.9 m". The above results are shown in the table. As shown above, it can be confirmed that an increase in the oxygen content causes a large amount of particles to be produced. Example 2) An atomized powder was prepared using a gas atomizing device for a GemSbnjTe55.6^% alloy raw material. The atomized powder had an average particle diameter of 15 " m and an oxygen content of 11 OO wtppm. The powder was hot pressed. As a result, the relative density was 97%, the flexural strength was 52 MPa, and a sintered body (target) having a low bending strength was obtained. Further, a cracked Q mark occurred. No reduction was performed using this. As a result, an arc occurred, 1 W· The average particle number after hr was 90. The surface roughness Ra of the sputtered surface after sputtering was 〇_5//m. The above results are shown in Table 1. As shown above, it was confirmed When the oxygen content is increased, a large amount of particles β will be produced (Comparative Example 3) The gas atomized powder of Comparative Example 2 is classified to have an average particle diameter η Mm. At this time, the oxygen content is i500 wtppm. 21 200946692 The powder was enthalpy. As a result, the relative density was 97%, and the flexural strength was 55 MPa' to obtain the anti-f strength. The sintered body is low (dry). X is cracked. This target is used for sputtering. As a result, there is an arc, and the average number of particles generated after 1 〇 kW · the heart is 70. The surface roughness Ra of the surface to be sputtered was 0.4 m. The above results are shown in the above table, and it was confirmed that an increase in oxygen content caused a large amount of particles. (Example 8) The mechanically pulverized powder shown in Example 1 was classified to have an average particle diameter of 30 / / m, and subjected to hydrogen reduction to have an average particle diameter of 26 m and an oxygen concentration of 550 ppm. The powder obtained in the manner was a high-density target having a relative density of 1% by weight. The target had a flexural strength of 65 MPa, and a sintered body (target) having high strength was obtained. Further, no crack occurred. Sputtering was carried out using this target. As a result, no arc occurred, and the average number of occurrences of particles after l〇kw·hr was 20, and the surface roughness Ra of the sputtered surface after sputtering was 0.9 em, which was a good result. Table (Example 9) Gas for Ag5.0In5.0Sb70 0Te2〇0 (at%) alloy raw material The atomizing device is made into an atomized powder. The atomized powder has an average particle diameter of 15/ζιη and an oxygen content of 9 〇wtppm. The gas atomized powder is subjected to 500 ° C under a hydrogen atmosphere atmosphere. After a small heat treatment, the reduction treatment is carried out. By this reduction treatment, the oxygen content of 22 200946692 is 350 wtppm. τ , ΡΡ , and the average particle diameter is 13 μm. By hot pressing, it will be paid by the above method. The powder was made to have a density of 100% of the same density, and the dry bending strength was 8 QMpa to obtain a sintered body (8) having a strength. Also, there were no cracks at all. Use this rough implementation to splash money. As a result, the electric fox did not occur, and the average particle generation amount after l 〇 kW · hr was _, and the surface roughness Ra of the (four) surface after the splashing was performed was 0·4 β m. The above results are shown in Table 1. (Embodiment 10)

D 對Ge21.lSb21lTe52.8B5.〇(at%)合金原料使用氣體霧化裝置製成霧化粉。藉此’得到平均粒徑15 " m之粉末。此粉碎籾之3氧量為1600wtppm。於此粉碎粉加入硼（B)，使其含置為5at%，藉由在氫環境氣氛下以5〇(rc進行2小時之熱處理，來進行還原處理。藉由此還原處理，使含氧量為 85wtpPm。又，平均粒徑為13从m。藉由熱壓’將以上述方式所得之粉末製成相對密度1〇〇 ^ %之两密度靶。此靶之抗彎強度為80MPa，得到具有極高強度的燒結體（靶）。又，完全沒有發生裂痕。使用此靶實施濺鍍。結果，沒有發生電弧，l〇kw · hr 後之平均粒子發生數為19個，實施濺鍍後之濺蝕面的表面粗链度Ha為〇·4 μ m。將以上之結果示於表1。從以上之實施例及比較例清楚可知，含氧量會造成極大之影響。若氧之含有量增加，則由於燒結體會有空孔殘留’且會發生裂痕，故無法充分提高相對密度，因此造成燒、结後之靶強度下降，在濺鍍時產生發生大量粒子的問題。 23 200946692 而本發明，可提供一種能夠解決此種問題之燒結用％ —Te系合金粉末。產業上之可利用性如以上之記載，藉由使用本發明之粉末，能夠得到可使得Sb—Te系合金濺鍍靶組織均一及微細化、燒結乾不會發生裂痕、在濺鍍時可抑制電弧之發生的優異效果。又， ❹ 具有濺鑛減姓所造成之表面的凹凸減少、無上面之再尤積膜剝離所造成之粒子發生減少的效果。又以此方式藉由對靶組織進行微細化及均質化，可抑制所製作之薄膜的面内及批次間的組成變動，具有使相變化上之記錄層之品質穩定的效果，並且可降低因濺鍍速率之不同所造成之結球的發生，結果可抑制粒子的發生。因此，極適用作為由燒結用Sb—Te系合金粉末，例如D A gas atomizing device was used to form an atomized powder for the Ge21.lSb21lTe52.8B5.〇 (at%) alloy material. Thereby, a powder having an average particle diameter of 15 " m is obtained. The amount of oxygen in this mash was 1600 wtppm. Boron (B) was added to the pulverized powder, and the content thereof was set to 5 at%, and the reduction treatment was carried out by heat treatment at 5 Torr (rc for 2 hours in a hydrogen atmosphere). By this reduction treatment, oxygenation was carried out. The amount of the target is 85 wtp Pm. Further, the average particle diameter is 13 m. The powder obtained in the above manner is made into two density targets having a relative density of 1 〇〇 ^ % by hot pressing. The bending strength of the target is 80 MPa, A sintered body (target) having extremely high strength. Further, no crack occurred. The sputtering was carried out using this target. As a result, no arc occurred, and the average number of occurrences after l〇kw·hr was 19, after sputtering The surface roughness Ha of the sputtered surface was 〇·4 μm. The above results are shown in Table 1. It is clear from the above examples and comparative examples that the oxygen content causes a great influence. When the amount is increased, since the sintered body has pores remaining and cracks occur, the relative density cannot be sufficiently increased, so that the target strength after firing and the junction is lowered, and a large number of particles are generated during sputtering. 23 200946692 Invention, can provide a solution As a matter of the above, the use of the powder of the present invention makes it possible to make the Sb-Te alloy sputtering target structure uniform and fine. Sintered dry does not cause cracks, and it can suppress the occurrence of arcing during sputtering. Moreover, ❹ has a reduction in the surface unevenness caused by splashing and reducing the surname, and the particle is reduced due to the peeling of the upper surface without the film. In this way, by miniaturizing and homogenizing the target structure, it is possible to suppress variations in composition of the film to be produced in-plane and between batches, and to stabilize the quality of the recording layer in phase change. Further, it is possible to reduce the occurrence of ball formation due to the difference in sputtering rate, and as a result, the occurrence of particles can be suppressed. Therefore, it is highly suitable as a Sb-Te alloy powder for sintering, for example,

Ag-In-Sb-Te合金或Ge—Sb—Te合金所構成之用以形成相變化記錄層的Sb—Te系合金_乾、適合用以製造該 ❹ 把之燒結用Sb-Te系合金粉末及燒結用m系合金粉末之製造方法。【圖式簡單說明】圖 1，係對 Ge22X , 4η/ x x 22 2Te55_6(at% )合金原料之氣體霧粉進行還原處理後之粉末的SEM照片（影像）。圖、Ge22 2Sb22.2Te55.6(at%)合金原料之氣趙霧化的SEM照片（影像）。【主要元件符號說明】無 24An Sb—Te alloy composed of an Ag—In—Sb—Te alloy or a Ge—Sb—Te alloy for forming a phase change recording layer—dry, suitable for the production of the Sb-Te alloy powder for sintering And a method for producing an m-based alloy powder for sintering. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a SEM photograph (image) of a powder obtained by reducing a gas mist of a Ge22X, 4η/ x x 22 2Te55_6 (at%) alloy material. Fig., SEM photograph (image) of gas atomization of Ge22 2Sb22.2Te55.6 (at%) alloy material. [Main component symbol description] None 24

Claims

200946692 VII. Patent application scope: 1. A Sb-Te alloy powder for sintering, characterized in that the oxygen content of the powder having an average particle diameter of 0 1 to 2 is 111 or less. 2. A cerium-Te alloy powder for sintering, characterized in that the oxygen content of the powder having an average particle diameter of 〇1 to 2 〇〇1 is less than 500 wtppm 〇3. The alloy powder is characterized in that it is composed of a powder having an average particle diameter of 〇.1 to 2〇〇#m, and the oxygen content is 100 wtppm or less. 4. The cerium-Te alloy powder for sintering according to any one of the above claims, wherein the average particle diameter is from the claw. 5. The sintering-based Te-based alloy powder according to any one of the claims i i 3, wherein the average particle diameter is 1 to 2 〇. 6. A method for producing a Sb—Te alloy powder for sintering, characterized in that:) a raw material composed of an Sb—Te alloy is melted and processed to form a step, and the money is used in this step. The obtained powder is reduced to a powder having an oxygen content of 1,000 or less and an average particle diameter of 0.1 to m. 7. A method for producing an Sb-Te alloy powder for sintering, characterized in that: VIII is formed by melting a raw material composed of an Sb-Te alloy and then processing it to form #末,1 further The obtained powder is also added to the original 25, 2009, 694, so that the oxygen content is below 50 〇 wtppm, and the average granule is the powder of 〇卜继# m. 8. A method for producing a Sb-Te alloy powder for sintering, comprising: dissolving a material composed of an Sb-Te alloy, processing the powder into a powder, and further preparing the powder The powder is reduced to a powder having an oxygen content of 1.0% by weight or less and an average particle diameter of 〇//m. 9. The method for producing a sintered bismuth-based alloy powder according to any one of the claims of the present invention, wherein the average particle diameter is 〇5〇μm 〇i〇. The method for producing a sintered sb-Te alloy powder according to any one of the above-mentioned items, wherein the average particle diameter is 2 〇μm 〇11. A sintered body target composed of an Sb-Te alloy, The oxygen content is below iOOOwtppm, and the anti-f strength is above 5 MPa and the relative density is above 99%. ❹ 12. A sintered body target composed of a Sb-Te alloy having an oxygen content of 5 〇〇 Wtppm or less and a flexural strength of 6 〇Mpa or more and a relative density of 99 5 % or more. U. For example, the Sb-Te alloy formed by the 11th or 12th item of Shen Qing Patent Range is burned, . For the body target, the surface roughness Ra of the splash surface of the target is below the melon. A sintered body target produced by using Sb-Te alloy powder for sintering according to any one of claims No. 1 to No. 26 200946692. Eight, schema: (such as the next page)

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