TW202130842A - Sputtering target material - Google Patents
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- TW202130842A TW202130842A TW110100410A TW110100410A TW202130842A TW 202130842 A TW202130842 A TW 202130842A TW 110100410 A TW110100410 A TW 110100410A TW 110100410 A TW110100410 A TW 110100410A TW 202130842 A TW202130842 A TW 202130842A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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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
Abstract
Description
本發明係關於濺鍍靶材。詳細而言，本發明關於能適宜使用於製造磁性層之濺鍍靶材。The present invention relates to sputtering targets. In detail, this invention relates to the sputtering target material which can be used suitably for manufacturing a magnetic layer.
磁頭、磁性隨機存取記憶體(MRAM)等之磁性裝置中會採用磁性穿隧接合(MTJ)元件。MTJ元件會展示高穿隧磁阻(TMR)信號、低切換電流密度(Jc)等之特徵。Magnetic tunnel junction (MTJ) elements are used in magnetic devices such as magnetic heads and magnetic random access memory (MRAM). MTJ devices will exhibit high tunneling magnetoresistance (TMR) signals, low switching current density (Jc) and other characteristics.
磁性穿隧接合(MTJ)元件通常具有以由Co-Fe-B系合金所構成之2枚磁性層來夾持由MgO所構成之遮蔽層的構造。該磁性層係藉由使用材質為Co-Fe-B系合金之靶材進行濺鍍而得之薄膜。藉由增加成為靶材之Co-Fe-B系合金中之硼(B)含量比率，而達成取得之磁性層之磁氣性能提升，MTJ元件之高TMR信號。A magnetic tunnel junction (MTJ) device generally has a structure in which a shielding layer made of MgO is sandwiched by two magnetic layers made of a Co-Fe-B-based alloy. The magnetic layer is a thin film obtained by sputtering a target material made of a Co-Fe-B series alloy. By increasing the boron (B) content ratio in the Co-Fe-B series alloy used as the target, the magnetic performance of the magnetic layer obtained is improved, and the high TMR signal of the MTJ element is achieved.
另一方面，伴隨硼含量比率之增加，而濺鍍時產生顆粒之頻度變高。尤其，在使用由硼含量比率33at.%以上之合金所構成之靶材時，顆粒之產生則為顯著。顆粒之產生係造成取得之磁性膜品質劣化的原因。品質劣化之磁性膜會使磁性裝置之性能不安定化。因此，有產率降低的問題。On the other hand, as the ratio of boron content increases, the frequency of particle generation during sputtering becomes higher. In particular, when a target made of an alloy with a boron content ratio of 33 at.% or more is used, the generation of particles is remarkable. The generation of particles is the cause of the deterioration of the quality of the obtained magnetic film. The degraded magnetic film will make the performance of the magnetic device unstable. Therefore, there is a problem of reduced yield.
日本特開2004-346423公報(專利文獻1)揭示一種Co-Fe-B系合金靶材，其係在剖面微組織中微細分散有硼化物相。日本特開2017-057477公報(專利文獻2)中提出一種濺鍍靶材，其係減少(CoFe)3 B、Co3 B及Fe3 B之形成。國際公開WO2016-140113公報(專利文獻3)揭示一種磁性材濺鍍靶，其含氧量為100質量ppm以下。 [先前技術文獻] [專利文獻]Japanese Patent Application Laid-Open No. 2004-346423 (Patent Document 1) discloses a Co-Fe-B-based alloy target in which a boride phase is finely dispersed in a cross-sectional microstructure. Japanese Patent Application Laid-Open No. 2017-057477 (Patent Document 2) proposes a sputtering target that reduces the formation of (CoFe) 3 B, Co 3 B, and Fe 3 B. International Publication WO2016-140113 (Patent Document 3) discloses a magnetic material sputtering target whose oxygen content is 100 mass ppm or less. [Prior Technical Documents] [Patent Documents]
[專利文獻1]日本特開2004-346423公報 [專利文獻2]日本特開2017-057477公報 [專利文獻3]國際公開WO2016-140113公報[Patent Document 1] Japanese Patent Application Publication No. 2004-346423 [Patent Document 2] Japanese Patent Application Publication No. 2017-057477 [Patent Document 3] International Publication WO2016-140113 Bulletin
[發明所欲解決之課題][The problem to be solved by the invention]
近年來為了提升MTJ元件之性能，而希望要求更加增加Co-Fe-B系合金中之硼含量比率。專利文獻1並未揭示硼含量比率超過30at.%之靶材。專利文獻2係從靶原料之Co-Fe-B系合金粉末來去除微粉。專利文獻3係從Co-Fe-B系合金之鑄錠切除氧化物多之部分。專利文獻2及3揭開之靶材在製造效率上皆並非係理想者。In recent years, in order to improve the performance of the MTJ element, it is desired to increase the boron content ratio in the Co-Fe-B series alloy.
本發明之目的在於提供一種濺鍍時顆粒之產生為少，且，能有效率製造之靶材。 [用以解決課題之手段]The object of the present invention is to provide a target material that produces less particles during sputtering and can be efficiently manufactured. [Means to solve the problem]
根據本發明者等之知識見解，燒結Co-Fe-B系合金粉末而成之靶材中所形成之金屬組織之構成相係以硼含量比率33at.%為分界而進行變化。詳細而言，硼含量比率為未滿33at.%之區域中，會形成合金相之CoFe相，與硼化物相之(CoFe)3 B相及/或(CoFe)2 B相，硼含量比率為33at.%以上之區域中，合金相之CoFe相會消失，且形成硼化物相之(CoFe)2 B相及/或(CoFe)B相。本發明者等著眼於該合金相之消失會對顆粒產生之增加賦予作用一事，進而完成本發明。According to the knowledge of the inventors, the structural phase of the metallic structure formed in the target material formed by sintering the Co-Fe-B alloy powder changes with the boron content ratio of 33 at.% as the boundary. In detail, in the area where the boron content ratio is less than 33at.%, the alloy phase CoFe phase, and the boride phase (CoFe) 3 B phase and/or (CoFe) 2 B phase are formed. The boron content ratio is In the area above 33 at.%, the CoFe phase of the alloy phase will disappear, and the (CoFe) 2 B phase and/or (CoFe) B phase of the boride phase will be formed. The inventors of the present invention focused on the effect of the disappearance of the alloy phase on the increase in particle generation, and completed the present invention.
即，本發明之濺鍍靶材之材質為包含B，與Co及/或Fe，且剩餘部分係由不可避免的雜質所構成之合金。該合金之B含量對Co含量、Fe含量及B含量之合計之比率為33at.%以上50at.%以下。該合金之金屬組織包含： (a)由第1相或第2相所形成之非B合金相、 (b)(CoFe)2 B相，及 (c)(CoFe)B相。 第1相係由Co含量對Co含量及Fe含量之合計之比率為未滿80at.%之CoFe相，或，Fe相所構成，第2相係由Co含量對Co含量及Fe含量之合計之比率為80at.%以上之CoFe相，或，Co相所構成。That is, the material of the sputtering target of the present invention is an alloy containing B, and Co and/or Fe, and the remainder is an alloy composed of unavoidable impurities. The ratio of the B content of the alloy to the total of the Co content, Fe content, and B content is 33 at.% or more and 50 at.% or less. The metal structure of the alloy includes: (a) a non-B alloy phase formed by the first phase or the second phase, (b) (CoFe) 2 B phase, and (c) (CoFe) B phase. The first phase is composed of CoFe phase or Fe phase whose ratio of Co content to the total of Co content and Fe content is less than 80at.%, and the second phase is composed of Co content to the total of Co content and Fe content The ratio is 80at.% or more CoFe phase, or, composed of Co phase.
較佳為藉由X光繞射法所求得之第1相之bcc(110)面之繞射峰強度為Ia，第2相之fcc(111)面之峰強度為Ib，(CoFe)2 B相之(211)面之繞射峰強度為Ic時，峰強度Ia與峰強度Ib之合計(Ia+Ib)對峰強度Ic之比(Ia+Ib)/Ic為0.02以上。 [發明效果]Preferably, the diffraction peak intensity of the bcc(110) plane of the first phase obtained by X-ray diffraction method is Ia, and the peak intensity of the fcc(111) plane of the second phase is Ib, (CoFe) 2 When the diffraction peak intensity of the (211) plane of phase B is Ic, the ratio of the sum of the peak intensity Ia and the peak intensity Ib (Ia+Ib) to the peak intensity Ic (Ia+Ib)/Ic is 0.02 or more. [Effects of the invention]
本發明之濺鍍靶材之材質為硼含量比率為33at.%以上50at.%以下之Co-Fe-B系合金。使用該靶材而得之磁性膜之磁氣性能為高。該靶材中所形成之金屬組織包含非B合金相。藉由該靶材，會減少濺鍍時之顆粒產生，且提高磁性膜製造之產率。藉由該靶材，可效率良好地製造高性能且高品質之磁性膜。該靶材係適合製造磁頭、MRAM等之磁性裝置所使用之磁性膜。The material of the sputtering target of the present invention is a Co-Fe-B series alloy with a boron content ratio of 33 at.% to 50 at.%. The magnetic film obtained by using the target material has high magnetic properties. The metal structure formed in the target includes a non-B alloy phase. With the target material, particle generation during sputtering can be reduced, and the yield of magnetic film manufacturing can be improved. With this target, a high-performance and high-quality magnetic film can be efficiently manufactured. The target material is suitable for manufacturing magnetic films used in magnetic devices such as magnetic heads and MRAM.
以下，基於較佳實施形態來詳細說明本發明。尚且，本案說明書中，表示範圍之「X~Y」係意指「X以上Y以下」。Hereinafter, the present invention will be described in detail based on preferred embodiments. Moreover, in the specification of this case, the "X~Y" indicating the range means "more than X and less than Y".
本發明之濺鍍靶材之材質為包含B，與Co及/或Fe，且剩餘部分係由不可避免的雜質所構成之合金。只要不阻礙本發明之效果，該合金亦可包含其他金屬元素作為任意成分。The material of the sputtering target of the present invention is an alloy composed of B, and Co and/or Fe, and the remainder is composed of unavoidable impurities. As long as the effect of the present invention is not hindered, the alloy may contain other metal elements as optional components.
該合金之，B含量對Co含量、Fe含量及B含量之合計之比率(以下亦稱為硼含量比率)為33at.%以上50at.%以下。藉由將B含量之比率作成33at.%以上，而取得之磁性膜之磁氣性能提升。藉由導入該磁性膜，而達成MTJ元件之高TMR信號。在B含量之比率超過50at.%之合金組成中，由於會形成純B相，故無法取得後述之金屬組織。B含量之比率係以33at.%以上48at.%以下為佳，較佳為33at.%以上45at.%以下，更佳為35at.%以上45at.%以下。In this alloy, the ratio of the B content to the total of the Co content, the Fe content, and the B content (hereinafter also referred to as the boron content ratio) is 33 at.% to 50 at.%. By setting the ratio of B content to 33at.% or more, the magnetic performance of the obtained magnetic film is improved. By introducing the magnetic film, the high TMR signal of the MTJ element can be achieved. In an alloy composition with a B content ratio exceeding 50 at.%, since a pure B phase is formed, the metal structure described later cannot be obtained. The ratio of B content is preferably 33at.% or more and 48at.% or less, preferably 33at.% or more and 45at.% or less, more preferably 35at.% or more and 45at.% or less.
該濺鍍靶材中形成包含 (a)由第1相或第2相所形成之非B合金相、 (b)(CoFe)2 B相，及 (c)(CoFe)B相 之金屬組織。該金屬組織包含由第1相所形成之非B合金相及由第2相所形成之非B合金相之中之一者。第1相係由Co含量對Co含量及Fe含量之合計之比率為未滿80at.%之CoFe相，或，Fe相所構成，第2相係由Co含量對Co含量及Fe含量之合計之比率為80at.%以上之CoFe相，或，Co相所構成。換言之，該非B合金相係意指本質上不包含硼之相。The sputtering target has a metal structure including (a) a non-B alloy phase formed by the first phase or the second phase, (b) (CoFe) 2 B phase, and (c) (CoFe) B phase. The metal structure includes one of a non-B alloy phase formed by the first phase and a non-B alloy phase formed by the second phase. The first phase is composed of CoFe phase or Fe phase whose ratio of Co content to the total of Co content and Fe content is less than 80 at.%, and the second phase is composed of Co content to the total of Co content and Fe content The ratio is 80at.% or more CoFe phase, or, composed of Co phase. In other words, the non-B alloy phase means a phase that does not substantially contain boron.
本發明之特徵在於：儘管該材質為硼含量比率33at.%以上之合金，在金屬組織中存在有合金相之由CoFe相、Fe相或Co相所構成之非B合金相。藉由具有該金屬組織之靶材，即會顯著減少濺鍍時之顆粒產生。The present invention is characterized in that although the material is an alloy with a boron content ratio of 33 at.% or more, there is an alloy phase in the metal structure that is a non-B alloy phase composed of a CoFe phase, an Fe phase, or a Co phase. With the target material with the metal structure, the particle generation during sputtering can be significantly reduced.
Co含量對Co含量及Fe含量之合計之比率為未滿80at.%之CoFe相中，Co含量對Co含量及Fe含量之合計之比率係以超過0at.%且75at.%以下為佳，較佳為超過0at.%且50at.%以下，更佳為超過0at.%且30at.%以下。尚且，Fe相中，Co含量對Co含量及Fe含量之合計之比率為0at.%。In the CoFe phase in which the ratio of Co content to the total of Co content and Fe content is less than 80at.%, the ratio of Co content to the total of Co content and Fe content is preferably more than 0at.% and less than 75at.%. It is preferably more than 0at.% and 50at.% or less, and more preferably more than 0at.% and 30at.% or less. Furthermore, in the Fe phase, the ratio of the Co content to the total of the Co content and the Fe content is 0 at.%.
Co含量對Co含量及Fe含量之合計之比率為80at.%以上之CoFe相中，Co含量對Co含量及Fe含量之合計之比率為80at.%以上且未滿100at.%，以80at.%以上95at.%以下為佳。尚且，Co相中，Co含量對Co含量及Fe含量之合計之比率為100at.%。In the CoFe phase where the ratio of Co content to the total of Co content and Fe content is 80at.% or more, the ratio of Co content to the total of Co content and Fe content is 80at.% or more and less than 100at.%, so 80at.% Above 95at.% is better. Furthermore, in the Co phase, the ratio of the Co content to the total of the Co content and the Fe content is 100 at.%.
(CoFe)2 B相及(CoFe)B相係藉由Co及/或Fe，與B之反應所形成之硼化物相。(CoFe)2 B相係意指Co含量及Fe含量之和(Co含量+Fe含量)與B含量之比[(Co含量+Fe含量)：B含量]以原子比計為2：1之相，(CoFe)B相係意指該比[(Co含量+Fe含量)：B含量]以原子比計為1：1之相。The (CoFe) 2 B phase and (CoFe)B phase are boride phases formed by the reaction of Co and/or Fe with B. (CoFe) 2 B phase refers to the ratio of the sum of Co content and Fe content (Co content + Fe content) to B content [(Co content + Fe content): B content] in atomic ratio of 2:1 , (CoFe)B phase means a phase in which the ratio [(Co content + Fe content): B content] is 1:1 in atomic ratio.
較佳係金屬組織中之非B合金相對(CoFe)2 B相之存在比率受到控制。該存在比率係將藉由X光繞射法所求得之各相之繞射峰強度作為指標來進行控制。具體而言，從藉由X光繞射法所得之繞射圖型，求出第1相之bcc(110)面之峰強度Ia、第2相之fcc(111)面之峰強度Ib，及(CoFe)2 B相之(211)面之峰強度Ic。第1相之bcc(110)面之繞射峰、第2相之fcc(111)面之繞射峰及(CoFe)2 B相之(211)面之繞射峰由於不會有其他化合物之波峰重複且為獨立者，故能精度良好地求出各個峰強度。Preferably, the ratio of the non-B alloy relative to the (CoFe) 2 B phase in the metal structure is controlled. The existence ratio is controlled by using the diffraction peak intensity of each phase obtained by the X-ray diffraction method as an index. Specifically, from the diffraction pattern obtained by the X-ray diffraction method, obtain the peak intensity Ia of the bcc(110) plane of the first phase, and the peak intensity Ib of the fcc(111) plane of the second phase, and (CoFe) 2 The peak intensity Ic of the (211) plane of the B phase. The diffraction peak of the bcc(110) plane of the first phase, the diffraction peak of the fcc(111) plane of the second phase, and the diffraction peak of the (211) plane of the (CoFe) 2 B phase because there are no other compounds. The peaks are repeated and independent, so the intensity of each peak can be obtained accurately.
在此，第1相之bcc(110)面之峰強度Ia與第2相之fcc(111)面之峰強度Ib之合計(Ia+Ib)對(CoFe)2 B相之(211)面之峰強度Ic之比(Ia+Ib)/Ic係以0.02以上為佳。藉由將比(Ia+Ib)/Ic為0.02以上之靶材使用於濺鍍，會減少顆粒產生，且提升取得之磁性膜之性能。基於該觀點，比(Ia+Ib)/Ic係以0.05以上為較佳，以0.10以上為特佳。比(Ia+Ib)/Ic係例如可為4.0以上，也可為10.0以上。尚且，上限值並無特別限定，比(Ia+Ib)/Ic係例如可為50以下，也可為30以下。金屬組織在包含由第1相所形成之非B合金相，但不包含由第2相所形成之非B合金相之情況，比(Ia+Ib)/Ic係意指比Ia/Ic。金屬組織在包含由第2相所形成之非B合金相，但不包含由第1相所形成之非B合金相之情況，比(Ia+Ib)/Ic係意指比Ib/Ic。Here, the sum of the peak intensity Ia of the bcc(110) plane of the first phase and the peak intensity Ib of the fcc(111) plane of the second phase (Ia+Ib) is relative to the (211) plane of the (CoFe) 2 B phase The ratio of peak intensity Ic (Ia+Ib)/Ic is preferably 0.02 or more. By using a target with a ratio (Ia+Ib)/Ic of 0.02 or more for sputtering, particle generation will be reduced and the performance of the obtained magnetic film will be improved. From this viewpoint, the ratio (Ia+Ib)/Ic is preferably 0.05 or more, and particularly preferably 0.10 or more. The ratio (Ia+Ib)/Ic system may be 4.0 or more, or 10.0 or more, for example. Furthermore, the upper limit is not particularly limited, and the ratio (Ia+Ib)/Ic may be 50 or less, or 30 or less, for example. When the metal structure includes the non-B alloy phase formed by the first phase, but does not include the non-B alloy phase formed by the second phase, the ratio (Ia+Ib)/Ic means the ratio Ia/Ic. When the metal structure includes the non-B alloy phase formed by the second phase but does not include the non-B alloy phase formed by the first phase, the ratio (Ia+Ib)/Ic means the ratio Ib/Ic.
該濺鍍靶材係藉由所謂之粉末冶金來進行製造。粉末冶金係藉由在高壓下加熱原料之粉末使其固化成形而形成燒結體。藉由機械性手段等將該燒結體加工成適當形狀而取得靶材。The sputtering target is manufactured by so-called powder metallurgy. Powder metallurgy is to form a sintered body by heating the powder of the raw material under high pressure to solidify and shape it. The target material is obtained by processing the sintered body into an appropriate shape by mechanical means or the like.
該濺鍍靶材之原料粉末(即，靶材用粉末)為第一粉末與第二粉末之混合粉末。第一粉末及第二粉末係分別由多數之粒子所構成。The raw material powder of the sputtering target (that is, the powder for the target) is a mixed powder of the first powder and the second powder. The first powder and the second powder are each composed of a large number of particles.
成為第一粉末之各粒子之材質為包含B，與Co及/或Fe，且剩餘部分係由不可避免的雜質所構成之合金M1。該合金M1之，B含量對Co含量、Fe含量及B含量之合計之比率為33at.%以上50at.%以下。由於B含量之比率為33at.%以上，故該合金M1之金屬組織包含硼化物相之(CoFe)2 B相及/或(CoFe)B相，但不包含非B合金相。B含量之比率係以35at.%以上50at.%以下為佳，較佳為40at.%以上50at.%以下，更佳為45at.%以上50at.%以下。The material of each particle that becomes the first powder is an alloy M1 that contains B, and Co and/or Fe, and the remainder is composed of unavoidable impurities. In the alloy M1, the ratio of B content to the total of Co content, Fe content, and B content is 33 at.% to 50 at.%. Since the ratio of the B content is 33at.% or more, the metal structure of the alloy M1 includes the boride phase (CoFe) 2 B phase and/or (CoFe)B phase, but does not include the non-B alloy phase. The ratio of B content is preferably 35at.% or more and 50at.% or less, preferably 40at.% or more and 50at.% or less, more preferably 45at.% or more and 50at.% or less.
成為第二粉末之各粒子之材質為包含B，與Co及/或Fe，且剩餘部分係由不可避免的雜質所構成之合金M2。該合金M2之，B含量對Co含量、Fe含量及B含量之合計之比率為15at.%以上且未滿33at.%。由於B含量之比率未滿33at.%，故該合金M2之金屬組織除了包含硼化物相之(CoFe)3 B相及/或(CoFe)2 B相，也包含非B合金相。B含量之比率係以15at.%以上30at.%以下為佳，較佳為15at.%以上25at.%以下，更佳為15at.%以上20at.%以下。The material of each particle that becomes the second powder is an alloy M2 that contains B, and Co and/or Fe, and the remainder is composed of unavoidable impurities. In this alloy M2, the ratio of B content to the total of Co content, Fe content, and B content is 15at.% or more and less than 33at.%. Since the ratio of the B content is less than 33 at.%, the metal structure of the alloy M2 includes not only the boride phase (CoFe) 3 B phase and/or (CoFe) 2 B phase, but also the non-B alloy phase. The ratio of B content is preferably 15at.% or more and 30at.% or less, preferably 15at.% or more and 25at.% or less, more preferably 15at.% or more and 20at.% or less.
該第一粉末與第二粉末之混合粉末即靶材用粉末中，B含量對Co含量、Fe含量及B含量之合計之比率為33at.%以上50at.%以下。B含量之比率之為佳範圍係如同上述。In the mixed powder of the first powder and the second powder, that is, the target powder, the ratio of the B content to the total of the Co content, the Fe content, and the B content is 33 at.% or more and 50 at.% or less. The preferable range of the ratio of B content is the same as above.
該靶材用粉末係可在將此作為原料粉末而得之靶材中形成包含非B合金相之金屬組織。詳細而言，該靶材用粉末係可形成包含非B合金相、(CoFe)2 B相、及(CoFe)B相之金屬組織。該金屬組織中，藉由X光繞射法所求得之第1相之bcc(110)面之峰強度Ia與第2相之fcc(111)面之峰強度Ib之合計(Ia+Ib)對(CoFe)2 B相之(211)面之峰強度Ic之比(Ia+Ib)/Ic為0.02以上。比(Ia+Ib)/Ic之為佳範圍係如同上述。The target powder can form a metal structure including a non-B alloy phase in a target obtained by using this as a raw material powder. Specifically, the powder for the target material can form a metallic structure including a non-B alloy phase, a (CoFe) 2 B phase, and a (CoFe)B phase. In this metal structure, the sum of the peak intensity Ia of the bcc(110) plane of the first phase and the peak intensity Ib of the fcc(111) plane of the second phase obtained by the X-ray diffraction method (Ia+Ib) The ratio (Ia+Ib)/Ic to the peak intensity Ic of the (211) plane of the (CoFe) 2 B phase is 0.02 or more. The preferable range of the ratio (Ia+Ib)/Ic is the same as above.
第一粉末及第二粉末係可分別藉由霧化法來製造。霧化法之種類並無特別限定，可為氣體霧化法，可為水霧化法，亦可為離心力霧化法。實施霧化法時，可適宜選擇使用既知之霧化裝置及製造條件。The first powder and the second powder can be manufactured by an atomization method, respectively. The type of atomization method is not particularly limited, and it may be a gas atomization method, a water atomization method, or a centrifugal force atomization method. When implementing the atomization method, a known atomization device and manufacturing conditions can be appropriately selected and used.
該靶材用粉末中，第一粉末與第二粉末之混合比並無特別限定。因應第一粉末及第二粉末之組成，以在混合後會取得前述組成之方式來適宜調節。第一粉末與第二粉末之混合係可使用既知之混合器。只要不會阻礙本發明之效果，除了第一粉末及第二粉末之外，亦可更加混合其他組成之粉末。In this target powder, the mixing ratio of the first powder and the second powder is not particularly limited. According to the composition of the first powder and the second powder, it is appropriately adjusted in such a way that the aforementioned composition will be obtained after mixing. A known mixer can be used for mixing the first powder and the second powder. As long as the effect of the present invention is not hindered, in addition to the first powder and the second powder, powders of other compositions may be mixed.
如先前所述，藉由加工使該靶材用粉末固化成形而得之燒結體來製造濺鍍靶材。較佳係在固化成形前對該靶材用粉末進行篩分級。亦可在第一粉末及第二粉末之混合前對各粉末進行篩分級。該篩分級之目的在於去除會阻礙燒結之粒子徑500μm以上之粒子(粗粉)。該靶材用粉末中，即使在不進行粗粉除去以外之粒度調整之情況，也可取得本發明之效果。As described above, the sputtering target is manufactured by processing the sintered body obtained by solidifying and forming the powder for the target. Preferably, the powder for the target material is sieved and classified before being solidified and formed. It is also possible to sieve each powder before mixing the first powder and the second powder. The purpose of this sieve classification is to remove particles (coarse powder) with a particle diameter of 500 μm or more that would hinder sintering. In the powder for a target material, the effect of the present invention can be obtained even when particle size adjustment other than coarse powder removal is not performed.
在製造靶材時，將該靶材用粉末予以固化成形之方法及條件並無特別限定。可適宜選擇例如，熱等靜壓法(HIP法)、熱壓法(hot press)、火花電漿燒結法(SPS法)、熱擠壓法(hot extrusion method)等。又，對固化成形而得之燒結體進行加工之方法也並無特別限定，可使用既知之機械性加工手段。When manufacturing a target material, the method and conditions for solidifying and forming the powder for a target material are not specifically limited. For example, a hot isostatic pressing method (HIP method), a hot press method (hot press), a spark plasma sintering method (SPS method), a hot extrusion method (hot extrusion method), etc. can be appropriately selected. In addition, the method of processing the sintered body obtained by curing and forming is not particularly limited, and known mechanical processing means can be used.
使用該靶材用粉末所得之靶材係適宜使用於例如，形成MTJ元件所使用之Co-Fe-B系合金之薄膜用之濺鍍。藉由該靶材，在以往視為困難之高硼含量比率下，仍會顯著地減少濺鍍時顆粒之產生。藉此，變得能效率良好地取性能優異之磁性膜，且提升製造之產率。 [實施例]The target material obtained by using the powder for the target material is suitable for use in, for example, sputtering for forming a thin film of a Co-Fe-B series alloy used in an MTJ element. With this target, the generation of particles during sputtering can still be significantly reduced under the high boron content ratio that was considered difficult in the past. As a result, it becomes possible to efficiently obtain a magnetic film with excellent performance, and to increase the production yield. [Example]
以下，藉由實施例來清楚展示本發明之效果，但不應該基於該實施例之記載來限定性地解釋本發明。Hereinafter, the effects of the present invention are clearly demonstrated through the examples, but the present invention should not be limitedly interpreted based on the description of the examples.
[第一粉末及第二粉末之製造] 以成為表1~2中表示作為第一粉末及第二粉末之組成之方式，秤量各原料並投入由耐火物所構成之坩堝，在減壓下、Ar氣環境下，藉由感應加熱使其溶解。其後，藉由使已溶解之熔湯從設置於坩堝下部之小孔(直徑8mm)流出，使用高壓之Ar氣進行氣體霧化，而取得靶材製造用之原料粉末。[Manufacturing of the first powder and the second powder] In order to become the composition of the first powder and the second powder shown in Tables 1~2, each raw material was weighed and put into a crucible made of refractory. Dissolve. After that, the melted broth was allowed to flow out of a small hole (diameter 8mm) provided in the lower part of the crucible, and the high-pressure Ar gas was used for gas atomization to obtain the raw material powder for the production of the target material.
[濺鍍靶材之製造] 使用取得之第一粉末及第二粉末，藉由以下操作順序，而製造出實施例之靶材No.1~13及比較例之靶材No.14~17。[Manufacturing of Sputtering Targets] Using the obtained first powder and second powder, the target materials No. 1 to 13 of the embodiment and the target materials No. 14 to 17 of the comparative example were manufactured by the following operation sequence.
首先，分別對以氣體霧化法取得之第一粉末及第二粉末進行篩分級而去除直徑500μm以上之粗粉。其次，以成為表1~2所示之混合比A：B(mass%)之方式來將篩分級後之第一粉末(A)及第二粉末(B)投入於V型混合器中，混合30~60分鐘而取得混合粉末。將取得之混合粉末填充至以碳鋼來形成之罐(外徑220mm，內徑210mm，長度200mm)並進行真空脫氣後，使用HIP裝置，在溫度800~1200℃、壓力100~150MPa、保持時間1~5小時之條件下製作出燒結體。藉由線切割、旋盤加工及平面研磨取得之燒結體，並加工成直徑180mm、厚度7mm之圓盤狀，從而作成濺鍍靶材。First, the first powder and the second powder obtained by the gas atomization method are respectively sieved and classified to remove coarse powder with a diameter of 500 μm or more. Next, put the first powder (A) and the second powder (B) after sieving into the V-shaped mixer so that the mixing ratio A:B (mass%) shown in Tables 1 and 2 will be mixed. 30-60 minutes to obtain the mixed powder. Fill the obtained mixed powder into a tank made of carbon steel (outer diameter 220mm, inner diameter 210mm, length 200mm) and vacuum degassing, use HIP device, temperature 800~1200℃, pressure 100~150MPa, hold The sintered body is produced under the condition of 1~5 hours. The sintered body is obtained by wire cutting, rotating disk processing and plane grinding, and processed into a disc shape with a diameter of 180mm and a thickness of 7mm to make a sputtering target.
除了並未實施利用V型混合器之混合以外，其他係藉由相同操作順序而製造出比較例之靶材No.18~19。Except that the mixing using the V-type mixer was not implemented, the target materials No. 18-19 of the comparative example were manufactured by the same operation sequence.
[比(Ia+Ib)/Ic] 從實施例及比較例之各靶材採取試驗片，使用雙面膠帶將該試驗片貼附在玻璃板，藉由使用X光繞射裝置進行測量而取得繞射圖型。繞射條件係如下述般。 X光源：Cu-α線 掃描速度：4°/min 繞射角2θ：20~80°[Ratio (Ia+Ib)/Ic] A test piece was collected from each target material of the Examples and Comparative Examples, the test piece was attached to a glass plate using a double-sided tape, and the diffraction pattern was obtained by measuring with an X-ray diffraction device. The diffraction conditions are as follows. X light source: Cu-α line Scanning speed: 4°/min Diffraction angle 2θ: 20~80°
使用繞射圖型，求出由Co含量對Co含量及Fe含量之合計之比率為未滿80at.%之CoFe相，或，Fe相所構成之第1相之bcc(110)面之峰強度Ia、由Co含量對Co含量及Fe含量之合計之比率為80at.%以上之CoFe相，或，Co相所構成之第2相之fcc(111)面之峰強度Ib、以及(CoFe)2 B相之(211)面之峰強度Ic，並算出比(Ia+Ib)/Ic。取得之比(Ia+Ib)/Ic係展示於下表1~2中。Using the diffraction pattern, find the CoFe phase whose ratio of the total of Co content to the total of Co content and Fe content is less than 80at.%, or the peak intensity of the bcc(110) plane of the first phase composed of Fe phase Ia. CoFe phase with a ratio of Co content to the total of Co content and Fe content of 80 at.% or more, or the peak intensity of the fcc (111) plane of the second phase composed of Co phase Ib, and (CoFe) 2 The peak intensity Ic of the (211) plane of phase B, and the ratio (Ia+Ib)/Ic is calculated. The obtained ratio (Ia+Ib)/Ic is shown in Table 1~2 below.
[顆粒評價] 使用實施例及比較例之靶材，利用DC磁控濺鍍進行濺鍍。濺鍍條件係如以下所示。 基板：鋁基板(直徑95mm、厚度1.75mm) 腔內環境：氬氣 腔內壓：壓力0.9Pa[Particle Evaluation] Using the targets of the Examples and Comparative Examples, DC magnetron sputtering was used for sputtering. The sputtering conditions are as follows. Substrate: aluminum substrate (diameter 95mm, thickness 1.75mm) Chamber environment: argon Cavity pressure: pressure 0.9Pa
濺鍍後，使用光學表面分析儀(Optical Surface Analyzer)，計數附著於直徑95mm鋁基板上之直徑0.1μm以上之顆粒，根據下述基準來進行分級。該結果係作為顆粒評價展示於下表1~2中。 A：顆粒數10個以下 B：顆粒數超過10個且200個以下 C：顆粒數超過200After sputtering, use an optical surface analyzer (Optical Surface Analyzer), count particles with a diameter of 0.1μm or more attached to an aluminum substrate with a diameter of 95mm, and classify them according to the following criteria. The results are shown as particle evaluation in Tables 1 to 2 below. A: The number of particles is less than 10 B: The number of particles exceeds 10 and less than 200 C: The number of particles exceeds 200
以實施例No.2之靶材取得之繞射圖型係展示於圖1中。圖1展示第1相之bcc(110)面之繞射峰，與(CoFe)2 B相之(211)面之繞射峰。實施例No.2並未檢測出第2相之fcc(111)面之繞射峰。The diffraction pattern obtained with the target material of Example No. 2 is shown in FIG. 1. Figure 1 shows the diffraction peak of the bcc (110) plane of the first phase and the diffraction peak of the (211) plane of the (CoFe) 2 B phase. In Example No. 2, the diffraction peak of the fcc (111) plane of the second phase was not detected.
以比較例No.16之靶材取得之繞射圖型係展示於圖2中。如圖2所示般，比較例No.16並未檢測出第1相之bcc(110)面之繞射峰及第2相之fcc(111)面之繞射峰。The diffraction pattern obtained with the target of Comparative Example No. 16 is shown in FIG. 2. As shown in Fig. 2, Comparative Example No. 16 did not detect the diffraction peak of the bcc(110) plane of the first phase and the diffraction peak of the fcc(111) plane of the second phase.
以實施例No.1及No.4~13以及比較例No.19之靶材取得之繞射圖型中，與No.2同樣地檢測出第1相之bcc(110)面之繞射峰，但並未檢測出第2相之fcc(111)面之繞射峰。以實施例No.3之靶材取得之繞射圖型中，雖檢測出第2相之fcc(111)面之繞射峰，但並未檢測出第1相之bcc(110)面之繞射峰。另一方面，以比較例No.14~17之靶材取得之繞射圖型中，與No.18同樣地並未檢測出第1相之bcc(110)面之繞射峰及第2相之fcc(111)面之繞射峰。In the diffraction pattern obtained with the targets of Example No. 1 and No. 4 to 13 and Comparative Example No. 19, the diffraction peak of the bcc (110) plane of the first phase was detected in the same manner as No. 2. , But the diffraction peak of the fcc(111) plane of the second phase was not detected. In the diffraction pattern obtained with the target material of Example No. 3, although the diffraction peak of the fcc(111) plane of the second phase was detected, the winding of the bcc(110) plane of the first phase was not detected. Shooting peak. On the other hand, in the diffraction patterns obtained with the targets of Comparative Examples No. 14 to 17, the diffraction peak of the bcc (110) plane of the first phase and the second phase were not detected in the same way as in No. 18. The diffraction peak of the fcc(111) plane.
如表1所示般，在包含形成有合金相之非B合金相之金屬組織的實施例No.1~13中，儘管其材質為硼含量比率33at.%以上之Co-Fe-B系合金，但仍已減少顆粒之產生。另一方面，如表2所示般，在硼含量比率為多且金屬組織不包含非B合金相之比較例No.14~18中，產生多數之顆粒。比較例No.19中，藉由在金屬組織包含非B合金相，從而已減少顆粒之產生，但由於該材質為硼含量比率未滿33at.%之Co-Fe-B系合金，故無法期待取得之磁性膜之性能提升效果。As shown in Table 1, in Example Nos. 1 to 13 including the metal structure of the non-B alloy phase in which the alloy phase is formed, although the material is a Co-Fe-B alloy with a boron content ratio of 33at.% or more , But it still reduces the generation of particles. On the other hand, as shown in Table 2, in Comparative Example Nos. 14 to 18 in which the boron content ratio is high and the metal structure does not include a non-B alloy phase, many particles are generated. In Comparative Example No. 19, by including non-B alloy phases in the metal structure, the generation of particles has been reduced. However, since the material is a Co-Fe-B alloy with a boron content ratio of less than 33 at.%, it cannot be expected The performance improvement effect of the obtained magnetic film.
如以上所說明，與比較例之靶材相比，實施例之靶材之評價較高。從該評價結果，可明確得知本發明之優異性。 [產業上之可利用性]As explained above, the evaluation of the target of the example is higher than that of the target of the comparative example. From the results of this evaluation, the superiority of the present invention can be clearly understood. [Industrial availability]
以上所說明之濺鍍靶材係能適用於使用由Co-Fe-B系合金所構成之薄膜之各種用途。The sputtering target material described above can be applied to various applications using thin films composed of Co-Fe-B series alloys.
[圖1]圖1為實施例之濺鍍靶材藉由X光繞射所得之繞射圖型。 [圖2]圖2為比較例之濺鍍靶材藉由X光繞射所得之繞射圖型。[Fig. 1] Fig. 1 is a diffraction pattern obtained by X-ray diffraction of the sputtering target of the embodiment. [Fig. 2] Fig. 2 is a diffraction pattern obtained by X-ray diffraction of the sputtering target of the comparative example.
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