200936789 九、發明說明 【發明所屬之技術領域】 本發明，係有關作爲磁記錄媒體之基底膜所使用之基 底膜製造用Cr-Mn-B系濺鍍靶材及使用此材所製造之薄膜 【先前技術】 〇 近年，隨著磁碟之小型化、高記錄密度化，磁記錄媒 體的硏究、開發，特別是各種Co系磁性層或基底層的改 良眾多地被進行著。最近，籍由使用將Cr-Mn合金作爲 Co系磁性層之基底層，可改善磁記錄媒體的磁氣特性之 事被發表。 如特開 2006-89776號公報所揭示，使用含有5~35 at%Mn之Cr-Mn靶材之薄膜，作爲磁記錄媒體之基底膜時 有良好之特性一事被提出。另一方面，爲使記錄密度提升 G ’此C r - Μ η系基底膜之結晶粒之微細化，係有效地。基底 膜的結晶粒之微細化之效果，被認爲係藉由將於其上所成 膜之記錄膜的結晶粒之微細化而提昇其保磁力。 又，如富士時報，乂〇1.77，：^〇.2,2004,第 121頁標題「 垂直磁記錄膜的構造控制」所揭示，媒體特性會強烈地受 基底層的結晶粒徑或表面形狀影響。於該基底層使用Ru 之C〇PtCr-Si02媒體中，籍由控制Ru的結晶粒徑或表面 構造來控制磁性結晶粒之粒徑或磁性分離構造之例有被揭 不 ° -5- 200936789 • 上述特開2006-89776號公報，確實可了觸 Μη靶材之薄膜作爲磁記錄媒體之基底膜時可 特性，但是，爲實現更高之記錄密度，Cr-Mn 晶粒之微細化係被認爲有必要的。但，現實中 得到更高記錄密度之Cr-Mn系薄膜的結晶粒徑 添加元素等之具體提案至今仍未被提出。 〇 【發明內容】 本發明者們，本次，籍由添加B至Cr-Mn 現可使薄膜的結晶粒極度地微細化。於是，如 粒經微細化之Cr-Mn-B系薄膜作爲基底膜製作 時，可得到極爲良好之記錄特性。 因此，本發明之目的，係提供作爲磁記錄 到極爲良好之記錄特性之Cr-Mn-B系基底膜用 粒薄膜製造用濺鏟靶材。 ❹ 依據本發明之一種形態，提供at%表示下 5〜3 5 %、B : 0.1〜1 〇%、以及剩餘部份Cr及不可 所成之磁記錄媒體之基底膜製造用Cr-Mn-B系: 依據本發明之其他形態，提供一種製造方 媒體之基底膜製造用Cr-Mn-B系濺鍍靶材之製 特徵爲該方法包含 at %表示下，準備由 Μη: 5〜35%、B: 0.1-餘部份爲Cr及不可避免之雜質所成之原料粉末 將該原料粉末以熱固化成型，at%表示下 ί到使用Cr-得到良好之 系薄膜的結 有助於爲可 之微細化之 系合金，發 此般以結晶 磁記錄媒體 媒體，可得 合金及微細 ，由 Μη : 避免之雜質 賤鍍靶材。 法，磁記錄 造方法，其 10%以及剩 ，由 Μη : 200936789 5〜3 5%、B : 0.1〜10%以及剩餘部份爲Cr及不可避免之雜 質所成之濺鍍靶材之形成步驟而成。 依據本發明之其他形態，提供經使用上述濺鍍靶材藉 由濺鍍而被製造之Cr-Mn-B系薄膜。 依據本發明之其他形態，提供使用藉由如上述方法所 製造之濺鍍靶材藉由濺鎪而被製造之Cr-Mn-B系薄膜。 〇 【實施方式】 以下，詳細說明有關本發明。 本發明之Cr-Mn-B系濺鍍靶材及製造所使用之原料粉 末，at%表示下，由 Μη : 5〜35%、Β:〇· 1〜10%，以及剩餘 部份爲Cr及不可避免之雜質所成。 本發明之濺鍍靶材及原料粉末，Μη含量爲5~35at% ，較佳爲5~25%，更佳爲5〜15%。爲改善作爲磁記錄媒體 的基底膜使用之際的磁記錄媒體之磁性，5%以上的Μη是 〇 必要的。但，超過3 5%的話該效果便會飽和。 本發明之濺鍍靶材及原料粉末中，Β的含量爲 0.1〜10.0%，較佳爲0.3〜5%，更佳爲0.4~4%。籍由添加Β 到Cr-Μη系合金，雖可使薄膜的結晶粒微細化，但未滿 0.1%的話添加之效果不彰，超過10%的話效果會飽和，而 阻礙記錄密度提昇之Cr系硼化物則大量產生。[Technical Field] The present invention relates to a Cr-Mn-B-based sputtering target for the production of a base film used as a base film of a magnetic recording medium, and a film produced using the same. [Prior Art] In recent years, with the miniaturization of magnetic disks and high recording density, research and development of magnetic recording media, in particular, improvement of various Co-based magnetic layers or underlayers have been carried out in many ways. Recently, the use of a Cr-Mn alloy as a base layer of a Co-based magnetic layer has been disclosed to improve the magnetic characteristics of a magnetic recording medium. As disclosed in Japanese Laid-Open Patent Publication No. Hei. No. 2006-89776, the use of a film containing a Cr-Mn target of 5 to 35 at% Mn as a base film of a magnetic recording medium has been proposed. On the other hand, in order to increase the recording density by G', the crystal grains of the C r - Μ η based base film are made finer. The effect of refining the crystal grains of the base film is considered to be to enhance the coercive force by refining the crystal grains of the recording film on which the film is formed. Moreover, as disclosed in Fuji Times, 乂〇 1.77, :^〇.2, 2004, p. 121, titled "Structural Control of Vertical Magnetic Recording Films", media characteristics are strongly influenced by the crystal grain size or surface shape of the underlying layer. . In the C〇PtCr-SiO2 medium using Ru in the underlayer, an example of controlling the particle size or magnetic separation structure of the magnetic crystal grains by controlling the crystal grain size or surface structure of Ru has been revealed. -5- 200936789 • In the above-mentioned Japanese Patent Publication No. 2006-89776, it is possible to distinguish the film of the target η target as a base film of a magnetic recording medium. However, in order to achieve higher recording density, the miniaturization of Cr-Mn crystal grains is recognized. As necessary. However, in reality, a specific proposal for obtaining a crystal grain size of a Cr-Mn-based film having a higher recording density and the like has not been proposed. SUMMARY OF THE INVENTION The present inventors have now made it possible to extremely finely crystallize the crystal grains of the film by adding B to Cr-Mn. Therefore, when a Cr-Mn-B film having a fine particle size is produced as a base film, extremely excellent recording characteristics can be obtained. In view of the above, it is an object of the present invention to provide a spatter target for producing a granular film for a Cr-Mn-B base film which is magnetically recorded to have excellent recording characteristics. ❹ According to one aspect of the present invention, Cr-Mn-B for base film production of at least 5 to 35%, B: 0.1 to 1% by weight, and the remaining part of Cr and a magnetic recording medium which cannot be formed is provided. According to another aspect of the present invention, a Cr-Mn-B-based sputtering target for producing a base film for producing a square medium is characterized in that, in the method comprising at %, it is prepared by Μη: 5 to 35%, B: 0.1-% of the raw material powder made of Cr and unavoidable impurities, the raw material powder is formed by heat curing, and at% means that the use of Cr- to obtain a good film is helpful. The fine-grained alloy is made of a crystal magnetic recording medium, and the alloy and the fine crystal are obtained, and the target is made of Μn: impurities which are avoided. Method, magnetic recording method, 10% and remaining, forming steps of sputtering target formed by Μη: 200936789 5~3 5%, B: 0.1~10%, and the remainder being Cr and unavoidable impurities Made. According to another aspect of the present invention, a Cr-Mn-B-based film produced by sputtering using the sputtering target is provided. According to another aspect of the present invention, a Cr-Mn-B-based film produced by sputtering using a sputtering target produced by the above method is provided. [Embodiment] Hereinafter, the present invention will be described in detail. The Cr-Mn-B-based sputtering target of the present invention and the raw material powder used for the production thereof are represented by at%: 〜η: 5 to 35%, Β: 〇·1 to 10%, and the remainder is Cr and Inevitable impurities are formed. The sputtering target and the raw material powder of the present invention have a Μη content of 5 to 35 at%, preferably 5 to 25%, more preferably 5 to 15%. In order to improve the magnetic properties of the magnetic recording medium used as the base film of the magnetic recording medium, 5% or more of Μη is necessary. However, if it exceeds 35%, the effect will be saturated. In the sputtering target material and the raw material powder of the present invention, the content of cerium is 0.1 to 10.0%, preferably 0.3 to 5%, more preferably 0.4 to 4%. When the ruthenium is added to the Cr-Μη alloy, the crystal grains of the film can be made finer. However, if the thickness is less than 0.1%, the effect of addition is not good. If the film is more than 10%, the effect is saturated, and the Cr-based boron which hinders the increase in recording density is inhibited. The compounds are produced in large quantities.
本發明之濺鍍靶材，可藉由將原料粉末以熱固化成型 而製造。固化成型係經HIP ( Hot Iso static Pressing ’熱等 靜壓）法進行爲佳，又，該固化成型溫度以1000〜1 250°C 200936789 ’ 爲佳，更佳爲1100〜1200 °C。未滿1000 °c下之固化成型， ' 會有濺鍍靶材的相對密度降低之情況。一方面，固化成型 溫度超過1250 °c的話’該效果便會飽和，經濟成本提高。 作爲此時的加壓條件，以140~150MPa爲佳。 [實施例] 以下，由實施例具體說明有關本發明。 Q 如表1所示之組成，純Cr、純Μη、純B粉末以V型 混合機混合’以其作爲原料粉末’除氣封入粉末塡充 Billet (小坯）於SC罐，在1200°C下以HIP (熱等靜壓） 法固化成型，經機械加工製作Cr-Mn-B系合金及Cr-Mn 系合金之濺鍍靶材。各詳細步驟如以下所示。 首先，將混合過之Cr-Mn-B系及Cr-Mn系粉末，除 氣封入外徑205mm、內徑190mm、長300mm的SC罐。 除氣時的真空到達度約爲1.3xl(T2Pa (約爲1Χ1〇·4Τ〇ΓΓ) 〇 。將上述粉末塡充Billet (小坯），在1200°c、147MPa 下以HIP成型。將上述方法所製之固化成型體，經線切割 、車削加工、平面硏磨，加工至直徑76.2mm、厚3mm， 再焊接於銅製曲度板（Bucking Plate)後，爲一濺鍍靶材 〇 表1所示之評價項目，係有關於Cr系硼化物之產生 ，將所製作之濺鍍靶材，濺鍍於直徑76.2mm的Si基板上 後。濺鍍條件爲，Ar壓：〇.5Pa、DC電力：500W、成膜 厚：500iim。此濺鍍以X線繞射’再由其繞射峰値觀察Cr -8 - 200936789 系硼化物的產生’以下述基準評價之。 〇：無產生Cr系硼化物 △:產生少量 X :產生多量 又，濺鍍膜的結晶粒徑，係經TEM觀察上述濺鍍膜 之斷層面，解析圖像所得之相當面積圓之徑長作爲結晶粒 0 徑。尙，表1的結晶粒徑係表示以No.l的結晶粒徑爲100 時之相對値，數値較小者之結晶粒徑較微細。 [0J1 成份組成 (以at%表示下） Cr系硼化物 結晶粒徑 備 N〇 Μη B Cr 註 1 5 0.1 剩餘部份 〇 100 2 10 3 剩餘部份 〇 70 3 15 10 剩餘部份 Δ 50 本 4 20 1 剩餘部份 〇 80 發 5 20 5 剩餘部份 〇 60 明 6 25 0.1 剩餘部份 〇 80 例 7 30 3 剩餘部份 〇 60 8 35 10 剩餘部份 Δ 50 9 3 0.05 剩餘部份 〇 500 10 5 12. 剩餘部份 X 50 11 20 0 剩餘部份 〇 470 一 一 1 2 25 12. 剩餘部份 X 50 比 13 35 0.05 剩餘部份 〇 450 較 14 40 12. 剩餘部份 X 50 例 15 5 0 剩餘部份 〇 600 16 10 0 剩餘部份 〇 520 17 40 0 剩餘部份 〇 350 200936789 ' 如表1所示，No.1〜8爲本發明例’ No.9〜17爲比較例 ♦ 〇 如表1所示，比較例No.9係因Μη含量低，特別是B 的含量低，結晶粒粗大化。比較例Νο.10及12係因Β的 含量高，產生多量Cr系硼化物。比較例No.l 1係因不含 有B，結晶粒粗大化。比較例No.13同比較例No.9，因B 的含量低，結晶粒粗大化。 0 比較例No.14係因Μη含量多，特別是B的含量多，The sputtering target of the present invention can be produced by molding a raw material powder by heat curing. The curing is preferably carried out by a HIP (Hot Iso static Pressing) method. Further, the curing temperature is preferably 1000 to 1 250 ° C 200936789 ', more preferably 1100 to 1200 ° C. Curing at less than 1000 °c, 'There will be a decrease in the relative density of the sputter target. On the one hand, if the curing temperature exceeds 1250 °c, the effect will be saturated and the economic cost will increase. As the pressurization conditions at this time, it is preferably 140 to 150 MPa. [Examples] Hereinafter, the present invention will be specifically described by way of examples. Q As shown in Table 1, pure Cr, pure Μ, pure B powder is mixed with a V-type mixer as 'raw material powder' degassed and sealed into a powder filling Billet (small billet) in an SC tank at 1200 ° C The HIP (hot isostatic pressing) method is used for solidification molding, and a Cr-Mn-B alloy and a Cr-Mn alloy sputtering target are mechanically processed. The detailed steps are as follows. First, the mixed Cr-Mn-B-based and Cr-Mn-based powders were degassed into an SC tank having an outer diameter of 205 mm, an inner diameter of 190 mm, and a length of 300 mm. The degree of vacuum arrival at degassing is about 1.3 x 1 (T2 Pa (about 1 Χ 1 〇 · 4 Τ〇ΓΓ) 〇. The above powder is filled with Billet (small billet), and HIP is molded at 1200 ° C and 147 MPa. The cured molded body is processed by wire cutting, turning, plane honing, and processed to a diameter of 76.2 mm and a thickness of 3 mm, and then welded to a copper curved plate (Bucking Plate), which is a sputtering target. The evaluation item is related to the generation of Cr-based boride, and the sputter target thus produced is sputtered on a Si substrate having a diameter of 76.2 mm. The sputtering condition is Ar pressure: 〇.5 Pa, DC power. : 500 W, film thickness: 500 iim. This sputtering was X-ray diffraction 'and its diffraction peak was observed. Cr -8 - 200936789 Boride production was evaluated by the following criteria. 〇: No Cr-based boron was produced. Compound △: a small amount of X is generated: a large amount of crystals is produced, and the crystal grain size of the sputtered film is observed by TEM, and the diameter of the circle of the corresponding area obtained by analyzing the image is taken as the crystal grain diameter of 0. Table 1, Table 1 The crystal grain size indicates the relative enthalpy when the crystal grain size of No. 1 is 100, and the smaller number is The crystal grain size is fine. [0J1 Composition (in at%) Cr-based boride crystal grain size N〇Μη B Cr Note 1 5 0.1 Remaining portion 〇100 2 10 3 Remaining portion 〇70 3 15 10 Remaining part Δ 50 This 4 20 1 Remaining part 〇 80 round 5 20 5 Remaining part 〇 60 Ming 6 25 0.1 Remaining part 〇 80 Case 7 30 3 Remaining part 〇 60 8 35 10 Remaining part Δ 50 9 3 0.05 Remaining part 〇 500 10 5 12. Remaining part X 50 11 20 0 Remaining part 〇 470 1-1 1 2 25 12. The remaining part X 50 is more than 13 35 0.05 The remaining part 〇 450 is compared with 14 40 12. Remaining part X 50 Example 15 5 0 Remaining part 〇 600 16 10 0 Remaining part 〇 520 17 40 0 Remaining part 〇 350 200936789 ' As shown in Table 1, No. 1 to 8 are examples of the invention 'No. 9 to 17 are comparative examples ♦ As shown in Table 1, Comparative Example No. 9 has a low content of Μη, particularly a low content of B, and coarsened crystal grains. Comparative Examples Νο.10 and 12 are high in strontium content. A large amount of Cr-based boride was produced. In Comparative Example No. 1, the crystal grains were coarsened because B was not contained. Comparative Example No. 13 was the same as Comparative Example No. 9, due to the low content of B, the crystal grains are coarsened. 0 Comparative Example No. 14 is due to the high content of Μη, especially the content of B.
Cr系硼化物多量產生。有關於比較例No .15〜17，No.17的 Μη含量多，特別是因爲其任一例皆不含有B，結晶粒粗 大化之現象可——辨明。對此，因本發明例No· 1〜8任何 一例皆可滿足本發明之條件，可了解到其極適合作爲薄膜 製造用之濺鍍靶材。 如以上所示，於磁記錄媒體之薄膜製造用濺鍍靶材， 藉由添加B至Cr-Mn系合金，可使薄膜的結晶粒極度地微 © 細化，爲可達成提供一種安定且高密度的Cr-Mn-B系薄膜 用合金及薄膜製造用濺鍍靶材之極優良效果者。 -10-A large amount of Cr-based boride is produced. Regarding Comparative Examples No. 15 to 17, No. 17 has a large content of Μη, and particularly, since any of the examples does not contain B, the phenomenon of coarsening of crystal grains can be discriminated. On the other hand, any of the examples of the present invention Nos. 1 to 8 can satisfy the conditions of the present invention, and it is understood that it is extremely suitable as a sputtering target for film production. As described above, by adding a B-to-Cr-Mn-based alloy to a sputtering target for film production in a magnetic recording medium, the crystal grains of the film can be extremely finely refined, thereby providing a stable and high quality. The alloy for Cr-Mn-B film of density and the sputtering target for film production have excellent effects. -10-