TW200407450A

TW200407450A - Fabrication of nanocomposite thin films for high density magnetic recording media

Info

Publication number: TW200407450A
Application number: TW91132912A
Authority: TW
Inventors: Y D Yao; Po-Cheng Kuo; Sheng-Chi Chen; An-Cheng Sun; Chen-Chieh Chiang
Original assignee: Academia Sinica
Priority date: 2002-10-31
Filing date: 2002-11-08
Publication date: 2004-05-16
Also published as: TW584670B

Abstract

Techniques for fabricating magnetic granular films for high-density magnetic data storage, where magnetic grains are dispersed in a non-magnetic amorphous matrix and each are surrounded by a grain-confining material which inhibits growth of grains during annealing.

Description

200407450 ⑴ 玖τ (發明說明應敘明：發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說明) 背景 [0 0 0 1 ]本申請案係關於形成於基板上之顆粒狀薄膜，及更明確g之’係關於供資料儲存用之磁性顆粒狀薄膜的製造。 [0002】各種磁性顆粒狀薄膜已被發展及研究以應用於磁性記錄媒體。可將此種薄膜設計成包括具高頑磁力及大殘田磁化量之磁性晶粒。磁性晶粒與來自適當磁頭的磁場又互作用’而在窝入操作中接受儲存用的資料，或在讀取操作中輸出先前儲存於晶粒中的資料。 [0003】此種磁性顆粒狀薄膜之一適當材料例如為 F e P t>基磁性薄膜。f e P t晶粒或顆粒展現適合於磁性資料儲存用的磁性質。尤其可將Fept晶粒散佈於非磁性之非晶質SiN基地中，使FePt晶粒可彼此分離或分開，如此可降低相鄰FePt晶粒之間其磁性耦合所造成之雜訊，因而增進此種薄膜應用於磁性記錄的性能。可將F e p t _基磁性薄膜設計成產生高頑磁力He、甚佳之殘留磁化量Mr、同磁阳異向性常數Ku、小晶粒尺寸、良好抗腐蝕性、及大的磁能積（BH)max。此種引人矚目的Fept_基顆粒狀薄膜可應用於高密度磁性記錄之媒體。概要 [0004]本申請案包括製造用於高密度記錄媒體之具散佈於非磁性基地中之分開磁性晶粒之複合顆粒狀薄膜的技術。根據一具體實施例，此製造可包括下列步驟。首先， 200407450200407450 ⑴ 玖 τ (The description of the invention should be stated: the technical field, prior art, content, embodiments, and drawings of the invention are briefly explained) Background [0 0 0 1] This application is about a granular film formed on a substrate , And more specifically, 'is related to the manufacture of magnetic granular films for data storage. [0002] Various magnetic granular films have been developed and studied for use in magnetic recording media. This thin film can be designed to include magnetic grains with high coercive force and large residual magnetization. The magnetic grains interact with the magnetic field from the appropriate magnetic head 'to accept the data for storage during the nesting operation, or output the data previously stored in the grain during the reading operation. [0003] One suitable material for such a magnetic granular film is, for example, a F e Pt> -based magnetic film. f e P t grains or particles exhibit magnetic properties suitable for magnetic data storage. In particular, Fept crystal grains can be dispersed in a non-magnetic amorphous SiN base, so that FePt crystal grains can be separated or separated from each other. This can reduce the noise caused by the magnetic coupling between adjacent FePt crystal grains, thereby enhancing this. The performance of this film for magnetic recording. The F ept _-based magnetic film can be designed to produce high coercivity He, very good residual magnetization Mr, co-magnetic anisotropy constant Ku, small grain size, good corrosion resistance, and large magnetic energy product (BH) max. This eye-catching Fept-based granular film can be applied to high-density magnetic recording media. SUMMARY [0004] The present application includes a technique for manufacturing a composite granular film for use in high-density recording media with separated magnetic grains dispersed in a non-magnetic base. According to a specific embodiment, the manufacturing may include the following steps. First, 200407450

將適當的磁性材料、晶粒限制材料、及非磁性非晶質材料濺鍍於基板上形成顆粒狀薄膜，其中磁性材料之晶粒係散佈於非磁性之非晶質材料基地中。選擇適當的晶粒限制材料（其可為非磁性材料）使其主要係位於磁性晶粒之晶界，以限制各晶粒之大小，以完成薄膜中期望的小晶粒尺寸。接下來使顆粒狀薄膜在高退火溫度下退火選定的期間，然後再於適當的淬火液體中淬火，以將磁性晶粒自軟磁相轉變為具期望磁性質之硬磁相。 [0005】根據本申請案之一態樣，在退火處理之前可於顆粒狀薄膜上形成鈍化覆蓋層，以防止薄膜在退火處理中氧化。可使用氮化矽，諸如 SiNy，或其他適當的鈍化材料，於形成此純化覆蓋層。 [00 0 6】在一種實行法中，磁性材料可為FePt，晶粒限制材料可為Cr，及非磁性材料可為氮化矽諸如Si3N4。用於支承薄膜之基板可為經自然氧化的矽基板或玻璃基板。利用以上製造方法之完成複合顆粒狀薄膜的性質對製程參數甚為敏感，因此，對FePt-基薄膜揭示方法參數之範例值，以獲致磁性記錄之期望薄膜性質。 [0 0 07] 現於以下圖式、文字說明、及申請專利範圍中更詳細說明此等及其他的特徵及相關優點。圖式簡單說明 [000 8】圖1顯示根據一具體實施例之製造此一用於高密度磁性儲存之顆粒狀薄膜之製作步驟的流程圖。 [0009】圖2顯示根據圖1所示之技術製造用於磁性記 200407450An appropriate magnetic material, a grain-limiting material, and a non-magnetic amorphous material are sputtered on the substrate to form a granular film. The grains of the magnetic material are dispersed in the non-magnetic amorphous material base. Select an appropriate grain-restricting material (which may be a non-magnetic material) so that it is mainly located at the grain boundaries of the magnetic grains to limit the size of each grain to achieve the desired small grain size in the film. The granular film is then annealed at a high annealing temperature for a selected period, and then quenched in a suitable quenching liquid to transform the magnetic grains from the soft magnetic phase to the hard magnetic phase with the desired magnetic properties. [0005] According to one aspect of the present application, a passivation cover layer may be formed on the granular film before the annealing process to prevent the film from being oxidized during the annealing process. Silicon nitride, such as SiNy, or other suitable passivation material can be used to form this purified cover layer. [00 0 6] In one implementation, the magnetic material may be FePt, the grain restriction material may be Cr, and the non-magnetic material may be silicon nitride such as Si3N4. The substrate for supporting the film may be a naturally oxidized silicon substrate or a glass substrate. The properties of the finished composite granular film using the above manufacturing method are very sensitive to the process parameters. Therefore, exemplary values of the method parameters are disclosed for FePt-based films to obtain the desired film properties for magnetic recording. [0 0] These and other features and related advantages will now be described in more detail in the following drawings, text description, and patent application scope. Brief Description of the Drawings [000 8] FIG. 1 shows a flowchart of manufacturing steps for manufacturing such a granular film for high-density magnetic storage according to a specific embodiment. [0009] FIG. 2 shows a magnetic device manufactured according to the technique shown in FIG.

(3) 錄之FePt-基顆粒狀薄膜之一範例的製作流程。 [0010] 圖 3 說明平均晶粒大小隨各種經退火 (Fe45Pt45Cri〇)i〇〇.5-(SiNy)3 薄膜之 SiNy 體積分率的變化，其中退火溫度分別係5 0 0 °c、5 5 0 °c、6 0 0 °c、及7 0 0 °c。 [0011】圖4說明不同SiNy體積分率之在δΜ與各種經退火（Fe45Pt45Cri〇)i〇〇.§-(SiNy)s薄膜之外加磁場Ha之間的關係。 [0012] 圖 5 說明平均晶粒大小隨經退火 (Fe5〇_x/2Pt5〇-x/2Crx)85-(SiNy)15 薄膜之 Cr 含量的變化，其中薄膜厚度係約1 0奈米及退火時間係約3 0分鐘。 [0013] 圖 6 說明不同 Ci·含量之在 δΜ 與各種 (Fe5〇-x/2Pt5〇-x/2Crx)85-(SiNy)i5 薄膜之 Ha 之間的關係。 [0014】圖7A及7B分別顯示在平行膜面角形比S"與經退火（Feso-xuPtso-x/^CrOw^SiNy)。薄膜之Cr含量之間的關係，及在S"與經退火（Fe45Pt45Cri〇)1()〇4-(SiNy)5薄膜之 SiNy體積分率之間的關係。 [0015】圖 8A及 8B分別顯示 He//及 Ms隨經退火 (Fe50_x/2Pt5〇-x/2Crx)85-(SiNy)15 薄膜之 Cr 含量之變化，及 He"及 Ms 隨經退火（Fe45Pt45Cri〇)i〇〇.s-(SiNy)5 薄膜之 SiNy 體積分率之變化。薄膜厚度為10奈米。 [0016】圖9係厚度10奈米，及在600 °C下退火約30 分鐘之經退火（Fe45Pt45Cri〇)85-(SiNy)i5薄膜的磁滞曲線 (M-H loop) 〇詳述 200407450(3) The manufacturing process of an example of the FePt-based granular thin film described in the document. [0010] FIG. 3 illustrates the change in average grain size as a function of SiNy volume fraction of various annealed (Fe45Pt45Cri〇) i〇〇.5- (SiNy) 3 films, where the annealing temperature is 50 ° C, 5 5 ° 0 ° c, 6 0 0 ° c, and 7 0 0 ° c. [0011] FIG. 4 illustrates the relationship between different SiNy volume fractions at δM and various annealed (Fe45Pt45Cri0) i ..- (SiNy) s thin films with a magnetic field Ha. [0012] FIG. 5 illustrates the change in average grain size as a function of the Cr content of annealed (Fe50_x / 2Pt50-x / 2Crx) 85- (SiNy) 15 films, where the film thickness is about 10 nm and annealing The time is about 30 minutes. [0013] FIG. 6 illustrates the relationship between δM of different Ci · contents and Ha of various (Fe50-x / 2Pt50-x / 2Crx) 85- (SiNy) i5 films. [0014] FIGS. 7A and 7B respectively show the angle ratio S " and the annealing (Feso-xuPtso-x / ^ CrOw ^ SiNy) of the parallel film surface. The relationship between the Cr content of the film and the relationship between S " and the SiNy volume fraction of the annealed (Fe45Pt45Cri0) 1 () 〇4- (SiNy) 5 film. [0015] FIGS. 8A and 8B show the changes in He // and Ms with the Cr content of the annealed (Fe50_x / 2Pt50-x / 2Crx) 85- (SiNy) 15 film, and He " and Ms with the annealing (Fe45Pt45Cri 〇) The change in SiNy volume fraction of i-〇.s- (SiNy) 5 film. The film thickness is 10 nm. [0016] FIG. 9 is a hysteresis curve (M-H loop) of an annealed (Fe45Pt45Cri0) 85- (SiNy) i5 thin film with a thickness of 10 nm and annealed at 600 ° C for about 30 minutes. 2004200450

[0017] 本申請案之製造技術部分係以希望降低相鄰磁性晶粒間之交互作用及顆粒狀薄膜中之各磁性晶粒之尺寸，以於磁性記錄中獲致高儲存密度的認知為基礎。相鄰磁性晶粒間之交互作用可經由使磁性晶粒散佈於非磁性之非晶質基地諸如氮化矽中，以使磁性晶粒分離而降低。此分離可降低晶粒間之交互作用，諸如晶粒間的靜磁作用及相鄰磁性晶粒之交換交互作用所產生之雜訊。 [0 0 1 8】除了用於降低雜訊之磁性晶粒的物理分離之外，各晶粒之物理尺寸亦會限制資料儲存之密度。因此，此申請案之另一態樣係將晶粒限制材料混合於顆粒狀薄膜中，使存在於各磁性晶粒之晶界上，而抑制磁性晶粒之成長。此降低的晶粒尺寸可使單位面積中之磁性晶粒的數目增加，因此而提高儲存密度。 [0019]在另一態樣中，磁性晶粒應具大的磁晶異向性常數，以獲致供磁性記錄用之大的平行膜面頑磁力。因此，如以下所說明，應適當選擇非磁性材料之添加量，包括非磁性之非晶質材料及晶粒限制材料之量，以獲致期望的磁晶異向性常數。 [0 02 0】圖1顯示根據一具體實施例之製造此一用於高密度磁性儲存之顆粒狀薄膜之製作步驟的流程圖。選擇用於支承顆粒狀薄膜之適當基板，並準備進行薄膜沈積。其中尤其可使用矽基板或玻璃基板。在步驟110，將用於形成磁性晶粒之磁性材料、待存在於各磁性晶粒之晶界之晶粒限制材料、及使磁性晶粒散佈之用於形成非晶質基地之 200407450[0017] The manufacturing technology of this application is based on the desire to reduce the interaction between adjacent magnetic grains and the size of each magnetic grain in the granular film, based on the recognition that high storage density is obtained in magnetic recording. The interaction between adjacent magnetic grains can be reduced by dispersing the magnetic grains in a nonmagnetic amorphous base such as silicon nitride to separate the magnetic grains. This separation reduces the interactions between grains, such as the magnetostatic interactions between grains and the noise generated by the exchange interactions between adjacent magnetic grains. [0 0 1 8] In addition to the physical separation of magnetic grains used to reduce noise, the physical size of each grain will also limit the density of data storage. Therefore, another aspect of this application is to mix the grain-restricting material in the granular film so as to exist on the grain boundaries of each magnetic grain, and suppress the growth of magnetic grains. This reduced grain size can increase the number of magnetic grains per unit area, thereby increasing the storage density. [0019] In another aspect, the magnetic crystal grains should have a large magnetic crystal anisotropy constant in order to obtain a large parallel film surface coercive force for magnetic recording. Therefore, as explained below, the amount of non-magnetic materials to be added should be appropriately selected, including the amount of non-magnetic amorphous materials and grain-limiting materials to achieve the desired magnetic crystal anisotropy constant. [0 02 0] FIG. 1 shows a flowchart of manufacturing steps for manufacturing such a granular film for high-density magnetic storage according to a specific embodiment. Select the appropriate substrate for supporting the granular film and prepare for film deposition. Among them, a silicon substrate or a glass substrate can be used. In step 110, a magnetic material for forming magnetic crystal grains, a grain-restricting material to be present at a grain boundary of each magnetic crystal grain, and a dispersion of magnetic crystal grains for forming an amorphous base 200407450

(5) 非磁性材料濺鍍於基板上，而形成具有各以晶粒限制材料為邊界且散佈於非晶質基地中之小磁性晶粒的初鐘軟磁性顆粒狀薄膜。 [0 0 2 1】如進一步說明於以下的實施例中，應適當選擇顆粒狀薄膜内磁性材料、晶粒限制材料及非磁性材料的比例，以獲致用於磁性記錄之期望的整體薄膜性質。舉例來說，當薄膜中之晶粒限制材料之含量增加時，可降低晶粒尺寸。然而，當薄膜中之晶粒限制材料增加時，在退火過 · 程中其會自各晶粒之晶界擴散至晶粒表面，而使磁性晶粒之磁晶異向性常數不利地降低。此外，如晶粒限制材料為非磁性如同FePt-基薄膜中之Cr，則增加晶粒限制材料之含量亦會使完成顆粒狀薄膜之飽和磁化量 Ms不利地降低。此種不利影響顯示晶粒限制材料之含量不應無限制的增加。因此，應選擇晶粒限制材料之最佳或接近最佳的值，以於相衝突的效應之間取得平衡。 [0022】關於非磁性材料，晶粒尺寸可隨非磁性材料之 φ 體積分率的增加而減小。因此，希望提高非磁性之體積分率，以減小晶粒尺寸。 [0023】另一方面，如於FePt-基薄膜中所展示，顆粒狀薄膜中之非磁性材料基地提供使磁性晶粒散佈及空間分離，而有利地降低由晶粒間耦合所造成之雜訊。因此，薄膜中之非磁性材料之體積分率的增加可有利地降低晶粒間耦合之強度。此外，顆粒狀薄膜中之非磁性材料之體積分率的少量增加可有利地提高完成顆粒狀薄膜之飽和磁 -10- 200407450(5) A non-magnetic material is sputtered on the substrate to form an initial soft magnetic granular film with small magnetic grains each bordered by a grain-restricting material and dispersed in an amorphous base. [0 0 2 1] As further explained in the following examples, the ratio of the magnetic material, the grain-limiting material, and the non-magnetic material in the granular film should be appropriately selected so as to obtain the desired overall film properties for magnetic recording. For example, when the content of the grain-restricting material in the film is increased, the grain size can be reduced. However, when the grain-restricting material in the film is increased, it will diffuse from the grain boundaries of the grains to the grain surface during the annealing process, so that the magnetic crystal anisotropy constant of the magnetic grains is disadvantageously reduced. In addition, if the grain-limiting material is non-magnetic like Cr in FePt-based films, increasing the content of the grain-limiting material will also unfavorably reduce the saturation magnetization Ms of the finished granular film. This adverse effect indicates that the content of the grain-restricting material should not increase indefinitely. Therefore, the best or near-optimal value of the grain-limiting material should be selected to strike a balance between conflicting effects. [0022] Regarding non-magnetic materials, the grain size can decrease as the φ volume fraction of non-magnetic materials increases. Therefore, it is desirable to increase the non-magnetic volume fraction to reduce the grain size. [0023] On the other hand, as shown in the FePt-based film, the non-magnetic material base in the granular film provides magnetic grain dispersion and spatial separation, and advantageously reduces noise caused by inter-grain coupling. . Therefore, an increase in the volume fraction of the non-magnetic material in the thin film can advantageously reduce the strength of the inter-grain coupling. In addition, a small increase in the volume fraction of the non-magnetic material in the granular film can advantageously increase the saturation magnetic of the finished granular film -10- 200407450

⑹ 化量。在此方面，飽和磁化量在最佳體積分率下達到最大值，及當體積分率進一步增加超過最佳值時則減低。 [0024】此外，顆粒狀薄膜中之非磁性材料基地亦可具有保護性作用，而有利地降低在高溫條件下諸如在退火過程中在磁性晶粒與下層基板之間的不利反應，其中此反應之主要不利影響為飽和磁化量之降低。由於非磁性材料基地亦可稀釋完成顆粒狀薄膜之飽和磁化量，因而其於薄膜中之體積分率具有一最佳值，在低於此最佳值下，體積分率之增加會使飽和磁化量提高，及高於此最佳值，體積分率之增加則會使飽和磁化量減小。 [002 5]以上與顆粒狀薄膜内三材料之比例相關的各種效應顯示在選擇三材料之各者之量時有相互衝突的效應。因此在選擇期望比例時，應考慮對最終顆粒狀薄膜之性質的所有影響。此外，各種製程參數亦會影響薄膜性質。以下舉出數個實施例以說明在實行圖1所示之製造方法時的此態樣。經發現FePt薄膜中之Fe:Pt:Cr*之原子比的一較佳範圍係在約 4 5 : 5 4 : 1至約 4 1 : 3 4 : 2 5之間，其中 45:45:1 0之比為較佳。FePtCr:SiN之體積分率係在約 9 0 : 1 0至約5 0 : 5 0之範圍内，其中約8 5 : 1 5之比為較佳。 [0 0 2 6】回來參照圖1中之步驟 1 1 0，濺鍍可於經通入 Ar氣體之真空腔體中進行。將電極設置於腔體中，其中施加電場，以使Ar離子化而產生Ar電漿。Ar電漿中之帶電的Ar離子經加.速，而撞擊設置靶材（即磁性材料、晶粒限制材料、及非磁性材料）之陰極表面。此Ar離子之轟 200407450⑹ Conversion. In this regard, the saturation magnetization reaches its maximum value at the optimum volume fraction, and decreases when the volume fraction further increases beyond the optimum value. [0024] In addition, the non-magnetic material base in the granular film can also have a protective effect, which advantageously reduces the adverse reaction between the magnetic grains and the underlying substrate under high temperature conditions, such as during annealing. The main adverse effect is a reduction in saturation magnetization. Since the non-magnetic material base can also be diluted to complete the saturation magnetization of the granular film, its volume fraction in the film has an optimal value. Below this optimal value, an increase in the volume fraction will cause saturation magnetization. As the amount increases, and above this optimal value, an increase in the volume fraction will reduce the amount of saturation magnetization. [002 5] The above various effects related to the ratio of the three materials in the granular film show that there are conflicting effects when selecting the amount of each of the three materials. Therefore, when selecting the desired ratio, all influences on the properties of the final granular film should be considered. In addition, various process parameters can also affect film properties. Several examples are given below to illustrate this aspect when the manufacturing method shown in FIG. 1 is implemented. It has been found that a preferred range of the atomic ratio of Fe: Pt: Cr * in the FePt film is between about 4 5: 5 4: 1 to about 4 1: 3 4: 2 5 of which 45: 45: 1 0 The ratio is better. The volume fraction of FePtCr: SiN is in the range of about 90:10 to about 50:50, with a ratio of about 85:15 being preferred. [0 0 2 6] Referring back to step 1 10 in FIG. 1, sputtering can be performed in a vacuum chamber through which Ar gas is passed. An electrode is set in the cavity, and an electric field is applied to ionize Ar to generate an Ar plasma. The charged Ar ions in the Ar plasma are accelerated and impinge on the surface of the cathode where the target materials (ie, magnetic materials, crystal-restricting materials, and non-magnetic materials) are set. This Ar ion bomber 200407450

⑺ 擊於靶材上造成靶材之濺鍍於設置在靠近陰極表面之基板上，而形成顆粒狀薄膜。基板溫度及Ar壓力係控制濺鍍速率之兩重要參數。經發現Ar壓力可在自約0.3毫托耳（mTor〇至約20毫托耳之範圍内，其中約 7毫托耳之 Ar氣體的壓力為較佳。可將基板溫度設在低於約4 5 °C的溫度下，以 2 5 °C左右較佳，而產生具期望性質之顆粒狀薄膜。 [0027】適用於製造之濺鍍系統可為磁控濺鍍系統，其 · 中於陰極產生磁場，以增進電子之捕捉。此一系統可達到高的沈積速率。在實行時，此種磁控濺鍍系統可於電極之兩端施加 DC電場而產生電漿，或者於電極之兩端施加 RF電場而產生電漿。 [0 0 2 8】由賤鍍方法形成之顆粒狀薄膜中之磁性晶粒一般係為軟磁相。必須進行額外的步騾，以使磁性晶粒轉變為供資料儲存用之硬磁相。在說明於此申請案之實行法中，使用示為步驟120之退火及示為步驟130之浮火於達 0 成此轉變。退火一般係在高溫下進行。為防止在顆粒狀薄膜中在軟磁相中產生不期望的氧化，可在進行退火之前將鈍化層沈積於軟磁顆粒狀薄膜上。在此可使用各種鈍化材料，包括氮化矽（例如，SiNy)。 [0029】在步驟 120，使顆粒狀薄膜於真空中在退火溫度下退火適當的退火期間。由於非磁性材料基地及晶粒限制材料的存在下，磁性晶粒之成長受到抑制。經發現在退火過程中真空可低於約1(Γ6托耳，退火溫度在約400 °C及 -12- 200407450击 Hitting the target causes the target to be sputtered on a substrate placed near the surface of the cathode to form a granular film. The substrate temperature and Ar pressure are two important parameters that control the sputtering rate. It was found that the Ar pressure can be in the range from about 0.3 millitorr (mTor0 to about 20 millitorr), of which the pressure of Ar gas of about 7 millitorr is better. The substrate temperature can be set below about 4 At a temperature of 5 ° C, a temperature of about 25 ° C is preferred to produce granular films with desired properties. [0027] The sputtering system suitable for manufacturing can be a magnetron sputtering system, which is produced in the cathode. Magnetic field to enhance the capture of electrons. This system can achieve a high deposition rate. In practice, this magnetron sputtering system can apply a DC electric field to both ends of the electrode to generate a plasma, or apply it to both ends of the electrode. The RF electric field generates a plasma. [0 0 2 8] The magnetic grains in the granular film formed by the base plating method are generally soft magnetic phases. Additional steps must be performed to transform the magnetic grains for data storage. The hard magnetic phase is used. In the implementation method described in this application, the annealing shown in step 120 and the floating fire shown in step 130 are used to achieve this transition at 0. Annealing is generally performed at high temperature. In order to prevent Undesirable oxygen generation in soft magnetic phase in granular films A passivation layer may be deposited on the soft magnetic granular film before annealing. Various passivation materials may be used here, including silicon nitride (eg, SiNy). [0029] In step 120, the granular film is placed in a vacuum in a vacuum. Annealing at an appropriate annealing period. The growth of magnetic grains is inhibited due to the presence of non-magnetic material bases and grain-restricting materials. It was found that the vacuum during the annealing process can be lower than about 1 (Γ6 Torr, annealing temperature At about 400 ° C and -12-200407450

約8 0 0 °C之間，其中在約6 0 0 °C下之溫度為較佳，及退火期間在約5至9 0分鐘之間，其中約3 0分鐘之期間為較佳。 [0 0 3 0] 當退火完成時，在圖1之步騾 130，接著使經退火之顆粒狀薄膜於淬火液體中快速冷卻下來，以完成磁性晶粒之自軟磁相轉變為硬磁相。淬火液體可為在低於約 5 °C之溫度下。舉例來說，在一實行法中，可將在約 0 °C 下之冰及水的混合物使用作為淬火液體。 [0 0 3 1 ] 以下詳細說明基於以上圖 1所示之方法製造 · FePt-基顆粒狀薄膜的例子。基板可為自然氧化的Si基板或玻璃基板。用於形成磁性晶粒之磁性材料為 F ePt。晶粒限制材料為 Cr，及用於非晶質基地之非磁性材料為氮化矽。 [0032】圖2顯示製造用於磁性記錄之FePt基顆粒狀薄膜的一範例製作流程，其中步驟 210、220、23 0及 240 分別呈現濺鍍方法、鈍化層之形成、退火方法、及浮火方法。具有FePt及Cr之FePtCrlfc可為FePtCr合金，或 g FePtCr複合靶（其中複合靶包括經覆蓋Cr片之FePt靶）。圖 2之方法可製造用於磁性記錄媒體之高頑磁力的 FePtCf-SiN顆粒狀奈米複合薄膜。 [0033] 在一種實行法中，將 (Fe5〇-x/2Pt5〇-x/2Crx)1()〇-3-(SiNy)§ 奈米複合薄膜（x = 0〜30 原子百分比，及 δ = 0〜30體積百分比）製造於玻璃諸如康寧 (Corning) 1 73 7F玻璃或經自然氧化的矽晶圓基板諸如 Si(100)上。濺鍍係經在環境溫度下對FePtCI·靶及Si3N4 -13 - 200407450The temperature is preferably between about 80 ° C, of which the temperature at about 600 ° C is preferred, and the annealing period is between about 5 and 90 minutes, with a duration of about 30 minutes being preferred. [0 0 3 0] When the annealing is completed, step 130 in FIG. 1 is followed by rapid cooling of the annealed granular film in the quenching liquid to complete the transition from the soft magnetic phase to the hard magnetic phase of the magnetic grains. The quenching liquid may be at a temperature below about 5 ° C. For example, in a practice, a mixture of ice and water at about 0 ° C can be used as the quenching liquid. [0 0 3 1] An example of manufacturing a FePt-based granular film based on the method shown in FIG. 1 above will be described in detail below. The substrate may be a naturally oxidized Si substrate or a glass substrate. The magnetic material used to form the magnetic grains is F ePt. The grain-limiting material is Cr, and the non-magnetic material used for the amorphous base is silicon nitride. [0032] FIG. 2 shows an example manufacturing process for manufacturing FePt-based granular films for magnetic recording, in which steps 210, 220, 230, and 240 present a sputtering method, a passivation layer formation, an annealing method, and a floating fire, respectively. method. The FePtCrlfc with FePt and Cr can be an FePtCr alloy, or a g FePtCr composite target (where the composite target includes a FePt target covered with a Cr sheet). The method of Fig. 2 can produce FePtCf-SiN granular nano composite films with high coercivity for magnetic recording media. [0033] In an implementation method, (Fe50-x / 2Pt50-x / 2Crx) 1 () 0-3- (SiNy) § nano composite film (x = 0 ~ 30 atomic percent, and δ = (0 to 30% by volume) are manufactured on glass such as Corning 1 73 7F glass or a naturally oxidized silicon wafer substrate such as Si (100). Sputtering system for FePtCI · target and Si3N4 -13-200407450 at ambient temperature

(9) 靶使用D C及RF磁控共鍍而達成。剛沈積得之薄膜具有軟磁性質之γ-FePt顆粒散佈於非晶質SiN基地中之顆粒狀結構。剛沈積得之薄膜一般由於其之低頑磁力，而無法被使用作為磁性記錄媒體。於在真空中在經控制的條件下退火期望的溫度及期間之後，薄膜亦維持其之顆粒狀結構，但軟磁性γ - F e P t相可轉變為硬磁性γ i - F e P t相。此經轉變之薄膜具有高頑磁力及小的晶粒尺寸。可將其使用於極高密度的磁性記錄媒體。 [0 03 4] 在步驟240，濺鍍方法使高頑磁力的FePt顆粒散佈於非磁性非晶質氮化矽基地中，而降低磁性記錄薄膜之晶粒大小，以致薄膜之記錄密度可提高。然而，若不存在作為晶粒限制材料之Cr，則薄膜中之FePt磁性顆粒對於特定的高密度記錄而言仍不夠小。舉例來說，FePt顆粒在FePt-Si3N4薄膜中係約30奈米，其會限制薄膜之記錄密度。因此，必需再減低磁性顆粒之大小，以提高記錄密度。此係經由將Cr加至FePt合金薄膜，以由於Cr會偏析於F e P t之晶界而抑制F e P t之晶粒成長所達成。磁性顆粒之顆粒大小可經由加入C r而減至低於1 0奈米。 [0 0 3 5 ] 在濺鍍過程中，使基板旋轉，以得到組成均勻之薄膜。在步驟220，將SiNy之薄覆蓋層覆蓋於磁性薄膜上作為鈍化層，以保護薄膜不致在後續退火過程中氧化。於沈積之後，使薄膜於真空中在不同溫度下退火，然後再於冰水中淬火（步驟2 3 0及2 4 0)。此等薄膜之易磁化軸係與膜面平行。經退火的FePtCr-SiN薄膜展現平行膜 200407450(9) The target is achieved by DC and RF magnetron co-plating. The newly deposited thin film has a granular structure in which soft magnetic γ-FePt particles are dispersed in an amorphous SiN base. The newly deposited film is generally unusable as a magnetic recording medium due to its low coercive force. After annealing in vacuum under controlled conditions for the desired temperature and period, the film also maintains its granular structure, but the soft magnetic γ-F e P t phase can be transformed into a hard magnetic γ i-F e P t phase . This transformed film has high coercivity and small grain size. It can be used for extremely high-density magnetic recording media. [0 03 4] In step 240, the sputtering method disperses FePt particles with high coercivity in the non-magnetic amorphous silicon nitride base, and reduces the crystal grain size of the magnetic recording film, so that the recording density of the film can be increased. However, if Cr is not present as a grain-restricting material, the FePt magnetic particles in the film are not small enough for a specific high-density recording. For example, FePt particles are about 30 nm in the FePt-Si3N4 film, which will limit the recording density of the film. Therefore, it is necessary to further reduce the size of the magnetic particles to increase the recording density. This is achieved by adding Cr to the FePt alloy thin film to suppress the grain growth of F e P t because Cr segregates at the grain boundaries of F e P t. The particle size of the magnetic particles can be reduced to less than 10 nm by adding C r. [0 0 3 5] During the sputtering process, the substrate is rotated to obtain a thin film having a uniform composition. In step 220, a thin cover layer of SiNy is covered on the magnetic thin film as a passivation layer to protect the thin film from oxidation during subsequent annealing. After deposition, the film is annealed at different temperatures in a vacuum and then quenched in ice water (steps 230 and 240). The easily magnetizable axis of these films is parallel to the film surface. Annealed FePtCr-SiN thin film exhibits parallel film 200407450

(ίο) 面頑磁力He"〉3500 Oe、飽和磁化量Ms > 425 emu/立方公分，且平行膜面角形比S / /，即M r / M s之比，係約〇 . 7 5。可將此薄膜使用於極高密度的磁性記錄媒體。 [003 6】表1列示FePtCr-SiN薄膜之製備的濺鍍參數。濺鍍腔體之背景壓力係大約3x1 (T7托耳，及薄膜係在0.3 及20毫托耳之間之氬壓力PAr下沈積，其中以PAr = 7毫托耳為較佳。將濺鍍槍分別設在如下的功率密度：對 FePtCr靶將外加DC電源設於2瓦/平方公分，及將Si3N4 · 靶之RF電源自1 .5變化至12瓦/平方公分。FePtCr之沈積速率係約0.3奈米/秒。基板溫度係低於4 5 °C，例如，約2 5 °C。使剛沈積得之薄膜於真空中在4 0 0 °C及8 0 0 °C之間之溫度下退火5〜90分鐘，然後再於冰水中淬火。淬火液體之溫度係低於5 °C，例如，約0 °C。表1 基板溫度（Ts) 環境溫度 RF功率密度對 Si3N4 靶 1 .5〜12 W/cm2 DC功率密度對 FePtCr 靶 2 W/cm2 背景真空 3x1 (Γ7托耳基板與靶之間之距離 6 cm 氬壓力 0.3〜20毫托耳氬流率 5 0 ml/min [0 03 7】以下記述更多例子，以說明圖1及2所示之技術的各種特徵。利用穿透式電子顯微鏡（TEM)觀察薄膜微結構，及由TEM明視野相片計算薄膜之平均晶粒大小。 -15 - 200407450(ίο) Surface coercivity He "> 3500 Oe, saturation magnetization Ms > 425 emu / cubic centimeter, and the parallel film surface angle ratio S //, that is, the ratio of M r / M s, is about 0.75. This film can be used for extremely high-density magnetic recording media. [003 6] Table 1 lists the sputtering parameters for the preparation of FePtCr-SiN thin films. The background pressure of the sputtering chamber is about 3x1 (T7 Torr, and the film is deposited under an argon pressure PAr between 0.3 and 20 mTorr, of which PAr = 7 mTorr is preferred. Sputter gun The power densities are set as follows: the external DC power source is set to 2 W / cm 2 for the FePtCr target, and the RF power of the Si3N4 · target is changed from 1.5 to 12 W / cm 2. The deposition rate of FePtCr is about 0.3 Nanometers / second. The substrate temperature is below 45 ° C, for example, about 25 ° C. The freshly deposited film is annealed in a vacuum at a temperature between 400 ° C and 800 ° C 5 ~ 90 minutes, and then quenched in ice water. The temperature of the quenching liquid is lower than 5 ° C, for example, about 0 ° C. Table 1 Substrate temperature (Ts) Ambient temperature RF power density for Si3N4 target 1.5 ~ 12 W / cm2 DC power density for FePtCr target 2 W / cm2 background vacuum 3x1 (the distance between the Γ7 Torr substrate and the target 6 cm argon pressure 0.3 ~ 20 millitorr argon flow rate 5 0 ml / min [0 03 7] More examples are described below to illustrate the various features of the technology shown in Figures 1 and 2. Using a transmission electron microscope (TEM) to observe the microstructure of the thin film, . The film is calculated by the bright-field TEM average grain size photo -15--200407450

00 薄膜磁性質是以試片振動測磁儀（VSM)及超導量子干涉測磁儀（SQUID)量測，其最大外加磁場分別為13及50 kOe。利用能量散射光譜儀（EDS)測定薄膜之組成及均勻度。利用原子力顯微鏡（AFM)測量薄膜之厚度。實施例1 [0038】基板溫度係在室溫下以75 rpm之轉速旋轉。於將濺鍍腔體抽真空至3x1 (Γ7托耳之後，將Ar氣體引入至腔體内。在整個濺鍍期間中將Ar壓力維持於7毫托耳。製造FePtCr-SiN薄膜之濺鍍條件示於表1。圖3顯示平均晶粒大小隨各種經退火（FeePteCqohoo.^SiNyh薄膜之SiNy體積分率的變化。退火溫度分別係在500°C、550 °C、600°C、及700°C °Cr含量係固定於10原子百分比。薄膜厚度為10奈米及退火時間係約3 0分鐘。其顯示 FePtCr薄膜之晶粒大小隨退火溫度之增加而增加，但隨 SiNy之體積分率的增加而減小。當在600 °C下退火時，經退火（FeoPtuCno)合金薄膜（siNy = 〇體積百分比）之平均晶粒大小係約1 8奈米，但當s iNy體積分率增加至i 5體積百分比時，其可減低至約9 5奈米。經由TEM明視野相片觀察經退火後不含SiNy之Fe45Pt45Cr1()合金薄膜之平均晶粒大小係約18奈米，然而對含siNy =20體積百分比之（Fe45Pt45Cri())8()-(SiNy)2()奈米複合薄膜則僅約8奈米。圖3及相關的TEM照片亦顯示當薄膜之SiNy體積分率增加時其顆粒間距離增加，且磁性顆粒變得較小。 [0039】圖4顯示不同SiNy體積分率之在5?4與各種經 20040745000 Thin film magnetic properties are measured with a test piece vibration magnetometer (VSM) and a superconducting quantum interference magnetometer (SQUID). The maximum external magnetic fields are 13 and 50 kOe, respectively. The composition and uniformity of the thin film were measured using an energy scattering spectrometer (EDS). The thickness of the film was measured using an atomic force microscope (AFM). Example 1 [0038] The substrate temperature was rotated at 75 rpm at room temperature. After the sputtering chamber was evacuated to 3 × 1 (Γ7 Torr), Ar gas was introduced into the chamber. The Ar pressure was maintained at 7 mTorr during the entire sputtering period. Sputtering conditions for manufacturing FePtCr-SiN film Exhibits are shown in Table 1. Figure 3 shows the average grain size as a function of SiNy volume fraction of various annealed (FeePteCqohoo. ^ SiNyh thin films. Annealing temperatures are at 500 ° C, 550 ° C, 600 ° C, and 700 ° The C ° Cr content is fixed at 10 atomic percent. The thickness of the film is 10 nm and the annealing time is about 30 minutes. It shows that the grain size of the FePtCr film increases with the increase of the annealing temperature, but with the volume fraction of SiNy. Increase and decrease. When annealing at 600 ° C, the average grain size of the annealed (FeoPtuCno) alloy film (siNy = 0 volume percentage) is about 18 nm, but when the s iNy volume fraction increases to i At 5 vol.%, It can be reduced to about 95 nm. The average grain size of the annealed Fe45Pt45Cr1 () alloy film without SiNy observed by TEM bright field photos is about 18 nm, but for siNy = 20 (Fe45Pt45Cri ()) 8 ()-(SiNy) 2 () Nano The composite film is only about 8 nanometers. Figure 3 and related TEM photos also show that when the SiNy volume fraction of the film increases, the inter-particle distance increases and the magnetic particles become smaller. [0039] Figure 4 shows different SiNy volumes The score is between 5 and 4

(12) 退火（Fe45Pt45Cri〇)i〇〇_5-(SiNy)5 薄膜之 Ha (間的關係。 C r含量係固定於1 0原子百分比。正的δΜ顯示在磁性顆粒之間的交互作用力較強，且顆粒間交互作用之型式為交換搞合（exchange coupling)。負的δΜ顯示弱的磁性顆粒交互作用，且顆粒間交互作用之型式為磁偶極交互作用 (dipoleinteraction)。實際上，希望媒體雜訊儘可能地低，因此對於磁性記錄媒體應用而言，磁性薄膜之負的δΜ為較佳。如圖4所示，其顯示（Fe45Pt45Cr·10)合金薄膜（SiNy = 〇體積百分比）之δΜ值為正，此薄膜中之磁性晶粒的交互作用為交換耦合。當薄膜之SiNy體積分率增加至約20體積百分比時，δΜ之值減低至約零，及當SiNy體積分率進一步增加時，其變為負值。當薄膜之SiNy體積分率達到 3 0體積百分比時，δΜ變為負值，此時顆粒間交互作用之型式為磁偶極交互作用。提高磁性薄膜之SiNy體積分率可使顆粒間交互作用之強度減弱，此係由於較高的 SiNy 體積分率使磁性顆粒間之距離擴大所致。實施例2 [0 0 4 0】濺鍍條件係與實施例1相同。圖5顯示平均晶粒大小隨經退火（Fe50-x/2Pt50-x/2Crx)85-(SiNy)i5 薄膜之 Cr 含量的變化。薄膜中之SiNy的體積分率係固定於15體積百分比。於圖5中明顯可見薄膜之平均晶粒大小隨薄膜之 Cr含量的增加而減小。對於經退火（Fe5〇Pt5〇)85-(SiNy)15 薄膜（Cr = 0原子百分比），平均晶粒大小係約3 5奈米，但當C r含量增加至1 0原子百分比時，其減小至約9 · 5奈 -17- 200407450(12) Ha (relationship between annealed (Fe45Pt45Cri〇) i〇〇 5- (SiNy) 5 film. C r content is fixed at 10 atomic percent. Positive δM shows the interaction force between magnetic particles Strong, and the type of interaction between particles is exchange coupling. A negative δM shows weak magnetic particle interaction, and the type of interaction between particles is magnetic dipole interaction. In fact, It is hoped that the media noise is as low as possible, so for magnetic recording media applications, the negative δM of the magnetic film is better. As shown in Figure 4, it shows (Fe45Pt45Cr · 10) alloy film (SiNy = 0 volume percent) The δM value is positive, and the interaction of the magnetic grains in this film is exchange coupling. When the SiNy volume fraction of the film increases to about 20% by volume, the δM value decreases to about zero, and when the SiNy volume fraction further increases When it increases, it becomes negative. When the SiNy volume fraction of the film reaches 30% by volume, δM becomes negative, and the type of interaction between particles at this time is magnetic dipole interaction. Improve the magnetic film The SiNy volume fraction can weaken the strength of the interaction between particles, which is caused by the higher SiNy volume fraction that enlarges the distance between magnetic particles. Example 2 [0 0 4 0] Sputtering conditions and examples 1 is the same. Figure 5 shows the average grain size as a function of the Cr content of the annealed (Fe50-x / 2Pt50-x / 2Crx) 85- (SiNy) i5 film. The volume fraction of SiNy in the film is fixed at 15 volumes Percentage. It can be clearly seen in Figure 5 that the average grain size of the film decreases with the increase of the Cr content of the film. For the annealed (Fe5〇Pt50) 85- (SiNy) 15 film (Cr = 0 atomic percent), the average The grain size is about 35 nanometers, but when the Cr content increases to 10 atomic percent, it decreases to about 9.5 nanometers-17-200407450

(13) 米。分別對經退火（Fe5GPt5())85-(SiNy)15薄膜（Cr = 0原子百分比）及（Fe42.5Pt42.5Cn5)85-(SiNy)15 薄膜（Cr =15 原子百分比）取得對應的 TEM 明視野相片比較，其中 (Fe5〇Pt5〇)85-(SiNy)15薄膜（Ci· = 0原子百分比）之平均晶粒大小係約 35 奈米，然而（Fe42.5Pt42.5Cri5)85-(SiNy)15 薄膜 (Ci· =15原子百分比）則僅約8奈米。圖4及相關的TEM 照片顯示當薄膜之C r含量增加時，磁性顆粒變得較小，且顆粒間距離增加。(13) meters. Obtain corresponding TEM details for the annealed (Fe5GPt5 ()) 85- (SiNy) 15 thin film (Cr = 0 atomic percent) and (Fe42.5Pt42.5Cn5) 85- (SiNy) 15 thin film (Cr = 15 atomic percent) Comparison of field-of-view photos, where the average grain size of (Fe5〇Pt50) 85- (SiNy) 15 film (Ci · = 0 atomic percent) is about 35 nm, while (Fe42.5Pt42.5Cri5) 85- (SiNy) 15 films (Ci · = 15 atomic percent) are only about 8 nm. Figure 4 and related TEM photos show that as the Cr content of the film increases, the magnetic particles become smaller and the distance between the particles increases.

[0041] 圖 6 顯示不同 Cr 含量之在 δΜ 與各種 (Fe5〇_x/2Pt5〇-x/2Crx)85-(SiNy)15 薄膜之外加磁場 Ha 之間的關係。薄膜中之SiNy的體積分率係固定於1 5體積百分比。薄膜厚度係 10 奈米及退火時間係 30 分鐘。 (Fe5〇Pt5〇)85-(SiNy)15薄膜（Cr = 0原子百分比）之δΜ值在外加磁場的作用下為正值，因此，此薄膜中之磁性顆粒交互作用的型式為交換搞合。當 Cr 含量增加時， (Fe50_x/2Pt50-x/2Crx)85-(SiNy)15薄膜中之磁性顆粒的尺寸減小且磁性顆粒間之距離變得較大，致磁性顆粒交互作用之強度降低。因此，如圖6所示，當Cr含量增加時，薄膜之δΜ減低。當Cr含量增加至2 5原子百分比時，薄膜之δΜ減小至輕微的負值，此時顆粒間交互作用變為磁偶極交互作用。ΤΕΜ相片亦證實圖4及6之δΜ-Ha曲線，即在磁性薄膜中增加C r或S iNy含量將使磁性顆粒間之距離增加，致顆粒間交互作用之強度降低。實施例3 -18- 200407450[0041] FIG. 6 shows the relationship between δM of different Cr contents and the applied magnetic field Ha of various (Fe50_x / 2Pt50-x / 2Crx) 85- (SiNy) 15 films. The volume fraction of SiNy in the film was fixed at 15 volume percent. The film thickness is 10 nm and the annealing time is 30 minutes. The value of δM of (Fe5〇Pt50) 85- (SiNy) 15 film (Cr = 0 atomic percent) is positive under the action of an external magnetic field. Therefore, the type of interaction of magnetic particles in this film is exchange interaction. When the Cr content increases, the size of the magnetic particles in the (Fe50_x / 2Pt50-x / 2Crx) 85- (SiNy) 15 film decreases and the distance between the magnetic particles becomes larger, which causes the strength of the magnetic particle interaction to decrease. Therefore, as shown in Fig. 6, when the Cr content increases, the? M of the thin film decreases. When the Cr content increases to 25 atomic percent, the δM of the film decreases to a slightly negative value, at which time the interaction between particles becomes a magnetic dipole interaction. The TEM photo also confirms the δM-Ha curves of Figures 4 and 6, that increasing the Cr or SiNy content in the magnetic film will increase the distance between the magnetic particles and reduce the strength of the interaction between the particles. Example 3 -18- 200407450

(14)(14)

[00 42】濺鍍條件係與實施例 1相同。圖7A顯示在平行膜面角形比 S"與經退火（Feso-x/zPtso-x/^Crxhs-CSiNy)。薄膜之Ci·含量之間的關係。薄膜之SiNy體積分率係固定於15體積百分比及薄膜厚度為10奈米，退火溫度為600 °C ，及退火時間為 30分鐘。圖 7B顯示 S//隨經退火 (Fe45Pt45Cri〇)1()〇4-(SiNy)3 薄膜之 SiNy 體積分率之變化。 Cr含量係固定於10原子百分比。明顯可見圖7A之S// 值隨Cr含量之增加而下降。當Cr = 0原子百分比時，S// 之值為0.81，及當Cr含量增加至15原子百分比時，S// 則下降至約0.53。同樣地，圖7B之S"值隨SiNy含量之增加而下降。當SiNy = 0體積百分比時，S"為0.8，及當磁性薄膜之SiNy體積分率增加至30體積百分比時，S" 則下降至約0.48。此顯示當FePtCr-SiN薄膜之Cr或SiNy 含量增加時，磁性FePtCr顆粒變為混亂排列且被Cr或 SiNy所孤立。 [0043] 經發現 Cr或 SiNy含量之增加會使經退火 (Fe5〇-x/2Pt5〇-x/2Crx)1()〇-5-(SiNy)5 薄膜之平行膜面頑磁力 HC//減低。如圖8A所示，當SiNy體積分率係固定於15 體積百分比時，經退火（Fe5〇.x/2Pt5〇_x/2Crx)85-(SiNy)15薄膜之 He//隨 Cr 含量之增加而減低，其中經退火 (Fe5〇Pt5())85-(SiNy)15 薄膜（Cr = 0 原子百分比）之 He"值係約80 00 Oe，但當Cr含量增加至10原子百分比時，其減低至約3 700 Oe。圖8A及8B之薄膜係於600°C下退火30 分鐘，及基板為矽晶圓。同樣地，如圖 8 B所示，當 C r -19- 200407450[0042] The sputtering conditions are the same as in Example 1. Fig. 7A shows the angular ratio S " and annealed (Feso-x / zPtso-x / ^ Crxhs-CSiNy) at the parallel film surface. The relationship between the Ci · content of the film. The SiNy volume fraction of the film is fixed at 15% by volume, the film thickness is 10 nm, the annealing temperature is 600 ° C, and the annealing time is 30 minutes. FIG. 7B shows the variation of S // with the SiNy volume fraction of the annealed (Fe45Pt45Cri〇) 1 () 〇4- (SiNy) 3 film. The Cr content is fixed at 10 atomic percent. It can be clearly seen that the S // value of FIG. 7A decreases as the Cr content increases. When Cr = 0 atomic percent, the value of S // is 0.81, and when the Cr content is increased to 15 atomic percent, S // decreases to about 0.53. Similarly, the S " value of Fig. 7B decreases as the SiNy content increases. When SiNy = 0% by volume, S " is 0.8, and when the SiNy volume fraction of the magnetic film is increased to 30% by volume, S " decreases to about 0.48. This shows that when the Cr or SiNy content of the FePtCr-SiN film is increased, the magnetic FePtCr particles become disorderly arrayed and isolated by Cr or SiNy. [0043] It was found that the increase in the content of Cr or SiNy will reduce the coercive force HC // of the parallel film surface of the annealed (Fe50-x / 2Pt50-x / 2Crx) 1 () 〇-5- (SiNy) 5 film . As shown in FIG. 8A, when the volume fraction of SiNy is fixed at 15% by volume, the He // of the annealed (Fe5〇.x / 2Pt50〇_x / 2Crx) 85- (SiNy) 15 film increases with the Cr content However, the He " value of the annealed (Fe5〇Pt5 ()) 85- (SiNy) 15 film (Cr = 0 atomic percent) is about 80 00 Oe, but it decreases when the Cr content increases to 10 atomic percent. To about 3 700 Oe. The films of FIGS. 8A and 8B are annealed at 600 ° C for 30 minutes, and the substrate is a silicon wafer. Similarly, as shown in Figure 8B, when C r -19- 200407450

含量係固定於10原子百分比時，經退火（Fe45Pt45Cr1())薄膜（SiNy = 0體積百分比）之He"值係約5 600 Oe，但當薄膜之S iNy體積分率增加至3 0體積百分比時，其可減低至約3 5 0 Ο e。提高磁性薄膜之C r或S iNy含量可抑制在退火過程中之磁性晶粒成長’因此而使晶粒大小偏離早磁區大小。事實上，一些晶粒甚至變為超順磁粒子。此外， Cr擴散至FePt晶粒表面區域中會導致FePt之磁晶異向性常數減低。基於以上原因，所以He/〆直會隨薄膜之Ci· 或S i N y含量的增加而減低。 [00 44]另一方面，Cr係非磁性物質，提高Cr含量會稀釋磁性薄膜之Ms值。如圖8A所示，當將SiNy體積分率固定於15體積百分比時，經退火（Fe5〇Pt5〇)85-(SiNy)15 薄膜（Cr = 0原子百分比）之Ms值係約490 emu/立方公分，但當C r含量增加至1 0原子百分比時，其會減低至約 450 emu/立方公分。如圖8B所示，由於純FePtCr合金薄膜與 Si基板會在高溫下產生反應，所以經退火 (卩€45?“5(：1：1。）合金薄膜（8丨^ = 0體積百分比）之^/15值僅係約2 7 5 e m u /立方公分，但當薄膜之S i N y體積分率增加至5體積百分比時，M s則可增加至約4 8 0 e m u /立方公分。此顯示SiNy於防止金屬磁性顆粒與Si基板在高溫下反應有良好的保護效果。但當SiNy體積分率高於約5 體積百分比時，Ms值會減低。如圖8B所示，由於SiNy 亦為非磁性物質，因此其亦會稀釋磁性薄膜之Ms值，當 SiNy體積分率自5體積百分比增加至30體積百分比時， -20- 200407450When the content is fixed at 10 atomic percent, the He " value of the annealed (Fe45Pt45Cr1 ()) film (SiNy = 0 volume percent) is about 5 600 Oe, but when the Si iNy volume fraction of the film increases to 30 volume percent , Which can be reduced to about 3 5 0 e. Increasing the Cr or SiNy content of the magnetic thin film can suppress the growth of magnetic grains during the annealing process', thereby deviating the grain size from the size of the early magnetic region. In fact, some grains even become superparamagnetic particles. In addition, the diffusion of Cr into the surface area of FePt crystal grains results in a decrease in the magnetic crystal anisotropy constant of FePt. Based on the above reasons, the He / zirconium will decrease as the Ci · or Si N y content of the film increases. [00 44] On the other hand, Cr is a non-magnetic substance. Increasing the Cr content will dilute the Ms value of the magnetic film. As shown in FIG. 8A, when the volume fraction of SiNy is fixed at 15% by volume, the Ms value of the annealed (Fe5〇Pt50) 85- (SiNy) 15 film (Cr = 0 atomic percent) is about 490 emu / cubic Cm, but when the Cr content increases to 10 atomic percent, it will decrease to about 450 emu / cm3. As shown in FIG. 8B, since the pure FePtCr alloy film and the Si substrate will react at a high temperature, annealed (卩 € 45? "5 (: 1: 1: 1)) alloy film (8 丨 ^ = 0% by volume) The value of ^ / 15 is only about 2 7 5 emu / cubic centimeter, but when the S i N y volume fraction of the film is increased to 5 volume percent, M s can be increased to about 4 8 0 emu / cubic centimeter. This display SiNy has a good protection effect to prevent metal magnetic particles from reacting with the Si substrate at high temperatures. However, when the volume fraction of SiNy is higher than about 5 volume percent, the Ms value will decrease. As shown in Figure 8B, since SiNy is also non-magnetic Substance, so it will also dilute the Ms value of the magnetic film. When the SiNy volume fraction increases from 5 volume percent to 30 volume percent, -20- 200407450

(16)(16)

Ms值則自480 emu/立方公分下降至約180 emu/立方公分。實施例4 [0 0 4 5】濺鍍條件係與實施例1相同。圖9顯示在約6 0 0 °C下退火30分鐘之（Fe45Pt45Cr*1())85-(SiNy)15薄膜的磁滯曲線。外加磁場係與膜面平行。測得其M s值係約4 5 0 e m u /立方公分及He//值係約3 700 Oe。 [0 0 4 6】僅揭示一些具體實施例。然而，應明瞭可不脫春離以下申請專利範圍之精神而進行變化及改進，且其係應涵蓋於以下之申請專利範圍内。The Ms value decreased from 480 emu / cm3 to about 180 emu / cm3. Example 4 [0 0 4 5] The sputtering conditions were the same as in Example 1. Figure 9 shows the hysteresis curve of the (Fe45Pt45Cr * 1 ()) 85- (SiNy) 15 film annealed at about 60 ° C for 30 minutes. The applied magnetic field is parallel to the film surface. The measured M s value is about 4 50 e m u / cm 3 and the He // value is about 3 700 Oe. [0 0 4 6] Only some specific embodiments are disclosed. However, it should be clear that changes and improvements can be made without departing from the spirit of the scope of patent application below, and it should be covered by the scope of patent application below.

-21 --twenty one -

Claims

200407450 拾、申請專利範圍 1 . 一種方法，包括：將用於形成磁性晶粒之磁性材料、待存在於各磁性晶粒之晶界之晶粒限制材料、及使磁性晶粒散佈之用於形成非晶質基地之非磁性材料錢鍍於基板上，而形成具有各以晶粒限制材料為邊界且散佈於非晶質基地中之小磁性晶粒的初鍍軟磁顆粒狀薄膜；使初鍍的顆粒狀薄膜於真空中在經控制的退火條件下在退火溫度下退火一退火期間；及接著使經退火之薄膜於淬火液體中淬火，以完成初鍍軟磁顆粒狀薄膜之轉變為具高平行膜面頑磁力及高飽和磁化量之硬磁顆粒狀薄膜。 2.根據申請專利範圍第1項之方法，其更包括在退火之前於初鍍的軟磁顆粒狀薄膜上形成一純化層，以防止薄膜在退火過程中之氧化。 3 .根據申請專利範圍第2項之方法，其中該鈍化層包括氮化矽之薄膜。 4. 根據申請專利範圍第1項之方法，其中該磁性材料包括FePt，該晶粒限制材料包括Cr，及該非磁性材料包括氮化矽。 5. 根據电.請專利範圍第4項之方法，其更包括選擇薄膜中各材料之比例，以使（Fe50-x/2Pt50-x/2Crx)100-5-(SiNy)5 顆粒狀硬磁薄膜具有優異的性質，其中X係在約0至約 3 0原子百分比之間，及δ係約0至約3 0體積百分比。 200407450200407450 Patent application scope 1. A method comprising: using a magnetic material for forming magnetic crystal grains, a grain-restricting material to be present at a grain boundary of each magnetic crystal grain, and dispersing the magnetic crystal grains for forming The non-magnetic material of the amorphous base is plated on the substrate to form an initially plated soft magnetic granular thin film having small magnetic grains each with a grain-restricting material as a boundary and dispersed in the amorphous base; The granular film is annealed in a vacuum under controlled annealing conditions at an annealing temperature for an annealing period; and then the annealed film is quenched in a quenching liquid to complete the conversion of the initially soft magnetic granular film into a highly parallel film Hard magnetic granular film with surface coercive force and high saturation magnetization. 2. The method according to item 1 of the scope of patent application, which further comprises forming a purification layer on the soft magnetic granular film that is initially plated before annealing to prevent oxidation of the film during annealing. 3. The method according to item 2 of the patent application, wherein the passivation layer comprises a thin film of silicon nitride. 4. The method according to item 1 of the scope of patent application, wherein the magnetic material includes FePt, the grain-restricting material includes Cr, and the non-magnetic material includes silicon nitride. 5. The method according to item 4 of the patent. It also includes selecting the ratio of each material in the film so that (Fe50-x / 2Pt50-x / 2Crx) 100-5- (SiNy) 5 granular hard magnetic The film has excellent properties, where X is between about 0 and about 30 atomic percent, and δ is between about 0 and about 30 volume percent. 200407450

6. 根據申請專利範圍第4項之方法，其更包括將薄膜中之Fe:Pt:Cr之原子比選為在自約45:54:1至約41:34:25 之範圍内。 7. 根據申請專利範圍第 6項之方法，其中該薄膜中之 Fe:Pt:Cr之原子比係約45:45:1 0。 8. 根據申請專利範圍第 4項之方法，其中將薄膜中之卩6?1(：1^3丨>^之體積分率選為在自約90:10至約50:50之範圍内。 9. 根據申請專利範圍第 8項之方法，其中該薄膜中之 FePtCr:SiN之體積分率係約85:15。 10. 根據申請專利範圍第4項之方法，其更包括在濺鍍中使用FePtCr靶，以供給作為磁性材料之FePt及作為晶粒限制材料之Cr。 11. 根據申請專利範圍第10項之方法，其中該FePtCr靶包括FePtCr合金|&。 12. 根據申請專利範圍第10項之方法，其中該FePtCr靶包括FePtCr複合靶，其包括經覆蓋Ci:片之FePt靶。 13. 根據申請專利範圍第1項之方法，其中該基板係經自然氧化之S i晶圓或玻璃基板。 14. 根據申請專利範圍第1項之方法，其更包括使用一磁控濺鍍系統進行濺鍍，其中施加直流（DC)或射頻（RF) 電場，以產生濺鍍用之電漿。 15·根據申請專利範圍第1項之方法，其更包括在濺鍍中將氬壓力設定於約0.3毫托耳（mTorr)及約20毫托耳之 2004074506. The method according to item 4 of the scope of patent application, further comprising selecting an atomic ratio of Fe: Pt: Cr in the film to be in a range from about 45: 54: 1 to about 41:34:25. 7. The method according to item 6 of the patent application, wherein the atomic ratio of Fe: Pt: Cr in the film is about 45:45:10. 8. The method according to item 4 of the scope of patent application, wherein the volume fraction of 卩 6? 1 (: 1 ^ 3 丨 > ^ in the film is selected in the range from about 90:10 to about 50:50 9. The method according to item 8 of the scope of patent application, wherein the volume fraction of FePtCr: SiN in the thin film is about 85:15. 10. The method according to item 4 of the scope of patent application, which is further included in sputtering The FePtCr target is used to supply FePt as a magnetic material and Cr as a grain-restricting material. 11. The method according to item 10 of the scope of patent application, wherein the FePtCr target includes FePtCr alloy | & The method according to item 10, wherein the FePtCr target includes a FePtCr composite target, which includes a FePt target covered with a Ci: sheet. 13. The method according to item 1 of the patent application scope, wherein the substrate is a naturally oxidized Si wafer or Glass substrate 14. The method according to item 1 of the scope of patent application, further comprising sputtering using a magnetron sputtering system in which a direct current (DC) or radio frequency (RF) electric field is applied to generate a plasma for sputtering 15. According to the method of item 1 of the scope of patent application, which It included in the argon sputtering pressure is set at about 0.3 millitorr (mTorr) and about 20 mTorr of 200,407,450

間。 16. 根據申請專利範圍第1 5項之方法，其中該氬壓力係約 7毫托耳。 17. 根據申請專利範圍第1項之方法，其更包括在濺鍍過程中將基板之溫度設定在低於約4 5 °C之溫度下。 18. 根據申請專利範圍第1 7項之方法，其中在濺鍍過程中將基板溫度設定於約2 5 °C之溫度下。 19. 根據申請專利範圍第1項之方法，其更包括在退火過程中將真空控制在低於約lxl (Γ6托耳之壓力下。 20. 根據申請專利範圍第1項之方法，其更包括將退火溫度設在約4 0 0 °C及8 0 0 °C之間，且退火期間控制在約5 至90分鐘之間。 21. 根據申請專利範圍第2 0項之方法，其中將退火溫度設至約600°C。 22. 根據申請專利範圍第2 0項之方法，其中將退火期間設至約3 0分鐘。 23. 根據申請專利範圍第1項之方法，其中該淬火液體具有低於約5 °C之溫度。 24. 根據申請專利範圍第1項之方法，其更包括控制材料之組成比、退火及淬火之條件，以使FePtCr-SiN顆粒狀薄膜具有Ms > 425 emu/立方公分及He > 3500 Oe 之磁性質，其中FePt係磁性材料，Cr係晶粒限制材料，及SiN係非磁性材料。 25. —種方法，包括： 200407450between. 16. The method according to item 15 of the application, wherein the argon pressure is about 7 millitorr. 17. The method according to item 1 of the scope of patent application, which further comprises setting the temperature of the substrate to a temperature below about 45 ° C during the sputtering process. 18. The method according to item 17 of the scope of patent application, wherein the substrate temperature is set to a temperature of about 25 ° C during the sputtering process. 19. The method according to item 1 of the scope of patent application, which further includes controlling the vacuum during the annealing process to a pressure lower than about lxl (Γ6 Torr. 20. The method according to item 1 of the scope of patent application, which further includes The annealing temperature is set between about 400 ° C and 800 ° C, and the annealing period is controlled between about 5 and 90 minutes. 21. The method according to item 20 of the scope of patent application, wherein the annealing temperature is Set to about 600 ° C. 22. The method according to item 20 of the scope of patent application, wherein the annealing period is set to about 30 minutes. 23. The method according to item 1 of scope of patent application, wherein the quenching liquid has a temperature lower than A temperature of about 5 ° C. 24. The method according to item 1 of the patent application scope further includes controlling the composition ratio of materials, annealing and quenching conditions so that the FePtCr-SiN granular film has Ms > 425 emu / cubic Cm and He > 3500 Oe magnetic properties, including FePt-based magnetic materials, Cr-based grain-limiting materials, and SiN-based non-magnetic materials. 25. One method, including: 200407450

於基板上形成軟磁性顆粒狀薄膜，其具有散佈於非晶質氮化矽基地中之磁性FePt晶粒，且具有設置於各 F e P t晶粒之晶界以限制住F e P t晶粒尺寸之晶粒限制材料Cr ; 使薄膜於真空中在退火溫度及期間經控制的條件下退火；及於退火之後使薄膜於淬火液體中淬火，以使薄膜轉變為具有顆粒狀結構之硬磁性薄膜，而展現Ms > 425 emu/立方公分之飽和磁化量及He > 3500 Oe之平行膜面頑磁力。 26. 根據申請專利範圍第2 5項之方法，其中於經控制之濺鍍腔體中，將含 Fe、Pt、Cr、及氮化碎之乾；賤鐘於基板上。 27. 根據申請專利範圍第26項之方法，其更包括選擇薄膜中之F e : P t: C r之原子比係在自約4 5 : 5 4 : 1至約4 1 : 3 4 : 2 5 之範圍内。 28. 根據申請專利範圍第27項之方法，其中該薄膜中之 Fe:Pt:Cr之原子比係約45:45:10。 29. 根據申請專利範圍第 2 6項之方法，其中將薄膜中 FePtCr及氮化矽之體積比選為在自約90:10至約50:50 之範圍内。 30. 根據申請專利範圍第 2 9項之方法，其中該薄膜中 FePtCr及氮化矽之體積比係約85:15。 31·根據申請專利範圍第2 6項之方法，其更包括使用一磁 200407450 控濺鍍系統進行濺鍍，其中施加直流（DC)或射頻（RF) 電場，以產生濺鍍用之電漿。 32. 根據申請專利範圍第2 6項之方法，其更包括在濺鍍中將氬壓力設定於約〇 . 3毫托耳及約2 0毫托耳之間。 33. 根據申請專利範圍第2 6項之方法，其更包括在濺鍍過程中將基板之溫度設定在低於約4 5 °C之溫度下。 34. 根據申請專利範圍第2 5項之方法，其更包括：在退火過程中將真空控制在低於約1 X 1 (Γ6托耳之壓力下；及將退火溫度設在約4 0 0 °C及8 0 0 °C之間，且退火期間控制在約5至9 0分鐘之間。 35. 根據申請專利範圍第2 5項之方法，其中該淬火液體具有低於約5 °C之溫度。 36. 根據申請專利範圍第2 5項之方法，其更包括在退火之前於軟磁顆粒狀薄膜上形成一鈍化層，以防止薄膜在退火過程中之氧化。A soft magnetic granular thin film is formed on a substrate, which has magnetic FePt grains dispersed in an amorphous silicon nitride base, and has grain boundaries provided on each F e P t grain to limit the F e P t crystal. Cr, a grain-limiting material with a grain size; annealing the film in a vacuum under controlled conditions of annealing temperature and duration; and quenching the film in a quenching liquid after annealing to transform the film into hard magnetic having a granular structure The film exhibits the saturation magnetization of Ms > 425 emu / cm3 and the coercive force of the parallel film surface of He > 3500 Oe. 26. The method according to item 25 of the scope of the patent application, wherein in a controlled sputtering chamber, Fe, Pt, Cr, and nitrided chips are dried; a base clock is on the base plate. 27. The method according to item 26 of the scope of patent application, which further comprises selecting an atomic ratio of F e: P t: C r in the film ranging from about 4 5: 5 4: 1 to about 4 1: 3 4: 2 Within the range of 5. 28. The method according to item 27 of the application, wherein the atomic ratio of Fe: Pt: Cr in the film is about 45:45:10. 29. The method according to item 26 of the patent application range, wherein the volume ratio of FePtCr and silicon nitride in the thin film is selected to be in a range from about 90:10 to about 50:50. 30. The method according to item 29 of the patent application, wherein the volume ratio of FePtCr and silicon nitride in the thin film is about 85:15. 31. The method according to item 26 of the patent application scope, which further includes sputtering using a magnetic 200407450 controlled sputtering system, in which a direct current (DC) or radio frequency (RF) electric field is applied to generate a plasma for sputtering. 32. The method according to item 26 of the scope of patent application, which further comprises setting the argon pressure between about 0.3 mTorr and about 20 mTorr during sputtering. 33. The method according to item 26 of the scope of patent application, further comprising setting the temperature of the substrate to a temperature lower than about 45 ° C during the sputtering process. 34. The method according to item 25 of the patent application scope, further comprising: controlling the vacuum during the annealing process to a pressure lower than about 1 X 1 (Γ6 Torr); and setting the annealing temperature at about 4 0 ° C and 800 ° C, and the annealing period is controlled between about 5 and 90 minutes. 35. The method according to item 25 of the patent application scope, wherein the quenching liquid has a temperature lower than about 5 ° C 36. The method according to item 25 of the scope of patent application, which further comprises forming a passivation layer on the soft magnetic granular film before annealing to prevent the film from being oxidized during the annealing process.