Patent Publication Number: US-8968891-B2

Title: Metallic glass, magnetic recording medium using the same, and method of manufacturing the magnetic recording medium

Description:
This application is a divisional of a pending application, U.S. Ser. No. 12/678,291 filed on Jul. 8, 2010, which is the National Stage Application of PCT International Application No. PCT/JP2008/066793, both of which are hereby incorporated by reference in their entireties. 
    
    
     TECHNICAL FIELD 
     The present invention relates to a metallic glass, more specifically, the metallic glass having a chemical composition Fe m Pt n (Si x B y P z ), a magnetic recording medium using the same, and a method of manufacturing the magnetic recording medium. 
     BACKGROUND ART 
     With the development of advanced information society in recent years, the need for larger capacity image information recording is increasing, and a surface recording density as high as 1 Terabit per square inch (Tb/inch 2 ) is required for magnetic recording media. As a magnetic recording medium providing such high recording density, a patterned magnetic recording medium, which isolates magnetic dots using a nonmagnetic material, has been a focus of attention (See Non-patent Reference 1.). 
     The technique described in Non-patent Reference 1 uses a mask on which resist is patterned by the nanoimprint technology, and isolates magnetic dots by etching a magnetic film using this mask. 
     It is known that a rapidly quenched Fe—Pt—B alloy ribbon has a double-phase structure consisting of a uniform nanosized amorphous phase and a fcc(γ)-FePt phase, and that structure transforms into a nanostructure exhibiting good hard magnetic property by heat treatment (See Non-patent Reference 2.).
     [Non-patent Reference 1] Tsutomu AOYAMA, Isamu SATO, Shunji ISHIO, “Fabrication and magnetic properties of patterned magnetic recording media”, OYO BUTURI, 2003, Vol. 72, No. 3, pp. 298-303   [Non-patent Reference 2] A. Inoue and W. Zhang, J. Appl. Phys., 97, 10H308, 2005   

     DISCLOSURE OF THE INVENTION 
     Problems to be Solved by the Invention 
     With the conventional patterned magnetic recording media as described in Non-patent Reference 1, since the resist is nanoimprinted, dot pitch is as large as 100 nm or larger. It is therefore difficult to achieve a surface recording density as high as 1 Tb/inch 2 . In addition, each of the magnetic recording media must undergo a series of fabrication processes as described in Non-patent Reference 1, which increases the processing cost. 
     Accordingly, the object of present invention is directed to provide a metallic glass, a magnetic recording medium using the metallic glass, and a method of manufacturing the magnetic recording medium that substantially obviate above mentioned problems due to limitations and disadvantages of the related arts. 
     Means to Solving the Problems 
     To achieve the above objectives, the present invention provides a metallic glass characterized in that its chemical composition is represented by formula (1) as shown below.
 
Fe m Pt n Si x B y P z  (wherein, 20&lt;m≦60 at %, 20&lt;n≦55 at %, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (1)
 
     The metallic glass represented by the above formula preferably has a chemical composition represented by formula (2) as shown below.
 
Fe 55 Pt 25 (Si x B y P z ) 20  (wherein, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (2)
 
     An another metallic glass of the present invention is characterized in that its chemical composition is represented by formula (3) as shown below.
 
(Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 100-x M x  (wherein, 0&lt;x≦6 at %; and M represents an element or a combination of any two or more of the elements selected from Zr, Nb, Ta, Hf, Ti, Mo, W, V, Cr, Mn, Al, Y, Ag, and rare earth elements.)  (3)
 
     In the chemical composition of the metallic glass represented by formula (3), M may be substituted by Zr. In the chemical composition of the metallic glass represented by formulae (1) to (3), a part of Fe may be substituted by Co or Ni, and a part of Pt can be substituted by Pd. 
     In another aspects, the present invention provides a magnetic recording medium characterized in that it comprising: a substrate; and a metallic glass layer, which is formed on the substrate and has a plurality of concave portions and convex portions, and the metallic glass layer is made of a metallic glass having a chemical composition represented by formula (1) as shown below, wherein concave portions are consisting of a soft magnetic layer, and convex portions are consisting of a hard magnetic layer.
 
Fe m Pt n Si x B y P z  (wherein, 20&lt;m≦60 at %, 20&lt;n≦55 at %, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (1)
 
     Preferably, the chemical composition is represented by formula (2) as shown below.
 
Fe 55 Pt 25 (Si x B y P z ) 20  (wherein, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (2)
 
     Furthermore, the metallic glass may have a chemical composition represented by formula (3) as shown below.
 
(Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 100 - x M x  (wherein, 0&lt;x≦6 at %; and M represents an element or a combination of any two of more of the elements selected from Zr, Nb, Ta, Hf, Ti, Mo, W, V, Cr, Mn, Al, Y, Ag, and rare earth elements.)  (3)
 
     In the above chemical composition, the concave portions and convex portions preferably has a surface protective layer covered with a nonmagnetic material, and the surface of the surface protective layer is flat. The concave portions and convex portions are preferably aligned in a matrix, houndstooth-check, or line sequence pattern. 
     In the chemical composition of the metallic glass represented by formula (3) as shown above, M may be substituted by Zr. In the chemical composition of the metallic glass represented by formulae (1) to (3) shown above, a part of Fe may be substituted by Co or Ni, and a part of Pt may be substituted by Pd. 
     In another aspects, the present invention provides a method of manufacturing a magnetic recording medium characterized in that it comprises steps: of forming a metallic glass layer on a substrate; forming concave portions and convex portions on the metallic glass layer using a mold; and processing a heat treatment of the convex portions of the metallic glass layer to have a hard magnetic property, wherein the metallic glass layer has a chemical composition represented by formula (1) as shown below.
 
Fe m Pt n Si x B y P z  (wherein, 20&lt;m≦60 at %, 20&lt;n≦55 at %, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (1)
 
     The metallic glass preferably has a chemical composition represented by formula (2) as shown below.
 
Fe 55 Pt 25 (Si x B y P z ) 20  (wherein, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (2)
 
     More preferably, the metallic glass may have a chemical composition represented by formula (3) as shown below.
 
(Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 100-x M x  (wherein, 0&lt;x≦6 at %; and M represents an element or a combination of any two of more of the elements selected from Zr, Nb, Ta, Hf, Ti, Mo, W, V, Cr, Mn, Al, Y, Ag, and rare earth elements.)  (3)
 
     In the chemical composition of the metallic glass represented by formula (3) as shown above, M may be substituted by Zr. The temperature of the heat treatment of the convex portions on the metallic glass layer preferably falls within the 750° C. to 850° C. range, and heat treatment may be processed for 10 to 30 minutes. 
     Effects of the Invention 
     According to the present inventions of the metallic glass, the magnetic recording medium using the same, and the method of manufacturing the magnetic recording medium, finer concave portions and convex portions can be formed on a ferromagnetic layer made of the metallic glass. Furthermore, since the ferromagnetic material at the convex portions only can be made to form a hard magnetic layer, the packing density of the magnetic recording medium can be improved. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       In the drawings, 
         FIG. 1  illustrates the embodiment of magnetic recording medium  1  in accordance with an embodiment of the present invention, in which (A) is a plain view, and (B) is a cross-sectional view taken along the line A-A in (A); 
         FIG. 2  is a cross-sectional view illustrating a typical variation of the magnetic recording medium of the present invention; 
         FIG. 3  illustrates an another sequence pattern of the convex portions, in which (A) shows a houndstooth-check pattern, and (B) shows a line pattern; 
         FIG. 4  sequentially illustrates a method of manufacturing a magnetic recording medium according to the present invention; 
         FIG. 5  illustrates a method of manufacturing a mold; 
         FIG. 6  sequentially illustrates the method of manufacturing the mold; 
         FIG. 7  is a chart illustrating the DSC trace of Example 2; 
         FIG. 8  is a chart illustrating the XRD profiles of Example 2; 
         FIG. 9  is a chart illustrating the magnetization property of the metallic glass in Example 2; 
         FIG. 10  is a chart illustrating the dependence of the coercive force of the metallic glass in Example 2 on the annealing temperature; 
         FIG. 11  is a chart illustrating the DSC trace of Example 3; 
         FIG. 12  is a chart illustrating the XRD profile of Example 3; 
         FIG. 13  is a chart illustrating the magnetization property of the metallic glass in Example 3; 
         FIG. 14  is a chart collectively illustrating the XRD profiles of the metallic glasses in Examples 1 to 3; 
         FIG. 15  is a chart collectively illustrating the magnetization properties of the metallic glasses in Examples 1 to 3; 
         FIG. 16  is a chart illustrating the dependence of parameters on Si and B compositions obtained from the magnetization properties of the metallic glasses Fe 55 Pt 25 Si x B y P 2 , in which (A) shows residual magnetic flux density, (B) shows coercive force, and (C) shows the maximum energy product ((BH) max ); 
         FIG. 17  illustrates the dependence of the coercive force of the metallic glass Fe 55 Pt 25 (Si x B y P z ) on the composition of Si, B, and P in Examples 1 to 13; and 
         FIG. 18  is a chart illustrating the DSC trace of Example 14. 
     
    
    
     DESCRIPTION OF REFERENCE NUMERALS 
     
         
           1 : Magnetic recording medium 
           11 : Substrate 
           12 : metallic glass layer 
           12 A: Convex portion 
           12 B: Concave portion 
           13 : Surface protective layer 
           15 : Mold 
           15 A: Convex portion 
           15 B: Concave portion 
           20 : Substrate 
           21 : SiO 2  film 
           22 : Mask pattern 
           25 : Convex portion 
       
    
     BEST MODES FOR CARRYING OUT THE INVENTION 
     Hereinafter, various embodiments of the present invention will be described in detail with reference to the figures. The same characters are used to designate same or corresponding components in each figure. 
     First, favorable forms of the metallic glass of the present invention are described. 
     A metallic glass of the present invention is a permanent magnet material having a chemical composition represented by formula (1) as below.
 
Fe m Pt n Si x B y P z  (wherein, 20&lt;m≦60 at %, 20&lt;n≦55 at %, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (1)
 
     The chemical composition of the metallic glass of the present invention is preferably represented by formula (2) shown below.
 
Fe 55 Pt 25 (Si x B y P z ) 20  (wherein, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %)  (2)
 
     The metallic glass of the present invention may have a chemical composition represented by formulae (3) shown below.
 
(Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 100-x M x  (wherein, 0&lt;x≦6 at %; and M represents an element or a combination of any two of more of the elements selected from Zr, Nb, Ta, Hf, Ti, Mo, W, V, Cr, Mn, Al, Y, Ag, and rare earth elements.)  (3)
 
     Addition of M in the above composition further enhances the metallic glass-forming ability. A preferable material as M is Zr, for example. In this case, it is possible to enhance metallic glass-forming ability even if the composition X of M X  exceeds 6 at %. However, since the magnetic property of the metallic glass (Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 100-x  decreases, which is not desirable, it is preferable to use the metallic glass (Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 96 Zr 4  to obtain sufficient magnetic property. 
     A part of Fe of the metallic glassy alloys represented by formulae (1) to (3) shown above can be substituted by Co or Ni, both of which are ferromagnetic elements similar to Fe. 
     A part of Pt of the metallic glassy alloys represented by formulae (1) to (3) shown above can be substituted by Pd for forming L1 0 -FePd phase, which will be described later. 
     The metallic glass of the present invention represented by formulae (1) to (3) as shown above has ferromagnetic property. This metallic glass exhibit soft magnetic property immediately after the formation, but after annealing at high-temperature for a predetermined period of time, the metallic glass of the present invention exhibits hard magnetic property due to crystallization. 
     The metallic glasses of the present invention can be produced from master alloys, obtained by melting in a radio-frequency melting furnace and an arc melting furnace, by the single-roll melt spinning method. 
     The metallic glass of the present invention is an alloy obtained by adding Si to Fe—Pt—B-P alloy, which has been found to have good magnetic properties by previous research. By adding Si to the above alloy according to the present invention, amorphous-forming ability can be further enhanced. When a melt-spun ribbon is subjected to heat treatment, a composite structure consisting of L1 0 -FePt phase, Fe 2 B phase, PtSi phase, and FeSi phase is formed, and the annealed melt-spun ribbon exhibits hard magnetic properties because of the L1 0 -FePt phase. The alloy that exhibits most favorable amorphous-forming ability has residual magnetic flux density (Br) of approximately 0.69 T, coercive force (Hc) of 172 kA/m, and maximum energy product of 44 kJ/m 3 . 
     It is preferable that the metallic glass of the present invention is produced by the quenching method having high cooling rate. By cooling a molten material at high cooling rate, finer magnetic particles and a non-equilibrium phase can be formed in the metallic glassy matrix. Specifically, by rapidly quenching the molten material, non-equilibrium phases such as supersaturated solid solution, namely the state in which added elements such as B and Si are forcibly dissolved into the metallic glass, and amorphous phase, can be formed easily. These non-equilibrium phases can be transformed into a more stable L1 0 -FePt phase easily, and as a result, high coercive force can be obtained. 
     As a rapid quenching method, it is preferable to use the liquid quenching method, such as single-roll method, double-roll method, and centrifugal quenching method, and the gas-phase quenching method, such as sputtering method and vacuum deposition method. By the liquid quenching method, which is known to be useful for manufacturing an amorphous alloy, for example, cooling is performed at the cooling rate as high as 100 K/sec. Consequently, this method is also effective for non-amorphous alloys to obtain finer crystal grain size and a non-equilibrium phase by the effect of rapid quenching. By the gas-phase cooling method, whose cooling rate is as high as or higher than that of the liquid cooling method, allows finer crystal grain size and a non-equilibrium phase to be obtained. 
     When the metallic glass of the present invention is manufactured by the liquid quenching, melt-spinning method, continuous or discontinuous glassy ribbons in thickness of several μm to several dozen μm can be obtained. The ribbons obtained in this way can also be crushed into powder. The thin metallic glassy ribbons are ideal as a permanent magnet material for small magnetic parts, with which processing of bulk materials incurs high cost and results in degradation of magnetic property, for example. 
     The metallic glassy powder obtained by the present invention is ideal as a bonded magnet material, mixed with resin, etc., for example. 
     According to the present invention, a metallic glassy thin film having thickness of several nm to several dozen nm can be formed on a substrate by the gas-phase quenching method. The thin film thus formed on a substrate is ideal as a medium for high-density magnetic recording. Thus, the hard magnetic property can be obtained by without requiring heat treatment or by crystallization by heat treatment at nearly 800 K. Consequently, inexpensive oxide-glass substrates can be used. With the metallic glass of the present invention, since the growth of crystal grains is suppressed, a very fine crystalline structure can be obtained, which allows the metallic glass of the present invention to satisfy the requirements of high-density magnetic recording media. 
     It is preferable that heat treatment for crystallization is processed at the temperature around 800 K, specifically from approximately 750 K to 850 K. heat treatment processed at a temperature lower than 750 K is not preferable because crystallization does not advance and good hard magnetic property cannot be obtained. In the heat treatment processed at 750 K or higher, with the increase of the annealing temperature, crystallization advances and coercive force increases, thus providing hard magnetic property. In the heat treatment processed at 850 K or higher, since the coercive force is saturated, further temperature increase is not necessary. 
     It is desirable that heat treatment is processed for the time of approximately 10 to 30 minutes under the above annealing conditions. Heat treatment processed for less than 10 minutes is not preferable because crystallization does not advance and consequently hard magnetic property cannot be obtained. On the other hand, the heat treatment processed for longer than 30 minutes, the coercive force due to crystallization is saturated, and so the duration of heat treatment need not be increased further. 
       FIG. 1  illustrates an embodiment of magnetic recording medium  1  of the present invention, in which (A) is a plain view, and (B) is a cross-sectional view taken along the line A-A in (A). Magnetic recording medium  1  of the present invention comprises: a substrate  11 ; and a metallic glassy layer  12 , which is provided on the substrate  11  and has a plurality of concave portion and convex portion. The plurality of concave portion  12 B are a soft magnetic layer. At least outer most surface of the plurality of convex portion  12 A are consisting of a hard magnetic layer that allows magnetic recording to be made. For the metallic glassy layer  12 , a metallic glass having a chemical composition represented by the above formulae (1) and (2) can be used. 
     A pitch P of the convex portions  12 A is identical to that of a pitch P of concave portions  12 B as shown in  FIG. 1 , and is set to be approximately 25 nm. The height t 3  of the convex portions  12 A is set to be approximately 25 nm. 
     By the way, oxide glasses are used for substrates for conventional magnetic recording media, namely a hard disk for Hard Disk Drive. According to the present invention, a metallic glass may be used as the substrate  11 . When a metallic glass is used as the substrate  11 , bulk metallic glassy material is sandwiched between tools, and by pressing the bulk material while maintaining it within the supercooled liquid temperature region, a substrate  11  having a desired thickness can be formed. 
     At this time, the surface of a mold is mirror-finished by using a chemical mechanical polishing (CMP) equipment. The load of the press work can be minimized by performing press work within the supercooled liquid temperature region of the metallic glass. The mirror-finished surface of the mold is copied to the surface of the substrate  11  with mirror accuracy, allowing the substrate  11  to have uniform thickness having excellent evenness or smoothness. Consequently, a metallic glassy substrate that has undergone press working only can be used as the substrate  11 , which reduces the machining cost of the substrate  11 . The metallic glassy substrate  11  thus formed can be used not only as a magnetic recording medium but also as a light weight substrate for DVDs, CDs, and HDs. 
     The metallic glass, which is an amorphous alloy, is high in strength, flexible, and has excellent anti-corrosion characteristics. Consequently, the substrate  11  can be made thin, allowing reduction in size and weight of the magnetic recording medium  1 . The magnetic recording medium in the embodiment of the present invention can be used not only for information recording but also as a scale for magnetic recording media on the order of nanometer (nm). 
       FIG. 2  is a cross-sectional view illustrating a modified embodiment of the magnetic recording medium of the present invention. The magnetic recording medium as shown in  FIG. 2  differs from that as shown in  FIG. 1  that a surface protective layer  13  made of a nonmagnetic material is provided on convex portions  12 A and concave portions  12 B. The surface protective layer  13  can cover the concave portions  12 B only, or the concave portions  12 B can be filled in and covered along with the surface of the convex portions  12 A. The surface protective layer  13  can remain flat. As a material for the surface protective layer  13 , a SiO 2  film, etc. can be used. 
       FIG. 3  illustrates an another sequence pattern of convex portions  12 A as shown in  FIG. 1 .  FIG. 3(A)  shows a houndstooth-check pattern, and  FIG. 3(B)  shows a line shaped pattern. The pitch P of the sequence pattern as shown in  FIG. 3(A)  is the same as the pattern as shown in  FIG. 1 , however the pitch between lines P 1  is set to be larger than the pitch P. The convex portions  12 B can also be arranged in a houndstooth-check pattern or line shaped pattern as in the case of convex portions  12 A. 
     The concave portions  12 B and the convex portions  12 A can also be made into any patterns at need or arbitrary other than the matrix, houndstooth-check, and line patterns described above. According to the present embodiment, since nanoimprint technology is employed to form the concave portions  12 B and convex portions  12 A on the metallic glassy layer  12  in an supercooled liquid temperature region as described later, high-precision formation of nano-ordered concave and convex portions can be possible. High-density magnetic recording media can thus be formed highly accurately. In addition, since concave portions  12 B and convex portions  12 A can be formed just by performing press work, processing time and cost can be minimized. 
     In the magnetic recording medium  1  as shown in  FIG. 1 , the convex portions  12 B consisting of a soft magnetic layer exist surrounding the convex portions  12 A, which surface consisting of a hard magnetic layer. The concave portions  12 B formed by a soft magnetic layer have the function to support the recording magnetic field from a magnetic head. Since the recording magnetic field of the magnetic head forms a closing loop while going through the convex portions  12 B, fetching of the recording magnetic field and the sensitivity of reading signal can be improved. 
     Furthermore, since the convex portions  12 B have a surface protective layer  13  covered with a nonmagnetic material, each of the hard magnetic layer of the convex portions  12 A serves as a magnetically independent recording bit. 
     A nonmagnetic material such as aluminum, oxide glass, and metallic glass can be used as the substrate  11 . As described later, the temperature of the entire substrate  11  is increased to the molding temperature Tm during the manufacturing process. When the substrate  11  is an amorphous material, amorphous material in which crystallization temperature is higher than the molding temperature Tm should be adopted. 
     The thickness t 1  of the entire metallic glassy layer  12  is approximately 20 nm, and the thickness t 2  of the concave portions  12 B is approximately several nm. The area other than the hard magnetic layer of the metallic glassy layer  12  is a soft magnetic layer. This soft magnetic layer corresponds to an interlayer of a conventional perpendicular magnetic recording medium. The recording density as high as 1 Tb/inch 2  can be achieved by keeping the pitch P of the concave portions  12 B formed in matrix sequence to be approximately 25 nm. The pitch P of the concave portions  12 B is determined by the accuracy of the mold used for nanoimprint molding described previously. When the mold is formed by using ion beam, etc, the pitch P can be reduced to the order of 10 nm. In this case, the recording density of the magnetic recording medium  1  will be increased up to several Tb/inch 2 . 
     Now, the method of manufacturing the magnetic recording medium  1  according to the present invention will be explained below. 
       FIG. 4  illustrates the method of manufacturing a magnetic recording medium according to the present invention. In this embodiment, fine concave and convex pattern of the metallic glassy layer  12  is formed by the nanoimprint method. At first, as shown in  FIG. 4(A) , a metallic glassy layer  12  having a predetermined thickness is formed on a substrate  11  by the evaporation using sputtering method etc. 
     Then, as shown in  FIG. 4(B) , concave portions and convex portions are formed on the metallic glassy layer  12  by the nanoimprint method using a mold  15 . The mold  15  has convex portions  15 A for forming concave portions  12 B on the metallic glassy layer  12  and concave portions  15 B for forming convex portions  12 A on the metallic glassy layer  12 . The method of manufacturing the mold  15  will be described later. 
     Amorphous alloys called as metallic glasses feature that the glass transition temperature Tg is lower than their crystallization temperature Tx, and there exists a stable supercooled liquid temperature region ΔTx (=Tx−Tg). Within this supercooled liquid temperature region, since the metallic glass exhibits complete Newtonian viscosity flow, low-stress viscosity flow processing can be performed. This is the reason why the metallic glass has excellent micro-formability i.e. micro-configuration transfer property. According to the present embodiment, using this property of the metallic glass, micro concave portions and convex portions on the order of nm formed on the mold  15  are transferred to a metallic glassy layer  12 , thus achieving highly accurate and easy micro-/nano-concave and convex formation. 
     In the process as shown in  FIG. 4(B) , the substrate  11 , on which the metallic glassy layer  12  has been formed, and the mold  15  are heated up to the molding temperature Tm, which is higher than the glass transition temperature Tg of the metallic glassy layer  12 , and a predetermined load is applied for a predetermined time, to form a metallic glassy layer  12  by imprint molding. The substrate  11  and the mold  15  are then cooled. When their temperature decreases to lower than the glass transition temperature Tg of the metallic glassy layer  12 , the load is removed. Through these processes, the concave portions  12 B having the depth of t 1 −t 2  are formed on the metallic glassy layer  12  as shown in  FIG. 4(C) . 
     Then, as shown in  FIG. 4(D) , by annealing the amorphous layer of the metallic glass, the only surface of the convex portions  12 A is crystallized to form a hard magnetic layer. Laser can be used for the heat treatment of the surface of the convex portions  12 A. 
     Amorphous alloys, namely metallic glassy alloys represented by the above chemical composition formulas (1) to (3) can be used. For example, an amorphous alloy having the composition Fe 55 Pt 25 Si 16 B 2 P 2  can preferably be used. This alloy remains a soft magnetic layer in an amorphous state. When this alloy is processed by heat treatment, it is crystallized and turns into a hard magnetic layer consisting of Fe—Pt phase having L1 0  structure. Meanwhile, when a part of Pt is substituted by Pd, a hard magnetic layer made of Fe—Pd phase having L1 0  structure can be obtained through crystallization processed by the heat treatment. 
       FIGS. 5 and 6  illustrate how to produce a mold  2 . In the first process as shown in  FIG. 5(A) , a SiO 2  film  21  having a thickness of approximately 100 nm is formed on a surface of a Si substrate  20  having a (100) surface by the thermal oxidation method. 
     In the second process as shown in  FIG. 5(B) , a tungsten (W) thin film is formed on the SiO 2  film  21  by the focused ion beam chemical vapor deposition (FIB-CVD) method, and a mask pattern  22  is formed on the SiO 2  film  21 . The patterning of this tungsten (W) thin film is processed by irradiating Ga +  ion beam to the area to be processed while spraying gasified W(CO) 6  (tungsten hexacarbonyl). A deposited tungsten (W) film is formed on the surface of the SiO 2  film  21  by decomposition of the W(CO) 6  gas into W and CO.  FIG. 5(C)  illustrates a mask pattern made of a plurality of masks  22  formed on the SiO 2  film  21 . 
     In the third process as shown in  FIG. 6(A) , using the tungsten mask pattern  22 , the SiO 2  film  21  is etched anisotropically by reactive ion etching (RIE) with CHF 3 . As shown in  FIG. 6(B) , a plurality of convex portions  25  that correspond to the concave portions  12 B of the metallic glassy layer  12  are formed on the surface of the mold  15 . 
     In the embodiment described above, the mold  15  which is formed by processing the Si substrate  20  by FIB was used, however a mold  15  made of metallic glass can also be used. In this case, a mother die is formed by processing the Si substrate  20  by FIB, and a mold  15  can be formed by imprinting the metallic glass using the mother die. The surface configuration i.e. concave portions and convex portions of the mother die should be identical to that of the metallic glassy layer  12  as shown in  FIG. 1 . 
     Example 1 
     The metallic glass of the present invention will be described further in detail by referring to various Examples below, but the Examples of the present invention are not limited to those described. 
     Using a mother alloy produced by melting in a radio-frequency melting furnace and an arc melting furnace, metallic glassy ribbons having the composition Fe 55 Pt 25 Si 13 B 5 P 2  was produced by the single-roll melt spinning method. The thermal property of a sample having a shape of ribbon of Example 1 was measured by the differential scanning calorimetry (DSC) to find the supercooled liquid region. 
     The “supercooled liquid region” determines the resistance to crystallization, namely the stability and processability, of amorphous material. In the present specification, the supercooled liquid region is defined as the difference between the glass transition temperature Tg and the crystallization temperature Tx, which can be obtained by conducting differential scanning calorimetry (DSC) at the heating rate of 40 K/min. The difference ΔTx (=Tx−Tg) between the crystallization start temperature Tx and the glass transition temperature Tg of the metallic glass in Example 1 was 25 K. The metallic glass in Example 1 exhibited enhanced amorphous-forming ability compared with FePtBP metallic glassy system to which Si was not added. 
     The sample of Example 1 was encapsulated into a quartz tube in vacuum, and was processed by the annealing for 900 seconds. Phase identification was performed by using X-ray diffraction (XRD), and magnetic property was measured by using a vibrating sample magnetometer (VSM). 
     By the heat treatment of the quenched ribbons of Example 1 at the temperature of 810 K or higher, a composite structure consisting of L1 0 -FePt phase, Fe 2 B phase, PtSi phase, and FeSi phase was formed. In the metallic glass having the most excellent amorphous-forming ability, the residual magnetic flux density (Br), coercive force (Hc), and the maximum energy product ((BH)max) were approximately 0.69 T, 172 kA/m and 44 kJ/m 3 , respectively. 
     Example 2 
     The metallic glass in Example 2 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 16 B 2 P 2 . ΔTx (=Tx−Tg) was found to be 37 K. 
       FIG. 7  is a chart illustrating the DSC trace of Example 2. The ordinate axis represents heat quantity and the abscissa axis represents temperature (K). In general, to examine phase transition phenomenon with a DSC trace, the exothermic reaction is observed. Meanwhile, in the metallic glass, taking into consideration the supercooled liquid region where the endothermic reaction is shown, the downward arrow on the ordinate axis is made to represent endotherm. As shown in  FIG. 7 , ΔTx (=Tx−Tg) of the metallic glass in Example 2 was 37 K. 
       FIG. 8  illustrates the XRD profiles of Example 2. The ordinate axis represents the intensity of X-ray diffraction, and the abscissa axis represents the angle (°), which is equivalent to the value twice the angle of incidence (θ) of X-ray into the atomic plane.  FIG. 8  indicates that the metallic glass having the composition in Example 2 started precipitating crystalline phases with the increase of annealing temperature immediately after the formation of the metallic glass (as-Q), and that L1 0 -FePt phase having a hard magnetic property was formed obviously at 810 K. It is understood that fcc-FePt phase, FeSi phase, and Pt 2 Si 3  phase are formed in addition to the L1 0 -FePt phase. 
       FIG. 9  is illustrates the magnetization property of the metallic glass in Example 2. The ordinate axis represents magnetization J (T: Tesla), and the abscissa axis represents magnetic field Hc (A/m). As shown in  FIG. 9 , the metallic glass having the composition of Example 2 exhibited soft magnetic property through the heat treatment processed at 675 K and 750 K after the formation of the metallic glass (as-Q), and after the heat treatment processed at 810 K, hard magnetic property was obtained. It is also apparent that in case of B is 2%, the formation of Pt—Si phase is not isolated from the transformation of the Fe—Pt phase. 
       FIG. 10  illustrates the dependence of the coercive force of the metallic glass in Example 2 on the annealing temperature. The ordinate axis represents the coercive force Hc (kA/m), and the abscissa axis represents annealing temperature (K). The annealing time is 900 seconds. As shown in  FIG. 10 , the metallic glass having the composition of Example 2 exhibited hard magnetic property by the heat treatment processed at 750 K or higher after the formation of the metallic glass. It was also found that the coercive force ranging from 100 kA/m to 170 kA/m was obtained at the annealing temperature of approximately 780 K to 830 K. 
     Example 3 
     The metallic glass in Example 3 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 18 P 2 .  FIG. 11  illustrates the DSC trace of Example 3. ΔTx was found to be 37 K. 
       FIG. 12  illustrates the XRD profile of Example 3. The ordinate axis represents the intensity of X-ray diffraction, and the abscissa axis represents angle (°), which is equivalent to the value twice the angle of incidence θ of the X-ray into the atomic plane.  FIG. 12  indicates that the metallic glass having the composition of Example 3 started precipitating crystalline phases with the increase of annealing temperature immediately after the formation of the metallic glass (as-Q), and that L1 0 -FePt phase having a hard magnetic property was formed obviously at the temperature of 795 K. It is also obvious that fcc-FePt phase, FeSi phase, and Pt 2 Si 3  phase were formed in addition to the L1 0 -FePt phase. 
       FIG. 13  illustrates the magnetization property of the metallic glass of Example 3. The ordinate axis represents magnetization J (T: Tesla) and the abscissa axis represents magnetic field H (A/m).  FIG. 13  indicates that the metallic glass having the composition of Example 3 exhibited soft magnetic property by the heat treatment processed at 750 K immediately after the formation of the metallic glass (as-Q), and that hard magnetic property was obtained after by the heat treatment processed at 795 K. 
       FIG. 14  collectively illustrates the XRD profiles of the metallic glasses in Examples 1 to 3. It is apparent that L1 0 -FePt crystalline phase was formed by the heat treatment processed at approximately 795 and 810 K. 
       FIG. 15  collectively illustrates the magnetization properties of the metallic glasses in Examples 1 to 3. It is obvious that the metallic glasses exhibited hard magnetic properties by the heat treatments processed at approximately 795 and 810 K. 
     Example 4 
     The metallic glass in Example 4 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 15 B 3 P 2 . ΔTx was found to be 37 K. 
       FIGS. 16  (A) to  16 (C) illustrate the dependence of residual magnetic flux density, coercive force, and the maximum energy product ((BH)max) on Si and B compositions obtained from the magnetization properties of the metallic glasses Fe 55 Pt 25 Si x B y P 2  in Examples 1 to 4. The upper abscissa axis represents B composition (at %) and the lower abscissa axis represents Si composition (at %). As shown in  FIG. 16(A) , residual magnetic flux density value of approximately 0.73 T to 0.8 T was obtained when Si composition varied from 18 at % to 10 at %. 
     As shown in  FIG. 16(B) , the coercive force of approximately 164 kA/m to 205 kA/m was obtained when Si composition varied from 18 at % to 10 at %. 
     As shown in  FIG. 16(C) , the maximum energy product of approximately 49 kJ/m 3  to 60 kJ/m 3  was obtained when Si composition varied from 18 at % to 10 at %. 
     Consequently, by varying Si and B compositions, the magnetic property of the metallic glass having the above composition; Fe 55 Pt 25 Si x B y P 2  can be changed. 
     Example 5 
     The metallic glass in Example 5 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 11 B 1 P 8 . ΔTx was found to be 26 K. 
     Example 6 
     The metallic glass in Example 6 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 13 B 1 P 6 . ΔTx was found to be 32 K. 
     Example 7 
     The metallic glass in Example 7 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 13 B 3 P 4 . ΔTx was found to be 26 K. 
     Example 8 
     The metallic glass in Example 8 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 14 B 4 P 2 . ΔTx was found to be 27 K. 
     Example 9 
     The metallic glass in Example 9 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 15 B 1 P 4 . ΔTx was found to be 31 K. 
     Example 10 
     The metallic glass in Example 10 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 15 B 2 P 3 . ΔTx was found to be 32 K. 
     Example 11 
     The metallic glass in Example 11 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 15 P 5 . ΔTx was found to be 17 K. 
     Example 12 
     The metallic glass in Example 12 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 16 B 3 P 1 . ΔTx was found to be 23 K. 
     Example 13 
     The metallic glass in Example 13 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 17 B 3 . ΔTx was found to be 29 K. 
     It was found that in any Examples from 4 to 13, L1 0 -FePt crystalline phases were produced by the heat treatment, and the hard magnetic properties were obtained. 
       FIG. 17  illustrates the dependence of the coercive force of the metallic glasses Fe 55 Pt 25 (Si x B y P z ) on the compositions of Si, B, and P in Examples 1 to 13. The positions marked with open circles (◯) exhibit the measured composition of the metallic glass, and the numeric values shown next to them represent the coercive force (kA/m). Each of the curves marked as 160 to 200 displays distributions of the coercive force. 
     It is obvious as shown in  FIG. 17  that the high coercive force was obtained at composition z of P ranging from 2 to 4 at %. 
     Example 14 
     The metallic glass in Example 14 was manufactured by the same method as Example 1, except that the chemical composition was changed to (Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 96 Zr 4 . 
       FIG. 18  illustrates the DSC trace of Example 14. The ordinate axis represents heat quantity and the abscissa axis represents temperature (K). In general, to examine phase transition phenomenon with a DSC trace, exothermic reaction is observed. Meanwhile, in the metallic glass, taking into consideration the supercooled liquid region where the endothermic reaction is shown, the downward arrow on the ordinate axis is made to represent endotherm. As shown in  FIG. 18 , ΔTx (=Tx−Tg) of the metallic glass in Example 14 was 48 K. 
     From the above, (Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 96 Zr 4  was found to be a metallic glassy alloy having a ΔTx value as large as that of Fe 55 Pt 25 (Si x B y P z ) 20  (wherein, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %). It was also found that the L1 0 -FePt phase is generated by annealing at 800 K for 900 seconds, and that hard magnetic property was obtained. 
     Comparative Examples are explained below. 
     Comparative Example 1 
     The alloy in Comparative Example 1 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 8 B 8 P 4 . The DSC trace revealed that this alloy was not a metallic glass. 
     Comparative Example 2 
     The alloy in Comparative Example 2 was manufactured by the same method as Example 1, except that the chemical composition was changed to Fe 55 Pt 25 Si 10 B 8 P 2 . The DSC trace revealed that this alloy was not a metallic glass. 
     According to Examples and Comparative Examples described above, it is identified to be able to manufacture metallic glasses having a large ΔTx in Fe 55 Pt 25 (Si x B y P z ) 20  (wherein, 11≦x&lt;19 at %, 0≦y&lt;8 at %, and 0&lt;z&lt;8 at %) and (Fe 0.55 Pt 0.25 Si 0.16 B 0.02 P 0.02 ) 96 Zr 4 . It is obvious that the crystalline phase of L1 0 -FePt can be generated by the heat treatment and that the hard magnetic property can be obtained. 
     The embodiments of the present invention are not limited to those described above. Various modifications are possible without departing from the scope of claims of the present invention. It is needless to say that those modifications are also included in the scope of the present invention.