Perpendicular magnetic recording medium
10388315 ยท 2019-08-20
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Abstract
The present invention relates to a magnetic recording medium, and this magnetic recording medium includes at least a non-magnetic substrate and a magnetic recording layer. In the magnetic recording medium of the present invention, the magnetic recording layer includes an ordered alloy having an L1.sub.0-ordered structure, includes Fe, Pt, and V, and has a composition of Pt>Fe. The magnetic recording layer preferably has a granular structure composed of magnetic crystal grains including the ordered alloy and a non-magnetic crystal grain boundary, and the non-magnetic crystal grain boundary includes V.
Claims
1. A magnetic recording medium comprising: at least a non-magnetic substrate; and a magnetic recording layer, said magnetic recording layer comprising an ordered alloy having an L1.sub.0-ordered structure, comprising Fe, Pt, and V, having a Fe content of 40 to 45 at % and a Pt content of 45 to 55 at % with the proviso that a composition of Fe and Pt is Pt>Fe, and having a V content of 3.7 to 11.6 at %.
2. The magnetic recording medium according to claim 1, wherein said magnetic recording layer has a granular structure composed of magnetic crystal grains comprising said ordered alloy and a non-magnetic crystal grain boundary, and said non-magnetic crystal grain boundary comprises V.
3. The magnetic recording medium according to claim 1, further comprising: a seed layer, said seed layer comprising Pt.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DESCRIPTION OF THE EMBODIMENTS
(7) A magnetic recording medium of the present invention comprises a non-magnetic substrate and a magnetic recording layer, and the magnetic recording layer is formed having an ordered alloy with an L1.sub.0-ordered structure. Moreover, the magnetic recording layer comprises Fe, Pt, and V and has a composition of Pt>Fe.
(8) The present invention will be described below with reference to the attached drawings but the present invention is not limited to them. In an embodiment of the present invention, the magnetic recording medium can include a non-magnetic substrate 10, a magnetic recording layer 30, and an optional seed layer 20 as illustrated in
(9) The non-magnetic substrate 10 may be various substrates whose surfaces are smooth. For the non-magnetic substrate, a material used in general for the magnetic recording medium can be used. For example, the material which can be used for the non-magnetic substrate 10 includes a NiP-plated Al alloy, reinforced glass, crystalized glass, MgO, or the like.
(10) The magnetic recording layer 30 comprises iron (Fe), platinum (Pt), and vanadium (V). The magnetic recording layer 30 comprises an ordered alloy, and the ordered alloy preferably has an L1.sub.0-structure. A particularly preferable L1.sub.0-ordered alloy is FePt.
(11) In the ordered alloy used in the present invention, a ratio between Fe and Pt is Fe<Pt by at %. Preferably, contents of Fe and Pt in the ordered alloy satisfy the condition of Fe (at %)<Pt (at %) in contents of the respective elements forming the L1.sub.0-ordered alloy. More preferably, the contents of Fe and Pt are such that Fe is 40 to 45 at % and Pt is 45 to 55 at % under the condition of Fe (at %)<Pt (at %). Moreover, a content of V in the magnetic recording layer is 3 to 12 at % or preferably 3.5 to 12 at %. The ordered alloy with the L1.sub.0-ordered structure which can improve the coercive force (Hc) can be obtained by use of the composition ratio within this range.
(12) The element V in the magnetic recording layer used in the present invention is preferably V in a zero-valent oxidized state, that is, V in a metal state. Although it is not intended to be restricted by any theory, V is considered to be precipitated to an outside of FePt of the L1.sub.0-ordered alloy to improve phase separation. In the present invention, the ordered alloy does not comprise V in the more highly oxidized state such as a V oxide.
(13) In the present invention, the order parameter of the ordered alloy can be obtained, for example, by measuring the magnetic recording layer using an X-ray diffraction method (XRD), and calculating a ratio between a measured value and a theoretical value when the alloy is completely ordered. In the case of the L1.sub.0-ordered alloy, it can be calculated by using integrated intensity of (001) and (002) peaks derived from the ordered alloy. The order parameter S can be obtained as a square root of a quotient of the ratio of (001) FePt peak integrated intensity to the measured (002) FePt peak integrated intensity divided by a ratio of the (001) peak integrated intensity to the (002) peak integrated intensity calculated theoretically when it is completely ordered.
(14) The magnetic recording layer of the magnetic recording medium of the present invention preferably has a granular structure composed of a non-magnetic amorphous grain boundary comprising V surrounding magnetic crystal grains made of FePt of the ordered alloy. In the granular structure, the respective magnetic crystal grains are magnetically separated by the non-magnetic grain boundary.
(15) In the present invention, the magnetic recording layer is preferably formed by a sputtering method with heating of the substrate. The sputtering method includes general processes such as a DC magnetron sputtering method and an RF sputtering method, well-known in the art, and these general methods can be used in the present invention. In this Description, the term sputtering method has the same meaning to the aforementioned general method unless otherwise specified. A substrate temperature when the magnetic recording layer is formed is preferably within a range of 400 to 500? C. The order parameter S of the L1.sub.0-ordered alloy material in the magnetic recording layer can be improved by employing the substrate temperature within this range. As a target to be used in the sputtering method, the sputtering method using two targets, that is, a target made of Fe and Pt and a target made of V, for example, can be employed. Alternatively, the sputtering method using three targets, that is, a target made of Fe, a target made of Pt, and a target made of V may be employed. In these cases, a ratio among Fe, Pt, and V in the ordered alloy of the magnetic recording layer 30 can be controlled by supplying power to the respective targets separately.
(16) When the magnetic recording layer having the granular structure is to be formed, a target in which a material for forming the magnetic crystal grains and a material for forming the non-magnetic crystal grain boundary are mixed at a predetermined ratio may be used. Alternatively, a target made of a material forming the magnetic crystal grains and a target made of a material forming the non-magnetic crystal grain boundary may be used. As described above, a plurality of targets can be used as the target for forming the magnetic crystal grains. In this case, a ratio between the magnetic crystal grains and the non-magnetic crystal grain boundary in the magnetic recording layer can be controlled by supplying power to the respective targets, separately.
(17) In the present invention, a layer for magnetic recording may be a single layer of the magnetic recording layer 30 or may be a laminated body of a plurality of layers with the other layers added to the magnetic recording layer 30. If the layer in charge of magnetic recording is constituted by a plurality of layers, the layers to be added to the magnetic recording layer 30 may be a layer for the purpose of Curie temperature (Tc) control, a cap layer for adjusting magnetization inversion, an exchange coupling control layer for controlling exchange coupling between two magnetic layers, a magnetic layer for controlling magnetic properties, a magnetic layer for controlling a ferromagnetic resonance frequency directed to a microwave assisted magnetic recording, and the like. These layers can be formed by using any process known in the art including the sputtering method. These layers are disposed integrally with and inseparably from the magnetic recording layer 30. If the laminated body of a plurality of the layers with the other layers added to the magnetic recording layer 30 is employed, description on arrangement such as above or below of the magnetic recording layer 30 should be understood as above, below, and the like, of the laminated body.
(18) The magnetic recording medium of the present invention may further include one or a plurality of layers selected from a group of an adhesive layer, a heat-sink layer, a soft magnetic under layer, an interlayer and the seed layer 20 between the non-magnetic substrate 10 and the magnetic recording layer 30. Moreover, the magnetic recording medium of the present invention may further include a protective layer on the magnetic recording layer 30. Furthermore, the magnetic recording medium of the present invention may further include a liquid-lubricant layer on the magnetic recording layer 30 or the protective layer.
(19) The adhesive layer which may be provided optionally is used for improving adhesiveness between the layer formed thereon and the layer (including the non-magnetic substrate 10) formed therebelow. If the adhesive layer is to be provided on an upper surface of the non-magnetic substrate 10, the adhesive layer 20 may be formed by using a material with favorable adhesiveness with the aforementioned material of the non-magnetic substrate 10. Such materials include metals such as Ni, W, Ta, Cr, and Ru, and an alloy comprising the aforementioned metal. Alternatively, the adhesive layer may be formed between two constituting layers other than the non-magnetic substrate 10. The adhesive layer may be a single layer or have a lamination structure of a plurality of layers.
(20) The soft magnetic under layer which may be provided optionally improves writing and reading characteristics of the magnetic recording medium by controlling a magnetic flux from the magnetic head. A material for forming the soft magnetic under layer includes crystalline materials such as an NiFe alloy, a Sendust (FeSiAl) alloy, and a CoFe alloy, fine crystalline materials such as FeTaC, CoFeNi, and CoNiP, and amorphous materials including Co alloys such as CoZrNb and CoTaZr. An optimal value of the thickness of the soft magnetic under layer depends on the structure and the characteristics of the magnetic head used for the magnetic recording. When forming the soft magnetic under layer continuously with the other layers, in view of productivity, the soft magnetic under layer preferably has a thickness within a range of 10 to 500 nm (both inclusive).
(21) When the magnetic recording medium of the present invention is to be used in a heat assisted magnetic recording method, a heat-sink layer may be provided. The heat-sink layer is a layer for effectively absorbing excess heat of the magnetic recording layer 30 generated in the heat assisted magnetic recording. The heat-sink layer can be formed by use of a material with high heat conductivity and specific heat capacity. Such materials include a Cu simple substance, an Ag simple substance, an Au simple substance or an alloy material mainly composed of them. Here, the phrase mainly composed of means that a content of the material concerned is 50 wt % or more. Moreover, from the viewpoint of strength or the like, the heat-sink layer can be formed by use of an AlSi alloy, a CuB alloy, and the like. Moreover, the heat-sink layer can be formed by use of a Sendust (FeSiAl) alloy, a soft magnetic CoFe alloy, or the like. A function of concentrating a magnetic field in a perpendicular direction generated by the head to the magnetic recording layer can be given to the heat-sink layer, and the function of the soft magnetic under layer can be also complemented, by use of the soft magnetic material. An optimal value of the thickness of the heat-sink layer is changed depending on a heat capacity and heat distribution in the heat assisted magnetic recording as well as layer constitution of the magnetic recording medium and a thickness of each constituent layer. In the case of continuous film formation with the other constituent layers or the like, the thickness of the heat-sink layer is preferably 10 nm or more and 100 nm or less in view of a balance with productivity. The heat-sink layer can be formed by use of any process known in the art such as a sputtering method and a vacuum deposition method. In normal cases, the heat-sink layer is formed by use of the sputtering method. The heat-sink layer can be provided between the non-magnetic substrate 10 and the adhesive layer, between the adhesive layer and the interlayer, and the like, in consideration of the properties required for the magnetic recording medium.
(22) The interlayer is a layer for controlling crystallinity and/or crystal orientation of the seed layer 20 formed thereabove. The interlayer may be a single layer or a multiple layer. The interlayer is preferably a non-magnetic film formed of Cr metal or an alloy in which at least one kind of metal selected from a group consisting of Mo, W, Ti, V, Mn, Ta, and Zr is added to Cr which is a main component. The interlayer can be formed by use of any process known in the art such as the sputtering method.
(23) Functions of the seed layer 20 are to ensure adhesiveness between a layer below that such as the interlayer and the magnetic recording layer 30, and to control a grain size and crystal orientation of the magnetic crystal grains of the magnetic recording layer 30 which is an upper layer. The seed layer 20 is preferably non-magnetic. In addition, when the magnetic recording medium of the present invention is used in the heat assisted magnetic recording method, the seed layer 20 preferably controls, as a thermal barrier, a temperature rise and temperature distribution of the magnetic recording layer 30. In order to control the temperature rise and the temperature distribution of the magnetic recording layer 30, the seed layer 20 preferably satisfies both a function of rapidly raising the temperature of the magnetic recording layer 30 when the magnetic recording layer 30 is heated during heat assisted recording and a function to transfer the heat in the magnetic recording layer 30 to the underlying layer such as the interlayer by heat conduction in a depth direction before an in-plane direction heat conduction in the magnetic recording layer 30 occurs.
(24) In order to achieve the aforementioned functions, a material of the seed layer 20 is appropriately selected in accordance with the material of the magnetic recording layer 30. More specifically, the material of the seed layer 20 is selected in accordance with the material of the magnetic crystal grain of the magnetic recording layer. For example, if the magnetic crystal grain of the magnetic recording layer 30 is formed of the L1.sub.0-ordered alloy, the seed layer is preferably formed by use of Pt metal or an NaCl type compound. Particularly, in the present invention, the seed layer 20 is preferably formed by use of Pt. If the seed layer 20 is formed by lamination of a plurality of layers, an oxide such as MgO or SrTiO.sub.3 or a nitride such as TiN can be also used in addition to the aforementioned materials. From viewpoints of improvement of crystallinity of the magnetic crystal grain of the magnetic recording layer 30 and of improvement of productivity, the seed layer 20 preferably has a thickness of 1 to 60 nm or preferably of 1 to 20 nm. The seed layer 20 can be formed by use of any process such as the sputtering method or the vacuum deposition method well-known in the technology concerned.
(25) The protective layer can be formed by use of a material conventionally used in a field of the magnetic recording medium. Specifically, the protective layer can be formed by use of a non-magnetic metal such as Pt, a carbon-based material such as diamond-like carbon or a silicon-based material such as silicon nitride. Moreover, the protective layer may be a single layer or have a lamination structure. The protective layer with the lamination structure may have a lamination structure of two kinds of carbon-based materials with different characteristics, a lamination structure of metal and the carbon-based material or a lamination structure of a metal oxide film and the carbon-based material, for example. The protective layer can be formed by use of any process known in the art such as the sputtering method, a CVD method, and the vacuum deposition method.
(26) The liquid lubricant layer can be formed by use of a material conventionally used in the field of the magnetic recording medium. A perfluoropolyether-based lubricant, for example, can be used. The liquid lubricant layer can be formed by use of a coating method such as a dip-coating method or a spin-coating method.
EXAMPLE
Example 1
(27) A (001) MgO single-crystal substrate (manufactured by Tateho Chemical Industries Co., Ltd.) having a smooth surface was washed, and the non-magnetic substrate 10 was prepared. The non-magnetic substrate 10 after the washing was introduced into a sputter device. After the non-magnetic substrate 10 was heated to 350? C., the Pt seed layer 20 having a thickness of 20 nm was formed by an RF magnetron sputtering method using a Pt target in an Ar gas at a pressure of 0.4 Pa.
(28) Subsequently, after the non-magnetic substrate 10 on which the seed layer 20 was formed was heated to 350? C., the FePtV magnetic recording layer 30 having a thickness of 10 nm was formed by the simultaneous RF magnetron sputtering method using an FePt target and a V target of a single element in an Ar gas at a pressure of 0.6 Pa, and the magnetic recording medium having the structure illustrated in
Comparative Examples 1 and 2
(29) Similarly to the aforementioned Example 1 except that targets with the Fe/Pt ratios of 50/50 (Comparative Example 1) and of 54/46 (Comparative Example 2) were used as the FePt targets, the magnetic recording medium was prepared. The compositions of the manufactured magnetic recording mediums are shown in Tables 2 and 3.
(30) (Evaluation)
(31) It was confirmed by XRD that the magnetic recording layer 30 of the resultant magnetic recording medium had the L1.sub.0-ordered structure. Moreover, lengths of the a-axis and the c-axis of the crystal lattice with the L1.sub.0-ordered structure were measured by XRD. Moreover, the order parameter S was obtained from XRD.
(32) Furthermore, saturation magnetization (Ms) of the obtained magnetic recording medium was obtained by use of a vibrating sample magnetometer (VSM). Moreover, a hysteresis curve was measured by VSM, and the coercive force (Hc) was measured. Moreover, the composition of the magnetic recording layer 30 of the resultant magnetic recording medium was measured by the Rutherford backscattering method (RBS). A torque working in each direction of the sample was measured by a torque magnetometer with the sample placed in a magnetic field being rotated, and a magnetic anisotropy constant (Ku) was obtained.
(33) A result of measurement of lengths of the a-axis and the c-axis of the crystal lattice with the L1.sub.0-ordered structure and the value of the order parameter S are shown in Tables 1 to 3. Table 1 is the result of the Fe/Pt ratio of 45/55 (Example 1), Table 2 is the result of the Fe/Pt ratio of 50/50 (Comparative Example 1), and Table 3 is the result of the Fe/Pt ratio of 54/46
Comparative Example 2
(34) TABLE-US-00001 TABLE 1 Composition of magnetic recording layer and evaluation of crystal structure V Fe Pt added c-axis a-axis Sample content content amount length length Order number (at. %) (at. %) (at. %) (?) (?) parameter S 1 44.8 55.2 0.0 3.703 3.907 0.55 2 44.1 54.1 1.8 3.706 3.902 0.54 3 43.7 52.6 3.7 3.710 3.898 0.55 4 42.8 51.1 6.1 3.699 3.903 0.47 5 41.8 49.4 8.8 3.704 3.896 0.58 6 40.7 47.7 11.6 3.702 3.893 0.55 7 39.6 46.1 14.4 3.707 3.884 0.60 8 38.3 44.7 17.0 3.728 3.860 0.64
(35) TABLE-US-00002 TABLE 2 Composition of magnetic recording layer and evaluation of crystal structure Fe Pt V added c-axis a-axis Sample content content amount length length Order number (at. %) (at. %) (at. %) (?) (?) parameter S 1 49.5 50.5 0.0 3.677 3.908 0.62 2 48.8 48.9 2.3 3.680 3.906 0.58 3 48.1 47.8 4.1 3.679 3.905 0.55 4 46.8 46.7 6.4 3.682 3.900 0.54 5 45.4 45.8 8.8 3.685 3.894 0.56 6 44.2 44.1 11.7 3.694 3.889 0.62 7 42.9 42.5 14.6 3.692 3.879 0.63 8 41.6 41.3 17.0 3.695 3.869 0.60 9 40.7 40.0 19.3 3.698 3.857 0.54
(36) TABLE-US-00003 TABLE 3 Composition of magnetic recording layer and evaluation of crystal structure Fe Pt V added c-axis a-axis Sample content content amount length length Order number (at. %) (at. %) (at. %) (?) (?) parameter S 1 54.2 45.8 0.0 3.661 3.903 0.60 2 51.1 46.7 2.2 3.669 3.902 0.61 3 50.8 44.9 4.3 3.669 3.898 0.55 4 49.4 44.2 6.4 3.674 3.891 0.53 5 48.4 42.9 8.7 3.679 3.884 0.60 6 47.1 41.2 11.7 3.682 3.880 0.63 7 45.7 39.7 14.6 3.720 3.836 0.64 8 44.5 38.4 17.1 3.689 3.860 0.55 9 42.9 37.6 19.5 3.733 3.839 0.46
(37) A relationship between the V content of the magnetic recording layer 30 and the lengths of the a-axis and the c-axis of the crystal lattice is shown in
(38) Subsequently, for each of samples 1 to 6 of the aforementioned Example 1 and Comparative Examples 1 and 2, measurement results of the saturation magnetization (Ms), the coercive force (Hc), and the magnetic anisotropy constant (Ku) are shown in Table 4 (Example 1), Table 5 (Comparative Example 1), and Table 6 (Comparative Example 2).
(39) TABLE-US-00004 TABLE 4 Composition of magnetic recording layer and evaluation of magnetic characteristics Saturation Magnetic magneti- anisotropy Fe Pt V added zation coercive constant Sample content content amount (Ms) force (Ku) number (at. %) (at. %) (at. %) (emu/cm.sup.3) (kOe) (Merg/cm.sup.3) 1 44.8 55.2 0.0 900 3.6 21.2 2 44.1 54.1 1.8 863 3.1 20.3 3 43.7 52.6 3.7 830 4.4 19.2 4 42.8 51.1 6.1 773 5.9 17.2 5 41.8 49.4 8.8 747 5.5 14.4 6 40.7 47.7 11.6 681 5.5 8.9
(40) TABLE-US-00005 TABLE 5 Composition of magnetic recording layer and evaluation of magnetic characteristics Saturation Magnetic magneti- coercive anisotropy Fe Pt V added zation force constant Sample content content amount (Ms) (Hc) (Ku) number (at. %) (at. %) (at. %) (emu/cm.sup.3) (kOe) (Merg/cm.sup.3) 1 49.5 50.5 0.0 982 3.2 30.0 2 48.8 48.9 2.3 917 2.8 26.7 3 48.1 47.8 4.1 889 3.6 22.7 4 46.8 46.7 6.4 838 3.1 17.0 5 45.4 45.8 8.8 769 2.2 12.8 6 44.2 44.1 11.7 683 2.0 7.9
(41) TABLE-US-00006 TABLE 6 Composition of magnetic recording layer and evaluation of magnetic characteristics Saturation Magnetic magneti- coercive anisotropy Fe Pt V added zation force constant Sample content content amount (Ms) (Hc) (Ku) number (at. %) (at. %) (at. %) (emu/cm.sup.3) (kOe) (Merg/cm.sup.3) 1 54.2 45.8 0.0 1068 2.4 31.2 2 51.1 46.7 2.2 984 2.2 27.6 3 50.8 44.9 4.3 920 1.7 20.1 4 49.4 44.2 6.4 856 1.6 13.7 5 48.4 42.9 8.7 776 1.2 11.0 6 47.1 41.2 11.7 706 1.2 6.4
(42) A relationship between the V content of the magnetic recording layer 30 and the saturation magnetization (Ms) is shown in
(43) From the aforementioned results, it was found that V was a material for increasing Hc with respect to the FePt ordered alloy.
(44) Moreover, in the present invention, as the V content increases, Hc increases even though both Ms and Ku decrease monotonously.
(45) The reason why Hc increases regardless of the decrease of Ms and Ku as in the present invention is not known at the present time, but presumption as below can be made.
(46) It is said that Hc has a relationship in the following equation with Ku and Ms.
Hc=A(2Ku/Ms)
wherein A is a coefficient representing a magnetic separation performance between the magnetic grains.
(47) In verification with the composition of Fe45Pt55, Ku/Ms is substantially constant in Example 1 as indicated in Table 7 below.
(48) TABLE-US-00007 TABLE 7 Ku/Ms value ample number Ms Ku Ku/Ms 1 900 21.2 0.023556 2 863 20.3 0.023523 3 830 19.2 0.023133 4 773 17.2 0.022251 5 747 14.4 0.019277 6 681 8.92 0.013098
(49) Therefore, the increase of Hc is considered to be caused by the increase of A. Moreover, considering together with the result of structural analysis indicated in
(50) From the result of the structural analysis, since a change in the axial lengths of the c-axis and the a-axis was small, and the order parameter S was substantially constant, it can be presumed that V is not contained in the crystal of FePt. That is, it can be considered that, a V grain boundary was formed outside the magnetic crystal grains of FePt by addition of V to the FePt ordered alloy, the separation performances between the magnetic crystal grains was improved, and as a result, Hc increased.
(51) Moreover, in the composition of FePt, the reason why Hc increases in the case of Fe<Pt is not known, but it can be considered that easier segregation of V to the grain boundary results in improvement of separability of the magnetic crystal grains.
(52) As described above, it is known that addition of V to the L1.sub.0-ordered alloy is effective for development of excellent magnetic properties.
(53) While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. The scope of the following claims is to be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures and functions.