Magnetic film-bearing member, thermoelectric conversion element, magnetic device, and method for producing magnetic film-bearing member

Abstract

A magnetic film-bearing member 1a comprises a magnetic film 10 and a first region 20. The first region 20 is in contact with the magnetic film-bearing member 1a. The oxygen content in the magnetic film 10 is not more than 1% based on the number of atoms. The difference yielded by subtracting, from the standard Gibbs energy of oxide formation ΔG1 of a first element, the standard Gibbs energy of oxide formation ΔG2 of a second element, is equal to or less than 0 kJ / mol. The first element is an element present as a simple substance in the first region 20. Alternatively, the first element is the element that has the lowest standard Gibbs energy of oxide formation of the elements present in the first region 20 and capable of bonding with oxygen. The second element is the element having the lowest standard Gibbs energy of oxide formation of the elements contained in the magnetic film 10.

Description

Magnetic film-attached member, thermoelectric conversion element, magnetic device, and method for manufacturing magnetic film-attached member

[0001] The present invention relates to a magnetic film-coated member, a thermoelectric conversion element, a magnetic device, and a method for manufacturing a magnetic film-coated member.

[0002] 2. Description of the Related Art Various studies have been conducted on elements and devices using magnetic materials.

[0003] For example, Patent Document 1 describes a thermoelectric power generation device having a power generator made of a ferromagnetic material magnetized in a predetermined direction. The power generator is configured to generate electricity using a temperature difference perpendicular to the direction of magnetization due to the anomalous Nernst effect. The power generator is provided as a thin film on a substrate having at least a surface layer made of MgO. The power generator is made of an L10-type ordered alloy with high magnetic anisotropy.

[0004] Non-Patent Document 1 describes that a DO type FeGa or FeAl ferromagnetic material exhibits a large anomalous Nernst effect, and that this large anomalous Nernst effect is derived from a topological band structure called a nodal web. This document also describes that a large anomalous Nernst effect is exhibited when a thin film of this ferromagnetic material is formed on an MgO substrate.

[0005] Japanese Patent Application Laid-Open No. 2012-72256

[0006] Nature, (UK), 2020, 581,53-57

[0007] With the development of the Internet of Things (IoT) society, there is an increasing demand for sensing of magnetism, heat, etc. In addition, with the increase in information processing speed, there is also a need for faster information processing devices such as random access memory.

[0008] Elements or devices with magnetic films are promising technologies that can meet these needs. According to Patent Document 1 and Non-Patent Document 1, a substrate or an MgO substrate with at least a surface layer made of MgO is used to form a predetermined magnetic film. It is also expected that there will be restrictions on the process conditions for obtaining the predetermined magnetic film. For example, Non-Patent Document 1 states that a back pressure of 1×10 -8A thin film of a ferromagnetic material is formed under ultra-high vacuum conditions of 100 Pa.

[0009] In view of the above circumstances, the present invention provides a magnetic film-coated member that is advantageous from the viewpoint of reducing the restrictions on obtaining a predetermined magnetic film.

[0010] The present invention provides a magnetic film-attached member comprising: a magnetic film; and a first portion in contact with the magnetic film; the oxygen content in the magnetic film is 1% or less on an atomic number basis; the difference obtained by subtracting the standard Gibbs energy of formation of an oxide of a second element from the standard Gibbs energy of formation of an oxide of a first element is 0 kJ / mol or less; the first element is an element that exists as a simple substance, or an element that exists in the first portion and is capable of bonding with oxygen, and has the lowest standard Gibbs energy of formation of an oxide; and the second element is an element that is contained in the magnetic film and has the lowest standard Gibbs energy of formation of an oxide.

[0011] The present invention also provides a thermoelectric conversion element comprising the above-described magnetic film-attached member, wherein the magnetic film contains a magnetic material that exhibits the anomalous Nernst effect.

[0012] The present invention also provides a magnetic device comprising the above-described magnetic film-attached member, wherein the magnetic film contains a magnetic material that exhibits the anomalous Hall effect.

[0013] The present invention also provides a method for manufacturing a magnetic film-coated member, which includes heating a film that is a precursor of the magnetic film while it is in contact with a first portion to obtain a magnetic film, wherein the oxygen content in the magnetic film is 1% or less based on the number of atoms, the difference obtained by subtracting the standard Gibbs energy of formation of an oxide of the second element from the standard Gibbs energy of formation of an oxide of the first element is 0 kJ / mol or less, the first element is an element that exists as a simple substance in the first portion, or an element that exists in the first portion and is capable of bonding with oxygen, and has the lowest standard Gibbs energy of formation of an oxide, and the second element is an element that exists in the magnetic film as a simple substance, and has the lowest standard Gibbs energy of formation of an oxide.

[0014] The above-mentioned magnetic film-attached member is advantageous in that it reduces the restrictions imposed on obtaining a predetermined magnetic film.

[0015] FIG. 1 is a cross-sectional view showing an example of a magnetic film-attached member. FIG. 2 is a cross-sectional view showing another example of a magnetic film-attached member. FIG. 3 is a cross-sectional view showing yet another example of a magnetic film-attached member. FIG. 4 is a plan view showing an example of a thermoelectric conversion element. FIG. 5 is a cross-sectional view of a thermoelectric conversion material taken along line V-V shown in FIG. 4. FIG. 6 is a schematic view showing an example of a magnetic device. FIG. 7 is a diagram showing an XRD pattern of a stack including a magnetic film and an underlayer film according to Example 1. FIG. 8 is a diagram showing an XRD pattern of a stack including a magnetic film and an underlayer film according to Example 2.

[0016] Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the following description is for illustrative purposes only and the present invention is not limited to the following embodiments. In the accompanying drawings, the X-axis, Y-axis, and Z-axis are perpendicular to one another.

[0017] As shown in FIG. 1 , the magnetic film-attached member 1a includes a magnetic film 10 and a first portion 20. The first portion 20 is a portion in contact with the magnetic film 10. The oxygen content in the magnetic film 10 is 1% or less on an atomic basis. Such a low oxygen content in the magnetic film 10 facilitates the magnetic film 10 to exhibit desired properties. In the magnetic film-attached member 1a, the difference ΔG1-ΔG2 obtained by subtracting ΔG2, the standard Gibbs energy of formation of an oxide of the second element, from ΔG1, is 0 kJ / mol or less. The first element is an element present as a simple substance in the first portion 20. Alternatively, the first element is an element present in the first portion 20 that is capable of bonding with oxygen and has the lowest standard Gibbs energy of formation of an oxide. The state in which the first element is capable of bonding with oxygen is, for example, a state in which the element is not bonded to oxygen but is capable of bonding with oxygen. The second element is an element present in the magnetic film 10 that has the lowest standard Gibbs energy of formation of an oxide. The oxide referred to in determining the standard Gibbs energies of formation ΔG 1 and ΔG 2 is the oxide having the smallest standard Gibbs energy of formation of the oxide per mole of oxygen atom.

[0018] As described above, the low oxygen content in the magnetic film 10 makes it easier for the magnetic film 10 to exhibit the desired properties. In the magnetic film-attached member 1a, the condition that the difference ΔG1 - ΔG2 is 0 kJ / mol or less is satisfied, so oxygen contained in the precursor of the magnetic film 10 is easily moved to the first portion 20 by heating or the like. Therefore, for example, the magnetic film 10 is likely to have the desired properties even without using an MgO substrate, and when forming the magnetic film 10, the back pressure is 1 x 10 -8 The magnetic film 10 is likely to have the desired characteristics even if the vacuum conditions are not adjusted to about Pa. In other words, the magnetic film-coated member 1a tends to reduce the constraints on obtaining the magnetic film 10.

[0019] The oxygen content in the magnetic film 10 is preferably 0.8% or less, more preferably 0.5% or less, and even more preferably 0.1% or less, on an atomic number basis.

[0020] The difference ΔG1−ΔG2 is preferably −200 kJ / mol or less, more preferably −500 kJ / mol or less, and even more preferably −600 kJ / mol or less.

[0021] The standard Gibbs energies of formation ΔG1 and ΔG2 are not limited to specific values ​​as long as the difference ΔG1 - ΔG2 is 0 kJ / mol or less. The standard Gibbs energy of formation ΔG1 is, for example, -500 to -2000 kJ / mol, or may be -1000 to -2000 kJ / mol. The standard Gibbs energy of formation ΔG2 is, for example, 0 to -2000 kJ / mol.

[0022] 1, the first portion 20 is, for example, in the form of a film. The first portion 20 is formed in contact with one of the main surfaces of the magnetic film 10, for example.

[0023] 1, the magnetic film-coated member 1a further includes, for example, a substrate 30. The first portion 20 is disposed, for example, between the substrate 30 and the magnetic film 10 in the thickness direction of the magnetic film 10. With this configuration, the temperature of the first portion 20 is likely to increase in a short period of time when the precursor of the magnetic film 10 is heated, and oxygen present in the precursor of the magnetic film 10 is likely to migrate to the first portion 20. This makes it easier for the magnetic film 10 to have the desired properties.

[0024] The thickness of the magnetic film 10 is not limited to a specific value. The thickness is, for example, 1 nm to 1000 nm. The thickness may be 5 nm or more, 10 nm or more, 20 nm or more, or 50 nm or more, or may be 500 nm or less, 100 nm or less, or 50 nm or less.

[0025] When the first portion 20 is in the form of a film, the thickness of the first portion 20 is not limited to a specific value. For example, the thickness of the first portion 20 is smaller than the thickness of the magnetic film 10. In this case, the time required to form the first portion 20 can be shortened, and the magnetic film-coated member 1a can be easily mass-produced.

[0026] The thickness of the first portion 20 is, for example, 1 nm to 50 nm, and may be 2 nm to 10 nm or 2 nm to 5 nm.

[0027] The substrate 30 is not limited to a specific substrate. The material of the substrate 30 may be an inorganic material or an organic material. The substrate 30 may be a silicon substrate having a thermally oxidized film, a silicon substrate having a surface formed with metal silicon, or a glass substrate. When the material of the substrate 30 is an organic material, examples of the organic material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), acrylic resin (PMMA), polycarbonate (PC), polyimide (PI), or cycloolefin polymer (COP).

[0028] The first portion 20 contains, for example, an alloy containing the first element. In this case, the characteristics of the first portion 20 are easy to adjust. Therefore, the first portion 20 is likely to have advantageous characteristics from the viewpoint of transferring oxygen contained in the precursor of the magnetic film 10 to the first portion 20 by heating or the like. As described above, the first portion 20 may contain a simple substance containing the first element.

[0029] When the first portion 20 includes an alloy, the alloy may be an ordered alloy or a disordered alloy. The first portion 20 preferably includes a first ordered alloy. Examples of the first ordered alloy include D03 type, L10 type, or D0 19 It is a type ordered alloy.

[0030] The magnetic material contained in the magnetic film 10 is not limited to a specific magnetic material. For example, the magnetic material contained in the magnetic film 10 may be a magnetic material that exhibits the anomalous Nernst effect or the anomalous Hall effect. The magnetic material has, for example, a topological band structure.

[0031] The magnetic film 10 contains, for example, a second ordered alloy as a magnetic material. In this case, the magnetic film 10 is likely to exhibit effects such as the anomalous Nernst effect and the anomalous Hall effect. Examples of the second ordered alloy include D03 type, L10 type, or D0 19 Examples of the second ordered alloy are D0 type Fe3Ga, D0 type Fe3Al, L10 type FePt, L10 type FeNi, L10 type FePt, D0 19 The types are Mn3Sn and Mn3Ge.

[0032] When the magnetic film 10 contains a magnetic material that exhibits the anomalous Nernst effect, the magnetic material has a magnetic field of 5×10 -3The magnetic film 10 may be a magnetic material having a saturation magnetic susceptibility of T or more, or a magnetic material having a band structure with a Weyl point near the Fermi energy. The magnetic material may be a ferrimagnetic material. The magnetic film 10 may contain, as a magnetic material exhibiting the anomalous Nernst effect, at least one material selected from the group consisting of (i), (ii), (iii), (iv), and (v) below: (i) a stoichiometric material having a composition represented by Fe3X; (ii) an off-stoichiometric material in which the composition ratio of Fe to X deviates from that of the material in (i) above; (iii) a material in which part of the Fe sites of the material in (i) above or part of the Fe sites of the material in (ii) above are substituted with a main group metal element or transition element other than X; or (iv) Fe3M1 1-x M2 x (v) A substance having a composition expressed by (0<x<1), in which M1 and M2 are different typical group elements. (i) A substance in which a part of the Fe site of the substance (i) is substituted with a transition element other than X, and a part of the X site of the substance (i) is substituted with a typical metal element other than X.

[0033] In the above substances (i) to (v), X is a typical element or a transition element. X is, for example, Al, Ga, Ge, Sn, Si, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Sc, Ni, Mn, or Co. In the above substance (iv), the combination of M1 and M2 is not limited to a specific combination as long as M1 and M2 are different typical elements. In the above substance (iv), the combination of M1 and M2 is, for example, Ga and Al, Si and Al, or Ga and B.

[0034] The magnetic film 10 may contain Co2MnGa or Mn3Sn as a magnetic material that exhibits the anomalous Nernst effect.

[0035] When the magnetic material contained in the magnetic film 10 exhibits the anomalous Hall effect, the magnetic material may contain Mn3Sn or Mn3Ge.

[0036] When the first portion 20 contains a first ordered alloy and the magnetic film 10 contains a second ordered alloy, the relationship between the first ordered alloy and the second ordered alloy is not limited to a specific relationship. For example, the ordering of the first ordered alloy contained in the first portion 20 is the same as the ordering of the second ordered alloy contained in the magnetic film 10. In this case, the magnetic film 10 is likely to exhibit desired characteristics.

[0037] For example, both the first ordered alloy and the second ordered alloy may be D03 type ordered alloys or L10 type ordered alloys.

[0038] The magnetic film 10 has, for example, a polycrystalline structure. In this case, the formation of grain boundaries tends to increase the coercive force of the magnetic material.

[0039] An example of a method for manufacturing the magnetic film-attached member 1a will be described. The magnetic film-attached member 1a can be manufactured by a method including, for example, heating a film that is a precursor of the magnetic film 10 while it is in contact with the first portion 20 to obtain the magnetic film 10. In this case, as the film that is the precursor of the magnetic film 10 is heated, oxygen contained in the precursor moves toward the first member 20. This reduces the oxygen content in the magnetic film 10, making it easier for the magnetic film 10 to exhibit the desired properties. If it is intended to form a magnetic film 10 with the desired properties without bringing the film that is the precursor of the magnetic film 10 into contact with the first portion 20, it is possible to use a substrate containing MgO and to set the vacuum conditions during film formation to a back pressure of 1×10 -8 In some cases, it may be necessary to adjust the pressure to about Pa. On the other hand, the above method makes these unnecessary.

[0040] For example, the back pressure during the deposition of the magnetic film 10 is, for example, 1×10 -7 Pa or less, and -6 The back pressure during the deposition of the magnetic film 10 may be, for example, 5×10 -4 Pa or more.

[0041] For example, a film that is a precursor of the magnetic film 10 is formed on the first portion 20. This film can be formed by methods such as sputtering, chemical vapor deposition (CVD), pulsed laser deposition (PLD), ion plating, and plating. Among these, by producing the film that is the precursor of the magnetic film 10 by sputtering, the uniformity of the film composition and thickness is increased, and the productivity of the magnetic film-coated member 1a is likely to be increased.

[0042] The temperature to which the film that is the precursor of the magnetic film 10 is heated is not limited to a specific value. The temperature may be, for example, 200°C to 700°C, 250°C to 700°C, 250°C to 650°C, 250°C to 600°C, or 250°C to 550°C.

[0043] For example, the film-like first portion 20 may be formed on the substrate 30 before the formation of a film that is a precursor of the magnetic film 10. In this case, the film-like first portion 20 may be formed by a method such as sputtering, CVD, PLD, ion plating, or plating.

[0044] The magnetic film-attached member 1a can be modified from various viewpoints. For example, the magnetic film-attached member 1a may further include a protective film. The protective film is arranged so that the magnetic film 10 is located between the protective film and the first portion 20 in the thickness direction of the magnetic film 10. This protects the magnetic film 10, and the magnetic film-attached member 1a is likely to have high durability. The material forming the protective film may be an inorganic material or an organic material.

[0045] The magnetic film-attached member 1a may be modified, for example, to a magnetic film-attached member 1b shown in Fig. 2 or a magnetic film-attached member 1c shown in Fig. 3. The magnetic film-attached members 1b and 1c are configured in the same manner as the magnetic film-attached member 1a, except for the parts that will be particularly described.

[0046] 2, in the magnetic film-attached member 1b, the magnetic film 10 is disposed, for example, between the substrate 30 and the first portion 20 in the thickness direction of the magnetic film 10. This configuration also tends to reduce the oxygen content in the magnetic film 10, making it easier for the magnetic film 10 to exhibit the desired characteristics. In addition, the first portion 20 can protect the magnetic film 10.

[0047] 3, the magnetic film-attached member 1c does not have a substrate 30, and the first portion 20 can function as a substrate for the magnetic film 10. With this configuration, the oxygen content in the magnetic film 10 tends to be low, and the magnetic film 10 tends to exhibit the desired characteristics. In addition, the magnetic film-attached member 1c tends to have a simple structure.

[0048] In the magnetic film-attached member 1a, when the magnetic film 10 contains a magnetic material exhibiting the anomalous Nernst effect, for example, a thermoelectric conversion element can be provided. As shown in Figures 4 and 5, the thermoelectric conversion element 3 includes the magnetic film-attached member 1a, and the magnetic film 10 contains a magnetic material exhibiting the anomalous Nernst effect. With this configuration, for example, a thermoelectromotive force due to the anomalous Nernst effect is generated in a direction perpendicular to the heat flow direction and the magnetization direction of the magnetic film 10, and heat sensing can be realized by processing a signal associated with this electromotive force.

[0049] In the thermoelectric conversion element 3, the magnetic film 10 is, for example, in the form of a thin wire. With this configuration, for example, by providing magnetization in the width direction of the thin wire of the magnetic film 10, when a temperature gradient occurs in the thickness direction (Z-axis direction) of the magnetic film 10, a thermoelectromotive force due to the anomalous Nernst effect can be generated in the length direction of the thin wire. In this case, a thermoelectromotive force according to the length of the thin wire can be generated, and the thermoelectric conversion element 3 is likely to exhibit the desired thermoelectric conversion performance.

[0050] The width of the thin wires constituting the magnetic film 10 is not limited to a specific value. The width of the thin wires is, for example, 500 μm or less. This reduces the amount of material used for the thin wires, making it easier to reduce the manufacturing costs of the thermoelectric conversion element 3. In addition, it is easy to arrange a large number of thin wires in the thermoelectric conversion element 3, making it easier for the thermoelectric conversion element 3 to exhibit the desired thermoelectric conversion performance. The width of the thin wires is, for example, 1 μm or more. This makes it less likely for the thin wires to break, making it easier for the thermoelectric conversion element 3 to have high durability.

[0051] The width of the thin line formed by the magnetic film 10 may be included in any of the ranges determined by all combinations of a lower limit value of any one of 1 μm, 2 μm, 5 μm, 10 μm, 20 μm, and 30 μm and an upper limit value of any one of 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, and 50 μm.

[0052] 4 and 5, in the thermoelectric conversion element 3, the magnetic film 10 is formed of a plurality of thin wires, and these thin wires form the thermoelectric conversion section 11. The thermoelectric conversion element 3 has, for example, a meander pattern including the thermoelectric conversion section 11. With this configuration, the total length of the thin wires formed by the magnetic film 10 in the thermoelectric conversion element 3 tends to be large. The electromotive force generated in the length direction (Y-axis direction) of the thin wires due to the temperature gradient in the thickness direction (Z-axis direction) of the magnetic film 10 tends to be large as the total length of the thin wires formed by the magnetic film 10 increases. Therefore, when the thermoelectric conversion element 3 has a meander pattern including the thermoelectric conversion section 11, the electromotive force generated in the thermoelectric conversion element 3 tends to be large.

[0053] As shown in FIGS. 4 and 5, in the thermoelectric conversion element 3, the first member 20 forms the above-mentioned thin wire together with the magnetic film 10, for example.

[0054] 4 and 5, the thermoelectric conversion element 3 further includes, for example, wiring 12. The wiring 12 electrically connects the magnetic films 10 each forming a thin wire. For example, the wiring 12 electrically connects the magnetic films 10 each forming a plurality of thin wires in series. The wiring 12 includes, for example, a plurality of wirings 14. The plurality of thin wires formed by the magnetic films 10 and the plurality of wirings 14 are electrically connected in series. With this configuration, a large electromotive force is likely to be generated in the thermoelectric conversion element 3 even if the area of ​​the surface on which the thermoelectric conversion section 11 and the wirings 14 are arranged is small.

[0055] The wiring 12 may be made of a single metal or an alloy.

[0056] The thickness of the wiring 12 is not limited to a specific value and may be within any range defined by all combinations of a lower limit of any one of 5 nm, 10 nm, 20 nm, 30 nm, and 50 nm and an upper limit of any one of 1000 nm, 750 nm, 500 nm, 400 nm, 300 nm, and 200 nm.

[0057] The width of the wiring 12 is not limited to a specific value and may be included in any of the ranges determined by all combinations of a lower limit of any one of 0.1 μm, 0.5 μm, 1 μm, 2 μm, 5 μm, 10 μm, 20 μm, and 30 μm and an upper limit of any one of 500 μm, 400 μm, 300 μm, 200 μm, 100 μm, and 50 μm.

[0058] 6, for example, a magnetic device 5a including a magnetic film-attached member 1a can be provided. In the magnetic device 5a, a magnetic film 10 includes a magnetic material that exhibits the anomalous Hall effect. With this configuration, for example, a memory or a sensor utilizing the anomalous Hall effect can be provided.

[0059] 6, the magnetic device 5a includes a signal processing device 51. The signal processing device 51 processes a signal generated due to the anomalous Hall effect in the magnetic film 10. Alternatively, the signal processing device 51 generates a predetermined signal to cause the anomalous Hall effect in the magnetic film 10, thereby changing the physical state of the magnetic film 10. This allows the magnetic device 5a to function as a memory or a sensor.

[0060] Each of the thermoelectric conversion element 3 and the magnetic device 5a may include a magnetic film-attached member 1b or 1c instead of the magnetic film-attached member 1a.

[0061] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to the following examples. First, the evaluation methods used in the examples will be described.

[0062] Example 1: An Al2O3 film having a thickness of 5 nm was formed on the thermal oxide film of a silicon substrate having a surface made of a thermal oxide film by RF magnetron sputtering using an Al2O3 target material. Next, a base film having a thickness of 5 nm was formed by DC magnetron sputtering using a target material containing Fe and Al. The back pressure in the DC magnetron sputtering for forming this base film was 5 × 10 -5 The pressure was adjusted to 0.1 Pa. In addition, argon gas was supplied as a process gas for DC magnetron sputtering at a pressure of 0.1 Pa. In the target material, the relationship of Fe content:Al content = 3:1 was satisfied on a substance mass basis.

[0063] Next, an alloy film having a thickness of 50 nm was formed by DC magnetron sputtering using a target material containing Fe and Ga. The back pressure in the DC magnetron sputtering for forming this alloy film was 5×10 -5 The pressure was adjusted to 0.1 Pa. In addition, argon gas was supplied as a process gas for DC magnetron sputtering at a pressure of 0.1 Pa. In the target material, the relationship of Fe content:Ga content = 3:1 was satisfied on a mass of substance basis.

[0064] Next, an AlO film having a thickness of 5 nm was formed by RF magnetron sputtering using an AlO target material, and then an upper film having a thickness of 5 nm was formed by DC magnetron sputtering using a target material containing Fe and Al.

[0065] Next, the temperature around the alloy film was adjusted to 500°C, and the alloy film was annealed. The annealing time at 500°C was 1 hour. In this way, a magnetic film-attached member according to Example 1 was obtained. The standard Gibbs energies of formation of Al2O3 and Ga2O3 are shown in Table 1.

[0066] Example 2 A magnetic film-coated member according to Example 2 was obtained in the same manner as Example 1, except that the temperature around the alloy film during the annealing treatment was adjusted to 300°C.

[0067] Comparative Example 1 A magnetic film-coated member according to Comparative Example 1 was obtained in the same manner as in Example 1, except that the formation of the undercoat film was omitted and an alloy film was formed on the Al2O3 film.

[0068] [Structure of Magnetic Film and Underlayer] Samples for X-ray diffraction (XRD) measurement were prepared from stacks including the magnetic film and underlayer of the magnetic film-coated members of each Example and Comparative Example. XRD measurements were performed on these samples using a Rigaku SmartLab XRD device. The crystalline structures of the magnetic film and underlayer were identified from the XRD patterns obtained by the XRD measurements. The results are shown in Table 1. Figure 7 shows the XRD pattern of the stack including the magnetic film and underlayer of Example 1. Figure 8 shows the XRD pattern of the stack including the magnetic film and underlayer of Example 2. As shown in Table 1, the underlayers and magnetic films of Examples 1 and 2 were composed of D03-type ordered alloys.

[0069] [Oxygen Concentration in Magnetic Film] Samples for X-ray photoelectron spectroscopy (XPS) analysis were prepared from the magnetic film of the magnetic film-attached member according to each example. XPS analysis was performed on these samples using an XPS analyzer, Quantera SXM, manufactured by ULVAC-PHI, Inc. Based on the results of the XPS analysis, the oxygen content in the magnetic film on an atomic basis was determined. The results are shown in Table 1. As shown in Table 1, the oxygen content in the magnetic film on an atomic basis was 1% or less.

[0070] [Evaluation of the anomalous Nernst effect] Using a physical property measurement system PPMS Dynacool manufactured by Quantum Design, the Nernst coefficient S ne and the Seebeck coefficient S se , resistivity ρ xx , Hall resistivity ρ yx Using these values, S ne = ρ xx α yx +S se ・ρ yx / ρ xx According to the relation of the transverse thermoelectric coefficient α yx The results are shown in Table 1. The Hall conductivity in Table 1 is calculated by multiplying the Hall resistivity ρ yxis the reciprocal of

[0071] [Grain Size] Samples for X-ray diffraction (XRD) measurement were prepared from the magnetic film and underlayer of the magnetic film-coated member according to each example and comparative example. XRD measurement was performed on these samples using an XRD device, SmartLab, manufactured by Rigaku Corporation. The grain size was estimated using the Scherrer equation from the peaks obtained by the XRD measurement. The results are shown in Table 1.

[0072] As shown in Table 1, the transverse thermoelectric coefficients α of the magnetic films according to Examples 1 and 2 yx The absolute value of the transverse thermoelectric coefficient α yx The Hall angle θ of the magnetic films according to Examples 1 and 2 was larger than the Hall angle θ of the magnetic film according to Comparative Example 1. The presence of the underlayer containing the predetermined element in the magnetic film-coated members according to Examples 1 and 2 reduced the back pressure of 1×10 in the formation of the magnetic film. -8 It was suggested that a magnetic film capable of exhibiting the anomalous Nernst effect, the anomalous Hall effect, or the spin Hall effect can be formed without increasing the pressure to about Pa.

[0073]

[0074] A first aspect of the present invention provides a magnetic film-attached member comprising: a magnetic film; and a first portion in contact with the magnetic film; the oxygen content in the magnetic film is 1% or less based on the number of atoms; the difference obtained by subtracting the standard Gibbs energy of formation of an oxide of a second element from the standard Gibbs energy of formation of an oxide of a first element is 0 kJ / mol or less; the first element is an element that exists as a simple substance, or an element that exists in the first portion and is capable of bonding with oxygen, and has the lowest standard Gibbs energy of formation of an oxide; and the second element is an element that is contained in the magnetic film and has the lowest standard Gibbs energy of formation of an oxide.

[0075] A second aspect of the present invention provides the magnetic film-attached member according to the first aspect, further comprising a substrate, wherein the first portion is disposed between the substrate and the magnetic film in the thickness direction of the magnetic film.

[0076] A third aspect of the present invention provides the magnetic film-attached member according to the first or second aspect, wherein the first portion includes an alloy containing the first element.

[0077] A fourth aspect of the present invention provides a magnetic film-attached member according to any one of the first to third aspects, wherein the first portion includes a first ordered alloy, the magnetic film includes a second ordered alloy, and the ordering of the first ordered alloy is the same as the ordering of the second ordered alloy.

[0078] A fifth aspect of the present invention provides the magnetic film-attached member according to any one of the first to fourth aspects, wherein the magnetic film has a polycrystalline structure.

[0079] A sixth aspect of the present invention provides a thermoelectric conversion element comprising a magnetic film-attached member according to any one of the first to fifth aspects, wherein the magnetic film includes a magnetic material that exhibits the anomalous Nernst effect.

[0080] A seventh aspect of the present invention provides a magnetic device comprising the magnetic film-attached member according to any one of the first to fifth aspects, wherein the magnetic film includes a magnetic material that exhibits the anomalous Hall effect.

[0081] An eighth aspect of the present invention provides a method for manufacturing a magnetic film-coated member, comprising heating a film that is a precursor of the magnetic film while in contact with a first portion to obtain the magnetic film, wherein the oxygen content in the magnetic film is 1% or less based on the number of atoms, the difference obtained by subtracting the standard Gibbs energy of formation of an oxide of the second element from the standard Gibbs energy of formation of an oxide of the first element is 0 kJ / mol or less, the first element is an element that exists as a simple substance in the first portion, or an element that exists in the first portion and is capable of bonding with oxygen, and has the lowest standard Gibbs energy of formation of an oxide, and the second element is an element that exists in the magnetic film as a simple substance, and has the lowest standard Gibbs energy of formation of an oxide.

Claims

1. A magnetic film-attached member comprising: a magnetic film; and a first portion in contact with the magnetic film; the oxygen content in the magnetic film is 1% or less on an atomic basis; the difference obtained by subtracting the standard Gibbs energy of formation of an oxide of a second element from the standard Gibbs energy of formation of an oxide of a first element is 0 kJ / mol or less; the first element is an element that exists as a simple substance, or an element that exists in the first portion and is capable of bonding with oxygen, and has the lowest standard Gibbs energy of formation of an oxide; and the second element is an element that is contained in the magnetic film and has the lowest standard Gibbs energy of formation of an oxide.

2. The magnetic film-coated member according to claim 1, further comprising a substrate, wherein the first portion is disposed between the substrate and the magnetic film in the thickness direction of the magnetic film.

3. The member with magnetic film according to claim 1, wherein the first portion includes an alloy containing the first element.

4. The member with magnetic film according to claim 1, wherein the first portion includes a first ordered alloy, the magnetic film includes a second ordered alloy, and the ordering of the first ordered alloy is the same as the ordering of the second ordered alloy.

5. The member with magnetic film according to claim 1, wherein the magnetic film has a polycrystalline structure.

6. A thermoelectric conversion element comprising the magnetic film-attached member according to any one of claims 1 to 5, wherein the magnetic film contains a magnetic material that exhibits the anomalous Nernst effect.

7. A magnetic device comprising the magnetic film-attached member according to any one of claims 1 to 5, wherein the magnetic film includes a magnetic material that exhibits the anomalous Hall effect.

8. A method for producing a member with a magnetic film, comprising heating a film that is a precursor of the magnetic film while it is in contact with a first portion to obtain the magnetic film, wherein the oxygen content in the magnetic film is 1% or less based on the number of atoms, the difference obtained by subtracting the standard Gibbs energy of formation of an oxide of the second element from the standard Gibbs energy of formation of an oxide of the first element is 0 kJ / mol or less, the first element is an element that exists as a simple substance in the first portion, or an element that exists in the first portion and is capable of bonding with oxygen, and has the lowest standard Gibbs energy of formation of an oxide, and the second element is an element that exists in the magnetic film as a simple substance, and has the lowest standard Gibbs energy of formation of an oxide.

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