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WO2021065254A1 - Aimant, membrane, stratifié, moteur, générateur et automobile - Google Patents

Aimant, membrane, stratifié, moteur, générateur et automobile Download PDF

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Publication number
WO2021065254A1
WO2021065254A1 PCT/JP2020/032132 JP2020032132W WO2021065254A1 WO 2021065254 A1 WO2021065254 A1 WO 2021065254A1 JP 2020032132 W JP2020032132 W JP 2020032132W WO 2021065254 A1 WO2021065254 A1 WO 2021065254A1
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Prior art keywords
magnet
phase
film
atomic
layer
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Ceased
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English (en)
Japanese (ja)
Inventor
有紀子 高橋
アミン ホセイン セペリ
大介 小川
広沢　哲
和博 宝野
敏之 嶋
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National Institute for Materials Science
TOHOKU Gakuin
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National Institute for Materials Science
TOHOKU Gakuin
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Priority to JP2021550429A priority Critical patent/JP7224582B2/ja
Publication of WO2021065254A1 publication Critical patent/WO2021065254A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/059—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and Va elements, e.g. Sm2Fe17N2
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K15/00—Processes or apparatus specially adapted for manufacturing, assembling, maintaining or repairing of dynamo-electric machines
    • H02K15/02—Processes or apparatus specially adapted for manufacturing, assembling, maintaining or repairing of dynamo-electric machines of stator or rotor bodies
    • H02K15/03—Processes or apparatus specially adapted for manufacturing, assembling, maintaining or repairing of dynamo-electric machines of stator or rotor bodies having permanent magnets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/64—Electric machine technologies in electromobility

Definitions

  • the present invention relates to magnets, membranes, laminates, motors, generators, and automobiles.
  • R is a rare earth element
  • rare earth magnets using a compound represented by R-Fe (iron) -B (boron) are used in motors of hybrid automobiles and electric automobiles, and have specific characteristics.
  • R-Fe iron
  • B boron
  • magnets (rare earth magnets) to which heavy rare earths (for example, Dy (dysprosium)) are added have been studied so that desired characteristics can be exhibited even in a high temperature environment for automobile motors.
  • rare earth magnets made of compounds having a "ThMn 12 type" crystal structure, which requires a small amount of rare earth elements to be used.
  • the ThMn 12 type crystal phase may be unstable, and in order to stabilize this, a method of substituting a part of the ThMn 12 type crystal phase with an element such as Ti has been proposed. However, according to the above method, the magnetization of the obtained rare earth magnet may be insufficient.
  • Non-Patent Document 1 states that a single crystal of a compound represented by Sm (Fe 0.8 Co 0.2 ) 12 can be synthesized, and that the obtained single crystal is saturated with magnetic anisotropy. It is described that the intrinsic magnetic characteristics such as the anisotropic magnetic field and the Curie temperature all have excellent characteristics exceeding Nd 2 Fe 14 B.
  • an object of the present invention is to provide a magnet (rare earth magnet) having an excellent coercive force.
  • Another object of the present invention is to provide a film, a laminate, a motor, a generator, and an automobile.
  • Another object of the present invention is to provide a method for producing a magnet layer containing the magnet by a sputtering method.
  • the overall composition is a group consisting of formula 1: (R 1 (1-x) R 2 x ) a T b M c (in the above formula, R 1 is Sm, Pm, Er, Tm, and Yb. at least one element more selective, at least 1 R 2 is, Zr, Y, La, Ce , Pr, Nd, Eu, Gd, Tb, Dy, Ho, and selected from the group consisting of Lu Species element, T is at least one element selected from the group consisting of Fe, Co, and Ni, M is boron, x is a number from 0 to 0.5, a.
  • [5] The magnet according to any one of [1] to [4], wherein at least one selected from the group consisting of a crystal orientation and an easy magnetization axis is preferentially oriented along a predetermined direction.
  • [6] The magnet according to any one of [1] to [5], wherein a is 6.0 to 10.0 atomic%.
  • [7] The magnet according to any one of [1] to [6], which has the ThMn 12 type crystal phase as the main phase and has an amorphous grain boundary phase existing between the main phases.
  • [8] The magnet according to [7], wherein the absolute value of the difference between the boron content in the main phase and the boron content in the grain boundary phase is 1.0 atomic% or more.
  • a magnet having an excellent coercive force it is possible to provide a magnet having an excellent coercive force. Further, according to the present invention, a film, a laminate, a method for manufacturing a magnet, a motor, a generator, and an automobile can also be provided. Further, according to the present invention, it is also possible to provide a method for producing a magnet layer containing the above magnet by a sputtering method.
  • IP In-Plane
  • OOP Out-of-Plane
  • Examples 21 (A) and (b) are the analysis results of the membrane of Example 19 by 3DAP. It is the analysis result by 3DAP of the membrane of (a) and (b) Example 20. It is a schematic diagram which shows the fine structure of the thin film of Example 19 and Example 20.
  • Examples 21 (a) and (b) to (e) are Sm (Fe 0.8 Co 0.2 ) 12 B film Out-of-Plane XRD patterns.
  • Examples 21 (a) and (f) to (i) are Sm (Fe 0.8 Co 0.2 ) 12 B film Out-of-Plane XRD patterns.
  • 9 is an in-plane and quadrangular magnetization curve of the films of Examples 21 (a) and (b) to (e).
  • Example 21 is an in-plane and quadrangular magnetization curve of the films of Examples 21 (a) and (f) to (i). It is a figure which shows the magnetic property of the film of Example 21 (c)-(i); (a) saturation magnetization (M s ), (b) coercive force (H c ), (c) residual magnetization ratio in a zero magnetic field. ( Mr / M s ), (d) Vertical anisotropy ( Ku ).
  • [magnet] Magnet according to an embodiment of the present invention, the whole composition, wherein 1: is represented by (R 1 (1-x) R 2 x) a T b M c, is a magnet having at least ThMn 12 type crystal phase .
  • R 1 is at least one element selected from the group consisting of Sm, Pm, Er, Tm, and Yb
  • R 2 is Zr, La, Ce, Pr, Nd. , Eu, Gd, Tb, Dy, Ho, and Lu
  • T is at least one element selected from the group consisting of Fe, Co, and Ni.
  • M is boron
  • x is a number from 0 to 0.5 (0 ⁇ x ⁇ 0.5)
  • a is a number from 6.0 to 13.7 atomic% (6.0).
  • c is a number greater than 0 atomic% and 12 atomic% or less (0 ⁇ c ⁇ 12), and b is a number represented by 100-ac atomic%.
  • the overall composition of the magnet according to the embodiment of the present invention is represented by (R 1 (1-x) R 2 x ) a T b M c .
  • the "overall composition” is determined by an ICP emission spectrophotometer (ICP-OES), and the measuring method thereof is as described in Examples.
  • R 1 is at least one element selected from the group consisting of Sm (samarium), Pm (promethium), Er (erbium), Tm (thulium), and Yb (ytterbium) (hereinafter, "" It is also called “specific rare earth element”).
  • Sm sinarium
  • Pm promethium
  • Er erbium
  • Tm thulium
  • Yb ytterbium
  • R 1 is at least one element selected from the group consisting of Sm (samarium), Pm (promethium), Er (erbium), Tm (thulium), and Yb (ytterbium) (hereinafter, "" It is also called “specific rare earth element”).
  • specific rare earth element of R 1 one kind may be used alone, or two or more kinds may be used in combination.
  • the specific rare earth element is a rare earth element having a Stevens factor.
  • the Stevens factor is a physical quantity related to the electrification density (shape) of 4f electrons in the inner shell of a rare earth element. If this is negative, the shape is contracted with respect to the axis of symmetry, and if it is positive, the shape is elongated from spherical symmetry. Since the 4f electron cloud receives a crystal field from surrounding ions and its stable direction is determined, the shape of the electron cloud determines the direction of magnetic anisotropy.
  • the magnet according to the embodiment of the present invention has excellent magnet characteristics because it contains an element in which the Stevens factor is positive.
  • the magnet has an effect of better present invention is obtained, as the R 1, at least one Stevens factor positive matrix Sm, Yb, Tm, and selected from the group consisting of Pm Is preferable, at least one selected from the group consisting of Sm, Yb, and Tm is more preferable, and at least one selected from the group consisting of Sm, Yb, and Tm is further preferable.
  • the R 1 at least one Stevens factor positive matrix Sm, Yb, Tm, and selected from the group consisting of Pm Is preferable, at least one selected from the group consisting of Sm, Yb, and Tm is more preferable, and at least one selected from the group consisting of Sm, Yb, and Tm is further preferable.
  • R 1 contains Sm, the obtained magnet is more excellent. It has the effect of the present invention. Therefore, it is preferable that R 1 contains at least Sm.
  • R 2 in the overall composition
  • R 2 is Zr (zylonium), Y (yttrium), La (lantern), Ce (cerium), Pr (praseodymium), Nd (neodymium), Eu (europium), Gd (gadolinium), Tb ( It is at least one selected from the group consisting of terbium), Dy (dysprosium), Ho (holmium), and Lu (lutetium) (hereinafter, also referred to as “specific element”). Specific element of R 2 may be used alone or in combination of two or more thereof.
  • R 2 is a component that contributes to the stabilization of the ThMn 12 type crystal phase of the magnet.
  • Y and Ce preferably Ce (IV) are elements that do not have magnetism by themselves, but the magnet obtained by containing the above as R 2 in the magnet is Has excellent stability.
  • Gd and Zr have a function of further improving the stability of the obtained magnet, and the effect is more remarkable especially when R 1 contains Sm. That is, when the magnet contains at least Sm as R 1 , the magnet preferably contains at least one specific element selected from the group consisting of Gd and Zr as R 2.
  • La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, and Lu have a negative or zero Stevens factor and contribute to the stabilization of the ThMn 12 type crystal phase of this magnet. To do.
  • the R 2 element since the R 2 element also has an action of weakening the magnetic anisotropy derived from the R 1 element, it is preferable to adjust the content thereof from both the stability of the crystal phase and the magnetic characteristics.
  • the content ratio of the content of R 2 based on the atomic% (at%) to the total content of R 1 and R 2 in this magnet (the number represented by x in the formula) is It is 0.5 or less, preferably 0.4 or less, and more preferably 0.3 or less.
  • the magnet may not contain R 2. That is, in this magnet, 0 ⁇ x ⁇ 0.5, 0 ⁇ x ⁇ 0.4 is preferable, and 0 ⁇ x ⁇ 0.3 is more preferable.
  • the total content a of R 1 and R 2 on an atomic% basis in the overall composition is 6.0 ⁇ a ⁇ 13.7.
  • a is preferably 6.0 ⁇ a ⁇ 10.
  • T is at least one element selected from the group consisting of Fe (iron), Co (cobalt), and Ni (nickel). These are classified as iron group elements and have common properties in that they exhibit ferromagnetism at normal temperature and pressure. Therefore, Fe, Co, and Ni as T can be replaced with each other, and as T, the above-mentioned iron group element may be used alone, or two or more kinds may be used in combination.
  • the content of T in the overall composition is not particularly limited as long as it satisfies 100-ac in relation to a described above and c described later, but is generally preferably 50 to 95 atomic%, preferably 60 to 85 atoms. % Is more preferable.
  • T contains at least one element selected from the group consisting of Fe and Co in that a magnet having a more excellent effect of the present invention can be obtained, and Fe and Co are used in combination. It is preferable to do so.
  • Co is contained as T, the magnetization of the magnet is further improved and the Curie temperature is further increased.
  • T is preferably Fe and Co. That is, the overall composition of the present magnet, formula 2: (R 1 (1- x) R 2 x) a (Fe p Co 1-p) is preferably represented by b M c. At this time, p is a number of 0.5 to 0.9. In particular, in that a magnet having the superior effect of the present invention can be obtained, the overall composition of the magnet is as follows: (Sm 1-x R 2 x ) a (Fe p Co 1-p ) b M c. It is more preferable to be represented by. At this time, p is a number of 0.5 to 0.9, preferably 0.7 to 0.8.
  • ⁇ M in the overall composition M is boron (boron element, B).
  • the content of boron in the overall composition is preferably greater than 0 atomic% and preferably 12 atomic% or less.
  • this magnet has a crystal phase such as ⁇ -Fe ( ⁇ - (Fe, Co)) phase in addition to the 1-12 phase. Nevertheless, it has an excellent coercive force.
  • the mixture of the other crystal phases in the structure of a magnet having the 1-12 phase as the main phase may cause a decrease in coercive force or a decrease in the squareness of the demagnetization curve.
  • the present magnet has particularly excellent performance that cannot be predicted by those skilled in the art even when the above-mentioned other crystal phases are contained. It was revealed.
  • the content of boron in the main phase (1-12 phase) and the amorphous grain boundary phase (the amorphous grain boundary phase) is preferably 1.0 atomic% or more.
  • the absolute value of the difference in the boron content may be a larger value depending on the boron content in the overall composition, and may be, for example, 1.5 atomic% or more. It may be 0 atomic% or more, 3.0 atomic% or more, 4.0 atomic% or more, 5.0 atomic% or more, 7.5 atomic% or more. It may be% or more, and may be 10 atomic% or more.
  • the content of boron in the main phase (1-12 phase) is more than 0 atomic%. Therefore, the content of boron in the amorphous grain boundary phase (B-concentrated phase) is preferably more than 1.0 atomic%. Further, the content of boron in the amorphous grain boundary phase (B-concentrated phase) may be 1.5 atomic% or more, 2.0 atomic% or more, or 3.0 atoms. % Or more, 4.0 atomic% or more, 5.0 atomic% or more, 7.5 atomic% or more, 10 atomic% or more. You may.
  • the upper limit of the boron content in the main phase (1-12 phase) is a value obtained by dividing 1.0 from half the value based on the boron content (atomic%) in the overall composition.
  • the value is preferably less than.
  • the boron content in the main phase (1-12 phase) is less than 5.0 atomic%. Is preferable, 4.0 atomic% or less is more preferable, 3.0 atomic% or less is further preferable, 2.0 atomic% or less is particularly preferable, 1.0 atomic% or less is most preferable, and 0.5 atomic% or less is preferable. More preferred.
  • the boron content in the amorphous grain boundary phase (B-concentrated phase) is preferably a value equal to or more than half of the boron content (atomic%) in the overall composition.
  • the boron content in the amorphous grain boundary phase (B concentrated phase) is 6. 0 atomic% or more is preferable, 6.5 atomic% or more is more preferable, 7.0 atomic% or more is further preferable, 8.0 atomic% or more is particularly preferable, 9.0 atomic% or more is most preferable, and 10 atomic% or more is 10 atomic%.
  • the upper limit of the boron content in the amorphous grain boundary phase is not particularly limited and may vary depending on the boron content in the overall composition.
  • the present magnet includes Ti (titanium), V (vanadium), Mo (molybdenum), Nb (niobium), Cr (chromium), and W. It is preferable that substantially none of (tungsten) (hereinafter, also referred to as “excluded element”) is contained. Magnets that are substantially free of the exclusion elements have a better maximum magnetic energy product and coercive force.
  • substantially free means that the content of the excluded element is 0.1 atomic% or less of all atoms when the elements contained in the main phase are analyzed by ICP-OES analysis. It is more preferably 0.01 atomic% or less, and further preferably 0.001 atomic% or less.
  • the main phase contains two or more kinds of excluded elements, it is preferable that the total of the two or more kinds of excluded elements is within the above numerical range.
  • This magnet may have another crystal phase as long as it has a ThMn 12 type crystal phase.
  • the other crystal phase is not particularly limited, but for example, when the overall composition is represented by Sm (Fe 0.8 Co 0.2 ) 12 B, ⁇ -Fe, ⁇ - (Fe, Co), Sm (FeCo). ) 7 and Sm 2 (FeCo) 17 phase and the like.
  • the main phase is a ThMn 12 type crystal phase, and ⁇ -Fe, ⁇ - (Fe, Co), Sm (FeCo) 7 , and Sm 2 (FeCo) It is preferable that the structure has a 17 phase or the like as another crystal phase.
  • the main phase means the phase having the highest peak intensity detected in the X-ray diffraction measurement of the magnet.
  • the crystal orientation and the orientation state of the easy magnetization axis are not particularly limited, but are selected from the group consisting of the crystal orientation and the easy magnetization axis in that the maximum energy product (BH) max tends to be larger. It is preferable that at least one of them is preferentially oriented along a predetermined direction.
  • a magnet in which at least one selected from the group consisting of a crystal orientation and an easy magnetization axis is preferentially oriented along a predetermined direction is also referred to as an anisotropic magnet. That is, the magnet according to the embodiment of the present invention is preferably an anisotropic magnet.
  • the [001] direction is the easy magnetization axis, and the easy magnetization axis is preferentially oriented in a predetermined direction. If so, an anisotropic magnet with a better maximum energy product (BH) max is obtained.
  • This magnet has a ThMn 12 type crystal phase, and when the crystal orientation and / or the easy magnetization axis is preferentially oriented in a predetermined direction, a magnet having a better effect of the present invention can be obtained. Easy to obtain.
  • the peak intensity of the diffraction line from (00L) of the ThMn 12 type crystal phase is 1 or more with respect to the peak intensity of the phase (second phase) other than the detected ThMn 12 type crystal phase. It means, and it is preferable that it is 2 or more.
  • This magnet may have a phase other than the ThMn 12 type crystal phase (such as the ⁇ -Fe phase already described). In this case, the peak derived from the ⁇ -Fe phase is that of the ThMn 12 type crystal phase. It is not included in the peaks derived from a predetermined crystal orientation or the like.
  • the magnet according to the embodiment of the present invention is not particularly limited as long as it has the above-mentioned material structure and properties.
  • the form of the magnet may be, for example, a particle shape, a flat plate shape, or a three-dimensional shape having a curved surface. Further, the magnet may have a flat plate shape (film).
  • the manufacturing method of this magnet is not particularly limited, and a known manufacturing method of a magnet can be applied.
  • Examples of the above-mentioned manufacturing method include Japanese Patent Application Laid-Open No. 2017-50396, and the above contents are incorporated in the present specification.
  • the method for forming the magnet is not particularly limited, and a sintering method, an ultra-quenching solidification method, a vapor deposition method, an HDDR (Hydrogenation Decomposition Decomposition) method, and the like can be applied. Above all, it is preferable to form the magnet (layer) on the support by the sputtering method because the magnet (layer) can be formed more easily. In the following, the form of forming the magnet layer by the sputtering method will be described in detail.
  • the support is not particularly limited, and a known support can be used. Among them, in that the magnet has an effect of better present invention is obtained, as the support, silicon, low-temperature co-fired ceramic, Al 2 O 3, LiTaO 3 , LiNbO, quartz, SiC, GaAs, GaN and, Examples include glass. Further, the support may be doped with another element (for example, arsenic and / or phosphorus-doped silicon), or may be a laminate having a plurality of layers (for example). , Silicon with thermal oxide film).
  • the pressure in the chamber of the film forming apparatus during sputtering is not particularly limited, but is preferably 10-6 Pa or less, preferably 10-8 Pa or less, from the viewpoint of further reducing the mixing of unintended components in the obtained magnet. Is more preferable.
  • the method for cleaning the surface of the support is not particularly limited, and examples thereof include a method of sputtering the support itself. According to the above, the oxide film of the support formed on the support, organic substances and the like can be removed. Further, the surface of the support may be cleaned by heating the support to a predetermined temperature (for example, about 600 to 800 ° C.), holding the support for a predetermined time (for example, about 10 to 30 minutes), and performing a heat treatment. ..
  • the sputtering method is not particularly limited, but the magnetron sputtering method, which enables sputtering in a lower pressure Ar atmosphere, is preferable.
  • the thickness of the target material by adjusting the thickness of the target material, the reduction of the leakage flux of the magnetron sputtering can be further suppressed, and the sputtering can be made easier.
  • the power source for sputtering can be either DC or RF, and can be appropriately selected depending on the target material.
  • the heating temperature of the support of the magnet, the film formation rate, and the film formation time are not particularly limited, and may be appropriately adjusted according to the required thickness of the magnet.
  • the film formation rate can be adjusted by the power of sputtering and / or the time.
  • the support heating temperature is preferably 250 to 400 ° C., more preferably 300 to 350 ° C., from the viewpoint of more efficiently obtaining the magnet according to the embodiment of the present invention having the above-mentioned structure. Further, it is preferable to cool the magnet layer at a temperature lower than the support heating temperature after forming the magnet layer on the support (lamination of magnets). Thereby, the effect of the magnet according to the embodiment of the present invention can be obtained more reliably.
  • the cooling means and the cooling time when cooling at a temperature lower than the support heating temperature are not particularly limited.
  • the magnet layer after the magnet layer is formed, it may be naturally cooled without heating and cooling the support. In the case of the above natural cooling, it depends on the value of the support heating temperature, the atmosphere in the chamber of the film forming apparatus, etc., but for example, under the condition that the support heating temperature is 300 to 350 ° C., the support is after about 20 to 50 minutes. The temperature drops to about 50-70 ° C.
  • the temperature of the support heating means may be set to a temperature lower than the support heating temperature and held for a predetermined time to cool the support.
  • the set temperature of the support heating means may be any temperature as long as it is lower than the support heating temperature, and the holding time may be any time. Further, cooling by the support heating means described above and natural cooling may be combined. Further, after the magnet layer is formed, the support may be cooled by using a cooling medium such as nitrogen gas, whereby the magnet according to the embodiment of the present invention can be obtained in a shorter production time. In the case of cooling using the above cooling medium, the temperature of the support drops to about 20 ° C. in about several minutes to 10 minutes, for example, when nitrogen gas is used, although it depends on the type of cooling medium and the value of the support heating temperature. To do.
  • a cooling medium such as nitrogen gas
  • the average cooling rate (° C./min) obtained by dividing the difference between the support heating temperature at the time of film formation of the magnet layer and the support temperature at the end of cooling by the cooling time is approximate.
  • it may be about 3 to 85 ° C./min.
  • the method for manufacturing the magnet may further include a step of forming a base layer on the support before forming the magnet.
  • the base layer is a layer formed between the support and the magnet layer, and is preferably formed so as to be in direct contact with the magnet layer. That is, the magnet layer is preferably formed on the base layer formed on the support. In other words, the magnet layer is preferably formed on the underlying layer with a support.
  • the magnet precursor By forming the magnet precursor on the base layer, it is preferable in that the crystal orientation of the magnet layer can be controlled.
  • the material of the base layer is not particularly limited, but a form capable of reducing lattice defects due to lattice mismatch with the magnet formed thereafter and improving crystallinity is preferable. That is, it is more preferable that the material of the base layer is about the same as the lattice constant of the magnet.
  • the material component of the base layer is not particularly limited and may be appropriately selected depending on the magnet formed thereafter. For example, crystals having higher crystallinity and / or higher orientation can be obtained. In terms of points, it is preferable to contain MgO, V and the like.
  • the material of the base layer preferably contains one or more of the above-mentioned material components, but may contain two or more. In that case, it may be a solid solution, a eutectic (eutectic mixture), an intermetallic compound, or a mixture thereof, or may be a laminate. That is, the base layer may be a laminated body of a plurality of layers.
  • the material of the base layer may be a single crystal or a polycrystal, but it is preferably a single crystal in that a magnet having a better effect of the present invention can be obtained.
  • the magnet layer formed thereafter is more likely to grow epitaxially, and as a result, a magnet having a better effect of the present invention can be obtained.
  • the method for forming the base layer is not particularly limited, and a known method can be applied. Among them, a method similar to the method for forming a magnet (layer) described above is preferable in that the base layer can be formed more easily.
  • a step of arranging the cap layer on the magnet layer may be further included.
  • the cap layer is a layer formed for the purpose of protecting the magnet layer and / or preventing modification (for example, oxidation) of the magnet layer.
  • the material component of the cap layer is not particularly limited, but the same material as the base layer already described can be used.
  • the method for forming the cap layer is not particularly limited, but the same method as for forming the magnet layer can be applied.
  • the film according to the embodiment of the present invention is a film containing a magnet as described above.
  • the content of the magnet in the film according to the embodiment of the present invention is not particularly limited, but generally, 50% by volume or more is preferable, 60% by volume or more is more preferable, 70% by volume or more is further preferable, and 80% by volume or more. Is particularly preferable.
  • the form in which the film contains a magnet is not particularly limited, and examples thereof include a form containing a particle-shaped magnet and a binder, and a form having a layer made of magnets (magnet layer).
  • the film containing the magnet according to the embodiment of the present invention may contain other components as long as the effects of the present invention are exhibited.
  • other components include binders and the like.
  • the binder is not particularly limited, and known materials can be used, and inorganic materials, organic materials, and composite materials thereof can be used. Examples of known binders include epoxy resins and the like.
  • the film according to the embodiment of the present invention may contain other components within the range in which the effects of the present invention are exhibited, and the other components include R 1 , R 2 , T, and M in Formula 1. Examples thereof include compounds containing at least one of each element described as described above.
  • the magnet in the film has a ThMn 12 type crystal phase which may be a single crystal, and is typically a polycrystalline phase as a whole.
  • the crystal orientation in the film and at least one orientation state selected from the group consisting of the easy magnetization axes are not particularly limited. Above all, it is preferable that the crystal orientation of the magnet is preferentially oriented in the [001] direction in that the maximum energy product (BH) max tends to be larger. That is, the film preferably contains a magnet whose crystal orientation is preferentially oriented in the [001] direction.
  • the thickness of the film is not particularly limited, but as shown in FIG. 11 described later, 1 nm to 10000 ⁇ m is preferable, 10 to 1000 nm is more preferable, and 15 to 300 nm is further preferable, in that a more excellent effect of the present invention can be obtained.
  • 20 to 200 nm is particularly preferable, 30 to 180 nm is most preferable, 50 to 150 nm is more preferable, 60 to 120 nm is even more preferable, and 80 to 120 nm is particularly preferable.
  • the laminate according to the embodiment of the present invention has a base layer and a magnet layer containing a magnet already described, which is formed so as to be in contact with the base layer, and the base layer has a single crystal structure.
  • the crystal orientation of the magnet layer is preferentially oriented in the [001] direction.
  • the laminated body 10 has a magnet layer 12, a base layer 13, and a support 14 in this order from the cap layer 11.
  • the form of the magnet layer 12 is not particularly limited as long as it contains the magnet, but it is preferably the film, and the preferred form thereof is also the same. Further, the configurations of the other layers are the same as those described in the method for manufacturing a magnet, and the preferred forms are also the same.
  • the magnet according to the embodiment of the present invention has an excellent coercive force, it can be applied to the field of MEMS (Micro Electro Mechanical Systems), the field of energy such as energy harvesting (environmental power generation), the field of medical equipment, and the like.
  • MEMS Micro Electro Mechanical Systems
  • the field of energy such as energy harvesting (environmental power generation)
  • the field of medical equipment and the like.
  • FIG. 2 shows a permanent magnet motor 20 as a motor according to an embodiment of the present invention.
  • the permanent magnet motor 20 has a stator 21 and a rotor 24 rotatably arranged in the stator 21.
  • the rotor 24 has a core material 22 and a plurality of magnets 23 arranged in the core material 22.
  • FIG. 2 shows a permanent magnet motor
  • the motor according to the embodiment of the present invention is not limited to the above, and can be applied to a variable magnetic flux motor and the like.
  • the generator according to the embodiment of the present invention is a generator having the above magnet.
  • FIG. 3 shows a generator according to an embodiment of the present invention.
  • the generator 30 has a stator 31 having the magnet and a rotor 32 rotatably provided.
  • the rotor 32 is arranged inside the stator 31, and the rotor 32 is connected to the turbine 33 by a shaft 34.
  • the turbine 33 is rotated by, for example, a fluid supplied from the outside, and the electromotive force generated by the rotation is taken out as the output of the generator 30.
  • the generator 30 may have other members known, such as a phase-separated bus, a main transformer, and a brush for removing charge.
  • the generator according to the embodiment of the present invention is not limited to the above, and the regenerative energy of an automobile or the like can be input. it can.
  • FIG. 4 is a conceptual diagram showing a power generation, storage, and drive mechanism of an automobile according to an embodiment of the present invention.
  • the automobile 40 has wheels 41 and a motor 42, which are connected by an axle 45.
  • the motor 42 is a motor having a magnet as described above, and the wheels 41 are rotated by the output of the motor.
  • the motor 42 is electrically connected to the storage battery 43, and electric energy is input to the motor 42 from the storage battery 43.
  • the storage battery 43 is electrically connected to the generator 44, and the electric power generated by the generator 44 is supplied to the storage battery 43.
  • the generator 44 is a generator having a magnet as described above.
  • the generator 44 is connected to an engine (not shown) by a shaft, and the rotor of the generator 44 is configured to rotate by mechanical energy generated from the engine.
  • both the motor 42 and the generator 44 have magnets, but the automobile according to the embodiment of the present invention is not limited to the above, and either the magnet or the generator can be used. It suffices to have a magnet.
  • the substrate was heated to 325 ° C., and the Sm, Fe, Fe 50 Co 50 , and Fe 80 B 20 targets were simultaneously sputtered. Further, V (10 nm) was deposited as a cap layer to prevent oxidation.
  • the relationship between the setting conditions of the DC magnetron sputtering apparatus and the film formation rate was measured in advance using a step meter, and the amount of boron introduced into each sample film was estimated from the film formation rate using this result.
  • the amount of boron introduced can be controlled by controlling the film formation rate, and if the film formation rate is constant, the samples having a constant boron content and different film thicknesses. Can also be formed.
  • Sm (Fe 0.8 Co 0.2 ) having a thickness of 5 nm or more on the substrate using the above materials, film forming conditions, and film forming apparatus. 12 It has been confirmed that the B layer can be formed. If necessary, it is also possible to make the thickness of the Sm (Fe 0.8 Co 0.2) 12 B layer less than 5 nm.
  • Table 1 summarizes the samples prepared in the examples, the amount of boron introduced (target), and the results of elemental analysis by ICP-OES.
  • the ICP-OES analysis was carried out according to the following procedure. First, the sample was taken in a quartz beaker, 5 ml of a 1: 1 (volume) solution of nitric acid and water, 10 ml of a 1: 1 (volume) solution of hydrochloric acid and water, and 1: 1 of sulfuric acid and water. (Volume) 3 ml of the solution was added, and the solution was heated at 120 ° C. for 30 minutes to dissolve it, and after allowing to cool, the volume was adjusted to 100 ml. The content of each element in this solution was measured by an ICP-OES apparatus "720-ES ICP-OES" manufactured by Agilent.
  • FIG. 5 shows a plane (Out-of-Plane) XRD pattern of Sm (Fe 0.8 Co 0.2) 12 B film of Example 1 and Example 3-9 The thickness of the film was 50nm. From the results of Out-of-Plane XRD, diffraction patterns derived from (002) and (004) (indicated by downward white triangles in the figure) were observed, and the (001) plane of the ThMn 12 type crystal phase was observed. it is strongly oriented, i.e., it was found that crystal orientation of Sm (Fe 0.8 Co 0.2) 12 B layer are preferentially oriented in the [001] direction.
  • FIG. 6 the lattice constants a, c, and c / a (vertical axis) and the content of B (horizontal axis) of the thin films of Examples 1 to 6 and Example 9 in which the film thickness is constant (50 nm) are shown.
  • A showed an almost constant value at about 8.56 ⁇ (angstrom) up to a B content of 4% by volume, but increased sharply when B exceeded 4% by volume.
  • c and c / a decreased monotonically as the B content increased.
  • FIG. 7 shows the in-plane and perpendicular-plane magnetization curves of the thin films of Examples 1 and 3 to 9 in which the B content was changed while the film thickness was constant.
  • a superconducting quantum interference magnetometer (SQUID) was used to measure the magnetic characteristics, and a magnetic field was applied in the range of ⁇ 7 T (70 kOe) at room temperature.
  • FIGS. 11, 14 (a) and 14 (b), which will be described later, and FIGS. 23 and 24 According to FIG. 7, when B is 0% by volume, it shows strong vertical anisotropy.
  • the coercive force is 0.14 T (in the figure, it is expressed as 1.4 kOe using the Oersted unit Oe). According to FIG.
  • the coercive force in the perpendicular direction increased with the increase in the B content, and the B content showed a coercive force of 0.75 T at 5.0% by volume. Moreover, in the above, it showed a high magnetization of 1.59T. Furthermore, the in-plane component also increased.
  • FIG. 8 shows the magnetization of a thin film with a constant film thickness (M s ), the residual magnetization ratio at zero magnetic field ( Mr / M s ), the coercive force (H c ), and the vertical anisotropy (K). The dependence of u ) on the B content was shown. Note that FIG. 8 also shows the results of samples prepared under film formation conditions different from the target amount of B introduced in Examples 1 to 9.
  • FIG. 9 shows the Out-of-Plane XRD patterns of the thin films of Examples 10, 13 to 16 and Example 18 in which the thickness of the film was changed from 20 nm to 200 nm.
  • the intensities of the diffraction lines from (002) and (004) (indicated by the downward white triangles in the figure) increase as the thickness of the film increases.
  • the intensity of the diffraction line (indicated by the downward black triangle mark in the figure) from the second phase ( ⁇ -Fe, Sm (FeCo) 7 , Sm 2 (FeCo) 17) observed near 65 ° is It did not change depending on the thickness of the film.
  • FIG. 10 shows changes in the lattice constants a, c, and c / a of the thin films of Examples 10 to 18 in which the film thickness (t SFC) was changed.
  • a increased to 8.70 ⁇ at 30 nm, then showed a constant value of 8.70 ⁇ up to 80 nm, and then decreased.
  • c decreased to 4.75 ⁇ at 30 nm and then showed a constant value of 4.75 ⁇ .
  • c / a decreased to 30 nm, but then showed a constant value.
  • FIG. 11 shows the magnetization curves of the thin films of Examples 10, 13 to 16 and Example 18 in which the thickness of the film was changed. Both were perpendicularly magnetized films. The coercive force in the vertical direction increases with the increase in the thickness of the film, and shows a maximum value of 0.94 T at 100 nm. This value was the largest value among the films of Examples 1 to 18.
  • the magnetization value is 1.55 T, which is a relatively high value.
  • the coercive force decreased.
  • FIG. 12 shows the magnetization of a thin film with a constant B content (M s ), the residual magnetization ratio at zero magnetic field ( Mr / M s ), coercive force (H c ), and vertical anisotropy ( Ku ). Dependence on the thickness of the film (t SFC ) was shown.
  • FIG. 13 shows the temperature dependence of the coercive force.
  • the horizontal axis represents the temperature (K) and the vertical axis represents the coercive force (T).
  • K the temperature
  • T the coercive force
  • SQUID-VSM equipped with a sample vibration magnetometer was used, and the temperature was changed in the range of 50 to 700 K.
  • the black circle plot is a sample obtained by adjusting the film formation conditions so that the boron content is 5% by volume, and the black square plot is Cu diffusion to Sm (Fe 0.8 Co 0.2 ) 12.
  • the black triangular plot is Sm (Fe 0.8 Co 0.2 ) 12 with Cu-Ga diffusion.
  • a total of three black solid lines and two black broken lines are commercial Nd 2 Fe 14 B magnets (NMX-36 (Dy content 8%), NMX-43 (Dy content 4%), NMX-52 (Dy content). Free)) shows the temperature dependence.
  • FIG. 13 it can be seen that the Sm (FeCo) 12 magnet exhibits a smaller temperature dependence than the Nd 2 Fe 14 B magnet.
  • the sample containing 5% by volume of boron showed a high coercive force over the entire temperature range, and the temperature coefficient ( ⁇ ) of the coercive force in the temperature range of 300 to 700 K was the lowest value (-0. It was 15% / K).
  • Example 14 (a) and 14 (b) show in-plane (In-Plane (IP)) and straight (Out-of-Plane) of the thin films of Example 19 and Example 20 having a film thickness of 100 nm, respectively.
  • the magnetization curve in the OOP)) direction is shown.
  • the film of Example 19 in which B is 0% by volume shows strong vertical anisotropy.
  • the coercive force was 0.1 T and the residual magnetization in a zero magnetic field was 0.2 T.
  • the film of Example 20 in which B is 0.5% by volume shows a strong vertical anisotropy comparable to that of Example 19 and 1.2T, which is significantly higher than that of Example 19.
  • the coercive force of was shown.
  • the residual magnetization in the zero magnetic field was 1.50 T.
  • the temperature coefficient ( ⁇ ) of the coercive force of the film of Example 20 in the temperature range of 300 to 500 K (27 to 227 ° C) was calculated to be ⁇ 0.22% / ° C. Since the temperature coefficient ( ⁇ ) of the coercive force of the conventionally reported anisotropic Nd-Fe-B magnet is about -0.4 to -0.6% / ° C., it was obtained for the film of Example 20.
  • the absolute value of the temperature coefficient is much smaller than that of the conventional Nd-Fe-B magnet, which means that the film according to the embodiment of the present invention has a coercive force as compared with the conventional Nd-Fe-B magnet. It shows that it has excellent thermal stability.
  • demagnetic correction is performed to set the demagnetization rate to 0.83 based on the result of the microstructure analysis of the thin film described later.
  • the value of the residual magnetization at zero magnetic field (1.50T) obtained from the film of Example 20 is the value (1.61T) of the previously reported anisotropic Nd 2 Fe 14 B / FeCo nanocomposite thin film. Although it is slightly smaller than that, as far as the present inventors know, it is the largest value among the anisotropic Sm (Fe 0.8 Co 0.2 ) 12 films.
  • FIG. 15 (a) and 15 (b) show in-plane and cross-sectional transmission electron microscope images (BF-TEM images) of the thin films of Examples 19 and 20, respectively.
  • FIG. 15A the film of Example 19
  • FIG. 15B film of Example 20
  • FIG. 15B columnar SmFe 12- based crystal grains were confirmed.
  • the average particle size of the columnar grains was about 40 to 50 nm, and the ratio of height to width (average particle size) was about 2.5: 1 (average aspect ratio of about 2.5).
  • the structure is such that the columnar grains are used as the main phase and grain boundary phases having a certain width (about 1 nm or more) exist between the main phases.
  • the main phase ThMn 12 type crystal phase (1-12 phase) grows in a columnar shape and is columnar. It was suggested that grain boundary phases having a certain thickness were formed between the crystal phases, and that such a fine structure exerted a high coercive force.
  • 16 (a) to 16 (d) show high-angle annular dark-field scanning transmission electron microscope (HAADF-STEM) images.
  • 16 (a) and 16 (b) are HAADF-STEM images of the thin film (Sm (Fe 0.8 Co 0.2 ) 12 film) of Example 19, and FIGS. 16 (c) and 16 (d) are examples. It is a HAADF-STEM image of 20 thin films (Sm (Fe 0.8 Co 0.2 ) 12 B 0.5 film).
  • FIG. 16A in the film of Example 19, no clear phase was observed between the two Sm (Fe, Co) 12 crystal grains, and the two crystal grains were in direct contact with each other.
  • FIG. 16B is a high-magnification image obtained along the crystal zone axis of [100] of Sm (Fe, Co) 12 crystal grains in the film of Example 19 (direction on the paper surface of FIG. 16A). .. Since contrast occurs in the HAADF-STEM image due to the number of atomic atoms of the elements contained in the sample, what is seen as a brighter spot in the image corresponds to the atomic column of the heavier element, that is, Sm (Fe). , Co) It is considered to be Sm in 12 compounds.
  • FIG. 16 (c) in the film of Example 20, an amorphous grain boundary phase (GB) having a thickness of about 3 nm was confirmed between two Sm (Fe, Co) 12 crystal grains.
  • FIG. 16 (d) is a high-magnification image obtained along the crystal zone axis of [100] of the Sm (Fe, Co) 12 crystal grains in the film of Example 20 (direction on the paper surface of FIG. 16 (c)). .. From the nanobeam electron diffraction patterns (upper right and upper left) inserted in FIG. 16 (d), the two Sm (Fe, Co) 12 crystal grains separated by the grain boundary phase both have a ThMn 12 type structure.
  • Misalignment is as small as about 2 °, and the [001] direction (c-axis) of 12 Sm (Fe 0.8 Co 0.2 ) crystal grains adjacent to each other is upward (the direction on the paper surface in FIG. 16 (d)). It was shown to be oriented to.
  • FIG. 17 (a) and 17 (b) show the results (STEM-EDS image) of the in-plane and cross-sectional scanning transmission electron microscope-energy dispersive X-ray analysis of the thin films of Examples 19 and 20, respectively. It was. According to FIG. 17A, it can be seen that in the film of Example 19, Sm, Fe and Co are uniformly distributed in the film. In addition, although a portion having a partially different concentration of Sm is observed, the portion is due to the existence of a second phase different from the main phase, and the second phase is shown in FIG. 16 (b).
  • FIGS. 18 (a) and 18 (b) show the results of analysis of the membrane of Example 19 by a three-dimensional atom probe (3DAP).
  • the 3DAP map shown in FIG. 18A was obtained by scanning the probe parallel to the plane of the thin film.
  • FIG. 18B shows a 3DAP map of Sm in the rectangular parallelepiped region shown in FIG. 18A (upper row), a composition profile of Sm, Co and Fe in the region (middle row), and Sm shown in the middle row. This is an enlarged composition profile (lower).
  • the content ratio of Co and Fe based on the atomic% (at%) is 1: 4, and the composition ratio predicted from the film forming conditions. It was the value of.
  • the Sm content As explained with reference to the STEM-EDS image shown in FIG. 17 (a), a portion where the Sm concentration is partially different is observed, and the Sm content is about 10 in this portion. Although it was ⁇ 11 atomic%, the average content of Sm was about 7.95 atomic%, and this value was anisotropic Sm (Fe 0.8 Co 0.2 ) 12 having a ThMn 12 type structure. It is consistent with the composition of Sm in the phase.
  • FIG. 19 (a) and 19 (b) show the results of analysis of the membrane of Example 20 by a three-dimensional atom probe (3DAP).
  • the 3DAP map shown in FIG. 19A was obtained by scanning the probe parallel to the plane of the thin film. That is, the paper surface penetration direction in FIG. 19A is the plane perpendicular direction of the thin film.
  • FIG. 19 (b) is a composition profile of the constituent elements (Sm, Co, Fe and B) in the region shown by the rectangular parallelepiped in FIG. 19 (a). According to FIG. 19 (a), it can be seen that a large amount of B is distributed in the portion where the concentration of Co is low, which was explained with reference to the STEM-EDS image shown in FIG. 17 (b).
  • B is distributed in both the main phase (1-12 phase) and the grain boundary phase (GB), and is particularly unevenly distributed in the grain boundary phase (uneven distribution).
  • GB grain boundary phase
  • the content of B in the grain boundary phase calculated based on the composition profile shown in FIG. 19B was about 10.3 atomic%.
  • the average content of Sm in the grain boundary phase was slightly lower than that in the 1-12 phase, and was about 5.8 atomic%.
  • B is also distributed in the main phase, but its amount is negligibly low.
  • the Co content was about 19.8 atomic% in the central portion of the 1-12 phase, but was about 10.6 atomic% in the grain boundary phase, which is the B-concentrated phase.
  • the overall composition of the membrane was Sm 7.7 Fe 72.1 Co 16.5 B 3.7 (atomic%), and the main phase 1-12 phase.
  • the composition of the amorphous grain boundary phase is Sm 8.0 Fe 71.9 Co 19.8 B 0.3 and Sm 5.8 Fe 73.3 Co 10.6 B 10.3 (both atomic%). )Met.
  • the grain boundary phase is considered to be ferromagnetic.
  • the grain boundary phase can act as a barrier for domain wall movement, which is a factor showing a high coercive force of 1.2T.
  • the film of Example 20 since all the phases were preferentially oriented in the [001] direction on the V base layer, it is considered that 1.50 T of residual magnetization was obtained.
  • Example 20 The thin film of Example 20 was described with reference to the microstructure as described with reference to FIGS. 16 (c) and 16 (d), and with reference to FIGS. 17 (b), 19 (a) and (b). The distribution and composition profile of such constituent elements were also confirmed from the HAADF-STEM image, nanobeam electron diffraction pattern, STEM-EDS image, and analysis results by 3DAP of the thin film of Example 15 above (data not shown).
  • FIG. 20 shows a schematic diagram of the fine structure of the thin films of Examples 19 and 20 derived from the results of the above-mentioned characteristic analysis.
  • the film of Example 19 there may be a second phase having a Sm content partially different from that of the main phase, but in addition to the second phase, it is structurally and structurally clearly distinguished from the main phase 1-12 phase.
  • the film of Example 20 since it is a Sm (Fe, Co) 12 film containing B, anisotropic crystal grains having a ThMn 12 type structure as the main phase (1-12 phase) are formed.
  • the main phase is surrounded by an amorphous grain boundary phase having a certain thickness, and the grain boundary phase is a B-concentrated phase.
  • a columnar 1-12 phase having an average particle size of about 40 to 50 nm is formed by using a Sm (Fe, Co) 12 film containing 3.7 atomic% of B.
  • the 1-12 phase is surrounded by an amorphous grain boundary phase having an average thickness of about 3 nm, and the grain boundary phase has a B concentration of about 10.3 atomic%. It is a chemical phase.
  • the film of Example 20 exhibited a coercive force of 1.2 T, which was not obtained with the conventional Sm (Fe, Co) 12 film containing no B.
  • Example 21 Next, using the same material and film forming apparatus as in Example 20, a sample having a thickness of 100 nm and a B content of 0.5% by volume (Sm (Fe 0.8 Co 0.). 2 ) 12 B 0.5 film) was prepared.
  • the substrate temperature at the time of forming the Sm (Fe 0.8 Co 0.2 ) 12 B layer is 350 ° C., and the temperature conditions after the V cap layer (10 nm) is deposited are set.
  • a total of 9 types of samples were prepared by setting as shown in (a) to (i) below.
  • condition (a) will be a normal process (Normal process), and the conditions (b) to (i) will be Sm (Fe 0.8 Co 0. 2 ) 12
  • the substrate temperature (350 ° C.) at the time of film formation of the B layer those below the temperature ((b) to (e)) are cooled and those above the temperature ((f)).
  • ⁇ (I)) is classified as an annealing condition, and the characteristics of the sample prepared under each condition will be described.
  • FIG. 21 shows the Out-of-Plane XRD pattern of the film obtained under the cooling conditions (Cooling) of the conditions (a) and the conditions (b) to (e).
  • diffraction patterns derived from (002) and (004) (indicated by downward white triangle marks in the figure) were observed, and the (001) plane was strongly oriented ThMn 12 type.
  • the crystal phase of Sm (Fe 0.8 Co 0.2 ) 12 B layer is the main phase, that is, the crystal orientation of the Sm (Fe 0.8 Co 0.2) 12 B layer is preferentially oriented in the [001] direction.
  • no significant change was observed in the peak intensity and position of the main phase.
  • FIG. 22 shows the Out-of-Plane XRD pattern of the film obtained under the conditions (a) and the heating conditions (Annealing) of the conditions (f) to (i).
  • a diffraction pattern derived from (002) and (004) (indicated by a downward white triangle mark in the figure) was observed, and the (001) plane was strongly oriented ThMn 12 type.
  • the crystal phase of Sm (Fe 0.8 Co 0.2 ) 12 B layer is the main phase, that is, the crystal orientation of the Sm (Fe 0.8 Co 0.2) 12 B layer is preferentially oriented in the [001] direction.
  • FIG. 23 shows the in-plane and perpendicular-plane magnetization curves of the film obtained under the cooling conditions (Cooling) of the conditions (a) and the conditions (b) to (e). According to FIG. 23, it was confirmed that all the samples had a coercive force of 11.6 kOe.
  • FIG. 24 shows the in-plane and perpendicular-plane magnetization curves of the film obtained under the conditions (a) and the heating conditions (Annealing) of the conditions (f) to (i).
  • the value of the coercive force is lower than the value (11.6 kOe) obtained in the sample of the condition (a), and the higher the holding temperature, the lower the value.
  • the value was a low result.
  • 25 (a) to 25 (d) show the magnetic characteristics (saturation magnetization, coercive force, residual magnetization ratio at zero magnetic field, and vertical anisotropy) of the samples under the conditions (c) to (i), respectively. Indicated. According to FIG. 25 (a), the saturation magnetization ( Ms ) tended to increase linearly as the holding temperature increased. According to FIG. 25 (b), it was confirmed that the coercive force (H c ) decreases under heating conditions (Annealing) in which the holding temperature is 350 ° C. or higher. According to FIG.
  • the magnet according to the embodiment of the present invention has an excellent coercive force, it can be applied to the field of MEMS (Micro Electro Electrical Systems), the field of energy such as energy harvesting (environmental power generation), the field of medical equipment, and the like.
  • MEMS Micro Electro Electrical Systems
  • the field of energy such as energy harvesting (environmental power generation)
  • the field of medical equipment and the like.
  • it can be preferably used as a motor and a generator used in transportation machines such as automobiles and trains.

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Abstract

La présente invention aborde la question de la fourniture d'un aimant ayant une excellente force coercitive. De plus, la présente invention aborde également le problème de la fourniture d'une membrane, d'un stratifié, d'un moteur, d'un générateur et d'une automobile.　Un aimant selon un mode de réalisation de la présente invention présente une composition globale représentée par la formule 1 : (R1 (1-x)R2 x)aTbMc, (dans la formule, R1<sp /> est au moins un élément choisi dans le groupe constitué par Sm, Pm, Er, Tm, et Yb, R2 est au moins un élément choisi dans le groupe constitué par Zr , Y, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, et Lu, T est au moins un élément choisi dans le groupe constitué par Fe, Co et Ni, M est le bore, x est un nombre de 0 à 0,5, a est un nombre de 6,0 à 13,7 % atomique, c est un nombre de 0 à 12 % atomique (à l'exclusion de 0), et b est un nombre représenté par 100-a-c en % atomique), et a au moins une phase cristalline de type ThMn12.
PCT/JP2020/032132 2019-10-02 2020-08-26 Aimant, membrane, stratifié, moteur, générateur et automobile Ceased WO2021065254A1 (fr)

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JP2025501432A (ja) * 2022-11-22 2025-01-22 中国科学院▲寧▼波材料技▲術▼与工程研究所 粒界相含有サマリウム鉄系希土類永久磁石材料およびその製造方法、並びに応用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04322405A (ja) * 1991-04-22 1992-11-12 Shin Etsu Chem Co Ltd 希土類永久磁石
JPH0565603A (ja) * 1990-10-05 1993-03-19 Hitachi Metals Ltd 鉄−希土類系永久磁石材料およびその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0565603A (ja) * 1990-10-05 1993-03-19 Hitachi Metals Ltd 鉄−希土類系永久磁石材料およびその製造方法
JPH04322405A (ja) * 1991-04-22 1992-11-12 Shin Etsu Chem Co Ltd 希土類永久磁石

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2025501432A (ja) * 2022-11-22 2025-01-22 中国科学院▲寧▼波材料技▲術▼与工程研究所 粒界相含有サマリウム鉄系希土類永久磁石材料およびその製造方法、並びに応用

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