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WO2010026703A1 - Magnetoresistive element, method for manufacturing same, and storage medium used in the manufacturing method - Google Patents

Magnetoresistive element, method for manufacturing same, and storage medium used in the manufacturing method Download PDF

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Publication number
WO2010026703A1
WO2010026703A1 PCT/JP2009/003871 JP2009003871W WO2010026703A1 WO 2010026703 A1 WO2010026703 A1 WO 2010026703A1 JP 2009003871 W JP2009003871 W JP 2009003871W WO 2010026703 A1 WO2010026703 A1 WO 2010026703A1
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layer
atoms
substrate
ferromagnetic layer
polycrystalline
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French (fr)
Japanese (ja)
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栗林正樹
ジュリアント ジャヤプラウィラダビッド
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Canon Anelva Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y25/00—Nanomagnetism, e.g. magnetoimpedance, anisotropic magnetoresistance, giant magnetoresistance or tunneling magnetoresistance
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • 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
    • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
    • C23C14/568—Transferring the substrates through a series of coating stations
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/127—Structure or manufacture of heads, e.g. inductive
    • G11B5/31—Structure or manufacture of heads, e.g. inductive using thin films
    • G11B5/3163—Fabrication methods or processes specially adapted for a particular head structure, e.g. using base layers for electroplating, using functional layers for masking, using energy or particle beams for shaping the structure or modifying the properties of the basic layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/127—Structure or manufacture of heads, e.g. inductive
    • G11B5/33—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only
    • G11B5/39—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only using magneto-resistive devices or effects
    • G11B5/3903—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only using magneto-resistive devices or effects using magnetic thin film layers or their effects, the films being part of integrated structures
    • G11B5/3906—Details related to the use of magnetic thin film layers or to their effects
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/127—Structure or manufacture of heads, e.g. inductive
    • G11B5/33—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only
    • G11B5/39—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only using magneto-resistive devices or effects
    • G11B5/3903—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only using magneto-resistive devices or effects using magnetic thin film layers or their effects, the films being part of integrated structures
    • G11B5/3906—Details related to the use of magnetic thin film layers or to their effects
    • G11B5/3909—Arrangements using a magnetic tunnel junction
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/32—Spin-exchange-coupled multilayers, e.g. nanostructured superlattices
    • H01F10/324—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer
    • H01F10/3254—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer the spacer being semiconducting or insulating, e.g. for spin tunnel junction [STJ]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/32—Spin-exchange-coupled multilayers, e.g. nanostructured superlattices
    • H01F10/324—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer
    • H01F10/3295—Spin-exchange coupled multilayers wherein the magnetic pinned or free layers are laminated without anti-parallel coupling within the pinned and free layers
    • 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
    • H01F41/14—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 applying magnetic films to substrates
    • H01F41/30—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 applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE]
    • H01F41/302—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 applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE] for applying spin-exchange-coupled multilayers, e.g. nanostructured superlattices
    • H01F41/305—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 applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE] for applying spin-exchange-coupled multilayers, e.g. nanostructured superlattices applying the spacer or adjusting its interface, e.g. in order to enable particular effect different from exchange coupling
    • H01F41/307—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 applying magnetic films to substrates for applying nanostructures, e.g. by molecular beam epitaxy [MBE] for applying spin-exchange-coupled multilayers, e.g. nanostructured superlattices applying the spacer or adjusting its interface, e.g. in order to enable particular effect different from exchange coupling insulating or semiconductive spacer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/10—Magnetoresistive devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/80—Constructional details
    • H10N50/85—Materials of the active region
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F10/00—Thin magnetic films, e.g. of one-domain structure
    • H01F10/32—Spin-exchange-coupled multilayers, e.g. nanostructured superlattices
    • H01F10/324—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer
    • H01F10/3268—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer the exchange coupling being asymmetric, e.g. by use of additional pinning, by using antiferromagnetic or ferromagnetic coupling interface, i.e. so-called spin-valve [SV] structure, e.g. NiFe/Cu/NiFe/FeMn
    • H01F10/3272—Exchange coupling of magnetic film pairs via a very thin non-magnetic spacer, e.g. by exchange with conduction electrons of the spacer the exchange coupling being asymmetric, e.g. by use of additional pinning, by using antiferromagnetic or ferromagnetic coupling interface, i.e. so-called spin-valve [SV] structure, e.g. NiFe/Cu/NiFe/FeMn by use of anti-parallel coupled [APC] ferromagnetic layers, e.g. artificial ferrimagnets [AFI], artificial [AAF] or synthetic [SAF] anti-ferromagnets

Definitions

  • the present invention relates to a magnetic reproducing head of a magnetic disk drive, a storage element of a magnetic random access memory, and a magnetoresistive element used for a magnetic sensor, preferably a tunnel magnetoresistive element (in particular, a spin valve tunnel magnetoresistive element). Further, the present invention relates to a method of manufacturing a magnetoresistive element and a storage medium used in the method.
  • Patent documents 1 to 6 and non-patent documents 1 and 2 disclose TMR (tunneling magnetoresistance) effect elements comprising a tunnel barrier layer and first and second ferromagnetic layers disposed on both sides thereof. Is described.
  • An alloy containing Co atoms, Fe atoms and B atoms (hereinafter referred to as a CoFeB alloy) is used as the first and / or second ferromagnetic layers constituting this element.
  • the CoFeB alloy layer a polycrystalline structure is described.
  • JP 2002-204004 A WO 2005/088745 pamphlet JP 2003-304010 A JP, 2006-080116, A US Patent Application Publication No. 2006/0056115 U.S. Pat. No. 7,252,852
  • An object of the present invention is to provide a magnetoresistive element having a further improved MR ratio as compared with the prior art, a method of manufacturing the same, and a storage medium used in the method of manufacturing.
  • the first aspect of the present invention is a substrate, A tunnel barrier layer located above the substrate, A crystalline first ferromagnetic layer formed of an alloy containing Co atoms, Fe atoms and B atoms, disposed on the first surface side of the tunnel barrier layer located on the substrate side, wherein the film is a film of the layer A crystalline first ferromagnetic layer in which the content of B atoms on the substrate side in the thickness direction is larger than the content of B atoms on the first surface side, and
  • the magnetoresistive element is characterized by including a crystalline second ferromagnetic layer disposed on the second surface side of the tunnel barrier layer located opposite to the first surface.
  • the second of the present invention is a substrate, A tunnel barrier layer located above the substrate, A crystalline first ferromagnetic layer disposed on the first surface side of the tunnel barrier layer located on the substrate side; A crystalline second ferromagnetic layer formed of an alloy containing Co atoms, Fe atoms and B atoms, disposed on the second surface side of the tunnel barrier layer located on the side opposite to the first surface; And a crystalline second ferromagnetic layer having a value in which the content of B atoms on the opposite surface side to the second surface is greater than the content of B atoms on the second surface in the thickness direction of the layer.
  • a magnetoresistive element characterized by having
  • the crystalline first ferromagnetic layer is made of an alloy containing Co atoms, Fe atoms and B atoms, and containing B atoms on the substrate side in the film thickness direction of the layer. It is preferred that the amount has a value larger than the content of B atoms on the first surface side.
  • the tunnel barrier layer is preferably made of crystalline magnesium oxide or crystalline boron magnesium oxide.
  • the third of the present invention is the step of preparing a substrate, In the film thickness direction, the content of B atoms in the region on the substrate side is larger than the content of B atoms in the region opposite to the substrate side in the film thickness direction by sputtering, Co atoms, Fe Depositing a first ferromagnetic layer of amorphous structure comprising an alloy containing atoms and B atoms on the substrate, Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the amorphous structure using a sputtering method; Forming a second ferromagnetic layer on the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide layer using a sputtering method; A method of manufacturing a magnetoresistive element comprising the step of crystallizing the first ferromagnetic layer of the amorphous structure, It is preferable that the second ferromagnetic layer formed by the sputtering method have an amorphous
  • the fourth of the present invention is the step of preparing a substrate, Forming a first ferromagnetic layer of an amorphous structure on the substrate using a sputtering method; Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the amorphous structure using a sputtering method; The content of B atoms in the region opposite to the substrate side in the film thickness direction by sputtering is larger than the content of B atoms in the region on the substrate side, Co atoms, Fe atoms And depositing a second ferromagnetic layer of an amorphous structure made of an alloy containing at least one of B and B on the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide layer, and A method of manufacturing a magnetoresistive element, comprising the step of crystallizing the first ferromagnetic layer of the amorphous structure and the second ferromagnetic layer of the amorphous structure.
  • the content of B atoms in the region on the substrate side in the film thickness direction is the content of B atoms in the region opposite to the substrate side in the film thickness direction using the step of preparing the substrate Depositing a first ferromagnetic layer of an amorphous structure formed of an alloy containing Co atoms, Fe atoms and B atoms having a large value as compared with the above, and forming the amorphous layer using a sputtering method Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the structure, using the sputtering method, forming the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide And controlling the production of the magnetoresistive element by using the step of forming a second ferromagnetic layer on the first layer and the step of crystallizing the first ferromagnetic layer of the amorphous structure.
  • a storage medium characterized by storing a ram, The second
  • a sixth aspect of the present invention is a step of preparing a substrate, a step of forming a first ferromagnetic layer of an amorphous structure on the substrate using sputtering, and a step of preparing the amorphous structure using sputtering.
  • the polycrystalline structure of the second ferromagnetic layer of the amorphous structure comprising an alloy containing Co atoms, Fe atoms and B atoms having a larger value of the atomic content compared to the B atomic content of the region on the substrate side Forming a film on the magnesium oxide layer or the polycrystalline magnesium boron layer, and crystallizing the first ferromagnetic layer of the amorphous structure and the second ferromagnetic layer of the amorphous structure That process using a storage medium characterized by storing a control program for executing the manufacture of the magnetoresistive element.
  • the MR ratio achieved by the conventional tunnel magnetoresistive effect element (hereinafter referred to as TMR element) can be significantly improved.
  • the present invention can be mass-produced and highly practical. Therefore, by using the present invention, a memory element of MRAM (Magnetoresistive Random Access Memory: ferroelectric memory) capable of achieving ultra-high integration can be efficiently provided. .
  • MRAM Magneticoresistive Random Access Memory: ferroelectric memory
  • FIG. 6 is a cross-sectional view of another tunnel barrier layer of the present invention. It is a model perspective view of the column-like crystal structure which concerns on the magnetoresistive element of this invention. It is sectional drawing of the TMR element of the other structure of the magnetoresistive element of this invention.
  • the magnetoresistive element of the present invention has a substrate, a crystalline first ferromagnetic layer, a tunnel barrier layer, and a crystalline second ferromagnetic layer. Then, an alloy containing Co atoms, Fe atoms, B atoms in which the first ferromagnetic layer and / or the second ferromagnetic layer has a content of B atoms on the side of the tunnel barrier layer smaller than that on the opposite side (hereinafter referred to as , CoFeB)).
  • At least the first ferromagnetic layer and / or the second ferromagnetic layer is a CoFeB layer having a high B atom content (hereinafter referred to as Brich), and a Brich layer It is composed of a CoFeB layer having a low B atom content (hereinafter referred to as Bpoor).
  • Brich a CoFeB layer having a high B atom content
  • Bpoor a CoFeB layer having a low B atom content
  • a crystalline magnesium oxide (hereinafter referred to as Mg oxide) layer or a crystalline boron magnesium oxide (hereinafter referred to as BMg oxide) layer is preferably used.
  • the substrate surface side of the tunnel barrier layer is the first surface side, and the surface side opposite to the first surface is the second surface side.
  • FIG. 1 shows an example of the laminated structure of the magnetoresistive element 10 of the present invention, and shows the laminated structure of the magnetoresistive element 10 using the TMR element 12.
  • a multilayer film of nine layers including the TMR element 12 is formed on the substrate 11.
  • the nine-layer multilayer film has a multilayer film structure from the lowermost first layer (Ta layer) to the uppermost ninth layer (Ru layer).
  • a PtMn layer 14, a CoFe layer 15, a nonmagnetic Ru layer 16, a CoFeB (Brich) layer 1211, a CoFeB (Bpoor) layer 1212 and a nonmagnetic Mg oxide or BMg oxide layer 122 are stacked.
  • a CoFeB (Bpoor) layer 1232, a CoFeB (Brich) layer 1231, a nonmagnetic Ta layer 17 and a nonmagnetic Ru layer 18 are stacked in this order.
  • the numerical values in parentheses in each layer in the drawing indicate the thickness of each layer, and the unit is nm.
  • the said thickness is an example, Comprising: It is not limited to this.
  • the PtMn layer is an alloy layer containing Pt atoms and Mn atoms
  • the CoFe layer is an alloy layer containing Co atoms and Fe atoms.
  • the crystalline first ferromagnetic layer according to the present invention in the stack corresponds to the CoFeB (Bpoor) layer 1212 and the CoFeB (Brich) layer 1211.
  • the crystalline second ferromagnetic layer corresponds to the CoFeB (Brich) layer 1231 and the CoFeB (Bpoor) layer 1232.
  • the first and second ferromagnetic layers are not limited to the two-layer structure.
  • a TMR element 12 is composed of a Brich ferromagnetic layer 1211, a Bpoor ferromagnetic layer 1212, a tunnel barrier layer 122, a Bpoor ferromagnetic layer 1232, and a Brich ferromagnetic layer 1231.
  • 13 is a lower electrode layer (base layer) of the first layer (Ta layer), and 14 is an antiferromagnetic layer of the second layer (PtMn layer).
  • 15 is a ferromagnetic layer of the third layer (CoFe layer), and 16 is a nonmagnetic layer for exchange coupling of the fourth layer (Ru layer).
  • the fifth layer is a laminate formed of the ferromagnetic layers 1211 and 1212 made of a crystalline CoFeB layer.
  • the B atom content (hereinafter referred to as B content) of the crystalline CoFeB layer 1211 is set to a value larger than the B content of the crystalline CoFeB layer 1212 It is done.
  • the B content in the crystalline CoFeB layers 1211 and 1212 constituting the fifth layer may be slope-distributed so that the B content becomes larger on the substrate 11 side in the film thickness direction of the fifth layer. .
  • the B content in the crystalline CoFeB layer 1211 is preferably 10 atomic% to 60 atomic%, and more preferably in the range of 15 atomic% to 50 atomic%.
  • the B content in the crystalline CoFeB layer 1212 is preferably set in the range of 0.1 atomic% to 40 atomic%, more preferably 0.5 atomic% to 10 atomic%.
  • the B content in the crystalline CoFeB layer 1212 / B content in the crystalline CoFeB layer 1211 is 1/5 to 1/100, preferably 1/10 to 1/50, in atomic% (atomic ratio). Can be set to
  • the crystalline CoFeB layers 1211 and 1212 constituting the fifth layer can be formed by sputtering using a CoFeB target whose B content is adjusted to be in the above range.
  • the B content in the above-described gradient distribution of B atoms can be determined by introducing a boron atom-containing gas such as monoborane (BH 3 ) gas or diborane (B 2 H 6 ) gas during sputtering using a CoFeB target. It is achieved by varying on the time axis.
  • a boron atom-containing gas such as monoborane (BH 3 ) gas or diborane (B 2 H 6 ) gas
  • the layer formed of the third layer 15, the fourth layer 16 and the fifth layers 121 and 1212 described above is the magnetization fixed layer 19.
  • the substantially magnetization fixed layer is the ferromagnetic layers 1211 and 1212 consisting of the crystalline CoFeB layer of the fifth layer.
  • Reference numeral 122 denotes a tunnel barrier layer of a sixth layer (polycrystalline BMg oxide or polycrystalline Mg oxide), which is an insulating layer.
  • the tunnel barrier layer 122 used in the present invention may be a single polycrystalline BMg oxide layer or a polycrystalline Mg oxide layer.
  • a crystalline BMg layer or Mg layer 1222 such as microcrystalline, polycrystalline or single crystal is provided in a polycrystalline BMg oxide layer or a polycrystalline Mg oxide layer. It is good.
  • the BMg layer is an alloy layer composed of B atoms and Mg atoms, and the Mg layer is a metal layer composed of Mg metal.
  • the tunnel barrier layer has a laminated structure in which polycrystalline BMg oxide layers or polycrystalline Mg oxide layers 1221 and 1223 are provided on both sides of the BMg layer or Mg layer 1222.
  • the BMg layer or the Mg layer 1222 may be a plurality of layers, and may be a plurality of layers, and may be alternately stacked with the BMg oxide layer or the Mg oxide layer.
  • FIG. 8 is an example of another TMR element 12 of the present invention.
  • Reference numerals 12, 1211, 1212, 1231 and 1232 in FIG. 8 are the same members as those in FIG.
  • the tunnel barrier layer 122 is a laminated film comprising a BMg oxide layer or Mg oxide layer 82 and BMg layers or Mg layers 81 and 83 on both sides of the layer 82.
  • the layer 81 may be a BMg layer and the layer 83 may be an Mg layer, or the layer 81 may be an Mg layer and the layer 83 may be a BMg layer.
  • the use of layer 81 is omitted, and layer 82 can be placed adjacent to crystalline ferromagnetic layer 1232.
  • the use of layer 83 can be omitted and layer 82 can be placed adjacent to crystalline ferromagnetic layer 1212.
  • FIG. 7 is a schematic perspective view of a polycrystalline structure composed of an aggregate 71 of column-like crystals 72 in the BMg oxide layer or the Mg oxide layer.
  • the polycrystalline structure also includes the structure of a polycrystalline-amorphous mixed region including a partially amorphous region in the polycrystalline region.
  • the column crystal is preferably a single crystal in which (001) crystal planes are preferentially oriented in the film thickness direction in each column.
  • the average diameter of the column-shaped single crystal is preferably 10 nm or less, more preferably 2 nm to 5 nm, and the film thickness is preferably 10 nm or less, more preferably 0.5 nm. To 5 nm.
  • the BMg oxide used in the present invention has a general formula B x Mg y O z (0.7 ⁇ Z / (X + Y) ⁇ 1.3, preferably 0.8 ⁇ Z / (X + Y) ⁇ It is indicated by 1.0).
  • B x Mg y O z 0.7 ⁇ Z / (X + Y) ⁇ 1.3, preferably 0.8 ⁇ Z / (X + Y) ⁇ It is indicated by 1.0).
  • a stoichiometric amount of BMg oxide a high MR ratio can be obtained even with an oxygen deficient BMg oxide.
  • Mg oxide used in the present invention has a general formula of Mg y O z (0.7 ⁇ Z / Y ⁇ 1.3, preferably 0.8 ⁇ Z / Y ⁇ 1.0) It is indicated by.
  • the polycrystalline Mg oxide or polycrystalline BMg oxide used in the present invention contains various trace components such as Zn atom, C atom, Al atom, Ca atom, Si atom, etc. in the range of 10 ppm to 100 ppm. be able to.
  • the seventh layer is a laminate formed of ferromagnetic layers 1231 and 1232 made of a crystalline CoFeB layer.
  • the B content of the crystalline CoFeB layer 1231 is set to a value larger than the B content of the crystalline CoFeB layer 1232.
  • the seventh layer can also function as a magnetization free layer.
  • the B content in the crystalline CoFeB layers 1231 and 1232 constituting the seventh layer is such that the B content is smaller on the side closer to the substrate 11 and larger on the side farther from the substrate 11 in the film thickness direction of the seventh layer.
  • the slope may be distributed.
  • the B content in the crystalline CoFeB layer 1231 is preferably set in the range of 10 atomic% to 60 atomic%, more preferably 15 atomic% to 50 atomic%.
  • the content of the crystalline CoFeB layer 1212 is preferably set in the range of 0.1 atomic% to 40 atomic%, more preferably 0.5 atomic% to 10 atomic%.
  • the B content in the crystalline CoFeB layer 1232 / the B content in the crystalline CoFeB layer 1211 is preferably 1/5 to 1/100, more preferably 1/10 to 1 in atomic% (atomic ratio). It is set to / 50.
  • the crystalline CoFeB layers 1231 and 1232 constituting the seventh layer can be formed by sputtering using a CoFeB target whose B content is adjusted to be in the above range.
  • the B content in the gradient distribution of B atoms described above refers to the introduction amount of a boron atom-containing gas such as monoborane (BH 3 ) gas or diborane (B 2 H 6 ) gas during sputtering using a CoFeB target. It is achieved by making the time axis variable.
  • the above-mentioned crystalline CoFeB layers 1211, 1212, 1231 and 1232 may have the same crystal structure as the column-like crystal structure 71 shown in FIG.
  • the crystalline CoFeB layers 1212 and 1232 are preferably provided adjacent to the tunnel barrier layer 122 located in the middle. In the manufacturing apparatus, these three layers are sequentially stacked without breaking the vacuum.
  • Reference numeral 17 denotes an electrode layer of an eighth layer (Ta layer).
  • the eighth layer may be removed from the magnetoresistive element when used as a hard mask.
  • FIG. 2 is a schematic plan view of an apparatus for manufacturing the magnetoresistive element 10.
  • This apparatus is an apparatus capable of producing a multilayer film including a plurality of magnetic layers and a nonmagnetic layer, and mass production type sputtering film formation It is an apparatus.
  • the magnetic multilayer film manufacturing apparatus 200 shown in FIG. 2 is a cluster type manufacturing apparatus, and includes three film forming chambers based on the sputtering method.
  • a transfer chamber 202 including a robot transfer device (not shown) is installed at a central position.
  • Two load lock / unload lock chambers 205 and 206 are provided in the transfer chamber 202 of the manufacturing apparatus 200 for manufacturing the magnetoresistance element, and loading and unloading of the substrate (for example, silicon substrate) 11 is performed by each of them. .
  • the tact time can be shortened, and the magnetoresistive element can be manufactured with high productivity.
  • the manufacturing apparatus 200 for manufacturing a magnetoresistive element three deposition magnetron sputtering chambers 201A to 201C and one etching chamber 203 are provided around the transfer chamber 202.
  • the required surface of the TMR element 10 is etched.
  • a gate valve 204 which can be opened and closed is provided between each of the chambers 201A to 201C and 203 and the transfer chamber 202.
  • Each of the chambers 201A to 201C and 202 is provided with an evacuation mechanism, a gas introduction mechanism, a power supply mechanism, and the like (not shown).
  • the respective films from the first layer to the ninth layer described above can be sequentially deposited on the substrate 11 using high frequency sputtering without breaking the vacuum. it can.
  • cathodes 31 to 35, 41 to 45, 51 to 54 disposed on suitable circumferences are disposed on the ceilings of the film forming magnetron sputtering chambers 201A to 201C, respectively.
  • the substrate 11 is disposed on a substrate holder located coaxially with the circumference.
  • high frequency power such as radio frequency (RF frequency) is applied to the cathodes 31 to 35, 41 to 45, 51 to 54 from the power input means 207A to 207C.
  • RF frequency radio frequency
  • power in the range of 0.3 MHz to 10 GHz, preferably in the range of 5 MHz to 5 GHz and in the range of 10 W to 500 W, preferably 100 W to 300 W can be used.
  • a CoFeB (Bpoor) target is attached to the cathode 31, a PtMn target to the cathode 32, and a CoFeB (Brich) target to the cathode 33, respectively. Further, a CoFe target is attached to the cathode 34 and a Ru target is attached to the cathode 35.
  • a BMg oxide target or a BMg target is attached to the cathode 41.
  • a reactive sputtering chamber (not shown) for performing reactive sputtering with an oxidizing gas can be connected to the transfer chamber 202.
  • polycrystalline BMg oxide is formed in an oxidation chamber (not shown) using an oxidizing gas (eg, oxygen gas, ozone gas, water vapor, etc.) It can be chemically changed into layers.
  • an oxidizing gas eg, oxygen gas, ozone gas, water vapor, etc.
  • a BMg oxide target can be attached to the cathode 41 and a BMg target can be attached to the cathode 42. At this time, targets can not be attached to the cathodes 43 to 45, and BMg oxide targets or BMg targets can also be attached to the cathodes 43 to 45.
  • a CoFeB target is attached to the cathode 51, a Ta target for the Ta layer of the first layer is attached to the cathode 52, a Ru target is attached to the cathode 53, and a Ta target for the eighth Ta layer is attached to the cathode 54. Be done.
  • the in-plane direction of each of the targets mounted on the cathodes 31 to 35, 41 to 45, and 51 to 54 and the in-plane direction of the substrate are preferably arranged non-parallel to each other.
  • the non-parallel arrangement it is possible to deposit a magnetic film and a nonmagnetic film with the same composition as the target composition with high efficiency by sputtering while rotating the target whose diameter is smaller than the substrate diameter.
  • both can be arranged non-parallel so that the crossing angle between the target central axis and the substrate central axis is 45 ° or less, preferably 5 ° to 30 °.
  • the substrate at this time can use a rotational speed of 10 rpm to 500 rpm, preferably, a rotational speed of 50 rpm to 200 rpm.
  • FIG. 3 is a block diagram of a film forming apparatus used in the present invention.
  • a transfer chamber 301 corresponds to the transfer chamber 202 in FIG. 2
  • a film forming chamber 302 corresponds to the film forming magnetron sputtering chamber 201A
  • a film forming chamber 303 corresponds to the film forming magnetron sputtering chamber 201B.
  • Reference numeral 304 denotes a film forming chamber corresponding to the film forming magnetron sputtering chamber 201C
  • 305 denotes a load lock and unload lock chamber corresponding to the load lock and unload lock chambers 205 and 206.
  • reference numeral 306 denotes a central processing unit (CPU) incorporating the storage medium 312.
  • Reference numerals 309 to 311 are bus lines connecting the CPU 306 and the processing chambers 301 to 305, and control signals for controlling the operations of the processing chambers 301 to 305 are transmitted from the CPU 306 to the processing chambers 301 to 305.
  • a substrate (not shown) in the load lock / unload lock chamber 305 is carried out to the transfer chamber 301.
  • the substrate unloading step is calculated based on the control program stored in the storage medium 312 by the CPU 306.
  • a control signal based on the calculation result is implemented by controlling the execution of various devices mounted on the load lock / unload lock chamber 305 and the transfer chamber 301 through the bus lines 307 and 311. Examples of the various devices include a gate valve (not shown), a robot mechanism, a transport mechanism, a drive system, etc., and the storage medium 312 corresponds to the storage medium of the present invention described above.
  • the substrate transported to the transport chamber 301 is carried out to the film forming chamber 302.
  • the first layer 13 of FIG. 1 is deposited on the substrate carried into the deposition chamber 302.
  • control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 are transferred to the transport chamber 301 and the deposition chamber 302 through the bus lines 307 and 310. It is implemented by controlling the execution.
  • a power input mechanism to a cathode not shown
  • a substrate rotation mechanism a gas introduction mechanism
  • an exhaust mechanism a gate valve
  • a robot mechanism a transport mechanism, a drive system, etc.
  • the substrate is returned to the transfer chamber 301, and then carried from the transfer chamber 301 to the film formation chamber 302, and the second layer 14 and the third layer in FIG. 15, the fourth layer 16 and the fifth layers 1211 and 1212 are sequentially stacked.
  • the CoFeB layers of the fifth layers 1211 and 1212 at this stage preferably have an amorphous structure, but both or one of the CoFeB layers of the fifth layers 1211 and 1212 at this stage are polycrystalline. It may be a structure.
  • control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 execute the various devices mounted on the transfer chamber 301 and the film forming chamber 302 through the bus lines 307 and 308. It is implemented by controlling. Examples of the various devices include a power input mechanism to a cathode (not shown), a substrate rotation mechanism, a gas introduction mechanism, an exhaust mechanism, a gate valve, a robot mechanism, a transport mechanism, a drive system, and the like.
  • the substrate having the laminated film up to the fifth layer is temporarily returned to the transfer chamber 301 and then carried into the film forming chamber 303.
  • a polycrystalline Mg oxide layer is formed as the sixth layer 122 on the amorphous CoFeB layers of the fifth layers 1211 and 1212.
  • control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 execute various devices mounted on the transfer chamber 301 and the film formation chamber 303 through the bus lines 307 and 309.
  • Is implemented by controlling the Examples of the various devices include a power input mechanism to a cathode (not shown), a substrate rotation mechanism, a gas introduction mechanism, an exhaust mechanism, a gate valve, a robot mechanism, a transport mechanism, a drive system, and the like.
  • the substrate having the laminated film up to the sixth layer 122 is once returned again to the transfer chamber 301, and is then carried into the film forming chamber 304.
  • the seventh layers 1231 and 1232 and the eighth layer 17 and the ninth layer 18 are sequentially stacked on the polycrystalline Mg oxide layer of the sixth layer 122.
  • the CoFeB layers of the seventh layers 1231 and 1232 at this stage preferably have an amorphous structure, but both the seventh layers 1231 and 1232 at this stage or one CoFeB layer have a polycrystalline structure. It is also good.
  • control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 execute various devices mounted on the transfer chamber 301 and the film forming chamber 304 through the bus lines 307 and 310.
  • Is implemented by controlling the Examples of the various devices include a power input mechanism to a cathode (not shown), a substrate rotation mechanism, a gas introduction mechanism, an exhaust mechanism, a gate valve, a robot mechanism, a transport mechanism, a drive system, and the like.
  • the storage medium 312 is a storage medium of the present invention, and the storage medium stores a control program for executing the manufacture of the magnetoresistive element using the following steps.
  • Step of preparing a substrate Step of depositing a first ferromagnetic layer of amorphous structure
  • the first magnetic layer and / or the second magnetic layer is composed of Brich and Bpoor CoFeB layers
  • a polycrystalline Mg oxide layer or a polycrystalline BMg oxide layer is formed in the corresponding film forming step.
  • the side is set to be Bpoor.
  • Examples of the storage medium 312 used in the present invention include hard disk media, magneto-optical disk media, floppy (registered trademark) disk media, nonvolatile memories such as flash memory and MRAM, and the like, including media capable of storing programs. It is
  • a laminate comprising the first to ninth layers
  • the membrane can be loaded into an annealing furnace (not shown).
  • the storage medium 312 stores a control program for performing the process in the annealing furnace. Therefore, according to a control signal obtained by the operation of the CPU 306 based on the control program, various devices in the annealing furnace (for example, a heater mechanism, an exhaust mechanism, a transport mechanism, etc. not shown) are controlled to execute the annealing process. Can.
  • any of the fifth layers 1211 and 1212 and the seventh layers 1231 and 1232 may be replaced with the above-described CoFeB layer, and another alloy layer may be used.
  • a B-containing polycrystalline ferromagnetic layer such as a CoFeTaZrB layer, a CoTaZrB alloy layer, a CoFeNbZrB layer, a CoFeZrB layer, a FeTaCB layer, an FeTaNB layer, or an FeCB layer can be used.
  • the above-described polycrystalline ferromagnetic layer can be further stacked on a CoFeB layer formed of two layers to form a stacked structure of three or more layers.
  • a Rh layer or an Ir layer can be used.
  • alloy layers such as IrMn layer, IrMnCr layer, NiMn layer, PdPtMn layer, RuRhMn layer and OsMn layer are preferably used.
  • the film thickness is preferably 10 to 30 nm.
  • the polycrystalline CoFe layer 15 located on the substrate side can be formed in a polycrystalline state on the PtMn layer 14 of the second layer by the sputtering method.
  • the present inventors confirmed that the CoFeB layer following the film formation of the polycrystalline CoFe layer 15 has an amorphous structure immediately after the sputtering film formation (before the annealing step).
  • the present invention by annealing a CoFeB layer having an amorphous structure, phase conversion to an epitaxial polycrystalline structure can be achieved.
  • FIG. 4 is a schematic view of an MRAM 401 using the magnetoresistive element of the present invention as a memory element.
  • 402 is a memory element of the present invention
  • 403 is a word line
  • 404 is a bit line.
  • Each of the large number of memory elements 402 is arranged at each intersection position of the plurality of word lines 403 and the plurality of bit lines 404, and is arranged in a lattice-like positional relationship.
  • Each of the multiple memory elements 402 can store one bit of information.
  • FIG. 5 is an equivalent circuit diagram configured by TMR element 10 storing 1-bit information at the intersection position of word line 403 and bit line 404 of MRAM 401, and transistor 501 having a switch function.
  • the magnetoresistive element shown in FIG. 1 was manufactured using the film forming apparatus shown in FIG.
  • the film formation conditions of the TMR element 12 which is the main part are as follows.
  • the CoFeB layer 1211 used a target having a CoFeB composition ratio (atomic: atomic ratio) of 60/20/20.
  • the CoFeB layer 1212 used a target having a CoFeB composition ratio (atomic: atomic ratio) of 65/25/5.
  • the CoFeB layers 1211 and 1212 use Ar gas as a sputtering gas, and set the pressure to 0.03 Pa.
  • the CoFeB layers 1211 and 1212 were formed by magnetron DC sputtering (chamber 201A) at a sputtering rate of 0.64 nm / sec.
  • the CoFeB layers (CoFeB layers 1211 and 1212) at this time had an amorphous structure.
  • a sputtering apparatus (chamber 201B).
  • a target having a BMgO composition ratio (atomic: atomic ratio) of 25/25/50 was used, Ar gas was used as a sputtering gas, and the pressure was set to 0.2 Pa within a pressure range of 0.01 to 0.4 Pa in a preferable range.
  • the tunnel barrier layer 122 which is a BMg oxide layer of the sixth layer was formed by magnetron RF sputtering (13.56 MHz) under these conditions.
  • the BMg oxide layer (tunnel barrier layer 122) had a polycrystalline structure composed of aggregates of columnar crystals.
  • the film-forming rate of magnetron RF sputtering (13.56 MHz) at this time was 0.14 nm / sec.
  • ferromagnetic layers 1231 and 1232 as the magnetization free layer (the seventh CoFeB layer) were formed.
  • the CoFeB layers 1231 and 1232 were formed using Ar gas as a sputtering gas, and the pressure was set to 0.03 Pa.
  • the CoFeB layers 1231 and 1232 were formed by magnetron DC sputtering (chamber 201A) at a sputtering rate of 0.64 nm / sec.
  • the CoFeB layer 1231 uses a target having a CoFeB composition ratio (atomic: atomic ratio) 55/15/30
  • the CoFeB layer 1232 uses a target having a CoFeB composition ratio (atomic: atomic ratio) 65/25/5. It was.
  • the CoFeB layers 1231 and 1232 had an amorphous structure.
  • the deposition rate of the BMg oxide film was 0.14 nm / sec, but there is no problem if the deposition rate is in the range of 0.01 nm to 1.0 nm / sec.
  • the sputtering process was performed in each of the chambers 201A, 201B and 201C to complete the lamination, and the magnetoresistive element 10 was annealed in a heat treatment furnace at about 300 ° C. and 4 hours in a magnetic field of 8 kOe.
  • the CoFeB layers 1211, 1212, 1231, and 1232 which are the fifth and seventh layers of the amorphous structure have a polycrystalline structure including the aggregate 71 of the column-like crystals 72 illustrated in FIG. It was done.
  • the magnetoresistive element 10 can act as a magnetoresistive element having a TMR effect. Further, by this annealing step, a predetermined magnetization is given to the antiferromagnetic layer 14 which is the PtMn layer of the second layer.
  • the MR ratio of the magnetoresistive element of the example and the magnetoresistive element of the comparative example was measured and compared, the MR ratio of the magnetoresistive element of the example was compared with the MR ratio of the magnetoresistive element of the comparative example. It has been improved by 2 times to 1.5 times or more.
  • the MR ratio is a parameter related to the magnetoresistance effect in which the electric resistance of the film changes as the magnetization direction of the magnetic film or magnetic multilayer film changes in response to an external magnetic field, and the rate of change of the electric resistance Rate (MR ratio).
  • a magnetoresistive element is formed in the same manner as the sixth embodiment except that a polycrystalline Mg oxide layer is used.
  • MR ratio was measured.
  • a target a target having an MgO composition ratio (atomic: atomic ratio) of 50/50 was used. As a result, an MR ratio higher than that of the above-described comparative example was obtained.
  • Magnetoresistance element 11: substrate, 12: TMR element, 1211: CoFeB (Brich) ferromagnetic layer (fifth layer), 1212: CoFeB (Bpoor) ferromagnetic layer (fifth layer), 122: tunnel Barrier layer (sixth layer), 1231: CoFeB (Brich) ferromagnetic layer (seventh layer; magnetization free layer), 1232: CoFeB (Bpoor) ferromagnetic layer (seventh layer; magnetization free layer), 13: Lower electrode layer (first layer; base layer), 14: antiferromagnetic layer (second layer), 15: ferromagnetic layer (third layer), 16: nonmagnetic layer for exchange coupling (fourth layer) , 17: upper electrode layer (eighth layer), 18: hard mask layer (ninth layer), 19: magnetization fixed layer, 200: magnetoresistive element manufacturing apparatus, 201A to 201C: film forming chamber, 202: transfer chamber, 203: etching chamber,

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Abstract

A magnetoresistive element having a higher MR ratio than conventional magnetoresistive elements, and a method for manufacturing the magnetoresistive element. The magnetoresistive element comprises a substrate, a first ferromagnetic layer, a tunnel barrier layer and a second ferromagnetic layer.  The first ferromagnetic layer and/or the second ferromagnetic layer is composed of an alloy layer containing Co atoms, Fe atoms and B atoms, wherein the B atom content on the tunnel barrier layer side is lower than that on the opposite side.

Description

磁気抵抗素子とその製造方法、該製造方法に用いる記憶媒体Magnetoresistive element, method of manufacturing the same, storage medium used in the method of manufacturing

　本発明は、磁気ディスク駆動装置の磁気再生ヘッド、磁気ランダムアクセスメモリの記憶素子及び磁気センサーに用いられる磁気抵抗素子、好ましくは、トンネル磁気抵抗素子（特に、スピンバルブ型トンネル磁気抵抗素子）に関する。さらに、磁気抵抗素子の製造方法と、該製造方法に用いる記憶媒体に関する。 The present invention relates to a magnetic reproducing head of a magnetic disk drive, a storage element of a magnetic random access memory, and a magnetoresistive element used for a magnetic sensor, preferably a tunnel magnetoresistive element (in particular, a spin valve tunnel magnetoresistive element). Further, the present invention relates to a method of manufacturing a magnetoresistive element and a storage medium used in the method.

　特許文献１乃至特許文献６、非特許文献１、２には、トンネルバリア層とその両側に設置した第一及び第二の強磁性体層からなるＴＭＲ（トンネル磁気抵抗；Ｔｕｎｎｅｌｉｎｇ　Ｍａｇｎｅｔｏ　Ｒｅｓｉｓｔａｎｃｅ）効果素子が記載されている。この素子を構成する第一及び／又は第二の強磁性体層としては、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有した合金（以下、ＣｏＦｅＢ合金と記す）が用いられている。また、該ＣｏＦｅＢ合金層として、多結晶構造のものが記載されている。 Patent documents 1 to 6 and non-patent documents 1 and 2 disclose TMR (tunneling magnetoresistance) effect elements comprising a tunnel barrier layer and first and second ferromagnetic layers disposed on both sides thereof. Is described. An alloy containing Co atoms, Fe atoms and B atoms (hereinafter referred to as a CoFeB alloy) is used as the first and / or second ferromagnetic layers constituting this element. Also, as the CoFeB alloy layer, a polycrystalline structure is described.

特開２００２－２０４００４号公報JP 2002-204004 A 国際公開第２００５／０８８７４５号パンフレットWO 2005/088745 pamphlet 特開２００３－３０４０１０号公報JP 2003-304010 A 特開２００６－０８０１１６号公報JP, 2006-080116, A 米国特許出願公開第２００６／００５６１１５号明細書US Patent Application Publication No. 2006/0056115 米国特許第７２５２８５２号明細書U.S. Pat. No. 7,252,852

Ｄ．Ｄ．Ｄｊａｙａｐｒａｗｉｒａら著「Ａｐｐｌｉｅｄ　Ｐｈｙｓｉｃｓ　Ｌｅｔｔｅｒｓ」，８６，０９２５０２（２００５）D. D. Djayaprawira et al., "Applied Physics Letters", 86, 092502 (2005) 湯浅新治ら著「Ｊａｐａｎｅｓｅ　Ｊｏｕｒｎａｌ　ｏｆ　Ａｐｐｌｉｅｄ　　Ｐｈｙｓｉｃｓ」Ｖｏｌ．４３，Ｎｏ．４８，ｐｐ５８８－５９０，２００４年４月２日発行Yuasa Shinji et al. "Japanese Journal of Applied Physics" Vol. 43, no. 48, pp 588-590, published on April 2, 2004

　本発明の課題は、従来技術と比較し、一層改善された高いＭＲ比を持った磁気抵抗素子とその製造方法及び、該製造方法に用いる記憶媒体を提供することにある。 An object of the present invention is to provide a magnetoresistive element having a further improved MR ratio as compared with the prior art, a method of manufacturing the same, and a storage medium used in the method of manufacturing.

　本発明の第１は、基板、
前記基板の上に位置するトンネルバリア層、
前記トンネルバリア層の前記基板側に位置する第一面側に設置された、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなる結晶性第一強磁性体層であって、該層の膜厚方向において、該基板側のＢ原子の含有量が該第一面側のＢ原子の含有量より大きい値を有する結晶性第一強磁性体層、並びに、
前記第一面とは反対側に位置する前記トンネルバリア層の第二面側に設置された結晶性第二強磁性体層
を有することを特徴とする磁気抵抗素子である。 The first aspect of the present invention is a substrate,
A tunnel barrier layer located above the substrate,
A crystalline first ferromagnetic layer formed of an alloy containing Co atoms, Fe atoms and B atoms, disposed on the first surface side of the tunnel barrier layer located on the substrate side, wherein the film is a film of the layer A crystalline first ferromagnetic layer in which the content of B atoms on the substrate side in the thickness direction is larger than the content of B atoms on the first surface side, and
The magnetoresistive element is characterized by including a crystalline second ferromagnetic layer disposed on the second surface side of the tunnel barrier layer located opposite to the first surface.

　本発明の第２は、基板、
前記基板の上に位置するトンネルバリア層、
前記トンネルバリア層の前記基板側に位置する第一面側に設置された結晶性第一強磁性体層、並びに、
前記第一面とは反対側に位置する前記トンネルバリア層の第二面側に設置された、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなる結晶性第二強磁性体層であって、該層の膜厚方向において、該第二面側とは反対面側のＢ原子の含有量が該第二面側のＢ原子の含有量より大きい値を有する結晶性第二強磁性体層
を有することを特徴とする磁気抵抗素子である。 The second of the present invention is a substrate,
A tunnel barrier layer located above the substrate,
A crystalline first ferromagnetic layer disposed on the first surface side of the tunnel barrier layer located on the substrate side;
A crystalline second ferromagnetic layer formed of an alloy containing Co atoms, Fe atoms and B atoms, disposed on the second surface side of the tunnel barrier layer located on the side opposite to the first surface; And a crystalline second ferromagnetic layer having a value in which the content of B atoms on the opposite surface side to the second surface is greater than the content of B atoms on the second surface in the thickness direction of the layer. A magnetoresistive element characterized by having

　本発明の第２においては、前記結晶性第一強磁性体層が、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなり、該層の膜厚方向において、該基板側のＢ原子の含有量が第一面側のＢ原子の含有量より大きい値を有することが好ましい。 In the second aspect of the present invention, the crystalline first ferromagnetic layer is made of an alloy containing Co atoms, Fe atoms and B atoms, and containing B atoms on the substrate side in the film thickness direction of the layer. It is preferred that the amount has a value larger than the content of B atoms on the first surface side.

　また、本発明の第１及び第２においては、前記トンネルバリア層は、結晶性酸化マグネシウム又は結晶性ボロンマグネシウム酸化物からなることが好ましい。 In the first and second aspects of the present invention, the tunnel barrier layer is preferably made of crystalline magnesium oxide or crystalline boron magnesium oxide.

　本発明の第３は、基板を用意する工程、
スパッタリング法を用いて、膜厚方向において、基板側の領域のＢ原子の含有量が該基板側とは反対面側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第一強磁性体層を前記基板の上に成膜する工程、
スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、
スパッタリング法を用いて、前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層の上に第二強磁性体層を成膜する工程、並びに、
前記アモルファス構造の第一強磁性体層を結晶化する工程
を有することを特徴とする磁気抵抗素子の製造方法であり、
前記スパッタリング法で成膜された第二強磁性体層がアモルファス構造を有し、前記結晶化工程を用いて結晶化されることが好ましい。 The third of the present invention is the step of preparing a substrate,
In the film thickness direction, the content of B atoms in the region on the substrate side is larger than the content of B atoms in the region opposite to the substrate side in the film thickness direction by sputtering, Co atoms, Fe Depositing a first ferromagnetic layer of amorphous structure comprising an alloy containing atoms and B atoms on the substrate,
Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the amorphous structure using a sputtering method;
Forming a second ferromagnetic layer on the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide layer using a sputtering method;
A method of manufacturing a magnetoresistive element comprising the step of crystallizing the first ferromagnetic layer of the amorphous structure,
It is preferable that the second ferromagnetic layer formed by the sputtering method have an amorphous structure and be crystallized using the crystallization step.

　本発明の第４は、基板を用意する工程、
スパッタリング法を用いて、前記基板の上にアモルファス構造の第一強磁性体層を成膜する工程、
スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、
スパッタリング法を用いて、膜厚方向において、基板側とは反対面側の領域のＢ原子の含有量が基板側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第二強磁性体層を前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層の上に成膜する工程、並びに、
前記アモルファス構造の第一強磁性体層及び前記アモルファス構造の第二強磁性体層を結晶化する工程
を有することを特徴とする磁気抵抗素子の製造方法である。 The fourth of the present invention is the step of preparing a substrate,
Forming a first ferromagnetic layer of an amorphous structure on the substrate using a sputtering method;
Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the amorphous structure using a sputtering method;
The content of B atoms in the region opposite to the substrate side in the film thickness direction by sputtering is larger than the content of B atoms in the region on the substrate side, Co atoms, Fe atoms And depositing a second ferromagnetic layer of an amorphous structure made of an alloy containing at least one of B and B on the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide layer, and
A method of manufacturing a magnetoresistive element, comprising the step of crystallizing the first ferromagnetic layer of the amorphous structure and the second ferromagnetic layer of the amorphous structure.

　本発明の第５は、基板を用意する工程、スパッタリング法を用いて、膜厚方向において、基板側の領域のＢ原子の含有量が基板側とは反対面側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第一強磁性体層を前記基板の上に成膜する工程、スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、スパッタリング法を用いて、前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層の上に第二強磁性体層を成膜する工程、並びに、前記アモルファス構造の第一強磁性体層を結晶化する工程を用いて、磁気抵抗素子の製造を実行する制御プログラムを記憶したことを特徴とした記憶媒体であり、
前記第二強磁性体層はアモルファス構造を有し、結晶化工程を用いて結晶化されることが好ましい。 According to a fifth aspect of the present invention, the content of B atoms in the region on the substrate side in the film thickness direction is the content of B atoms in the region opposite to the substrate side in the film thickness direction using the step of preparing the substrate Depositing a first ferromagnetic layer of an amorphous structure formed of an alloy containing Co atoms, Fe atoms and B atoms having a large value as compared with the above, and forming the amorphous layer using a sputtering method Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the structure, using the sputtering method, forming the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide And controlling the production of the magnetoresistive element by using the step of forming a second ferromagnetic layer on the first layer and the step of crystallizing the first ferromagnetic layer of the amorphous structure. A storage medium characterized by storing a ram,
The second ferromagnetic layer preferably has an amorphous structure and is crystallized using a crystallization process.

　本発明の第６は、基板を用意する工程、スパッタリング法を用いて、前記基板の上にアモルファス構造の第一強磁性体層を成膜する工程、スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、スパッタリング法を用いて、膜厚方向において、基板側とは反対面側の領域のＢ原子の含有量が基板側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第二強磁性体層を前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム層の上に成膜する工程、並びに、前記アモルファス構造の第一強磁性体層及び前記アモルファス構造の第二強磁性体層を結晶化する工程を用いて、磁気抵抗素子の製造を実行するための制御プログラムを記憶したことを特徴とした記憶媒体である。 A sixth aspect of the present invention is a step of preparing a substrate, a step of forming a first ferromagnetic layer of an amorphous structure on the substrate using sputtering, and a step of preparing the amorphous structure using sputtering. A step of forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on one ferromagnetic layer, and sputtering of a region on the side opposite to the substrate side in the film thickness direction. The polycrystalline structure of the second ferromagnetic layer of the amorphous structure comprising an alloy containing Co atoms, Fe atoms and B atoms having a larger value of the atomic content compared to the B atomic content of the region on the substrate side Forming a film on the magnesium oxide layer or the polycrystalline magnesium boron layer, and crystallizing the first ferromagnetic layer of the amorphous structure and the second ferromagnetic layer of the amorphous structure That process using a storage medium characterized by storing a control program for executing the manufacture of the magnetoresistive element.

　本発明によれば、従来のトンネル磁気抵抗効果素子（以下、ＴＭＲ素子と記す）で達成されていたＭＲ比を大幅に改善することができる。また、本発明は、量産可能で実用性が高く、よって本発明を用いることにより、超高集積化が可能なＭＲＡＭ（Ｍａｇｎｅｔｏｒｅｓｉｓｔｉｖｅ　Ｒａｎｄｏｍ　Ａｃｃｅｓｓ　Ｍｅｍｏｒｙ：強誘電体メモリ）のメモリ素子が効率良く提供される。 According to the present invention, the MR ratio achieved by the conventional tunnel magnetoresistive effect element (hereinafter referred to as TMR element) can be significantly improved. In addition, the present invention can be mass-produced and highly practical. Therefore, by using the present invention, a memory element of MRAM (Magnetoresistive Random Access Memory: ferroelectric memory) capable of achieving ultra-high integration can be efficiently provided. .

本発明の磁気抵抗素子の一例の断面模式図である。It is a cross-sectional schematic diagram of an example of the magnetoresistive element of this invention. 本発明の磁気抵抗素子を製造する成膜装置の一例の構成を模式的に示す図である。It is a figure which shows typically the structure of an example of the film-forming apparatus which manufactures the magnetoresistive element of this invention. 図２の装置のブロック図である。Figure 3 is a block diagram of the device of Figure 2; 本発明の磁気抵抗素子を用いて構成されるＭＲＡＭの模式斜視図である。It is a model perspective view of MRAM comprised using the magnetoresistive element of this invention. 本発明の磁気抵抗素子を用いて構成されるＭＲＡＭの等価回路図である。It is an equivalent circuit schematic of MRAM comprised using the magnetoresistive element of this invention. 本発明の別のトンネルバリア層の断面図である。FIG. 6 is a cross-sectional view of another tunnel barrier layer of the present invention. 本発明の磁気抵抗素子に係るカラム状結晶構造の模式斜視図である。It is a model perspective view of the column-like crystal structure which concerns on the magnetoresistive element of this invention. 本発明の磁気抵抗素子の他の構成のＴＭＲ素子の断面図である。It is sectional drawing of the TMR element of the other structure of the magnetoresistive element of this invention.

　本発明の磁気抵抗素子は、基板と、結晶性第一強磁性体層と、トンネルバリア層と、結晶性第二強磁性体層とを有する。そして、第一強磁性体層及び／又は第二強磁性体層が、トンネルバリア層側のＢ原子の含有量が反対側よりも小さい、Ｃｏ原子、Ｆｅ原子、Ｂ原子を含有する合金（以下、ＣｏＦｅＢと記す）層からなる。具体的には、好ましくは、少なくとも第一強磁性体層及び／又は第二強磁性体層をＢ原子の含有量が大である（以下、Ｂｒｉｃｈと記す）ＣｏＦｅＢ層と、該Ｂｒｉｃｈ層よりもＢ原子の含有量が少ない（以下、Ｂｐｏｏｒと記す）ＣｏＦｅＢ層とから構成する。トンネルバリア層としては、結晶性酸化マグネシウム（以下、Ｍｇ酸化物と記す）層又は結晶性ボロンマグネシウム酸化物（以下、ＢＭｇ酸化物と記す）層が好ましく用いられる。 The magnetoresistive element of the present invention has a substrate, a crystalline first ferromagnetic layer, a tunnel barrier layer, and a crystalline second ferromagnetic layer. Then, an alloy containing Co atoms, Fe atoms, B atoms in which the first ferromagnetic layer and / or the second ferromagnetic layer has a content of B atoms on the side of the tunnel barrier layer smaller than that on the opposite side (hereinafter referred to as , CoFeB)). Specifically, preferably, at least the first ferromagnetic layer and / or the second ferromagnetic layer is a CoFeB layer having a high B atom content (hereinafter referred to as Brich), and a Brich layer It is composed of a CoFeB layer having a low B atom content (hereinafter referred to as Bpoor). As the tunnel barrier layer, a crystalline magnesium oxide (hereinafter referred to as Mg oxide) layer or a crystalline boron magnesium oxide (hereinafter referred to as BMg oxide) layer is preferably used.

　尚、本発明において、トンネルバリア層の基板面側が第一面側、該第一面とは反対面側が第二面側である。 In the present invention, the substrate surface side of the tunnel barrier layer is the first surface side, and the surface side opposite to the first surface is the second surface side.

　以下に、本発明の好適な実施形態を挙げてより詳細に説明する。 Hereinafter, preferred embodiments of the present invention will be described in more detail.

　図１は、本発明の磁気抵抗素子１０の積層構造の一例を示し、ＴＭＲ素子１２を用いた磁気抵抗素子１０の積層構造を示している。この磁気抵抗素子１０によれば、基板１１の上に、このＴＭＲ素子１２を含め、例えば、９層の多層膜が形成されている。この９層の多層膜では、最下層の第１層（Ｔａ層）から最上層の第９層（Ｒｕ層）に向かった多層膜構造体となっている。具体的には、ＰｔＭｎ層１４、ＣｏＦｅ層１５、非磁性Ｒｕ層１６、ＣｏＦｅＢ（Ｂｒｉｃｈ）層１２１１、ＣｏＦｅＢ（Ｂｐｏｏｒ）層１２１２、非磁性Ｍｇ酸化物又はＢＭｇ酸化物層１２２が積層されている。さらにその上に、ＣｏＦｅＢ（Ｂｐｏｏｒ）層１２３２、ＣｏＦｅＢ（Ｂｒｉｃｈ）層１２３１、非磁性Ｔａ層１７及び非磁性Ｒｕ層１８がこの順序で積層されている。尚、図中の各層の括弧中の数値は、各層の厚みを示し、単位はｎｍである。当該厚みは一例であって、これに限定されるものではない。また、ＰｔＭｎ層はＰｔ原子とＭｎ原子とを含有する合金層、ＣｏＦｅ層はＣｏ原子とＦｅ原子を含有する合金層である。 FIG. 1 shows an example of the laminated structure of the magnetoresistive element 10 of the present invention, and shows the laminated structure of the magnetoresistive element 10 using the TMR element 12. According to the magnetoresistive element 10, for example, a multilayer film of nine layers including the TMR element 12 is formed on the substrate 11. The nine-layer multilayer film has a multilayer film structure from the lowermost first layer (Ta layer) to the uppermost ninth layer (Ru layer). Specifically, a PtMn layer 14, a CoFe layer 15, a nonmagnetic Ru layer 16, a CoFeB (Brich) layer 1211, a CoFeB (Bpoor) layer 1212 and a nonmagnetic Mg oxide or BMg oxide layer 122 are stacked. Furthermore, a CoFeB (Bpoor) layer 1232, a CoFeB (Brich) layer 1231, a nonmagnetic Ta layer 17 and a nonmagnetic Ru layer 18 are stacked in this order. The numerical values in parentheses in each layer in the drawing indicate the thickness of each layer, and the unit is nm. The said thickness is an example, Comprising: It is not limited to this. The PtMn layer is an alloy layer containing Pt atoms and Mn atoms, and the CoFe layer is an alloy layer containing Co atoms and Fe atoms.

　上記積層体のうち、本発明に係る結晶性第一強磁性体層は、ＣｏＦｅＢ（Ｂｐｏｏｒ）層１２１２及びＣｏＦｅＢ（Ｂｒｉｃｈ）層１２１１に相当する。また、結晶性第二強磁性体層は、ＣｏＦｅＢ（Ｂｒｉｃｈ）層１２３１及びＣｏＦｅＢ（Ｂｐｏｏｒ）層１２３２に相当する。 The crystalline first ferromagnetic layer according to the present invention in the stack corresponds to the CoFeB (Bpoor) layer 1212 and the CoFeB (Brich) layer 1211. In addition, the crystalline second ferromagnetic layer corresponds to the CoFeB (Brich) layer 1231 and the CoFeB (Bpoor) layer 1232.

　また、本発明では、上述の第一及び第二強磁性体層は、上記２層構造に限定されるものではない。 In the present invention, the first and second ferromagnetic layers are not limited to the two-layer structure.

　１１はウエハー基板、ガラス基板やサファイヤ基板などの基板である。１２はＴＭＲ素子で、Ｂｒｉｃｈの強磁性体層１２１１、Ｂｐｏｏｒの強磁性体層１２１２、トンネルバリア層１２２、Ｂｐｏｏｒの強磁性体層１２３２、及びＢｒｉｃｈの強磁性体層１２３１によって構成されている。 11 is a substrate such as a wafer substrate, a glass substrate or a sapphire substrate. A TMR element 12 is composed of a Brich ferromagnetic layer 1211, a Bpoor ferromagnetic layer 1212, a tunnel barrier layer 122, a Bpoor ferromagnetic layer 1232, and a Brich ferromagnetic layer 1231.

　１３は第１層（Ｔａ層）の下電極層（下地層）であり、１４は、第２層（ＰｔＭｎ層）の反強磁性体層である。１５は第３層（ＣｏＦｅ層）の強磁性体層で、１６は第４層（Ｒｕ層）の交換結合用非磁性体層である。 13 is a lower electrode layer (base layer) of the first layer (Ta layer), and 14 is an antiferromagnetic layer of the second layer (PtMn layer). 15 is a ferromagnetic layer of the third layer (CoFe layer), and 16 is a nonmagnetic layer for exchange coupling of the fourth layer (Ru layer).

　第５層は、結晶性ＣｏＦｅＢ層からなる上記強磁性体層１２１１及び１２１２で構成した積層体である。該第５層の膜厚方向において、結晶性ＣｏＦｅＢ層１２１１のＢ原子の含有量（率）（以下、Ｂ含有量と記す）は、結晶性ＣｏＦｅＢ層１２１２のＢ含有量よりも大きい値に設定されている。尚、第５層を構成する結晶性ＣｏＦｅＢ層１２１１及び１２１２におけるＢ含有量は、第５層の膜厚方向において、基板１１側でＢ含有量が大きくなるように、傾斜分布されていても良い。 The fifth layer is a laminate formed of the ferromagnetic layers 1211 and 1212 made of a crystalline CoFeB layer. In the film thickness direction of the fifth layer, the B atom content (hereinafter referred to as B content) of the crystalline CoFeB layer 1211 is set to a value larger than the B content of the crystalline CoFeB layer 1212 It is done. The B content in the crystalline CoFeB layers 1211 and 1212 constituting the fifth layer may be slope-distributed so that the B content becomes larger on the substrate 11 side in the film thickness direction of the fifth layer. .

　結晶性ＣｏＦｅＢ層１２１１でのＢ含有量は、１０ａｔｏｍｉｃ％乃至６０ａｔｍｉｃ％が好ましく、より好ましくは１５ａｔｏｍｉｃ％乃至５０ａｔｍｉｃ％の範囲に設定される。また、結晶性ＣｏＦｅＢ層１２１２でのＢ含有量は、好ましくは０．１ａｔｏｍｉｃ％乃至４０ａｔｍｉｃ％、より好ましくは０．５ａｔｏｍｉｃ％乃至１０ａｔｍｉｃ％の範囲に設定される。 The B content in the crystalline CoFeB layer 1211 is preferably 10 atomic% to 60 atomic%, and more preferably in the range of 15 atomic% to 50 atomic%. The B content in the crystalline CoFeB layer 1212 is preferably set in the range of 0.1 atomic% to 40 atomic%, more preferably 0.5 atomic% to 10 atomic%.

　また、結晶性ＣｏＦｅＢ層１２１２でのＢ含有量／結晶性ＣｏＦｅＢ層１２１１でのＢ含有量は、ａｔｏｍｉｃ％（原子比）で１／５乃至１／１００、好ましくは、１／１０乃至１／５０に設定されることができる。 In addition, the B content in the crystalline CoFeB layer 1212 / B content in the crystalline CoFeB layer 1211 is 1/5 to 1/100, preferably 1/10 to 1/50, in atomic% (atomic ratio). Can be set to

　第５層を構成する結晶性ＣｏＦｅＢ層１２１１及び１２１２は、上記Ｂ含有量が上記の範囲となるように調整したＣｏＦｅＢターゲットを用いたスパッタリングにより成膜することができる。また、上述したＢ原子の傾斜分布でのＢ含有量は、ＣｏＦｅＢターゲットを用いたスパッタリング中で、モノボラン（ＢＨ3）ガスやジボラン（Ｂ2Ｈ6）ガス等のボロン原子含有ガスの導入量を時間軸で可変することで、達成される。 The crystalline CoFeB layers 1211 and 1212 constituting the fifth layer can be formed by sputtering using a CoFeB target whose B content is adjusted to be in the above range. In addition, the B content in the above-described gradient distribution of B atoms can be determined by introducing a boron atom-containing gas such as monoborane (BH 3 ) gas or diborane (B 2 H 6 ) gas during sputtering using a CoFeB target. It is achieved by varying on the time axis.

　上述の第３層１５、第４層１６及び第５層１２１１，１２１２とから成る層が、磁化固定層１９である。実質的な磁化固定層は、第５層の結晶性ＣｏＦｅＢ層から成る強磁性体層１２１１及び１２１２である。 The layer formed of the third layer 15, the fourth layer 16 and the fifth layers 121 and 1212 described above is the magnetization fixed layer 19. The substantially magnetization fixed layer is the ferromagnetic layers 1211 and 1212 consisting of the crystalline CoFeB layer of the fifth layer.

　１２２は、第６層（多結晶ＢＭｇ酸化物又は多結晶Ｍｇ酸化物）のトンネルバリア層で、絶縁層である。本発明で用いたトンネルバリア層１２２は、単一の多結晶ＢＭｇ酸化物層又は多結晶Ｍｇ酸化物層であってもよい。 Reference numeral 122 denotes a tunnel barrier layer of a sixth layer (polycrystalline BMg oxide or polycrystalline Mg oxide), which is an insulating layer. The tunnel barrier layer 122 used in the present invention may be a single polycrystalline BMg oxide layer or a polycrystalline Mg oxide layer.

　また、本発明は、図６に図示したように、多結晶ＢＭｇ酸化物層又は多結晶Ｍｇ酸化物層の中に微結晶、多結晶又は単結晶等の結晶性ＢＭｇ層又はＭｇ層１２２２を設けても良い。ＢＭｇ層はＢ原子とＭｇ原子からなる合金層、Ｍｇ層はＭｇ金属からなる金属層である。この場合、ＢＭｇ層又はＭｇ層１２２２の両側に多結晶ＢＭｇ酸化物層又は多結晶Ｍｇ酸化物層１２２１及び１２２３を設けた積層構造のトンネルバリア層とする。また、ＢＭｇ層又はＭｇ層１２２２を２層以上とした複数層とし、ＢＭｇ酸化物層又はＭｇ酸化物層と交互に積層した交互層とすることができる。 In the present invention, as shown in FIG. 6, a crystalline BMg layer or Mg layer 1222 such as microcrystalline, polycrystalline or single crystal is provided in a polycrystalline BMg oxide layer or a polycrystalline Mg oxide layer. It is good. The BMg layer is an alloy layer composed of B atoms and Mg atoms, and the Mg layer is a metal layer composed of Mg metal. In this case, the tunnel barrier layer has a laminated structure in which polycrystalline BMg oxide layers or polycrystalline Mg oxide layers 1221 and 1223 are provided on both sides of the BMg layer or Mg layer 1222. Alternatively, the BMg layer or the Mg layer 1222 may be a plurality of layers, and may be a plurality of layers, and may be alternately stacked with the BMg oxide layer or the Mg oxide layer.

　図８は、本発明の別のＴＭＲ素子１２の例である。図８中の符号１２、１２１１、１２１２、１２３１及び１２３２は、図１と同一部材である。本例では、トンネルバリア層１２２は、ＢＭｇ酸化物層又はＭｇ酸化物層８２、並びに、該層８２の両側のＢＭｇ層又はＭｇ層８１及び８３からなる積層膜である。また、層８１がＢＭｇ層で、層８３がＭｇ層であってもよく、或いは、層８１がＭｇ層で、層８３がＢＭｇ層であってもよい。さらに、本例では、層８１の使用が省略され、層８２を結晶性強磁性体層１２３２に隣接配置させることができる。或いは、層８３の使用が省略され、層８２を結晶性強磁性体層１２１２に隣接配置させることができる。 FIG. 8 is an example of another TMR element 12 of the present invention. Reference numerals 12, 1211, 1212, 1231 and 1232 in FIG. 8 are the same members as those in FIG. In this example, the tunnel barrier layer 122 is a laminated film comprising a BMg oxide layer or Mg oxide layer 82 and BMg layers or Mg layers 81 and 83 on both sides of the layer 82. Further, the layer 81 may be a BMg layer and the layer 83 may be an Mg layer, or the layer 81 may be an Mg layer and the layer 83 may be a BMg layer. Furthermore, in this example, the use of layer 81 is omitted, and layer 82 can be placed adjacent to crystalline ferromagnetic layer 1232. Alternatively, the use of layer 83 can be omitted and layer 82 can be placed adjacent to crystalline ferromagnetic layer 1212.

　図７は、ＢＭｇ酸化物層又はＭｇ酸化物層のカラム状結晶７２の集合体７１からなる多結晶構造の模式斜視図である。該多結晶構造には、多結晶領域内に部分的なアモルファス領域を含む多結晶－アモルファス混合領域の構造物も包含される。該カラム条結晶は、各カラム毎において、膜厚方向で（００１）結晶面が優先的に配向した単結晶であることが好ましい。また、該カラム状単結晶の平均的な直径は、好ましくは１０ｎｍ以下であり、より好ましくは２ｎｍ乃至５ｎｍの範囲であり、その膜厚は、好ましくは１０ｎｍ以下であり、より好ましくは０．５ｎｍ乃至５ｎｍの範囲である。 FIG. 7 is a schematic perspective view of a polycrystalline structure composed of an aggregate 71 of column-like crystals 72 in the BMg oxide layer or the Mg oxide layer. The polycrystalline structure also includes the structure of a polycrystalline-amorphous mixed region including a partially amorphous region in the polycrystalline region. The column crystal is preferably a single crystal in which (001) crystal planes are preferentially oriented in the film thickness direction in each column. The average diameter of the column-shaped single crystal is preferably 10 nm or less, more preferably 2 nm to 5 nm, and the film thickness is preferably 10 nm or less, more preferably 0.5 nm. To 5 nm.

　また、本発明で用いられるＢＭｇ酸化物は、一般式ＢxＭｇyＯz（０．７≦Ｚ／（Ｘ＋Ｙ）≦１．３であり、好ましくは、０．８≦Ｚ／（Ｘ＋Ｙ）＜１．０である）で示される。本発明では、化学論量のＢＭｇ酸化物を用いるのが好ましいが、酸素欠損のＢＭｇ酸化物であっても、高いＭＲ比を得ることができる。 Further, the BMg oxide used in the present invention has a general formula B x Mg y O z (0.7 ≦ Z / (X + Y) ≦ 1.3, preferably 0.8 ≦ Z / (X + Y) < It is indicated by 1.0). In the present invention, although it is preferable to use a stoichiometric amount of BMg oxide, a high MR ratio can be obtained even with an oxygen deficient BMg oxide.

　また、本発明で用いられるＭｇ酸化物は、一般式ＭｇyＯz（０．７≦Ｚ／Ｙ≦１．３であり、好ましくは、０．８≦Ｚ／Ｙ＜１．０である）で示される。本発明では、化学論量のＭｇ酸化物を用いるのが好ましいが、酸素欠損のＭｇ酸化物であっても、高いＭＲ比を得ることができる。 In addition, Mg oxide used in the present invention has a general formula of Mg y O z (0.7 ≦ Z / Y ≦ 1.3, preferably 0.8 ≦ Z / Y <1.0) It is indicated by. In the present invention, it is preferable to use a stoichiometric amount of Mg oxide, but even with oxygen deficient Mg oxide, a high MR ratio can be obtained.

　また、本発明で用いられる多結晶Ｍｇ酸化物又は多結晶ＢＭｇ酸化物には、各種微量成分、例えばＺｎ原子、Ｃ原子、Ａｌ原子、Ｃａ原子、Ｓｉ原子等を１０ｐｐｍ乃至１００ｐｐｍの範囲で含有することができる。 The polycrystalline Mg oxide or polycrystalline BMg oxide used in the present invention contains various trace components such as Zn atom, C atom, Al atom, Ca atom, Si atom, etc. in the range of 10 ppm to 100 ppm. be able to.

　第７層は、結晶性ＣｏＦｅＢ層からなる強磁性体層１２３１及び１２３２で構成した積層体である。該第７層の膜厚方向において、結晶性ＣｏＦｅＢ層１２３１のＢ含有量は、結晶性ＣｏＦｅＢ層１２３２のＢ含有量より大きい値に設定されている。また、該第７層は、磁化自由層として機能することが出来る。 The seventh layer is a laminate formed of ferromagnetic layers 1231 and 1232 made of a crystalline CoFeB layer. In the film thickness direction of the seventh layer, the B content of the crystalline CoFeB layer 1231 is set to a value larger than the B content of the crystalline CoFeB layer 1232. The seventh layer can also function as a magnetization free layer.

　第７層を構成する結晶性ＣｏＦｅＢ層１２３１及び１２３２におけるＢ含有量は、第７層の膜厚方向において、基板１１に近い側でＢ含有量が小さく、基板１１より遠い側で大きくなるように、傾斜分布されていても良い。 The B content in the crystalline CoFeB layers 1231 and 1232 constituting the seventh layer is such that the B content is smaller on the side closer to the substrate 11 and larger on the side farther from the substrate 11 in the film thickness direction of the seventh layer. The slope may be distributed.

　結晶性ＣｏＦｅＢ層１２３１でのＢ含有量は、好ましくは１０ａｔｏｍｉｃ％乃至６０ａｔｍｉｃ％、より好ましくは１５ａｔｏｍｉｃ％乃至５０ａｔｍｉｃ％の範囲に設定される。結晶性ＣｏＦｅＢ層１２１２での含有量は、好ましくは０．１ａｔｏｍｉｃ％乃至４０ａｔｍｉｃ％、より好ましくは０．５ａｔｏｍｉｃ％乃至１０ａｔｍｉｃ％の範囲に設定される。 The B content in the crystalline CoFeB layer 1231 is preferably set in the range of 10 atomic% to 60 atomic%, more preferably 15 atomic% to 50 atomic%. The content of the crystalline CoFeB layer 1212 is preferably set in the range of 0.1 atomic% to 40 atomic%, more preferably 0.5 atomic% to 10 atomic%.

　また、結晶性ＣｏＦｅＢ層１２３２でのＢ含有量／結晶性ＣｏＦｅＢ層１２１１でのＢ含有量は、ａｔｏｍｉｃ％（原子比）で好ましくは１／５乃至１／１００、より好ましくは１／１０乃至１／５０に設定される。 Further, the B content in the crystalline CoFeB layer 1232 / the B content in the crystalline CoFeB layer 1211 is preferably 1/5 to 1/100, more preferably 1/10 to 1 in atomic% (atomic ratio). It is set to / 50.

　第７層を構成する結晶性ＣｏＦｅＢ層１２３１及び１２３２は、上記Ｂ含有量が上記の範囲となるように調整したＣｏＦｅＢターゲットを用いたスパッタリングにより成膜することができる。また、上述したＢ原子の傾斜分布でのＢ含有は、ＣｏＦｅＢターゲットを用いたスパッタリング中で、モノボラン（ＢＨ3）ガスやジボラン（Ｂ2Ｈ6）ガス等のボロン原子含有ガスの導入量を、時間軸で、可変することで達成される。 The crystalline CoFeB layers 1231 and 1232 constituting the seventh layer can be formed by sputtering using a CoFeB target whose B content is adjusted to be in the above range. In addition, the B content in the gradient distribution of B atoms described above refers to the introduction amount of a boron atom-containing gas such as monoborane (BH 3 ) gas or diborane (B 2 H 6 ) gas during sputtering using a CoFeB target. It is achieved by making the time axis variable.

　上記した結晶性ＣｏＦｅＢ層１２１１、１２１２、１２３１及び１２３２は、前述の図７に図示したカラム状結晶構造７１と同一の構造の結晶構造のものであってもよい。 The above-mentioned crystalline CoFeB layers 1211, 1212, 1231 and 1232 may have the same crystal structure as the column-like crystal structure 71 shown in FIG.

　また、結晶性ＣｏＦｅＢ層１２１２と１２３２とは、中間に位置するトンネルバリア層１２２と隣接させて設けることが好ましい。製造装置においては、これら３層は真空を破ることなく、順次、積層される。 The crystalline CoFeB layers 1212 and 1232 are preferably provided adjacent to the tunnel barrier layer 122 located in the middle. In the manufacturing apparatus, these three layers are sequentially stacked without breaking the vacuum.

　１７は、第８層（Ｔａ層）の電極層である。 Reference numeral 17 denotes an electrode layer of an eighth layer (Ta layer).

　１８は、第９層（Ｒｕ層）のハードマスク層である。第９層は、ハードマスクとして用いられた際には、磁気抵抗素子から除去されていてもよい。 18 is a hard mask layer of a ninth layer (Ru layer). The ninth layer may be removed from the magnetoresistive element when used as a hard mask.

　次に、図２を参照して、上記の積層構造を有する磁気抵抗素子１０を製造する装置と製造方法を説明する。図２は磁気抵抗素子１０を製造する装置の概略的な平面図であり、本装置は複数の磁性層及び非磁性層を含む多層膜を作製することのできる装置であり、量産型スパッタリング成膜装置である。 Next, with reference to FIG. 2, an apparatus and a method of manufacturing the magnetoresistive element 10 having the above-described laminated structure will be described. FIG. 2 is a schematic plan view of an apparatus for manufacturing the magnetoresistive element 10. This apparatus is an apparatus capable of producing a multilayer film including a plurality of magnetic layers and a nonmagnetic layer, and mass production type sputtering film formation It is an apparatus.

　図２に示された磁性多層膜作製装置２００は、クラスタ型製造装置であり、スパッタリング法に基づく３つの成膜チャンバを備えている。本装置２００では、ロボット搬送装置（不図示）を備える搬送チャンバ２０２が中央位置に設置している。磁気抵抗素子製造のための製造装置２００の搬送チャンバ２０２には、２つのロードロック・アンロードロックチャンバ２０５及び２０６が設けられ、それぞれにより基板（例えば、シリコン基板）１１の搬入及び搬出が行われる。これらのロードロック・アンロードロックチャンバ２０５及び２０６を交互に、基板の搬入搬出を実施することによって、タクトタイムを短縮させ、生産性よく磁気抵抗素子を作製できる構成となっている。 The magnetic multilayer film manufacturing apparatus 200 shown in FIG. 2 is a cluster type manufacturing apparatus, and includes three film forming chambers based on the sputtering method. In the present apparatus 200, a transfer chamber 202 including a robot transfer device (not shown) is installed at a central position. Two load lock / unload lock chambers 205 and 206 are provided in the transfer chamber 202 of the manufacturing apparatus 200 for manufacturing the magnetoresistance element, and loading and unloading of the substrate (for example, silicon substrate) 11 is performed by each of them. . By alternately carrying the substrate into and out of the load lock / unload lock chamber 205 and 206, the tact time can be shortened, and the magnetoresistive element can be manufactured with high productivity.

　磁気抵抗素子製造のための製造装置２００では、搬送チャンバ２０２の周囲に、３つの成膜用マグネトロンスパッタリングチャンバ２０１Ａ乃至２０１Ｃと、１つのエッチングチャンバ２０３とが設けられている。エッチングチャンバ２０３では、ＴＭＲ素子１０の所要表面をエッチング処理する。各チャンバ２０１Ａ乃至２０１Ｃ及び２０３と搬送チャンバ２０２との間には、開閉自在なゲートバルブ２０４が設けられている。尚、各チャンバ２０１Ａ乃至２０１Ｃ及び２０２には、不図示の真空排気機構、ガス導入機構、電力供給機構などが付設されている。成膜用マグネトロンスパッタリングチャンバ２０１Ａ乃至２０１Ｃは、高周波スパッタリング法を用いて、基板１１の上に、真空を破らずに、前述した第１層から第９層までの各膜を順次に堆積することができる。 In the manufacturing apparatus 200 for manufacturing a magnetoresistive element, three deposition magnetron sputtering chambers 201A to 201C and one etching chamber 203 are provided around the transfer chamber 202. In the etching chamber 203, the required surface of the TMR element 10 is etched. A gate valve 204 which can be opened and closed is provided between each of the chambers 201A to 201C and 203 and the transfer chamber 202. Each of the chambers 201A to 201C and 202 is provided with an evacuation mechanism, a gas introduction mechanism, a power supply mechanism, and the like (not shown). In the magnetron sputtering chambers 201A to 201C for film formation, the respective films from the first layer to the ninth layer described above can be sequentially deposited on the substrate 11 using high frequency sputtering without breaking the vacuum. it can.

　成膜用マグネトロンスパッタリングチャンバ２０１Ａ乃至２０１Ｃの天井部には、それぞれ、適当な円周の上に配置された４基または５基のカソード３１乃至３５、４１乃至４５、５１乃至５４が配置される。さらに当該円周と同軸上に位置する基板ホルダ上に基板１１が配置される。また、上記カソード３１乃至３５、４１乃至４５、５１乃至５４に装着したターゲットの背後にマグネットを配置したマグネトロンスパッタリング装置とするのが好ましい。 Four or five cathodes 31 to 35, 41 to 45, 51 to 54 disposed on suitable circumferences are disposed on the ceilings of the film forming magnetron sputtering chambers 201A to 201C, respectively. Furthermore, the substrate 11 is disposed on a substrate holder located coaxially with the circumference. Moreover, it is preferable to set it as the magnetron sputtering apparatus which has arrange | positioned the magnet behind the target with which said cathodes 31 to 35, 41 to 45, 51 to 54 were mounted.

　上記装置においては、電力投入手段２０７Ａ乃至２０７Ｃから、上記カソード３１乃至３５、４１乃至４５、５１乃至５４にラジオ周波数（ＲＦ周波数）のような高周波電力が印加される。高周波電力としては、０．３ＭＨｚ乃至１０ＧＨｚの範囲、好ましくは、５ＭＨｚ乃至５ＧＨｚの範囲の周波数及び１０Ｗ乃至５００Ｗの範囲、好ましくは、１００Ｗ乃至３００Ｗの範囲の電力を用いることができる。 In the above apparatus, high frequency power such as radio frequency (RF frequency) is applied to the cathodes 31 to 35, 41 to 45, 51 to 54 from the power input means 207A to 207C. As high frequency power, power in the range of 0.3 MHz to 10 GHz, preferably in the range of 5 MHz to 5 GHz and in the range of 10 W to 500 W, preferably 100 W to 300 W can be used.

　上記において、例えば、カソード３１にはＣｏＦｅＢ（Ｂｐｏｏｒ）ターゲットが、カソード３２にはＰｔＭｎターゲットが、カソード３３にはＣｏＦｅＢ（Ｂｒｉｃｈ）ターゲットがそれぞれ装着される。また、カソード３４にはＣｏＦｅターゲットが、カソード３５にはＲｕターゲットがそれぞれ装着される。カソード４１にはＢＭｇ酸化物ターゲット又はＢＭｇターゲットが装着される。ＢＭｇターゲットを用いる時は、酸化性ガスとともに反応性スパッタリングを実施するための反応性スパッタリング用チャンバ（不図示）を搬送チャンバ２０２に接続して実施することができる。 In the above, for example, a CoFeB (Bpoor) target is attached to the cathode 31, a PtMn target to the cathode 32, and a CoFeB (Brich) target to the cathode 33, respectively. Further, a CoFe target is attached to the cathode 34 and a Ru target is attached to the cathode 35. A BMg oxide target or a BMg target is attached to the cathode 41. When a BMg target is used, a reactive sputtering chamber (not shown) for performing reactive sputtering with an oxidizing gas can be connected to the transfer chamber 202.

　また、ＢＭｇターゲットを用いたスパッタリングにより多結晶ＢＭｇ層を成膜した後、酸化性ガス（例えば、酸素ガス、オゾンガス、水蒸気等）を用いた酸化チャンバ（不図示）にて、多結晶ＢＭｇ酸化物層に化学変化させることができる。 In addition, after a polycrystalline BMg layer is formed by sputtering using a BMg target, polycrystalline BMg oxide is formed in an oxidation chamber (not shown) using an oxidizing gas (eg, oxygen gas, ozone gas, water vapor, etc.) It can be chemically changed into layers.

　また、別の形態例として、カソード４１にＢＭｇ酸化物ターゲットを、カソード４２にＢＭｇターゲットを装着することもできる。この時、カソード４３乃至４５にはターゲットを未装着とすることができ、また、カソード４３乃至４５にも、ＢＭｇ酸化物ターゲット、又はＢＭｇターゲットが装着することもできる。 Further, as another embodiment, a BMg oxide target can be attached to the cathode 41 and a BMg target can be attached to the cathode 42. At this time, targets can not be attached to the cathodes 43 to 45, and BMg oxide targets or BMg targets can also be attached to the cathodes 43 to 45.

　カソード５１にはＣｏＦｅＢターゲットが、カソード５２には第１層のＴａ層のためのＴａターゲットが、カソード５３にはＲｕターゲットが、カソード５４には第８層のＴａ層のためのＴａターゲットが装着される。 A CoFeB target is attached to the cathode 51, a Ta target for the Ta layer of the first layer is attached to the cathode 52, a Ru target is attached to the cathode 53, and a Ta target for the eighth Ta layer is attached to the cathode 54. Be done.

　上記カソード３１乃至３５、４１乃至４５、並びに、５１乃至５４に装着した各ターゲットの各面内方向と基板の面内方向とは、互いに、非平行に配置することが好ましい。該非平行な配置を用いることによって、基板径より小径のターゲットを回転させながら、スパッタリングすることによって、高効率で、且つ、ターゲット組成と同一組成の磁性膜及び非磁性膜を堆積させることができる。 The in-plane direction of each of the targets mounted on the cathodes 31 to 35, 41 to 45, and 51 to 54 and the in-plane direction of the substrate are preferably arranged non-parallel to each other. By using the non-parallel arrangement, it is possible to deposit a magnetic film and a nonmagnetic film with the same composition as the target composition with high efficiency by sputtering while rotating the target whose diameter is smaller than the substrate diameter.

　上記非平行な配置は、例えば、ターゲット中心軸と基板中心軸との交差角を４５°以下、好ましくは５°乃至３０°となる様に両者を非平行に配置することができる。また、この時の基板は、１０ｒｐｍ乃至５００ｒｐｍの回転速度、好ましくは、５０ｒｐｍ乃至２００ｒｐｍの回転速度を用いることができる。 In the non-parallel arrangement, for example, both can be arranged non-parallel so that the crossing angle between the target central axis and the substrate central axis is 45 ° or less, preferably 5 ° to 30 °. Also, the substrate at this time can use a rotational speed of 10 rpm to 500 rpm, preferably, a rotational speed of 50 rpm to 200 rpm.

　図３は、本発明に用いられる成膜装置のブロック図である。図中、３０１は図２中の搬送チャンバ２０２に相当する搬送チャンバ、３０２は成膜用マグネトロンスパッタリングチャンバ２０１Ａに相当する成膜チャンバ、３０３は成膜用マグネトロンスパッタリングチャンバ２０１Ｂに相当する成膜チャンバである。また、３０４は成膜用マグネトロンスパッタリングチャンバ２０１Ｃに相当する成膜チャンバ、３０５はロードロック・アンロードロックチャンバ２０５及び２０６に相当するロードロック・アンロードロックチャンバである。さらに、３０６は記憶媒体３１２を内蔵した中央演算器（ＣＰＵ）である。符号３０９乃至３１１は、ＣＰＵ３０６と各処理チャンバ３０１乃至３０５とを接続するバスラインで、各処理チャンバ３０１乃至３０５の動作を制御する制御信号がＣＰＵ３０６より各処理チャンバ３０１乃至３０５に送信される。 FIG. 3 is a block diagram of a film forming apparatus used in the present invention. 2, a transfer chamber 301 corresponds to the transfer chamber 202 in FIG. 2, a film forming chamber 302 corresponds to the film forming magnetron sputtering chamber 201A, and a film forming chamber 303 corresponds to the film forming magnetron sputtering chamber 201B. is there. Reference numeral 304 denotes a film forming chamber corresponding to the film forming magnetron sputtering chamber 201C, and 305 denotes a load lock and unload lock chamber corresponding to the load lock and unload lock chambers 205 and 206. Further, reference numeral 306 denotes a central processing unit (CPU) incorporating the storage medium 312. Reference numerals 309 to 311 are bus lines connecting the CPU 306 and the processing chambers 301 to 305, and control signals for controlling the operations of the processing chambers 301 to 305 are transmitted from the CPU 306 to the processing chambers 301 to 305.

　本発明の磁気抵抗素子の製造においては、例えば、ロードロック・アンロードロックチャンバ３０５内の基板（図示せず）は搬送チャンバ３０１に搬出される。この基板搬出工程は、ＣＰＵ３０６が記憶媒体３１２に記憶させた制御プログラムに基づいて演算する。そして、この演算結果に基づく制御信号が、バスライン３０７及び３１１を通して、ロードロック・アンロードロックチャンバ３０５及び搬送チャンバ３０１に搭載した各種装置の実行を制御することによって実施される。上記各種装置としては、例えば、不図示のゲートバルブ、ロボット機構、搬送機構、駆動系等が挙げられ、記憶媒体３１２が前述した本発明の記憶媒体に相当する。 In the manufacture of the magnetoresistive element of the present invention, for example, a substrate (not shown) in the load lock / unload lock chamber 305 is carried out to the transfer chamber 301. The substrate unloading step is calculated based on the control program stored in the storage medium 312 by the CPU 306. A control signal based on the calculation result is implemented by controlling the execution of various devices mounted on the load lock / unload lock chamber 305 and the transfer chamber 301 through the bus lines 307 and 311. Examples of the various devices include a gate valve (not shown), a robot mechanism, a transport mechanism, a drive system, etc., and the storage medium 312 corresponds to the storage medium of the present invention described above.

　搬送チャンバ３０１に搬送された基板は、成膜チャンバ３０２に搬出される。成膜チャンバ３０２に搬入された基板は、ここで、図１の第１層１３が成膜される。搬送から成膜までは、ＣＰＵ３０６内で、記憶媒体３１２に記憶させた制御プログラムに基づいて演算された制御信号が、バスライン３０７，３１０を通して搬送チャンバ３０１及び成膜チャンバ３０２に搭載した各種装置の実行を制御することで実施される。係る各種装置としては、例えば、不図示のカソードへの電力投入機構、基板回転機構、ガス導入機構、排気機構、ゲートバルブ、ロボット機構、搬送機構、駆動系等が挙げられる。 The substrate transported to the transport chamber 301 is carried out to the film forming chamber 302. Here, the first layer 13 of FIG. 1 is deposited on the substrate carried into the deposition chamber 302. From transport to deposition, control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 are transferred to the transport chamber 301 and the deposition chamber 302 through the bus lines 307 and 310. It is implemented by controlling the execution. As various devices which concern, for example, a power input mechanism to a cathode (not shown), a substrate rotation mechanism, a gas introduction mechanism, an exhaust mechanism, a gate valve, a robot mechanism, a transport mechanism, a drive system, etc. are mentioned.

　上記第１層の成膜工程が終了した後、基板は、搬送チャンバ３０１に戻され、続いて、この搬送チャンバ３０１から成膜チャンバ３０２に搬入され、図１の第２層１４、第３層１５、第４層１６及び第５層１２１１と１２１２が順次積層される。尚、この段階での第５層１２１１と１２１２のＣｏＦｅＢ層は、好ましくはアモルファス構造となっているが、この段階での第５層１２１１と１２１２のＣｏＦｅＢ層の両方、又はその一方は、多結晶構造であってもよい。 After the film formation process of the first layer is completed, the substrate is returned to the transfer chamber 301, and then carried from the transfer chamber 301 to the film formation chamber 302, and the second layer 14 and the third layer in FIG. 15, the fourth layer 16 and the fifth layers 1211 and 1212 are sequentially stacked. The CoFeB layers of the fifth layers 1211 and 1212 at this stage preferably have an amorphous structure, but both or one of the CoFeB layers of the fifth layers 1211 and 1212 at this stage are polycrystalline. It may be a structure.

　上記積層は、ＣＰＵ３０６内で、記憶媒体３１２に記憶させた制御プログラムに基づいて演算された制御信号が、バスライン３０７，３０８を通して、搬送チャンバ３０１及び成膜チャンバ３０２に搭載した各種装置の実行を制御することによって実施される。該各種装置としては、例えば、不図示のカソードへの電力投入機構、基板回転機構、ガス導入機構、排気機構、ゲートバルブ、ロボット機構、搬送機構、駆動系等が挙げられる。 In the stack, control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 execute the various devices mounted on the transfer chamber 301 and the film forming chamber 302 through the bus lines 307 and 308. It is implemented by controlling. Examples of the various devices include a power input mechanism to a cathode (not shown), a substrate rotation mechanism, a gas introduction mechanism, an exhaust mechanism, a gate valve, a robot mechanism, a transport mechanism, a drive system, and the like.

　上記第５層までの積層膜を持った基板は、一旦、搬送チャンバ３０１に戻され、その後成膜チャンバ３０３に搬入される。成膜チャンバ３０３内で、上記第５層１２１１と１２１２のアモルファスＣｏＦｅＢ層の上に、第６層１２２として、多結晶Ｍｇ酸化物層の成膜を実行する。係る成膜は、ＣＰＵ３０６内で、記憶媒体３１２に記憶させた制御プログラムに基づいて演算された制御信号が、バスライン３０７及び３０９を通して、搬送チャンバ３０１及び成膜チャンバ３０３に搭載した各種装置の実行を制御することで実施される。該各種装置としては、例えば、不図示のカソードへの電力投入機構、基板回転機構、ガス導入機構、排気機構、ゲートバルブ、ロボット機構、搬送機構、駆動系等が挙げられる。 The substrate having the laminated film up to the fifth layer is temporarily returned to the transfer chamber 301 and then carried into the film forming chamber 303. In the film forming chamber 303, a polycrystalline Mg oxide layer is formed as the sixth layer 122 on the amorphous CoFeB layers of the fifth layers 1211 and 1212. In the film formation, control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 execute various devices mounted on the transfer chamber 301 and the film formation chamber 303 through the bus lines 307 and 309. Is implemented by controlling the Examples of the various devices include a power input mechanism to a cathode (not shown), a substrate rotation mechanism, a gas introduction mechanism, an exhaust mechanism, a gate valve, a robot mechanism, a transport mechanism, a drive system, and the like.

　上記第６層１２２までの積層膜を持った基板は、再度、一旦、搬送チャンバ３０１に戻され、その後成膜チャンバ３０４に搬入される。成膜チャンバ３０４内で、上記第６層１２２の多結晶Ｍｇ酸化物層の上に、第７層１２３１と１２３２、第８層１７及び第９層１８が順次積層される。この段階での第７層１２３１と１２３２のＣｏＦｅＢ層は、好ましくはアモルファス構造となっているが、この段階での第７層１２３１及び１２３２の両方、又は一方のＣｏＦｅＢ層が多結晶構造であってもよい。 The substrate having the laminated film up to the sixth layer 122 is once returned again to the transfer chamber 301, and is then carried into the film forming chamber 304. In the film forming chamber 304, the seventh layers 1231 and 1232 and the eighth layer 17 and the ninth layer 18 are sequentially stacked on the polycrystalline Mg oxide layer of the sixth layer 122. The CoFeB layers of the seventh layers 1231 and 1232 at this stage preferably have an amorphous structure, but both the seventh layers 1231 and 1232 at this stage or one CoFeB layer have a polycrystalline structure. It is also good.

　係る積層工程は、ＣＰＵ３０６内で、記憶媒体３１２に記憶させた制御プログラムに基づいて演算された制御信号が、バスライン３０７及び３１０を通して、搬送チャンバ３０１及び成膜チャンバ３０４に搭載した各種装置の実行を制御することで実施される。該各種装置としては、例えば、不図示のカソードへの電力投入機構、基板回転機構、ガス導入機構、排気機構、ゲートバルブ、ロボット機構、搬送機構、駆動系等が挙げられる。 In the stacking process, control signals calculated based on the control program stored in the storage medium 312 in the CPU 306 execute various devices mounted on the transfer chamber 301 and the film forming chamber 304 through the bus lines 307 and 310. Is implemented by controlling the Examples of the various devices include a power input mechanism to a cathode (not shown), a substrate rotation mechanism, a gas introduction mechanism, an exhaust mechanism, a gate valve, a robot mechanism, a transport mechanism, a drive system, and the like.

　記憶媒体３１２は、本発明の記憶媒体であり、係る記憶媒体には次の工程を用いて磁気抵抗素子の製造を実行するための制御プログラムが記憶されている。
基板を用意する工程
アモルファス構造の第一強磁性体層を成膜する工程
多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層を成膜する工程
アモルファス構造の第二強磁性体層を成膜する工程 The storage medium 312 is a storage medium of the present invention, and the storage medium stores a control program for executing the manufacture of the magnetoresistive element using the following steps.
Step of preparing a substrate Step of depositing a first ferromagnetic layer of amorphous structure Step of depositing a polycrystalline Mg oxide layer or polycrystalline BMg oxide layer Step of depositing a second ferromagnetic layer of amorphous structure Process

　尚、上記第一磁性体層及び／又は第二磁性体層が、Ｂｒｉｃｈ及びＢｐｏｏｒのＣｏＦｅＢ層からなる場合には、対応する成膜工程において、多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層側がＢｐｏｏｒになるように設定される。 When the first magnetic layer and / or the second magnetic layer is composed of Brich and Bpoor CoFeB layers, a polycrystalline Mg oxide layer or a polycrystalline BMg oxide layer is formed in the corresponding film forming step. The side is set to be Bpoor.

　本発明で用いられる記憶媒体３１２としては、ハードディスク媒体、光磁気ディスク媒体、フロッピー（登録商標）ディスク媒体、フラッシュメモリやＭＲＡＭ等の不揮発性メモリ全般を挙げることができ、プログラム格納可能な媒体を含むものである。 Examples of the storage medium 312 used in the present invention include hard disk media, magneto-optical disk media, floppy (registered trademark) disk media, nonvolatile memories such as flash memory and MRAM, and the like, including media capable of storing programs. It is

　上記第５層１２１１，１２１２、第７層１２３１，１２３２のアモルファスＣｏＦｅＢ層のアニーリングによる多結晶化と第２層１４のＰｔＭｎ層の磁気付与を促すために、第１層乃至第９層からなる積層膜をアニーリング炉（不図示）に搬入することができる。 In order to promote the polycrystallization of the amorphous CoFeB layers of the fifth layers 1211, 1212, and the seventh layers 1231, 1232 by annealing and the magnetic application of the PtMn layer of the second layer 14, a laminate comprising the first to ninth layers The membrane can be loaded into an annealing furnace (not shown).

　上記記憶媒体３１２には、アニーリング炉での工程を実施するための制御プログラムが記憶されている。よって、該制御プログラムに基づく、ＣＰＵ３０６の演算により得た制御信号によって、アニーリング炉内の各種装置（例えば、不図示のヒータ機構、排気機構、搬送機構等）を制御し、アニーリング工程を実行することができる。 The storage medium 312 stores a control program for performing the process in the annealing furnace. Therefore, according to a control signal obtained by the operation of the CPU 306 based on the control program, various devices in the annealing furnace (for example, a heater mechanism, an exhaust mechanism, a transport mechanism, etc. not shown) are controlled to execute the annealing process. Can.

　また、本発明では、上記第５層１２１１及び１２１２、並びに、第７層１２３１及び１２３２のいずれか一方を、上述のＣｏＦｅＢ層に換えて、他の合金層を用いることができる。具体的には、ＣｏＦｅＴａＺｒＢ層、ＣｏＴａＺｒＢ合金層、ＣｏＦｅＮｂＺｒＢ層、ＣｏＦｅＺｒＢ層、ＦｅＴａＣＢ層、ＦｅＴａＮＢ層、又はＦｅＣＢ層などのＢ含有の多結晶強磁性体層を用いることができる。 In the present invention, any of the fifth layers 1211 and 1212 and the seventh layers 1231 and 1232 may be replaced with the above-described CoFeB layer, and another alloy layer may be used. Specifically, a B-containing polycrystalline ferromagnetic layer such as a CoFeTaZrB layer, a CoTaZrB alloy layer, a CoFeNbZrB layer, a CoFeZrB layer, a FeTaCB layer, an FeTaNB layer, or an FeCB layer can be used.

　また、第５層及び第７層は、２層の積層からなるＣｏＦｅＢ層に、更に、上述の多結晶強磁性体層を積層して、３層以上の積層構造とすることができる。 In the fifth and seventh layers, the above-described polycrystalline ferromagnetic layer can be further stacked on a CoFeB layer formed of two layers to form a stacked structure of three or more layers.

　また、本発明では、上記第４層１６のＲｕ層に換えて、Ｒｈ層又はＩｒ層を用いることができる。 In the present invention, in place of the Ru layer of the fourth layer 16, a Rh layer or an Ir layer can be used.

　さらに、本発明では、上記第２層１４のＰｔＭｎ層に換えて、ＩｒＭｎ層、ＩｒＭｎＣｒ層、ＮｉＭｎ層、ＰｄＰｔＭｎ層、ＲｕＲｈＭｎ層やＯｓＭｎ層等の各合金層が好ましく用いられる。又、その膜厚は、１０乃至３０ｎｍが好ましい。 Furthermore, in the present invention, instead of the PtMn layer of the second layer 14, alloy layers such as IrMn layer, IrMnCr layer, NiMn layer, PdPtMn layer, RuRhMn layer and OsMn layer are preferably used. The film thickness is preferably 10 to 30 nm.

　また、基板側に位置する多結晶ＣｏＦｅ層１５は、スパッタリング法により、第２層のＰｔＭｎ層１４の上に、多結晶状態での成膜が可能である。 In addition, the polycrystalline CoFe layer 15 located on the substrate side can be formed in a polycrystalline state on the PtMn layer 14 of the second layer by the sputtering method.

　本発明者らは、上記多結晶ＣｏＦｅ層１５の成膜に続くＣｏＦｅＢ層は、スパッタリング成膜直後（アニーリング工程前）でアモルファス構造であることを確認した。本発明では、アモルファス構造のＣｏＦｅＢ層をアニーリングすることにより、エピタキシャル多結晶構造に相変換させることができる。 The present inventors confirmed that the CoFeB layer following the film formation of the polycrystalline CoFe layer 15 has an amorphous structure immediately after the sputtering film formation (before the annealing step). In the present invention, by annealing a CoFeB layer having an amorphous structure, phase conversion to an epitaxial polycrystalline structure can be achieved.

　図４は、本発明の磁気抵抗素子をメモリ素子として用いたＭＲＡＭ４０１の模式図である。ＭＲＡＭ４０１において、４０２は本発明のメモリ素子、４０３はワード線、４０４はビット線である。多数のメモリ素子４０２のそれぞれは、複数のワード線４０３と複数のビット線４０４の各交点位置に配置され、格子状の位置関係に配置される。多数のメモリ素子４０２のそれぞれが１ビットの情報を記憶することができる。 FIG. 4 is a schematic view of an MRAM 401 using the magnetoresistive element of the present invention as a memory element. In the MRAM 401, 402 is a memory element of the present invention, 403 is a word line, and 404 is a bit line. Each of the large number of memory elements 402 is arranged at each intersection position of the plurality of word lines 403 and the plurality of bit lines 404, and is arranged in a lattice-like positional relationship. Each of the multiple memory elements 402 can store one bit of information.

　図５は、ＭＲＡＭ４０１のワード線４０３とビット線４０４の交点位置において、１ビットの情報を記憶するＴＭＲ素子１０と、スイッチ機能を有するトランジスタ５０１とで構成した等価回路図である。 FIG. 5 is an equivalent circuit diagram configured by TMR element 10 storing 1-bit information at the intersection position of word line 403 and bit line 404 of MRAM 401, and transistor 501 having a switch function.

　図１に示した磁気抵抗素子を図２に示した成膜装置を用いて作製した。主要部であるＴＭＲ素子１２の成膜条件は以下の通りである。 The magnetoresistive element shown in FIG. 1 was manufactured using the film forming apparatus shown in FIG. The film formation conditions of the TMR element 12 which is the main part are as follows.

　ＣｏＦｅＢ層１２１１は、ＣｏＦｅＢ組成比（ａｔｏｍｉｃ：原子比）６０／２０／２０のターゲットを用いた。ＣｏＦｅＢ層１２１２は、ＣｏＦｅＢ組成比（ａｔｏｍｉｃ：原子比）６５／２５／５のターゲットを用いた。 The CoFeB layer 1211 used a target having a CoFeB composition ratio (atomic: atomic ratio) of 60/20/20. The CoFeB layer 1212 used a target having a CoFeB composition ratio (atomic: atomic ratio) of 65/25/5.

　ＣｏＦｅＢ層１２１１及び１２１２は、Ａｒガスをスパッタガスとし、その圧力を０．０３Ｐａとした。ＣｏＦｅＢ層１２１１及び１２１２の成膜は、マグネトロンＤＣスパッタ（チャンバ２０１Ａ）によりスパッタレート０．６４ｎｍ／ｓｅｃで成膜した。この時のＣｏＦｅＢ層（ＣｏＦｅＢ層１２１１と１２１２）は、アモルファス構造を有していた。 The CoFeB layers 1211 and 1212 use Ar gas as a sputtering gas, and set the pressure to 0.03 Pa. The CoFeB layers 1211 and 1212 were formed by magnetron DC sputtering (chamber 201A) at a sputtering rate of 0.64 nm / sec. The CoFeB layers (CoFeB layers 1211 and 1212) at this time had an amorphous structure.

　続いて、スパッタリング装置（チャンバ２０１Ｂ）に換えた。ＢＭｇＯ組成比（ａｔｏｍｉｃ：原子比）２５／２５／５０のターゲットを用い、スパッタガスとしてＡｒガスを用い、好適範囲０．０１乃至０．４Ｐａの圧力範囲のうち、０．２Ｐａの圧力とした。この条件でマグネトロンＲＦスパッタリング（１３．５６ＭＨｚ）により、第６層のＢＭｇ酸化物層であるトンネルバリア層１２２を成膜した。この際、ＢＭｇ酸化物層（トンネルバリア層１２２）は、カラム状結晶の集合体よりなる多結晶構造であった。また、この時のマグネトロンＲＦスパッタリング（１３．５６ＭＨｚ）の成膜レートは、０．１４ｎｍ／ｓｅｃであった。 Subsequently, it was changed to a sputtering apparatus (chamber 201B). A target having a BMgO composition ratio (atomic: atomic ratio) of 25/25/50 was used, Ar gas was used as a sputtering gas, and the pressure was set to 0.2 Pa within a pressure range of 0.01 to 0.4 Pa in a preferable range. The tunnel barrier layer 122 which is a BMg oxide layer of the sixth layer was formed by magnetron RF sputtering (13.56 MHz) under these conditions. At this time, the BMg oxide layer (tunnel barrier layer 122) had a polycrystalline structure composed of aggregates of columnar crystals. Moreover, the film-forming rate of magnetron RF sputtering (13.56 MHz) at this time was 0.14 nm / sec.

　さらに続けて、スパッタリング装置（チャンバ２０１Ｃ）に換えて、磁化自由層（第７層のＣｏＦｅＢ層）である強磁性体層１２３１と１２３２を成膜した。 Further, instead of the sputtering apparatus (chamber 201C), ferromagnetic layers 1231 and 1232 as the magnetization free layer (the seventh CoFeB layer) were formed.

　ＣｏＦｅＢ層１２３１及び１２３２は、Ａｒガスをスパッタガスとし、その圧力を０．０３Ｐａとした。ＣｏＦｅＢ層１２３１及び１２３２の成膜は、マグネトロンＤＣスパッタ（チャンバ２０１Ａ）によりスパッタレート０．６４ｎｍ／ｓｅｃで成膜した。この時、ＣｏＦｅＢ層１２３１は、ＣｏＦｅＢ組成比（ａｔｏｍｉｃ：原子比）５５／１５／３０のターゲットを用い、ＣｏＦｅＢ層１２３２は、ＣｏＦｅＢ組成比（ａｔｏｍｉｃ：原子比）６５／２５／５のターゲットを用いた。この成膜直後において、ＣｏＦｅＢ層１２３１と１２３２はアモルファス構造であった。 The CoFeB layers 1231 and 1232 were formed using Ar gas as a sputtering gas, and the pressure was set to 0.03 Pa. The CoFeB layers 1231 and 1232 were formed by magnetron DC sputtering (chamber 201A) at a sputtering rate of 0.64 nm / sec. At this time, the CoFeB layer 1231 uses a target having a CoFeB composition ratio (atomic: atomic ratio) 55/15/30, and the CoFeB layer 1232 uses a target having a CoFeB composition ratio (atomic: atomic ratio) 65/25/5. It was. Immediately after this film formation, the CoFeB layers 1231 and 1232 had an amorphous structure.

　この本例では、ＢＭｇ酸化物膜の成膜速度は０．１４ｎｍ／ｓｅｃであったが、０．０１ｎｍ乃至１．０ｎｍ／ｓｅｃの範囲で成膜しても問題ない。 In this example, the deposition rate of the BMg oxide film was 0.14 nm / sec, but there is no problem if the deposition rate is in the range of 0.01 nm to 1.0 nm / sec.

　チャンバ２０１Ａ、２０１Ｂ及び２０１Ｃのそれぞれでスパッタリング成膜を行って積層が完了した磁気抵抗素子１０は、熱処理炉において、約３００℃及び４時間で、８ｋＯｅの磁場中で、アニーリング処理を実施した。その結果、アモルファス構造の第５層及び第７層であるＣｏＦｅＢ層１２１１、１２１２、１２３１及び１２３２は、図７に図示したカラム状結晶７２の集合体７１よりなる多結晶構造であったことが確認された。 The sputtering process was performed in each of the chambers 201A, 201B and 201C to complete the lamination, and the magnetoresistive element 10 was annealed in a heat treatment furnace at about 300 ° C. and 4 hours in a magnetic field of 8 kOe. As a result, it is confirmed that the CoFeB layers 1211, 1212, 1231, and 1232 which are the fifth and seventh layers of the amorphous structure have a polycrystalline structure including the aggregate 71 of the column-like crystals 72 illustrated in FIG. It was done.

　このアニーリング工程により、磁気抵抗素子１０は、ＴＭＲ効果を持った磁気抵抗素子として作用することができる。また、このアニーリング工程により、第２層のＰｔＭｎ層である反強磁性体層１４には所定の磁化が付与されていた。 By this annealing step, the magnetoresistive element 10 can act as a magnetoresistive element having a TMR effect. Further, by this annealing step, a predetermined magnetization is given to the antiferromagnetic layer 14 which is the PtMn layer of the second layer.

　比較例として、上記第５層及び第７層のＣｏＦｅＢ層の層中のＢ含有量を、膜厚方向において、一定の２０ａｔｏｍｉｃ％とした他は、上記実施例と同様の方法を用いて、磁気抵抗素子を作成した。 As a comparative example, using the same method as that of the above example except that the B content in the layers of the fifth and seventh CoFeB layers is set to a constant 20 atomic% in the film thickness direction, A resistive element was created.

　実施例の磁気抵抗素子と比較例の磁気抵抗素子とのＭＲ比を測定し、対比したところ、実施例の磁気抵抗素子のＭＲ比は、比較例の磁気抵抗素子のＭＲ比と比較し、１．２倍乃至１．５倍以上の数値で改善されていた。 When the MR ratio of the magnetoresistive element of the example and the magnetoresistive element of the comparative example was measured and compared, the MR ratio of the magnetoresistive element of the example was compared with the MR ratio of the magnetoresistive element of the comparative example. It has been improved by 2 times to 1.5 times or more.

　ＭＲ比は、外部磁界に応答して磁性膜または磁性多層膜の磁化方向が変化するのに伴って膜の電気抵抗も変化する磁気抵抗効果に関するパラメータで、その電気抵抗の変化率を磁気抵抗変化率（ＭＲ比）としたものである。 The MR ratio is a parameter related to the magnetoresistance effect in which the electric resistance of the film changes as the magnetization direction of the magnetic film or magnetic multilayer film changes in response to an external magnetic field, and the rate of change of the electric resistance Rate (MR ratio).

　また、上述の実施例で用いた第６層の多結晶ＢＭｇ酸化物層に換えて、第６層として多結晶Ｍｇ酸化物層を用いた他は、全く同様の方法で磁気抵抗素子を作成し、ＭＲ比を測定した。ターゲットとしてはＭｇＯ組成比（ａｔｏｍｉｃ：原子比）５０／５０のターゲットを用いた。その結果、上述の比較例よりも高いＭＲ比が得られた。 Also, in place of the polycrystalline BMg oxide layer of the sixth layer used in the above-described embodiment, a magnetoresistive element is formed in the same manner as the sixth embodiment except that a polycrystalline Mg oxide layer is used. , MR ratio was measured. As a target, a target having an MgO composition ratio (atomic: atomic ratio) of 50/50 was used. As a result, an MR ratio higher than that of the above-described comparative example was obtained.

　１０：磁気抵抗素子、１１：基板、１２：ＴＭＲ素子、１２１１：ＣｏＦｅＢ（Ｂｒｉｃｈ）強磁性体層（第５層）、１２１２：ＣｏＦｅＢ（Ｂｐｏｏｒ）強磁性体層（第５層）、１２２：トンネルバリア層（第６層）、１２３１：ＣｏＦｅＢ（Ｂｒｉｃｈ）強磁性体層（第７層；磁化自由層）、１２３２：ＣｏＦｅＢ（Ｂｐｏｏｒ）強磁性体層（第７層；磁化自由層）、１３：下電極層（第１層；下地層）、１４：反強磁性体層（第２層）、１５：強磁性体層（第３層）、１６：交換結合用非磁性層（第４層）、１７：上電極層（第８層）、１８：ハードマスク層（第９層）、１９：磁化固定層、２００：磁気抵抗素子作成装置、２０１Ａ乃至２０１Ｃ：成膜チャンバ、２０２：搬送チャンバ、２０３：エッチングチャンバ、２０４：ゲートバルブ、２０５，２０６：ロードロック・アンロードロックチャンバ、３１乃至３５，４１乃至４５，５１乃至５４：カソード、２０７Ａ乃至２０７Ｃ：電力投入部、３０１：搬送チャンバ、３０２乃至３０４：成膜チャンバ、３０５：ロードロック・アンロードロックチャンバ、３０６：中央演算器（ＣＰＵ）、３０７乃至３１１：バスライン、３１２：記憶媒体、４０１：ＭＲＡＭ、４０２：メモリ素子、４０３：ワード線、４０４：ビット線、５０１：トランジスタ、７１：カラム状結晶の集合体、７２：カラム状結晶、８１：ＢＭｇ層又はＭｇ層、８２：ＢＭｇ酸化物層又はＭｇ酸化物層、８３：ＢＭｇ層又はＭｇ層 10: Magnetoresistance element, 11: substrate, 12: TMR element, 1211: CoFeB (Brich) ferromagnetic layer (fifth layer), 1212: CoFeB (Bpoor) ferromagnetic layer (fifth layer), 122: tunnel Barrier layer (sixth layer), 1231: CoFeB (Brich) ferromagnetic layer (seventh layer; magnetization free layer), 1232: CoFeB (Bpoor) ferromagnetic layer (seventh layer; magnetization free layer), 13: Lower electrode layer (first layer; base layer), 14: antiferromagnetic layer (second layer), 15: ferromagnetic layer (third layer), 16: nonmagnetic layer for exchange coupling (fourth layer) , 17: upper electrode layer (eighth layer), 18: hard mask layer (ninth layer), 19: magnetization fixed layer, 200: magnetoresistive element manufacturing apparatus, 201A to 201C: film forming chamber, 202: transfer chamber, 203: etching chamber, 204: Valve 205, 206: load lock / unlock chamber, 31 to 35, 41 to 45, 51 to 54: cathode, 207A to 207C: power input part, 301: transfer chamber, 302 to 304: film forming chamber, 305 Load lock unload lock chamber 306 Central processing unit (CPU) 307 to 311: bus line 312: storage medium 401: MRAM 402: memory element 403: word line 404: bit line 501 A transistor 71: an aggregate of columnar crystals 72: columnar crystals 81: BMg layer or Mg layer 82: BMg oxide layer or Mg oxide layer 83: BMg layer or Mg layer

Claims (11)

　基板、
前記基板の上に位置するトンネルバリア層、
前記トンネルバリア層の前記基板側に位置する第一面側に設置された、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなる結晶性第一強磁性体層であって、該層の膜厚方向において、該基板側のＢ原子の含有量が該第一面側のＢ原子の含有量より大きい値を有する結晶性第一強磁性体層、並びに、
前記第一面とは反対側に位置する前記トンネルバリア層の第二面側に設置された結晶性第二強磁性体層
を有することを特徴とする磁気抵抗素子。 substrate,
A tunnel barrier layer located above the substrate,
A crystalline first ferromagnetic layer formed of an alloy containing Co atoms, Fe atoms and B atoms, disposed on the first surface side of the tunnel barrier layer located on the substrate side, wherein the film is a film of the layer A crystalline first ferromagnetic layer in which the content of B atoms on the substrate side in the thickness direction is larger than the content of B atoms on the first surface side, and
A magnetoresistive element comprising a crystalline second ferromagnetic layer disposed on the second surface side of the tunnel barrier layer located opposite to the first surface. 　前記トンネルバリア層は、結晶性酸化マグネシウム又は結晶性ボロンマグネシウム酸化物からなることを特徴とする請求項１に記載の磁気抵抗素子。 The magnetoresistive element according to claim 1, wherein the tunnel barrier layer is made of crystalline magnesium oxide or crystalline boron magnesium oxide. 　基板、
前記基板の上に位置するトンネルバリア層、
前記トンネルバリア層の前記基板側に位置する第一面側に設置された結晶性第一強磁性体層、並びに、
前記第一面とは反対側に位置する前記トンネルバリア層の第二面側に設置された、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなる結晶性第二強磁性体層であって、該層の膜厚方向において、該第二面側とは反対面側のＢ原子の含有量が該第二面側のＢ原子の含有量より大きい値を有する結晶性第二強磁性体層
を有することを特徴とする磁気抵抗素子。 substrate,
A tunnel barrier layer located above the substrate,
A crystalline first ferromagnetic layer disposed on the first surface side of the tunnel barrier layer located on the substrate side;
A crystalline second ferromagnetic layer formed of an alloy containing Co atoms, Fe atoms and B atoms, disposed on the second surface side of the tunnel barrier layer located on the side opposite to the first surface; And a crystalline second ferromagnetic layer having a value in which the content of B atoms on the opposite surface side to the second surface is greater than the content of B atoms on the second surface in the thickness direction of the layer. A magnetoresistive element characterized by having. 　前記トンネルバリア層は、結晶性酸化マグネシウム又は結晶性ボロンマグネシウム酸化物からなることを特徴とする請求項３に記載の磁気抵抗素子。 4. The magnetoresistive element according to claim 3, wherein the tunnel barrier layer is made of crystalline magnesium oxide or crystalline boron magnesium oxide. 　前記結晶性第一強磁性体層が、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなり、該層の膜厚方向において、該基板側のＢ原子の含有量が第一面側のＢ原子の含有量より大きい値を有することを特徴とする請求項３又は４に記載の磁気抵抗素子。 The crystalline first ferromagnetic layer is made of an alloy containing Co atoms, Fe atoms and B atoms, and in the film thickness direction of the layer, the content of B atoms on the substrate side is B on the first surface side 5. The magnetoresistive element according to claim 3, wherein the magnetoresistive element has a value larger than the content of atoms. 　基板を用意する工程、
スパッタリング法を用いて、膜厚方向において、基板側の領域のＢ原子の含有量が該基板側とは反対面側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第一強磁性体層を前記基板の上に成膜する工程、
スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、
スパッタリング法を用いて、前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層の上に第二強磁性体層を成膜する工程、並びに、
前記アモルファス構造の第一強磁性体層を結晶化する工程
を有することを特徴とする磁気抵抗素子の製造方法。 A step of preparing a substrate,
In the film thickness direction, the content of B atoms in the region on the substrate side is larger than the content of B atoms in the region opposite to the substrate side in the film thickness direction by sputtering, Co atoms, Fe Depositing a first ferromagnetic layer of amorphous structure comprising an alloy containing atoms and B atoms on the substrate,
Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the amorphous structure using a sputtering method;
Forming a second ferromagnetic layer on the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide layer using a sputtering method;
And a step of crystallizing the first ferromagnetic layer of the amorphous structure. 　前記スパッタリング法で成膜された第二強磁性体層がアモルファス構造を有し、前記結晶化工程を用いて結晶化されることを特徴とする請求項６に記載の磁気抵抗素子の製造方法。 The method of manufacturing a magnetoresistive element according to claim 6, wherein the second ferromagnetic layer formed by the sputtering method has an amorphous structure, and is crystallized using the crystallization step. 　基板を用意する工程、
スパッタリング法を用いて、前記基板の上にアモルファス構造の第一強磁性体層を成膜する工程、
スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、
スパッタリング法を用いて、膜厚方向において、基板側とは反対面側の領域のＢ原子の含有量が基板側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第二強磁性体層を前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層の上に成膜する工程、並びに、
前記アモルファス構造の第一強磁性体層及び前記アモルファス構造の第二強磁性体層を結晶化する工程
を有することを特徴とする磁気抵抗素子の製造方法。 A step of preparing a substrate,
Forming a first ferromagnetic layer of an amorphous structure on the substrate using a sputtering method;
Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the first ferromagnetic layer of the amorphous structure using a sputtering method;
The content of B atoms in the region opposite to the substrate side in the film thickness direction by sputtering is larger than the content of B atoms in the region on the substrate side, Co atoms, Fe atoms And depositing a second ferromagnetic layer of an amorphous structure made of an alloy containing at least one of B and B on the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide layer, and
And a step of crystallizing the first ferromagnetic layer of the amorphous structure and the second ferromagnetic layer of the amorphous structure. 　基板を用意する工程、スパッタリング法を用いて、膜厚方向において、基板側の領域のＢ原子の含有量が基板側とは反対面側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第一強磁性体層を前記基板の上に成膜する工程、スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、スパッタリング法を用いて、前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層の上に第二強磁性体層を成膜する工程、並びに、前記アモルファス構造の第一強磁性体層を結晶化する工程を用いて、磁気抵抗素子の製造を実行する制御プログラムを記憶したことを特徴とした記憶媒体。 In the step of preparing the substrate and sputtering, the content of B atoms in the region on the substrate side in the film thickness direction is larger than the content of B atoms in the region opposite to the substrate side. Depositing a first ferromagnetic layer of an amorphous structure comprising an alloy containing Co, Fe and B atoms on the substrate, sputtering using the first ferromagnetic body of the amorphous structure Forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer on the layer, using a sputtering method, forming a second strong magnetic layer on the polycrystalline magnesium oxide layer or the polycrystalline boron magnesium oxide layer Storing a control program for executing manufacture of a magnetoresistive element using the step of forming a magnetic layer and the step of crystallizing the first ferromagnetic layer of the amorphous structure; Storage medium, wherein the. 　前記第二強磁性体層はアモルファス構造を有し、結晶化工程を用いて結晶化されることを特徴とする請求項９に記載の記憶媒体。 The storage medium according to claim 9, wherein the second ferromagnetic layer has an amorphous structure and is crystallized using a crystallization process. 　基板を用意する工程、スパッタリング法を用いて、前記基板の上にアモルファス構造の第一強磁性体層を成膜する工程、スパッタリング法を用いて、前記アモルファス構造の第一強磁性体層の上に、多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム酸化物層を成膜する工程、スパッタリング法を用いて、膜厚方向において、基板側とは反対面側の領域のＢ原子の含有量が基板側の領域のＢ原子の含有量と比較して大きい値を有するＣｏ原子、Ｆｅ原子及びＢ原子を含有した合金からなるアモルファス構造の第二強磁性体層を前記多結晶酸化マグネシウム層又は多結晶ボロンマグネシウム層の上に成膜する工程、並びに、前記アモルファス構造の第一強磁性体層及び前記アモルファス構造の第二強磁性体層を結晶化する工程を用いて、磁気抵抗素子の製造を実行するための制御プログラムを記憶したことを特徴とした記憶媒体。 A step of preparing a substrate, a step of forming a first ferromagnetic layer of an amorphous structure on the substrate by sputtering, a step of forming a first ferromagnetic layer of the amorphous structure by sputtering In the step of forming a polycrystalline magnesium oxide layer or a polycrystalline boron magnesium oxide layer, a sputtering method is used, and the content of B atoms in the region opposite to the substrate side in the film thickness direction is the substrate side The second ferromagnetic layer of amorphous structure comprising an alloy containing Co atoms, Fe atoms and B atoms having a large value as compared with the content of B atoms in the region of the polycrystalline magnesium oxide layer or polycrystalline boron Forming a film on the magnesium layer, and crystallizing the first ferromagnetic layer of the amorphous structure and the second ferromagnetic layer of the amorphous structure Storage medium characterized by storing a control program for executing the manufacture of the magnetoresistive element.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014513866A (en) * 2011-02-11 2014-06-05 マグアイシー テクノロジーズ インコーポレイテッド Magnetic element and manufacturing method thereof
WO2017015294A1 (en) * 2015-07-20 2017-01-26 Headway Technologies, Inc. Magnetic tunnel junction with low defect rate after high temperature anneal for magnetic device applications

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018056388A (en) * 2016-09-29 2018-04-05 Tdk株式会社 Magnetoresistive effect element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004349687A (en) * 2003-04-17 2004-12-09 Applied Materials Inc Method of manufacturing coercive random access memory (MRAM) device
JP2008004956A (en) * 2004-03-12 2008-01-10 Japan Science & Technology Agency Magnetoresistive element and manufacturing method thereof
JP2008085170A (en) * 2006-09-28 2008-04-10 Toshiba Corp Magnetoresistive element and magnetoresistive random access memory
JP2008103661A (en) * 2006-09-21 2008-05-01 Alps Electric Co Ltd Tunnel type magnetic detection element and manufacturing method therefor
JP2009152333A (en) * 2007-12-20 2009-07-09 Fujitsu Ltd Ferromagnetic tunnel junction element, magnetic head, and magnetic storage device

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004349687A (en) * 2003-04-17 2004-12-09 Applied Materials Inc Method of manufacturing coercive random access memory (MRAM) device
JP2008004956A (en) * 2004-03-12 2008-01-10 Japan Science & Technology Agency Magnetoresistive element and manufacturing method thereof
JP2008103661A (en) * 2006-09-21 2008-05-01 Alps Electric Co Ltd Tunnel type magnetic detection element and manufacturing method therefor
JP2008085170A (en) * 2006-09-28 2008-04-10 Toshiba Corp Magnetoresistive element and magnetoresistive random access memory
JP2009152333A (en) * 2007-12-20 2009-07-09 Fujitsu Ltd Ferromagnetic tunnel junction element, magnetic head, and magnetic storage device

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014513866A (en) * 2011-02-11 2014-06-05 マグアイシー テクノロジーズ インコーポレイテッド Magnetic element and manufacturing method thereof
WO2017015294A1 (en) * 2015-07-20 2017-01-26 Headway Technologies, Inc. Magnetic tunnel junction with low defect rate after high temperature anneal for magnetic device applications
US9842988B2 (en) 2015-07-20 2017-12-12 Headway Technologies, Inc. Magnetic tunnel junction with low defect rate after high temperature anneal for magnetic device applications
CN108028315A (en) * 2015-07-20 2018-05-11 海德威科技公司 For having the magnetic tunnel junction of Low Defectivity after the high annealing of magnetic devices
US20180175287A1 (en) * 2015-07-20 2018-06-21 Headway Technologies, Inc. Magnetic Tunnel Junction with Low Defect Rate after High Temperature Anneal for Magnetic Device Applications
US10763428B2 (en) 2015-07-20 2020-09-01 Taiwan Semiconductor Manufacturing Company, Ltd. Magnetic tunnel junction with low defect rate after high temperature anneal for magnetic device applications
CN108028315B (en) * 2015-07-20 2021-08-27 台湾积体电路制造股份有限公司 Magnetic tunnel junction with low defect rate after high temperature annealing for magnetic devices
US11309489B2 (en) 2015-07-20 2022-04-19 Taiwan Semiconductor Manufacturing Company, Ltd. Magnetic tunnel junction with low defect rate after high temperature anneal for magnetic device applications
US20220238798A1 (en) * 2015-07-20 2022-07-28 Taiwan Semiconductor Manufacturing Company, Ltd. Magnetic Tunnel Junction with Low Defect Rate after High Temperature Anneal for Magnetic Device Applications
US12167701B2 (en) 2015-07-20 2024-12-10 Taiwan Semiconductor Manufacturing Company, Ltd. Magnetic tunnel junction with low defect rate after high temperature anneal for magnetic device applications

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