WO2010029701A1 - 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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WO2010029701A1
WO2010029701A1 PCT/JP2009/004247 JP2009004247W WO2010029701A1 WO 2010029701 A1 WO2010029701 A1 WO 2010029701A1 JP 2009004247 W JP2009004247 W JP 2009004247W WO 2010029701 A1 WO2010029701 A1 WO 2010029701A1
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atoms
layer
alloy containing
forming
atom
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PCT/JP2009/004247
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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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キヤノンアネルバ株式会社
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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
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • 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
    • G01—MEASURING; TESTING
    • G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
    • G01R33/00—Arrangements or instruments for measuring magnetic variables
    • G01R33/02—Measuring direction or magnitude of magnetic fields or magnetic flux
    • G01R33/06—Measuring direction or magnitude of magnetic fields or magnetic flux using galvano-magnetic devices
    • G01R33/09—Magnetoresistive devices
    • G01R33/098—Magnetoresistive devices comprising tunnel junctions, e.g. tunnel magnetoresistance sensors
    • 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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11C—STATIC STORES
    • G11C11/00—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor
    • G11C11/02—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using magnetic elements
    • G11C11/16—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using magnetic elements using elements in which the storage effect is based on magnetic spin effect
    • G11C11/161—Digital stores characterised by the use of particular electric or magnetic storage elements; Storage elements therefor using magnetic elements using elements in which the storage effect is based on magnetic spin effect details concerning the memory cell structure, e.g. the layers of the ferromagnetic memory cell
    • 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
    • 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.
  • Patent documents 2 to 5 disclose TMR elements using a crystalline magnesium oxide film consisting of a single crystal or a polycrystal as a tunnel barrier film. ing.
  • 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 crystalline first ferromagnetic layer located on the substrate and made of an alloy containing Co atoms, Fe atoms and B atoms, A tunnel barrier layer located on the crystalline first ferromagnetic layer and having a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer, A crystalline second ferromagnetic layer located on the tunnel barrier layer and comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and Fe atoms, An intermediate layer made of a nonmagnetic material located on the crystalline second ferromagnetic layer, and A crystalline ferromagnetic material layer located on the intermediate layer and made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms, Ni atoms, Fe atoms and B It is a magnetoresistive element characterized by having a third ferromagnetic layer having a crystalline
  • a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method A method of manufacturing a magnetoresistive element having The step of forming the tunnel barrier layer includes the step of forming a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer by sputtering.
  • Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms
  • a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms
  • a nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material.
  • Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer.
  • a third aspect of the present invention is a process of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method.
  • a method of manufacturing a magnetoresistive element having In the step of forming the tunnel barrier layer, a layer made of crystalline metal magnesium or crystalline boron magnesium alloy is formed by sputtering, and the metal magnesium or boron magnesium alloy is oxidized to form a crystalline magnesium oxide layer.
  • Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms
  • a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms
  • a nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material.
  • Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer.
  • a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method is provided.
  • a storage medium storing a control program for executing the manufacture of a magnetoresistive element having A control program for executing the step of forming the tunnel barrier layer and the magnetization free layer is Forming a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer by a sputtering method using a target made of magnesium oxide or boron magnesium oxide; Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms, A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material.
  • a process of filming, and Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer.
  • a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate using a sputtering method A storage medium storing a control program for executing the manufacture of a magnetoresistive element having A control program for executing the step of forming the tunnel barrier layer and the magnetization free layer is A layer of crystalline metallic magnesium or crystalline boron magnesium alloy is formed by sputtering using a target of metallic magnesium or boron magnesium alloy, and the metallic magnesium or boron magnesium alloy is oxidized to form crystalline magnesium oxide.
  • Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms
  • a layer comprising an alloy containing or an alloy containing Co atoms and B atoms
  • a nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material.
  • a process of filming, and Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer.
  • 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 comprises a substrate, a crystalline first ferromagnetic layer, a tunnel barrier layer, a crystalline second ferromagnetic layer, a nonmagnetic intermediate layer, and a crystalline third ferromagnetic layer.
  • the first ferromagnetic layer is made of an alloy containing Co atoms, Fe atoms, and B atoms (hereinafter referred to as CoFeB).
  • the tunnel barrier layer has a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer.
  • the second ferromagnetic layer is made of CoFeB or an alloy containing Co atoms and Fe atoms (hereinafter referred to as CoFe).
  • the third ferromagnetic layer comprises a crystalline ferromagnetic layer comprising a CoFe layer or a CoFeB layer, and a crystalline strong layer comprising an alloy containing Ni atoms, Fe atoms and B atoms, or an alloy containing Ni atoms and Fe atoms It consists of a laminated film with a magnetic layer.
  • an alloy containing Ni atoms, Fe atoms and B atoms is referred to as NiFeB
  • an alloy containing Ni atoms and Fe atoms is referred to as NiFe.
  • magnesium oxide is described as Mg oxide, boron magnesium oxide as BMg oxide, metal magnesium as Mg, and a boron magnesium alloy as BMg.
  • FIG. 1 shows an example of the laminated structure of the magnetoresistive element 10 according to the present invention, and shows the laminated structure of the magnetoresistive element 10 using the TMR element 12.
  • a multilayer film of 12 layers including the TMR element 12 is formed on the substrate 11.
  • the twelve-layer multilayer film is a multilayer film structure from the lowermost first layer (Ta layer) to the uppermost twelfth layer (Ru layer).
  • the PtMn layer 14 the CoFe layer 15, the nonmagnetic metal layer (Ru) layer 161, the first ferromagnetic layer CoFeB layer 121, the tunnel barrier layer nonmagnetic polycrystalline Mg oxide layer or BMg
  • An oxide layer 122 is stacked.
  • a second ferromagnetic layer, a polycrystalline CoFe layer or CoFeB layer 1233, a nonmagnetic Ta layer 162, a third ferromagnetic layer, a polycrystalline CoFe layer or CoFeB layer 1232 and a polycrystalline NiFe layer A NiFeB layer 1231 is stacked. Furthermore, the nonmagnetic Ta layer 17 and the 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 first ferromagnetic layer 121 described above may have a laminated structure of two or more layers in which a CoFeB layer and another ferromagnetic layer are added.
  • a substrate such as a wafer substrate, a glass substrate or a sapphire substrate.
  • Reference numeral 12 denotes a TMR element, which is formed of a laminated structure of a first ferromagnetic layer 121 made of polycrystalline CoFeB, a tunnel barrier layer 122, a second ferromagnetic layer 1233, and a third ferromagnetic layer 1232 and 1231.
  • the tunnel barrier layer 122 has a polycrystalline Mg oxide layer or a polycrystalline BMg oxide layer
  • the second ferromagnetic layer 1232 is made of a polycrystalline CoFe layer or a polycrystalline CoFeB layer.
  • the third ferromagnetic layer is formed of a laminated film of a polycrystalline CoFe layer or CoFeB layer 1232 and a polycrystalline NiFe layer or NiFeB layer 1231.
  • an intermediate layer 162 made of a nonmagnetic metal or a nonmagnetic material of a nonmagnetic insulator is disposed.
  • the polycrystalline CoFe can contain a small amount (5 atomic% or less, preferably 0.01 to 1 atomic%) of other atoms such as Pt or the like.
  • 13 is a lower electrode layer (underlayer) of a first layer (Ta layer), and 14 is an antiferromagnetic layer of a second layer (PtMn layer).
  • 15 is a ferromagnetic layer of the third layer (CoFe layer), and 161 is a nonmagnetic layer for exchange coupling of the fourth layer (Ru layer).
  • the fifth layer is a ferromagnetic layer formed of the crystalline CoFeB layer 121.
  • the B atom content (hereinafter referred to as B content) in the crystalline CoFeB layer 121 is preferably set in the range of 0.1 atomic% to 60 atomic%, more preferably 10 atomic% to 50 atomic%.
  • the crystalline CoFeB layer 121 can contain other atoms, for example, Pt, Ni, Mn, etc. in a trace amount (5 atomic% or less, preferably 0.01 to 1 atomic%).
  • the layer formed of the third layer, the fourth layer, and the fifth layer described above is the magnetization fixed layer 19.
  • the substantial magnetization fixed layer 19 is a ferromagnetic layer of the crystalline CoFeB layer 121 of the fifth layer.
  • Reference numeral 122 denotes a tunnel barrier layer of a sixth layer (polycrystalline Mg oxide layer or BMg oxide layer), which is an insulating layer.
  • the tunnel barrier layer 122 may be a single polycrystalline Mg oxide layer or a polycrystalline BMg oxide layer.
  • the tunnel barrier layer 122 can be configured as illustrated in FIG. That is, it is a stacked structure of a polycrystalline Mg oxide layer or polycrystalline BMg oxide layer 1221, a polycrystalline Mg layer or polycrystalline BMg layer 1222, and a polycrystalline Mg oxide layer or polycrystalline BMg oxide layer 1223. Furthermore, it may be a laminated structure in which a plurality of three layers consisting of the laminated films 1221, 1222 and 1223 shown in FIG. 6 are provided.
  • FIG. 8 is an example of another TMR element 12 of the present invention.
  • Reference numerals 12, 121, 122, 162, 1231 to 1233 in FIG. 8 are the same members as those described above.
  • the tunnel barrier layer 122 is a laminated film composed of a polycrystalline Mg oxide layer or polycrystalline BMg oxide layer 82 and Mg layers or BMg layers 81 and 83 on both sides of the layer 82.
  • the use of the layer 81 can be omitted, and the layer 82 can be disposed adjacent to the crystalline CoFe layer or the crystalline CoFeB layer 1233.
  • the use of layer 83 can be omitted and layer 82 can be placed adjacent to crystalline CoFeB layer 121.
  • 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-like crystal is preferably a single crystal in which the (001) crystal plane is 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 minor components such as Zn atom, C atom, Al atom, Ca atom, Si atom, etc. in the range of 10 ppm to 100 ppm. Can.
  • the seventh, ninth, and tenth layers are each a ferromagnetic layer comprising a crystalline CoFe layer or CoFeB layer 1233, a ferromagnetic layer comprising a crystalline CoFe layer or CoFeB layer 1232, a crystalline NiFe layer or a crystalline NiFe layer or It is a ferromagnetic layer composed of a NiFeB layer.
  • the laminated film consisting of the seventh, ninth and tenth layers can function as a magnetization free layer.
  • an eighth layer Ta layer 162 which is an intermediate layer made of a nonmagnetic material, is disposed between the seventh layer and the ninth layer.
  • the eighth layer is made of nonmagnetic metal such as Ru or Ir, nonmagnetic insulator such as Al 2 O 3 (aluminum oxide), SiO 2 (silicon oxide), Si 3 N 4 (silicon nitride), etc. in addition to Ta. It can be used. Further, the film thickness can be set preferably in the range of 50 nm or less, more preferably 5 nm to 40 nm.
  • the crystalline CoFe layer or the crystalline CoFeB layer 1232 constituting the seventh layer and the ninth layer can be deposited by sputtering using a CoFe target or a CoFeB target.
  • the crystalline NiFe layer or the crystalline NiFeB layer 1231 constituting the tenth layer can be deposited by sputtering using a NiFe target or a NiFeB target.
  • the crystalline CoFeB layer 121, the CoFe layer or CoFeB layer 1233, 1232 and the NiFe layer or NiFeB layer 1231 have the same crystal structure as the aggregate 71 composed of the column-like crystal structure 72 shown in FIG. It may be
  • the crystalline CoFeB layer 121 and the CoFe layer or CoFeB layer 1233 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 a tenth layer (Ta layer).
  • Reference numeral 18 denotes a hard mask layer of an eleventh layer (Ru layer).
  • the eleventh 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 eleventh 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 Ta target is attached to the cathode 31, a PtMn target to the cathode 32, a CoFeB target to the cathode 33, a CoFe target to the cathode 34, and a Ru target to the cathode 35.
  • a Mg oxide target is attached to the cathode 51, a BMg oxide target to the cathode 52, a Mg target to the cathode 53, and a BMg target to the cathode 54.
  • the TMR element 122 of the structure illustrated in FIG. 8 can be manufactured by using this cathode 53 or 54.
  • the cathode 41 has a CoFe target for the ninth layer
  • the cathode 42 has a CoFeB target for the seventh layer
  • the cathode 43 has a Ta target for the eighth layer and the eleventh layer
  • the cathode 44 The Ru target for the 12th layer is attached.
  • a NiFe target or a NiFeB target for the tenth layer is attached.
  • the in-plane directions 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 be nonparallel 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 a target 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.
  • a crystalline (preferably polycrystalline) Mg layer is formed by sputtering using a Mg target, and the Mg is introduced into an oxidation chamber (not shown) for introducing an oxidizing gas. Can be obtained by oxidation.
  • a crystalline (preferably polycrystalline) BMg layer is formed by a sputtering method using a BMg target, and the BMg is formed in an oxidation chamber (not shown) for introducing an oxidizing gas. Can be obtained by oxidation.
  • oxidizing gas examples include oxygen gas, ozone gas, water vapor and the like.
  • 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.
  • the 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.
  • Control signals based on the operation result are 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, and a drive system.
  • the substrate transported to the transport chamber 301 is carried out to the film forming chamber 302.
  • the substrate carried into the film forming chamber 302 is the first layer (Ta layer 13), the second layer (PtMn layer 14), the third layer (CoFe layer 15), and the fourth layer (Ru layer) of FIG. 161) and the fifth layer (CoFeB layer 121) are sequentially stacked.
  • the CoFeB layer 121 of the fifth layer at this stage preferably has an amorphous structure, but may have a polycrystalline 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 or a polycrystalline BMg oxide layer 122 is formed as a sixth layer on the amorphous CoFeB 121 layer of the fifth layer.
  • 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.
  • 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 Mg oxide layer or the BMg oxide layer 122 of the sixth layer is once returned again to the transfer chamber 301, and is then carried to the film formation chamber 304.
  • an eleventh layer (Ta layer 17) and a twelfth layer (Ru layer 18) are sequentially stacked.
  • the seventh layer CoFe layer or CoFeB layer 1233, the ninth layer CoFe layer or CoFeB layer 1232 and the tenth layer NiFe layer or NiFeB layer 1231 at this stage preferably has an amorphous structure, but is 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 in the transfer chamber 301 and the film forming chamber 304 through the bus lines 307 and 310. It is implemented by controlling.
  • 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 eighth Ta layer 162 and the eleventh Ta layer 17 are formed using the same target attached to the cathode 54.
  • the storage medium 312 is a storage medium of the present invention, and a control program for executing the manufacture of the magnetoresistive element is stored in the storage medium.
  • 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, and include media capable of storing programs. .
  • the fifth layer (CoFeB layer 121), the seventh layer and the ninth layer (CoFe layer or CoFeB layer 1233, 1232) and the tenth layer (NiFe layer or NiFeB layer 1231) immediately after film formation are used.
  • the amorphous state can be crystallized by annealing. As a result, the polycrystalline structure shown in FIG. 7 can be obtained.
  • the magnetoresistive element 10 immediately after film formation is carried into an annealing furnace (not shown), where the fifth layer 121, the seventh layer 1233, the ninth layer 1232 and the tenth layer 1231 are used.
  • the amorphous state can be phase-changed to the crystalline state.
  • magnetism can be imparted to the PtMn layer 14 which is the second layer.
  • 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 (for example, a heater mechanism, an exhaust mechanism, a transport mechanism, etc.) in the annealing furnace are controlled to execute the annealing process. Can.
  • a Rh layer or an Ir layer can be used.
  • an alloy layer such as an IrMn layer, an IrMnCr layer, an NiMn layer, a PdPtMn layer, a RuRhMn layer, or an OsMn layer is preferably used.
  • the film thickness is preferably 10 to 30 nm.
  • 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 121 uses a target having a CoFeB composition ratio (atomic: atomic ratio) of 60/20/20, Ar as a sputtering gas, and a pressure of 0.03 Pa.
  • the CoFeB layer 121 was formed at a sputtering rate of 0.64 nm / sec by magnetron DC sputtering (chamber 201A).
  • the CoFeB layer 121 at this time had an amorphous structure.
  • the tunnel barrier layer 122 was formed using an MgO target having an MgO composition ratio (atomic: atomic ratio) of 50/50.
  • An Mg oxide layer was formed by magnetron RF sputtering (13.56 MHz) using Ar as a sputtering gas and using a pressure of 0.2 Pa out of a pressure range of 0.01 to 0.4 Pa as a preferable range.
  • the Mg oxide layer had a polycrystalline structure composed of the aggregate 71 of column-like crystals 72 shown in FIG.
  • the film-forming rate of magnetron RF sputtering (13.56 MHz) at this time was 0.14 nm / sec.
  • the substrate is introduced into a sputtering apparatus (chamber 201 B), and the magnetization free layer (the seventh CoFeB layer 1233, the eighth Ta layer 162, the ninth CoFe layer 1232 and the tenth NiFe layer 1231 ) was deposited.
  • the CoFeB layer 1233, the CoFe layer 1232 and the NiFe layer 1231 were formed using Ar as a sputtering gas, a pressure of 0.03 Pa, and a magnetron DC sputtering (chamber 201B) at a sputtering rate of 0.64 nm / sec.
  • targets of CoFeB composition ratio (atomic) 25/25/50, CoFe composition ratio (atomic) 50/50 and NiFe composition ratio (atomic) 40/60 were used, respectively.
  • the CoFeB layer 1233, the CoFe layer 1232 and the NiFe layer 1231 had an amorphous structure.
  • the deposition rate of the Mg oxide layer is 0.14 nm / sec.
  • the deposition rate of the Mg oxide layer is 0.14 nm / sec.
  • the magnetoresistive element 10 which has been deposited by sputtering in each of the magnetron sputtering chambers 201A, 201B and 201C for film formation, is annealed in a heat treatment furnace at a temperature of about 300 ° C. and 4 hours in a magnetic field of 8 kOe. Carried out. As a result, it was confirmed that the amorphous structure of CoFeB layer 121, BoFeB layer 1233, CoFe layer 1232 and NiFe layer 1231 had a polycrystalline structure comprising aggregate 71 of columnar crystals 72 shown in FIG.
  • the magnetoresistive element 10 can act as a magnetoresistive element having a TMR effect. Moreover, predetermined magnetization was given to the antiferromagnetic material layer 14 which is a PtMn layer of a 2nd layer by this annealing process.
  • a magnetoresistive element is manufactured using the same method as the above example except that the use of the eighth layer Ta layer 162, the ninth layer CoFe layer 1232 and the tenth layer NiFe layer 1231 is omitted. Was produced.
  • 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).
  • the magnetoresistive element was manufactured using the same method as that of the ninth example except that the CoFe layer 1232 of the ninth layer was changed to CoFeB (atomic composition ratio: 50/30/20). The same effect as in the example was obtained.
  • the magnetoresistive element was manufactured using the same method as that of the tenth example except that the NiFe layer 1231 of the tenth layer was changed to NiFeB (atomic composition ratio: 50/30/20). The same effect as in the example was obtained.
  • a magnetoresistive element is manufactured by the same method as that of the sixth embodiment except that a polycrystalline BMg oxide layer is used.
  • MR ratio was measured.
  • the deposition rate was 0.14 nm / sec using a BMgO target with a BMgO composition ratio (atomic: atomic ratio) of 25/25/50.
  • the MR ratio significantly improved (compared to the MR ratio according to the embodiment using the polycrystalline Mg oxide layer).
  • MR ratio of 5 times or more was obtained.
  • a magnetoresistive element is manufactured using the completely same method as the above example except that the CoFeB layer 121 of the magnetization fixed layer is changed to a CoFe (atomic composition ratio; 50/50) layer, The MR ratio was measured. As a result, the measurement results were as low as 1/100 or less of the MR ratio obtained by the magnetoresistive element of the present invention.

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Abstract

A magnetoresistive element having a higher MR ratio than conventional ones and a method for manufacturing the magnetoresistive element. The magnetoresistive element comprises a substrate, a crystalline first ferromagnetic layer, a tunnel barrier layer, a crystalline second ferromagnetic layer, a non-magnetic intermediate layer, and a crystalline third ferromagnetic layer.  The first ferromagnetic layer is composed of an alloy containing Co atoms, Fe atoms and B atoms; the tunnel barrier layer has a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer; the second ferromagnetic layer is composed of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms; and the third ferromagnetic layer is composed of a layer which is composed of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms, and a layer which is composed of an alloy containing Ni atoms, Fe atoms and B atoms or an alloy containing Ni atoms and Fe atoms.

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.
　また、特許文献２乃至特許文献５、特許文献７、非特許文献１乃至非特許文献５には、単結晶又は多結晶からなる結晶性酸化マグネシウム膜をトンネルバリア膜として用いたＴＭＲ素子が記載されている。 Patent documents 2 to 5, patent documents 7 and non-patent documents 1 to 5 disclose TMR elements using a crystalline magnesium oxide film consisting of a single crystal or a polycrystal as a tunnel barrier film. ing.
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 特開２００３－３１８４６５号公報JP 2003-318465 A
　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し、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金からなる結晶性第一強磁性体層、
前記結晶性第一強磁性体層の上に位置し、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を有するトンネルバリア層、
前記トンネルバリア層の上に位置し、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる結晶性第二強磁性体層、
前記結晶性第二強磁性体層の上に位置し、非磁性材からなる中間層、並びに、
前記中間層の上に位置し、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる結晶性強磁性体層、及び、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる結晶性強磁性体層を有する第三強磁性体層
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 crystalline first ferromagnetic layer located on the substrate and made of an alloy containing Co atoms, Fe atoms and B atoms,
A tunnel barrier layer located on the crystalline first ferromagnetic layer and having a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer,
A crystalline second ferromagnetic layer located on the tunnel barrier layer and comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and Fe atoms,
An intermediate layer made of a nonmagnetic material located on the crystalline second ferromagnetic layer, and
A crystalline ferromagnetic material layer located on the intermediate layer and made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms, Ni atoms, Fe atoms and B It is a magnetoresistive element characterized by having a third ferromagnetic layer having a crystalline ferromagnetic layer made of an alloy containing atoms or an alloy containing Ni atoms and Fe atoms.
　本発明の第２は、スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する磁気抵抗素子の製造方法であって、
　前記トンネルバリア層を成膜する工程は、スパッタリング法により、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を成膜する工程を有し、
　前記磁化自由層を成膜する工程は、
　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、
　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程である
ことを特徴とする磁気抵抗素子の製造方法である。 According to a second aspect of the present invention, there is provided a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method. A method of manufacturing a magnetoresistive element having
The step of forming the tunnel barrier layer includes the step of forming a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer by sputtering.
In the step of forming the magnetization free layer,
Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. Filming process,
Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom Forming a layer of an alloy containing Ni atoms, Fe atoms and B atoms, or an alloy containing Ni atoms and Fe atoms by a sputtering method using It is a manufacturing method of a magnetoresistive element.
　本発明の第３は、スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する磁気抵抗素子の製造方法であって、
　前記トンネルバリア層を成膜する工程は、スパッタリング法により、結晶性金属マグネシウム又は結晶性ボロンマグネシウム合金からなる層を成膜し、該金属マグネシウム又はボロンマグネシウム合金を酸化して、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を形成する工程を有し、
　前記磁化自由層を成膜する工程は、
　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、
　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程である
ことを特徴とする磁気抵抗素子の製造方法である。 A third aspect of the present invention is a process of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method. A method of manufacturing a magnetoresistive element having
In the step of forming the tunnel barrier layer, a layer made of crystalline metal magnesium or crystalline boron magnesium alloy is formed by sputtering, and the metal magnesium or boron magnesium alloy is oxidized to form a crystalline magnesium oxide layer. Or forming a crystalline boron magnesium oxide layer,
In the step of forming the magnetization free layer,
Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. Filming process,
Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom Forming a layer of an alloy containing Ni atoms, Fe atoms and B atoms, or an alloy containing Ni atoms and Fe atoms by a sputtering method using It is a manufacturing method of a magnetoresistive element.
　本発明の第４は、スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する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記憶媒体であって、
　前記トンネルバリア層及び磁化自由層を成膜する工程を実行する制御プログラムは、
　酸化マグネシウム又はボロンマグネシウム酸化物からなるターゲットを用いたスパッタリング法により、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を成膜する工程、
　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、並びに、
　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程
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する記憶媒体である。 According to a fourth aspect of the present invention, there is provided a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method. A storage medium storing a control program for executing the manufacture of a magnetoresistive element having
A control program for executing the step of forming the tunnel barrier layer and the magnetization free layer is
Forming a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer by a sputtering method using a target made of magnesium oxide or boron magnesium oxide;
Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. A process of filming, and
Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom A control program for executing a step of forming a laminated film by depositing a layer composed of an alloy containing Ni atoms, Fe atoms and B atoms or an alloy containing Ni atoms and Fe atoms by a sputtering method using A storage medium characterized in that
　本発明の第５は、スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する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記憶媒体であって、
　前記トンネルバリア層及び磁化自由層を成膜する工程を実行する制御プログラムは、
　金属マグネシウム又はボロンマグネシウム合金からなるターゲットを用いたスパッタリング法により、結晶性金属マグネシウム又は結晶性ボロンマグネシウム合金からなる層を成膜し、該金属マグネシウム又はボロンマグネシウム合金を酸化して、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を形成する工程、
　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、並びに、
　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程
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する記憶媒体である。 According to a fifth aspect of the present invention, there is provided a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer positioned between the magnetization fixed layer and the magnetization free layer on a substrate using a sputtering method. A storage medium storing a control program for executing the manufacture of a magnetoresistive element having
A control program for executing the step of forming the tunnel barrier layer and the magnetization free layer is
A layer of crystalline metallic magnesium or crystalline boron magnesium alloy is formed by sputtering using a target of metallic magnesium or boron magnesium alloy, and the metallic magnesium or boron magnesium alloy is oxidized to form crystalline magnesium oxide. Forming a layer or a crystalline boron magnesium oxide layer,
Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. A process of filming, and
Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom A control program for executing a step of forming a laminated film by depositing a layer composed of an alloy containing Ni atoms, Fe atoms and B atoms or an alloy containing Ni atoms and Fe atoms by a sputtering method using A storage medium characterized in that
　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、トンネルバリア層、結晶性第二強磁性体層、非磁性中間層、結晶性第三強磁性体層を有する。そして、第一強磁性体層が、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金（以下、ＣｏＦｅＢと記す）からなる。また、トンネルバリア層は、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を有する。さらに、第二強磁性体層はＣｏＦｅＢ或いは、Ｃｏ原子とＦｅ原子を含有する合金（以下、ＣｏＦｅと記す）からなる。第三強磁性体層は、ＣｏＦｅ層又はＣｏＦｅＢ層からなる結晶性強磁性体層と、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる結晶性強磁性体層との積層膜からなる。尚、以下の説明においては、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金をＮｉＦｅＢ、Ｎｉ原子とＦｅ原子を含有する合金をＮｉＦｅと記す。また、酸化マグネシウムをＭｇ酸化物、ボロンマグネシウム酸化物をＢＭｇ酸化物、金属マグネシウムをＭｇ、ボロンマグネシウム合金をＢＭｇと記す。 The magnetoresistive element of the present invention comprises a substrate, a crystalline first ferromagnetic layer, a tunnel barrier layer, a crystalline second ferromagnetic layer, a nonmagnetic intermediate layer, and a crystalline third ferromagnetic layer. The first ferromagnetic layer is made of an alloy containing Co atoms, Fe atoms, and B atoms (hereinafter referred to as CoFeB). In addition, the tunnel barrier layer has a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer. Furthermore, the second ferromagnetic layer is made of CoFeB or an alloy containing Co atoms and Fe atoms (hereinafter referred to as CoFe). The third ferromagnetic layer comprises a crystalline ferromagnetic layer comprising a CoFe layer or a CoFeB layer, and a crystalline strong layer comprising an alloy containing Ni atoms, Fe atoms and B atoms, or an alloy containing Ni atoms and Fe atoms It consists of a laminated film with a magnetic layer. In the following description, an alloy containing Ni atoms, Fe atoms and B atoms is referred to as NiFeB, and an alloy containing Ni atoms and Fe atoms is referred to as NiFe. Further, magnesium oxide is described as Mg oxide, boron magnesium oxide as BMg oxide, metal magnesium as Mg, and a boron magnesium alloy as BMg.
　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、本発明に係る磁気抵抗素子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、１２層の多層膜が形成されている。この１２層の多層膜では、最下層の第１層（Ｔａ層）から最上層の第１２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、非磁性金属層（Ｒｕ）層１６１、第一強磁性体層であるＣｏＦｅＢ層１２１、トンネルバリア層である非磁性多結晶Ｍｇ酸化物層又はＢＭｇ酸化物層１２２が積層されている。さらにその上に、第二強磁性体層である多結晶ＣｏＦｅ層又はＣｏＦｅＢ層１２３３、非磁性Ｔａ層１６２、第三強磁性体層である多結晶ＣｏＦｅ層又はＣｏＦｅＢ層１２３２及び多結晶ＮｉＦｅ層又はＮｉＦｅＢ層１２３１が積層されている。さらにまた、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。 FIG. 1 shows an example of the laminated structure of the magnetoresistive element 10 according to 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 12 layers including the TMR element 12 is formed on the substrate 11. The twelve-layer multilayer film is a multilayer film structure from the lowermost first layer (Ta layer) to the uppermost twelfth layer (Ru layer). Specifically, the PtMn layer 14, the CoFe layer 15, the nonmagnetic metal layer (Ru) layer 161, the first ferromagnetic layer CoFeB layer 121, the tunnel barrier layer nonmagnetic polycrystalline Mg oxide layer or BMg An oxide layer 122 is stacked. Furthermore, a second ferromagnetic layer, a polycrystalline CoFe layer or CoFeB layer 1233, a nonmagnetic Ta layer 162, a third ferromagnetic layer, a polycrystalline CoFe layer or CoFeB layer 1232 and a polycrystalline NiFe layer A NiFeB layer 1231 is stacked. Furthermore, the nonmagnetic Ta layer 17 and the 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.
　また、本発明では、上述の第一強磁性体層１２１は、ＣｏＦｅＢ層と他の強磁性体層とを加えた２層以上の積層構造としても良い。 In the present invention, the first ferromagnetic layer 121 described above may have a laminated structure of two or more layers in which a CoFeB layer and another ferromagnetic layer are added.
　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。 11 is a substrate such as a wafer substrate, a glass substrate or a sapphire substrate.
　１２はＴＭＲ素子で、多結晶ＣｏＦｅＢからなる第一強磁性体層１２１、トンネルバリア層１２２、第二強磁性体層１２３３及び第三強磁性体層１２３２，１２３１の積層構造体によって構成されている。トンネルバリア層１２２は多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層を有し、第二強磁性体層１２３２は多結晶ＣｏＦｅ層又は多結晶ＣｏＦｅＢ層からなる。第三強磁性体層は多結晶ＣｏＦｅ層又はＣｏＦｅＢ層１２３２及び多結晶ＮｉＦｅ層又はＮｉＦｅＢ層１２３１の積層膜からなる。 Reference numeral 12 denotes a TMR element, which is formed of a laminated structure of a first ferromagnetic layer 121 made of polycrystalline CoFeB, a tunnel barrier layer 122, a second ferromagnetic layer 1233, and a third ferromagnetic layer 1232 and 1231. . The tunnel barrier layer 122 has a polycrystalline Mg oxide layer or a polycrystalline BMg oxide layer, and the second ferromagnetic layer 1232 is made of a polycrystalline CoFe layer or a polycrystalline CoFeB layer. The third ferromagnetic layer is formed of a laminated film of a polycrystalline CoFe layer or CoFeB layer 1232 and a polycrystalline NiFe layer or NiFeB layer 1231.
　上記第二強磁性体層１２３３と第三強磁性体層１２３２との間には、非磁性金属又は非磁性絶縁物の非磁性材からなる中間層１６２が配置される。 Between the second ferromagnetic layer 1233 and the third ferromagnetic layer 1232, an intermediate layer 162 made of a nonmagnetic metal or a nonmagnetic material of a nonmagnetic insulator is disposed.
　本発明によれば、上記多結晶ＣｏＦｅには、他の原子、例えばＰｔ等を微量含有（５ａｔｏｍｉｃ％以下、好ましくは、０．０１乃至１ａｔｏｍｉｃ％）させることができる。 According to the present invention, the polycrystalline CoFe can contain a small amount (5 atomic% or less, preferably 0.01 to 1 atomic%) of other atoms such as Pt or the like.
　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、１６１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 (underlayer) of a first layer (Ta layer), and 14 is an antiferromagnetic layer of a second layer (PtMn layer). 15 is a ferromagnetic layer of the third layer (CoFe layer), and 161 is a nonmagnetic layer for exchange coupling of the fourth layer (Ru layer).
　第５層は、結晶性ＣｏＦｅＢ層１２１からなる強磁性体層である。結晶性ＣｏＦｅＢ層１２１でのＢ原子の含有量（以下、Ｂ含有量と記す）は、好ましくは０．１ａｔｏｍｉｃ％乃至６０ａｔｍｉｃ％、より好ましくは１０ａｔｏｍｉｃ％乃至５０ａｔｍｉｃ％の範囲に設定される。 The fifth layer is a ferromagnetic layer formed of the crystalline CoFeB layer 121. The B atom content (hereinafter referred to as B content) in the crystalline CoFeB layer 121 is preferably set in the range of 0.1 atomic% to 60 atomic%, more preferably 10 atomic% to 50 atomic%.
　本発明では、結晶性ＣｏＦｅＢ層１２１には、他の原子、例えば、Ｐｔ、Ｎｉ、Ｍｎ等を微量（５ａｔｏｍｉｃ％以下、好ましくは、０．０１乃至１ａｔｏｍｉｃ％）含有させることができる。 In the present invention, the crystalline CoFeB layer 121 can contain other atoms, for example, Pt, Ni, Mn, etc. in a trace amount (5 atomic% or less, preferably 0.01 to 1 atomic%).
　上述の第３層、第４層及び第５層とからなる層は磁化固定層１９である。実質的な磁化固定層１９は、第５層の結晶性ＣｏＦｅＢ層１２１の強磁性体層である。 The layer formed of the third layer, the fourth layer, and the fifth layer described above is the magnetization fixed layer 19. The substantial magnetization fixed layer 19 is a ferromagnetic layer of the crystalline CoFeB layer 121 of the fifth layer.
　１２２は、第６層（多結晶Ｍｇ酸化物層又はＢＭｇ酸化物層）のトンネルバリア層で、絶縁層である。トンネルバリア層１２２は、単一の多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層であってもよい。 Reference numeral 122 denotes a tunnel barrier layer of a sixth layer (polycrystalline Mg oxide layer or BMg oxide layer), which is an insulating layer. The tunnel barrier layer 122 may be a single polycrystalline Mg oxide layer or a polycrystalline BMg oxide layer.
　また、本発明は、トンネルバリア層１２２を図６に図示した構成とすることができる。即ち、多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層１２２１、多結晶Ｍｇ層又は多結晶ＢＭｇ層１２２２及び多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層１２２３の積層構造である。さらに、図６に図示した積層膜１２２１、１２２２及び１２２３からなる３層を複数設けた積層構造体であってもよい。 Further, in the present invention, the tunnel barrier layer 122 can be configured as illustrated in FIG. That is, it is a stacked structure of a polycrystalline Mg oxide layer or polycrystalline BMg oxide layer 1221, a polycrystalline Mg layer or polycrystalline BMg layer 1222, and a polycrystalline Mg oxide layer or polycrystalline BMg oxide layer 1223. Furthermore, it may be a laminated structure in which a plurality of three layers consisting of the laminated films 1221, 1222 and 1223 shown in FIG. 6 are provided.
　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、１２１、１２２、１６２、１２３１乃至１２３３は、上述のものと同一部材である。本例では、トンネルバリア層１２２は、多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層８２と、該層８２の両側のＭｇ層又はＢＭｇ層８１及び８３とからなる積層膜である。また、本発明では、層８１の使用を省略し、層８２を結晶性ＣｏＦｅ層又は結晶性ＣｏＦｅＢ層１２３３に隣接配置させることができる。又は、層８３の使用を省略し、層８２を結晶性ＣｏＦｅＢ層１２１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, 121, 122, 162, 1231 to 1233 in FIG. 8 are the same members as those described above. In this example, the tunnel barrier layer 122 is a laminated film composed of a polycrystalline Mg oxide layer or polycrystalline BMg oxide layer 82 and Mg layers or BMg layers 81 and 83 on both sides of the layer 82. Also, in the present invention, the use of the layer 81 can be omitted, and the layer 82 can be disposed adjacent to the crystalline CoFe layer or the crystalline CoFeB layer 1233. Alternatively, the use of layer 83 can be omitted and layer 82 can be placed adjacent to crystalline CoFeB layer 121.
　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。該カラム状結晶は、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-like crystal is preferably a single crystal in which the (001) crystal plane is 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 minor components such as Zn atom, C atom, Al atom, Ca atom, Si atom, etc. in the range of 10 ppm to 100 ppm. Can.
　第７層、第９層及び第１０層は、それぞれ、結晶性ＣｏＦｅ層又はＣｏＦｅＢ層１２３３からなる強磁性体層、結晶性ＣｏＦｅ層又はＣｏＦｅＢ層１２３２からなる強磁性体層、結晶性ＮｉＦｅ層又はＮｉＦｅＢ層からなる強磁性体層である。該第７層、第９層及び第１０層からなる積層膜は、磁化自由層として機能することができる。 The seventh, ninth, and tenth layers are each a ferromagnetic layer comprising a crystalline CoFe layer or CoFeB layer 1233, a ferromagnetic layer comprising a crystalline CoFe layer or CoFeB layer 1232, a crystalline NiFe layer or a crystalline NiFe layer or It is a ferromagnetic layer composed of a NiFeB layer. The laminated film consisting of the seventh, ninth and tenth layers can function as a magnetization free layer.
　本発明においては、該第７層と該第９層との間に、非磁性材からなる中間層である第８層のＴａ層１６２が配置される。第８層は、Ｔａの他に、ＲｕやＩｒ等の非磁性金属、Ａｌ2Ｏ3（酸化アルミニウム）、ＳｉＯ2（酸化シリコン）やＳｉ3Ｎ4（窒化シリコン）等の非磁性絶縁物を用いることができる。また、膜厚は、好ましくは５０ｎｍ以下、より好ましくは５ｎｍ乃至４０ｎｍの範囲に設定することができる。 In the present invention, an eighth layer Ta layer 162, which is an intermediate layer made of a nonmagnetic material, is disposed between the seventh layer and the ninth layer. The eighth layer is made of nonmagnetic metal such as Ru or Ir, nonmagnetic insulator such as Al 2 O 3 (aluminum oxide), SiO 2 (silicon oxide), Si 3 N 4 (silicon nitride), etc. in addition to Ta. It can be used. Further, the film thickness can be set preferably in the range of 50 nm or less, more preferably 5 nm to 40 nm.
　第７層及び第９層を構成する結晶性ＣｏＦｅ層又は結晶性ＣｏＦｅＢ層１２３２は、ＣｏＦｅターゲット又は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。 The crystalline CoFe layer or the crystalline CoFeB layer 1232 constituting the seventh layer and the ninth layer can be deposited by sputtering using a CoFe target or a CoFeB target.
　第１０層を構成する結晶性ＮｉＦｅ層又は結晶性ＮｉＦｅＢ層１２３１は、ＮｉＦｅターゲット又はＮｉＦｅＢ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。 The crystalline NiFe layer or the crystalline NiFeB layer 1231 constituting the tenth layer can be deposited by sputtering using a NiFe target or a NiFeB target.
　上記した結晶性ＣｏＦｅＢ層１２１と、ＣｏＦｅ層又はＣｏＦｅＢ層１２３３、１２３２、ＮｉＦｅ層又はＮｉＦｅＢ層１２３１は、前述の図７に図示したカラム状結晶構造７２からなる集合体７１と同一の構造の結晶構造のものであってもよい。 The crystalline CoFeB layer 121, the CoFe layer or CoFeB layer 1233, 1232 and the NiFe layer or NiFeB layer 1231 have the same crystal structure as the aggregate 71 composed of the column-like crystal structure 72 shown in FIG. It may be
　結晶性ＣｏＦｅＢ層１２１とＣｏＦｅ層又はＣｏＦｅＢ層１２３３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 layer 121 and the CoFe layer or CoFeB layer 1233 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１０層（Ｔａ層）の電極層である。 Reference numeral 17 denotes an electrode layer of a tenth layer (Ta layer).
　１８は、第１１層（Ｒｕ層）のハードマスク層である。第１１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。 Reference numeral 18 denotes a hard mask layer of an eleventh layer (Ru layer). The eleventh 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１１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 eleventh 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Ｔａ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ターゲットが、カソード３４にはＣｏＦｅターゲットが、カソード３５にはＲｕターゲットが装着される。 In the above, for example, a Ta target is attached to the cathode 31, a PtMn target to the cathode 32, a CoFeB target to the cathode 33, a CoFe target to the cathode 34, and a Ru target to the cathode 35.
　また、カソード５１にはＭｇ酸化物ターゲットが、カソード５２にはＢＭｇ酸化物ターゲットが、カソード５３にＭｇターゲットが、カソード５４にはＢＭｇターゲットが装着される。図８に図示した構造のＴＭＲ素子１２２は、このカソード５３又は５４を用いることによって作製することができる。 Further, a Mg oxide target is attached to the cathode 51, a BMg oxide target to the cathode 52, a Mg target to the cathode 53, and a BMg target to the cathode 54. The TMR element 122 of the structure illustrated in FIG. 8 can be manufactured by using this cathode 53 or 54.
　カソード４１には、第９層のためのＣｏＦｅターゲットが、カソード４２には第７層のためのＣｏＦｅＢターゲットが、カソード４３には第８層及び第１１層のためのＴａターゲットが、カソード４４には第１２層のためのＲｕターゲットが装着される。カソード４５には、第１０層のためのＮｉＦｅターゲット又はＮｉＦｅＢターゲットが装着される。 The cathode 41 has a CoFe target for the ninth layer, the cathode 42 has a CoFeB target for the seventh layer, the cathode 43 has a Ta target for the eighth layer and the eleventh layer, and the cathode 44 The Ru target for the 12th layer is attached. On the cathode 45, a NiFe target or a NiFeB target for the tenth layer is attached.
　上記カソード３１乃至３５、４１乃至４５、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。 It is preferable that the in-plane directions 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 be nonparallel 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 a target 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.
　また、結晶性Ｍｇ酸化物層は、Ｍｇターゲットを用いたスパッタリング法により、結晶性（好ましくは、多結晶）Ｍｇ層を成膜し、該Ｍｇを酸化性ガス導入の酸化チャンバ（不図示）内で酸化することにより得ることができる。 In addition, as the crystalline Mg oxide layer, a crystalline (preferably polycrystalline) Mg layer is formed by sputtering using a Mg target, and the Mg is introduced into an oxidation chamber (not shown) for introducing an oxidizing gas. Can be obtained by oxidation.
　また、結晶性ＢＭｇ酸化物層は、ＢＭｇターゲットを用いたスパッタリング法により、結晶性（好ましくは、多結晶）ＢＭｇ層を成膜し、該ＢＭｇを酸化性ガス導入の酸化チャンバ（不図示）内で酸化することにより得ることができる。 In addition, as the crystalline BMg oxide layer, a crystalline (preferably polycrystalline) BMg layer is formed by a sputtering method using a BMg target, and the BMg is formed in an oxidation chamber (not shown) for introducing an oxidizing gas. Can be obtained by oxidation.
　上記酸化性ガスとしては、酸素ガス、オゾンガス、水蒸気等が挙げられる。 Examples of the oxidizing gas include oxygen gas, ozone gas, water vapor and the like.
　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.
　本発明では、ロードロック・アンロードロックチャンバ３０５内の基板（不図示）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。この演算結果に基づく制御信号が、バスライン３０７，３１１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。該各種装置としては、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る。 In the present invention, the 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. Control signals based on the operation result are 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, and a drive system.
　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（Ｔａ層１３）、第２層（ＰｔＭｎ層１４）、第３層（ＣｏＦｅ層１５）、第４層（Ｒｕ層１６１）及び第５層（ＣｏＦｅＢ層１２１）が順次積層される。この段階での第５層のＣｏＦｅＢ層１２１は、好ましくはアモルファス構造となっているが、多結晶構造であってもよい。 The substrate transported to the transport chamber 301 is carried out to the film forming chamber 302. Here, the substrate carried into the film forming chamber 302 is the first layer (Ta layer 13), the second layer (PtMn layer 14), the third layer (CoFe layer 15), and the fourth layer (Ru layer) of FIG. 161) and the fifth layer (CoFeB layer 121) are sequentially stacked. The CoFeB layer 121 of the fifth layer at this stage preferably has an amorphous structure, but may have a polycrystalline 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。 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.
　成膜チャンバ３０３内で、上記第５層のアモルファスＣｏＦｅＢ１２１層の上に、第６層として、多結晶Ｍｇ酸化物層又は多結晶ＢＭｇ酸化物層１２２の成膜を実行する。該成膜は、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３０７，３０９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 film forming chamber 303, a polycrystalline Mg oxide layer or a polycrystalline BMg oxide layer 122 is formed as a sixth layer on the amorphous CoFeB 121 layer of the fifth layer. 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. 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層のＭｇ酸化物層又はＢＭｇ酸化物層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。 The substrate having the laminated film up to the Mg oxide layer or the BMg oxide layer 122 of the sixth layer is once returned again to the transfer chamber 301, and is then carried to the film formation chamber 304.
　成膜チャンバ３０４内で、上記第６層１２２の上に、第７層（ＣｏＦｅ層又はＣｏＦｅＢ層１２３３）、第８層（Ｔａ層１６２）、第９層（ＣｏＦｅ層又はＣｏＦｅ層１２３２）、第１０層（ＮｉＦｅ層又はＮｉＦｅＢ層１２３１）が積層される。次いで、第１１層（Ｔａ層１７）及び第１２層（Ｒｕ層１８）が順次積層される。この段階での第７層のＣｏＦｅ層又はＣｏＦｅＢ層１２３３、第９層のＣｏＦｅ層又はＣｏＦｅＢ層１２３２及び第１０層のＮｉＦｅ層又はＮｉＦｅＢ層１２３１は、好ましくはアモルファス構造となっているが、多結晶構造であってもよい。 In the film forming chamber 304, the seventh layer (CoFe layer or CoFeB layer 1233), the eighth layer (Ta layer 162), the ninth layer (CoFe layer or CoFe layer 1232), the seventh layer (CoFe layer or CoFeB layer 1233), Ten layers (NiFe layer or NiFeB layer 1231) are stacked. Next, an eleventh layer (Ta layer 17) and a twelfth layer (Ru layer 18) are sequentially stacked. The seventh layer CoFe layer or CoFeB layer 1233, the ninth layer CoFe layer or CoFeB layer 1232 and the tenth layer NiFe layer or NiFeB layer 1231 at this stage preferably has an amorphous structure, but is 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３０７，３１０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 in the transfer chamber 301 and the film forming chamber 304 through the bus lines 307 and 310. 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.
　尚、第８層のＴａ層１６２及び第１１層のＴａ層１７は、カソード５４に装着した同一のターゲットを用いて成膜される。 The eighth Ta layer 162 and the eleventh Ta layer 17 are formed using the same target attached to the cathode 54.
　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。 The storage medium 312 is a storage medium of the present invention, and a control program for executing the manufacture of the magnetoresistive element is stored in the storage medium.
　本発明で用いる記憶媒体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, and include media capable of storing programs. .
　また、本発明は、成膜直後の上記第５層（ＣｏＦｅＢ層１２１）、第７層及び第９層（ＣｏＦｅ層又はＣｏＦｅＢ層１２３３，１２３２）及び第１０層（ＮｉＦｅ層又はＮｉＦｅＢ層１２３１）のアモルファス状態をアニーリングにより結晶化することができる。その結果、図７に図示した多結晶構造とすることができる。このため、本発明では、成膜直後の磁気抵抗素子１０をアニーリング炉（不図示）に搬入し、ここで、上記第５層１２１、第７層１２３３、第９層１２３２及び第１０層１２３１のアモルファス状態を結晶状態に相変化させることができる。 Further, according to the present invention, the fifth layer (CoFeB layer 121), the seventh layer and the ninth layer (CoFe layer or CoFeB layer 1233, 1232) and the tenth layer (NiFe layer or NiFeB layer 1231) immediately after film formation are used. The amorphous state can be crystallized by annealing. As a result, the polycrystalline structure shown in FIG. 7 can be obtained. For this reason, in the present invention, the magnetoresistive element 10 immediately after film formation is carried into an annealing furnace (not shown), where the fifth layer 121, the seventh layer 1233, the ninth layer 1232 and the tenth layer 1231 are used. The amorphous state can be phase-changed to the crystalline state.
　また、この時、第２層であるＰｔＭｎ層１４に磁気を付与することができる。 At this time, magnetism can be imparted to the PtMn layer 14 which is the second layer.
　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（図示せず、例えば、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 (for example, a heater mechanism, an exhaust mechanism, a transport mechanism, etc.) in the annealing furnace are controlled to execute the annealing process. Can.
　また、本発明では、上記第４層１６１のＲｕ層に換えて、Ｒｈ層又はＩｒ層を用いることができる。 Further, in the present invention, in place of the Ru layer of the fourth layer 161, a Rh layer or an Ir layer can be used.
　また、本発明では、上記第２層のＰｔＭｎ１４層に換えて、ＩｒＭｎ層、ＩｒＭｎＣｒ層、ＮｉＭｎ層、ＰｄＰｔＭｎ層、ＲｕＲｈＭｎ層やＯｓＭｎ層等の合金層も好ましく用いられる。又、その膜厚は、１０乃至３０ｎｍが好ましい。 In the present invention, instead of the PtMn 14 layer of the second layer, an alloy layer such as an IrMn layer, an IrMnCr layer, an NiMn layer, a PdPtMn layer, a RuRhMn layer, or an OsMn layer is preferably used. The film thickness is preferably 10 to 30 nm.
　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１２１は、ＣｏＦｅＢ組成比（ａｔｏｍｉｃ：原子比）６０／２０／２０のターゲットを用い、Ａｒをスパッタガスとし、その圧力を０．０３Ｐａとした。ＣｏＦｅＢ層１２１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１２１は、アモルファス構造を有していた。 The CoFeB layer 121 uses a target having a CoFeB composition ratio (atomic: atomic ratio) of 60/20/20, Ar as a sputtering gas, and a pressure of 0.03 Pa. The CoFeB layer 121 was formed at a sputtering rate of 0.64 nm / sec by magnetron DC sputtering (chamber 201A). The CoFeB layer 121 at this time had an amorphous structure.
　続いて、スパッタリング装置（チャンバ２０１Ｃ）に換えて、ＭｇＯ組成比（ａｔｏｍｉｃ：原子比）５０／５０のＭｇＯターゲットを用いてトンネルバリア層１２２を成膜した。スパッタガスとしてＡｒを用い、好適範囲０．０１乃至０．４Ｐａの圧力範囲のうち、０．２Ｐａの圧力を用いて、マグネトロンＲＦスパッタリング（１３．５６ＭＨｚ）によりＭｇ酸化物層を成膜した。この時、Ｍｇ酸化物層は、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。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, in place of the sputtering apparatus (chamber 201C), the tunnel barrier layer 122 was formed using an MgO target having an MgO composition ratio (atomic: atomic ratio) of 50/50. An Mg oxide layer was formed by magnetron RF sputtering (13.56 MHz) using Ar as a sputtering gas and using a pressure of 0.2 Pa out of a pressure range of 0.01 to 0.4 Pa as a preferable range. At this time, the Mg oxide layer had a polycrystalline structure composed of the aggregate 71 of column-like crystals 72 shown in FIG. Moreover, the film-forming rate of magnetron RF sputtering (13.56 MHz) at this time was 0.14 nm / sec.
　さらに、基板をスパッタリング装置（チャンバ２０１Ｂ）に導入して、磁化自由層（第７層のＣｏＦｅＢ層１２３３、第８層のＴａ層１６２、第９層のＣｏＦｅ層１２３２及び第１０層のＮｉＦｅ層１２３１）である強磁性体層を成膜した。 Furthermore, the substrate is introduced into a sputtering apparatus (chamber 201 B), and the magnetization free layer (the seventh CoFeB layer 1233, the eighth Ta layer 162, the ninth CoFe layer 1232 and the tenth NiFe layer 1231 ) Was deposited.
　ＣｏＦｅＢ層１２３３とＣｏＦｅ層１２３２とＮｉＦｅ層１２３１とは、Ａｒをスパッタガスとし、その圧力を０．０３Ｐａとし、マグネトロンＤＣスパッタ（チャンバ２０１Ｂ）によりスパッタレート０．６４ｎｍ／ｓｅｃで成膜した。この時、それぞれ、ＣｏＦｅＢ組成比（ａｔｏｍｉｃ）２５／２５／５０、ＣｏＦｅ組成比（ａｔｏｍｉｃ）５０／５０及びＮｉＦｅ組成比（ａｔｏｍｉｃ）４０／６０のターゲットを用いた。この成膜直後において、ＣｏＦｅＢ層１２３３、ＣｏＦｅ層１２３２と、ＮｉＦｅ層１２３１とは、アモルファス構造であった。 The CoFeB layer 1233, the CoFe layer 1232 and the NiFe layer 1231 were formed using Ar as a sputtering gas, a pressure of 0.03 Pa, and a magnetron DC sputtering (chamber 201B) at a sputtering rate of 0.64 nm / sec. At this time, targets of CoFeB composition ratio (atomic) 25/25/50, CoFe composition ratio (atomic) 50/50 and NiFe composition ratio (atomic) 40/60 were used, respectively. Immediately after this film formation, the CoFeB layer 1233, the CoFe layer 1232 and the NiFe layer 1231 had an amorphous structure.
　本例では、Ｍｇ酸化物層の成膜速度は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 Mg oxide layer is 0.14 nm / sec. However, there is no problem in depositing in the range of 0.01 nm to 1.0 nm / sec.
　成膜用マグネトロンスパッタリングチャンバ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。この結果、アモルファス構造のＣｏＦｅＢ層１２１、ＢｏＦｅＢ層１２３３、ＣｏＦｅ層１２３２及びＮｉＦｅ層１２３１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 magnetoresistive element 10, which has been deposited by sputtering in each of the magnetron sputtering chambers 201A, 201B and 201C for film formation, is annealed in a heat treatment furnace at a temperature of about 300 ° C. and 4 hours in a magnetic field of 8 kOe. Carried out. As a result, it was confirmed that the amorphous structure of CoFeB layer 121, BoFeB layer 1233, CoFe layer 1232 and NiFe layer 1231 had a polycrystalline structure comprising aggregate 71 of columnar crystals 72 shown in FIG.
　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. Moreover, predetermined magnetization was given to the antiferromagnetic material layer 14 which is a PtMn layer of a 2nd layer by this annealing process.
　比較例として、上記第８層のＴａ層１６２、第９層のＣｏＦｅ層１２３２及び第１０層のＮｉＦｅ層１２３１の使用を省略した他は、上記実施例と同様の方法を用いて、磁気抵抗素子を作製した。 As a comparative example, a magnetoresistive element is manufactured using the same method as the above example except that the use of the eighth layer Ta layer 162, the ninth layer CoFe layer 1232 and the tenth layer NiFe layer 1231 is omitted. Was produced.
　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、上記実施例において、第７層のＣｏＦｅＢ層１２３３をＣｏＦｅ（原子組成比５０／５０）に変更した他は、全く同様の方法を用いて、磁気抵抗素子を作製したところ、上記実施例と同様の効果が得られた。 Moreover, when the magnetoresistive element was manufactured using the completely same method except changing the CoFeB layer 1233 of the 7th layer into CoFe (atomic composition ratio 50/50) in the said Example, with the said Example and Similar effects were obtained.
　また、上記実施例において、第９層のＣｏＦｅ層１２３２をＣｏＦｅＢ（原子組成比；５０／３０／２０）に変更した他は、全く同様の方法を用いて、磁気抵抗素子を作製したところ、上記実施例と同様の効果が得られた。 Further, in the above example, the magnetoresistive element was manufactured using the same method as that of the ninth example except that the CoFe layer 1232 of the ninth layer was changed to CoFeB (atomic composition ratio: 50/30/20). The same effect as in the example was obtained.
　また、上記実施例において、第１０層のＮｉＦｅ層１２３１をＮｉＦｅＢ（原子組成比；５０／３０／２０）に変更した他は、全く同様の方法を用いて、磁気抵抗素子を作製したところ、上記実施例と同様の効果が得られた。 Also, in the above example, the magnetoresistive element was manufactured using the same method as that of the tenth example except that the NiFe layer 1231 of the tenth layer was changed to NiFeB (atomic composition ratio: 50/30/20). The same effect as in the example was obtained.
　また、上述の実施例で用いた第６層の多結晶Ｍｇ酸化物層に換えて、第６層として多結晶ＢＭｇ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製し、ＭＲ比を測定した。ＢＭｇＯ組成比（ａｔｏｍｉｃ：原子比）２５／２５／５０のＢＭｇＯターゲットを用い、成膜速度は０．１４ｎｍ／ｓｅｃとした。その結果、上述の多結晶Ｍｇ酸化物層を用いた実施例と比較して、一層、顕著に改善されたＭＲ比（多結晶Ｍｇ酸化物層を用いた実施例によるＭＲ比に対し、１．５倍以上のＭＲ比）が得られた。 Moreover, in place of the polycrystalline Mg oxide layer of the sixth layer used in the above-described embodiment, a magnetoresistive element is manufactured by the same method as that of the sixth embodiment except that a polycrystalline BMg oxide layer is used. , MR ratio was measured. The deposition rate was 0.14 nm / sec using a BMgO target with a BMgO composition ratio (atomic: atomic ratio) of 25/25/50. As a result, compared with the embodiment using the polycrystalline Mg oxide layer described above, the MR ratio significantly improved (compared to the MR ratio according to the embodiment using the polycrystalline Mg oxide layer). MR ratio of 5 times or more was obtained.
　さらに、比較例として、磁化固定層のＣｏＦｅＢ層１２１をＣｏＦｅ（原子組成比；５０／５０）層に変更した他は、上記実施例と全く同様の方法を用いて、磁気抵抗素子を作製し、ＭＲ比を測定した。その結果、本発明の磁気抵抗素子により得たＭＲ比の１／１００以下と全く低い測定結果であった。 Furthermore, as a comparative example, a magnetoresistive element is manufactured using the completely same method as the above example except that the CoFeB layer 121 of the magnetization fixed layer is changed to a CoFe (atomic composition ratio; 50/50) layer, The MR ratio was measured. As a result, the measurement results were as low as 1/100 or less of the MR ratio obtained by the magnetoresistive element of the present invention.
　１０：磁気抵抗素子、１１：基板、１２：ＴＭＲ素子、１２１：ＣｏＦｅＢ強磁性体層（第５層）、１２２：トンネルバリア層（第６層）、１２３１：ＮｉＦｅ／ＮｉＦｅＢ強磁性体層（第１０層；磁化自由層）、１２３２：ＣｏＦｅ／ＣｏＦｅＢ強磁性体層（第９層；磁化自由層）、１２３３：ＣｏＦｅＢ／ＣｏＦｅＢ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：反強磁性層（第２層）、１５：強磁性体層（第３層）、１６１：交換結合用非磁性層（第４層）、１６２：非磁性中間層（第８層）、１７：上電極層（第１１層）、１８：ハードマスク層（第１２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：カラム状結晶群の集合体、７２：カラム状結晶、８１：Ｍｇ層又はＢＭｇ層、８２：Ｍｇ酸化物層又はＢＭｇ酸化物層、８３：Ｍｇ層又はＢＭｇ層 10: magnetoresistive element, 11: substrate, 12: TMR element, 121: CoFeB ferromagnetic layer (fifth layer), 122: tunnel barrier layer (sixth layer), 1231: NiFe / NiFeB ferromagnetic layer (fifth layer) 10 layers: magnetization free layer), 1232: CoFe / CoFeB ferromagnetic layer (ninth layer; magnetization free layer), 1233: CoFeB / CoFeB 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), 161: nonmagnetic layer for exchange coupling (fourth layer), 162: Nonmagnetic intermediate layer (eighth layer), 17: upper electrode layer (eleventh layer), 18: hard mask layer (12th layer), 19: magnetization fixed layer, 200: magnetoresistive element formation device, 201A to 201C: Deposition chamber, 202: transfer chamber, 203: etch Chamber, 204: gate valve, 205, 206: load lock / unload lock chamber, 31 to 35, 41 to 45, 51 to 54: cathode, 207A to 207C: power input part, 301: transfer chamber, 302 to 304: Deposition chamber 305: load lock / unlock 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: transistor 71: aggregate of columnar crystals 72: columnar crystals 81: Mg layer or BMg layer 82: Mg oxide layer or BMg oxide layer 83: Mg layer or BMg layer

Claims (6)

  1. 　基板、
    前記基板の上に位置し、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金からなる結晶性第一強磁性体層、
    前記結晶性第一強磁性体層の上に位置し、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を有するトンネルバリア層、
    前記トンネルバリア層の上に位置し、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる結晶性第二強磁性体層、
    前記結晶性第二強磁性体層の上に位置し、非磁性材からなる中間層、並びに、
    前記中間層の上に位置し、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる結晶性強磁性体層、及び、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる結晶性強磁性体層を有する第三強磁性体層
    を有することを特徴とする磁気抵抗素子。     substrate,
    A crystalline first ferromagnetic layer located on the substrate and made of an alloy containing Co atoms, Fe atoms and B atoms,
    A tunnel barrier layer located on the crystalline first ferromagnetic layer and having a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer,
    A crystalline second ferromagnetic layer located on the tunnel barrier layer and comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and Fe atoms,
    An intermediate layer made of a nonmagnetic material located on the crystalline second ferromagnetic layer, and
    A crystalline ferromagnetic material layer located on the intermediate layer and made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms, Ni atoms, Fe atoms and B A magnetoresistive element comprising a third ferromagnetic layer having a crystalline ferromagnetic layer made of an alloy containing atoms or an alloy containing Ni atoms and Fe atoms.
  2. 　前記非磁性材は、非磁性金属又は非磁性絶縁物であ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 nonmagnetic material is a nonmagnetic metal or a nonmagnetic insulator.
  3. 　スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する磁気抵抗素子の製造方法であって、
    　前記トンネルバリア層を成膜する工程は、スパッタリング法により、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を成膜する工程を有し、
    　前記磁化自由層を成膜する工程は、
    　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
    　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、
    　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程である
    ことを特徴とする磁気抵抗素子の製造方法。     Production of a magnetoresistive element having a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer located between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method Method,
    The step of forming the tunnel barrier layer includes the step of forming a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer by sputtering.
    In the step of forming the magnetization free layer,
    Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
    A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. Filming process,
    Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom Forming a layer of an alloy containing Ni atoms, Fe atoms and B atoms, or an alloy containing Ni atoms and Fe atoms by a sputtering method using Method of manufacturing a magnetoresistive element
  4. 　スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する磁気抵抗素子の製造方法であって、
    　前記トンネルバリア層を成膜する工程は、スパッタリング法により、結晶性金属マグネシウム又は結晶性ボロンマグネシウム合金からなる層を成膜し、該金属マグネシウム又はボロンマグネシウム合金を酸化して、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を形成する工程を有し、
    　前記磁化自由層を成膜する工程は、
    　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
    　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、
    　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程である
    ことを特徴とする磁気抵抗素子の製造方法。     Production of a magnetoresistive element having a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer located between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method Method,
    In the step of forming the tunnel barrier layer, a layer made of crystalline metal magnesium or crystalline boron magnesium alloy is formed by sputtering, and the metal magnesium or boron magnesium alloy is oxidized to form a crystalline magnesium oxide layer. Or forming a crystalline boron magnesium oxide layer,
    In the step of forming the magnetization free layer,
    Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
    A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. Filming process,
    Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom Forming a layer of an alloy containing Ni atoms, Fe atoms and B atoms, or an alloy containing Ni atoms and Fe atoms by a sputtering method using Method of manufacturing a magnetoresistive element
  5. 　スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する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記憶媒体であって、
    　前記トンネルバリア層及び磁化自由層を成膜する工程を実行する制御プログラムは、
    　酸化マグネシウム又はボロンマグネシウム酸化物からなるターゲットを用いたスパッタリング法により、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を成膜する工程、
    　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
    　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、並びに、
    　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程
    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する記憶媒体。     Production of a magnetoresistive element having a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer located between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method A storage medium storing a control program for executing
    A control program for executing the step of forming the tunnel barrier layer and the magnetization free layer is
    Forming a crystalline magnesium oxide layer or a crystalline boron magnesium oxide layer by a sputtering method using a target made of magnesium oxide or boron magnesium oxide;
    Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
    A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. A process of filming, and
    Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom A control program for executing a step of forming a laminated film by depositing a layer composed of an alloy containing Ni atoms, Fe atoms and B atoms or an alloy containing Ni atoms and Fe atoms by a sputtering method using A storage medium characterized by storing
  6. 　スパッタリング法を用いて、基板の上に、磁化固定層、磁化自由層、及び該磁化固定層と該磁化自由層との間に位置するトンネルバリア層を成膜する工程を有する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記憶媒体であって、
    　前記トンネルバリア層及び磁化自由層を成膜する工程を実行する制御プログラムは、
    　金属マグネシウム又はボロンマグネシウム合金からなるターゲットを用いたスパッタリング法により、結晶性金属マグネシウム又は結晶性ボロンマグネシウム合金からなる層を成膜し、該金属マグネシウム又はボロンマグネシウム合金を酸化して、結晶性酸化マグネシウム層又は結晶性ボロンマグネシウム酸化物層を形成する工程、
    　Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなるターゲットを用いたスパッタリング法により、前記トンネルバリア層に隣接させて、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層を成膜する工程、
    　非磁性材からなるターゲットを用いたスパッタリング法により、前記Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＢ原子を含有する合金からなる層に隣接させて、非磁性中間層を成膜する工程、並びに、
    　前記非磁性中間層の上に、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなるターゲットを用いたスパッタリング法により、Ｃｏ原子、Ｆｅ原子及びＢ原子を含有する合金又はＣｏ原子とＦｅ原子とを含有する合金からなる層を成膜し、次いで、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなるターゲットを用いたスパッタリング法により、Ｎｉ原子、Ｆｅ原子及びＢ原子を含有する合金又はＮｉ原子とＦｅ原子を含有する合金からなる層を成膜して積層膜を形成する工程
    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する記憶媒体。     Production of a magnetoresistive element having a step of forming a magnetization fixed layer, a magnetization free layer, and a tunnel barrier layer located between the magnetization fixed layer and the magnetization free layer on a substrate by using a sputtering method A storage medium storing a control program for executing
    A control program for executing the step of forming the tunnel barrier layer and the magnetization free layer is
    A layer of crystalline metallic magnesium or crystalline boron magnesium alloy is formed by sputtering using a target of metallic magnesium or boron magnesium alloy, and the metallic magnesium or boron magnesium alloy is oxidized to form crystalline magnesium oxide. Forming a layer or a crystalline boron magnesium oxide layer,
    Co atoms, Fe atoms and B atoms are made to be adjacent to the tunnel barrier layer by sputtering using a target comprising an alloy containing Co atoms, Fe atoms and B atoms, or an alloy containing Co atoms and B atoms Forming a layer comprising an alloy containing or an alloy containing Co atoms and B atoms,
    A nonmagnetic intermediate layer is formed adjacent to a layer made of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and B atoms by sputtering using a target made of nonmagnetic material. A process of filming, and
    Co atoms, Fe atoms and B atoms are formed by sputtering using a target consisting of an alloy containing Co atoms, Fe atoms and B atoms or an alloy containing Co atoms and Fe atoms on the nonmagnetic interlayer. Forming a layer comprising an alloy containing Fe or a Co atom and an Fe atom, and then forming an alloy containing an Ni atom, an Fe atom and a B atom, or an alloy containing an Ni atom and an Fe atom A control program for executing a step of forming a laminated film by depositing a layer composed of an alloy containing Ni atoms, Fe atoms and B atoms or an alloy containing Ni atoms and Fe atoms by a sputtering method using A storage medium characterized by storing
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JP2004172599A (en) * 2002-11-01 2004-06-17 Nec Corp Magnetoresistive device and method of manufacturing the same
JP2004349687A (en) * 2003-04-17 2004-12-09 Applied Materials Inc Method of fabricating magnetoresistive random access memory (mram) device
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JP2008085170A (en) * 2006-09-28 2008-04-10 Toshiba Corp Magnetoresistance effect-type element and magnetoresistance effect-type random access memory

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JP2002204002A (en) * 2000-12-28 2002-07-19 Nec Corp Spin tunnel magnetoresistance effect film and element, and magnetoresistance sensor using the same, and magnetic device and method of manufacturing the same
JP2004172599A (en) * 2002-11-01 2004-06-17 Nec Corp Magnetoresistive device and method of manufacturing the same
JP2004349687A (en) * 2003-04-17 2004-12-09 Applied Materials Inc Method of fabricating magnetoresistive random access memory (mram) device
JP2007294737A (en) * 2006-04-26 2007-11-08 Hitachi Ltd Tunnel magnetoresistance effect element, and magnetic memory cell and magnetic random access memory using the same
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