WO2010044134A1 - Process for producing magnetoresistance effect element and program for producing magnetoresistance effect element - Google Patents

Process for producing magnetoresistance effect element and program for producing magnetoresistance effect element Download PDF

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Publication number
WO2010044134A1
WO2010044134A1 PCT/JP2008/068556 JP2008068556W WO2010044134A1 WO 2010044134 A1 WO2010044134 A1 WO 2010044134A1 JP 2008068556 W JP2008068556 W JP 2008068556W WO 2010044134 A1 WO2010044134 A1 WO 2010044134A1
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layer
forming
ferromagnetic layer
barrier layer
chamber
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PCT/JP2008/068556
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French (fr)
Japanese (ja)
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ヨンスック チョイ
裕一 大谷
フランク エルヌ
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キヤノンアネルバ株式会社
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Priority to PCT/JP2008/068556 priority Critical patent/WO2010044134A1/en
Publication of WO2010044134A1 publication Critical patent/WO2010044134A1/en

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    • 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
    • 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
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/127—Structure or manufacture of heads, e.g. inductive
    • G11B5/31—Structure or manufacture of heads, e.g. inductive using thin films
    • G11B5/3163—Fabrication methods or processes specially adapted for a particular head structure, e.g. using base layers for electroplating, using functional layers for masking, using energy or particle beams for shaping the structure or modifying the properties of the basic layers
    • G—PHYSICS
    • G11—INFORMATION STORAGE
    • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
    • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
    • G11B5/127—Structure or manufacture of heads, e.g. inductive
    • G11B5/33—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only
    • G11B5/39—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only using magneto-resistive devices or effects
    • G11B5/3903—Structure or manufacture of flux-sensitive heads, i.e. for reproduction only; Combination of such heads with means for recording or erasing only using magneto-resistive devices or effects using magnetic thin film layers or their effects, the films being part of integrated structures
    • G11B5/3906—Details related to the use of magnetic thin film layers or to their effects
    • 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

Definitions

  • the present invention relates to a magnetoresistive effect element manufacturing method and a magnetoresistive effect element manufacturing program excellent in MR ratio.
  • Non-Patent Document 1 and Patent Document 1 As a magnetoresistive effect element used for a magnetic reproducing head of a magnetic disk drive device, a storage element of a magnetic random access memory, and a magnetic sensor, for example, as shown in Non-Patent Document 1 and Patent Document 1, on both sides of the tunnel barrier layer There is known a TMR (Tunneling Magneto Resistance) effect element that includes first and second ferromagnetic layers that are installed as basic components.
  • TMR Transmission Magneto Resistance
  • this basic component portion is CoFeB / MgO / CoFeB, and the CoFeB layer is formed in an amorphous state, thereby achieving an MR ratio of 220%.
  • Patent Document 1 solves problems such as the possibility of film contamination due to generation of particles when the magnesium oxide layer is formed by sputtering a magnesium oxide target by high frequency sputtering and the oxidation state tends to be non-uniform. Therefore, a method of spontaneous oxidation after forming a magnesium film is disclosed.
  • An object of this invention is to provide the manufacturing method of the magnetoresistive effect which has high MR ratio, and its manufacturing program.
  • One embodiment of the present invention is a first ferromagnetic layer forming step for forming a first ferromagnetic layer, and a barrier layer for forming a tunnel barrier layer made of a metal oxide on the first ferromagnetic layer. And a second ferromagnetic layer forming step for forming a second ferromagnetic layer on the tunnel barrier layer, wherein the barrier layer forming step includes forming a metal film. And natural oxidation of the metal film under heating conditions.
  • natural oxidation is a process in which a processing target is exposed to oxygen gas or a gas containing oxygen gas (for example, a mixture of an inert gas and an oxygen gas), and the oxygen gas is oxidized without being converted to plasma or the like. is there.
  • a high MR ratio can be obtained. Moreover, the oxidation treatment time can be shortened.
  • FIG. 1 A configuration example of the magnetoresistive element is shown in FIG. FIG. 1 is an example of the TMR element 100.
  • An MTJ Magnetic Tunnel Junction
  • the MTJ is configured by laminating an antiferromagnetic layer 103, a magnetization fixed layer, a tunnel barrier layer 107, and a magnetization free layer.
  • a cap layer 109 in contact with the upper electrode 110 is formed on the magnetization free layer 108.
  • the magnetization fixed layer includes a pinned layer 104, a spacer (non-magnetic film for exchange coupling) 105, and a reference layer 106.
  • the reference layer 106 and the magnetization free layer 108 are ferromagnetic layers and correspond to the first ferromagnetic layer and the second ferromagnetic layer of the present invention.
  • the reference layer 106 and the magnetization free layer 108 can be configured by using a ferromagnetic element such as Fe, Co, Ni, or an alloy thereof as a main component, and appropriately adding components such as B, C, Cr.
  • the tunnel barrier layer 107 is an insulator layer made of a metal oxide, and the present invention is characterized by a method for forming the tunnel barrier layer 107.
  • the tunnel barrier layer 107 can be made of, for example, magnesium oxide, alumina, or a metal oxide in which a metal element is appropriately added to these, and among these, magnesium oxide is preferable because of its excellent MR ratio.
  • FIG. 2 is a schematic plan view showing a manufacturing apparatus used for forming a TMR element
  • FIG. 3 is a view showing an oxidation chamber for performing an oxidation treatment.
  • the manufacturing apparatus 700 in FIG. 2 is a cluster-type apparatus, and includes a degas chamber 704 for performing degas processing, an etching chamber 705 for performing etching processing, an oxidation chamber 706, and film formation chambers 707 to 709. Yes. Further, in the manufacturing apparatus 700, a transfer chamber 701 including a robot transfer apparatus (not shown) is installed at the central position, and substrates introduced from the two load / unload chambers 702 and 703 can be transferred into and out of the respective chambers 704 to 709. It has become.
  • Each of the chambers 701 to 709 is independently provided with a vacuum pump for bringing the inside of the chamber into a predetermined low pressure state, and the transfer chamber 701 and each of the chambers 702 to 709 are connected to each other via a gate valve. Substrate transport under conditions is possible.
  • the manufacturing apparatus 700 includes an apparatus controller 710 for outputting a command to each of the chambers 701 to 709 according to a program that defines a predetermined process flow (hereinafter also referred to as a recipe) to execute a predetermined process.
  • the device controller 710 includes, for example, a computer and various drivers.
  • At least one of the deposition chambers 707 to 709 includes a seed layer 102, an antiferromagnetic layer 103, a pinned layer 104, a spacer 105, a reference layer 106, a tunnel barrier layer 107, a magnetization free layer 108, and a cap layer 109.
  • a target capable of film formation is provided, and each of these layers 102 to 109 can be formed by a sputtering method. In the present invention, what is used for the target material and in which chamber it is arranged are not particularly limited.
  • a layer made of an alloy or a composite material such as CoFeB may use a target made of CoFeB, or may be formed by co-sputtering three targets of a Co target, an Fe target, and a B target. Also good.
  • the sputtering method is not particularly limited, and for example, any of DC-sputtering discharged by DC power, RF-sputtering discharging by high-frequency power, and sputtering by superimposing DC power and high-frequency power may be used.
  • the oxidation chamber 706 is a chamber for subjecting the substrate to natural oxidation treatment.
  • the oxidation chamber 706 of FIG. 3 includes a gas introduction system 602 capable of introducing oxygen gas into the vacuum vessel 601 and an exhaust system 602 capable of exhausting the inside of the vacuum vessel 601. Gas can be supplied.
  • the gas introduction system 602 includes a mass flow controller and the like, and can introduce oxygen gas at a predetermined flow rate.
  • the exhaust system 602 includes a valve, a pump, and the like, and can exhaust the chamber to a predetermined pressure by adjusting conductance.
  • a diffusion plate 604 for diffusing oxygen gas, in which a plurality of through holes are formed, is disposed between the gas introduction system 602 and the exhaust system 602 in the drawing.
  • the oxidation chamber 706 includes a substrate stage 610 that can be held while heating the substrate during natural oxidation treatment.
  • the substrate stage 610 includes an electrostatic adsorption mechanism for holding the substrate by an electrostatic adsorption action.
  • the electrostatic adsorption mechanism includes a dielectric 611, an electrode 615 for generating an electrostatic adsorption force between the substrate and the dielectric 611, and an adsorption power source 616.
  • the substrate stage 610 includes a heater 613 for heating the substrate stage 610 and a heat transfer gas introduction system 614 for supplying a heat transfer gas between the substrate stage 610 and the substrate.
  • the substrate stage 610 includes a temperature sensor (not shown), and based on this value, adjustment of supply gas pressure via the heat transfer gas introduction system 614 or adjustment of power supply from the heater power source 617 to the heater 613 is adjusted.
  • the substrate can be adjusted to a predetermined temperature.
  • the oxidation chamber controller 605 is based on various inputs such as a pressure sensor for detecting the pressure in the chamber, and the oxygen gas introduction system 602, the exhaust system 603, the heat transfer gas introduction system 614, the adsorption power supply 616, and the heater power supply. 617 is controlled and a process instructed by the device controller 710 is executed.
  • the oxidation chamber 706 is not limited to the above-described configuration, and for example, the substrate may be mechanically held or may be in a state in which the substrate is placed without depending on electrostatic adsorption. Further, the heating is not limited to the contact with the substrate stage 610 but may be performed by radiant heat such as a lamp heater.
  • FIG. 4 is a diagram showing a specific example of a method for forming the tunnel barrier layer 107
  • FIG. 10 is a manufacturing flow executed by the apparatus controller 710.
  • a substrate on which a lower electrode 101 having a predetermined pattern is formed is introduced into a manufacturing apparatus 700, and a seed layer 102 and an antiferromagnetic layer 103 (in FIG. 4) are formed in film forming chambers 707 to 709.
  • PtMn layer 803, pinned layer 104 (CoFe layer 806 in FIG. 4), spacer 105 (Ru layer 805 in FIG. 4), reference layer 106 (CoFeB layer 806 in FIG. 4), and Mg layer 107 are stacked in this order ( This corresponds to steps S101 to S104 in FIG.
  • the substrate is vacuum-transferred from the deposition chamber to the oxidation chamber 706.
  • oxygen gas is introduced to a predetermined pressure, and the Mg layer 107 formed on the outermost surface is oxidized while the substrate is heated to a predetermined temperature by the heater 613 (step S105 in FIG. 10).
  • Oxidation conditions such as oxygen gas pressure and oxidation treatment time at this time are not particularly limited as long as the formed Mg layer 107 can be converted into a magnesium oxide layer.
  • the pressure is in the range of 1.0 ⁇ 10 ⁇ 4 to 2.0 ⁇ 10 2 Pa
  • the oxidation treatment time is in the range of 20 seconds to 1000 seconds.
  • the temperature of the substrate is heated (that is, exceeds room temperature), an effect of improving the MR ratio can be obtained, but if it is heated too much, the lower layer and the substrate are deteriorated. Therefore, it is preferably 50 ° C. or more and 200 ° C. or less, and more preferably 70 ° C. or more and 120 ° C.
  • it is preferable to heat during a natural oxidation process you may make it heat only for the one part period during a natural oxidation process. Therefore, it is preferable to heat the substrate stage 610 in advance so that the temperature of the substrate can be raised immediately when the substrate is loaded.
  • the substrate stage 610 may be heated after the substrate is loaded or during the natural oxidation treatment. The heating may be stopped during the natural oxidation treatment.
  • the substrate is transferred again to the film forming chambers 707 to 709, and as shown in FIG. 4B, the Mg layer 308, the magnetization free layer 108 (CoFeB in FIG. 4), the cap layer 109, and the upper electrode 110 are removed. These are formed in order (steps S106 and S107 in FIG. 10).
  • the Mg layer 308 is a metal cap layer for appropriately maintaining oxygen diffusion, and constitutes the tunnel barrier layer 107.
  • the substrate is unloaded from the manufacturing apparatus 700, and a magnetic annealing process is performed in a heat treatment furnace.
  • the annealing conditions are, for example, about 360 ° C. and 2 hours in a magnetic field of 10 kOe. Thereby, the required magnetization is given to the antiferromagnetic layer 103.
  • the lower electrode, the PtMn layer 303 is 15 nm, the CoFe layer 304 is 2.5 nm, the Ru layer 305 is 0.9 nm, the CoFeB layer 306 is 3 nm, and the Mg layer 307 is 1.1 nm in order.
  • natural oxidation treatment was performed, and an Mg layer 308 of 0.3 nm, a CoFeB layer 309 of 3 nm, a cap layer 109 (Ta layer) of 8.0 nm, and an upper electrode 311 were formed thereon.
  • the CoFe layer 304 is Co (70 atomic%) Fe (30 atomic%)
  • the CoFeB layers 306 and 309 are Co (60 atomic%) Fe (20 atomic%) B (atomic%). is there.
  • the natural oxidation treatment was performed under a heating condition with a substrate temperature of 100 ° C., with an oxygen gas flow rate of 700 sccm and an oxygen gas pressure of 6.5 ⁇ 10 ⁇ 1 Pa.
  • the substrate was not heated, and natural oxidation was performed under the same conditions.
  • the magnetoresistive effect element to which the present invention can be applied is not limited to the one having the above-described configuration, and can be applied to the elements shown in FIGS.
  • FIGS. 6 to 9 in order to make the explanation easy to understand, “natural oxidation” is written on the layer to be subjected to the natural oxidation treatment, so that the layer is oxidized under the heating condition. Indicates that processing is to be performed. Although not shown, after the oxidation treatment, the oxidized layer becomes an oxide layer (a magnesium oxide layer in the examples of FIGS. 6 to 9).
  • the reference layer 106 is formed of two layers, a CoFeB layer 806 located on the spacer 105 side and a CoFe layer 807 thereon.
  • the CoFeB layer 806 is a layer that contains 12 atomic% or more of B and becomes an amorphous state during sputtering film formation.
  • the tunnel barrier layer 107 in an amorphous state forms microcrystal grains having a (001) plane preferentially oriented at the interface using the CoFe layer 807 as a template during the magnetic annealing, High MR ratio is shown.
  • each layer of this MTJ is PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / CoFe1.5 / Mg1.1 / Mg0.3 / CoFeB3.
  • the thickness of the CoFeB layer is preferably 1 nm to 4 nm.
  • the thickness of the CoFe layer 807 is preferably 0.5 nm to 2 nm, and the CoFe layer 807 is preferably formed with a thickness equal to or less than that of the CoFeB layer 806.
  • FIG. 7 is substantially the same as FIG. 6, but the CoFe layer 410 and the CoFeB layer 411 are formed on the opposite side of the tunnel barrier layer 107 from the reference layer 106 to configure the magnetization free layer 108. . By doing so, a TMR element having an excellent MR ratio can be obtained.
  • each layer of this MTJ is PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / CoFe1.5 / Mg1.1 / Mg0.3 / CoFe1.5 / CoFeB1.5.
  • the preferable thickness range of the CoFe layer and the CoFeB layer is the same as in FIG.
  • the CoFe layers 407 and 410 in contact with the tunnel barrier layer 107 are CoFeB layers 1407 and 1411, respectively, which are substantially the same as those in FIG.
  • the CoFeB layers 1407 and 1411 have a B content of less than 12 atomic%, and are formed as crystals of the bcc structure in which the (001) plane is oriented parallel to the interface in the same manner as the CoFe layer at the time of sputtering film formation. Therefore, it functions in the same manner as the CoFe layers 407 and 410 in FIG. 7 and promotes the preferential orientation of the (001) plane of the tunnel barrier layer 107.
  • MTJ layers are PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / CoFeB1.5 / Mg1.1 / Mg0.3 / CoFeB1.5 / CoFeB1.5.
  • the layers in contact with the tunnel barrier layer 107 are formed by forming Fe layers 1707 and 1711 as ferromagnetic materials capable of promoting the preferential orientation of the (001) plane of the tunnel barrier layer 107. Yes.
  • each layer of this MTJ is PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / Fe1-4 / Mg1.1 / Mg0.3 / Fe1-4 / CoFeB1.5.

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Abstract

This invention provides a process for producing a magnetoresistance effect element having a high MR ratio. The production process comprises forming a first ferromagnetic layer constituting a first ferromagnetic body layer, forming a barrier layer constituting a tunnel barrier layer formed of a metal oxide on the first ferromagnetic body layer, and forming a second ferromagnetic layer constituting a second ferromagnetic body layer on the tunnel barrier layer. The formation of the barrier layer is characterized in that a metal film is formed and the metal film is then naturally oxidized under heating conditions. The natural oxidation is a treatment in which a treatment object is exposed to an oxygen gas or an oxygen gas-containing gas (for example, a mixture composed of an inert gas and an oxygen gas). In this natural oxidation, oxidation is carried out without subjecting the oxygen gas to plasmatization or the like.

Description

磁気抵抗効果素子の製造方法及び磁気抵抗効果素子製造プログラムMagnetoresistive element manufacturing method and magnetoresistive element manufacturing program
　本発明は、ＭＲ比に優れた磁気抵抗効果素子の製造方法及び磁気抵抗効果素子製造プログラムに関する。 The present invention relates to a magnetoresistive effect element manufacturing method and a magnetoresistive effect element manufacturing program excellent in MR ratio.
　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効果素子として、例えば、非特許文献１や特許文献１に示されるようにトンネルバリア層とその両側に設置した第１及び第２の強磁性体層を基本構成部分として含むＴＭＲ（トンネル磁気抵抗；Ｔｕｎｎｅｌｉｎｇ　Ｍａｇｎｅｔｏ　Ｒｅｓｉｓｔａｎｃｅ）効果素子が知られている。 As a magnetoresistive effect element used for a magnetic reproducing head of a magnetic disk drive device, a storage element of a magnetic random access memory, and a magnetic sensor, for example, as shown in Non-Patent Document 1 and Patent Document 1, on both sides of the tunnel barrier layer There is known a TMR (Tunneling Magneto Resistance) effect element that includes first and second ferromagnetic layers that are installed as basic components.
　非特許文献１では、この基本構成部分をＣｏＦｅＢ／ＭｇＯ／ＣｏＦｅＢとし、ＣｏＦｅＢ層をアモルファス状に形成することで、２２０％のＭＲ比を達成している。 In Non-Patent Document 1, this basic component portion is CoFeB / MgO / CoFeB, and the CoFeB layer is formed in an amorphous state, thereby achieving an MR ratio of 220%.
　また、特許文献１では、酸化マグネシウムターゲットを高周波スパッタリングによりスパッタすることで酸化マグネシウム層を形成した場合における、酸化状態が不均一になりやすい、パーティクルの発生による膜汚染の可能性等の問題を解決すべく、マグネシウム膜を形成後に自然酸化する方法を開示している。 Further, Patent Document 1 solves problems such as the possibility of film contamination due to generation of particles when the magnesium oxide layer is formed by sputtering a magnesium oxide target by high frequency sputtering and the oxidation state tends to be non-uniform. Therefore, a method of spontaneous oxidation after forming a magnesium film is disclosed.
特開２００７－１４２４２４号公報JP 2007-142424 A
　しかしながら、特許文献１に示す方法では十分なＭＲ比を得ることができない。
　本発明は、高いＭＲ比を有する磁気抵抗効果の製造方法及びその製造プログラムを提供することを目的とする。 However, the method shown in Patent Document 1 cannot obtain a sufficient MR ratio.
An object of this invention is to provide the manufacturing method of the magnetoresistive effect which has high MR ratio, and its manufacturing program.
　本発明の一形態は、第１の強磁性体層を形成する第１強磁性層形成ステップと、前記第１の強磁性体層上に、金属酸化物からなるトンネルバリア層を形成するバリア層形成ステップと、前記トンネルバリア層上に第２の強磁性体層を形成する第２強磁性層形成ステップと、を有し、前記バリア層形成ステップは、金属膜を成膜する金属成膜ステップと、加熱条件下で、前記金属膜を自然酸化するステップと、を有することを特徴とする。
　ここで、自然酸化は、酸素ガス又は酸素ガスを含むガス（例えば、不活性ガスと酸素ガスの混合）に処理対象を晒す処理であり、酸素ガスをプラズマ化等をすることなく酸化する処理である。 One embodiment of the present invention is a first ferromagnetic layer forming step for forming a first ferromagnetic layer, and a barrier layer for forming a tunnel barrier layer made of a metal oxide on the first ferromagnetic layer. And a second ferromagnetic layer forming step for forming a second ferromagnetic layer on the tunnel barrier layer, wherein the barrier layer forming step includes forming a metal film. And natural oxidation of the metal film under heating conditions.
Here, natural oxidation is a process in which a processing target is exposed to oxygen gas or a gas containing oxygen gas (for example, a mixture of an inert gas and an oxygen gas), and the oxygen gas is oxidized without being converted to plasma or the like. is there.
　本発明によれば、高いＭＲ比が得られる。また、酸化処理時間を短縮できる。 According to the present invention, a high MR ratio can be obtained. Moreover, the oxidation treatment time can be shortened.
ＴＭＲ素子の層構成を示す図である。It is a figure which shows the layer structure of a TMR element. 製造装置の概略平面図である。It is a schematic plan view of a manufacturing apparatus. 酸化チャンバの概略構成図である。It is a schematic block diagram of an oxidation chamber. トンネルバリア層の製造方法の工程Ｉを示す図である。It is a figure which shows the process I of the manufacturing method of a tunnel barrier layer. トンネルバリア層の製造方法の工程IIを示す図である。It is a figure which shows process II of the manufacturing method of a tunnel barrier layer. 比較例と実施例のＲＡに対するＭＲ比を示す図である。It is a figure which shows MR ratio with respect to RA of a comparative example and an Example. 比較例と実施例の自然酸化時間に対するＭＲ比を示す図である。It is a figure which shows MR ratio with respect to the natural oxidation time of a comparative example and an Example. 他のＴＭＲ素子の製造方法を説明するための図である。It is a figure for demonstrating the manufacturing method of another TMR element. 他のＴＭＲ素子の製造方法を説明するための図である。It is a figure for demonstrating the manufacturing method of another TMR element. 他のＴＭＲ素子の製造方法を説明するための図である。It is a figure for demonstrating the manufacturing method of another TMR element. 他のＴＭＲ素子の製造方法を説明するための図である。It is a figure for demonstrating the manufacturing method of another TMR element. 製造方法を説明するためのフローチャートである。It is a flowchart for demonstrating a manufacturing method.
符号の説明Explanation of symbols
７０１　　　　　搬送チャンバ
７０２，７０３　ロード／アンロードチャンバ
７０４　　　　　脱ガスチャンバ
７０５　　　　　エッチングチャンバ
７０６　　　　　酸化チャンバ
７０７～７０９　成膜チャンバ
６０１　　　　　真空容器
６０４　　　　　拡散板
６１０　　　　　基板ステージ
６１１　　　　　誘電体
６１２　　　　　基台
６１３　　　　　ヒータ
６１５　　　　　電極（吸着用）
６１６　　　　　吸着用電源
６１７　　　　　ヒータ用電源 701 Transfer chamber 702, 703 Load / unload chamber 704 Degas chamber 705 Etching chamber 706 Oxidation chamber 707-709 Deposition chamber 601 Vacuum vessel 604 Diffusion plate 610 Substrate stage 611 Dielectric 612 Base 613 Heater 615 Electrode (for adsorption)
616 Power supply for adsorption 617 Power supply for heater
［第１実施形態］
　磁気抵抗効果素子の構成例を図１に示す。
　図１は、ＴＭＲ素子１００の一例である。下部電極１０１やシード層１０２などの下地層が形成されたＳｉ基板（図示せず）の上に、ＭＴＪ（Ｍａｇｎｅｔｉｃ　ｔｕｎｎｅｌ　ｊｕｎｃｔｉｏｎ）が形成される。ＭＴＪは、反強磁性層１０３、磁化固定層、トンネルバリア層１０７、及び、磁化自由層１０８が積層されて構成されている。磁化自由層１０８上には上部電極１１０に接するキャップ層１０９が形成される。また、磁化固定層は、図１の例では、ピンド層１０４、スペーサ（交換結合用非磁性膜）１０５、及び、リフェレンス層１０６を含んで構成される。 [First Embodiment]
A configuration example of the magnetoresistive element is shown in FIG.
FIG. 1 is an example of the TMR element 100. An MTJ (Magnetic Tunnel Junction) is formed on a Si substrate (not shown) on which a base layer such as the lower electrode 101 and the seed layer 102 is formed. The MTJ is configured by laminating an antiferromagnetic layer 103, a magnetization fixed layer, a tunnel barrier layer 107, and a magnetization free layer. A cap layer 109 in contact with the upper electrode 110 is formed on the magnetization free layer 108. In the example of FIG. 1, the magnetization fixed layer includes a pinned layer 104, a spacer (non-magnetic film for exchange coupling) 105, and a reference layer 106.
　リフェレンス層１０６及び磁化自由層１０８は、強磁性層であり、本発明の第１の強磁性層、第２の強磁性層に相当する。リフェレンス層１０６及び磁化自由層１０８は、Ｆｅ、Ｃｏ、Ｎｉなどの強磁性元素又はこれらの合金を主成分とし、これに適宜Ｂ、Ｃ、Ｃｒなどの成分を添加して構成することができる。 The reference layer 106 and the magnetization free layer 108 are ferromagnetic layers and correspond to the first ferromagnetic layer and the second ferromagnetic layer of the present invention. The reference layer 106 and the magnetization free layer 108 can be configured by using a ferromagnetic element such as Fe, Co, Ni, or an alloy thereof as a main component, and appropriately adding components such as B, C, Cr.
　また、トンネルバリア層１０７は、金属酸化物からなる絶縁体層であり、本発明はこのトンネルバリア層１０７の形成方法に特徴がある。トンネルバリア層１０７は、例えば、酸化マグネシウム、アルミナ、又は、これらに適宜金属元素を添加した金属酸化物などから構成することができ、このうち酸化マグネシウムはＭＲ比に優れるので好ましい。 Further, the tunnel barrier layer 107 is an insulator layer made of a metal oxide, and the present invention is characterized by a method for forming the tunnel barrier layer 107. The tunnel barrier layer 107 can be made of, for example, magnesium oxide, alumina, or a metal oxide in which a metal element is appropriately added to these, and among these, magnesium oxide is preferable because of its excellent MR ratio.
　次に、上述のＴＭＲ素子の製造装置について説明する。図２はＴＭＲ素子の形成に用いる製造装置を示す概略平面図、及び、図３は酸化処理を行うための酸化チャンバを示す図である。 Next, an apparatus for manufacturing the above-described TMR element will be described. FIG. 2 is a schematic plan view showing a manufacturing apparatus used for forming a TMR element, and FIG. 3 is a view showing an oxidation chamber for performing an oxidation treatment.
　図２の製造装置７００はクラスタ型装置であり、脱ガス処理を行うための脱ガスチャンバ７０４、エッチング処理を行うためのエッチングチャンバ７０５、酸化チャンバ７０６、及び、成膜チャンバ７０７～７０９を備えている。また、製造装置７００では、図示しないロボット搬送装置を備える搬送チャンバ７０１が中央位置に設置され、２つのロード／アンロードチャンバ７０２，７０３から導入される基板を、各チャンバ７０４～７０９に搬出入可能になっている。各チャンバ７０１～７０９は夫々独自にチャンバ内を所定の低圧状態にするための真空ポンプを備えると共に、搬送チャンバ７０１と各チャンバ７０２～７０９とはゲートバルブを介して接続されており、所定の低圧条件下での基板搬送が可能である。また、製造装置７００は、所定のプロセスフロー（以下、レシピとも言う）を規定したプログラムに従って、各チャンバ７０１～７０９に指令を出力し、所定のプロセスを実施させるための装置コントローラ７１０を備える。装置コントローラ７１０は、例えば、コンピュータと、各種のドライバを備えて構成される。 The manufacturing apparatus 700 in FIG. 2 is a cluster-type apparatus, and includes a degas chamber 704 for performing degas processing, an etching chamber 705 for performing etching processing, an oxidation chamber 706, and film formation chambers 707 to 709. Yes. Further, in the manufacturing apparatus 700, a transfer chamber 701 including a robot transfer apparatus (not shown) is installed at the central position, and substrates introduced from the two load / unload chambers 702 and 703 can be transferred into and out of the respective chambers 704 to 709. It has become. Each of the chambers 701 to 709 is independently provided with a vacuum pump for bringing the inside of the chamber into a predetermined low pressure state, and the transfer chamber 701 and each of the chambers 702 to 709 are connected to each other via a gate valve. Substrate transport under conditions is possible. In addition, the manufacturing apparatus 700 includes an apparatus controller 710 for outputting a command to each of the chambers 701 to 709 according to a program that defines a predetermined process flow (hereinafter also referred to as a recipe) to execute a predetermined process. The device controller 710 includes, for example, a computer and various drivers.
　成膜チャンバ７０７～７０９は、少なくともいずれかが、シード層１０２、反強磁性層１０３、ピンド層１０４、スペーサ１０５、リフェレンス層１０６、トンネルバリア層１０７、磁化自由層１０８、及び、キャップ層１０９を成膜可能なターゲットを備えており、これらの各層１０２～１０９をスパッタリング法により成膜可能である。ターゲット材料に何を用いるか、どのチャンバに配置するかは、本発明では特に限定されない。例えば、ＣｏＦｅＢなどのように合金又は複合材料から構成される層は、ＣｏＦｅＢからなるターゲットを用いてもよいし、Ｃｏターゲット、Ｆｅターゲット、Ｂターゲットの３つのターゲットを同時スパッタリングさせることで形成してもよい。また、スパッタリング方法は、特に限定されず、例えば、直流電力により放電させるＤＣ－スパッタ、高周波電力により放電させるＲＦ－スパッタ、直流電力と高周波電力の重畳によるスパッタのいずれでもよい。 At least one of the deposition chambers 707 to 709 includes a seed layer 102, an antiferromagnetic layer 103, a pinned layer 104, a spacer 105, a reference layer 106, a tunnel barrier layer 107, a magnetization free layer 108, and a cap layer 109. A target capable of film formation is provided, and each of these layers 102 to 109 can be formed by a sputtering method. In the present invention, what is used for the target material and in which chamber it is arranged are not particularly limited. For example, a layer made of an alloy or a composite material such as CoFeB may use a target made of CoFeB, or may be formed by co-sputtering three targets of a Co target, an Fe target, and a B target. Also good. Further, the sputtering method is not particularly limited, and for example, any of DC-sputtering discharged by DC power, RF-sputtering discharging by high-frequency power, and sputtering by superimposing DC power and high-frequency power may be used.
　酸化チャンバ７０６は、基板に自然酸化処理を施すチャンバである。図３の酸化チャンバ７０６は、真空容器６０１内に酸素ガスを導入可能なガス導入系６０２と、真空容器６０１内を排気可能な排気系６０２と、を備えており、チャンバ内に所定圧力の酸素ガスを供給可能である。具体的には、本実施形態ではガス導入系６０２はマスフローコントローラなどを備えて構成され、所定流量で酸素ガスを導入可能である。また、排気系６０２はバルブとポンプなどを備え、コンダクタンスの調整によりチャンバ内を所定圧に排気可能である。なお、図中のガス導入系６０２と排気系６０２の間には、複数の貫通孔を形成した、酸素ガスを拡散させるための拡散板６０４が配されている。 The oxidation chamber 706 is a chamber for subjecting the substrate to natural oxidation treatment. The oxidation chamber 706 of FIG. 3 includes a gas introduction system 602 capable of introducing oxygen gas into the vacuum vessel 601 and an exhaust system 602 capable of exhausting the inside of the vacuum vessel 601. Gas can be supplied. Specifically, in this embodiment, the gas introduction system 602 includes a mass flow controller and the like, and can introduce oxygen gas at a predetermined flow rate. The exhaust system 602 includes a valve, a pump, and the like, and can exhaust the chamber to a predetermined pressure by adjusting conductance. Note that a diffusion plate 604 for diffusing oxygen gas, in which a plurality of through holes are formed, is disposed between the gas introduction system 602 and the exhaust system 602 in the drawing.
　また、酸化チャンバ７０６は、自然酸化処理時に、基板を加熱しながら保持可能な基板ステージ６１０を備える。具体的に図３の形態では、基板ステージ６１０は、静電吸着作用により基板を保持するための静電吸着機構を備える。静電吸着機構は、誘電体６１１、基板及び誘電体６１１間に静電吸着力を発生させるための電極６１５、及び、吸着用電源６１６を含んで構成されている。また、基板ステージ６１０は、基板ステージ６１０を加熱するためのヒータ６１３、及び、基板ステージ６１０と基板の間に伝熱用のガスを供給する伝熱ガス導入系６１４を備える。また、基板ステージ６１０は、図示しない温度センサを備え、この値に基づいて、伝熱ガス導入系６１４を介した供給ガス圧の調整、又は、ヒータ用電源６１７からヒータ６１３への電力供給を調整することで、基板を所定の温度に調整可能になっている。 Also, the oxidation chamber 706 includes a substrate stage 610 that can be held while heating the substrate during natural oxidation treatment. Specifically, in the form of FIG. 3, the substrate stage 610 includes an electrostatic adsorption mechanism for holding the substrate by an electrostatic adsorption action. The electrostatic adsorption mechanism includes a dielectric 611, an electrode 615 for generating an electrostatic adsorption force between the substrate and the dielectric 611, and an adsorption power source 616. In addition, the substrate stage 610 includes a heater 613 for heating the substrate stage 610 and a heat transfer gas introduction system 614 for supplying a heat transfer gas between the substrate stage 610 and the substrate. Further, the substrate stage 610 includes a temperature sensor (not shown), and based on this value, adjustment of supply gas pressure via the heat transfer gas introduction system 614 or adjustment of power supply from the heater power source 617 to the heater 613 is adjusted. Thus, the substrate can be adjusted to a predetermined temperature.
　酸化チャンバコントローラ６０５は、チャンバ内の圧力を検知する圧力センサなど各種の入力に基づき、上記酸素ガス導入系６０２、排気系６０３、伝熱ガス導入系６１４、吸着用電源６１６、及び、ヒータ用電源６１７をコントロールし、装置コントローラ７１０から指示されるプロセスを実行する。 The oxidation chamber controller 605 is based on various inputs such as a pressure sensor for detecting the pressure in the chamber, and the oxygen gas introduction system 602, the exhaust system 603, the heat transfer gas introduction system 614, the adsorption power supply 616, and the heater power supply. 617 is controlled and a process instructed by the device controller 710 is executed.
　なお、酸化チャンバ７０６は上記構成に限定されず、例えば、静電吸着によらず、基板を機械的に保持したり、基板を載置したままの状態としてもよい。また、基板ステージ６１０との接触による加熱に限られず、ランプヒータなどの輻射熱により加熱してもよい。 Note that the oxidation chamber 706 is not limited to the above-described configuration, and for example, the substrate may be mechanically held or may be in a state in which the substrate is placed without depending on electrostatic adsorption. Further, the heating is not limited to the contact with the substrate stage 610 but may be performed by radiant heat such as a lamp heater.
　次に、上記製造装置７００を用いたＭＴＪの製造方法について説明する。 Next, an MTJ manufacturing method using the manufacturing apparatus 700 will be described.
　図４はトンネルバリア層１０７の形成方法の具体例を示す図であり、図１０は装置コントローラ７１０により実行される製造フローである。 FIG. 4 is a diagram showing a specific example of a method for forming the tunnel barrier layer 107, and FIG. 10 is a manufacturing flow executed by the apparatus controller 710.
　まず、図４Ａに示すように、予め所定パターンの下部電極１０１を形成した基板を製造装置７００に導入し、成膜チャンバ７０７～７０９内で、シード層１０２、反強磁性層１０３（図４ではＰｔＭｎ層８０３）、ピンド層１０４（図４ではＣｏＦｅ層８０６）、スペーサ１０５（図４ではＲｕ層８０５）、リフェレンス層１０６（図４ではＣｏＦｅＢ層８０６）、及び、Ｍｇ層１０７を順に積層する（図１０のステップＳ１０１～１０４に相当）。
　その状態で、基板を成膜チャンバから酸化チャンバ７０６に真空搬送する。基板搬入後、所定圧力まで酸素ガスを導入し、ヒータ６１３により基板を所定温度に加熱しながら最表面に形成されたＭｇ層１０７を酸化する（図１０のステップＳ１０５）。 First, as shown in FIG. 4A, a substrate on which a lower electrode 101 having a predetermined pattern is formed is introduced into a manufacturing apparatus 700, and a seed layer 102 and an antiferromagnetic layer 103 (in FIG. 4) are formed in film forming chambers 707 to 709. (PtMn layer 803), pinned layer 104 (CoFe layer 806 in FIG. 4), spacer 105 (Ru layer 805 in FIG. 4), reference layer 106 (CoFeB layer 806 in FIG. 4), and Mg layer 107 are stacked in this order ( This corresponds to steps S101 to S104 in FIG.
In this state, the substrate is vacuum-transferred from the deposition chamber to the oxidation chamber 706. After carrying in the substrate, oxygen gas is introduced to a predetermined pressure, and the Mg layer 107 formed on the outermost surface is oxidized while the substrate is heated to a predetermined temperature by the heater 613 (step S105 in FIG. 10).
　このときの酸素ガスの圧力、酸化処理時間等の酸化条件は、形成したＭｇ層１０７を酸化マグネシウム層に変換できる条件であれば特に限定されない。通常、圧力は１．０×１０-4～２．０×１０2Ｐａの範囲であり、酸化処理時間は２０秒～１０００秒の範囲である。これら酸素ガス圧や酸化処理時間は、酸化処理する膜の厚さ、ＲＡ値等に応じ任意に設定する。 Oxidation conditions such as oxygen gas pressure and oxidation treatment time at this time are not particularly limited as long as the formed Mg layer 107 can be converted into a magnesium oxide layer. Usually, the pressure is in the range of 1.0 × 10 −4 to 2.0 × 10 2 Pa, and the oxidation treatment time is in the range of 20 seconds to 1000 seconds. These oxygen gas pressure and oxidation treatment time are arbitrarily set according to the thickness of the film to be oxidized, the RA value, and the like.
　また、基板の温度は、加熱されていれば（つまり室温を超えれば）ＭＲ比向上の効果が得られるが、あまりに加熱すると下層や基板が劣化する。したがって、５０℃以上２００℃以下とすることが好ましく、７０℃以上１２０℃とすることがさらに好ましい。また、自然酸化処理の間中加熱することが好ましいが、自然酸化処理中の一部の期間だけ加熱するようにしてもよい。従って、基板搬入時にすぐに基板を昇温できるように予め基板ステージ６１０を加熱しておくことが好ましいが、基板を搬入してから又は自然酸化処理の途中で基板ステージ６１０を加熱してもよく、自然酸化処理の途中で加熱を停止してもよい。また、加熱中に設定温度を変更させてもよい。 Also, if the temperature of the substrate is heated (that is, exceeds room temperature), an effect of improving the MR ratio can be obtained, but if it is heated too much, the lower layer and the substrate are deteriorated. Therefore, it is preferably 50 ° C. or more and 200 ° C. or less, and more preferably 70 ° C. or more and 120 ° C. Moreover, although it is preferable to heat during a natural oxidation process, you may make it heat only for the one part period during a natural oxidation process. Therefore, it is preferable to heat the substrate stage 610 in advance so that the temperature of the substrate can be raised immediately when the substrate is loaded. However, the substrate stage 610 may be heated after the substrate is loaded or during the natural oxidation treatment. The heating may be stopped during the natural oxidation treatment. Moreover, you may change preset temperature during a heating.
　上述の自然酸化処理後、再び成膜チャンバ７０７～７０９に基板を搬送し、図４Ｂに示すように、Ｍｇ層３０８、磁化自由層１０８（図４ではＣｏＦｅＢ）及びキャップ層１０９、上部電極１１０を順に形成する（図１０のステップＳ１０６、Ｓ１０７）。Ｍｇ層３０８は、酸素拡散を適正に保つための金属キャップ層であり、トンネルバリア層１０７を構成するものである。その後、製造装置７００から基板を搬出し、熱処理炉において、磁気アニーリング処理を行う。アニーリング条件は、例えば、１０ｋＯｅの磁場中で、約３６０℃、２時間とする。これにより、反強磁性層１０３に所要の磁化を与える。 After the natural oxidation treatment described above, the substrate is transferred again to the film forming chambers 707 to 709, and as shown in FIG. 4B, the Mg layer 308, the magnetization free layer 108 (CoFeB in FIG. 4), the cap layer 109, and the upper electrode 110 are removed. These are formed in order (steps S106 and S107 in FIG. 10). The Mg layer 308 is a metal cap layer for appropriately maintaining oxygen diffusion, and constitutes the tunnel barrier layer 107. Thereafter, the substrate is unloaded from the manufacturing apparatus 700, and a magnetic annealing process is performed in a heat treatment furnace. The annealing conditions are, for example, about 360 ° C. and 2 hours in a magnetic field of 10 kOe. Thereby, the required magnetization is given to the antiferromagnetic layer 103.
　次に、上記実施形態についての実施例を作製し、その効果について確認したので説明する。 Next, an example of the above embodiment will be made and the effect thereof will be confirmed.
　まず、図４に示すように、下部電極、ＰｔＭｎ層３０３を１５ｎｍ、ＣｏＦｅ層３０４を２．５ｎｍ、Ｒｕ層３０５を０．９ｎｍ、ＣｏＦｅＢ層３０６を３ｎｍ、Ｍｇ層３０７を１．１ｎｍを順にマグネトロン－ＤＣ－スパッタにより積層した後、自然酸化処理を行い、その上にＭｇ層３０８を０．３ｎｍ、ＣｏＦｅＢ層３０９を３ｎｍ、キャップ層１０９（Ｔａ層）を８．０ｎｍ、上部電極３１１を形成した。なお、図４に示す工程では、ＣｏＦｅ層３０４はＣｏ（７０原子％）Ｆｅ（３０原子％）、ＣｏＦｅＢ層３０６、３０９はＣｏ（６０原子％）Ｆｅ（２０原子％）Ｂ（原子％）である。 First, as shown in FIG. 4, the lower electrode, the PtMn layer 303 is 15 nm, the CoFe layer 304 is 2.5 nm, the Ru layer 305 is 0.9 nm, the CoFeB layer 306 is 3 nm, and the Mg layer 307 is 1.1 nm in order. After stacking by -DC-sputtering, natural oxidation treatment was performed, and an Mg layer 308 of 0.3 nm, a CoFeB layer 309 of 3 nm, a cap layer 109 (Ta layer) of 8.0 nm, and an upper electrode 311 were formed thereon. . In the step shown in FIG. 4, the CoFe layer 304 is Co (70 atomic%) Fe (30 atomic%), and the CoFeB layers 306 and 309 are Co (60 atomic%) Fe (20 atomic%) B (atomic%). is there.
　自然酸化処理は、実施例では、基板温度１００℃の加熱条件下で、酸素ガスの流量を７００ｓｃｃｍ、酸素ガス圧力が６．５×１０－１Ｐａで行った。一方、比較例は、基板を加熱せず、それ以外の条件は同一として自然酸化を行った。 In the examples, the natural oxidation treatment was performed under a heating condition with a substrate temperature of 100 ° C., with an oxygen gas flow rate of 700 sccm and an oxygen gas pressure of 6.5 × 10 −1 Pa. On the other hand, in the comparative example, the substrate was not heated, and natural oxidation was performed under the same conditions.
　図５に、結果を示す。 Figure 5 shows the results.
　自然酸化時間を調整して所望のＲＡ（Ω・μｍ２；素子面積１μｍ２当たりの素子抵抗）値を有するＴＭＲ素子を作製した場合、図５Ａに示すように、実用的なＲＡの範囲（通常５～２０Ω・μｍ2）内で、実施例が比較例よりも高いＭＲ比を有することが確認された。 When a TMR element having a desired RA (Ω · μm 2 ; element resistance per element area 1 μm 2 ) value is prepared by adjusting the natural oxidation time, a practical RA range (usually as shown in FIG. 5A) Within 5-20 Ω · μm 2 ), it was confirmed that the example had a higher MR ratio than the comparative example.
　また、図５Ｂに示すように、自然酸化時間とＭＲ比の関係を調べたところ、実施例は短い酸化時間で比較例よりもＭＲ比に優れることが確認された。従って、本発明によれば、高いＭＲ比を得ることが可能であると共に、磁気抵抗効果素子製造時において酸化処理に要する時間を大幅に短縮でき、タクトタイムの短縮に寄与する。 Further, as shown in FIG. 5B, when the relationship between the natural oxidation time and the MR ratio was examined, it was confirmed that the example was superior in MR ratio to the comparative example in a short oxidation time. Therefore, according to the present invention, it is possible to obtain a high MR ratio, and it is possible to greatly shorten the time required for the oxidation process when manufacturing the magnetoresistive effect element, thereby contributing to the reduction of the tact time.
［ＴＭＲ素子の他の構成例］
　次に、本発明の他の実施形態について説明する。 [Other configuration examples of TMR elements]
Next, another embodiment of the present invention will be described.
　本発明を適用可能な磁気抵抗効果素子は、上記構成のものに限定されず、図６～図９に示すようなものにも適用可能である。なお、図６～図９においては、説明を分かりやすくするために、自然酸化処理の対象となる層の上に「自然酸化」と記述することで、その層に対して加熱条件下での酸化処理を行うことを示す。図示しないが、当該酸化処理後は、当該酸化処理された層は酸化物層（図６～図９の例では、酸化マグネシウム層）となる。 The magnetoresistive effect element to which the present invention can be applied is not limited to the one having the above-described configuration, and can be applied to the elements shown in FIGS. In FIGS. 6 to 9, in order to make the explanation easy to understand, “natural oxidation” is written on the layer to be subjected to the natural oxidation treatment, so that the layer is oxidized under the heating condition. Indicates that processing is to be performed. Although not shown, after the oxidation treatment, the oxidized layer becomes an oxide layer (a magnesium oxide layer in the examples of FIGS. 6 to 9).
　図６の例では、リフェレンス層１０６が、図４の例と異なり、スペーサ１０５側に位置するＣｏＦｅＢ層８０６とその上のＣｏＦｅ層８０７の２層から形成されている。このＣｏＦｅＢ層８０６は、Ｂを１２原子％以上含み、スパッタ成膜時にアモルファス状態となる層である。図６のような構成であると、アモルファス状態であるトンネルバリア層１０７が、上記磁気アニールの際にＣｏＦｅ層８０７を鋳型として、界面に（００１）面が優先配向したマイクロ結晶粒を形成し、高いＭＲ比を示す。 In the example of FIG. 6, unlike the example of FIG. 4, the reference layer 106 is formed of two layers, a CoFeB layer 806 located on the spacer 105 side and a CoFe layer 807 thereon. The CoFeB layer 806 is a layer that contains 12 atomic% or more of B and becomes an amorphous state during sputtering film formation. With the configuration as shown in FIG. 6, the tunnel barrier layer 107 in an amorphous state forms microcrystal grains having a (001) plane preferentially oriented at the interface using the CoFe layer 807 as a template during the magnetic annealing, High MR ratio is shown.
　このＭＴＪの各層の具体例としては、ＰｔＭｎ１５／ＣｏＦｅ２．５／Ｒｕ０．９／ＣｏＦｅＢ１．５／ＣｏＦｅ１．５／Ｍｇ１．１／Ｍｇ０．３／ＣｏＦｅＢ３である。（基板側から順に、構成材料と積層厚さ（ｎｍ）を／で区切って示す。以下、同じ。）なお、この構成に限定されないが、ＣｏＦｅＢ層の厚さは１ｎｍ～４ｎｍであることが好ましく、ＣｏＦｅ層８０７の厚さは０．５ｎｍ～２ｎｍであることが好ましく、ＣｏＦｅ層８０７はＣｏＦｅＢ層８０６と同等以下の厚さで形成されることが好ましい。 A specific example of each layer of this MTJ is PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / CoFe1.5 / Mg1.1 / Mg0.3 / CoFeB3. (In order from the substrate side, the constituent material and the stacking thickness (nm) are shown separated by /. The same applies hereinafter.) Although not limited to this configuration, the thickness of the CoFeB layer is preferably 1 nm to 4 nm. The thickness of the CoFe layer 807 is preferably 0.5 nm to 2 nm, and the CoFe layer 807 is preferably formed with a thickness equal to or less than that of the CoFeB layer 806.
　図７の例では、図６と略同様であるが、トンネルバリア層１０７のリフェレンス層１０６とは反対側にも、ＣｏＦｅ層４１０及びＣｏＦｅＢ層４１１を形成し、磁化自由層１０８を構成している。このようにすることで、さらに、ＭＲ比の優れたＴＭＲ素子とすることができる。 The example of FIG. 7 is substantially the same as FIG. 6, but the CoFe layer 410 and the CoFeB layer 411 are formed on the opposite side of the tunnel barrier layer 107 from the reference layer 106 to configure the magnetization free layer 108. . By doing so, a TMR element having an excellent MR ratio can be obtained.
　このＭＴＪの各層の具体例としては、ＰｔＭｎ１５／ＣｏＦｅ２．５／Ｒｕ０．９／ＣｏＦｅＢ１．５／ＣｏＦｅ１．５／Ｍｇ１．１／Ｍｇ０．３／ＣｏＦｅ１．５／ＣｏＦｅＢ１．５である。ＣｏＦｅ層やＣｏＦｅＢ層の好ましい厚さの範囲については図６と同様である。 A specific example of each layer of this MTJ is PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / CoFe1.5 / Mg1.1 / Mg0.3 / CoFe1.5 / CoFeB1.5. The preferable thickness range of the CoFe layer and the CoFeB layer is the same as in FIG.
　図８の例では、図７と略同様であるが、トンネルバリア層１０７に接するＣｏＦｅ層４０７、４１０がＣｏＦｅＢ層１４０７、１４１１になっている。このＣｏＦｅＢ層１４０７、１４１１は、Ｂ含有量が１２原子％未満であり、スパッタ成膜時にはＣｏＦｅ層と同様に、（００１）面が界面に平行に配向したｂｃｃ構造の結晶として形成される。従って、図７のＣｏＦｅ層４０７、４１０と同様に機能し、トンネルバリア層１０７の（００１）面の優先配向を促進する。 8, the CoFe layers 407 and 410 in contact with the tunnel barrier layer 107 are CoFeB layers 1407 and 1411, respectively, which are substantially the same as those in FIG. The CoFeB layers 1407 and 1411 have a B content of less than 12 atomic%, and are formed as crystals of the bcc structure in which the (001) plane is oriented parallel to the interface in the same manner as the CoFe layer at the time of sputtering film formation. Therefore, it functions in the same manner as the CoFe layers 407 and 410 in FIG. 7 and promotes the preferential orientation of the (001) plane of the tunnel barrier layer 107.
　このＭＴＪの各層の具体例としては、ＰｔＭｎ１５／ＣｏＦｅ２．５／Ｒｕ０．９／ＣｏＦｅＢ１．５／ＣｏＦｅＢ１．５／Ｍｇ１．１／Ｍｇ０．３／ＣｏＦｅＢ１．５／ＣｏＦｅＢ１．５である。 Specific examples of the MTJ layers are PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / CoFeB1.5 / Mg1.1 / Mg0.3 / CoFeB1.5 / CoFeB1.5.
　図９の例では、図８と同様に、トンネルバリア層１０７に接する層はトンネルバリア層１０７の（００１）面の優先配向を促進可能な強磁性材料として、Ｆｅ層１７０７、１７１１を形成している。 In the example of FIG. 9, as in FIG. 8, the layers in contact with the tunnel barrier layer 107 are formed by forming Fe layers 1707 and 1711 as ferromagnetic materials capable of promoting the preferential orientation of the (001) plane of the tunnel barrier layer 107. Yes.
　このＭＴＪの各層の具体例としては、ＰｔＭｎ１５／ＣｏＦｅ２．５／Ｒｕ０．９／ＣｏＦｅＢ１．５／Ｆｅ１～４／Ｍｇ１．１／Ｍｇ０．３／Ｆｅ１～４／ＣｏＦｅＢ１．５である。 Specific examples of each layer of this MTJ are PtMn15 / CoFe2.5 / Ru0.9 / CoFeB1.5 / Fe1-4 / Mg1.1 / Mg0.3 / Fe1-4 / CoFeB1.5.

Claims (4)

  1. 　第１の強磁性体層を形成する第１強磁性層形成ステップと、
    　前記第１の強磁性体層上に、金属酸化物からなるトンネルバリア層を形成するバリア層形成ステップと、
    　前記トンネルバリア層上に第２の強磁性体層を形成する第２強磁性層形成ステップと、を有し、
    　前記バリア層形成ステップは、
    　金属膜を成膜する金属成膜ステップと、
    　加熱条件下で、前記金属膜を自然酸化するステップと、
    　を有することを特徴とする磁気抵抗効果素子の製造方法。     A first ferromagnetic layer forming step of forming a first ferromagnetic layer;
    A barrier layer forming step of forming a tunnel barrier layer made of a metal oxide on the first ferromagnetic layer;
    A second ferromagnetic layer forming step of forming a second ferromagnetic layer on the tunnel barrier layer,
    The barrier layer forming step includes
    A metal film forming step for forming a metal film;
    Spontaneously oxidizing the metal film under heating conditions;
    A method for manufacturing a magnetoresistive effect element, comprising:
  2. 　前記第１強磁性体層形成ステップは、
    　アモルファス強磁性層を形成するステップと、
    　前記アモルファス強磁性層上に結晶性強磁性層を形成するステップと、を有し、
    　前記バリア層形成ステップの前記金属成膜ステップは、前記結晶性強磁性層上に前記金属膜を形成することを特徴とする請求項１に記載の磁気抵抗効果素子の製造方法。     The first ferromagnetic layer forming step includes
    Forming an amorphous ferromagnetic layer;
    Forming a crystalline ferromagnetic layer on the amorphous ferromagnetic layer,
    2. The method of manufacturing a magnetoresistive effect element according to claim 1, wherein the metal film forming step of the barrier layer forming step forms the metal film on the crystalline ferromagnetic layer.
  3. 　前記第１強磁性体層形成ステップは、アモルファス強磁性層を形成するステップを有し、
    　前記バリア層形成ステップの前記金属成膜ステップは、前記アモルファス強磁性層上に前記金属膜を形成することを特徴とする請求項１に記載の磁気抵抗効果素子の製造方法。     The first ferromagnetic layer forming step includes a step of forming an amorphous ferromagnetic layer,
    2. The method of manufacturing a magnetoresistive effect element according to claim 1, wherein the metal film forming step of the barrier layer forming step forms the metal film on the amorphous ferromagnetic layer.
  4. 　スパッタリング法による成膜を実行させる成膜装置を備えた成膜チャンバと、基板を加熱する加熱装置、ガス導入系及びチャンバ内を排気するための排気系を備えた酸化チャンバと、前記成膜チャンバと前記酸化チャンバとの間で基板を搬送する搬送装置と、プログラムの実行により、前記成膜装置、加熱装置、ガス導入系、排気系及び搬送装置を制御するための制御装置と、を備えた磁気抵抗効果素子の製造装置に用いられるプログラムであって、
    　前記成膜チャンバ内で成膜装置により、第１の強磁性体層を形成させる第１強磁性層形成ステップと、
    　前記成膜チャンバ内で成膜装置により、前記第１の強磁性体層上に、金属酸化物からなるトンネルバリア層を形成させるバリア層形成ステップと、
    　前記トンネルバリア層上に第２の強磁性体層を形成させる第２強磁性層形成ステップと、を有し、
    　前記バリア層形成ステップは、
    　前記成膜チャンバ内で成膜装置により、金属膜を成膜する金属成膜ステップと、
    　前記成膜チャンバから前記酸化チャンバに基板を搬送するステップと、
    　前記酸化チャンバ内で、加熱条件下で、前記金属膜を自然酸化するステップと、
    　を有することを特徴とする磁気抵抗効果素子製造プログラム。     A film forming chamber having a film forming apparatus for performing film formation by sputtering, a heating apparatus for heating a substrate, a gas introduction system, an oxidation chamber having an exhaust system for exhausting the inside of the chamber, and the film forming chamber And a control device for controlling the film forming device, the heating device, the gas introduction system, the exhaust system, and the transport device by executing a program. A program used in a magnetoresistive element manufacturing apparatus,
    A first ferromagnetic layer forming step of forming a first ferromagnetic layer by a film forming apparatus in the film forming chamber;
    A barrier layer forming step of forming a tunnel barrier layer made of a metal oxide on the first ferromagnetic layer by a film forming apparatus in the film forming chamber;
    A second ferromagnetic layer forming step of forming a second ferromagnetic layer on the tunnel barrier layer,
    The barrier layer forming step includes
    A metal film forming step of forming a metal film with a film forming apparatus in the film forming chamber;
    Transporting the substrate from the deposition chamber to the oxidation chamber;
    Natural oxidation of the metal film under heating conditions in the oxidation chamber;
    A magnetoresistive element manufacturing program characterized by comprising:
PCT/JP2008/068556 2008-10-14 2008-10-14 Process for producing magnetoresistance effect element and program for producing magnetoresistance effect element WO2010044134A1 (en)

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