WO2023019519A1 - 磁性器件及其制作方法、磁性存储器、电子设备 - Google Patents

磁性器件及其制作方法、磁性存储器、电子设备 Download PDF

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WO2023019519A1
WO2023019519A1 PCT/CN2021/113579 CN2021113579W WO2023019519A1 WO 2023019519 A1 WO2023019519 A1 WO 2023019519A1 CN 2021113579 W CN2021113579 W CN 2021113579W WO 2023019519 A1 WO2023019519 A1 WO 2023019519A1
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layer
transition metal
rare earth
thin film
oxide layer
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English (en)
French (fr)
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徐仲棋
秦青
周雪
焦慧芳
丘学鹏
朱伟
杨黄林
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Huawei Technologies Co Ltd
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Huawei Technologies Co Ltd
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Priority to EP21953763.6A priority Critical patent/EP4358139A4/en
Priority to PCT/CN2021/113579 priority patent/WO2023019519A1/zh
Priority to CN202180097023.7A priority patent/CN117178362A/zh
Publication of WO2023019519A1 publication Critical patent/WO2023019519A1/zh
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/10—Magnetoresistive devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00—Galvanomagnetic devices
    • H10N50/01—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
    • H10N50/80—Constructional details
    • H10N50/85—Materials of the active region
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10B—ELECTRONIC MEMORY DEVICES
    • H10B61/00—Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices
    • H10B61/20—Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices comprising components having three or more electrodes, e.g. transistors
    • H10B61/22—Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices comprising components having three or more electrodes, e.g. transistors of the field-effect transistor [FET] type

Definitions

  • the present application relates to the technical field of magnetic tunnel junctions, in particular to a magnetic device and a manufacturing method thereof, a magnetic memory, and electronic equipment.
  • Ferrimagnetic material is a kind of material which is different from ferromagnetism and antiferromagnetism and has the characteristics of both.
  • Transition metal rare earth ferrimagnetic alloy transition metal rare earth ferrimagnetic alloy, TM-RE
  • TM-RE transition metal rare earth ferrimagnetic alloy
  • b-PMA bulk perpendicular magnetic anisotropy
  • TM-RE materials have broad application prospects in magnetic tunneling junctions (magnetic tunneling junctions, MTJs), but due to the poor annealing tolerance of the perpendicular magnetic anisotropy of TM-RE materials, it is difficult to prepare magnetic devices containing MTJs. During the process, because the temperature of the subsequent annealing process often exceeds 400°C and is maintained for more than half an hour, the TM-RE material cannot be directly applied in the MTJ.
  • Embodiments of the present application provide a magnetic device and its manufacturing method, magnetic memory, and electronic equipment, which can solve the problem that the TM-RE alloy material cannot be used in MTJ due to poor annealing tolerance of perpendicular magnetic anisotropy.
  • the present application provides a magnetic device (also referred to as an MTJ device), which includes a magnetic tunnel junction (MTJ).
  • the magnetic tunnel junction includes a pinned layer, a reference layer, a barrier layer, and a free layer stacked in sequence; at least one of the pinned layer or the free layer includes: a transition metal-rare earth ferrimagnetic alloy thin film (TM-RE thin film ) and the oxide layer located on the surface of the TM-RE film; that is, the oxide layer is located on the surface of the TM-RE film near or away from the barrier layer.
  • TM-RE thin film transition metal-rare earth ferrimagnetic alloy thin film
  • the free layer of MTJ includes a TM-RE film and an oxide layer; it may also be that a pinned layer of an MTJ includes a TM-RE film and an oxide layer; it may also be a free layer and a pinned layer of an MTJ TM-RE films and oxide layers are provided in both.
  • a TM-RE thin film is used by setting a part of the film layer of the MTJ, and an oxide layer is set on at least one surface of the TM-RE thin film.
  • the oxygen atoms in the oxide layer of the magnetic device diffuse into the TM-RE material during the subsequent annealing process, and the 2p orbital of the oxygen atom and the 3d orbital of the transition metal element in the TM-RE material contain a z component (That is, the component in the direction perpendicular to the TM-RE) orbital hybridization makes the electron spin arrangement and orientation of the TM-RE material biased towards the vertical film direction, that is, the oxide layer provides the TM-RE film with additional perpendicular magnetic anisotropy The source of anisotropy, thereby improving the annealing resistance of the perpendicular magnetic anisotropy of the TM-RE film, and thus enabling the application of the TM-RE material to the MTJ.
  • TM-RE materials due to the amorphous nature of TM-RE materials, the films grown adjacent to it will not cause interlayer stress due to lattice mismatch and the accumulation of roughness due to the growth of multilayer structures. In this way, other film layers that require high interface flatness can be directly formed on the surface of the TM-RE film, without the need to make an additional intermediate film layer to ensure the flatness of the interface, thereby improving the overall flatness of each film layer of the magnetic device , improving the overall performance of the magnetic device.
  • the TM-RE film includes a TM-RE material; the transition metal element in the TM-RE material includes at least one of Co, Fe or Ni; the rare earth element in the TM-RE material includes Tb , at least one of Gd, Dy or Eu.
  • the TM-RE material further includes at least one doping element of Ta, W, Si, B or C.
  • the TM-RE film includes at least one of CoTb, FeTb, CoGd, CoTbB, FeTbB or CoGdB.
  • the oxides in the oxide layer include oxides containing magnesium, oxides containing copper, oxides containing aluminum, oxides containing zinc, oxides containing nickel, oxides containing chromium, oxides containing titanium , at least one of silicon-containing oxides or selenium-containing oxides.
  • the oxide layer includes at least one of MgO, SiO 2 or MgAlO 3 .
  • the free layer of the MTJ adopts a composite free layer, which includes a ferromagnetic layer, an interlayer coupling layer, a TM-RE film, and an oxide layer stacked in sequence; wherein, the ferromagnetic layer and barrier layer contact. That is, the TM-RE film and oxide layer can be applied to the free layer of the MTJ.
  • TM-RE film and the oxide layer into the composite free layer of the MTJ, on the one hand, an additional source of perpendicular magnetic anisotropy is provided to the TM-RE film through the oxide layer, thus improving the Annealing tolerance of perpendicular magnetic anisotropy of TM-RE films; on the other hand, composite free layer based TM-RE films can provide bulk perpendicular magnetic anisotropy (b-PMA).
  • the pinning layer of the MTJ may include one or more TM-RE thin films; wherein at least one TM-RE thin film is provided with oxide on the surface near and/or away from the barrier layer layer. That is to say, in the pinning layer, an oxide layer can be provided on the upper surface of at least one TM-RE film; an oxide layer can also be provided on the lower surface of at least one TM-RE film; The lower surface and lower surface of the TM-RE film are respectively provided with oxide layers.
  • the TM-RE film and the oxide layer into the pinning layer of the MTJ, on the one hand, an additional source of perpendicular magnetic anisotropy is provided to the TM-RE film through the oxide layer, thereby improving the The annealing resistance of the perpendicular magnetic anisotropy of the TM-RE film;
  • the magnetic field reduces the bias field (offset) to the free layer.
  • the pinned layer is in direct contact with the reference layer through the TM-RE film.
  • the reference layer can be fabricated directly on the surface of the TM-RE film located in the pinning layer. Since the TM-RE film formed by the amorphous TM-RE material can improve the flatness of the subsequent growth film, there is no need to consider the stress and roughness accumulation caused by lattice mismatch, so there is no need to make an additional structural conversion layer to meet the reference requirements. The requirements of the layer on the flatness of the interface, while simplifying the manufacturing process.
  • the pinning layer includes a TM-RE film and an oxide layer; the surface of the TM-RE film on a side away from the barrier layer is provided with an oxide layer.
  • the pinning layer includes two TM-RE films and an oxide layer; the oxide layer is located between the two TM-RE films.
  • the pinning layer includes two oxide layers and a TM-RE film; the TM-RE film is located between the two oxide layers.
  • the embodiment of the present application also provides a method for fabricating a magnetic device, which may include: fabricating a magnetic tunnel junction; wherein the magnetic tunnel junction includes a pinned layer, a reference layer, a barrier layer, and a free layer that are stacked in sequence; At least one of the pinned layer or the free layer includes: a transition metal-rare earth ferrimagnetic alloy thin film and an oxide layer on the surface of the transition metal-rare earth ferrimagnetic alloy thin film. Annealing is performed on the formed magnetic tunnel junction.
  • Adopt the manufacturing method of the magnetic device of the present application by making TM-RE thin film and the oxide layer that is in contact with TM-RE thin film in the process of forming pinning layer and/or free layer, thereby the magnetic tunnel formed in the follow-up
  • an additional source of perpendicular magnetic anisotropy is provided to the TM-RE film through the oxide layer, which improves the annealing tolerance of the perpendicular magnetic anisotropy of the TM-RE film, and thus solves the problem in related technologies. Due to the poor annealing tolerance of the perpendicular magnetic anisotropy of the TM-RE alloy material, it cannot be applied in the MTJ.
  • the above-mentioned manufacturing of the magnetic tunnel junction may include: sequentially manufacturing a reference layer, a barrier layer, a ferromagnetic layer, an interlayer coupling layer, a transition metal-rare earth ferrimagnetic alloy thin film, and an oxide layer to form A magnetic tunnel junction; wherein, a ferromagnetic layer, an interlayer coupling layer, a transition metal-rare earth ferrimagnetic alloy thin film and an oxide layer are sequentially fabricated to form a free layer.
  • the above-mentioned manufacturing of the magnetic tunnel junction may include: sequentially manufacturing an oxide layer, a transition metal-rare earth ferrimagnetic alloy thin film, an interlayer coupling layer, a ferromagnetic layer, a barrier layer, and a reference layer to form A magnetic tunnel junction; wherein the oxide layer, the transition metal-rare earth ferrimagnetic alloy film, the interlayer coupling layer, and the ferromagnetic layer are sequentially fabricated to form a free layer.
  • the magnetic tunnel junction formed in the follow-up During the annealing treatment, an additional source of perpendicular magnetic anisotropy is provided to the TM-RE film through the oxide layer, thereby improving the annealing tolerance of the perpendicular magnetic anisotropy of the TM-RE film.
  • the formed composite free layer based on TM-RE film can provide bulk perpendicular magnetic anisotropy.
  • the above-mentioned manufacturing of the magnetic tunnel junction may include: sequentially manufacturing an oxide layer, a transition metal-rare earth ferrimagnetic alloy film, a reference layer, a barrier layer, and a free layer to form a magnetic tunnel junction; wherein, The oxide layer and the transition metal-rare earth ferrimagnetic alloy thin film fabricated in sequence form a pinning layer.
  • the above-mentioned manufacturing of the magnetic tunnel junction may include: sequentially manufacturing a free layer, a barrier layer, a reference layer, a transition metal-rare earth ferrimagnetic alloy thin film, and an oxide layer to form a magnetic tunnel junction; wherein, The transition metal-rare earth ferrimagnetic alloy film and the oxide layer fabricated in sequence form a pinning layer.
  • the oxide layer An additional source of perpendicular magnetic anisotropy is provided to the TM-RE film, thereby enhancing the annealing tolerance of the perpendicular magnetic anisotropy of the TM-RE film.
  • the TM-RE material used in the formed TM-RE film is a ferrimagnetic material, its own magnetic moment is very small, which can reduce the leakage magnetic field of the pinning layer, thereby reducing the impact on the free magnetic field.
  • the layer's bias field offset
  • the TM-RE film formed by the amorphous TM-RE material can improve the flatness of the subsequent growth film, there is no need to consider the stress and roughness accumulation caused by lattice mismatch.
  • the TM-RE thin film can be directly contacted with the reference layer, and there is no need to make an additional structural transformation layer to meet the requirements of the reference layer on the flatness of the interface, while simplifying the manufacturing process.
  • the embodiment of the present application also provides a magnetic memory, which includes a controller and a magnetic device as provided in any of the foregoing possible implementation manners; the magnetic device is connected to the controller.
  • the embodiment of the present application also provides an electronic device, the electronic device includes a printed circuit board and the magnetic memory provided in any one of the foregoing possible implementation manners; the magnetic memory is connected to the printed circuit board.
  • FIG. 1 is a schematic structural diagram of an MTJ provided in an embodiment of the present application.
  • FIG. 2 is a schematic structural diagram of an MTJ provided in an embodiment of the present application.
  • FIG. 3 is a schematic diagram of the working principle of an MTJ provided in the embodiment of the present application.
  • FIG. 4 is a schematic structural diagram of an MTJ device provided in an embodiment of the present application.
  • FIG. 5 is a schematic structural diagram of an MTJ device provided in an embodiment of the present application.
  • FIG. 6 is a schematic diagram of a manufacturing process of an MTJ device provided in an embodiment of the present application.
  • Fig. 7 is three kinds of TM-RE film hysteresis loop diagrams provided by the embodiment of the present application.
  • FIG. 8 is a schematic structural diagram of an MTJ device provided in an embodiment of the present application.
  • FIG. 9 is a schematic structural diagram of an MTJ device provided in an embodiment of the present application.
  • FIG. 10 is a schematic diagram of a fabrication process of an MTJ device provided in an embodiment of the present application.
  • FIG. 11 is a schematic structural diagram of an electronic device provided by an embodiment of the present application.
  • FIG. 12 is a schematic structural diagram of a memory cell in a magnetic memory provided by an embodiment of the present application.
  • At least one (item) means one or more, and “multiple” means two or more.
  • “And/or” is used to describe the association relationship of associated objects, indicating that there can be three types of relationships, for example, “A and/or B” can mean: only A exists, only B exists, and A and B exist at the same time , where A and B can be singular or plural.
  • the character “/” generally indicates that the contextual objects are an “or” relationship.
  • At least one of the following” or similar expressions refer to any combination of these items, including any combination of single or plural items.
  • At least one item (piece) of a, b or c can mean: a, b, c, "a and b", “a and c", “b and c", or "a and b and c ", where a, b, c can be single or multiple.
  • An embodiment of the present application provides an electronic device, which includes a printed circuit board (printed circuit board, PCB) and a magnetic device connected to the printed circuit board.
  • the magnetic device is provided with a magnetic tunneling junction (magnetic tunneling junction, MTJ), and the magnetic device may also be called an MTJ device or an MTJ element.
  • MTJ magnetic tunneling junction
  • the electronic device may be electronic products such as a mobile phone, a tablet computer, a notebook, a vehicle computer, a smart watch, and a smart bracelet.
  • the present application does not limit the application fields of the above-mentioned MTJ devices.
  • the MTJ device can be applied to magnetic random access memory (magnetic random access memory, MRAM), magnetic sensor (also called MTJ sensor) and other fields.
  • MRAM magnetic random access memory
  • M sensor also called MTJ sensor
  • TM-RE transition metal-rare earth ferrimagnetic alloy
  • Anisotropy (perpendicular magnetic anisotropy, PMA) source thereby improving the annealing resistance of the perpendicular magnetic anisotropy of the TM-RE thin film, and then solving the problem of the perpendicular magnetic anisotropy of the TM-RE alloy material in the related technology
  • the poor annealing tolerance cannot be applied in MTJ.
  • the MTJ is a device that can change its resistance state according to the state of the magnetic material inside the device.
  • the MTJ includes a reference layer 1 (reference layer), a barrier layer 2 (tunneling barrier layer; also called a tunneling layer), and a free layer 3 (free layer) that are stacked in sequence.
  • the MTJ can also be provided with a pinning layer 4 (hard layer) on the side of the reference layer 1 away from the barrier layer 2, so as to fix the reference layer 4 through the pinning layer 4.
  • the pinning layer 4 may be in direct contact with the reference layer 1 , or other film layers (such as a structural conversion layer, etc.) may be arranged between the pinning layer 4 and the reference layer 1 , which can be selected according to actual needs.
  • film layers such as a structural conversion layer, etc.
  • the magnetization direction of the reference layer 1 remains unchanged (that is, the magnetism remains unchanged), and the magnetism of the free layer 3 changes with the change of the control current or other magnetic switching mechanisms, so that the free layer 3 and the reference The layer 1 magnetization direction is parallel or antiparallel.
  • the resistance of the current passing along the barrier direction of the MTJ (that is, the direction perpendicular to the film) is small, and the MTJ presents a low resistance (that is, a low resistance state);
  • the resistance of the current passing along the barrier direction of the MTJ is relatively large, and the MTJ presents a high resistance (that is, a high resistance state) at this time. That is to say, MTJ can switch between two resistance states (ie, high resistance state and low resistance state), and this property is called tunneling magnetoresistance (TMR) effect.
  • TMR tunneling magnetoresistance
  • MRAM For MRAM, there are MTJ devices and a controller connected to the MTJ device inside the MRAM. MRAM utilizes the tunneling magnetoresistance effect of MTJ, and can use the high and low resistance of MTJ through the controller to correspond to the information storage respectively. The "0" and "1" of one-byte binary information are used to judge the "0" state or "1" state of the stored data, and then realize information storage.
  • an MTJ device and an induction circuit connected to the MTJ device are arranged inside the magnetic sensor.
  • the magnetic sensor uses the tunneling magnetoresistance effect of MTJ to change the magnetization direction of the free layer through the external magnetic field change, and read the resistance of the MTJ through the induction circuit to deduce the magnetization state of the free layer, and then determine the direction or magnitude of the external magnetic field.
  • the reference layer 1, the barrier layer 2, and the free layer 3 are stacked sequentially from bottom to top as an example for schematic illustration.
  • the reference layer 1 , the barrier layer 2 , and the free layer 3 may be stacked sequentially from top to bottom.
  • the pinning layer 4 is disposed above the reference layer 1 .
  • the magnetization direction of the reference layer 1 is only shown as an example for illustration. In other embodiments, the magnetization direction of the reference layer 1 may also be directed downward.
  • the stacked structure of the MTJ can be arranged between the bottom electrode E1 and the top electrode E2, and a control electrical signal can be applied to the MTJ through the bottom electrode E1 and the top electrode E2.
  • the structural seed layer 5 can be formed on the surface of the bottom electrode E1 first, and then the MTJ is fabricated on the structural seed layer 5 to provide a better growth plane for the fabrication of the MTJ.
  • a cover layer 6 can be provided on the surface of the free layer 3; wherein, the cover layer 6 can be made of metal (such as Pt, Ta, etc.), or a non-metal oxide (such as SiO 2 ), and the thickness of the cover layer 6 is generally It may be 2 nm to 3 nm, but it is not limited thereto.
  • metal such as Pt, Ta, etc.
  • non-metal oxide such as SiO 2
  • At least one of the free layer 3 and the pinned layer 4 of the MTJ can be set to include a TM-RE film, and at least one surface (ie, the upper surface and the upper surface) of the TM-RE film At least one of) provides an oxide layer comprising an oxide material.
  • the free layer 3 that may be an MTJ includes a TM-RE thin film and an oxide layer (for details, refer to Embodiment 1 below).
  • the pinning layer 4 that may be an MTJ includes a TM-RE thin film and an oxide layer (for details, refer to Embodiment 2 below).
  • it may be that both the free layer 3 and the pinned layer 4 of the MTJ are provided with a TM-RE thin film and an oxide layer.
  • the oxygen atoms in the oxide layer diffuse into the TM-RE material during the post-annealing process of the MTJ device, and the 2p orbital of the oxygen atom and the 3d orbital of the transition metal element in the TM-RE material contain the z component (that is, the component perpendicular to the TM-RE direction) orbital hybridization makes the electron spin arrangement of the TM-RE material biased towards the vertical film direction, that is, the oxide layer provides the TM-RE film with additional vertical magnetic properties.
  • the source of the anisotropy (perpendicular magnetic anisotropy, PMA), thereby improving the annealing resistance of the perpendicular magnetic anisotropy of the TM-RE film, and thus enabling the application of the TM-RE material to the MTJ.
  • TM-RE materials due to the amorphous nature of TM-RE materials, the films grown adjacent to it will not cause interlayer stress due to lattice mismatch and the accumulation of roughness due to the growth of multilayer structures. In this way, other film layers that require higher interface flatness can be directly formed on the surface of the TM-RE film, without the need to make an additional intermediate film layer to ensure the interface flatness (for details, please refer to the relevant settings in Example 2 below) , thereby improving the overall flatness of each film layer of the MTJ device, and improving the overall performance of the MTJ device.
  • the perpendicular magnetic anisotropy in this application means that the spins of the outer electrons in the ferrimagnetic layer are selected to be oriented perpendicular to the The orientation of the interface of the ferromagnetic layer.
  • the interface of the ferrimagnetic layer may be the interface where the ferrimagnetic layer is in contact with other layers; for example, the interface where the TM-RE thin film is in contact with the oxide layer in this application.
  • annealing tolerance the perpendicular magnetic anisotropy of the TM-RE material does not change greatly when the subsequent annealing process or other types of annealing processes are performed on the MTJ.
  • the ability to maintain magnetic anisotropy to a certain extent after annealing is called annealing tolerance.
  • the annealing resistance is related to the element selection, composition ratio, doping type and other factors of TM-RE materials.
  • the transition metal element in the TM-RE material may include at least one of cobalt (Co), iron (Fe) or nickel (Ni), but the present application It is not limited to this.
  • the rare earth elements in the TM-RE material may include at least one of terbium (Tb), gadolinium (Gd), dysprosium (Dy) or europium (Eu), but the application is not limited thereto.
  • the TM-RE material may also include doping elements.
  • the doping element may be at least one of tantalum (Ta), tungsten (W), silicon (Si), boron (B) or carbon (C), but the application is not limited thereto.
  • the TM-RE material used in the TM-RE thin film may include cobalt terbium (CoTb), iron terbium (FeTb), cobalt gadolinium (CoGd), cobalt terbium boron (CoTbB), iron terbium boron ( FeTbB) or cobalt gadolinium boron (CoGdB), but the present application is not limited thereto.
  • CoTb cobalt terbium
  • FeTb iron terbium
  • CoGd cobalt gadolinium
  • CoTbB cobalt terbium boron
  • FeTbB iron terbium boron
  • CoGdB cobalt gadolinium boron
  • composition ratio of each element (transition metal element, rare earth element, doping element) of the TM-RE material in the TM-RE film is not limited to a specific composition ratio. In practice, it can be based on Setup is required.
  • the oxide material forming the oxide layer may include magnesium-containing oxides (such as MgO), copper-containing oxides (such as CuO), aluminum-containing oxides (such as Al 2 O 3 ), Zinc-containing oxides (such as ZnO), nickel-containing oxides (such as NiO), chromium-containing oxides (such as Cr 2 O 3 , CrO 2 ), titanium-containing oxides (such as TiO 2 ), silicon-containing oxides (such as SiO 2 ) or at least one of selenium-containing oxides (such as SeO 2 ), but the application is not limited thereto.
  • magnesium-containing oxides such as MgO
  • copper-containing oxides such as CuO
  • aluminum-containing oxides such as Al 2 O 3
  • Zinc-containing oxides such as ZnO
  • nickel-containing oxides such as NiO
  • chromium-containing oxides such as Cr 2 O 3 , CrO 2
  • titanium-containing oxides such as TiO 2
  • silicon-containing oxides such as SiO 2
  • the oxide used for the oxide layer may include at least one of MgO, SiO 2 or MgAlO 3 , but is not limited thereto.
  • the thickness of the oxide layer and the TM-RE thin film in the MTJ device there is no specific limitation on the thickness of the oxide layer and the TM-RE thin film in the MTJ device in this application, and the thickness of the oxide layer and the TM-RE thin film is determined according to the specific material and process flow used in practice.
  • the following is a schematic illustration of the arrangement of the TM-RE thin film and the oxide layer in the MTJ device through specific examples.
  • the TM-RE thin film and the oxide layer can be applied to the free layer 3 of the MTJ.
  • the free layer 3 of the MTJ can use a composite free layer (hybrid free layer, HFL ), the specific settings can be as follows:
  • the free layer 3 may include a ferromagnetic layer 30 (ferromagnetic layer), an interlayer coupling layer 31 (interlayer spacer or coupling spacer), a TM-RE thin film 100 and an oxide layer stacked sequentially from bottom to top. 200.
  • the ferromagnetic layer 30 is in contact with the barrier layer 2 .
  • the oxide layer 200 is disposed on the upper surface of the TM-RE thin film 100 (that is, the surface away from the barrier layer 2 ).
  • the oxide layer 200 in the case of using a thinner oxide layer 200, if the thickness of the oxide layer 200 is below 0.5 nm, the oxide layer 200 can also be disposed on the TM-RE thin film 100 The lower surface (that is, the surface on the side close to the barrier layer 2). The following embodiments are all described by taking the oxide layer 200 disposed on the surface of the TM-RE thin film 100 away from the barrier layer 2 as an example.
  • a structural conversion layer 41 is provided between the pinning layer 4 and the reference layer 1, and the formation of the structural conversion layer 41 can provide better growth to the reference layer 1. flat.
  • the structural transformation layer 41 may not be provided by selecting a suitable pinning layer 4 .
  • the first embodiment also provides a manufacturing method of the above-mentioned MTJ device, the manufacturing method may include:
  • Step 11 sequentially fabricate the pinning layer 4, the structural conversion layer 41, the reference layer 1, the barrier layer 2, the ferromagnetic layer 30, the interlayer coupling layer 31, the TM-RE thin film 100 and the oxide layer 200 to form the MTJ.
  • the ferromagnetic layer 30 , the interlayer coupling layer 31 , the TM-RE thin film 100 and the oxide layer 200 as a whole serve as the free layer 3 (that is, the composite free layer) in the MTJ.
  • the above-mentioned pinning layer 4 can adopt Co/Pt (cobalt/platinum) multilayer film, Co/Pd (cobalt/palladium) multilayer film, Co/Ir (cobalt/iridium) multilayer film, etc., but not limited to this.
  • the above-mentioned structure conversion layer 41 can be made of tantalum (Ta), titanium (Ti), titanium nitride (TiN), aluminum (Al), magnesium (Mg), titanium magnesium (TiMg), tungsten (W) or molybdenum ( Mo) and other materials, but not limited thereto.
  • the above-mentioned reference layer 1 may use one or more materials such as CoFeB (cobalt iron boron), FeB (iron boron), CoFe (cobalt iron) or CoB (cobalt boron), but is not limited thereto.
  • CoFeB cobalt iron boron
  • FeB iron boron
  • CoFe cobalt iron
  • CoB cobalt boron
  • the aforementioned barrier layer 2 can be made of MgO, MgAlO 3 , AlO x (aluminum oxide), MgGdO, TiO x (titanium oxide), TaO x (tantalum oxide) or MgTiO x (magnesium titanium oxide), etc.
  • AlO x aluminum oxide
  • MgGdO aluminum oxide
  • TiO x titanium oxide
  • TaO x tantalum oxide
  • MgTiO x manganesium titanium oxide
  • the above-mentioned ferromagnetic layer 30 may use one or more of materials such as CoFeB, FeB, CoFe or CoB, but is not limited thereto.
  • the interlayer coupling layer 31 may use one or more materials such as Ta (tantalum) or Ru (ruthenium), but is not limited thereto.
  • the above-mentioned TM-RE film 100 may use one or more of materials such as CoTb, FeTb, CoGd, CoTbB, FeTbB or CoGdB, but is not limited thereto.
  • the above-mentioned oxide layer 200 may use one or more of materials such as MgO, SiO 2 or MgAlO 3 , but is not limited thereto.
  • a stacked bottom electrode E1 and a structural seed layer 5 may be sequentially formed on the substrate;
  • the surface of the structural conversion layer 41 is subjected to the fabrication of the pinning layer 4 , the structural conversion layer 41 , the reference layer 1 , the barrier layer 2 and the free layer 3 in step 11 .
  • the fabrication of other film layers can be continued on the surface of the free layer 3, such as the fabrication of the covering layer 6 and the top electrode E2.
  • the fabrication of the TM-RE thin film 100 and the oxide layer 200 in the above step 11 may include:
  • the TM-RE film 100 can be formed by sputtering growth on the surface of the interlayer coupling layer 31 using a TM-RE target, and then an oxide layer can be sputtered on the surface of the TM-RE film 100 200 (such as MgO layer).
  • the TM-RE thin film 100 may also be grown on the surface of the interlayer coupling layer 31 by co-sputtering with the TM target and the RE target.
  • the TM-RE thin film 100 can be grown at room temperature, and the bottom structure before growth is brought into a vacuum sputtering chamber at a room temperature at room temperature, and the vacuum degree is higher than 10 ⁇ 8 Torr.
  • Steps including but not limited to chemical mechanical polishing, ion etching, and ultrasonic cleaning can be used to make the bottom structure before the growth The bottom structure meets the requirements and will not affect the growth of the TM-RE thin film 100 .
  • Step 12 annealing the fabricated MTJ.
  • the device containing MTJ can be placed in a vacuum environment with a vacuum degree higher than 10 -8 Torr for annealing; for example, the annealing time can be 1.5h, and the annealing temperature It can be greater than 400°C; and after the annealing process is completed, the device is placed in a vacuum environment and naturally cooled to room temperature before being taken out.
  • the perpendicular magnetic anisotropy and properties after annealing of the M-RE thin film 100 can be adjusted by adjusting parameters such as the oxide type, sputtering power, gas pressure, and thickness of the oxide layer 200 .
  • the type and thickness of the oxide layer 200 are not limited. Experiments have found that the oxide layer 200 formed by using different types of oxides at the same thickness can improve the perpendicular magnetic anisotropy of the TM-RE thin film 100 after annealing. The (hold) effect is not the same. For example, when the thickness of the oxide layer 200 is the same, the oxide layer 200 using MgO is better than the oxide layer 200 using SiO 2 in improving the perpendicular magnetic anisotropy of the TM-RE thin film 100 . When the types of oxides are the same, the greater the thickness of the oxide layer 200 , the more significantly the perpendicular magnetic anisotropy of the TM-RE thin film 100 after annealing is improved.
  • S0 is the hysteresis loop of the multi-layer structure without the oxide layer 200 on the surface of the TM-RE thin film 100 after annealing at 400° C. for 1.5 h.
  • S1 is the hysteresis loop of the multilayer structure of the TM-RE thin film 100 with a MgO layer (200) with a thickness of 0.4 nm on the surface after annealing at 400° C. for 1.5 h.
  • S2 is the hysteresis loop of the multilayer structure of the TM-RE thin film 100 with a MgO layer (200) with a thickness of 1.0 nm on the surface after annealing at 400° C. for 1.5 h.
  • the hysteresis loop in Fig. 7 is the relationship curve between the magnitude of the magnetization (i.e. the abscissa) applied in the direction (i.e. the z direction) perpendicular to the TM-RE film 100 and the Hall voltage V H (i.e. the ordinate); Those skilled in the art can understand that the larger the Hall voltage V H is, the larger the magnetization in the z direction of the TM-RE film 100 is. Based on this, comparing S0 with S1 and S2, it can be seen that compared with no oxide layer 200 (refer to S0), setting the oxide layer 200 can significantly improve the annealing of the perpendicular magnetic anisotropy of the TM-RE thin film 100 tolerance. Comparing S1 and S2, it can be seen that when the oxide layer 200 uses the same oxide, the thicker the oxide layer 200 is, the better the annealing resistance of the perpendicular magnetic anisotropy of the TM-RE thin film 100 is.
  • step 11 is only schematically taking the reference layer 1, the barrier layer 2, the ferromagnetic layer 30, the interlayer coupling layer 31, the TM-RE thin film 100 and the oxide layer 200 as an example. Be explained. In other possible implementations, the oxide layer 200, the TM-RE thin film 100, the interlayer coupling layer 31, the ferromagnetic layer 30, the barrier layer 2, the reference layer 1, and the structure conversion layer 41 can be sequentially fabricated through step 11. , pinning the layer 4 to form the MTJ.
  • the free layer 3 is located on the side of the barrier layer 2 close to the bottom electrode E1
  • the reference layer 1 the structure conversion layer 41, and the pinning layer 4 are located on the side of the barrier layer 2 close to the top electrode E2.
  • the settings are stacked one after the other.
  • the oxide layer provides the TM-RE film with additional perpendicular magnetic anisotropy Anisotropy sources, thereby improving the annealing resistance of the perpendicular magnetic anisotropy of TM-RE thin films; on the other hand, the composite free layer based on TM-RE thin films can provide bulk perpendicular magnetic anisotropy (b-PMA).
  • the TM-RE film and the oxide layer can be applied to the pinning layer 4 of the MTJ.
  • one or more TM-RE thin films may be disposed in the pinning layer 4 of the MTJ; wherein, at least one surface of part or all of the TM-RE thin films is disposed with an oxide layer.
  • an oxide layer may be provided on the upper surface of at least one TM-RE film; an oxide layer may also be provided on the lower surface of at least one TM-RE film; - the lower surface and lower surface of the RE thin film are respectively provided with oxide layers.
  • the pinning layer 4 may include a TM-RE film 100 and an oxide layer 200; One side of the layer 2 , that is, the oxide layer 200 is located on the lower surface of the TM-RE thin film 100 .
  • the oxide layer 200 may also be disposed on the upper surface of the TM-RE thin film 100 .
  • the pinning layer 4 may include two TM-RE thin films 100 and one oxide layer 200; RE film between 100.
  • the pinning layer 4 may include a TM-RE film 100 and two oxide layers 200 ; wherein, the TM-RE film 100 may be disposed between the two oxide layers 200 .
  • the TM-RE thin film 100 and the oxide layer 200 in the pinning layer 4 are not limited to the above-mentioned multiple arrangements.
  • three TM-REs can be arranged in the pinning layer 4 Film 100, in this case, an oxide layer 200 can be provided between two adjacent TM-RE films 100, or an oxide layer 200 can be provided on the lower surface or upper surface of each TM-RE film 100 respectively.
  • the object layer 200 and the like are not limited in the present application, and the TM-RE thin film 100 and the oxide layer 200 in the pinning layer 4 can be arranged according to actual needs.
  • the TM-RE film formed by using amorphous TM-RE material can improve the flatness of the subsequent growth film, it does not need to consider the stress and roughness accumulation caused by lattice mismatch. Therefore, the TM-RE film 100
  • the top layer of the pinning layer 4 can be set to use a TM-RE film 100, and a reference layer 1 is directly formed on the surface of the TM-RE film 100, That is, the reference layer 1 is in direct contact with the TM-RE film 100 on the top layer of the pinning layer 4 .
  • the second embodiment also provides a manufacturing method of the above-mentioned MTJ device, as shown in FIG. 10 , the manufacturing method may include:
  • Step 21 sequentially fabricate the pinning layer 4, the reference layer 1, the barrier layer 2, and the free layer 3 to form an MTJ; wherein, the pinning layer 4 includes one or more TM- RE film 100, and an oxide layer 200 is provided on the surface of at least one TM-RE film 100.
  • the above step 21 may include sequentially fabricating the oxide layer 200, the TM-RE thin film 100, the reference layer 1, the barrier layer 2, and the free layer 3 to form the MTJ.
  • the above step 21 may include sequentially fabricating the TM-RE film 100 , the oxide layer 200 , the TM-RE film 100 , the reference layer 1 , the barrier layer 2 , and the free layer 3 to form the MTJ.
  • a stacked bottom electrode E1 and a structural seed layer 5 may be sequentially formed on the substrate; and then The pinning layer 4 , reference layer 1 , barrier layer 2 , and free layer 3 in step 21 are fabricated on the surface of the structural conversion layer 41 .
  • other film layers such as the cover layer 6 and the top electrode E2 can be continued to be fabricated on the surface of the free layer 3 .
  • Step 22 annealing the fabricated MTJ.
  • the device containing MTJ can be placed in a vacuum environment with a vacuum degree higher than 10 -8 Torr for annealing, the annealing time can be 1.5h, and the annealing temperature can be greater than 400°C; and after the annealing process, the device was placed in a vacuum environment and naturally cooled to room temperature before being taken out.
  • the pinning layer 4 is located on the side of the barrier layer 2 close to the bottom electrode E1, and the free layer is located on the side of the barrier layer 2 close to the top electrode E2 as an example. illustrate. In some other possible implementation manners, the pinning layer 4 may be located on the side of the barrier layer 2 close to the top electrode E2 , and the free layer is located on the side of the barrier layer 2 close to the bottom electrode E1 .
  • the order of the film layers formed in step 2 can be adjusted; for example, in some possible implementations, the free layer 3, barrier layer 2, reference layer 1, TM-RE film 100 and oxide layer 200 to form MTJ.
  • the free layer 3, the barrier layer 2, the reference layer 1, the TM-RE film 100, the oxide layer 200, and the TM-RE film 100 can be sequentially fabricated through step 21 to form an MTJ .
  • the oxide layer provides the TM-RE film with additional perpendicular magnetic anisotropy source, thereby improving the annealing resistance of the perpendicular magnetic anisotropy of the TM-RE film;
  • the TM-RE material forming the TM-RE film 100 is a ferrimagnetic material, and its own magnetic The moment is very small, so that the leakage magnetic field of the pinned layer can be reduced, thereby reducing the bias field (offset) to the free layer.
  • the TM-RE film formed by the amorphous TM-RE material can improve the flatness of the subsequent growth film, there is no need to consider the stress and roughness accumulation caused by lattice mismatch.
  • the TM-RE thin film can be directly contacted with the reference layer, and there is no need to make an additional structural transformation layer to meet the requirements of the reference layer on the flatness of the interface, while simplifying the manufacturing process.
  • the first embodiment is schematically illustrated by taking the application of the TM-RE thin film 100 and the oxide layer 200 in the free layer 3 of the MTJ as an example.
  • the second embodiment is schematically illustrated by taking the application of the TM-RE thin film 100 and the oxide layer 200 in the pinning layer 4 of the MTJ as an example.
  • the present application is not limited thereto.
  • the TM-RE thin film 100 and the oxide layer 200 can be used in both the free layer 3 and the pinned layer 4 of the MTJ.
  • refer to the first embodiment and The related description of the second embodiment will not be repeated here.
  • the structure and process of the MTJ device used in the embodiment of the present application are relatively simple, and the perpendicular magnetic anisotropy and Control of annealing properties.
  • the oxide layer 200 can be grown at room temperature, and the thickness of the oxide layer 200 only needs to be one to several nanometers to achieve a significant effect; it can not only broaden the integration conditions of MTJ devices, promote the development and application of MTJ devices, but also contribute to the development and application of MTJ devices. Device fabrication and properties studies.
  • FIG. 11 is a schematic structural diagram of an electronic device exemplarily provided in an embodiment of the present application.
  • the electronic device 01 may include: a storage device 11, a processor 12, an input device 13, an output device 14 and other components.
  • the storage device 11 is used to store software programs and modules.
  • the storage device 11 mainly includes a program storage area and a data storage area, wherein the program storage area can store an operating system, at least one application program required by a function (such as a sound playback function, an image playback function, etc.); Data created by the use of electronic devices (such as audio data, image data, phonebook, etc.), etc.
  • the above storage device 11 may include an external memory 111 and an internal memory 112 .
  • the data stored in the external memory 111 and the internal memory 112 can be transferred to each other.
  • the external storage 111 includes, for example, a hard disk, a U disk, a floppy disk, and the like.
  • the internal memory 112 includes, for example, a random access memory, a read-only memory, etc., wherein the random access memory may be a magnetic random access memory (MRAM) provided in any possible implementation manner in the foregoing embodiments.
  • MRAM magnetic random access memory
  • the processor 12 is the control center of the electronic device 01. It uses various interfaces and lines to connect various parts of the entire electronic device 01. By running or executing the software programs and/or modules stored in the storage device 11, and calling the The data in the device 11 executes various functions of the electronic device 01 and processes data, so as to monitor the electronic device 01 as a whole.
  • the input device 13 is used for receiving inputted number or character information, and generating key signal input related to user setting and function control of the electronic device 01 .
  • the output device 14 is used to output the signal corresponding to the data input by the input device 13 and stored in the internal memory 112 .
  • the output device 14 outputs a sound signal or a video signal.
  • the controller in the above-mentioned processor 12 can also control the output device 14 to output a signal or not to output a signal.
  • MRAM is a new type of non-volatile memory, wherein the spin transfer torque magnetic random access memory (STT MRAM) in MRAM has high speed and low power consumption.
  • STT MRAM spin transfer torque magnetic random access memory
  • COMS complementary metal-oxide-semiconductor, complementary metal oxide semiconductor
  • the storage unit of the STT MRAM may include a transistor T and an MTJ device provided in any of the possible implementation manners provided in the embodiments of the present application.
  • the top electrode of the MTJ device is electrically connected to the bit line
  • the bottom electrode of the MTJ device is electrically connected to the drain of the transistor T
  • the gate of the transistor T is electrically connected to the word line
  • the source is electrically connected to the source line.

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Abstract

本申请提供了一种磁性器件及其制作方法、磁性存储器、电子设备，涉及磁性隧道结技术领域；能够解决因过渡金属-稀土亚铁磁合金材料的垂直磁各向异性的退火耐受性较差而无法应用在磁性隧道结中的问题。该磁性器件包括磁性隧道结；磁性隧道结包括依次堆叠设置的钉扎层、参考层、势垒层、自由层。其中，钉扎层或自由层中的至少一个包括：过渡金属-稀土亚铁磁合金薄膜以及位于过渡金属-稀土亚铁磁合金薄膜表面的氧化物层。

Description

磁性器件及其制作方法、磁性存储器、电子设备 技术领域
本申请涉及磁性隧道结技术领域，尤其涉及一种磁性器件及其制作方法、磁性存储器、电子设备。
背景技术
亚铁磁材料是一种区别于铁磁和反铁磁，又兼具二者特点的材料。过渡金属-稀土亚铁磁合金(transition metal rare earth ferrimagnetic alloy，TM-RE)材料作为亚铁磁材料中重要的一类材料，因其无定型态，并能通过调节合金元素及组分配比调控其宏观净磁矩、体垂直磁各向异性(bulk perpendicular magnetic anisotropy，b-PMA)等性质而被广泛研究和应用。
TM-RE材料在磁性隧道结(magnetic tunneling junction，MTJ)中具有广阔的应用前景，但是由于TM-RE材料的垂直磁各向异性的退火耐受性较差，在制备包含MTJ的磁性器件的过程中，由于后道退火工艺的温度常常会超过400℃并维持半个小时以上，从而导致TM-RE材料无法直接应用在MTJ中。
发明内容
本申请实施例提供一种磁性器件及其制作方法、磁性存储器、电子设备，能够解决因TM-RE合金材料的垂直磁各向异性的退火耐受性较差而无法应用在MTJ中的问题。
本申请提供一种磁性器件(也可以称为MTJ器件)，该磁性器件中包括磁性隧道结(MTJ)。其中，磁性隧道结包括依次堆叠设置的钉扎层、参考层、势垒层、自由层；钉扎层或自由层中的至少一个包括：过渡金属-稀土亚铁磁合金薄膜(TM-RE薄膜)和以及位于TM-RE薄膜表面的氧化物层；也即氧化物层位于TM-RE薄膜靠近或远离势垒层一侧的表面。也即，可以是MTJ的自由层中包括TM-RE薄膜和氧化物层；也可以是MTJ的钉扎层中包括TM-RE薄膜和氧化物层；还可以是MTJ的自由层和钉扎层中均设置有TM-RE薄膜和氧化物层。
在该磁性器件中，通过设置MTJ的部分膜层采用TM-RE薄膜，并且在TM-RE薄膜的至少一个表面设置氧化物层。这样一来，磁性器件在进行后道退火过程中氧化物层中的氧原子扩散进入TM-RE材料，氧原子的2p轨道与TM-RE材料中的过渡金属元素的3d轨道中含有z分量(即垂直TM-RE的方向的分量)轨道杂化，使得TM-RE材料的电子自旋排布取向偏向垂直薄膜方向，也即通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性，进而使得TM-RE材料能够应用至MTJ。
另外，由于TM-RE材料具有非晶态的特性，从而能够使得与之相邻生长的薄膜不会因为晶格不匹配而导致层间的应力以及由于多层结构生长导致的粗糙度的累积，这样一来，可以直接在TM-RE薄膜表面形成对界面平整度要求较高的其他膜层，而无需额外制 作中间膜层来保证界面平整度，进而提升了磁性器件各膜层整体的平整度，提升了磁性器件的整体性能。
在一些可能实现的方式中，TM-RE薄膜中包括TM-RE材料；TM-RE材料中的过渡金属元素包括Co，Fe或Ni中的至少一种；TM-RE材料中的稀土元素包括Tb，Gd，Dy或Eu中的至少一种。
在一些可能实现的方式中，TM-RE材料还包括Ta，W，Si，B或C中的至少一种掺杂元素。
在一些可能实现的方式中，TM-RE薄膜中包括CoTb，FeTb，CoGd，CoTbB，FeTbB或CoGdB中的至少一种。
在一些可能实现的方式中，氧化物层中的氧化物包括含镁氧化物，含铜氧化物，含铝氧化物，含锌氧化物，含镍氧化物，含铬氧化物，含钛氧化物，含硅氧化物或含硒氧化物中的至少一种。
在一些可能实现的方式中，氧化物层中包括MgO，SiO 2或MgAlO 3中的至少一种。
在一些可能实现的方式中，MTJ的自由层采用复合自由层，该复合自由层包括依次堆叠设置的铁磁层、层间耦合层、TM-RE薄膜和氧化物层；其中，铁磁层与势垒层接触。也就是说，可以将TM-RE薄膜和氧化物层应用至MTJ的自由层中。在此情况下，通过将TM-RE薄膜和氧化物层应用至MTJ的复合自由层中，一方面，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性；另一方面，复合自由层基于TM-RE薄膜能够提供体垂直磁各向异性(b-PMA)。
在一些可能实现的方式中，MTJ的钉扎层中可以包括一个或多个TM-RE薄膜；其中，至少一个TM-RE薄膜在靠近和/或远离势垒层一侧的表面设置有氧化物层。也就是说，在钉扎层中，可以在至少一个TM-RE薄膜的上表面设置有氧化物层；也可以在至少一个TM-RE薄膜的下表面设置有氧化物层；还可以在至少一个TM-RE薄膜的下表面和下表面分别设置有氧化物层。在此情况下，通过将TM-RE薄膜和氧化物层应用至MTJ的钉扎层中，一方面，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性；另一方面，由于TM-RE材料作为一种亚铁磁铁料，其自身的磁矩很小，从而能够减小钉扎层的漏磁场，进而减小了对自由层的偏置场(offset)。
在一些可能实现的方式中，钉扎层通过TM-RE薄膜与参考层直接接触。在此情况下，可以直接在位于钉扎层中的TM-RE薄膜表面直接制作参考层。由于采用非晶态的TM-RE材料形成的TM-RE薄膜能够提升后续生长薄膜的平整度，无需考虑晶格不匹配产生的应力以及粗糙度累积，从而无需额外单独制作结构转化层来满足参考层对界面平整度的要求，同时简化了制作工艺。
在一些可能实现的方式中，钉扎层中包括一个TM-RE薄膜和一个氧化物层；TM-RE薄膜在远离势垒层一侧的表面设置有氧化物层。
在一些可能实现的方式中，钉扎层中包括两个TM-RE薄膜和一个氧化物层；氧化物层位于两个TM-RE薄膜之间。
在一些可能实现的方式中，钉扎层中包括两个氧化物层和一个TM-RE薄膜；TM-RE薄膜位于两个氧化物层之间。
本申请实施例还提供一种磁性器件的制作方法，该制作方法可以包括：制作磁性隧道结；其中，磁性隧道结包括依次堆叠设置的钉扎层、参考层、势垒层、自由层；钉扎层或自由层中的至少一个包括：过渡金属-稀土亚铁磁合金薄膜以及位于过渡金属-稀土亚铁磁合金薄膜表面的氧化物层。对制作形成的磁性隧道结进行退火处理。
采用本申请的磁性器件的制作方法，通过在形成钉扎层和/或自由层的过程中，制作TM-RE薄膜以及与TM-RE薄膜接触的氧化物层，从而在后续对形成的磁性隧道结进行退火处理时，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，提升了TM-RE薄膜的垂直磁各向异性的退火耐受性，进而解决了相关技术中因TM-RE合金材料的垂直磁各向异性的退火耐受性较差而无法应用在MTJ中的问题。
在一些可能实现的方式中，上述制作磁性隧道结可以包括：依次制作参考层、势垒层、铁磁层、层间耦合层、过渡金属-稀土亚铁磁合金薄膜和氧化物层，以形成磁性隧道结；其中，依次制作的铁磁层、层间耦合层、过渡金属-稀土亚铁磁合金薄膜和氧化物层形成自由层。
在一些可能实现的方式中，上述制作磁性隧道结可以包括：依次制作氧化物层、过渡金属-稀土亚铁磁合金薄膜、层间耦合层、铁磁层、势垒层、参考层，以形成磁性隧道结；其中，依次制作的氧化物层、过渡金属-稀土亚铁磁合金薄膜、层间耦合层、铁磁层形成自由层。
对于上述在制作磁性隧道结的自由层(复合自由层)时采用过渡金属-稀土亚铁磁合金薄膜和氧化物层的两种制作方式而言：一方面，在后续对形成的磁性隧道结进行退火处理时，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性。另一方面，形成的复合自由层基于TM-RE薄膜能够提供体垂直磁各向异性。
在一些可能实现的方式中，上述制作磁性隧道结可以包括：依次制作氧化物层、过渡金属-稀土亚铁磁合金薄膜、参考层、势垒层、自由层，以形成磁性隧道结；其中，依次制作的氧化物层、过渡金属-稀土亚铁磁合金薄膜形成钉扎层。
在一些可能实现的方式中，上述制作磁性隧道结可以包括：依次制作自由层、势垒层、参考层、过渡金属-稀土亚铁磁合金薄膜、氧化物层，以形成磁性隧道结；其中，依次制作的过渡金属-稀土亚铁磁合金薄膜、氧化物层形成钉扎层。
对于上述在制作钉扎层时采用过渡金属-稀土亚铁磁合金薄膜和氧化物层的两种制作方式而言：一方面，在后续对形成的磁性隧道结进行退火处理时，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性。另一方面，由于形成的TM-RE薄膜采用的TM-RE材料为一种亚铁磁铁材料，其自身的磁矩很小，从而能够减小钉扎层的漏磁场，进而减小了对自由层的偏置场(offset)。
另外，由于采用非晶态的TM-RE材料形成的TM-RE薄膜能够提升后续生长薄膜的平整度，无需考虑晶格不匹配产生的应力以及粗糙度累积，因此上述在制作钉扎层采用TM-RE薄膜的情况下，可以直接将TM-RE薄膜与参考层直接接触，无需额外单独制作结构转化层来满足参考层对界面平整度的要求，同时简化了制作工艺。
本申请实施例还提供一种磁性存储器，该磁性存储器包括控制器以及如前述任一种可 能实现的方式中提供的磁性器件；磁性器件与控制器连接。
本申请实施例还提供一种电子设备，该电子设备包括印刷线路板以及如前述任一种可能实现的方式中提供的磁性存储器；磁性存储器与印刷线路板连接。
附图说明
图1为本申请实施例提供的一种MTJ的结构示意图；
图2为本申请实施例提供的一种MTJ的结构示意图；
图3为本申请实施例提供的一种MTJ的工作原理示意图；
图4为本申请实施例提供的一种MTJ器件的结构示意图；
图5为本申请实施例提供的一种MTJ器件的结构示意图；
图6为本申请实施例提供的一种MTJ器件的制作流程示意图；
图7为本申请实施例提供的三种TM-RE薄膜磁滞回线图；
图8为本申请实施例提供的一种MTJ器件的结构示意图；
图9为本申请实施例提供的一种MTJ器件的结构示意图；
图10为本申请实施例提供的一种MTJ器件的制作流程示意图；
图11为本申请实施例提供的一种电子设备的架构示意图；
图12为本申请实施例提供的一种磁性存储器中的存储单元结构示意图。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚，下面将结合本申请中的附图，对本申请中的技术方案进行清楚地描述，显然，所描述的实施例是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请的说明书实施例和权利要求书及附图中的术语“第一”、“第二”等仅用于区分描述的目的，而不能理解为指示或暗示相对重要性，也不能理解为指示或暗示顺序。“连接”、“相连”等类似的词语，用于表达不同组件之间的互通或互相作用，可以包括直接相连或通过其他组件间接相连。此外，术语“包括”和“具有”以及他们的任何变形，意图在于覆盖不排他的包含，例如，包含了一系列步骤或单元。方法、系统、产品或设备不必限于清楚地列出的那些步骤或单元，而是可包括没有清楚地列出的或对于这些过程、方法、产品或设备固有的其它步骤或单元。“上”、“下”、“左”、“右”等仅用于相对于附图中的部件的方位而言的，这些方向性术语是相对的概念，它们用于相对于的描述和澄清，其可以根据附图中的部件所放置的方位的变化而相应地发生变化。
应当理解，在本申请中，“至少一个(项)”是指一个或者多个，“多个”是指两个或两个以上。“和/或”，用于描述关联对象的关联关系，表示可以存在三种关系，例如，“A和/或B”可以表示：只存在A，只存在B以及同时存在A和B三种情况，其中A，B可以是单数或者复数。字符“/”一般表示前后关联对象是一种“或”的关系。“以下至少一项(个)”或其类似表达，是指这些项中的任意组合，包括单项(个)或复数项(个)的任意组合。例如，a，b或c中的至少一项(个)，可以表示：a，b，c，“a和b”，“a和c”，“b和c”，或“a和b和c”，其中a，b，c可以是单个，也可以是多个。
本申请实施例提供一种电子设备，该电子设备中包括印刷线路板(printed circuit board，PCB)以及与该印刷线路板连接的磁性器件。其中，该磁性器件中设置有磁性隧道结(magnetic tunneling junction，MTJ)，该磁性器件也可以称为MTJ器件或MTJ元件。
本申请对于上述电子设备的设置形式不做限制。例如，该电子设备可以为手机、平板电脑、笔记本、车载电脑、智能手表、智能手环等电子产品。
本申请对于上述MTJ器件的应用领域不做限制。例如，该MTJ器件可以应用至磁随机存储器(magnetic random access memory，MRAM)、磁传感器(也可以称为MTJ sensor)等领域。
在本申请实施例提供的MTJ器件中，通过设置MTJ的部分膜层包含过渡金属-稀土亚铁磁合金(transition metal-rare earth ferrimagnetic alloy，TM-RE)材料，也即MTJ的部分膜层包含TM-RE薄膜。并且在TM-RE薄膜至少一个表面(也即上表面和下表面中的至少一个)设置与TM-RE薄膜直接接触的氧化物层，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性(perpendicular magnetic anisotropy，PMA)来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性，进而解决了相关技术中因TM-RE合金材料的垂直磁各向异性的退火耐受性较差而无法应用在MTJ中的问题。
以下结合MTJ对TM-RE薄膜和氧化物层的设置进行示意的说明。
MTJ是一种可以根据器件内部的磁性材料的状态改变自身的电阻状态的器件。如图1所示，MTJ中包括依次堆叠设置的参考层1(reference layer)、势垒层2(tunneling barrier layer；也可以称为隧穿层)、自由层3(free layer)。当然，在一些可能实现的方式中，如图2所示，MTJ在参考层1远离势垒层2的一侧还可以设置有钉扎层4(hard layer)，以通过钉扎层4固定参考层1的磁矩。该钉扎层4可以与参考层1直接接触，也可以在钉扎层4与参考层1之间设置有其他的膜层(如结构转化层等)，实际中可以根据需要进行选择设置。以下实施例均是以MTJ中设置有钉扎层4为例进行示意说明的。
参考图3所示，在MTJ中，参考层1的磁化方向不变(也即磁性不变)，自由层3的磁性随控制电流或者其他磁性翻转机制改变而改变，从而使得自由层3与参考层1磁化方向平行或者反平行。当自由层3与参考层1的磁化方向同向平行时，电流沿MTJ层垒方向(也即垂直薄膜方向)通过时的电阻较小，此时MTJ呈现低电阻(即低阻态)；当自由层3与参考层1的磁化方向反向平行时，电流沿MTJ层垒方向通过时的电阻较大，此时MTJ呈现高电阻(即高阻态)。也就是说，MTJ可以在两种电阻状态(即高阻态和低阻态)中切换，这种性能被称作隧穿磁阻(tunneling magnetoresistance，TMR)效应。
对于MRAM而言，在MRAM的内部设置有MTJ器件以及与MTJ器件连接的控制器，MRAM利用MTJ的隧穿磁阻效应，能够通过控制器基于MTJ的高、低电阻，分别对应于信息存储中一字节二进制信息的“0”和“1”，来判断存储数据的“0”态或者“1”态，进而实现信息存储。
对于磁传感器而言，在磁传感器的内部设置有MTJ器件以及与MTJ器件连接的感应电路。磁传感器利用MTJ的隧穿磁阻效应，能够通过外部的磁场变化改变自由层的磁化方向，并通过感应电路读取MTJ的电阻可以推出自由层的磁化状态，进而确定外磁场的方向或大小。
此处需要说明的是，图1和图2中均是以参考层1、势垒层2、自由层3从下到上依 次堆叠设置为例进行示意说明的。在另一些实施例中，参考层1、势垒层2、自由层3可以是从上到下依次堆叠，在此情况下，钉扎层4则设置在参考层1的上方。还需要说明的是，图3中仅是示意的以参考层1的磁化方向朝上为例进行示意说明的，在另一些实施例中，参考层1的磁化方向也可以朝下。
另外，本领域的技术人员可以理解的是，基于MTJ器件的制作以及控制，通常需要在MTJ的两侧设置有其他的膜层结构，如图4中示出的底电极E1、顶电极E2、结构种子层5(seed layer)、覆盖层6(capping layer)等等。
示意的，可以将MTJ的叠层结构设置在底电极E1和顶电极E2之间，能够通过底电极E1和顶电极E2向MTJ施加控制电信号。示意的，可以在底电极E1的表面先形成结构种子层5，然后在结构种子层5上在进行MTJ的制作，以为MTJ的制作提供较好的生长平面。示意的，可以在自由层3的表面设置覆盖层6；其中，覆盖层6可以采用金属(如Pt、Ta等)，也可以采用非金属氧化物(如SiO 2)的，覆盖层6厚度通常可以为2nm～3nm，但并不限制于此。
在本申请实施例提供的MTJ器件中，可以设置MTJ的自由层3和钉扎层4的至少一个包含TM-RE薄膜，并在TM-RE薄膜的至少一个表面(即上表面和上表面中的至少一个)设置包含氧化物材料的氧化物层。例如，可以是MTJ的自由层3中包括TM-RE薄膜和氧化物层(具体可以参考下文的实施例一)。又例如，可以是MTJ的钉扎层4中包括TM-RE薄膜和氧化物层(具体可以参考下文的实施例二)。再例如，可以是MTJ的自由层3和钉扎层4中均设置有TM-RE薄膜和氧化物层。
在此情况下，在MTJ器件进行后道退火过程中氧化物层中的氧原子扩散进入TM-RE材料，氧原子的2p轨道与TM-RE材料中的过渡金属元素的3d轨道中含有z分量(即垂直TM-RE的方向的分量)轨道杂化，使得TM-RE材料的电子自旋排布取向偏向垂直薄膜方向，也即通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性(perpendicular magnetic anisotropy，PMA)来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性，进而使得TM-RE材料能够应用至MTJ。
另外，由于TM-RE材料具有非晶态的特性，从而能够使得与之相邻生长的薄膜不会因为晶格不匹配而导致层间的应力以及由于多层结构生长导致的粗糙度的累积，这样一来，可以直接在TM-RE薄膜表面形成对界面平整度要求较高的其他膜层，而无需额外制作中间膜层来保证界面平整度(具体可以参考下文实施例二中的相关设置)，进而提升了MTJ器件各膜层整体的平整度，提升了MTJ器件的整体性能。
对于上述垂直磁各向异性(PMA)而言，可以理解的是，在本申请中的垂直磁各向异性是指亚铁磁层中外层电子的自旋在空间自由度中选择取向于垂直于铁磁层的界面的方向。其中，亚铁磁层的界面可以亚铁磁层与其它层相接触的界面；例如，本申请中TM-RE薄膜与氧化物层相接触的界面。
对于上述退火耐受性而言，可以理解的是，在对MTJ进行后道退火工艺或者其它类型的退火工艺时，TM-RE材料的垂直磁各向异性不发生较大改变。这种退火过后磁各向异性在一定程度上的保持能力称为退火耐受性。退火耐受性与TM-RE材料的元素选择，组分配比，掺杂类型等因素相关。
以下对本申请实施例中形成TM-RE薄膜和氧化物层的材料组分进行示意的说明。
对于TM-RE薄膜中采用的TM-RE材料而言，该TM-RE材料中的过渡金属元素可以包括钴(Co)，铁(Fe)或镍(Ni)中的至少一种，但本申请并不限制于此。该TM-RE材料中的稀土元素可以包括铽(Tb)，钆(Gd)，镝(Dy)或铕(Eu)中的至少一种，但本申请并不限制于此。
在一些可能实现的方式中，TM-RE材料还可以包括掺杂元素。示意的，该掺杂元素可以为钽(Ta)，钨(W)，硅(Si)，硼(B)或碳(C)中的至少一种，但本申请并不限制于此。
示意的，在一些实施例中，TM-RE薄膜采用的TM-RE材料可以包括钴铽(CoTb)，铁铽(FeTb)，钴钆(CoGd)，钴铽硼(CoTbB)，铁铽硼(FeTbB)或钴钆硼(CoGdB)中的至少一种，但本申请并不限制于此。
需要说明的是，TM-RE薄膜中TM-RE材料的各元素(过渡金属元素、稀土元素、掺杂元素)所占的组分配比并不限制于某一特定组分配比，实际中可以根据需要进行设置。
另外，对于氧化物层而言，形成该氧化物层的氧化物材料可以包括含镁氧化物(如MgO)，含铜氧化物(如CuO)，含铝氧化物(如Al 2O 3)，含锌氧化物(如ZnO)，含镍氧化物(如NiO)，含铬氧化物(如Cr 2O 3、CrO 2)，含钛氧化物(如TiO 2)，含硅氧化物(如SiO 2)或含硒氧化物(如SeO 2)中的至少一种，但本申请并不限制于此。
示意的，在一些实施例中，氧化物层采用的氧化物可以包括MgO，SiO 2或MgAlO 3中的至少一种，但并不限制于此。
另外，本申请中对于MTJ器件中氧化物层和TM-RE薄膜的厚度不作具体限制，实际中根据使用的具体材料和工艺流程来确定氧化物层和TM-RE薄膜的厚度。
以下通过具体实施例，对TM-RE薄膜和氧化物层在MTJ器件中的设置，进行示意的说明。
实施例一
在该实施例提供的MTJ器件中，可以将TM-RE薄膜以及氧化物层应用至MTJ的自由层3中，在此情况下，MTJ的自由层3可以采用复合自由层(hybrid free layer，HFL)，具体设置可以如下：
如图5所示，自由层3可以包括从下到上依次堆叠设置的铁磁层30(ferromagnetic layer)、层间耦合层31(interlayer spacer或者coupling spacer)、TM-RE薄膜100和氧化物层200。其中，铁磁层30与势垒层2接触。氧化物层200设置在TM-RE薄膜100的上表面(也即远离势垒层2一侧的表面)。
当然，在另一些可能实现的方式中，在采用较薄的氧化物层200的情况下，如氧化物层200的厚度在0.5nm以下，氧化物层200也可以设置在TM-RE薄膜100的下表面(也即靠近势垒层2一侧的表面)。以下实施例均是以氧化物层200设置在TM-RE薄膜100远离势垒层2一侧的表面为例进行说明的。
另外，参考图5所示，MTJ器件的中的其他膜层，如位于自由层3的下方，从下到上依次设置的底电极E1、结构种子层5、钉扎层4、结构转化层41、参考层1、势垒层2，以及位于自由层3上方的覆盖层6、顶电极E2等膜层，可以参考前述内容以及相关技术，根据实际的需要进行设置，此处不再赘述。
需要说明的是，如图5所示，在一些实施例中，在钉扎层4与参考层1之间设置结构 转化层41，通过制作结构转化层41能够向参考层1提供较好的生长平面。当然，在一些可能实现的方式中，通过选择合适的钉扎层4也可以不设置结构转化层41。
另外，如图6所示，本实施例一还提供一种如上述MTJ器件的制作方法，该制作方法可以包括：
步骤11、参考图5所示，依次制作钉扎层4、结构转化层41、参考层1、势垒层2、铁磁层30、层间耦合层31、TM-RE薄膜100和氧化物层200，以形成MTJ。
上述铁磁层30、层间耦合层31、TM-RE薄膜100和氧化物层200整体作为MTJ中的自由层3(也即复合自由层)。
示意的，上述钉扎层4可以采用Co/Pt(钴/铂)多层膜、Co/Pd(钴/钯)多层膜、Co/Ir(钴/铱)多层膜等，但并不限制于此。
示意的，上述结构转化层41可以采用钽(Ta)，钛(Ti)，氮化钛(TiN)，铝(Al)，镁(Mg)，钛镁(TiMg)，钨(W)或钼(Mo)等材料中的一种或多种，但并不限制于此。
示意的，上述参考层1可以采用CoFeB(钴铁硼)、FeB(铁硼)、CoFe(钴铁)或CoB(钴硼)等材料中的一种或多种，但并不限制于此。
示意的，上述势垒层2可以采用MgO，MgAlO 3，AlO x(铝氧化物)，MgGdO，TiO x(钛氧化物)，TaO x(钽氧化物)或MgTiO x(镁钛氧化物)等材料中的一种或多种，但并不限制于此。
示意的，上述铁磁层30可以采用CoFeB，FeB，CoFe或CoB等材料中的一种或多种，但并不限制于此。
示意的，上述层间耦合层31可以采用Ta(钽)或Ru(钌)等材料中的一种或多种，但并不限制于此。
示意的，上述TM-RE薄膜100可以采用CoTb，FeTb，CoGd，CoTbB，FeTbB或CoGdB等材料中的一种或多种，但并不限制于此。
示意的，上述氧化物层200可以采用MgO，SiO 2或MgAlO 3等材料中的一种或多种，但并不限制于此。
当然，参考图5所示，应当理解的是，对于整个MTJ器件的制作而言，在进行步骤11之前，可以在衬底上先依次形成堆叠设置的底电极E1、结构种子层5；然后在结构转化层41的表面进行步骤11中钉扎层4、结构转化层41、参考层1、势垒层2、自由层3的制作。在步骤11之后可以在自由层3的表面继续进行其他膜层的制作，如覆盖层6、顶电极E2的制作。
以下对上述步骤11中自由层3中TM-RE薄膜100和氧化物层200的制作进行示意的说明。
示意的，上述步骤11中TM-RE薄膜100和氧化物层200的制作可以包括：
例如，在一些可能实现的方式中，可以采用TM-RE靶材在层间耦合层31的表面溅射生长形成TM-RE薄膜100，然后在TM-RE薄膜100的表面溅射生长氧化物层200(如MgO层)。当然，作为另一种可能实现的方式，也可以采用TM靶材和RE靶材以共溅的方式在层间耦合层31的表面溅射生长形成TM-RE薄膜100。
示意的，TM-RE薄膜100可以采用常温生长，并在将生长前底部结构在室内常温情 况下传入真空溅射腔，真空度高于10 -8Torr。
可以理解的是，在生长TM-RE薄膜100之前，需要保证生长前底部结构干净，粗糙度符合要求，可以利用包括但不仅限于化学机械抛光，离子刻蚀，超声清洗等步骤来使生长前的底部结构达到要求，不会影响该TM-RE薄膜100的生长。
步骤12、对制作形成的MTJ进行退火处理。
示意的，在完成包含MTJ的器件(或部件)后，可以将形成包含MTJ的器件置于真空度高于10 -8Torr的真空环境中进行退火；例如，退火时间可以为1.5h，退火温度可以大于400℃；并在退火工艺结束将器件置于真空环境中自然冷却至室温后取出。
另外，可以理解的是，在溅射形成氧化物层200时，不同的溅射速率和厚度会直接影响氧化物层200的粗糙度和缺陷数量。一般而言，氧化物层200的粗糙度越低，TM-RE薄膜100的垂直磁各向异性越好，反之TM-RE薄膜100的垂直磁各向异性越差。因此实际中，可以通过调控氧化物层200的氧化物种类、溅射功率、气压和厚度等参数，来调控M-RE薄膜100的垂直磁各向异性和退火后的性质。
本实施例中对于氧化物层200的种类和厚度并不限定，实验发现相同厚度下采用不同种类氧化物形成的氧化物层200，对TM-RE薄膜100退火后的垂直磁各向异性的提升(保持)效果并不相同。例如，在氧化物层200的厚度相同时，采用MgO的氧化物层200要优于采用SiO 2的氧化物层200对TM-RE薄膜100的垂直磁各向异性的提升效果。在氧化物种类相同时，氧化物层200厚度越大，TM-RE薄膜100退火后的垂直磁各向异性提升地越显著。
另外，实际中通过具体的实验对通过氧化物层200提升TM-RE薄膜100的垂直磁各向异性的退火耐受性进行了验证。参考图7所示，S0为TM-RE薄膜100表面未设置氧化物层200的多膜层结构在400℃、1.5h退火后的磁滞回线。S1为TM-RE薄膜100表面设置有厚度为0.4nm的MgO层(200)的多膜层结构在400℃、1.5h退火后的磁滞回线。S2为TM-RE薄膜100表面设置有厚度为1.0nm的MgO层(200)的多膜层结构在400℃、1.5h退火后的磁滞回线。
图7中的磁滞回线为在垂直TM-RE薄膜100的方向(也即z方向)施加的磁化大小(即横坐标)与霍尔电压V H(即纵坐标)的关系曲线；本领域的技术人员可以理解的是，霍尔电压V H越大，TM-RE薄膜100的z方向的磁化越大。基于此，对比S0与S1、S2可以看出，相比于未设置氧化物层200(参考S0)而言，设置氧化物层200能够明显提升TM-RE薄膜100的垂直磁各向异性的退火耐受性。对比S1和S2可以看出，在氧化物层200采用相同氧化物的情况下，氧化物层200的厚度越厚，TM-RE薄膜100的垂直磁各向异性的退火耐受性越好。
另外，需要说明的是，上述步骤11中仅是示意的以依次制作参考层1、势垒层2、铁磁层30、层间耦合层31、TM-RE薄膜100和氧化物层200为例进行说明。在另一些可能实现的方式中，可以通过步骤11依次制作氧化物层200、TM-RE薄膜100、层间耦合层31、铁磁层30、势垒层2、参考层1、结构转化层41、钉扎层4，以形成MTJ。在此情况下，自由层3位于势垒层2靠近底电极E1的一侧，而参考层1、结构转化层41、钉扎层4位于势垒层2的靠近顶电极E2一侧从下到上依次堆叠设置。
综上所述，在实施例一中，通过将TM-RE薄膜和氧化物层应用至MTJ的复合自由层 中，一方面，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性；另一方面，复合自由层基于TM-RE薄膜能够提供体垂直磁各向异性(b-PMA)。
实施例二
在该实施例提供的MTJ器件中，可以将TM-RE薄膜以及氧化物层应用至MTJ的钉扎层4中。在此情况下，MTJ的钉扎层4中可以设置一个或多个TM-RE薄膜；其中，部分或全部的TM-RE薄膜的至少一个表面设置有氧化物层。例如，在钉扎层4中，可以在至少一个TM-RE薄膜的上表面设置有氧化物层；也可以在至少一个TM-RE薄膜的下表面设置有氧化物层；还可以在至少一个TM-RE薄膜的下表面和下表面分别设置有氧化物层。
以下对钉扎层4中TM-RE薄膜和氧化物层的具体设置进行示意的说明。
例如，在一些可能实现的方式中，如图8所示，钉扎层4可以包括一个TM-RE薄膜100和一个氧化物层200；其中，氧化物层200位于TM-RE薄膜100远离势垒层2的一侧，也即氧化物层200位于TM-RE薄膜100的下表面。当然，作为另一种可能实现的方式，氧化物层200也可以设置于TM-RE薄膜100的上表面。
又例如，在一些可能实现的方式中，如图9所示，钉扎层4可以包括两个TM-RE薄膜100和一个氧化物层200；其中，氧化物层200可以设置在两个TM-RE薄膜100之间。
再例如，在一些可能实现的方式中，钉扎层4可以包括一个TM-RE薄膜100和两个氧化物层200；其中，TM-RE薄膜100可以设置在两个氧化物层200之间。
当然，钉扎层4中TM-RE薄膜100和氧化物层200并不限于上述的多种设置方式，示意的，在一些可能实现的方式中，钉扎层4中可以设置三个TM-RE薄膜100，在此情况下，可以在相邻的两个TM-RE薄膜100之间分别设置一个氧化物层200，也可以在每一TM-RE薄膜100的下表面或上表面分别设置一个氧化物层200等等，本申请对此不作限制，实际中可以根据需要设置钉扎层4中的TM-RE薄膜100和氧化物层200。
另外，由于采用非晶态的TM-RE材料形成的TM-RE薄膜能够提升后续生长薄膜的平整度，无需考虑晶格不匹配产生的应力以及粗糙度累积，因此，在将TM-RE薄膜100应用至钉扎层4的情况下，如图8和图9所示，可以设置该钉扎层4的顶层采用TM-RE薄膜100，并直接在TM-RE薄膜100的表面形成参考层1，也即参考层1与钉扎层4顶层的TM-RE薄膜100直接接触。在此情况下，无需额外单独制作结构转化层(对应可参考图5)来满足参考层1对界面平整度的要求，同时简化了制作工艺。
另外，本实施例二还提供一种如上述MTJ器件的制作方法，如图10所示，该制作方法可以包括：
步骤21、参考图8、图9所示，依次制作钉扎层4、参考层1、势垒层2、自由层3，以形成MTJ；其中，钉扎层4中包括一个或多个TM-RE薄膜100，并且在至少一个TM-RE薄膜100的表面设置有氧化物层200。
示意的，参考8所示，上述步骤21可以包括依次制作氧化物层200、TM-RE薄膜100、参考层1、势垒层2、自由层3，以形成MTJ。
示意的，参考图9所示，上述步骤21可以包括依次制作TM-RE薄膜100、氧化物层200、TM-RE薄膜100、参考层1、势垒层2、自由层3，以形成MTJ。
应当理解的是，参考图8、图9所示，对于整个MTJ器件的制作而言，在进行步骤 21之前，可以在衬底上先依次形成堆叠设置的底电极E1、结构种子层5；然后在结构转化层41的表面进行步骤21中钉扎层4、参考层1、势垒层2、自由层3的制作。在步骤11之后可以在自由层3的表面继续进行覆盖层6、顶电极E2等其他膜层的制作。
步骤22、对制作形成的MTJ进行退火处理。
示意的，在完成包含MTJ的器件(或部件)后，可以将形成包含MTJ的器件置于真空度高于10 -8Torr的真空环境中进行退火，退火时间可以为1.5h，退火温度可以大于400℃；并在退火工艺结束将器件置于真空环境中自然冷却至室温后取出。
另外，关于各膜层的具体材料、TM-RE薄膜100和氧化物层200的制作工艺以及相关解释说明，可以参考前述实施例一中的相关内容此处不再赘述。
需要说明的是，图8、图9中仅是示意的以钉扎层4位于势垒层2靠近底电极E1的一侧，自由层位于势垒层2靠近顶电极E2的一侧为例进行说明。在另一些可能实现的方式中，钉扎层4可以位于势垒层2靠近顶电极E2的一侧，自由层位于势垒层2靠近底电极E1的一侧。当然，在此情况下，可以对步骤2形成的各膜层的顺序进行调整；例如，在一些可能实现的方式中，可以通过步骤21依次制作自由层3、势垒层2、参考层1、TM-RE薄膜100、氧化物层200，以形成MTJ。又例如，在一些可能实现的方式中，可以通过步骤21依次制作自由层3、势垒层2、参考层1、TM-RE薄膜100、氧化物层200、TM-RE薄膜100，以形成MTJ。
综上所述，在该实施例二中，通过将TM-RE薄膜和氧化物层应用至MTJ的钉扎层中，一方面，通过氧化物层向TM-RE薄膜提供了额外的垂直磁各向异性来源，从而提升了TM-RE薄膜的垂直磁各向异性的退火耐受性；另一方面，形成TM-RE薄膜100的TM-RE材料为一种亚铁磁铁材料，其自身的磁矩很小，从而能够减小钉扎层的漏磁场，进而减小了对自由层的偏置场(offset)。
另外，由于采用非晶态的TM-RE材料形成的TM-RE薄膜能够提升后续生长薄膜的平整度，无需考虑晶格不匹配产生的应力以及粗糙度累积，因此上述在制作钉扎层采用TM-RE薄膜的情况下，可以直接将TM-RE薄膜与参考层直接接触，无需额外单独制作结构转化层来满足参考层对界面平整度的要求，同时简化了制作工艺。
由前述内容可知，实施例一是以TM-RE薄膜100和氧化物层200在MTJ的自由层3中的应用为例进行示意说明的。实施例二是以TM-RE薄膜100和氧化物层200在MTJ的钉扎层4中的应用为例进行示意说明的。但本申请并不限制于此，在另一些实施例中，MTJ的自由层3和钉扎层4中均可以采用TM-RE薄膜100和氧化物层200，具体设置可以参考前述实施例一以及实施例二的相关描述，此处不再赘述。
综上可知，本申请实施例中采用的MTJ器件结构和工艺都较为简单，通过在TM-RE薄膜100的表面设置氧化物层200即可实现对TM-RE薄膜100的垂直磁各向异性和退火特性的调控。氧化物层200采用常温生长即可，氧化物层200的厚度仅需一至数纳米即可起到显著的效果；不仅可以拓宽MTJ器件的集成条件，推动MTJ器件的发展与应用，也有助于MTJ器件的制备与性质的研究。
以下以本申请实施例提供的MTJ器件在磁性存储器中的应用为例，并结合电子设备进行说明。
示例的，图11为本申请实施例示例性的提供的一种电子设备的架构示意图。参考图 11所示，在一些可能实现的方式中，该电子设备01可以包括：存储装置11、处理器12、输入设备13、输出设备14等部件。存储装置11用于存储软件程序以及模块。存储装置11主要包括存储程序区和存储数据区，其中，存储程序区可存储操作系统、至少一个功能所需的应用程序(比如声音播放功能、图像播放功能等)等；存储数据区可存储根据电子设备的使用所创建的数据(比如音频数据、图像数据、电话本等)等。
上述存储装置11可以包括外存储器111和内存储器112。外存储器111和内存储器112存储的数据可以相互传输。外存储器111例如包括硬盘、U盘、软盘等。内存储器112例如包括随机存储器、只读存储器等，其中，随机存储器可以采用前述实施例中任一种可能实现的方式中提供的磁随机存储器(MRAM)。
处理器12是该电子设备01的控制中心，利用各种接口和线路连接整个电子设备01的各个部分，通过运行或执行存储在存储装置11内的软件程序和/或模块，以及调用存储在存储装置11内的数据，执行电子设备01的各种功能和处理数据，从而对电子设备01进行整体监控。
输入设备13用于接收输入的数字或字符信息，以及产生与电子设备01的用户设置以及功能控制有关的键信号输入。输出设备14用于输出输入设备13输入，并存储在内存储器112中的数据对应的信号。例如，输出设备14输出声音信号或视频信号。上述处理器12中的控制器还可以控制输出设备14输出信号或不输出信号。
应当理解的是，MRAM是一种新型非易失性存储器，其中，MRAM中的自旋转移距磁性随机存取存储器(spin transfer torque magnetic random access memory，STT MRAM)因其具有速度快、功耗低、COMS(complementary metal-oxide-semiconductor，互补式金属氧化物半导体)兼容性好等优势。
STT MRAM的读写功能由内部设置的存储单元来实现。示意的，参考图12所示，在一些可能实现的方式中，STT MRAM的存储单元可以包括晶体管T以及本申请实施例提供的任一种可能实现的方式中提供的MTJ器件。其中，MTJ器件的顶电极与位线电连接，MTJ器件的底电极与晶体管T的漏极电连接，晶体管T的栅极与字线电连接，源极与源极线电连接。
以上所述，仅为本申请的具体实施方式，但本申请的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本申请揭露的技术范围内，可轻易想到变化或替换，都应涵盖在本申请的保护范围之内。因此，本申请的保护范围应以所述权利要求的保护范围为准。

Claims (16)

  1. 一种磁性器件，其特征在于，包括磁性隧道结；
    所述磁性隧道结包括依次堆叠设置的钉扎层、参考层、势垒层、自由层；
    所述钉扎层或所述自由层中的至少一个包括：过渡金属-稀土亚铁磁合金薄膜以及位于所述过渡金属-稀土亚铁磁合金薄膜表面的氧化物层。
  2. 根据权利要求1所述的磁性器件，其特征在于，所述过渡金属-稀土亚铁磁合金薄膜中包括过渡金属-稀土亚铁磁合金材料；
    所述过渡金属-稀土亚铁磁合金材料中的过渡金属元素包括Co，Fe或Ni中的至少一种；
    所述过渡金属-稀土亚铁磁合金材料中的稀土元素包括Tb，Gd，Dy或Eu中的至少一种。
  3. 根据权利要求2所述的磁性器件，其特征在于，
    所述过渡金属-稀土亚铁磁合金材料还包括Ta，W，Si，B或C中的至少一种掺杂元素。
  4. 根据权利要求1-3任一项所述的磁性器件，其特征在于，
    所述过渡金属-稀土亚铁磁合金薄膜中包括CoTb，FeTb，CoGd，CoTbB，FeTbB或CoGdB中的至少一种。
  5. 根据权利要求1-4任一项所述的磁性器件，其特征在于，
    所述氧化物层中的氧化物包括含镁氧化物，含铜氧化物，含铝氧化物，含锌氧化物，含镍氧化物，含铬氧化物，含钛氧化物，含硅氧化物或含硒氧化物中的至少一种。
  6. 根据权利要求1-5任一项所述的磁性器件，其特征在于，
    所述氧化物层中包括MgO，SiO 2或MgAlO 3中的至少一种。
  7. 根据权利要求1-6任一项所述的磁性器件，其特征在于，
    所述自由层包括依次堆叠设置的铁磁层、层间耦合层、所述过渡金属-稀土亚铁磁合金薄膜和所述氧化物层；
    所述铁磁层与所述势垒层接触。
  8. 根据权利要求1-6任一项所述的磁性器件，其特征在于，
    所述钉扎层中包括一个或多个所述过渡金属-稀土亚铁磁合金薄膜；其中，至少一个所述过渡金属-稀土亚铁磁合金薄膜在靠近和/或远离所述势垒层一侧的表面设置有所述氧化物层。
  9. 根据权利要求8所述的磁性器件，其特征在于，
    所述钉扎层通过所述过渡金属-稀土亚铁磁合金薄膜与所述参考层直接接触。
  10. 根据权利要求8或9所述的磁性器件，其特征在于，
    所述钉扎层中包括一个所述过渡金属-稀土亚铁磁合金薄膜和一个所述氧化物层；
    所述过渡金属-稀土亚铁磁合金薄膜在远离所述势垒层一侧的表面设置有所述氧化物层。
  11. 根据权利要求8或9所述的磁性器件，其特征在于，
    所述钉扎层中包括两个所述过渡金属-稀土亚铁磁合金薄膜和一个所述氧化物层；
    所述氧化物层位于两个所述过渡金属-稀土亚铁磁合金薄膜之间。
  12. 一种磁性器件的制作方法，其特征在于，包括：
    制作磁性隧道结；其中，所述磁性隧道结包括依次堆叠设置的钉扎层、参考层、势垒层、自由层；所述钉扎层或所述自由层中的至少一个包括：过渡金属-稀土亚铁磁合金薄膜以及位于所述过渡金属-稀土亚铁磁合金薄膜表面的氧化物层；
    对制作形成的所述磁性隧道结进行退火处理。
  13. 根据权利要求12所述的磁性器件的制作方法，其特征在于，
    所述制作磁性隧道结包括：
    依次制作所述参考层、所述势垒层、铁磁层、层间耦合层、所述过渡金属-稀土亚铁磁合金薄膜和所述氧化物层，以形成所述磁性隧道结；其中，依次制作的所述铁磁层、所述层间耦合层、所述过渡金属-稀土亚铁磁合金薄膜和所述氧化物层形成所述自由层；
    或者，依次制作所述氧化物层、所述过渡金属-稀土亚铁磁合金薄膜、层间耦合层、铁磁层、所述势垒层、所述参考层，以形成所述磁性隧道结；其中，依次制作的所述氧化物层、所述过渡金属-稀土亚铁磁合金薄膜、所述层间耦合层、所述铁磁层形成所述自由层。
  14. 根据权利要求12所述的磁性器件的制作方法，其特征在于，包括：
    所述制作磁性隧道结包括：
    依次制作所述氧化物层、所述过渡金属-稀土亚铁磁合金薄膜、所述参考层、所述势垒层、所述自由层，以形成所述磁性隧道结；其中，依次制作的所述氧化物层、所述过渡金属-稀土亚铁磁合金薄膜形成所述钉扎层；
    或者，依次制作所述自由层、所述势垒层、所述参考层、所述过渡金属-稀土亚铁磁合金薄膜、所述氧化物层；其中，依次制作的所述过渡金属-稀土亚铁磁合金薄膜、所述氧化物层形成所述钉扎层。
  15. 一种磁性存储器，其特征在于，包括控制器以及如权利要求1-11任一项所述的磁性器件；所述磁性器件与所述控制器连接。
  16. 一种电子设备，其特征在于，包括印刷线路板以及如权利要求15所述的磁性存储器；所述磁性存储器与所述印刷线路板连接。
PCT/CN2021/113579 2021-08-19 2021-08-19 磁性器件及其制作方法、磁性存储器、电子设备 Ceased WO2023019519A1 (zh)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119522029A (zh) * 2024-11-15 2025-02-25 北京大学 一种弱畴壁钉扎的亚铁磁材料及其应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110063899A1 (en) * 2008-02-08 2011-03-17 Fuji Electric Holdings Co., Ltd Magnetic memory element, method of driving same, and nonvolatile storage device
CN102024903A (zh) * 2009-09-11 2011-04-20 三星电子株式会社 磁存储器件
US20130221460A1 (en) * 2012-02-29 2013-08-29 Headway Technologies, Inc. Engineered Magnetic Layer with Improved Perpendicular Anisotropy using Glassing Agents for Spintronic Applications
CN108665921A (zh) * 2017-03-27 2018-10-16 三星电子株式会社 半导体器件
CN110412081A (zh) * 2019-07-16 2019-11-05 三峡大学 一种稀土（re）-过渡族金属（tm）合金中非共线反铁磁耦合原子磁矩间夹角测量方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7489541B2 (en) * 2005-08-23 2009-02-10 Grandis, Inc. Spin-transfer switching magnetic elements using ferrimagnets and magnetic memories using the magnetic elements
JP2007266498A (ja) * 2006-03-29 2007-10-11 Toshiba Corp 磁気記録素子及び磁気メモリ
US20150303373A1 (en) * 2014-04-17 2015-10-22 Qualcomm Incorporated Spin-transfer switching magnetic element formed from ferrimagnetic rare-earth-transition-metal (re-tm) alloys
WO2022205235A1 (zh) * 2021-03-31 2022-10-06 华为技术有限公司 一种存储器及电子设备

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110063899A1 (en) * 2008-02-08 2011-03-17 Fuji Electric Holdings Co., Ltd Magnetic memory element, method of driving same, and nonvolatile storage device
CN102024903A (zh) * 2009-09-11 2011-04-20 三星电子株式会社 磁存储器件
US20130221460A1 (en) * 2012-02-29 2013-08-29 Headway Technologies, Inc. Engineered Magnetic Layer with Improved Perpendicular Anisotropy using Glassing Agents for Spintronic Applications
CN108665921A (zh) * 2017-03-27 2018-10-16 三星电子株式会社 半导体器件
CN110412081A (zh) * 2019-07-16 2019-11-05 三峡大学 一种稀土（re）-过渡族金属（tm）合金中非共线反铁磁耦合原子磁矩间夹角测量方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4358139A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119522029A (zh) * 2024-11-15 2025-02-25 北京大学 一种弱畴壁钉扎的亚铁磁材料及其应用
CN119522029B (zh) * 2024-11-15 2026-02-03 北京大学 一种弱畴壁钉扎的亚铁磁材料及其应用

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