US20140084401A1 - Magnetoresistive element and magnetic memory - Google Patents
Magnetoresistive element and magnetic memory Download PDFInfo
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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
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- H10N50/85—Magnetic active materials
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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
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- 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
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- 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
- Embodiments described herein relate generally to magnetoresistive elements and magnetic memories.
- a basic structure of a magnetic tunnel junction (MTJ) element serving as a magnetoresistive element is a stacked structure including a storage layer, the magnetization direction of which is changeable, a reference layer, the magnetization direction of which is fixed, and an insulating layer provided between the storage layer and the reference layer. It is known that an MTJ element shows a tunneling magnetoresistive (TMR) effect. Thus, an MTJ element is used as a storage element of a memory cell in a magnetic random access memory (MRAM).
- MRAM magnetic random access memory
- An MRAM stores information (“1”, “0”) in accordance with a change in relative angle between magnetizations of magnetic layers included in an MTJ element, and is nonvolatile. Since the magnetization switching speed of an MRAM is a few nanoseconds, it is possible to write and read data at a high speed with an MRAM. Accordingly, MRAMs are expected to be next-generation high-speed nonvolatile memories. Furthermore, by using a method called “spin transfer torque switching” for controlling magnetization by means of a spin polarized current, a current density can be increased by decreasing the cell size of an MRAM. Accordingly, it is possible to easily switch the magnetization in a storage layer, resulting in that it is possible to obtain an MRAM with a high density and a low power consumption.
- an MRAM using a perpendicular magnetization MTJ element in which the direction of the magnetization of a ferromagnetic material is perpendicular to the film plane, be formed.
- a perpendicular magnetization MTJ element generally a ferromagnetic material with a high magnetic crystalline anisotropy is used.
- a critical current for magnetization reversal by the spin transfer torque switching method is dependent on the saturation magnetization and the Gilbert damping constant of a storage layer. Accordingly, in order to switch the magnetization of a storage layer by means of low-current spin transfer torque switching, it is necessary to reduce the saturation magnetization and the Gilbert damping constant of the storage layer. Furthermore, the influence of strayed magnetic field from a reference layer becomes more remarkable as the element is miniaturized. Accordingly, in order to improve the degree of integration of a magnetoresistive element, it is also necessary to reduce the saturation magnetization of the reference layer thereof with a high magnetic anisotropy energy of the reference layer being maintained.
- FIG. 1 is a sectional view showing a magnetoresistive element according to a first embodiment.
- FIG. 1A is a sectional view showing a magnetoresistive element according to a modification of the first embodiment.
- FIG. 2 is a sectional view showing a magnetoresistive element according to a second embodiment.
- FIG. 2A is a sectional view showing a magnetoresistive element according to a modification of the second embodiment.
- FIG. 3 is a sectional view showing a magnetoresistive element according to a third embodiment.
- FIG. 3A is a sectional view showing a magnetoresistive element according to a modification of the third embodiment.
- FIG. 4 is a sectional view showing a magnetoresistive element according to a fourth embodiment.
- FIG. 5 is a sectional view showing a magnetoresistive element according to a modification of the fourth embodiment.
- FIG. 5A is a sectional view showing a magnetoresistive element according to another modification of the fourth embodiment.
- FIGS. 6( a ) and 6 ( b ) are for explaining a method of manufacturing an MTJ element including a magnetic film with a single crystal structure.
- FIGS. 7( a ) to 7 ( c ) are for explaining a method of manufacturing an MTJ element including a magnetic film with a single crystal structure.
- FIGS. 8( a ) to 8 ( c ) show examples of x-ray diffraction on a MnGe alloy.
- FIG. 9 shows examples of magnetization curve of a MnGe alloy.
- FIGS. 10( a ) and 10 ( b ) show examples of the characteristics that the saturation magnetization of a MnGe alloy is dependent on the composition and the substrate temperature.
- FIG. 11 shows examples of magnetization curve in the cases where Al is slightly added to a MnGe alloy on a thermally oxidized Si substrate.
- FIGS. 12( a ) and 12 ( b ) show the band structure and the density of states of a bulk MnGe alloy, which are obtained by calculation.
- FIG. 13 is a sectional view showing a memory cell of a magnetic memory according to a fifth embodiment.
- FIG. 14 is a circuit diagram of the main part of the magnetic memory according to the fifth embodiment.
- FIG. 1 shows a magnetoresistive element according to a first embodiment.
- FIG. 1 is a sectional view of the magnetoresistive element 1 of the first embodiment.
- the magnetoresistive element 1 of this embodiment is an MTJ element having such a structure that a ferromagnetic layer 2 , a nonmagnetic layer 4 (hereinafter also referred to as “tunnel barrier layer 4 ”), and a ferromagnetic layer 8 are formed on a base layer 100 in this order.
- the base layer 100 is used to control the crystallinity such as crystal orientation, crystal grain size, etc. of the ferromagnetic layer 2 and the layers above the ferromagnetic layer 2 , and the detailed explanation thereof will be provided later.
- the resistance value of the MTJ element is determined by the angle between the directions of the magnetizations of the two magnetic layers arranged with the tunnel barrier layer sandwiched therebetween. It is possible to control the angle between the directions of the magnetizations by means of an external magnetic field or current caused to flow through the element. On such an occasion, it is possible to control the angle between the directions of the magnetizations more stably by differentiating the magnitudes of coercive force, anisotropic magnetic field Hk and/or Gilbert damping constant ⁇ of the two magnetic layers.
- the magnetic layer with a higher coercive force, a higher anisotropic magnetic field Hk or a higher Gilbert damping constant ⁇ will be called “reference layer,” and a magnetic layer with a lower coercive force, a lower anisotropic magnetic field Hk or a lower Gilbert damping constant ⁇ will be called “storage layer.”
- reference layer a magnetic layer with a higher coercive force, a higher anisotropic magnetic field Hk or a higher Gilbert damping constant ⁇
- a magnetic layer with a lower coercive force, a lower anisotropic magnetic field Hk or a lower Gilbert damping constant ⁇ be used as a storage layer.
- the c-axis is an easy magnetization axis. Accordingly, it is possible to manufacture a perpendicular magnetization MTJ element by controlling the orientation in crystallization so that the c-axis is along the direction perpendicular to the film plane.
- an oxide insulator be used for the nonmagnetic layer 4 .
- an MTJ element has a stacked structure in which for example, a ferromagnetic layer of CoFe(B), a nonmagnetic layer of crystalline MgO, and a ferromagnetic layer of MnGe are stacked in this order, an orientation relationship of MnGe(001)/MgO(001)/CoFe(B)(001) can be established.
- MnGe(001) or MgO(001) means that the crystalline orientation is such that the (001) surface is exposed on the top surface of each material. In this manner, it is possible to improve the wavenumber selectability of tunnel electrons, thereby obtaining a higher MR ratio.
- the magnetoresistive element 1 can be not only an in-plane magnetization MTJ element but also a so-called “perpendicular magnetization MTJ element,” in which the directions of the magnetizations of the ferromagnetic layer 2 and the ferromagnetic layer 8 are perpendicular to the film planes, respectively.
- the “film plane” means a plane perpendicular to the direction in which each ferromagnetic layer is stacked.
- the “easy magnetization direction” means a direction in a ferromagnetic material with a certain macro size, and if a spontaneous magnetization is along this direction in a state where there is no external magnetic field, the internal energy becomes the lowest.
- the “hard magnetization direction” means a direction of a ferromagnetic material with a certain macro size, and if a spontaneous magnetization is along this direction in a state where there is no external magnetic field, the internal energy becomes the highest.
- the magnetization direction does not change between before and after a write operation, by which a write current flows through the MTJ element 1 , and in the other, the magnetization direction changes.
- the ferromagnetic layer in which the magnetization direction does not change will also be called a “reference layer,” and the ferromagnetic layer in which the magnetization direction changes will also be called a “storage layer.”
- the ferromagnetic layer 2 serves as a storage layer
- the ferromagnetic layer 8 serves as a reference layer.
- the write current is caused to flow between the ferromagnetic layer 2 and the ferromagnetic layer 8 in a direction perpendicular to the film plane.
- the write current is caused to flow from the ferromagnetic layer 2 to the ferromagnetic layer 8 .
- electrons flow from the ferromagnetic layer 8 toward the ferromagnetic layer 2 via the nonmagnetic layer 4 .
- the direction of the magnetization of the ferromagnetic layer 2 is switched so as to be in parallel with (the same as) the direction of the magnetization of the ferromagnetic layer 8 .
- the write current is caused to flow from the ferromagnetic layer 8 toward the ferromagnetic layer 2 .
- electrons flow from the ferromagnetic layer 2 toward the ferromagnetic layer 8 via the nonmagnetic layer 4 .
- the electrons spin-polarized by passing through the ferromagnetic layer 2 flow into the ferromagnetic layer 8 .
- the spin-polarized electrons with the spin in the same direction as the magnetization of the ferromagnetic layer 8 pass through the ferromagnetic layer 8 , the spin-polarized electrons with the spin in the direction opposite to the magnetization of the ferromagnetic layer 8 are reflected at the interface between the nonmagnetic layer 4 and the ferromagnetic layer 8 , and pass through the nonmagnetic layer 4 to flow into the ferromagnetic layer 2 .
- the spin torque is exerted on the magnetization of the ferromagnetic layer 2 , and the direction of the magnetization of the ferromagnetic layer 2 is caused to be opposite to the direction of the magnetization of the ferromagnetic layer 8 . Accordingly, the direction of the magnetization of the ferromagnetic layer 2 is switched to be antiparallel to the direction of the magnetization of the ferromagnetic layer 8 .
- the first embodiment has a structure in which the ferromagnetic layer 2 , the nonmagnetic layer 4 , and the ferromagnetic layer 8 are stacked on the base layer 100 in this order.
- the order can be reversed on the base layer 100 , as in a magnetoresistive element according to a modification of the first embodiment shown in FIG. 1A . That is to say, the ferromagnetic layer 8 , the nonmagnetic layer 4 , and the ferromagnetic layer 2 can be stacked on the base layer 100 in this order.
- FIG. 2 shows a magnetoresistive element 1 A according to a second embodiment.
- the magnetoresistive element 1 A has a structure obtained by providing an interface magnetic layer 6 between the nonmagnetic layer 4 and the ferromagnetic layer 8 in the magnetoresistive element 1 of the first embodiment shown in FIG. 1 .
- the magnetoresistive element 1 A of this embodiment can be not only an in-plane magnetization MTJ element but also a so-called “perpendicular magnetization MTJ element,” in which the directions of the magnetizations of the ferromagnetic layer 2 and the ferromagnetic layer 8 are perpendicular to the film planes, respectively.
- the magnetization direction does not change between before and after a write operation, by which a write current flows through the MTJ element 1 , and in the other, the magnetization direction changes.
- the ferromagnetic layer 2 serves as a storage layer
- the ferromagnetic layer 8 serves as a reference layer.
- the write current is caused to flow between the ferromagnetic layer 2 and the ferromagnetic layer 8 in a direction perpendicular to the film plane.
- the interface magnetic layer 6 is provided to increase the spin polarization.
- the interface magnetic layer 6 of MnGe when the interface magnetic layer 6 of MnGe is formed on the nonmagnetic layer 4 of crystalline MgO, it is possible to perform epitaxial growth of the ferromagnetic layer 8 containing Mn and one or more elements selected from Al, Ge, and Ga on the interface magnetic layer 6 .
- the ferromagnetic layer 8 containing Mn and one or more elements selected from Al, Ge, and Ga
- an alloy containing Mn and Ga is selected to form the ferromagnetic layer 8
- the ferromagnetic layer 2 , the nonmagnetic layer 4 , the interface magnetic layer 6 , and the ferromagnetic layer 8 are stacked on the base layer 100 in this order in the second embodiment, the order can be reversed on the base layer 100 , as in a magnetoresistive element according to a modification of the second embodiment shown in FIG. 2A . That is to say, the ferromagnetic layer 8 , the interface magnetic layer 6 , the nonmagnetic layer 4 , and the ferromagnetic layer 2 can be stacked on the base layer 100 in this order.
- FIG. 3 shows a magnetoresistive element 1 B according to a third embodiment.
- the magnetoresistive element 1 B is obtained by inserting an interface magnetic layer 3 between the ferromagnetic layer 2 and the nonmagnetic layer 4 and inserting an interface magnetic layer 6 between the nonmagnetic layer 4 and the ferromagnetic layer 8 in the magnetoresistive element 1 according to the first embodiment shown in FIG. 1 .
- the magnetoresistive element 1 B of the third embodiment can be not only an in-plane magnetization MTJ element but also a perpendicular magnetization MTJ element. Furthermore, like the magnetoresistive elements of the first and the second embodiments, the interface magnetic layer 3 and the interface magnetic layer 6 of the third embodiment are provided to increase the spin polarization.
- the order can be reversed on the base layer 100 , as in a magnetoresistive element according to a modification of the third embodiment shown in FIG. 3A . That is to say, the ferromagnetic layer 8 , the interface magnetic layer 6 , the nonmagnetic layer 4 , the interface magnetic layer 3 , and the ferromagnetic layer 2 can be stacked on the base layer 100 in this order.
- FIG. 4 shows a magnetoresistive element 1 C according to a fourth embodiment.
- the magnetoresistive element 1 C is obtained by stacking a nonmagnetic layer 10 and a ferromagnetic layer 11 on the ferromagnetic layer 8 in the magnetoresistive element 1 B according to the third embodiment shown in FIG. 3 .
- the interface magnetic layer 6 and the ferromagnetic layer 8 serve as a reference layer.
- the ferromagnetic layer 11 is also called a “bias layer,” and has a magnetization that is anti-parallel (opposite direction) with the magnetization of the ferromagnetic layer 8 .
- the ferromagnetic layer 11 can be coupled with the ferromagnetic layer 8 via the nonmagnetic layer 10 by synthetic-antiferromagnetic coupling. In this manner, it is possible to reduce and adjust the shift of the switching current of the storage layer formed of the interface magnetic layer 3 and the ferromagnetic layer 2 caused by the strayed magnetic field from the reference layer formed of the interface magnetic layer 6 and the ferromagnetic layer 8 . It is desirable that the nonmagnetic layer 10 should have a heat resistance so that the ferromagnetic layer 8 and the ferromagnetic layer 11 are not mixed with each other in a heating process, and have a function of controlling crystalline orientation when the ferromagnetic layer 11 is formed.
- the thickness of the nonmagnetic layer 10 When the thickness of the nonmagnetic layer 10 is increased, the distance between the ferromagnetic layer 11 and the storage layer (in this embodiment, the ferromagnetic layer 2 , for example) is increased. Accordingly, the shift adjustment magnetic field applied from the ferromagnetic layer 11 to the storage layer is decreased. Therefore, it is desirable that the thickness of the nonmagnetic layer 10 be 5 nm or less.
- the ferromagnetic layer 11 is formed of a ferromagnetic material with an easy magnetization axis in a direction perpendicular to the film plane.
- the ferromagnetic layer 11 Since the ferromagnetic layer 11 is more distant from the storage layer than the reference layer, in order to adjust the strayed magnetic field to be applied to the storage layer by means of the ferromagnetic layer 11 , it is necessary to set the thickness or the magnitude of the saturation magnetization Ms of the ferromagnetic layer 11 to be greater than the thickness or the magnitude of the saturation magnetization Ms of the reference layer. That is to say, as a result of the study by the inventors of the present invention, it is necessary to meet the following relational expression wherein the thickness and the saturation magnetization of the reference layer are t 2 and Ms 2 , respectively, and the thickness and the saturation magnetization of the ferromagnetic layer 11 are t 3 and Ms 3 , respectively.
- the ferromagnetic layer 11 of the fourth embodiment can be applied to the magnetoresistive elements of the first and the second embodiments.
- the ferromagnetic layer 11 is formed above the ferromagnetic layer serving as the reference layer with the nonmagnetic layer 10 being sandwiched therebetween.
- the fourth embodiment has a top bias structure, in which the ferromagnetic layer 2 , the interface magnetic layer 3 , the nonmagnetic layer 4 , the interface magnetic layer 6 , the ferromagnetic layer 8 , the nonmagnetic layer 10 , and the ferromagnetic layer 11 are stacked on the base layer 100 in this order, the ferromagnetic layer 11 can be stacked below the base layer 100 . That is to say, like a magnetoresistive element 1 D according to a modification of the fourth embodiment shown in FIG.
- a bottom bias structure can be employed, in which the base layer 100 , the ferromagnetic layer 2 , the interface magnetic layer 3 , the nonmagnetic layer 4 , the interface magnetic layer 6 , and the ferromagnetic layer 8 are stacked in this order on the ferromagnetic layer 11 .
- the ferromagnetic layer 2 be used as a reference layer.
- the staking order can be reversed as in a magnetoresistive element according to another modification of the fourth embodiment shown in FIG. 5A .
- the base layer 100 , the ferromagnetic layer 11 , the nonmagnetic layer 10 , the ferromagnetic layer 8 , the interface magnetic layer 6 , the nonmagnetic layer 4 , the interface magnetic layer 3 , and the ferromagnetic layer 2 can be stacked in this order.
- an MTJ element including a magnetic film with a single crystal structure (hereinafter also referred to as “single crystal MTJ element”) will be explained. It is desirable that in a magnetoresistive element (MTJ element) according to any of the first to the fourth embodiments, at least one of the ferromagnetic layer 2 , the ferromagnetic layer 8 , the interface magnetic layer 3 , and the interface magnetic layer 6 should be with a single crystal structure. The reason for this is that it is possible to suppress the dispersion of magnetic characteristics considerably by forming a magnetic film with a single crystal structure, in which the crystalline orientations in the in-plane directions of the film are aligned along one direction, thereby enhancing the magnetic coupling in the film.
- MR ratio magnetoresistive ratio
- the wiring of a circuit includes a polycrystalline or amorphous structure, and thus it is not possible to grow a single crystal film thereon. Accordingly, it is difficult to grow a single crystal MTJ on a substrate on which transistors are implemented.
- an MRAM including a single crystal MTJ element by preparing a substrate with a single crystal structure on which an MTJ element with a single crystal structure is formed and a substrate on which a transistor is formed, bonding the MTJ element formed on the single crystal substrate and the substrate on which the transistor is formed, and removing the single crystal substrate, which is unnecessary. This will be explained with reference to FIG. 6( a ) to FIG. 7( c ).
- an MTJ element according to any of the first to the fourth embodiments is formed on a Si single crystal substrate under appropriate film growth conditions.
- a base layer 100 , a ferromagnetic layer 2 , a nonmagnetic layer 4 , and a ferromagnetic layer 8 are formed on a Si single crystal substrate 200 in this order by a sputtering method or MBE (Molecular Beam Epitaxy) method, thereby obtaining an MTJ element 1 of the first embodiment.
- the crystallinity of the Si single crystal substrate 200 is conveyed to the base layer 100 , the ferromagnetic layer 2 , the nonmagnetic layer 4 , and the ferromagnetic layer 8 , resulting in that the MTJ element 1 formed is a single crystal MTJ element 1 .
- a metal bonding layer 20 a is formed on the ferromagnetic layer 8 ( FIG. 6( a )).
- a substrate 220 on which a transistor circuit and wiring are formed, is prepared, and a metal bonding layer 20 b is formed on the substrate 220 ( FIG. 6( a )).
- the materials for forming the metal bonding layers 20 a , 20 b can be Al, Au, Cu, Ti, Ta, etc.
- the substrate 200 on which the single crystal MTJ element 1 is formed, and the substrate 220 , on which the transistor circuit is formed, are positioned so that the metal bonding layers 20 a , 20 b are opposed to each other.
- the metal bonding layers 20 a , 20 b are opposed to each other.
- the metal bonding layers 20 a , 20 b are contacted to each other.
- the metal bonding layers 20 a , 20 b can be bonded to each other by applying a pressure.
- the metal bonding layers 20 a , 20 b can be heated in order to improve the bonding force.
- the single crystal substrate 200 on which the single crystal MTJ element 1 is formed, is removed.
- the removal is performed in such a manner that first the substrate 200 is thinned by a BSG (Back Side Grinding) method, and then the thinned single crystal substrate 200 is mechanically polished by a CMP (Chemical Mechanical Polishing) method or the like as shown in FIG. 7( b ). In this manner, the manufacturing of the MTJ element 1 is completed ( FIG. 7( c )).
- a single crystal MTJ element according to any of the first to the fourth embodiments can be formed above the substrate by a manufacturing method including a series of the processes of preparing the single crystal substrate 200 on which a single crystal MTJ element according to any of the first to the fourth embodiments is formed and the substrate 220 on which a transistor circuit is formed, bonding the substrate on which transistors etc. are formed onto the single crystal MTJ element 1 , and then removing the single crystal substrate 200 that is unnecessary.
- the ferromagnetic layer 2 is a perpendicular magnetization film.
- the material of the ferromagnetic layer 2 be with a low saturation magnetization Ms, a high magnetic anisotropy energy Ku that is high enough to maintain a thermal stability factor ⁇ , and a coercive force, an anisotropic magnetic field and a Gilbert damping constant that are lower than those of the material used for the ferromagnetic layer 8 .
- the material show a high spin polarization. The following is the specific explanation thereof.
- a first example of the ferromagnetic layer 2 is formed of a MnGe alloy.
- the magnetization of a MnGe alloy is oriented along a specific crystal orientation. By changing the forming conditions, it is possible to form a MnGe alloy with a coercive force, an anisotropic field and a Gilbert damping constant that are lower than those of a material used to form the ferromagnetic layer 8 .
- a second example of the ferromagnetic layer 2 is formed of, for example, an alloy containing one element selected from the group consisting of Mn, Fe, Co, and Ni, and two elements selected from the group consisting of Zn, Al, Ga, In, Si, Ge, Sn, As, Sb, and Bi. Specific examples are MnAlGe, MnGaGe, MnZnSb, and so on.
- the c-axis be grown perpendicular to the film plane, i.e., grown to be (001) oriented.
- the base layer 100 it is possible to control the crystal orientation in the growth of the ferromagnetic layer 2 . The details of the base layer 100 will be described later.
- a third example of the ferromagnetic layer 2 is formed of an alloy containing at least one metal selected from the group consisting of Fe and Co.
- at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge may be added thereto. That is, the ferromagnetic layer 2 can be formed of an alloy containing at least one element selected from the group consisting of Fe and Co, and at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge.
- CoFeSi, CoFeP, CoFeW, CoFeNb, etc. may be used besides CoFeB.
- the ferromagnetic layer 8 have an easy magnetization axis in a direction perpendicular to the film plane, a low saturation magnetization Ms, a high magnetic anisotropy energy Ku that is high enough to maintain a thermal stability factor ⁇ , and a coercive force, an anisotropic magnetic field and a Gilbert damping constant that are higher than those of the material used for the ferromagnetic layer 2 . Furthermore, it is desirable that the material show a high spin polarization.
- a MnGe alloy magnetic material containing Mn and Ge is one of the material that meet such requirements. The following is the specific explanation thereof.
- a specific example of the ferromagnetic layer 8 is formed of a MnGe alloy.
- the magnetization of a MnGe alloy with a high crystal magnetic anisotropy is oriented along a specific crystal orientation.
- By changing the composition ratios and the crystallinity of the constituent elements it is possible to control the degree of crystal magnetic anisotropy. Accordingly, it is possible to control the direction of magnetization by changing the direction of crystal growth.
- a MnGe alloy itself has a high crystal magnetic anisotropy, it is possible to adjust the aspect ratio of the device with it.
- a MnGe alloy has a high thermal stability, it is suitable to be integrated.
- FIGS. 8( a ), 8 ( b ) and 8 ( c ) show the results of x-ray diffraction of MnGe (with the composition ratios of Mn being 79 atm %, and Ge being 21 atm %) formed on MgO (001), and FIG. 9 shows magnetization curves.
- the composition ratios given here are calculated by an analysis by ICP (Inductively Coupled Plasma). It is confirmed that by forming a MnGe film by heat treatment on MgO, the orientation of which is controlled, it is possible to form the MnGe film that is highly (001)-oriented (see FIGS. 8( a ), 8 ( b ) and 8 ( c )).
- the graph g 1 of FIG. 9 shows the magnetization curve in the case where a magnetic field is applied in a direction parallel to the film plane of the MnGe film
- the graph g 2 shows the magnetization curve in the case where a magnetic field is applied in a direction perpendicular to the film plane of the MnGe film.
- the effect of a strayed magnetic field from a reference layer becomes more remarkable as an MTJ element is miniaturized.
- the introduction of a bias layer is effective.
- a detailed explanation of a bias layer will be provided later. According to a prestudy by calculation, assuming that the shape of an MTJ element is cylindrical (pillar shape), when the thickness of a reference layer is 6 nm, the allowable size (diameter size) in the miniaturization process of an MTJ element is about 38 nm when the saturation magnetization Ms of the reference layer is 1000 emu/cc, about 28 nm when Ms is 750 emu/cc, and about 20 nm when Ms is 500 emu/cc.
- a low Ms material of 200 emu/cc or less be used for a reference layer.
- Mn x Ge y can be used for a reference layer.
- the saturation magnetization Ms of an MnGe alloy is as low as 97 emu/cc.
- an MnGe alloy be used as a low Ms reference layer.
- the thermal stability of a ferromagnetic material constituting a magnetoresistive element deteriorates.
- the perpendicular magnetic anisotropy energy Ku can be improved.
- the effective perpendicular magnetic anisotropy energy Ku of a MnGe alloy obtained by a calculation using the values of saturation magnetization and anisotropic magnetic field obtained from FIG. 9 is as high as 3.2 ⁇ 10 6 erg/cc. Thus, it is possible to use this alloy to form a reference layer that is superior in thermal stability.
- a magnetic film formed of an MnGe alloy is a perpendicular magnetic film with a low saturation magnetization and a high perpendicular magnetic anisotropy energy, and is especially suitable to form a reference layer.
- FIG. 10( a ) shows the dependency of saturation magnetization of a MnGe alloy on the composition ratio
- FIG. 10( b ) shows the dependency thereof on the substrate temperature. It could be confirmed from FIGS. 10( a ) and 10 ( b ) that it is possible to control the saturation magnetization by selecting optimum composition ratio and substrate temperature.
- the c-axis should be (001)-oriented, i.e., in the direction perpendicular to the film plane. Specifically, by appropriately selecting the tunnel barrier layer and the interface magnetic layer, the (001) orientation growth can be achieved.
- FIG. 11 shows examples of the magnetization curve of a thin film obtained by adding 5 atm % of Al to MnGe formed on a thermally oxidized Si substrate.
- FIG. 11 shows the magnetization curve in the case where a magnetic field is applied in a direction parallel to the film plane of this ferromagnetic layer
- the graph g 2 shows the magnetization curve in the case where a magnetic field is applied in a direction perpendicular to the film plane of the ferromagnetic layer.
- the magnetoresistive element has an interface magnetic layer 6 as in the second to the fourth embodiments
- the following materials can be used to form the ferromagnetic layer 8 .
- a metal that has the (111) crystalline orientation of a face-centered cubic (FCC) structure or has the (0001) crystalline orientation of a hexagonal close-packed (HCP) structure, or a metal that can form an artificial lattice, or an alloy containing Mn and at least one element selected from the group consisting of Al, Ge, and Ga can be used.
- An example of a metal that has the (111) crystalline orientation of a FCC structure or the (0001) crystalline orientation of a HCP structure is an alloy containing at least one element selected from the first group consisting of Fe, Co, Ni, and Cu and at least one element selected from the second group consisting of Pt, Pd, Rh, and Au.
- ferromagnetic alloys such as CoPd, CoPt, NiCo, NiPt, and the like can be used.
- alloy containing Mn and at least one element selected from the group consisting of Al, Ge, and Ga are ferromagnetic alloys such as MnGa, MnAlGe, and MnGaGe.
- the artificial lattice to be used for the ferromagnetic layer 8 has a structure in which layers each containing one or more elements selected from the group consisting of Fe, Co, and Ni or an alloy containing the one or more elements (ferromagnetic films) and layers each containing one element selected from the group consisting of Cr, Pt, Pd, Ir, Rh, Ru, Os, Re, Au, and Cu or an alloy containing the one element (nonmagnetic films) are alternately stacked.
- Co/Pt artificial lattice Co/Pd artificial lattice, CoCr/Pt artificial lattice, Co/Ru artificial lattice, Co/Os artificial lattice, Co/Au artificial lattice, Ni/Cu artificial lattice, and the like can be used. It is possible to adjust the magnetic anisotropy energy density and the saturation magnetization of such artificial lattices by adding an element to the ferromagnetic film, or by adjusting the ratio of thicknesses between the ferromagnetic film and the nonmagnetic film.
- the material of the ferromagnetic layer 8 can be an alloy containing at least one element selected from the group consisting of transition metals Fe, Co, and Ni, and at least one element selected from the group consisting of rare earth metals Tb, Dy, and Gd.
- examples are TbFe, TbCo, TbFeCo, DyTbFeCo, GdTbCo and the like.
- a multi-layer structure in which these alloys are alternately stacked can be employed. Specific examples are multi-layer films of TbFe/Co, TbCo/Fe, TbFeCo/CoFe, DyFe/Co, DyCo/Fe, DyFeCo/CoFe, and the like. It is possible to adjust the magnetic anisotropy energy density and the saturation magnetization of these alloys by adjusting the thickness ratio or composition.
- a material used to form the ferromagnetic layer 8 can be an alloy containing one or more elements selected from the first group consisting of Fe, Co, Ni, and Cu and one or more elements selected from the second group consisting of Pt, Pd, Rh, and Au. Specific examples are ferromagnetic alloys of FeRh, FePt, FePd, CoPt, and the like.
- the base layer 100 is used to control the crystallinity such as crystalline orientation, grain size, etc. of the ferromagnetic layer 2 and the layers above the ferromagnetic layer 2 . Accordingly, the selection of the material of the base layer 100 is important. Hereinafter, the material and the structure of the base layer 100 will be explained. Incidentally, although both conductive and insulating materials can be used to form a base layer, if a current should flow through the base layer, it is preferable that a conductive material be used.
- a first example of the base layer 100 is a layer of nitride having a (001) oriented NaCl structure and containing at least one element selected from the group consisting of Ti, Zr, Nb, V, Hf, Ta, Mo, W, B, Al, and Ce.
- a second example of the base layer 100 is a (002) oriented perovskite conductive oxide layer of ABO 3 .
- the A-site contains at least one element selected from the group consisting of Sr, Ce, Dy, La, K, Ca, Na, Pb, and Ba
- the B-site contains at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Nb, Mo, Ru, Ir, Ta, Ce, and Pb.
- a third example of the base layer 100 is a layer of oxide having a (001) oriented NaCl structure and containing at least one element selected from the group consisting of Mg, Al, and Ce.
- a fourth example of the base layer 100 is a layer having a (001) oriented tetragonal or cubic structure and containing at least one element selected from the group consisting of Al, Cr, Fe, Co, Rh, Pd, Ag, Ir, Pt, Au, Mo, and W.
- a fifth example of the base layer 100 is a layer having a stacked structure with a combination of two or more of the layers of the above first to fourth examples.
- the nonmagnetic layer 4 can have a conductive or insulating property. However, it is preferable that a tunnel barrier layer of an insulating material be used. With respect to the nonmagnetic layer 4 , it is possible to achieve a selective tunnel conduction and a high MR ratio by appropriately combining the nonmagnetic layer 4 with the adjacent ferromagnetic layer or interface magnetic layer. Accordingly, the selection of the material of the nonmagnetic layer 4 is important. Hereinafter, the material for forming the nonmagnetic layer 4 will be explained.
- an oxide containing at least one element selected from the group consisting of Mg, Ca, Ba, Al, Be, Sr, Zn, Ti, V, and Nb can be considered.
- Specific examples are MgO, AlO, ZnO, SrO, BaO, TiO, and the like.
- an oxide with a crystal structure of NaCl structure is preferable.
- Specific examples thereof are MgO, CaO, SrO, BaO, TiO, VO, NbO, and the like.
- crystal growth of such an oxide with NaCl structure is performed on a (001) surface of any of Fe, Co, and Ni, or an alloy containing two or more of these elements as main ingredients, or any of metals having a body-centered tetragonal structure with preferred orientation of (001), or an alloy containing two or more of such metals as main ingredients, or a MnGe alloy
- the crystal growth can be performed easily with the (001) surface being a preferred orientation surface.
- it is possible to achieve preferred orientation of (001) surface if crystal growth is performed on a CoFe—X amorphous alloy, which includes a very small amount of B, C, N, Ti, Ta, P, Mo, Si, W, Nb, and the like to improve the amorphous property.
- X indicates an added element such as B, C, N, and the like.
- the tunnel barrier layer can be of a mixed crystal containing two or more materials selected from the aforementioned group of oxides, or have a stacked structure with layers of such oxides.
- a mixed crystal examples of such a mixed crystal are MgAlO, MgZnO, MgTiO, MgCaO, and the like.
- the materials of a two-layer stacked structure are MgO/ZnO, MgO/AlO, TiO/AlO, MgAlO/MgO, and the like.
- Examples of the materials of a three-layer stacked structure are AlO/MgO/AlO, ZnO/MgO/ZnO, MgAlO/MgO/MgAlO, and the like.
- a second example of the tunnel barrier layer is a (002) oriented perovskite oxide of ABO 3 .
- the A-site contains at least one element selected from the group consisting of Sr, Ce, Dy, La, K, Ca, Na, Pb, and Ba
- the B-site contains at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Nb, Mo, Ru, Ir, Ta, Ce, and Pb.
- the specific examples are SrTiO 3 , SrRuO 3 , SrNbO 3 , BaTiO 3 , PbTiO 3 , and the like.
- the lattice constant of the [100] plane of each of these oxides is about 3.7 ⁇ -4.0 ⁇ , which is close to the lattice constant of about 3.8 ⁇ of the [100] plane of a MnGe alloy. Accordingly, these oxides are suitable for forming an interface with good quality to obtain a higher MR ratio.
- a third example of the tunnel barrier layer is a spinel oxide of MgAlO.
- the lattice constant of MgAl 2 O 4 having the spinet structure is about 4.05 ⁇
- the lattice mismatch of which relative to the lattice constant of the [100] plane of a MnGe alloy, which is about 3.8 ⁇ , is as small as 6.6%. Accordingly, this material is suitable for forming an interface with good quality to obtain a higher MR ratio.
- the tunnel barrier layer can be formed of either a crystalline or amorphous material.
- the tunnel barrier layer is formed of a crystalline material, the scattering of electrons in a tunnel barrier is curbed, resulting in that the probability would increase that the electrons would be selectively conducted by tunneling from the ferromagnetic layer with the wavenumber thereof being maintained. Accordingly, it is possible to increase the MR ratio. Therefore, in order to obtain a higher MR ratio, a crystalline tunnel barrier is preferable.
- an MTJ element has a stacked structure including a ferromagnetic layer of CoFe(B), a nonmagnetic layer of crystalline MgO, and a ferromagnetic layer of MnGe, which layers are stacked in this order, an orientation relationship of MnGe(001)/MgO(001)/CoFe(B)(001) can be established.
- MnGe(001)/MgO(001)/CoFe(B)(001) can be established.
- the lattice mismatch obtained from the bulk lattice constants of MnGe and MgO in the in-plane direction is as high as about 11.0%.
- the lattice mismatch is defined by the following expression:
- a(MgO) and a(MnGe) are the lattice constants of MgO and MnGe in the in-plane direction of the film, respectively. If a lattice mismatch is large, a dislocation or the like is caused at the interface in order to reduce the interface energy generated by lattice distortion. In this case, an epitaxial relationship is established between crystal grains, and it is difficult to perform a uniform epitaxial growth in the film plane. When a current is caused to flow through an MTJ element, a dislocation works as a source of the scattering of electrons, and the MR ratio is decreased.
- a perovskite oxide, a spinel oxide, a NaCl structure oxide are suitable materials for forming a nonmagnetic layer.
- Both the interface magnetic layer 3 and the interface magnetic layer 6 are perpendicular magnetization films.
- these layers be formed of a material with a low saturation magnetization Ms, a high magnetic anisotropy energy Ku to maintain a thermal stability factor ⁇ , and a high spin polarization.
- An example of such a material meeting the aforementioned requirements is a MnGe alloy magnetic material containing Mn and Ge. This material will be specifically explained below.
- the interface magnetic layer 3 and the interface magnetic layer 6 are formed of a MnGe alloy.
- the characteristic of Mn x Ge y as a perpendicular magnetization film appears when the composition ratio x of Mn is in the range of 77 atm % ⁇ x ⁇ 82 atm %, and the composition ratio y of Ge is in the range of 18 atm % ⁇ y ⁇ 23 atm %.
- the c-axis is grown in the direction perpendicular to the film plane, i.e., (001) oriented.
- MnGe is a material formed of light elements, it is expected that the Gilbert damping constant thereof is low. Accordingly, the energy required for magnetization switching thereof is low. Therefore, the current density for magnetization reversal by spin polarized electrons can be considerably reduced. Thus, MnGe can be effectively applied to the interface ferromagnetic layer 3 .
- FIG. 12( a ) shows the band structures of a bulk MnGe alloy, which are obtained by calculation.
- FIG. 12( b ) shows the density of states thereof. It could be understood from FIG. 12( a ) that in the Majority state, the M band crosses the Fermi energy E F while in the Minority state, the M band does not cross the Fermi energy E F . This means that the spin of the electrons moving in the c-axis direction is completely polarized. From FIG. 12( b ), the spin polarization P could be estimates as ⁇ 78% and the saturation magnetization Ms could be estimated as 183 emu/cc. Thus, it is understood that such a material is suitable to form an interface magnetic layer of a storage layer or reference layer.
- a second example of the interface magnetic layer 3 and the interface magnetic layer 6 can be formed of, for example, an alloy containing one element selected from the group consisting of Mn, Fe, Co, and Ni, and two elements selected from the group consisting of Zn, Al, Ga, In, Si, Ge, Sn, As, Sb, and Bi. Specifically, MnAlGe, MnGaGe, MnZnSb, and the like can be used.
- a third example of the interface magnetic layer 3 and the interface magnetic layer 6 can be formed of, for example, an alloy containing at least one metal selected from the group consisting of Fe and Co.
- the interface magnetic layer 6 be formed of an alloy containing at least one metal selected from the group consisting of Fe and Co.
- an interface magnetic layer of CoFe, a nonmagnetic layer of MgO, and an interface magnetic layer of CoFe are stacked, it is possible to establish the orientation relationship of CoFe(001)/MgO(001)/CoFe(001). In such a case, it is possible to improve the wavenumber selectability of tunnel electrons, resulting in that it is possible to obtain a high MR ratio.
- the interface magnetic layer 3 and the interface magnetic layer 6 can be formed of an alloy containing at least one element selected from the group consisting of Fe and Co, and at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge.
- the interface magnetic layer 3 and the interface magnetic layer 6 can be formed of an alloy containing at least one element selected from the group consisting of Fe and Co, and at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge.
- CoFeSi, CoFeP, CoFeW, CoFeNb, and the like, besides CoFeB can be such an alloy.
- a Heusler alloy such as Co 2 FeSi, Co 2 MnSi, Co 2 MnGe and the like can be used.
- a Heusler alloy has a spin polarization equivalent to or higher than that of CoFeB. Accordingly, a Heusler alloy is suitable as a material of the interface magnetic layers.
- a fourth example of the interface magnetic layer 3 and the interface magnetic layer 6 can be formed of a MnAl alloy, for example. Since a MnAl alloy is formed of light metals, the Gilbert damping constant thereof is low, resulting in that the energy required for magnetization switching would be low. Accordingly, it is possible to considerably reduce the current density for switching magnetization by means of spin polarized electrons. Moreover, since a MnAl alloy has an energy gap relative to either the spinband of up-spin or the spinband of down-spin in the (001) direction, it has a half-metallic characteristic and a high spin polarization, resulting in that it is possible to obtain a high MR ratio.
- the interface magnetic layer 3 and the interface magnetic layer 6 contacting the nonmagnetic layer 4 can expand or shrink in the direction perpendicular to the film plane.
- MRAM magnetic memory
- the MRAM according to this embodiment includes a plurality of memory cells.
- FIG. 13 is a sectional view of the main part of a memory cell of the MRAM according to this embodiment.
- Each memory cell has a magnetoresistive element according to any of the first to the fourth embodiments as a storage element.
- the storage element is assumed to be the magnetoresistive element (MTJ element) 1 of the first embodiment.
- the top surface of the MTJ element 1 is connected to a bit line 32 via an upper electrode 31 . Furthermore, the bottom surface of the MTJ element 1 is connected to a drain region 37 a of source/drain regions of a surface of a semiconductor substrate 36 via a lower electrode 33 , a leading electrode 34 , and a plug 35 .
- the drain region 37 a constitutes a selection transistor Tr with a source region 37 b , a gate insulating film 38 formed on the substrate 36 , and a gate electrode 39 formed on the gate insulating film 38 .
- the selection transistor Tr and the MTJ element 1 constitute one memory cell of the MRAM.
- the source region 37 b is connected to another bit line 42 via a plug 41 .
- the bit lines 32 and 42 , the electrodes 31 and 33 , the leading electrode 34 , and the plugs 35 and 41 are formed of any one of W, Al, AlCu, Cu, and the like.
- FIG. 14 is a circuit diagram showing the main part of the MRAM according to this embodiment.
- FIG. 14 shows that a plurality of memory cells 53 each including an MTJ element 1 and a selection transistor Tr are arranged in a matrix form. One end of each of the memory cells 53 in the same column is connected to the same bit line 32 , and the other is connected to the same bit line 42 .
- the gate electrodes (word line) 39 of the selection transistors Tr of the memory cells 53 belonging to the same row are mutually connected, and further connected to a row decoder 51 .
- the bit line 32 is connected to a current source/sink circuit 55 via a switching circuit 54 such as a transistor. Furthermore, the bit line 42 is connected to a current source/sink circuit 57 via a switching circuit 56 such as a transistor.
- the current source/sink circuits 55 and 57 supply a write current to the bit lines 32 and 42 connected thereto, or sink a current from the bit lines 32 and 42 connected thereto.
- the bit line 42 is also connected to a read circuit 52 .
- the read circuit 52 can be connected to the bit line 32 .
- the read circuit 52 includes a read current circuit, a sense amplifier, and the like.
- a write operation by turning on the switching circuits 54 and 56 connected to a memory cell, on which the write operation is performed, and the selection transistor Tr, a current path passing through the target memory cell is formed.
- One of the current source/sink circuits 55 and 57 functions as a current source, and the other functions as a current sink depending on information to be written. As a result, a write current flows in a direction depending on the information to be written.
- a read current that is low enough to prevent magnetization switching is supplied to the MTJ element 1 specified in the same manner as the write operation.
- the read circuit 52 determines the resistance state of the MTJ element 1 by comparing a current value or voltage value, which is derived from the resistance value that depends on the magnetization state of the MTJ element 1 , with a reference value.
- the current pulse width in a read operation be narrower than that in a write operation. In this manner, the occurrences of writing errors caused by a current in a read operation can be reduced. This is based on the fact that the narrower the pulse width of a write current is, the higher the absolute value of the write current becomes.
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Abstract
Description
- This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2012-208293, filed on Sep. 21, 2012, the entire contents of which are incorporated herein by reference.
- Embodiments described herein relate generally to magnetoresistive elements and magnetic memories.
- A basic structure of a magnetic tunnel junction (MTJ) element serving as a magnetoresistive element is a stacked structure including a storage layer, the magnetization direction of which is changeable, a reference layer, the magnetization direction of which is fixed, and an insulating layer provided between the storage layer and the reference layer. It is known that an MTJ element shows a tunneling magnetoresistive (TMR) effect. Thus, an MTJ element is used as a storage element of a memory cell in a magnetic random access memory (MRAM).
- An MRAM stores information (“1”, “0”) in accordance with a change in relative angle between magnetizations of magnetic layers included in an MTJ element, and is nonvolatile. Since the magnetization switching speed of an MRAM is a few nanoseconds, it is possible to write and read data at a high speed with an MRAM. Accordingly, MRAMs are expected to be next-generation high-speed nonvolatile memories. Furthermore, by using a method called “spin transfer torque switching” for controlling magnetization by means of a spin polarized current, a current density can be increased by decreasing the cell size of an MRAM. Accordingly, it is possible to easily switch the magnetization in a storage layer, resulting in that it is possible to obtain an MRAM with a high density and a low power consumption.
- In improving the density of a nonvolatile memory, it is essential to improve the degree of integration of a magnetoresistive element. However, as the size of a magnetoresistive element decreases, the thermal stability of a ferromagnetic material for forming the magnetoresistive element deteriorates. Therefore, a problem arises in that the magnetic anisotropy energy and the thermal stability of the ferromagnetic material should be improved.
- In order to solve this problem, recently, it is attempted that an MRAM using a perpendicular magnetization MTJ element, in which the direction of the magnetization of a ferromagnetic material is perpendicular to the film plane, be formed. In a perpendicular magnetization MTJ element, generally a ferromagnetic material with a high magnetic crystalline anisotropy is used.
- Generally, a critical current for magnetization reversal by the spin transfer torque switching method is dependent on the saturation magnetization and the Gilbert damping constant of a storage layer. Accordingly, in order to switch the magnetization of a storage layer by means of low-current spin transfer torque switching, it is necessary to reduce the saturation magnetization and the Gilbert damping constant of the storage layer. Furthermore, the influence of strayed magnetic field from a reference layer becomes more remarkable as the element is miniaturized. Accordingly, in order to improve the degree of integration of a magnetoresistive element, it is also necessary to reduce the saturation magnetization of the reference layer thereof with a high magnetic anisotropy energy of the reference layer being maintained.
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FIG. 1 is a sectional view showing a magnetoresistive element according to a first embodiment. -
FIG. 1A is a sectional view showing a magnetoresistive element according to a modification of the first embodiment. -
FIG. 2 is a sectional view showing a magnetoresistive element according to a second embodiment. -
FIG. 2A is a sectional view showing a magnetoresistive element according to a modification of the second embodiment. -
FIG. 3 is a sectional view showing a magnetoresistive element according to a third embodiment. -
FIG. 3A is a sectional view showing a magnetoresistive element according to a modification of the third embodiment. -
FIG. 4 is a sectional view showing a magnetoresistive element according to a fourth embodiment. -
FIG. 5 is a sectional view showing a magnetoresistive element according to a modification of the fourth embodiment. -
FIG. 5A is a sectional view showing a magnetoresistive element according to another modification of the fourth embodiment. -
FIGS. 6( a) and 6(b) are for explaining a method of manufacturing an MTJ element including a magnetic film with a single crystal structure. -
FIGS. 7( a) to 7(c) are for explaining a method of manufacturing an MTJ element including a magnetic film with a single crystal structure. -
FIGS. 8( a) to 8(c) show examples of x-ray diffraction on a MnGe alloy. -
FIG. 9 shows examples of magnetization curve of a MnGe alloy. -
FIGS. 10( a) and 10(b) show examples of the characteristics that the saturation magnetization of a MnGe alloy is dependent on the composition and the substrate temperature. -
FIG. 11 shows examples of magnetization curve in the cases where Al is slightly added to a MnGe alloy on a thermally oxidized Si substrate. -
FIGS. 12( a) and 12(b) show the band structure and the density of states of a bulk MnGe alloy, which are obtained by calculation. -
FIG. 13 is a sectional view showing a memory cell of a magnetic memory according to a fifth embodiment. -
FIG. 14 is a circuit diagram of the main part of the magnetic memory according to the fifth embodiment. - A magnetoresistive element according to an embodiment includes a first magnetic layer, a second magnetic layer, and a first nonmagnetic layer provided between the first magnetic layer and the second magnetic layer, the first magnetic layer including a magnetic film of MnxGey (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %).
- Hereinafter, embodiments will be explained with reference to the accompanying drawings. In the following explanations, elements having the same function and the same structure are denoted by the same reference numeral, and a repeated explanation will be performed only when it is necessary to do so.
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FIG. 1 shows a magnetoresistive element according to a first embodiment.FIG. 1 is a sectional view of themagnetoresistive element 1 of the first embodiment. Themagnetoresistive element 1 of this embodiment is an MTJ element having such a structure that aferromagnetic layer 2, a nonmagnetic layer 4 (hereinafter also referred to as “tunnel barrier layer 4”), and aferromagnetic layer 8 are formed on abase layer 100 in this order. Thebase layer 100 is used to control the crystallinity such as crystal orientation, crystal grain size, etc. of theferromagnetic layer 2 and the layers above theferromagnetic layer 2, and the detailed explanation thereof will be provided later. One of theferromagnetic layer 2 and theferromagnetic layer 8 includes a magnetic film of MnxGey (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %). - The resistance value of the MTJ element is determined by the angle between the directions of the magnetizations of the two magnetic layers arranged with the tunnel barrier layer sandwiched therebetween. It is possible to control the angle between the directions of the magnetizations by means of an external magnetic field or current caused to flow through the element. On such an occasion, it is possible to control the angle between the directions of the magnetizations more stably by differentiating the magnitudes of coercive force, anisotropic magnetic field Hk and/or Gilbert damping constant α of the two magnetic layers. Herein, the magnetic layer with a higher coercive force, a higher anisotropic magnetic field Hk or a higher Gilbert damping constant α will be called “reference layer,” and a magnetic layer with a lower coercive force, a lower anisotropic magnetic field Hk or a lower Gilbert damping constant α will be called “storage layer.” Generally, it is desirable that a magnetic layer with a higher coercive force, a higher anisotropic magnetic field Hk or a higher Gilbert damping constant α be used as a reference layer, and a magnetic layer with a lower coercive force, a lower anisotropic magnetic field Hk or a lower Gilbert damping constant α be used as a storage layer. As will be described later, since a magnetic layer of MnxGey (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %) has a high spin polarization, a high coercive force, and a high anisotropic magnetic field, such a magnetic layer is more suitable to be used as a reference layer.
- In a MnGe alloy used for a ferromagnetic layer, the c-axis is an easy magnetization axis. Accordingly, it is possible to manufacture a perpendicular magnetization MTJ element by controlling the orientation in crystallization so that the c-axis is along the direction perpendicular to the film plane.
- In the first embodiment, it is desirable that an oxide insulator be used for the
nonmagnetic layer 4. When an MTJ element has a stacked structure in which for example, a ferromagnetic layer of CoFe(B), a nonmagnetic layer of crystalline MgO, and a ferromagnetic layer of MnGe are stacked in this order, an orientation relationship of MnGe(001)/MgO(001)/CoFe(B)(001) can be established. Here, MnGe(001) or MgO(001) means that the crystalline orientation is such that the (001) surface is exposed on the top surface of each material. In this manner, it is possible to improve the wavenumber selectability of tunnel electrons, thereby obtaining a higher MR ratio. - It is possible to make the easy magnetization directions of the
ferromagnetic layer 2 and theferromagnetic layer 8 perpendicular to the film plane by controlling the direction of crystalline orientation. That is to say, themagnetoresistive element 1 according to this embodiment can be not only an in-plane magnetization MTJ element but also a so-called “perpendicular magnetization MTJ element,” in which the directions of the magnetizations of theferromagnetic layer 2 and theferromagnetic layer 8 are perpendicular to the film planes, respectively. Incidentally, in this specification, the “film plane” means a plane perpendicular to the direction in which each ferromagnetic layer is stacked. Furthermore, the “easy magnetization direction” means a direction in a ferromagnetic material with a certain macro size, and if a spontaneous magnetization is along this direction in a state where there is no external magnetic field, the internal energy becomes the lowest. In contrast, the “hard magnetization direction” means a direction of a ferromagnetic material with a certain macro size, and if a spontaneous magnetization is along this direction in a state where there is no external magnetic field, the internal energy becomes the highest. - In one of the
ferromagnetic layer 2 and theferromagnetic layer 8, the magnetization direction does not change between before and after a write operation, by which a write current flows through theMTJ element 1, and in the other, the magnetization direction changes. The ferromagnetic layer in which the magnetization direction does not change will also be called a “reference layer,” and the ferromagnetic layer in which the magnetization direction changes will also be called a “storage layer.” In this embodiment, for example, theferromagnetic layer 2 serves as a storage layer, and theferromagnetic layer 8 serves as a reference layer. Incidentally, the write current is caused to flow between theferromagnetic layer 2 and theferromagnetic layer 8 in a direction perpendicular to the film plane. In a case where theferromagnetic layer 2 is a storage layer and theferromagnetic layer 8 is a reference layer, and the magnetization direction of theferromagnetic layer 2 and the magnetization direction of theferromagnetic layer 8 are antiparallel (reverse directions) to each other, the write current is caused to flow from theferromagnetic layer 2 to theferromagnetic layer 8. In this case, electrons flow from theferromagnetic layer 8 toward theferromagnetic layer 2 via thenonmagnetic layer 4. The electrons having been subjected to spin polarization by passing through theferromagnetic layer 8 then flow into theferromagnetic layer 2. The spin-polarized electrons with the spin in the same direction as the direction of the magnetization of theferromagnetic layer 2 pass through theferromagnetic layer 2, but the spin-polarized electrons with the spin in the direction opposite to the direction of the magnetization of theferromagnetic layer 2 exert spin torque on the magnetization of theferromagnetic layer 2 so that the direction of the magnetization of theferromagnetic layer 2 becomes the same as the direction of the magnetization of theferromagnetic layer 8. As a result, the direction of the magnetization of theferromagnetic layer 2 is switched so as to be in parallel with (the same as) the direction of the magnetization of theferromagnetic layer 8. - In contrast, in a case where the direction of the magnetization of the
ferromagnetic layer 2 and the direction of the magnetization of theferromagnetic layer 8 are parallel with each other, the write current is caused to flow from theferromagnetic layer 8 toward theferromagnetic layer 2. In this case, electrons flow from theferromagnetic layer 2 toward theferromagnetic layer 8 via thenonmagnetic layer 4. The electrons spin-polarized by passing through theferromagnetic layer 2 flow into theferromagnetic layer 8. Although the spin-polarized electrons with the spin in the same direction as the magnetization of theferromagnetic layer 8 pass through theferromagnetic layer 8, the spin-polarized electrons with the spin in the direction opposite to the magnetization of theferromagnetic layer 8 are reflected at the interface between thenonmagnetic layer 4 and theferromagnetic layer 8, and pass through thenonmagnetic layer 4 to flow into theferromagnetic layer 2. As a result, the spin torque is exerted on the magnetization of theferromagnetic layer 2, and the direction of the magnetization of theferromagnetic layer 2 is caused to be opposite to the direction of the magnetization of theferromagnetic layer 8. Accordingly, the direction of the magnetization of theferromagnetic layer 2 is switched to be antiparallel to the direction of the magnetization of theferromagnetic layer 8. - The first embodiment has a structure in which the
ferromagnetic layer 2, thenonmagnetic layer 4, and theferromagnetic layer 8 are stacked on thebase layer 100 in this order. However, the order can be reversed on thebase layer 100, as in a magnetoresistive element according to a modification of the first embodiment shown inFIG. 1A . That is to say, theferromagnetic layer 8, thenonmagnetic layer 4, and theferromagnetic layer 2 can be stacked on thebase layer 100 in this order. -
FIG. 2 shows amagnetoresistive element 1A according to a second embodiment. Themagnetoresistive element 1A has a structure obtained by providing an interfacemagnetic layer 6 between thenonmagnetic layer 4 and theferromagnetic layer 8 in themagnetoresistive element 1 of the first embodiment shown inFIG. 1 . At least one of theferromagnetic layer 2, theferromagnetic layer 8, and the interfacemagnetic layer 6 includes a magnetic film of MnxGey (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %). - Like the first embodiment, by controlling the crystalline orientation, the
ferromagnetic layer 2 and theferromagnetic layer 8 are caused to have magnetic anisotropy energy perpendicular to the film plane, by which it is possible to make the directions of the easy magnetizations thereof perpendicular to the film plane. That is to say, themagnetoresistive element 1A of this embodiment can be not only an in-plane magnetization MTJ element but also a so-called “perpendicular magnetization MTJ element,” in which the directions of the magnetizations of theferromagnetic layer 2 and theferromagnetic layer 8 are perpendicular to the film planes, respectively. In one of theferromagnetic layer 2 and theferromagnetic layer 8, the magnetization direction does not change between before and after a write operation, by which a write current flows through theMTJ element 1, and in the other, the magnetization direction changes. In this embodiment, for example, theferromagnetic layer 2 serves as a storage layer, and theferromagnetic layer 8 serves as a reference layer. Like the first embodiment, the write current is caused to flow between theferromagnetic layer 2 and theferromagnetic layer 8 in a direction perpendicular to the film plane. Incidentally, the interfacemagnetic layer 6 is provided to increase the spin polarization. - In the second embodiment, for example, when the interface
magnetic layer 6 of MnGe is formed on thenonmagnetic layer 4 of crystalline MgO, it is possible to perform epitaxial growth of theferromagnetic layer 8 containing Mn and one or more elements selected from Al, Ge, and Ga on the interfacemagnetic layer 6. For example, in a case where an alloy containing Mn and Ga is selected to form theferromagnetic layer 8, it is possible to have an epitaxial relationship of MnGa(001)/MnGe(001)/MgO(001). In this manner, it is possible to improve the wavenumber selectability of tunnel electrons, thereby obtaining a high MR ratio and at the same time obtaining a reference layer with a low-saturation magnetization. - Furthermore, although the
ferromagnetic layer 2, thenonmagnetic layer 4, the interfacemagnetic layer 6, and theferromagnetic layer 8 are stacked on thebase layer 100 in this order in the second embodiment, the order can be reversed on thebase layer 100, as in a magnetoresistive element according to a modification of the second embodiment shown inFIG. 2A . That is to say, theferromagnetic layer 8, the interfacemagnetic layer 6, thenonmagnetic layer 4, and theferromagnetic layer 2 can be stacked on thebase layer 100 in this order. -
FIG. 3 shows amagnetoresistive element 1B according to a third embodiment. Themagnetoresistive element 1B is obtained by inserting an interfacemagnetic layer 3 between theferromagnetic layer 2 and thenonmagnetic layer 4 and inserting an interfacemagnetic layer 6 between thenonmagnetic layer 4 and theferromagnetic layer 8 in themagnetoresistive element 1 according to the first embodiment shown inFIG. 1 . At least one of the interfacemagnetic layer 3 and the interfacemagnetic layer 6 includes a magnetic film of MnxGey (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %). The details of the properties of the interfacemagnetic layer 3 and the interfacemagnetic layer 6 will be described later. - The
magnetoresistive element 1B of the third embodiment, like the magnetoresistive elements of the first and the second embodiments, can be not only an in-plane magnetization MTJ element but also a perpendicular magnetization MTJ element. Furthermore, like the magnetoresistive elements of the first and the second embodiments, the interfacemagnetic layer 3 and the interfacemagnetic layer 6 of the third embodiment are provided to increase the spin polarization. - Although the
ferromagnetic layer 2, the interfacemagnetic layer 3, thenonmagnetic layer 4, the interfacemagnetic layer 6, and theferromagnetic layer 8 are stacked on thebase layer 100 in this order in the third embodiment, the order can be reversed on thebase layer 100, as in a magnetoresistive element according to a modification of the third embodiment shown inFIG. 3A . That is to say, theferromagnetic layer 8, the interfacemagnetic layer 6, thenonmagnetic layer 4, the interfacemagnetic layer 3, and theferromagnetic layer 2 can be stacked on thebase layer 100 in this order. -
FIG. 4 shows amagnetoresistive element 1C according to a fourth embodiment. Themagnetoresistive element 1C is obtained by stacking anonmagnetic layer 10 and aferromagnetic layer 11 on theferromagnetic layer 8 in themagnetoresistive element 1B according to the third embodiment shown inFIG. 3 . Incidentally, in this embodiment, for example, the interfacemagnetic layer 6 and theferromagnetic layer 8 serve as a reference layer. Theferromagnetic layer 11 is also called a “bias layer,” and has a magnetization that is anti-parallel (opposite direction) with the magnetization of theferromagnetic layer 8. Theferromagnetic layer 11 can be coupled with theferromagnetic layer 8 via thenonmagnetic layer 10 by synthetic-antiferromagnetic coupling. In this manner, it is possible to reduce and adjust the shift of the switching current of the storage layer formed of the interfacemagnetic layer 3 and theferromagnetic layer 2 caused by the strayed magnetic field from the reference layer formed of the interfacemagnetic layer 6 and theferromagnetic layer 8. It is desirable that thenonmagnetic layer 10 should have a heat resistance so that theferromagnetic layer 8 and theferromagnetic layer 11 are not mixed with each other in a heating process, and have a function of controlling crystalline orientation when theferromagnetic layer 11 is formed. - When the thickness of the
nonmagnetic layer 10 is increased, the distance between theferromagnetic layer 11 and the storage layer (in this embodiment, theferromagnetic layer 2, for example) is increased. Accordingly, the shift adjustment magnetic field applied from theferromagnetic layer 11 to the storage layer is decreased. Therefore, it is desirable that the thickness of thenonmagnetic layer 10 be 5 nm or less. Theferromagnetic layer 11 is formed of a ferromagnetic material with an easy magnetization axis in a direction perpendicular to the film plane. Since theferromagnetic layer 11 is more distant from the storage layer than the reference layer, in order to adjust the strayed magnetic field to be applied to the storage layer by means of theferromagnetic layer 11, it is necessary to set the thickness or the magnitude of the saturation magnetization Ms of theferromagnetic layer 11 to be greater than the thickness or the magnitude of the saturation magnetization Ms of the reference layer. That is to say, as a result of the study by the inventors of the present invention, it is necessary to meet the following relational expression wherein the thickness and the saturation magnetization of the reference layer are t2 and Ms2, respectively, and the thickness and the saturation magnetization of theferromagnetic layer 11 are t3 and Ms3, respectively. -
Ms 2 ×t 2 <Ms 3 ×t 3 - Incidentally, the
ferromagnetic layer 11 of the fourth embodiment can be applied to the magnetoresistive elements of the first and the second embodiments. In this case, theferromagnetic layer 11 is formed above the ferromagnetic layer serving as the reference layer with thenonmagnetic layer 10 being sandwiched therebetween. - Although the fourth embodiment has a top bias structure, in which the
ferromagnetic layer 2, the interfacemagnetic layer 3, thenonmagnetic layer 4, the interfacemagnetic layer 6, theferromagnetic layer 8, thenonmagnetic layer 10, and theferromagnetic layer 11 are stacked on thebase layer 100 in this order, theferromagnetic layer 11 can be stacked below thebase layer 100. That is to say, like amagnetoresistive element 1D according to a modification of the fourth embodiment shown inFIG. 5 , a bottom bias structure can be employed, in which thebase layer 100, theferromagnetic layer 2, the interfacemagnetic layer 3, thenonmagnetic layer 4, the interfacemagnetic layer 6, and theferromagnetic layer 8 are stacked in this order on theferromagnetic layer 11. In this case, it is preferable that theferromagnetic layer 2 be used as a reference layer. Furthermore, the staking order can be reversed as in a magnetoresistive element according to another modification of the fourth embodiment shown inFIG. 5A . That is to say, thebase layer 100, theferromagnetic layer 11, thenonmagnetic layer 10, theferromagnetic layer 8, the interfacemagnetic layer 6, thenonmagnetic layer 4, the interfacemagnetic layer 3, and theferromagnetic layer 2 can be stacked in this order. - (MTJ Element Including Magnetic Film with Single Crystal Structure)
- Next, a method of manufacturing an MTJ element including a magnetic film with a single crystal structure (hereinafter also referred to as “single crystal MTJ element”) will be explained. It is desirable that in a magnetoresistive element (MTJ element) according to any of the first to the fourth embodiments, at least one of the
ferromagnetic layer 2, theferromagnetic layer 8, the interfacemagnetic layer 3, and the interfacemagnetic layer 6 should be with a single crystal structure. The reason for this is that it is possible to suppress the dispersion of magnetic characteristics considerably by forming a magnetic film with a single crystal structure, in which the crystalline orientations in the in-plane directions of the film are aligned along one direction, thereby enhancing the magnetic coupling in the film. Furthermore, since the formation of grain boundary is curbed, it is possible to form a magnetic film or insulating layer, which is flattened in the atomic level, and which has good crystallinity. Accordingly, it can be expected that a magnetoresistive ratio (MR ratio) that is higher than the MR ratios of conventional MTJ elements can be obtained. - Therefore, in order to achieve a large capacity MRAM of a few tens Gbits, it is necessary to manufacture a single crystal MTJ element.
- However, generally, the wiring of a circuit includes a polycrystalline or amorphous structure, and thus it is not possible to grow a single crystal film thereon. Accordingly, it is difficult to grow a single crystal MTJ on a substrate on which transistors are implemented.
- However, it is possible to form an MRAM including a single crystal MTJ element by preparing a substrate with a single crystal structure on which an MTJ element with a single crystal structure is formed and a substrate on which a transistor is formed, bonding the MTJ element formed on the single crystal substrate and the substrate on which the transistor is formed, and removing the single crystal substrate, which is unnecessary. This will be explained with reference to
FIG. 6( a) toFIG. 7( c). - Specifically, first, an MTJ element according to any of the first to the fourth embodiments is formed on a Si single crystal substrate under appropriate film growth conditions. For example, as shown in
FIG. 6( a), abase layer 100, aferromagnetic layer 2, anonmagnetic layer 4, and aferromagnetic layer 8 are formed on a Sisingle crystal substrate 200 in this order by a sputtering method or MBE (Molecular Beam Epitaxy) method, thereby obtaining anMTJ element 1 of the first embodiment. At this time, the crystallinity of the Sisingle crystal substrate 200 is conveyed to thebase layer 100, theferromagnetic layer 2, thenonmagnetic layer 4, and theferromagnetic layer 8, resulting in that theMTJ element 1 formed is a singlecrystal MTJ element 1. Thereafter, ametal bonding layer 20 a is formed on the ferromagnetic layer 8 (FIG. 6( a)). Similarly, asubstrate 220, on which a transistor circuit and wiring are formed, is prepared, and ametal bonding layer 20 b is formed on the substrate 220 (FIG. 6( a)). The materials for forming the metal bonding layers 20 a, 20 b can be Al, Au, Cu, Ti, Ta, etc. - Next, the
substrate 200, on which the singlecrystal MTJ element 1 is formed, and thesubstrate 220, on which the transistor circuit is formed, are positioned so that the metal bonding layers 20 a, 20 b are opposed to each other. For example, as shown inFIG. 6( a), the metal bonding layers 20 a, 20 b are opposed to each other. Thereafter, as shown inFIG. 6( b), the metal bonding layers 20 a, 20 b are contacted to each other. At this time, the metal bonding layers 20 a, 20 b can be bonded to each other by applying a pressure. When a pressure is applied, the metal bonding layers 20 a, 20 b can be heated in order to improve the bonding force. - Next, as shown in
FIG. 7( a), thesingle crystal substrate 200, on which the singlecrystal MTJ element 1 is formed, is removed. The removal is performed in such a manner that first thesubstrate 200 is thinned by a BSG (Back Side Grinding) method, and then the thinnedsingle crystal substrate 200 is mechanically polished by a CMP (Chemical Mechanical Polishing) method or the like as shown inFIG. 7( b). In this manner, the manufacturing of theMTJ element 1 is completed (FIG. 7( c)). - As explained above, a single crystal MTJ element according to any of the first to the fourth embodiments can be formed above the substrate by a manufacturing method including a series of the processes of preparing the
single crystal substrate 200 on which a single crystal MTJ element according to any of the first to the fourth embodiments is formed and thesubstrate 220 on which a transistor circuit is formed, bonding the substrate on which transistors etc. are formed onto the singlecrystal MTJ element 1, and then removing thesingle crystal substrate 200 that is unnecessary. - Next, the specific composition of each layer included in the
MTJ elements ferromagnetic layer 2, theferromagnetic layer 8, thebase layer 100, thenonmagnetic layer 4, the interfacemagnetic layer 3, and the interfacemagnetic layer 6. - The
ferromagnetic layer 2 is a perpendicular magnetization film. In order to achieve both a high thermal stability and a low-current magnetization switching, it is desirable that the material of theferromagnetic layer 2 be with a low saturation magnetization Ms, a high magnetic anisotropy energy Ku that is high enough to maintain a thermal stability factor Δ, and a coercive force, an anisotropic magnetic field and a Gilbert damping constant that are lower than those of the material used for theferromagnetic layer 8. Furthermore, it is desirable that the material show a high spin polarization. The following is the specific explanation thereof. - A first example of the
ferromagnetic layer 2 is formed of a MnGe alloy. MnxGey has a characteristic of a perpendicular magnetization film when the composition ratio x of Mn is in the range of 77 atm %≦x≦82 atm %, and the composition ratio y of Ge is in the range of 18 atm %≦y≦23 atm % (x+y=100 atom %). The magnetization of a MnGe alloy is oriented along a specific crystal orientation. By changing the forming conditions, it is possible to form a MnGe alloy with a coercive force, an anisotropic field and a Gilbert damping constant that are lower than those of a material used to form theferromagnetic layer 8. - A second example of the
ferromagnetic layer 2 is formed of, for example, an alloy containing one element selected from the group consisting of Mn, Fe, Co, and Ni, and two elements selected from the group consisting of Zn, Al, Ga, In, Si, Ge, Sn, As, Sb, and Bi. Specific examples are MnAlGe, MnGaGe, MnZnSb, and so on. - In order to cause the aforementioned materials to have perpendicular magnetic anisotropy, it is required that the c-axis be grown perpendicular to the film plane, i.e., grown to be (001) oriented. Specifically, by appropriately selecting the
base layer 100, it is possible to control the crystal orientation in the growth of theferromagnetic layer 2. The details of thebase layer 100 will be described later. - A third example of the
ferromagnetic layer 2 is formed of an alloy containing at least one metal selected from the group consisting of Fe and Co. Incidentally, in order to control the saturation magnetization of theferromagnetic layer 2, at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge may be added thereto. That is, theferromagnetic layer 2 can be formed of an alloy containing at least one element selected from the group consisting of Fe and Co, and at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge. For example, CoFeSi, CoFeP, CoFeW, CoFeNb, etc. may be used besides CoFeB. - It is preferable that the
ferromagnetic layer 8 have an easy magnetization axis in a direction perpendicular to the film plane, a low saturation magnetization Ms, a high magnetic anisotropy energy Ku that is high enough to maintain a thermal stability factor Δ, and a coercive force, an anisotropic magnetic field and a Gilbert damping constant that are higher than those of the material used for theferromagnetic layer 2. Furthermore, it is desirable that the material show a high spin polarization. A MnGe alloy magnetic material containing Mn and Ge is one of the material that meet such requirements. The following is the specific explanation thereof. - A specific example of the
ferromagnetic layer 8 is formed of a MnGe alloy. The characteristics of MnxGey as a perpendicular magnetization film appear when the composition ratio x of Mn is in the range of 77 atm %≦x≦82 atm %, and the composition ratio y of Ge is in the range of 18 atm %≦y≦23 atm % (x+y=100 atm %). - The magnetization of a MnGe alloy with a high crystal magnetic anisotropy is oriented along a specific crystal orientation. By changing the composition ratios and the crystallinity of the constituent elements, it is possible to control the degree of crystal magnetic anisotropy. Accordingly, it is possible to control the direction of magnetization by changing the direction of crystal growth. Furthermore, since a MnGe alloy itself has a high crystal magnetic anisotropy, it is possible to adjust the aspect ratio of the device with it. Moreover, since a MnGe alloy has a high thermal stability, it is suitable to be integrated.
- As examples,
FIGS. 8( a), 8(b) and 8(c) show the results of x-ray diffraction of MnGe (with the composition ratios of Mn being 79 atm %, and Ge being 21 atm %) formed on MgO (001), andFIG. 9 shows magnetization curves. The composition ratios given here are calculated by an analysis by ICP (Inductively Coupled Plasma). It is confirmed that by forming a MnGe film by heat treatment on MgO, the orientation of which is controlled, it is possible to form the MnGe film that is highly (001)-oriented (seeFIGS. 8( a), 8(b) and 8(c)). Furthermore, it is confirmed that the characteristics required for a reference layer have been met since the saturation magnetization Ms of MnGe thus obtained is as low as 97 emu/cc, and the effective perpendicular magnetic anisotropy energy Ku thereof is as high as 3.2×106 erg/cc (seeFIG. 9) . The graph g1 ofFIG. 9 shows the magnetization curve in the case where a magnetic field is applied in a direction parallel to the film plane of the MnGe film, and the graph g2 shows the magnetization curve in the case where a magnetic field is applied in a direction perpendicular to the film plane of the MnGe film. - The effect of a strayed magnetic field from a reference layer becomes more remarkable as an MTJ element is miniaturized. As a method of solving this problem, the introduction of a bias layer is effective. A detailed explanation of a bias layer will be provided later. According to a prestudy by calculation, assuming that the shape of an MTJ element is cylindrical (pillar shape), when the thickness of a reference layer is 6 nm, the allowable size (diameter size) in the miniaturization process of an MTJ element is about 38 nm when the saturation magnetization Ms of the reference layer is 1000 emu/cc, about 28 nm when Ms is 750 emu/cc, and about 20 nm when Ms is 500 emu/cc.
- From the above, it is desirable that in order to highly integrate an MTJ element having a diameter of 15 nm or less, a low Ms material of 200 emu/cc or less be used for a reference layer. In order to achieve this, MnxGey can be used for a reference layer. From
FIG. 9 , the saturation magnetization Ms of an MnGe alloy is as low as 97 emu/cc. Thus, it is more preferable that an MnGe alloy be used as a low Ms reference layer. - As the element size is decreased, the thermal stability of a ferromagnetic material constituting a magnetoresistive element deteriorates. As an option for solving this problem, the perpendicular magnetic anisotropy energy Ku can be improved. The effective perpendicular magnetic anisotropy energy Ku of a MnGe alloy obtained by a calculation using the values of saturation magnetization and anisotropic magnetic field obtained from
FIG. 9 is as high as 3.2×106 erg/cc. Thus, it is possible to use this alloy to form a reference layer that is superior in thermal stability. - From the foregoing viewpoints, it could be understood that a magnetic film formed of an MnGe alloy is a perpendicular magnetic film with a low saturation magnetization and a high perpendicular magnetic anisotropy energy, and is especially suitable to form a reference layer.
FIG. 10( a) shows the dependency of saturation magnetization of a MnGe alloy on the composition ratio, andFIG. 10( b) shows the dependency thereof on the substrate temperature. It could be confirmed fromFIGS. 10( a) and 10(b) that it is possible to control the saturation magnetization by selecting optimum composition ratio and substrate temperature. - In order to cause the perpendicular magnetic anisotropy energy to appear, the c-axis should be (001)-oriented, i.e., in the direction perpendicular to the film plane. Specifically, by appropriately selecting the tunnel barrier layer and the interface magnetic layer, the (001) orientation growth can be achieved.
- An example of the material of the
ferromagnetic layer 8 is an alloy containing MnxGey (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %) and 10 atm % or less of at least one element selected from the group consisting of Al, Si, B, C, P, Ti, Zn, Mg, Ca, Cr, and Ga. That is, if the aforementioned element is expressed as “X,” the alloy can be expressed as (MnxGey)100-zXz (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %, z≦10 atm %).FIG. 11 shows examples of the magnetization curve of a thin film obtained by adding 5 atm % of Al to MnGe formed on a thermally oxidized Si substrate. The graph g1 ofFIG. 11 shows the magnetization curve in the case where a magnetic field is applied in a direction parallel to the film plane of this ferromagnetic layer, and the graph g2 shows the magnetization curve in the case where a magnetic field is applied in a direction perpendicular to the film plane of the ferromagnetic layer. It could be confirmed fromFIG. 11 that MnGe with a slight amount of Al being added thereto is not easily affected by the base layer, and has a characteristic of a perpendicular magnetization film. Furthermore, it could be confirmed that the addition of a slight amount of a light element represented by Al, which has a low melting point and a high diffusing property, would effectively contribute to a further lowering of magnetization of perpendicular magnetic film. - In the case where the magnetoresistive element has an interface
magnetic layer 6 as in the second to the fourth embodiments, the interfacemagnetic layer 6 being formed of MnxGey (77 atm %≦x≦82 atm %, 18 atm %≦y≦23 atm %, x+y=100 atm %), the following materials can be used to form theferromagnetic layer 8. As a material of theferromagnetic layer 8, for example, a metal that has the (111) crystalline orientation of a face-centered cubic (FCC) structure or has the (0001) crystalline orientation of a hexagonal close-packed (HCP) structure, or a metal that can form an artificial lattice, or an alloy containing Mn and at least one element selected from the group consisting of Al, Ge, and Ga can be used. An example of a metal that has the (111) crystalline orientation of a FCC structure or the (0001) crystalline orientation of a HCP structure is an alloy containing at least one element selected from the first group consisting of Fe, Co, Ni, and Cu and at least one element selected from the second group consisting of Pt, Pd, Rh, and Au. Specifically, ferromagnetic alloys such as CoPd, CoPt, NiCo, NiPt, and the like can be used. Specific examples of alloy containing Mn and at least one element selected from the group consisting of Al, Ge, and Ga are ferromagnetic alloys such as MnGa, MnAlGe, and MnGaGe. - The artificial lattice to be used for the
ferromagnetic layer 8 has a structure in which layers each containing one or more elements selected from the group consisting of Fe, Co, and Ni or an alloy containing the one or more elements (ferromagnetic films) and layers each containing one element selected from the group consisting of Cr, Pt, Pd, Ir, Rh, Ru, Os, Re, Au, and Cu or an alloy containing the one element (nonmagnetic films) are alternately stacked. For example, Co/Pt artificial lattice, Co/Pd artificial lattice, CoCr/Pt artificial lattice, Co/Ru artificial lattice, Co/Os artificial lattice, Co/Au artificial lattice, Ni/Cu artificial lattice, and the like can be used. It is possible to adjust the magnetic anisotropy energy density and the saturation magnetization of such artificial lattices by adding an element to the ferromagnetic film, or by adjusting the ratio of thicknesses between the ferromagnetic film and the nonmagnetic film. - Furthermore, the material of the
ferromagnetic layer 8 can be an alloy containing at least one element selected from the group consisting of transition metals Fe, Co, and Ni, and at least one element selected from the group consisting of rare earth metals Tb, Dy, and Gd. Examples are TbFe, TbCo, TbFeCo, DyTbFeCo, GdTbCo and the like. Furthermore, a multi-layer structure in which these alloys are alternately stacked can be employed. Specific examples are multi-layer films of TbFe/Co, TbCo/Fe, TbFeCo/CoFe, DyFe/Co, DyCo/Fe, DyFeCo/CoFe, and the like. It is possible to adjust the magnetic anisotropy energy density and the saturation magnetization of these alloys by adjusting the thickness ratio or composition. - Moreover, a material used to form the
ferromagnetic layer 8 can be an alloy containing one or more elements selected from the first group consisting of Fe, Co, Ni, and Cu and one or more elements selected from the second group consisting of Pt, Pd, Rh, and Au. Specific examples are ferromagnetic alloys of FeRh, FePt, FePd, CoPt, and the like. - The
base layer 100 is used to control the crystallinity such as crystalline orientation, grain size, etc. of theferromagnetic layer 2 and the layers above theferromagnetic layer 2. Accordingly, the selection of the material of thebase layer 100 is important. Hereinafter, the material and the structure of thebase layer 100 will be explained. Incidentally, although both conductive and insulating materials can be used to form a base layer, if a current should flow through the base layer, it is preferable that a conductive material be used. - A first example of the
base layer 100 is a layer of nitride having a (001) oriented NaCl structure and containing at least one element selected from the group consisting of Ti, Zr, Nb, V, Hf, Ta, Mo, W, B, Al, and Ce. - A second example of the
base layer 100 is a (002) oriented perovskite conductive oxide layer of ABO3. The A-site contains at least one element selected from the group consisting of Sr, Ce, Dy, La, K, Ca, Na, Pb, and Ba, and the B-site contains at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Nb, Mo, Ru, Ir, Ta, Ce, and Pb. - A third example of the
base layer 100 is a layer of oxide having a (001) oriented NaCl structure and containing at least one element selected from the group consisting of Mg, Al, and Ce. - A fourth example of the
base layer 100 is a layer having a (001) oriented tetragonal or cubic structure and containing at least one element selected from the group consisting of Al, Cr, Fe, Co, Rh, Pd, Ag, Ir, Pt, Au, Mo, and W. - A fifth example of the
base layer 100 is a layer having a stacked structure with a combination of two or more of the layers of the above first to fourth examples. Thus, by devising the structure of the base layer as mentioned above, it is possible to control the crystallinity of theferromagnetic layer 2 and the layers above theferromagnetic layer 2, thereby improving the magnetic characteristics. - The
nonmagnetic layer 4 can have a conductive or insulating property. However, it is preferable that a tunnel barrier layer of an insulating material be used. With respect to thenonmagnetic layer 4, it is possible to achieve a selective tunnel conduction and a high MR ratio by appropriately combining thenonmagnetic layer 4 with the adjacent ferromagnetic layer or interface magnetic layer. Accordingly, the selection of the material of thenonmagnetic layer 4 is important. Hereinafter, the material for forming thenonmagnetic layer 4 will be explained. - As a material of a tunnel barrier layer, an oxide containing at least one element selected from the group consisting of Mg, Ca, Ba, Al, Be, Sr, Zn, Ti, V, and Nb can be considered. Specific examples are MgO, AlO, ZnO, SrO, BaO, TiO, and the like. In particular, an oxide with a crystal structure of NaCl structure is preferable. Specific examples thereof are MgO, CaO, SrO, BaO, TiO, VO, NbO, and the like. If crystal growth of such an oxide with NaCl structure is performed on a (001) surface of any of Fe, Co, and Ni, or an alloy containing two or more of these elements as main ingredients, or any of metals having a body-centered tetragonal structure with preferred orientation of (001), or an alloy containing two or more of such metals as main ingredients, or a MnGe alloy, the crystal growth can be performed easily with the (001) surface being a preferred orientation surface. In particular, it is possible to achieve preferred orientation of (001) surface if crystal growth is performed on a CoFe—X amorphous alloy, which includes a very small amount of B, C, N, Ti, Ta, P, Mo, Si, W, Nb, and the like to improve the amorphous property. Here, X indicates an added element such as B, C, N, and the like.
- The tunnel barrier layer can be of a mixed crystal containing two or more materials selected from the aforementioned group of oxides, or have a stacked structure with layers of such oxides. Examples of such a mixed crystal are MgAlO, MgZnO, MgTiO, MgCaO, and the like. Examples of the materials of a two-layer stacked structure are MgO/ZnO, MgO/AlO, TiO/AlO, MgAlO/MgO, and the like. Examples of the materials of a three-layer stacked structure are AlO/MgO/AlO, ZnO/MgO/ZnO, MgAlO/MgO/MgAlO, and the like.
- A second example of the tunnel barrier layer is a (002) oriented perovskite oxide of ABO3. Here, the A-site contains at least one element selected from the group consisting of Sr, Ce, Dy, La, K, Ca, Na, Pb, and Ba, and the B-site contains at least one element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Ga, Nb, Mo, Ru, Ir, Ta, Ce, and Pb. The specific examples are SrTiO3, SrRuO3, SrNbO3, BaTiO3, PbTiO3, and the like. The lattice constant of the [100] plane of each of these oxides is about 3.7 Å-4.0 Å, which is close to the lattice constant of about 3.8 Å of the [100] plane of a MnGe alloy. Accordingly, these oxides are suitable for forming an interface with good quality to obtain a higher MR ratio.
- A third example of the tunnel barrier layer is a spinel oxide of MgAlO. The lattice constant of MgAl2O4 having the spinet structure is about 4.05 Å, the lattice mismatch of which relative to the lattice constant of the [100] plane of a MnGe alloy, which is about 3.8 Å, is as small as 6.6%. Accordingly, this material is suitable for forming an interface with good quality to obtain a higher MR ratio.
- The tunnel barrier layer can be formed of either a crystalline or amorphous material. However, if the tunnel barrier layer is formed of a crystalline material, the scattering of electrons in a tunnel barrier is curbed, resulting in that the probability would increase that the electrons would be selectively conducted by tunneling from the ferromagnetic layer with the wavenumber thereof being maintained. Accordingly, it is possible to increase the MR ratio. Therefore, in order to obtain a higher MR ratio, a crystalline tunnel barrier is preferable.
- For example, when an MTJ element has a stacked structure including a ferromagnetic layer of CoFe(B), a nonmagnetic layer of crystalline MgO, and a ferromagnetic layer of MnGe, which layers are stacked in this order, an orientation relationship of MnGe(001)/MgO(001)/CoFe(B)(001) can be established. As a result, it is possible to improve the wavenumber selectivity of tunnel electrons, and to obtain a higher MR ratio. However, the lattice mismatch obtained from the bulk lattice constants of MnGe and MgO in the in-plane direction is as high as about 11.0%. The lattice mismatch is defined by the following expression:
-
(a(MgO)−a(MnGe))/a(MnGe)×100 - where a(MgO) and a(MnGe) are the lattice constants of MgO and MnGe in the in-plane direction of the film, respectively. If a lattice mismatch is large, a dislocation or the like is caused at the interface in order to reduce the interface energy generated by lattice distortion. In this case, an epitaxial relationship is established between crystal grains, and it is difficult to perform a uniform epitaxial growth in the film plane. When a current is caused to flow through an MTJ element, a dislocation works as a source of the scattering of electrons, and the MR ratio is decreased. Therefore, in order to perform a uniform epitaxial growth in the film plane without causing a dislocation, it is important to form a stacked structure using materials with smaller lattice mismatch. Accordingly, from the viewpoint of lattice mismatch, a perovskite oxide, a spinel oxide, a NaCl structure oxide, with the preference set in this order, are suitable materials for forming a nonmagnetic layer.
- Both the interface
magnetic layer 3 and the interfacemagnetic layer 6 are perpendicular magnetization films. In order to meet the requirements of a high thermal stability and a low-current magnetization switching, it is preferable that these layers be formed of a material with a low saturation magnetization Ms, a high magnetic anisotropy energy Ku to maintain a thermal stability factor Δ, and a high spin polarization. An example of such a material meeting the aforementioned requirements is a MnGe alloy magnetic material containing Mn and Ge. This material will be specifically explained below. - Specific examples of the interface
magnetic layer 3 and the interfacemagnetic layer 6 are formed of a MnGe alloy. The characteristic of MnxGey as a perpendicular magnetization film appears when the composition ratio x of Mn is in the range of 77 atm %≦x≦82 atm %, and the composition ratio y of Ge is in the range of 18 atm %≦y≦23 atm %. In order to cause perpendicular magnetic anisotropy energy to appear, it is necessary that the c-axis is grown in the direction perpendicular to the film plane, i.e., (001) oriented. Specifically, it is possible to control the crystalline orientation of theferromagnetic layer 2 and the interfacemagnetic layer 3 by appropriately selecting the material of thebase layer 100. Furthermore, it is possible to control the crystalline orientation of the interfacemagnetic layer 6 and theferromagnetic layer 8 by appropriately selecting the material of thenonmagnetic layer 4. - Generally, there is a correlation between a Gilbert damping constant and a magnitude of spin-orbit interaction of a material. A material having a higher atomic number has greater spin-orbit interaction, and a higher Gilbert damping constant. Since MnGe is a material formed of light elements, it is expected that the Gilbert damping constant thereof is low. Accordingly, the energy required for magnetization switching thereof is low. Therefore, the current density for magnetization reversal by spin polarized electrons can be considerably reduced. Thus, MnGe can be effectively applied to the interface
ferromagnetic layer 3. - As examples,
FIG. 12( a) shows the band structures of a bulk MnGe alloy, which are obtained by calculation.FIG. 12( b) shows the density of states thereof. It could be understood fromFIG. 12( a) that in the Majority state, the M band crosses the Fermi energy EF while in the Minority state, the M band does not cross the Fermi energy EF. This means that the spin of the electrons moving in the c-axis direction is completely polarized. FromFIG. 12( b), the spin polarization P could be estimates as −78% and the saturation magnetization Ms could be estimated as 183 emu/cc. Thus, it is understood that such a material is suitable to form an interface magnetic layer of a storage layer or reference layer. - A second example of the interface
magnetic layer 3 and the interfacemagnetic layer 6 can be formed of, for example, an alloy containing one element selected from the group consisting of Mn, Fe, Co, and Ni, and two elements selected from the group consisting of Zn, Al, Ga, In, Si, Ge, Sn, As, Sb, and Bi. Specifically, MnAlGe, MnGaGe, MnZnSb, and the like can be used. - A third example of the interface
magnetic layer 3 and the interfacemagnetic layer 6 can be formed of, for example, an alloy containing at least one metal selected from the group consisting of Fe and Co. For example, it is desirable that the interfacemagnetic layer 6 be formed of an alloy containing at least one metal selected from the group consisting of Fe and Co. For example, when an interface magnetic layer of CoFe, a nonmagnetic layer of MgO, and an interface magnetic layer of CoFe are stacked, it is possible to establish the orientation relationship of CoFe(001)/MgO(001)/CoFe(001). In such a case, it is possible to improve the wavenumber selectability of tunnel electrons, resulting in that it is possible to obtain a high MR ratio. Incidentally, in order to control the saturation magnetizations of the interfacemagnetic layer 3 and the interfacemagnetic layer 6, it is possible to add at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge thereto. That is to say, the interfacemagnetic layer 3 and the interfacemagnetic layer 6 can be formed of an alloy containing at least one element selected from the group consisting of Fe and Co, and at least one element selected from the group consisting of Ni, B, C, P, Ta, Ti, Mo, Si, W, Nb, Mn, and Ge. For example, CoFeSi, CoFeP, CoFeW, CoFeNb, and the like, besides CoFeB, can be such an alloy. These alloys have a spin polarization equivalent to that of CoFeB. Furthermore, a Heusler alloy such as Co2FeSi, Co2MnSi, Co2MnGe and the like can be used. A Heusler alloy has a spin polarization equivalent to or higher than that of CoFeB. Accordingly, a Heusler alloy is suitable as a material of the interface magnetic layers. - Furthermore, a fourth example of the interface
magnetic layer 3 and the interfacemagnetic layer 6 can be formed of a MnAl alloy, for example. Since a MnAl alloy is formed of light metals, the Gilbert damping constant thereof is low, resulting in that the energy required for magnetization switching would be low. Accordingly, it is possible to considerably reduce the current density for switching magnetization by means of spin polarized electrons. Moreover, since a MnAl alloy has an energy gap relative to either the spinband of up-spin or the spinband of down-spin in the (001) direction, it has a half-metallic characteristic and a high spin polarization, resulting in that it is possible to obtain a high MR ratio. - Since it is possible to obtain a high MR ratio as long as the interface
magnetic layer 3 and the interfacemagnetic layer 6 are epitaxially grown against thenonmagnetic layer 4, the interfacemagnetic layer 3 and the interfacemagnetic layer 6 contacting thenonmagnetic layer 4 can expand or shrink in the direction perpendicular to the film plane. - Next, a magnetic memory (MRAM) of spin transfer torque writing type according to a fifth embodiment will be explained below.
- The MRAM according to this embodiment includes a plurality of memory cells.
FIG. 13 is a sectional view of the main part of a memory cell of the MRAM according to this embodiment. Each memory cell has a magnetoresistive element according to any of the first to the fourth embodiments as a storage element. In the explanation of the fifth embodiment, the storage element is assumed to be the magnetoresistive element (MTJ element) 1 of the first embodiment. - As shown in
FIG. 13 , the top surface of theMTJ element 1 is connected to abit line 32 via anupper electrode 31. Furthermore, the bottom surface of theMTJ element 1 is connected to adrain region 37 a of source/drain regions of a surface of asemiconductor substrate 36 via alower electrode 33, a leadingelectrode 34, and aplug 35. Thedrain region 37 a constitutes a selection transistor Tr with asource region 37 b, agate insulating film 38 formed on thesubstrate 36, and agate electrode 39 formed on thegate insulating film 38. The selection transistor Tr and theMTJ element 1 constitute one memory cell of the MRAM. Thesource region 37 b is connected to anotherbit line 42 via aplug 41. Incidentally, it is possible to exclude the leadingelectrode 34, to provide theplug 35 below thelower electrode 33, and to connect thelower electrode 33 theplug 35 directly. The bit lines 32 and 42, theelectrodes electrode 34, and theplugs - In the MRAM according to this embodiment, a plurality of memory cells, each being the one shown in
FIG. 13 , are arranged in a matrix form, thereby forming a memory cell array of the MRAM.FIG. 14 is a circuit diagram showing the main part of the MRAM according to this embodiment. -
FIG. 14 shows that a plurality ofmemory cells 53 each including anMTJ element 1 and a selection transistor Tr are arranged in a matrix form. One end of each of thememory cells 53 in the same column is connected to thesame bit line 32, and the other is connected to thesame bit line 42. The gate electrodes (word line) 39 of the selection transistors Tr of thememory cells 53 belonging to the same row are mutually connected, and further connected to arow decoder 51. - The
bit line 32 is connected to a current source/sink circuit 55 via aswitching circuit 54 such as a transistor. Furthermore, thebit line 42 is connected to a current source/sink circuit 57 via aswitching circuit 56 such as a transistor. The current source/sink circuits - The
bit line 42 is also connected to aread circuit 52. Theread circuit 52 can be connected to thebit line 32. Theread circuit 52 includes a read current circuit, a sense amplifier, and the like. - In a write operation, by turning on the switching
circuits sink circuits - With respect to the write speed, it is possible to perform the spin transfer writing with a current having a pulse width from a few nanoseconds to a few microseconds.
- In a read operation, a read current that is low enough to prevent magnetization switching is supplied to the
MTJ element 1 specified in the same manner as the write operation. Theread circuit 52 determines the resistance state of theMTJ element 1 by comparing a current value or voltage value, which is derived from the resistance value that depends on the magnetization state of theMTJ element 1, with a reference value. - Incidentally, it is preferable that the current pulse width in a read operation be narrower than that in a write operation. In this manner, the occurrences of writing errors caused by a current in a read operation can be reduced. This is based on the fact that the narrower the pulse width of a write current is, the higher the absolute value of the write current becomes.
- As described above, according to this embodiment, it is possible to obtain a magnetic memory using a magnetoresistive element with a low saturation magnetization and a high perpendicular magnetic anisotropy energy.
- While certain embodiments have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the inventions. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems described herein may be made without departing from the spirit of the inventions. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fail within the scope and spirit of the inventions.
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