CN102364618B - Multilayer film material with vertical magnetic anisotropy - Google Patents

Multilayer film material with vertical magnetic anisotropy Download PDF

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CN102364618B
CN102364618B CN 201110354377 CN201110354377A CN102364618B CN 102364618 B CN102364618 B CN 102364618B CN 201110354377 CN201110354377 CN 201110354377 CN 201110354377 A CN201110354377 A CN 201110354377A CN 102364618 B CN102364618 B CN 102364618B
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film material
thickness
mgo
magnetic anisotropy
cofeb
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CN102364618A (en
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刘涛
蔡建旺
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Institute of Physics of CAS
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Abstract

The invention relates to a multilayer film material with vertical magnetic anisotropy. The multilayer film material comprises a basal piece, a core buffer layer, an amorphous ferromagnetic layer and an oxide barrier layer. In the multilayer film material with a 'CoFeB/MgO' interface and the vertical magnetic anisotropy, Ta in a 'Ta/CoFeB/MgO' structure is replaced by Mo or Hf, so the vertical magnetic anisotropy of a system is increased by about 22 percent or 37 percent respectively. Besides, for a 'Mo/CoFeB/MgO' system, the thermal stability is also greatly enhanced, and after two hours of annealing at 400 DEG C, the vertical magnetic anisotropy of the system is still stable and unchanged, so the application value is promoted, and the multilayer film material can be applied to vertical magnetic tunnels.

Description

A kind of multi-layer film material with perpendicular magnetic anisotropic
Technical field
The present invention relates to a kind of composite material with enhancing " CoFeB/MgO " interface perpendicular magnetic anisotropy performance.
Background technology
Because have high magnetic resistivity, magnetic tunnel-junction receives much concern always.Usually, the magnetic moment of the ferromagnetic electrode of magnetic tunnel-junction is parallel to face, is referred to as magnetic tunnel-junction in the face.But, the magnetic channel (hereinafter to be referred as vertical tunnel junction) that has a perpendicular magnetic anisotropic ferromagnetic electrode was considered to be used for realizing high-density nonvolatile memory-magnetic RAM of future generation (MRAM) in recent years.This mainly is because with respect to magnetic tunnel-junction in the face, and vertical tunnel junction: can overcome the edge effect under the small scale, magnetic resistivity is larger, signal to noise ratio is higher; Anisotropy energy is larger, and heat resistanceheat resistant disturbance ability is stronger, superparamagnetic dimension limit is less, so the density of device can do more more reliable; Critical reset current has reduced one comparatively speaking with the relevant amount of magnetostatic energy, therefore can be less.The common multi-layer film material with perpendicular magnetic anisotropic has: transition-rare earth alloy (such as TbFeCo, GdFeCo etc.), L10 phase (Co, Fe)-(Pt, Pd) alloy, and Co/ (Pd, Pt, Ni) multilayer film.But these materials all do not reach the requirement of application, and main cause has: poor heat stability or preparation condition are harsh; Perpendicular magnetic anisotropy can be large not; Crystal structure and barrier layer MgO(001) do not mate so that the magnetoelectricity resistance is too little; And magneto damped coefficient is too large so that critical reset current value is large.The people such as S.Ikeda [S. Ikeda et al, Nature Mater. 9,721 (2010)] propose a kind of new multi-layer film material Ta/CoFeB/MgO with magnetic perpendicular magnetic anisotropy.This system utilize CoFeB/MgO Interface Anisotropy at the interface can overcome demagnetization can impact, thereby so that the magnetic moment of ferromagnetic layer CoFeB perpendicular to face; It is emphasized that the Ta layer is considered to be conducive to the perpendicular magnetic anisotropy of CoFeB, perpendicular magnetic anisotropy CoFeB film all be unable to do without Ta neighbour layer [D. C. Worledge et al, Appl. Phys. Lett. 98,022501 (2011)] so far.With respect to the vertical magnetism anisotropic film of above three kinds of routines, the Ta/CoFeB/MgO structure is conveniently used in the MgO magnetic tunnel-junction, and the preparation method is simple; And, this system is through after the simple annealing in process, the crystal structure of ferromagnetic electrode CoFeB and barrier layer MgO mates (be respectively bcc (001) and fcc (100), mismatch is less than 4%) very much, and the tunnel that therefore utilizes this system to prepare has very high magnetic resistivity; Thereby the little critical reset current value of CoFeB magneto damped coefficient is little simultaneously.Yet, the perpendicular magnetic anisotropic of this system that not enough is can or too little, to such an extent as to along with the thickness of CoFeB increases to when only having about 1.5 nm, its magnetic moment has just been got back in the face from vertical direction.Moreover, W. G. Wang [W. G. Wang et al, Appl. Phys. Lett. 99,102502 (2011)] etc. the people find that Ta/CoFeB/MgO system perpendicular magnetic anisotropic after tens of second by annealing more than 300 ℃ can will descend rapidly.This will be fatal undoubtedly, because reduce simultaneously the surface resistivity tied for the magnetoelectricity resistance that increases magnetic tunnel-junction, tunnel junction need to be annealed under the above temperature of 350 degree usually guarantee the good crystallization of barrier layer MgO.
Summary of the invention
For the existing problem of the multi-layer film material that has perpendicular magnetic anisotropic in the prior art, the invention discloses a kind of novel multi-layer film material with perpendicular magnetic anisotropic, this material has increased perpendicular magnetic anisotropic energy and thermal stability by adopting Mo or Hf as the core cushioning layer material.
For achieving the above object, of the present invention 1, a kind of multi-layer film material with perpendicular magnetic anisotropic is characterized in that described multi-layer film material is from the bottom to top: substrate, core resilient coating, amorphous iron magnetosphere and oxide barrier layer.
Further, the material of described substrate is the material of silicon, glass or other stable chemical performance and surfacing.
Further, the material of described core resilient coating is Mo or Hf; Thickness is 0.5-200 nm.
Further, it is amorphous Co, Fe, B three metaclass alloys that the material of described amorphous iron magnetosphere prepares under the attitude, or other non-crystal class ferromagnetic material.The thickness of this amorphous iron magnetosphere is 0.5-10 nm.
Further, the material of described oxide barrier layer is MgO; The thickness of this oxide barrier layer is 0.5-10 nm.
A kind of multi-layer film material with perpendicular magnetic anisotropic, described multi-layer film material is provided with from the bottom to top: substrate, oxide barrier amorphous iron magnetosphere and core protective layer.
Further, the material of described substrate is the material of silicon, glass or other stable chemical performance and surfacing.
Further, the material of described core protective layer is Mo or Hf; Thickness is 0.5-200 nm.
Further, it is amorphous Co, Fe, B three metaclass alloys that the material of described amorphous iron magnetosphere prepares under the attitude, or other non-crystal class ferromagnetic material.The thickness of this amorphous iron magnetosphere is 0.5-10 nm.
Further, the material of described oxide barrier layer is MgO; The thickness of this oxide barrier layer is 0.5-10 nm.
The multi-layer film material of this " CoFeB/MgO " interface perpendicular magnetic anisotropy among the present invention, this material is by the Ta in " Ta/CoFeB/MgO " structure is replaced with Mo or Hf, so that the perpendicular magnetic anisotropic of system can increase respectively about 22% and 37%.And for " Mo/CoFeB/MgO " system, thermal stability also strengthens greatly, can still stablize through its perpendicular magnetic anisotropy after 400 ℃ of annealing in two hours constant, thereby using value is promoted, and this material be may be used in the vertical magnetic channel.
Description of drawings
A kind of structural representation with magnetic perpendicular magnetic anisotropy multi-layer film material of Fig. 1 for using method provided by the invention to obtain;
The another kind of structural representation with magnetic perpendicular magnetic anisotropy multi-layer film material of Fig. 2 for using method provided by the invention to obtain;
Fig. 3 shows multi-layer film material among the embodiment 1 at the magnetization curve perpendicular to the face direction;
Fig. 4 shows multi-layer film material among the embodiment 1 at the magnetization curve that is parallel to the face direction;
Fig. 5 shows the Kt of the multi-layer film material among the embodiment 1 with the variation of t;
Fig. 6 shows embodiment 4 samples perpendicular to face be parallel to the magnetization curve of face direction.
Embodiment
Embodiment 1:
The present embodiment is the multi-layer film material that the first of using method provided by the invention to obtain has perpendicular magnetic anisotropic, and as shown in Figure 1, its structure be from the bottom to top order setting: the silicon chip 1 of thermal oxidation; Mo core resilient coating 2, its thickness are 5nm; Co 40Fe 40B 20 Amorphous iron magnetosphere 3, its thickness are 0.6 nm-1.8nm; MgO oxide barrier layer 4, its thickness are 2 nm.
The preparation method of the perpendicular magnetic anisotropy multi-layer film material of the present embodiment is: adopt the method for magnetron sputtering, base vacuum is better than 5 * 10 -5Pa, as sputter gas, sputtering pressure is 0.5 Pa with Ar gas, deposits successively each tunic of perpendicular magnetic anisotropy multi-layer film material on the Si of surface oxidation sheet.Wherein, after deposition is finished, with the vacuum annealing two hours under 300 degree of perpendicular magnetic anisotropy multi-layer film material.
Fig. 3 and 4 has provided respectively part typical sample in the present embodiment multi-layer film material perpendicular to face be parallel to the magnetization curve of face direction.Multi-layer film material shows obvious perpendicular magnetic anisotropy as we can see from the figure, and along with Co 40Fe 40B 20The reduction of thickness and increasing.Work as Co 40Fe 40B 20Thickness when being 1.3 nm, perpendicular magnetic anisotropy can be enough to overcome the demagnetization energy, thereby so that the easy axle of magnetic moment perpendicular to face.And " Ta/CoFeB/MgO " multi-layer film material that adopts same method to prepare, " the Mo core resilient coating 2 " that be about in the present embodiment change Ta into, as a result Co 40Fe 40B 20Only magnetic moment could be perpendicular to face during less than 1.1nm at thickness.Obviously, the multi-layer film material that provides in the present embodiment has higher perpendicular magnetic anisotropy energy than " Ta/CoFeB/MgO " system that usually adopts at present.The perpendicular magnetic anisotropy of " Mo/CoFeB/MgO " and " Ta/CoFeB/MgO " multi-layer film material can all derive from " CoFeB/MgO " Interface Anisotropy energy at the interface, and this Interface Anisotropy can size can cut square from their Y-axis of Kt-t curve and obtain [M. T. Johnson et al, Rep. Prog. Phys. 59,1409 (1996)].Here K is the perpendicular magnetic anisotropy constant, works as Co 40Fe 40B 20For just (bearing), it equals Co to magnetic moment during perpendicular to (being parallel to) face 40Fe 40B 20Be parallel to (perpendicular to) saturation field of the magnetization curve of face and saturation magnetization product 1/2; T is Co 40Fe 40B 20Thickness.Fig. 5 has provided the Kt-t curve of above two multi-layer film materials.Can obtain from figure: substitute after the Ta that commonly uses at present with the Mo resilient coating, " CoFeB/MgO " Interface Anisotropy at the interface can be by 1.7erg/cm 22.08 erg/cm have been increased to 2, increased by 22%.
Also need to prove: the interface perpendicular magnetic anisotropy of CoFeB/MgO is also closely related with the composition of CoFeB, thereby when adopting CoFeB research " Ta/CoFeB/MgO " perpendicular magnetic anisotropy of heterogeneity, the thickness limit that the CoFeB film magnetic moment that each seminar obtains can hang down is different: S.Ikeda adopts Co 20Fe 60B 20The time thickness limit be 1.4 nm[S. Ikeda et al, Nature Mater. 9,721 (2010]; D. the people such as C. Worledge adopts Co 60Fe 20B 20The time thickness limit be 1 nm[D. C. Worledge et al, Appl. Phys. Lett. 98,022501 (2011)]; And we adopt Co 40Fe 40B 20The thickness limit that obtains then is 1.1 nm.In any case but the Mo layer should have similar enhancement effect to the perpendicular magnetic anisotropy of the CoFeB film of other composition in principle.
Embodiment 2:
Multi-layer film structure in the present embodiment is substantially the same manner as Example 1, and its structure is from the bottom to top: the silicon chip 1 of thermal oxidation; Mo core resilient coating 2, its thickness are 5nm; Co 40Fe 40B 20 Amorphous iron magnetosphere 3, its thickness are 0.6nm-1.8nm; MgO oxide barrier layer 4, its thickness are 2nm.
The preparation method of the perpendicular magnetic anisotropy multi-layer film material of the present embodiment is: adopt the method for magnetron sputtering, base vacuum is better than 5 * 10 -5Pa, as sputter gas, sputtering pressure is 0.5 Pa with Ar gas, deposits successively each tunic of perpendicular magnetic anisotropy multi-layer film material on the Si of surface oxidation sheet.After deposition is finished, with the vacuum annealing two hours under 400 degree of perpendicular magnetic anisotropy multi-layer film material.
The magnetic property of the present embodiment multi-layer film material is compared basic identical with the multi-layer film material of embodiment 1, specifically: Co 40Fe 40B 20Magnetic moment still is 1.3 nm by the thickness that turns to vertical direction in the face, and " CoFeB/MgO " Interface Anisotropy at the interface can still be 2.1erg/cm 2About.That is to say that the annealing temperature in the performance of " Mo/CoFeB/MgO " vertical multi-layer membrane material good thermal stability, particularly the present embodiment is 400 degree, exceeded needed 350 degree of MgO tunnel junction.And for " Ta/CoFeB/MgO " multi-layer film material, " the Mo core resilient coating 2 " that be about in the present embodiment change into after the Ta, after 350 times degree are only annealed half an hour, to such an extent as to the perpendicular magnetic anisotropy of system can be just rapid Co under any thickness of decline 40Fe 40B 20Magnetic moment all be parallel to face, the people's such as this result and W. G. Wang result basically identical [W. G. Wang et al, Appl. Phys. Lett. 99,102502 (2011)].
Embodiment 3:
The multi-layer film material with perpendicular magnetic anisotropic in the present embodiment, its structure is substantially the same manner as Example 1, is from the bottom to top: the silicon chip 1 of thermal oxidation; H fCore resilient coating 2, its thickness are 5nm; Co 40Fe 40B 20 Amorphous iron magnetosphere 3, its thickness are 0.6nm-1.8nm; MgO oxide barrier layer 4, its thickness are 2nm.
The preparation method of the perpendicular magnetic anisotropy multi-layer film material of the present embodiment is: adopt the method for magnetron sputtering, base vacuum is better than 5 * 10 -5Pa uses A rGas is as sputter gas, and sputtering pressure is 0.5 Pa, deposits successively each tunic of perpendicular magnetic anisotropy multi-layer film material on the Si of surface oxidation sheet.After deposition is finished, with the vacuum annealing two hours under 300 degree of perpendicular magnetic anisotropy multi-layer film material.
Similar to Example 1, the result of the perpendicular magnetic anisotropy multi-layer film material " Hf/CoFeB/MgO " in the present embodiment is compared as can be known with normally used " Ta/CoFeB/MgO ": substitute after the Ta that commonly uses at present with the Hf resilient coating, " CoFeB/MgO " Interface Anisotropy at the interface can be increased to 2.34 erg/cm by 1.7erg/cm2 2, increased by 37%, thus so that Co 40Fe 40B 20Magnetic moment can be increased to 1.5nm by original 1.1nm perpendicular to the thickness limit of face.
Embodiment 4:
The present embodiment has the multi-layer film material of perpendicular magnetic anisotropic for the second that uses method provided by the invention to obtain, as shown in Figure 2, its concrete structure is from the bottom to top: the silicon chip 1 of thermal oxidation; MgO oxide barrier layer 4, its thickness are 5 nm; Co 40Fe 40B 20 Amorphous iron magnetosphere 3, its thickness are 1.2 nm; Mo core protective layer 5, its thickness are 5 nm.
The preparation method of the perpendicular magnetic anisotropy multi-layer film material of the present embodiment is: adopt the method for magnetron sputtering, base vacuum is better than 5 * 10 -5Pa, as sputter gas, sputtering pressure is 0.5 Pa with Ar gas, deposits successively each tunic of perpendicular magnetic anisotropy multi-layer film material on the Si of surface oxidation sheet.After deposition is finished, with the vacuum annealing two hours under 300 degree of perpendicular magnetic anisotropy multi-layer film material.
Fig. 6 has provided the present embodiment perpendicular magnetic anisotropy film perpendicular to face be parallel to the magnetization curve of face direction.As we can see from the figure: reveal obvious magnetic easy axis feature at the curve table perpendicular to the face direction--square remanent magnetism rate is 1 substantially, the curve that is parallel to the face direction then shows obvious hard axis magnetization characteristic--and linear remanent magnetism rate is zero substantially, that is to say that the easy magnetizing axis of multi-layer film material is perpendicular to face.
Embodiment 5:
Basic identical among the multi-layer film material with perpendicular magnetic anisotropic in the present embodiment and the embodiment 4, concrete structure is from the bottom to top: the silicon chip 1 of thermal oxidation; MgO oxide barrier layer 4, its thickness are 5 nm; Co 40Fe 40B 20 Amorphous iron magnetosphere 3, its thickness are 1.2 nm; Hf core protective layer 5, its thickness are 5 nm.
The preparation method of the perpendicular magnetic anisotropy multi-layer film material of the present embodiment is: adopt the method for magnetron sputtering, base vacuum is better than 5 * 10 -5Pa, as sputter gas, sputtering pressure is 0.5 Pa with Ar gas, deposits successively each tunic of perpendicular magnetic anisotropy multi-layer film material on the Si of surface oxidation sheet.After deposition is finished, with the vacuum annealing two hours under 300 degree of perpendicular magnetic anisotropy multi-layer film material.
Similar with the result of embodiment 4, the multi-layer film material that the present embodiment provides has perpendicular magnetic anisotropic, and its direction of easy axis is perpendicular to face.
Certainly; given each layer thickness and the composition of alloy material only are the examples that provides as preferred embodiment among above all embodiment; according to concrete application; can appropriate change; the thickness of each tunic can be selected according to actual conditions in following scope: the thickness of core resilient coating/protective layer is 0.5-200 nm; the thickness of amorphous iron magnetosphere is 0.5-10 nm, and the thickness of oxide barrier layer is 0.5-10 nm.In addition, what pay special attention to is: as implement 1 last narrate, although the composition of the CoFeB among the above embodiment is Co 40Fe 40B 20, but in principle, Mo or Hf layer should have similar enhancement effect to the perpendicular magnetic anisotropy of the CoFeB film of other composition.
It should be noted last that, above embodiment is only unrestricted in order to technical scheme of the present invention to be described.Although with reference to embodiment the present invention is had been described in detail, those of ordinary skill in the art is to be understood that, technical scheme of the present invention is made amendment or is equal to replacement, do not break away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.

Claims (2)

1. the multi-layer film material with perpendicular magnetic anisotropic is characterized in that, described multi-layer film material is from the bottom to top: substrate, core resilient coating, amorphous iron magnetosphere and oxide barrier layer; The material of described substrate is silicon or glass; The material of described core resilient coating is Mo or Hf, and thickness is 0.5-200 nm; It is amorphous Co, Fe, B three metaclass alloys that the material of described amorphous iron magnetosphere prepares under the attitude; The thickness of this amorphous iron magnetosphere is 0.5-10 nm; The material of described oxide barrier layer is MgO; The thickness of this oxide barrier layer is 0.5-10 nm.
2. the multi-layer film material with perpendicular magnetic anisotropic is characterized in that, described multi-layer film material is provided with from the bottom to top: substrate, oxide barrier layer, amorphous iron magnetosphere and core protective layer; The material of described substrate is silicon or glass; The material of described core protective layer is Mo or Hf, and thickness is 0.5-200 nm; It is amorphous Co, Fe, B three metaclass alloys that the material of described amorphous iron magnetosphere prepares under the attitude; The thickness of this amorphous iron magnetosphere is 0.5-10 nm; The material of described oxide barrier layer is MgO; The thickness of this oxide barrier layer is 0.5-10 nm.
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US9214624B2 (en) * 2012-07-27 2015-12-15 Qualcomm Incorporated Amorphous spacerlattice spacer for perpendicular MTJs
CN103956249B (en) * 2014-04-03 2017-06-30 中国科学院物理研究所 A kind of artificial antiferromagnetic coupling multi-layer film material of perpendicular magnetic anisotropy
CN109164145A (en) * 2018-08-10 2019-01-08 武汉钢铁有限公司 The anisotropic evaluation method of silicon steel material and characterizing method
CN109830597A (en) * 2019-01-11 2019-05-31 中国科学院物理研究所 A kind of vertical magnetism tunnel knot multi-layer film structure and preparation method thereof, storage unit
CN110927636A (en) * 2019-11-27 2020-03-27 北京航空航天大学青岛研究院 Sensor for measuring vertical magnetic field and method thereof
CN115094380B (en) * 2022-06-02 2023-06-02 山东麦格智芯机电科技有限公司 FeCoCr magnetic material and preparation method and application thereof

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