CN110165045A - W-B alloy material and spin electric device based on spin-orbit torque - Google Patents

W-B alloy material and spin electric device based on spin-orbit torque Download PDF

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CN110165045A
CN110165045A CN201910275284.8A CN201910275284A CN110165045A CN 110165045 A CN110165045 A CN 110165045A CN 201910275284 A CN201910275284 A CN 201910275284A CN 110165045 A CN110165045 A CN 110165045A
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spin
alloy material
orbit torque
electric device
magnetic
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CN110165045B (en
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李刚
蔡建旺
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Institute of Physics of CAS
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    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10BELECTRONIC MEMORY DEVICES
    • H10B61/00Magnetic memory devices, e.g. magnetoresistive RAM [MRAM] devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00Galvanomagnetic devices
    • H10N50/10Magnetoresistive devices
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00Galvanomagnetic devices
    • H10N50/80Constructional details
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10NELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N50/00Galvanomagnetic devices
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    • H10N50/85Magnetic active materials

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Abstract

The present invention provides a kind of W-B alloy material, with following below formula: W1‑xBx, wherein 0.03≤x≤0.3.The present invention also provides a kind of spin electric devices based on spin-orbit torque, including substrate, core layer, amorphous iron magnetosphere and oxide barrier layer, wherein the core layer includes W-B alloy material of the invention.By the way that B is mixed the disordered structure that metal W makes W become amorphous, W-B alloy material provided by the invention, it has big spin Hall angle, and still can keep amorphous state (up to 450 DEG C) at high temperature, and resistivity is held essentially constant after high annealing.W-B alloy material provided by the invention can obtain perpendicular magnetic anisotropic in conjunction with amorphous iron magnetosphere simultaneously, require to match with CMOS annealing process.

Description

W-B alloy material and spin electric device based on spin-orbit torque
Technical field
The present invention relates to spintronics.In particular it relates to W-B alloy material and be based on spin-orbit torque Spin electric device.
Background technique
At present with magnetic tunnel become core magnetic RAM (Magnetic Random Access Memory, MRAM main writing mode) is spin-transfer torque (Spin Transfer Torque, STT), but it there is information to write Enter speed and tunnel junction barrier layer the neck of reliability.It is realized using spin-orbit torque (Spin-Orbit Torque, SOT) fast Fast and reliable magnetization reversal is expected to break through the performance bottleneck of conventional spin transfer square, and the research of spin-orbit torque exists Many key developments [L.Q.Liu, et al, Phy.Rev.Lett.109,096602 (2012) were obtained in recent years;G.Q.Yu,et Al, Nat.Nanotech.9,548, (2014)], more improve the confidence of people.Realize that magnetization is turned over using spin-orbit torque Turn to require in one layer of heavy metal film of ferromagnetic layer surrounding growth with perpendicular magnetic anisotropic, usually tungsten (W), platinum (Pt) or Tantalum (Ta) causes spin current since SO coupling acts on, spin current injects ferromagnetic layer pair when electric current flows through heavy metal Its magnetic moment generates torque (SOT), can drive ferromagnetic layer magnetization reversal.Electric current is to the transfer efficiency of spin current generally with spin Hall Angle indicates, closely related with the SO coupling size of material.Heavy metal is due to big SO coupling, usually Big spin Hall angle is shown, current density needed for corresponding SOT magnetization reversal is lower.In heavy metal, the β-of high-impedance state W, the SO coupling of Pt and Ta is strong, and spin Hall angle is big, and wherein the spin Hall angle of β-W is maximum, and in particular people are closed Note.They can realize the perpendicular magnetization of CoFeB with traditional CoFeB/MgO system combinations simultaneously, it can make CoFeB's Magnetic moment is perpendicular to film surface.For metal W, although W/CoFeB/MgO system still can be with after high annealing Perpendicular magnetic anisotropic is obtained, but the β-W of high annealing easily becomes α phase, spin Hall angle substantially reduces, corresponding electricity Resistance also becomes smaller, application [the P.M.Petroff and which prevent W in the magnetization reversal device based on spin-orbit torque W.A.Reed,Thin Solid Films,21,73(1974);Q.Hao,et al,Appl.Phys.Lett.106,182403 (2015)]。
Summary of the invention
In order to solve following problems existing in the prior art: β-W is not able to maintain high-resistance state after the high temperature anneal Big spin Hall angle, with magnetic system (such as CoFeB/ that matches in CMOS (complementary metal oxide semiconductor) technique MgO it can not realize that electric current overturns magnetosphere magnetic moment using SOT in).The present invention provides a kind of W-B alloy (W-B alloy) materials Material, the material is after 350 DEG C of -450 DEG C of annealing still with the big spin Hall angle of high resistivity.Meanwhile the present invention also mentions For a kind of spin electric device based on spin-orbit torque including W-B alloy material of the invention.
On the one hand, the present invention provides a kind of W-B alloy material, with following below formula: W1-xBx, wherein 0.03≤x≤ 0.3。
W-B alloy material of the invention can be by including the following steps prepared by method:
Boron piece is placed in symmetrical position on metal W target, and W-B target uses radio frequency method in sputtering.It is raw in W-B alloy Pre-sputtering is first carried out before long, then carries out the growth of official sample again.The ingredient (atomic ratio) of W-B is by inductively coupled plasma body Atomic emission spectrometry determines.
On the other hand, the present invention also provides a kind of spin electric devices based on spin-orbit torque, including substrate, core Central layer, amorphous iron magnetosphere and oxide barrier layer, wherein the core layer includes W-B alloy material of the invention.
Preferably, it in the spin electric device of the present invention based on spin-orbit torque, wraps from the bottom to top It includes: substrate, core layer, amorphous iron magnetosphere and oxide barrier layer;Preferably, the core layer is by W-B alloy material of the invention Material is formed.
Preferably, in the spin electric device of the present invention based on spin-orbit torque, the W-B alloy material Material is to be formed by high vacuum Grown by Magnetron Sputtering at thin-film material.
Preferably, in the spin electric device of the present invention based on spin-orbit torque, the substrate by silicon or Glass is formed.
Preferably, in the spin electric device of the present invention based on spin-orbit torque, the amorphous iron magnetosphere Include amorphous Co, Fe, B ternary alloy three-partalloy.
Preferably, described amorphous in the spin electric device of the present invention based on spin-orbit torque Co, Fe, B ternary alloy three-partalloy have following below formula: (Co1-xFex)1-yBy, wherein 0.2≤x≤1,0.1≤y≤0.3.
Preferably, in the spin electric device of the present invention based on spin-orbit torque, the thickness of the core layer Degree is 0.5-200nm.
Preferably, in the spin electric device of the present invention based on spin-orbit torque, the amorphous iron magnetosphere With a thickness of 0.5-10nm.
Preferably, in the spin electric device of the present invention based on spin-orbit torque, the oxide barrier Layer is comprising being selected from MgO, Al2O3, MgAlO and SiO2At least one of oxide.
Preferably, in the spin electric device of the present invention based on spin-orbit torque, the oxide barrier Layer with a thickness of 0.5-10nm.
The invention has the following beneficial effects:
W is made to have become the disordered structure of amorphous by the way that B is mixed metal W, W-B alloy material provided by the invention, Amorphous state still can be kept (up to 450 DEG C) with big spin Hall angle, and at high temperature, the resistivity base after high annealing Originally it remains unchanged.W-B alloy material provided by the invention can obtain perpendicular magnetic anisotropic in conjunction with amorphous iron magnetosphere simultaneously, It requires to match with CMOS annealing process.It is passed through direct current in W-B alloy material and pulse current can be by amorphous iron magnetosphere The direction of magnetization overturn, the critical current density of overturning is 4 × 106A/cm2
Detailed description of the invention
Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, in which:
Fig. 1 is the structural schematic diagram of the spin electric device based on spin-orbit torque of the embodiment of the present invention 1;
Fig. 2 be sample in embodiment 1 after 350 DEG C of annealing perpendicular to film surface and be parallel to film surface direction magnetization it is bent Line;
Fig. 3 is the unit area saturation magnetization m of the sample in embodiment 1 after 350 DEG C of annealing with CoFeB thickness t Change curve;
Fig. 4 is the effective anisotropy constant K of the sample in embodiment 1 after 350 DEG C of annealingeffWith CoFeB thickness t's Product with CoFeB thickness t change curve;
Fig. 5 be sample in embodiment 1 after 400 DEG C of annealing perpendicular to film surface and be parallel to film surface direction magnetization it is bent Line;
Fig. 6 be sample in embodiment 1 after 450 DEG C of annealing perpendicular to film surface and be parallel to film surface direction magnetization it is bent Line;
Fig. 7 be after W-B (200nm) in embodiment 1/CoFeB (1.1nm)/350 DEG C of sample of MgO (3nm) annealing perpendicular to Film surface and the magnetization curve for being parallel to film surface direction;
Fig. 8 is the unusual Hall Curve of sample in embodiment 2;
Fig. 9 is the curve that sample assists magnetization reversal off field in ± 550Oe in embodiment 2.
Figure 10 is sample in embodiment 2 in the curve of ± 5500Oe auxiliary magnetization reversal off field.
Figure 11 is variation relation of the sample effective magnetic field in embodiment 2 with electric current.
Specific embodiment
The present invention is further described in detail With reference to embodiment, and the embodiment provided is only for explaining The bright present invention, the range being not intended to be limiting of the invention.
Embodiment 1
Using W-B alloy material provided by the invention, wherein the atom accounting of W and B is 0.94:0.06, that is, this implementation The W-B alloy material that example uses is W0.94B0.06.It is combined with traditional CoFeB/MgO system, preparation is based on spin-orbit force The spin electric device of square should have the multilayer film of perpendicular magnetic anisotropic based on the spin electric device of spin-orbit torque Material, as shown in Figure 1, its structure from the bottom to top sequence are as follows: the silicon chip of thermal oxide;SiO2Buffer layer, with a thickness of 5nm;W-B The core layer of alloy material, with a thickness of 6nm;Co40Fe40B20Amorphous iron magnetosphere, with a thickness of 1.0-3.0nm;MgO oxide Barrier layer, with a thickness of 3nm;SiO2Protective layer, with a thickness of 5nm.
The vertical magnetic anisotropic multi-layer film material (including W-B alloy) of the present embodiment the preparation method comprises the following steps: using magnetic control Prepared by the method for sputtering, the background vacuum of instrument is better than 4 × 10 when preparation-5Pa uses Ar gas as sputter gas, sputtering pressure For 0.35Pa, on surface, the Si on piece of thermal oxide is sequentially depositing each tunic.Deposition complete after, by sample respectively 350 DEG C, 1 hour of vacuum annealing at 400 DEG C and 450 DEG C, annealing vacuum degree are better than 1 × 10-4Pa.It illustrates, the preparation side of W-B alloy Method: W-B alloy is prepared using Film by Sputtering of Composite Target, and the detail of composition target is that boron is placed in symmetrical position on metal W target Piece.The purity of W target is 99.9%, and diameter 50mm, B piece is 2 to 5mm thick.W-B target uses radio frequency method, power in sputtering Rate for 40W, sputtering is 0.0418nm/s, and sputtering pressure is also 0.35Pa.Pre-sputtering is first carried out before W-B alloy growth Then 10min carries out the growth of official sample again.The ingredient (atomic ratio) of W-B is by inductively coupled plasma body atomic emissions light Spectrometry determines.
Fig. 2 shows sample W-B/Co in the present embodiment40Fe40B20(1.1nm)/MgO is perpendicular to film surface and being parallel to film The magnetization curve in face direction.As can be seen from the figure sample shows apparent perpendicular magnetic anisotropic.Perpendicular to film surface side To loop line rectangular degree it is very good, remanence ratio Mr/Ms=1, coercivity has 16Oe.When magnetic field is 35Oe, magnetic moment just reaches full Be magnetic easy axis direction perpendicular to film surface direction.Direction is obviously magnetic beach axis direction in face, when magnetic field reaches 6000Oe, Magnetic moment just reaches saturation.This is that typically have the characteristics that the hysteresis loop of perpendicular magnetic anisotropic.In fact, W-B/ Co40Fe40B20The magnetic easy axis of (1.0nm)/MgO sample is also just no longer to show here perpendicular to film surface direction.When Co40Fe40B20With a thickness of 1.3nm when, W-B/Co40Fe40B20The magnetic easy axis of/MgO has become in face from perpendicular to film surface direction Direction, is parallel to the loop line in film surface direction at this time, and magnetic field reaches saturation when being 50Oe.It is magnetic beach axis side perpendicular to film surface direction To magnetic field could be saturated when being 1700Oe.Work as Co40Fe40B20With a thickness of 1.2nm when, magnetic easy axis between vertical film surface with it is parallel Between film surface, work as Co40Fe40B20Thickness be greater than 1.3nm, magnetic easy axis, which is constantly in, is parallel to film surface direction.This with it is typical Ta/Co40Fe40B20The case where/MgO is similar, Co40Fe40B20Thickness increase to a certain extent, shape anisotropy accounts for master It leads, Interface Anisotropy is not enough to overcome shape anisotropy, and magnetic easy axis is caused to be parallel to film surface direction.
Fig. 3 shows W-B/Co40Fe40B20The saturated magnetization of/MgO sample unit area after 350 DEG C of vacuum annealings is strong M is spent with Co40Fe40B20The variation relation of thickness t.Co has been obtained by linear fit40Fe40B20Saturation magnetization be 1380emu/cm3, magnetic dead layer thickness is very small, only about
Co40Fe40B20The perpendicular magnetic anisotropic of/MgO system derives from Co40Fe40B20The interface /MgO, with hanging down for interface Straight anisotropy constant KsIts size is characterized, K is usually usedeff× t obtained with thickness t change curve interface it is vertical respectively to Anisotropic constant.Specifically formula is
Keff× t=(Kv-2πMs 2)×t+Ks
Wherein -2 π Ms 2For demagnetization energy, KvFor Co40Fe40B20Body perpendicular magnetic anisotropy constant, KeffFor effectively it is vertical respectively to Anisotropic constant, the Y intercept of curve indicate the perpendicular magnetic anisotropy constant K of interfacesSize [M.T.Johnson, et al, Rep.Prog.Phys.59,1409(1996)].When the direction of magnetization of sample is perpendicular or parallel to film surface, Keff× t be positive or It is negative.KeffIt can be determined by hysteresis loop,
Keff=HkMs/2
Wherein HkFor magnetic beach axis saturation field, the H of perpendicular magnetic filmkIt is positive, the H of easy magnetization film in facekIt is negative, it can be with It is obtained from magnetization curve measurement result.Fig. 4 is 350 DEG C of annealing W-B/Co40Fe40B20(t nm)/MgO sample it is effective vertical each Anisotropy constant Keff× t and Co40Fe40B20The variation relation of thickness t.As shown, the present invention can obtain in W-B/ Co40Fe40B20Co in/MgO system40Fe40B20The perpendicular magnetic anisotropy of the interface /MgO is 1.6erg/cm2, this and Ta/ Co40Fe40B20Perpendicular magnetic anisotropy (the 1.7erg/cm of/MgO interface2) be not much different.It should be noted that Co40Fe40B20The Interface Anisotropy and Co of/MgO40Fe40B20Ingredient it is related, the present embodiment is with Co:Fe:B=40:40: It is analyzed for 20.
Fig. 5 and Fig. 6 is respectively typical sample W-B/Co40Fe40B20(1.1nm)/MgO is respectively in 400 DEG C and 450 DEG C annealing 1 Hour perpendicular to film surface and the magnetization curve for being parallel to film surface direction.It can be seen that annealing until 450 DEG C from curve, W-B/ Co40Fe40B20(1.1nm)/MgO sample still has perpendicular magnetic anisotropic, and coercivity only has 18Oe, magnetic beach axis at this time Saturation field has 2000Oe.This illustrates W-B/Co40Fe40B20The thermal stability of/MgO sample is very good, this is also W-B/ Co40Fe40B20The industrial application of/MgO provides guarantee.
Change W-B alloy with a thickness of 200nm, Co40Fe40B20With a thickness of 1.1nm, and other materials is such as in multilayer film The thickness of MgO is constant, is prepared for multilayer film W-B (200nm)/Co40Fe40B20(1.1nm)/MgO.The sample prepared is placed in Vacuum annealing furnace carries out 350 DEG C and anneals 1 hour.Sample after annealing is carried out perpendicular to film surface and the magnetic for being parallel to film surface direction Change the measurement of curve, as shown in Figure 7.It is upper from figure we have seen that the magnetic easy axis of sample is still perpendicular to film surface direction, this and W-B (6nm)/Co40Fe40B20The performance of (1.1nm)/MgO sample is the same.
Embodiment 2
W-B/Co is prepared using method in the same manner as in Example 140Fe40B20(1.1nm)/MgO multilayer film, and 350 It is made annealing treatment at DEG C, multilayer film obtains perpendicular magnetic anisotropic.In order to facilitate the measurement of extraordinary Hall effect, the present invention is adopted It by sample making is Hall bar shaped (Hall bar) with the technology of uv-exposure combination argon ion etching, line width is 20 μm, then Carry out the measurement of Hall resistance and the measurement of the electric current SOT overturning direction of magnetization.Extraordinary Hall effect can be used to characterize Co40Fe40B20Magnetized state.The high low resistance state of unusual Hall resistance represents Co40Fe40B20Layer magnetic moment perpendicular to film surface to It is upper or downward.Extraordinary Hall effect is to characterize Co other than hysteresis loop40Fe40B20A kind of common hand of film magnetic moment direction Section, and resistance measurement can be more succinct convenient.The unusual Hall Curve of sample is as shown in figure 8, from the figure it may be seen that curve Shape it is very similar with, perpendicular to the magnetization curve in film surface direction, rectangular degree is fine, and coercivity has 87Oe in Fig. 2.It rectifys Stupid power is different from the magnetization curve in corresponding vertical film surface direction, this is because sample size after micro Process becomes smaller, side There are caused by some pinnings on boundary.The present invention can obtain the unusual Hall resistances of sample 0.7 Ω from figure.
The present invention each leads into DC current and pulse current in W-B alloy material, to overturn Co40Fe40B20The magnetic of layer Change direction.The present invention is by taking DC current is overturn as an example, as shown in figure 9, in the auxiliary Co off field of 550Oe40Fe40B20Magnetization side To under the action of positive current, from the direction that vertical film faces upward, overturning is the direction of vertical film downwards.And in the auxiliary of -550Oe It helps off field
Co40Fe40B20The direction of magnetization under the action of positive pulse electric current from vertical film downwards direction overturning be vertical Film surface upwardly direction.This illustrates that the spin Hall angle of W-B alloy material is negative as β-W, and the Hall angle that spins It is sufficiently large, Co can be overturn40Fe40B20Magnetic moment.Critical current overturning density at this time is 8 × 106A/cm2, this is not deduct Co40Fe40B20Shunt effect as a result, if deduct shunt effect, critical current overturn density can be smaller.As shown in Figure 10, when When auxiliary field is added to 5500Oe, the overturning of the direction of magnetization can be very fast, and critical current density reaches 4 × 106A/cm2Although this One critical current density ratio β-W (280 DEG C, the 1 minute obtained W/Co that anneal40Fe40B20/ MgO system, Q.Hao and G.Xiao, Phys.Rev.Applied 3,034009 (2015)) want larger.It has been obtained effectively by the method for stress_responsive genes Magnetic field with curent change relationship, as shown in figure 11.Utilize formulaThe W- of available 6nm The spin Hall angle of B is 0.24.This value and the W spin Hall angle of 6nm reported in the literature are not much different, from experiment of the invention As a result it can be seen that the material for the spin Hall angle having greatly that W-B is can compare with W.The big spin of W-B alloy material is suddenly Still stable property under that angle and high temperature, so that it becomes a kind of very potential material, for magnetization reversal Spin electric device.

Claims (10)

1. a kind of W-B alloy material, with following below formula: W1-xBx, wherein 0.03≤x≤0.3.
2. a kind of spin electric device based on spin-orbit torque, including substrate, core layer, amorphous iron magnetosphere and oxide Barrier layer, wherein the core layer includes W-B alloy material described in claim 1.
3. the spin electric device according to claim 2 based on spin-orbit torque, include: from the bottom to top substrate, Core layer, amorphous iron magnetosphere and oxide barrier layer;Preferably, the core layer is by W-B alloy material described in claim 1 It is formed;
Preferably, the W-B alloy material is to be formed by high vacuum Grown by Magnetron Sputtering at thin-film material.
4. the spin electric device according to claim 2 based on spin-orbit torque, wherein the substrate by silicon or Glass is formed.
5. the spin electric device according to claim 2 based on spin-orbit torque, wherein the amorphous iron magnetosphere Include amorphous Co, Fe, B ternary alloy three-partalloy.
6. the spin electric device according to claim 5 based on spin-orbit torque, wherein amorphous Co, Fe, B ternary alloy three-partalloy have following below formula: (Co1-xFex)1-yBy, wherein 0.2≤x≤1,0.1≤y≤0.3.
7. W-B alloy material according to claim 2, wherein the core layer with a thickness of 0.5-200nm.
8. the spin electric device according to claim 2 based on spin-orbit torque, wherein the amorphous iron magnetosphere With a thickness of 0.5-10nm.
9. the spin electric device according to claim 2 based on spin-orbit torque, wherein the oxide barrier Layer is comprising being selected from MgO, Al2O3, MgAlO and SiO2At least one of oxide.
10. the spin electric device according to claim 2 based on spin-orbit torque, wherein the oxide barrier Layer with a thickness of 0.5-10nm.
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WO2023082456A1 (en) * 2021-11-15 2023-05-19 北京大学 Magnetization reversal device based on orbital transfer torque and implementation method therefor

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