In today's magnetic random access memory (MRAM) the basic storage element is a magnetic tunnel junction (MTJ) which is composed of two magnetic layers separated by an ultra-thin insulating layer referred to as a “tunnel barrier”. The resistance of the MTJ depends on the relative orientation of the magnetization of the two magnetic layers. The magnetization of the so-called storage or memory layer is toggled between being parallel or anti-parallel to the magnetization of the reference magnetic layer. Currently, the change in magnetic state of the MTJ is achieved by passing an electric current through the device. In today's MRAM, the magnetic electrodes of the MTJ are formed from ferromagnetic alloys of Co, Fe, and B with their magnetic moment aligned perpendicular to the layer. This perpendicular alignment of magnetization of a CoFeB alloy arises from interfacial effects which are typically weak limiting the MRAM devices to sizes >=20 nm. It is essential to find alternate magnetic material for use within MTJs which has perpendicular magnetic anisotropy (PMA) due to its bulk properties.
Various embodiments of the invention are disclosed in the following detailed description and the accompanying drawings.
The invention can be implemented in numerous ways, including as a process; an apparatus; a system; and/or a composition of matter. In this specification, these implementations, or any other form that the invention may take, may be referred to as techniques. In general, the order of the steps of disclosed processes may be altered within the scope of the invention.
A detailed description of one or more embodiments of the invention is provided below along with accompanying figures that illustrate the principles of the invention. The invention is described in connection with such embodiments, but the invention is not limited to any embodiment. The scope of the invention is limited only by the claims and the invention encompasses numerous alternatives, modifications and equivalents. Numerous specific details are set forth in the following description in order to provide a thorough understanding of the invention. These details are provided for the purpose of example and the invention may be practiced according to the claims without some or all of these specific details. For the purpose of clarity, technical material that is known in the technical fields related to the invention has not been described in detail so that the invention is not unnecessarily obscured.
The invention may be embodied in other specific forms without departing from its spirit or essential characteristics. The described embodiments are to be considered in all respects only as illustrative and not restrictive. The scope of the invention is therefore indicated by the appended claims rather than the foregoing description. All changes within the meaning and range of equivalency of the claims are to be embraced within that scope.
In some embodiments, a device includes a tetragonal Heusler and a substrate. The tetragonal Heusler of the form Mn3-xCoxGe, wherein 0<x≤1, wherein Co accounts for at least 0.4 atomic percent of the Heusler compound. The substrate is oriented in the direction (001) and of the form YMn1+d, wherein Y includes an element selected from the group consisting of Ir and Pt, and 0≤d≤4. The tetragonal Heusler and the substrate are in proximity with each other, thereby allowing spin-polarized current to pass from one through the other. In one aspect, Y is Ir. In one embodiment, a tunnel barrier is in contact with the tetragonal Heusler. The tunnel barrier may include Mg and O. In some embodiments, the device further includes a TaN layer between and in contact with the tetragonal Heusler and the substrate. In some embodiments, the tetragonal Heusler is of the form Mn3-xCoxGe, wherein 0<x≤1, and the substrate is of the form IrMn3. In some embodiments, a magnetization of the Heusler compound is substantially perpendicular to the film plane. The thickness of the Heusler compound may be at least 10 Angstroms and not more than 500 angstroms. In some embodiments, a TaN layer is underneath the substrate and in contact with the substrate. The device may be used in a memory element in some embodiments.
In some embodiments, a device includes a tetragonal Heusler, a multi-layered structure and a substrate. The tetragonal Heusler is of the form Mn3-xCoxGe, wherein 0<x≤1, wherein Co accounts for at least 0.4 atomic percent of the Heusler compound. The multi-layered structure is non-magnetic at room temperature. The multi-layered structure includes alternating layers of Co and E, wherein E comprises at least one other element that includes Al and wherein the composition of the multi-layered structure is represented by Co1-yEy, with y being in the range from 0.45 to 0.55. The tetragonal Heusler and the substrate are in proximity with each other, thereby allowing spin-polarized current to pass from one through the other. In some embodiments the device includes a tunnel barrier overlying the tetragonal Heusler layer, thereby permitting current to pass through both the tunnel barrier and the tetragonal Heusler layer. The tunnel barrier may include Mg and O. In some embodiments, E is an AlGe alloy. In some embodiments, the device may be used as a memory element.
In some embodiments, a device includes a substrate, an underlayer, a first magnetic layer, a tunnel barrier and a second magnetic layer. The underlayer is oriented in the direction (001) and is non-magnetic at room temperature. The first magnetic layer includes a Heusler compound Mn3-xCoxGe, wherein 0<x≤1. The first magnetic layer is in contact with the underlayer and the magnetic moment of the first layer is switchable. The tunnel barrier overlies the first magnetic layer. The second magnetic layer is in contact with the tunnel barrier. In some embodiments, the device includes a capping layer in contact with the second magnetic layer. In some embodiments, the magnetic moment of the first magnetic layers is substantially perpendicular to the interface between the structure and the first magnetic layer.
The structural and magnetic properties of several Mn3-xCoxGe Heusler compounds were investigated theoretically and experimentally. The structure evolves from a tetragonal to a cubic phase with increasing Co content as well as a transition from a ferri-magnetic phase to a ferro-magnetic phase but at a higher Co content. Therefore, intermediate compositions, which have low magnetization and PMA, may be of interest for STT-MRAM applications. Our theoretical studies show that the Brillouin zone filtering effect, which was responsible for the compensated tunneling magnetoresistance at the Mn3Ge/MgO interface of perpendicularly-magnetized MTJs, is suppressed in compounds with Co concentrations in the range xc<x≤1 with xc˜0.2. Therefore, the compensation between the SP and BZF effects can be eliminated, leading to a significant increase of the TMR in a Mn3-xCoxGe/MgO/Fe MTJ with x=0.25 (TMR 500%), as compared to that with x=0 (TMR<100%), for the same range of MgO thicknesses (NMgO=8-12).
Computational Study
A. Crystal and magnetic structure of ordered Mn3-xCoxGe compounds with x=0, 0.25, 0.5, 1, 1.5, and 2
To find the ground state structure of various Mn3-xCoxGe compounds, whether cubic or tetragonal, and whether regular or inverse, and the corresponding lattice constants and magnetic configuration, we carried out calculations using the generalized gradient approximation within density functional theory implemented within the VASP program with projector augmented wave potentials. The lowest energy configurations for x=0, 0.25, 0.5, 1, 1.5, 2 were found from total energy calculations for various atomic orderings of the Mn and Co atoms within the unit cell. The unit cell was varied in size according to x: for x=0, 1 and 2 the unit cell has 4 atoms; for x=0.5 and 1.5 the unit cell has 8 atoms; and for x=0.25 the unit cell has 16 atoms [in subsection A we consider only ordered compounds, while disordered compounds are considered in subsection D by using the virtual crystal approximation]. To find the ground state magnetic configuration the energy was calculated for many different initial magnetic configurations. For compounds with 4 atoms in the unit cell, a 6×6×6 k-point mesh was used for an initial rough estimate of the lattice parameters, and a 10×10×10 k-point mesh with the energy cut-off equal to 400 eV was used for fine-tuning the lattice parameters. For compounds with 8 and 16 atoms per unit cell, the number of k-divisions was reduced along the elongated axes.
Table I summarizes the ground state structure and the corresponding magnetic state for both cubic and tetragonal structures. In some cases no metastable tetragonal state was found. The minimum energy configuration was found to be tetragonal for Mn3Ge, tetragonal-inverse for Mn2CoGe, and cubic-regular for MnCo2Ge. The minimum energy configuration for 8 and 16 atoms in the unit cell was found to be a stack of several 4 atom unit cells along the z axis. Thus, for x=0.5, the ground state is composed of a tetragonal-inverse Mn2CoGe unit cell placed above a tetragonal Mn3Ge unit cell. For x=0.25, the ground state consists of a tetragonal-inverse Mn2CoGe unit cell placed above three tetragonal Mn3Ge unit cells aligned along the z-direction. Finally, for x=1.5, the ground state is composed of the cubic-inverse Mn2CoGe unit cell placed above the cubic-regular MnCo2Ge unit cell. The calculations showed that the ground state remains tetragonal for x varying up to and including 1. For x>1 the ground state becomes cubic.
0.79
0.79
0.40
0.90
0.96
1.05
1.05
0.99
0.99
For the cubic phase, the magnetic moment was found to satisfy the Slater-Pauling rule for all x values that we studied. The Slater-Pauling rule states that the magnetic moment, m, per 4 atom unit cell varies with the number of the valence electrons, Nv, per 4 atom unit cell, namely, m=Nv−24. The individual calculated moments of the Mn and Co atoms located at the O and the two T sites are shown in Table I. Note that, for all compositions considered here, the O site is preferentially occupied by Mn (in both cubic and tetragonal phases) in agreement with the “lightest atom” rule, which states that the O site in cubic X2YZ Heusler compounds should always be occupied by the X or Y atom having lower valence. Furthermore, the magnitude of the moment of the Mn atom on the O site is robust and shows only a small variation with Co composition. The sign of this moment changes according to whether this moment is dominant or not for the FiM case. The moments of the Mn and Co atoms on the T sites change significantly from the cubic to the tetragonal phase but they have similar values, independent of the Co content, for each of these phases, within the corresponding 4-atom unit cell building blocks. In both the cubic and tetragonal phases the Co atoms (which are always on the T sites) have their moments always aligned ferromagnetically with the Mn moments on the O sites, while the moments of the Mn atoms on the T sites are always aligned anti-parallel to the Mn moments on the O sites. When Co is added it substitutes for Mn atoms on T sites so that when x=2 there are no more Mn atoms on the T sites and the magnetic configuration becomes FM. In the cubic phase the net moment of Mn3Ge has the same sign as the Mn moment on the O site. On the other hand, in the tetragonal phase the total moment of Mn3Ge has the opposite sign as the Mn moment on the O site. Therefore, the addition of Co (again on the T site) initially reduces the total moment until at x=0.5 (
From the partial density of states (pDOS), that are calculated from the different electronic structures, we can extract a layer-dependent SP defined as follows:
SP=[pDOS(maj)−pDOS(min)]/[pDOS(maj)+pDOS(min)], (1)
where pDOS(maj) and pDOS(min) are, respectively, the majority and minority spin polarized partial DOS calculated at the Fermi energy (EF), for each layer in the unit cell. Note that each layer has two atoms, as shown in Table II. Here, the calculated SP is shown only for the ground state configuration. All the cubic phases, regardless of the Co content, are half-metallic (SP=1). Note that the SP of each layer in the unit cell for the compounds shown in Table II has the same sign, for all compositions and phases, and it always corresponds to the sign of the moment of the Mn atom on the O site (i.e. Mn—Ge layer). Thus, the polarization changes sign at x=1.
B. Brillouin Zone Spin Filtering Effect
The so-called Brillouin zone spin filtering (BZF) effect in a ME/MgO/ME MTJ system occurs if a magnetic electrode (ME) has electronic states at EF along the Γ-Z line in one spin channel, σ1, and does not have states at EF along the F-Z line in the other spin channel, σ2. The F-Z line in the Brillouin zone (BZ) is the line along the kz direction with in-plane wavevector k∥=(kx, ky)=0. It is well known that the smallest (at a given k11) attenuation constant γ(k∥) of an MgO insulating spacer, for evanescent states propagating along the z direction with energies within the MgO band gap, reaches a minimum, γ0, at k∥=0. When k∥ increases, γ(k∥) increases as γ(k∥)=γ0+αk∥2 with α>0 (α is a coefficient of the Taylor expansion for small k∥). Therefore, considering the ME described above, the evanescent states in the σ1 spin channel at EF that propagate along the z direction with k∥=0 will decay inside MgO as exp[−γ0z], whereas the evanescent states in the σ2 spin channel at EF will decay as exp[(−γ0+αk∥2)z] with k∥>0, since the σ2 spin channel does not have states at EF with k∥=0. As a result, the TMR of a ME/MgO/ME MTJ increases exponentially with increasing MgO thickness, dMgO, as
TMR∝exp[2α{tilde over (k)}∥2dMgO], (2)
where {tilde over (k)}∥ is the smallest k∥≠0 vector for which the ME has states in the σ2 spin channel at EF. Such exponential dependence of the TMR on dMgO is much stronger than the TMR∝dMgOn dependence in conventional Fe/MgO/Fe MTJs arising from the symmetry spin filtering effect22, 23, where the power factor n can only take three values n=0,1,2 for MTJ systems with square symmetry in the xy-plane. For simplicity, we assumed above that both electrodes are made from the same ME material but, in general, it is enough to have just one electrode with the above properties to predict the exponential increase of the TMR with dMgO thanks to the BZF effect.
C. BZF Effect in Ordered Mn3-xCoxGe Compounds with x=0, 0.25, 0.5, 1, 1.5 and 2.
Bulk Mn3Ge (x=0) has several majority bands (
The Mn1.5Co1.5Ge (x=1.5) and MnCo2Ge (x=2) compounds are predicted to have a cubic ground state configuration with a half-metallic character (100% spin polarization for every layer, as shown in Table II). These compounds have an energy gap at EF in the minority channel not only for wave vectors k along the Γ-Z line (as shown in
D. BZF Effect and DOS in Disordered Mn3-xCoxGe Compounds with x≤0.25
Disordered Mn3-xCoxGe compounds with small values of 0≤x≤0.25 were modeled using the virtual crystal approximation (VCA) in a framework of the full-potential linear muffin-tin orbitals (LMTO) approach using the Barth-Hedin local density approximation (LDA)/DFT functional. Within this approximation, the charge of the nucleus, ZMn=25, of the Mn atoms of an ordered Mn3Ge system is substituted by the charge of a ‘virtual’ atom
Z=(1−x/3)ZMn+(x/3)ZCo, (3)
which mimics the random occupation of a x/3 share of Mn sites by Co atoms (ZCo=27) in a disordered Mn3-xCoxGe system. The VCA calculations were performed using the experimentally determined lattice constants from earlier studies of the tetragonal Mn3Ge Heusler compound (a=3.816 Å and c=7.261 Å).
The majority and minority electron bands along the Γ-Z line were calculated for x=0.00, 0.05, 0.10, 0.15, 0.20, and 0.25. It was found that only for x=0.00, 0.05, 0.10, and 0.15 there are no minority bands crossing EF along the Γ-Z line, while for x=0.20 and 0.25 there is one minority band that crosses EF along the Γ-Z line. Therefore, the calculations for both ordered and disordered Mn3-xCoxGe systems indicate that the BZF effect occurs only for small x<xc with estimated xc≃0.2. Moreover, the majority and minority DOS of the Mn3-xCoxGe compounds calculated for x=0.00, 0.05, 0.10, 0.15, 0.20, and 0.25 within the VCA indicate that the large negative SP is preserved for all x considered here.
E. TMR Calculations for Mn3-xCoxGe/MgO/Fe Systems with x=0 and x=0.25
In order to investigate the different regimes of the TMR behavior for x<xc and x>xc due to the presence and absence of the BZF effect at the Mn3-xCoxGe/MgO interface, we performed calculations of the transmission functions of the Mn3-xCoxGe/MgO/Fe MTJ systems with x=0 and x=0.25 using a tight-binding linear muffin-tin orbital method in the atomic sphere approximation (LMTO-ASA) with the local density approximation of DFT for the exchange-correlation energy. For the x=0.25 case we used the VCA as described above.
Regarding the Mn3Ge/MgO/Fe MTJ, the in-plane lattice constant was fixed to the experimental lattice constant for bulk tetragonal Mn3Ge (a=3.816 Å). The relaxed position of atoms at the Mn3Ge/MgO interfaces (for both Mn—Mn and Mn—Ge terminations) was determined using the VASP molecular dynamic program. The O-top configuration was found to be the most stable configuration (as compared with Mg-top and hollow) for both terminations. For the MgO/Fe interface, the atomic positions from literature were used. These same atomic positions were used for the Mn2.75Co0.25Ge/MgO/Fe MTJ system. Lastly, the number of MgO layers, NMgO, was varied from 2 to 12.
The TMR as a function of NMgO for both terminations is shown in
TMR=(TP−TAP)/min(TP,TAP), (4)
where TP=T[Fe(↑) Mn3Ge(↑)]+T[Fe(↓) Mn3Ge(↓)] and TAP=T[Fe(↑) Mn3Ge(↓)]+T[Fe(↓) Mn3Ge(↑)] are the total transmissions at EF for the P and AP configurations, respectively. Qualitatively, the behavior of the TMR presented on
In real MTJ devices there will be inevitable atomic scale fluctuations in the morphology of the Mn3Ge Heusler layer that give rise to regions with Mn—Mn and Mn—Ge terminations that will interface the MgO barrier. The simplest way to model such fluctuations is to average the transmission functions over the different terminations (separately for P and AP), assuming that the MgO thickness is the same across the device. The TMR calculated from this simple model with an assumption of equal areas occupied by Mn—Mn and Mn—Ge terminations is also shown in
Experimental Study
Thin Film Growth
The samples were prepared in an ultra-high vacuum magnetron sputtering chamber with a base pressure of 4×10−1° Torr. The film stacks used for this study were as follows: Si(001)/250 Å SiO2/200 Å TaN/100 Å IrMn3/300 Å Mn3-xCoxGe/30 Å Ta. The TaN/IrMn3 bilayer underlayer was used to promote the (001) crystallographic orientation of the Heusler films, and the thin Ta cap serves as a protective layer. The TaN layer, which was formed by reactive magnetron sputtering of a Ta target in a mixture of Ar and N2 gases, induces the (001)-textured growth of IrMn3, which would otherwise favor the (111) orientation when deposited directly on the amorphous SiO2 surface. The IrMn3 film and the Ta capping layer were deposited by ion-beam sputtering using Kr. The Mn3-xCoxGe films were grown at 3 mTorr (using Ar) either by sputtering of a single Mn3Ge target (x=0) or by co-sputtering of Mn, Co and Co10Mn45Ge45 targets (0<x≤2), using a 3-step process: an initial 20 Å of Mn3-xCoxGe layer was deposited at 450° C., followed by the deposition of a 280 Å Mn3-xCoxGe layer at 150° C., and final in-situ anneal at 450° C. for 1-2 h in vacuum. All the other layers were deposited at RT. All the films were smooth with root-mean square surface roughness of less than 7 Å. The ratio between Mn and Co in the Mn3-xCoxGe films was tuned by varying the powers of the Mn and Co magnetron guns while keeping constant the power of the Co10Mn45Ge45 magnetron gun.
Measurement Methods
The film compositions were measured by Rutherford backscattering spectrometry (RBS) measurements, while the film structures were investigated by x-ray diffraction (XRD) measurements using a Bruker D8 General Area Detector Diffraction System (GADDS) with Cu Kα radiation. Atomic force microscopy (AFM) measurements were carried out using a Bruker Icon Dimension with ScanAsyst system to determine the sample surface roughness. The in-plane and out-of-plane magnetic properties were investigated using a Quantum Design superconducting quantum interference device vibrating sample magnetometer (SQUID-VSM) at RT, with applied magnetic fields of up to ±7 T.
Structure and Magnetic Properties
Alternatively, tetragonal Mn3-xCoxGe films with their c-axis largely coincident with film normal can be grown on underlayers which comprise of CoAl or CoGa or CoGe or CoSn or a layer of Co and at least one other element preferably Al; or Al alloyed with Ga, Ge, Sn or any combination thereof, such as AlSn, AlGe, AlGaGe, AlGaSn, AlGeSn, and AlGaGeSn. These type of underlayers could be referred to as templating layer.
The structures described herein lend themselves to a variety of applications, including MRAM elements and a racetrack memory device. Examples of such MRAM elements are shown in
Note that in
The tunnel barrier is preferably MgO (001), although other (001)-oriented tunnel barriers may be used, such as CaO and LiF. Alternatively, MgAl2θ4 can be used as a tunnel barrier whose lattice spacing can be tuned by controlling Mg—Al composition which could result in better lattice matching with the Heusler compounds. The magnetic electrode overlying the tunnel barrier may comprise Fe, a CoFe alloy, or a CoFeB alloy, for example.
Certain structures described herein may also be used in racetrack memory devices. In this case, the racetrack is a nanowire that may include a substrate, an optional seed layer, a templating layer, and a first magnetic layer of a Heusler compound. (See the discussion above with respect to
The various layers described herein may be deposited through any one or more of a number of methods, including magnetron sputtering, electrodeposition, ion beam sputtering, atomic layer deposition, chemical vapor deposition, and thermal evaporation.
Although the foregoing embodiments have been described in some detail for purposes of clarity of understanding, the invention is not limited to the details provided. There are many alternative ways of implementing the invention. The disclosed embodiments are illustrative and not restrictive.
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Number | Date | Country | |
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20200243755 A1 | Jul 2020 | US |