Interface characterization of epitaxial Fe/MgO/Fe magnetic tunnel junctions

Following predictions by first-principles theory of a huge tunnel magnetoresistance (TMR) effect in epitaxial Fe/MgO/Fe magnetic tunnel junctions (MTJs), measured magnetoresistance (MR) ratios of about 200% at room temperature (RT) have been reported in MgO-based epitaxial MTJs. Recently, a MR ratio of about 600% has been reported at RT in MgO-based MTJs prepared by magnetron sputtering, using amorphous CoFeB as the ferromagnetic electrode. These MTJs show great potential for application in spintronic devices. Fully epitaxial MTJs are excellent model systems that enhance our understanding of the spin-dependent tunneling process as the interface is well defined and can be fully characterized. Both theoretical calculations and experimental results clearly indicate that the interfacial structure plays a crucial role in the coherent tunneling across a single crystal MgO barrier, especially in epitaxial MgO-based MTJs grown by molecular beam epitaxy (MBE). Surface X-ray diffraction, Auger electron spectroscopy, X-ray absorption spectra, and X-ray magnetic circular dichroism techniques have been reported previously for interface characterization. However, no consistent viewpoint has been reached on the interfacial structures (such as FeO layer formation at the bottom Fe/MgO interface), and it is still an open issue. In this article, our recent studies on the interface characterization of MgO-based epitaxial MTJs by X-ray photoelectron spectroscopy, high resolution transmission electron microscopy, and spin-dependent tunneling spectroscopy, will be presented.     

Fabrication and characterization of L1/sub 0/-ordered FePt/AlO/FeCo magnetic tunnel junctions

Magnetic tunnel junctions (MTJs) with an L1/sub 0/-ordered FePt alloy were fabricated and characterized. As a bottom electrode, an in-plane magnetized L1/sub 0/ FePt(110) layer was grown epitaxially on an Au buffer layer. A multiple oxidation process was used for the formation of Al oxide barriers. The L1/sub 0/-FePt/AlO/FeCo MTJ prepared shows tunnel magnetoresistance of 18% and 40% at room temperature (RT) and 4.2 K, respectively. The observed RT magnetoresistance is improved, compared to the previously reported results for the L1/sub 0/-FePt MTJs by a conventional single oxidation process.     

Giant room-temperature magnetoresistance in single-crystal Fe/MgO/Fe magnetic tunnel junctions

The tunnel magnetoresistance (TMR) effect in magnetic tunnel junctions (MTJs) is the key to developing magnetoresistive random-access-memory (MRAM), magnetic sensors and novel programmable logic devices. Conventional MTJs with an amorphous aluminium oxide tunnel barrier, which have been extensively studied for device applications, exhibit a magnetoresistance ratio up to 70% at room temperature. This low magnetoresistance seriously limits the feasibility of spintronics devices. Here, we report a giant MR ratio up to 180% at room temperature in single-crystal Fe/MgO/Fe MTJs. The origin of this enormous TMR effect is coherent spin-polarized tunnelling, where the symmetry of electron wave functions plays an important role. Moreover, we observed that their tunnel magnetoresistance oscillates as a function of tunnel barrier thickness, indicating that coherency of wave functions is conserved across the tunnel barrier. The coherent TMR effect is a key to making spintronic devices with novel quantum-mechanical functions, and to developing gigabit-scale MRAM.     

Consistent Relationship Between the Tunnel Magnetoresistance of CoFeB/MgO/CoFeB Junctions and X-Ray Diffraction Properties

We have investigated the effect of Ar pressure during MgO sputtering on the tunnel magnetoresistance (TMR) and resistance area (RA) product of CoFeB/MgO/CoFeB magnetic tunnel junctions (MTJs). The TMR of MTJs with a thin MgO tunnel barrier deposited at different Ar pressures (1.3, 4, 10, and 25 mTorr) shows a consistent relationship with x-ray diffraction (XRD) properties of thick MgO films deposited with the same conditions. The deposition of the MgO-barrier at 1.3 mTorr results in a low TMR ratio and a high RA product due to the disordered MgO barrier and the oxidation of the bottom electrode of the MTJ, while the deposition at 25 mTorr results in a rough MgO barrier, and thereby gives rise to a large shift of switching field of the free layer due to the orange-peel coupling.      

Magnetization switching by spin-polarized current in low-resistance magnetic tunnel junction with MgO [001] barrier

Current-induced magnetization switching (CIMS) was demonstrated in low resistance magnetic tunnel junctions (MTJs) with thin MgO [001] barrier. The resistance change by CIMS was more than 100%, which is much larger than the previous report in Al-O based MTJs. The switching current density was about 2/spl times/10/sup 7/ A/cm/sup 2/, which was comparable with that reported values in metallic multilayers.     

Effect of nitrogen incorporation to oxidation process on the reliability of magnetic tunnel junctions

Magnetic tunnel junctions (MTJs) were fabricated using nitrogen-mixed oxygen plasma (O/sub 2/:N/sub 2/=10:1). From the measurements of time-dependent dielectric breakdown (TDDB) under a constant voltage stress, the reliability of MTJs with an oxy-nitride barrier was investigated and compared with that of MTJs fabricated using pure oxygen plasma. The reliability of MTJs with an oxy-nitride barrier is much improved with the incorporation of nitrogen to oxidation process. In addition, the reliability of the oxy-nitride barrier is gradually enhanced with increasing oxy-nitridation time even after the time exceeds the optimal value. It is believed that the enhancement is due to the bonding of nitrogen to electron traps both in the oxide barriers and at the bottom interface. The characteristics of the bonding were examined by XPS measurements, which reveal a nitrogen 1s peak in Al-N bond. The lifetime of the two barriers was also estimated for comparison.     

MgO-Based Epitaxial Magnetic Tunnel Junctions Using Fe-V Electrodes

To examine the influence of the barrier quality in fully epitaxial Fe/MgO/Fe(001) magnetic tunnel junctions (MTJs), we propose to use Fe-V alloys as magnetic electrodes. This leads to a reduced misfit with MgO. We actually observe, by high-resolution electron microscopy (HREM) and local strain measurements, that the misfit dislocations density in the MgO barrier is lower when it is grown on Fe-V(001). This improvement of the crystalline quality of the MgO barrier actually leads to a significant increase of the tunnel magneto-resistance (TMR), despite the loss of spin polarization (SP) in these alloys, which was measured by spin-polarized X-ray photoelectron spectroscopy (SR-XPS).     

Influence of Diffused Boron Into MgO Barrier on Pinhole Creation in CoFeB/MgO/CoFeB Magnetic Tunnel Junctions

A relationship between boron (B) diffusion into the MgO barrier and pinhole creation in CoFeB/MgO/CoFeB-magnetic tunnel junctions (MTJs) was investigated. The diffused B in the MgO layer was identified by secondary ion mass spectrometry for the MTJs annealed at 350degC , which provide the giant magnetoresistance (TMR) ratio. The pinhole density, estimated from the statistic distribution of breakdown voltage of the TMR properties, increased as either the thickness or the B content of the CoFeB layer became thicker or higher. These experimental findings imply that the diffused B into the MgO barrier creates pinholes to short-circuit the tunnel conduction, since the amount of diffused B into the MgO barrier might be related to the total amount of the B content in the CoFeB layer. Three different techniques were found to be useful for the reduction of diffused B into the MgO barrier layer; usage of materials having boron affinity for capping layer, decrease of the total amount of B-content in CoFeB layer, and reduction of grain boundaries in the MgO barrier layer.     

Perpendicular Magnetic Tunnel Junctions with CoFe/Pd Multilayer Electrodes and an MgO Barrier

We studied the magnetic and magnetoresistance characteristics of pseudospin-valve magnetic tunnel junctions (MTJs) based on CoFe/Pd multilayer electrodes with perpendicular magnetic anisotropy and an MgO barrier. The MTJs at annealing temperature (T _a) of 473 K showed a tunnel-magnetoresistance (TMR) ratio of 1.5%. An fcc (111)-oriented texture of the bottom and top Co₉₀Fe₁₀/Pd multilayer electrodes, together with an imperfectly crystallized MgO, were revealed by cross-sectional TEM images. The TMR properties of perpendicular MTJs with a Co₂₀Fe₆₀B₂₀ or Co₅₀Fe₅₀ layer inserted between the CoFe/Pd multilayer electrodes and the MgO barrier were also studied. The TMR ratio with Co₂₀Fe₆₀B₂₀ insertion was 1.7% at T _a= 473 K and monotonically decreased at T _a over 523 K. The TMR ratio with Co₅₀Fe₅₀ insertion increased up to 3% at T _a= 573 K and then decreased to 0.4% at T _a= 598 K. The influence of the Pd layer on CoFeB was studied by using the simplified structures of Pd/CoFeB/MgO/CoFeB/Pd and Ta/CoFeB/MgO/CoFeB/Ta with inplane anisotropy. A former structure with Pd resulted in reduced TMR ratio which decreases with increasing T _a, whereas MTJs with a Ta-based structure showed a monotonic increase of a TMR ratio. The low TMR ratio observed in Pd-containing structures appears to result from crystallization of CoFeB in an unfavorable crystal orientation.     

Surface morphology of epitaxial magnetic tunnel junctions

The surface morphology of epitaxial Fe(001)/MgO(001)/Fe(001) magnetic tunnel junctions, which show the giant tunneling magnetoresistance effect, was investigated by in situ scanning tunneling microscopy. It was observed that an epitaxial MgO barrier layer forms flat surface structures. The surface was flatter with distinct steps and terraces after annealing, which would lead to an increase of the tunneling magnetoresistance ratio. Examination of the local electronic structures of 1.05-nm-thick MgO barrier layers by scanning tunneling spectroscopy revealed no pinholes in the layers, so they would be perfect barriers in magnetic tunnel junctions.     

Highly spin-polarized materials and devices for spintronics?

The performance of spintronics depends on the spin polarization of the current. In this study half-metallic Co-based full-Heusler alloys and a spin filtering device (SFD) using a ferromagnetic barrier have been investigated as highly spin-polarized current sources. The multilayers were prepared by magnetron sputtering in an ultrahigh vacuum and microfabricated using photolithography and Ar ion etching. We investigated two systems of Co-based full-Heusler alloys, Co₂Cr_{1 − x}Fe_xAl (CCFA(x)) and Co₂FeSi_{1 − x}Al_x (CFSA(x)) and revealed the structure and magnetic and transport properties. We demonstrated giant tunnel magnetoresistance (TMR) of up to 220% at room temperature and 390% at 5 K for the magnetic tunnel junctions (MTJs) using Co₂FeSi_0.5Al_0.5 (CFSA(0.5)) Heusler alloy electrodes. The 390% TMR corresponds to 0.81 spin polarization for CFSA(0.5) at 5 K. We also investigated the crystalline structure and local structure around Co atoms by x-ray diffraction (XRD) and nuclear magnetic resonance (NMR) analyses, respectively, for CFSA films sputtered on a Cr-buffered MgO (001) substrate followed by post-annealing at various temperatures in an ultrahigh vacuum. The disordered structures in CFSA films were clarified by NMR measurements and the relationship between TMR and the disordered structure was discussed. We clarified that the TMR of the MTJs with CFSA(0.5) electrodes depends on the structure, and is significantly higher for L2₁ than B2 in the crystalline structure. The second part of this paper is devoted to a SFD using a ferromagnetic barrier. The Co ferrite is investigated as a ferromagnetic barrier because of its high Curie temperature and high resistivity. We demonstrate the strong spin filtering effect through an ultrathin insulating ferrimagnetic Co-ferrite barrier at a low temperature. The barrier was prepared by the surface plasma oxidization of a CoFe₂ film deposited on a MgO (001) single crystal substrate, wherein the spinel structure of CoFe₂O₄ (CFO) and an epitaxial relationship of MgO(001)[100]/CoFe₂ (001)]110]/CFO(001)[100] were induced. A SFD consisting of CoFe₂ /CFO/Ta on a MgO (001) substrate exhibits the inverse TMR of - 124% at 10 K when the configuration of the magnetizations of CFO and CoFe₂ changes from parallel to antiparallel. The inverse TMR suggests the negative spin polarization of CFO, which is consistent with the band structure of CFO obtained by first principle calculation. The - 124% TMR corresponds to the spin filtering efficiency of 77% by the CFO barrier.     

Highly spin-polarized materials and devices for spintronics∗

Abstract

The performance of spintronics depends on the spin polarization of the current. In this study half-metallic Co-based full-Heusler alloys and a spin filtering device (SFD) using a ferromagnetic barrier have been investigated as highly spin-polarized current sources. The multilayers were prepared by magnetron sputtering in an ultrahigh vacuum and microfabricated using photolithography and Ar ion etching. We investigated two systems of Co-based full-Heusler alloys, Co₂Cr_{1 ? x}Fe_xAl (CCFA(x)) and Co₂FeSi_{1 ? x}Al_x (CFSA(x)) and revealed the structure and magnetic and transport properties. We demonstrated giant tunnel magnetoresistance (TMR) of up to 220% at room temperature and 390% at 5 K for the magnetic tunnel junctions (MTJs) using Co₂FeSi_0.5Al_0.5 (CFSA(0.5)) Heusler alloy electrodes. The 390% TMR corresponds to 0.81 spin polarization for CFSA(0.5) at 5 K. We also investigated the crystalline structure and local structure around Co atoms by x-ray diffraction (XRD) and nuclear magnetic resonance (NMR) analyses, respectively, for CFSA films sputtered on a Cr-buffered MgO (001) substrate followed by post-annealing at various temperatures in an ultrahigh vacuum. The disordered structures in CFSA films were clarified by NMR measurements and the relationship between TMR and the disordered structure was discussed. We clarified that the TMR of the MTJs with CFSA(0.5) electrodes depends on the structure, and is significantly higher for L2₁ than B2 in the crystalline structure. The second part of this paper is devoted to a SFD using a ferromagnetic barrier. The Co ferrite is investigated as a ferromagnetic barrier because of its high Curie temperature and high resistivity. We demonstrate the strong spin filtering effect through an ultrathin insulating ferrimagnetic Co-ferrite barrier at a low temperature. The barrier was prepared by the surface plasma oxidization of a CoFe₂ film deposited on a MgO (001) single crystal substrate, wherein the spinel structure of CoFe₂O₄ (CFO) and an epitaxial relationship of MgO(001)[100]/CoFe₂ (001)]110]/CFO(001)[100] were induced. A SFD consisting of CoFe₂ /CFO/Ta on a MgO (001) substrate exhibits the inverse TMR of - 124% at 10 K when the configuration of the magnetizations of CFO and CoFe₂ changes from parallel to antiparallel. The inverse TMR suggests the negative spin polarization of CFO, which is consistent with the band structure of CFO obtained by first principle calculation. The - 124% TMR corresponds to the spin filtering efficiency of 77% by the CFO barrier.     

Spin filtering effects in monocristalline Fe/MgO/Fe magnetic tunnel junctions

Single-crystal magnetic tunnel junctions employing bcc (1 0 0) Fe electrodes and MgO(1 0 0) insulating barrier are elaborated by molecular beam epitaxy. Two extreme regimes have been investigated. First, for extremely thin MgO thickness we show that the equilibrium tunnel transport in Fe/MgO/Fe systems leads to antiferromagnetic interactions, mediated by the tunneling of the minority spin interfacial resonance state. Second, for large MgO barrier thickness, the tunnel transport validates specific spin filtering effect in terms of symmetry of the electronic Bloch function and symmetry-dependent wave function attenuation in the single-crystal barrier. Within this framework, we present giant tunnel magnetoresistive effects at room temperature (125–150%). Moreover, we illustrate that the interfacial chemical and electronic structure plays a crucial role in the filtering. We show that the insertion of carbon impurities at the Fe/MgO interface changes radically the voltage response of the tunnel magnetoresistance. Moreover, we provide experimental evidence for the electronic interfacial resonance states contribution to the spin polarized tunnel transport.     

Giant tunnelling magnetoresistance at room temperature with MgO (100) tunnel barriers

Magnetically engineered magnetic tunnel junctions (MTJs) show promise as non-volatile storage cells in high-performance solid-state magnetic random access memories (MRAM). The performance of these devices is currently limited by the modest (< approximately 70%) room-temperature tunnelling magnetoresistance (TMR) of technologically relevant MTJs. Much higher TMR values have been theoretically predicted for perfectly ordered (100) oriented single-crystalline Fe/MgO/Fe MTJs. Here we show that sputter-deposited polycrystalline MTJs grown on an amorphous underlayer, but with highly oriented (100) MgO tunnel barriers and CoFe electrodes, exhibit TMR values of up to approximately 220% at room temperature and approximately 300% at low temperatures. Consistent with these high TMR values, superconducting tunnelling spectroscopy experiments indicate that the tunnelling current has a very high spin polarization of approximately 85%, which rivals that previously observed only using half-metallic ferromagnets. Such high values of spin polarization and TMR in readily manufactureable and highly thermally stable devices (up to 400 degrees C) will accelerate the development of new families of spintronic devices.     

Influence of Boron Diffusion on Transport and Magnetic Properties in CoFeB/MgO/CoFeB Magnetic Tunnel Junction

Influence of boron concentration in CoFeB on the transport properties of CoFeB (B 20% and B 16%)/MgO/CoFeB magnetic tunnel junction (MTJ) was investigated. Boron distribution was studied by using X-ray photoelectron spectroscopy (XPS). High-resolution transmission electron microscope was utilized for analysis of the texture and interface quality. The MTJ with the boron diluted CoFeB (B 16%) pinned layer shows 10% higher MR than the CoFeB (B 20%). HRTEM shows that the MgO/CoFeB interface for the sample with diluted CoFeB layer has a better epitaxial MgO/CoFeB growth. Higher boron concentration in the as-deposited CoFeB stays high after annealing but boron content in the MgO increases as well. These results suggest that that MR improvement is directly related to the distribution of the boron in CoFeB/MgO/CoFeB MTJs after annealing.     

Mg/sub x/Zn/sub 1-x/O: a new piezoelectric material

Piezoelectric ZnO thin films have been successfully used for multilayer surface acoustic wave (SAW) and bulk acoustic wave (BAW) devices. Magnesium zinc oxide (Mg/sub x/Zn/sub 1-x/O) is a new piezoelectric material, which is formed by alloying ZnO and MgO. Mg/sub x/Zn/sub 1-x/O allows for flexibility in thin film SAW device design, as its piezoelectric properties can be tailored by controlling the Mg composition, as well as by using Mg/sub x/Zn/sub 1-x/O/ZnO multilayer structures. We report the metal-organic chemical vapor deposition (MOCVD) growth, structural characterization and SAW evaluation of piezoelectric Mg/sub x/Zn/sub 1-x/O (x<0.35) thin films grown on (011~2) r-plane sapphire substrates. The primary axis of symmetry, the c-axis, lies on the Mg/sub x/Zn/sub 1-x/O growth plane, resulting in the in-plane anisotropy of piezoelectric properties. SAW test devices for Rayleigh and Love wave modes, propagating parallel and perpendicular to the c-axis, were designed and fabricated. Their SAW properties, including velocity dispersion and piezoelectric coupling, were characterized. It has been found that the acoustic velocity increases, whereas the piezoelectric coupling decreases with increasing Mg composition in piezoelectric Mg/sub x/Zn/sub 1-x/O films.     

Preparation of ferroelectric Ba(Ti/sub 0.85/Sn/sub 0.15/)O/sub 3/ thin films by metal-organic decomposition

Ferroelectric Ba(Ti/sub 0.85/Sn/sub 0.15/)O/sub 3/ (BTS/sub 15/) thin film is newly prepared on the Pt/Ti/SiO/sub 2//Si substrate by metal-organic decomposition. The firing condition is determined by thermogravimetric and differential thermal analysis. The BTS/sub 15/ thin film with a flat surface and uniform thickness is obtained by spin coating in N/sub 2/ atmosphere that avoids moisture. The BTS/sub 15/ film has a perovskite phase and a preferential [110] texture. It is also found that the crystalline structure is cubic at 24/spl deg/C with a lattice constant of 4.01 /spl Aring/, and a grain size of about 30 nm was estimated by Scherrer equation and SEM image. From P-E hysteresis loop at 20/spl deg/C, the polarization at E=0 and the electric field at P=0 are found to be 1.07 /spl mu/C/cm/sup 2/ and 24.0 kV/cm, respectively. It is observed that the dielectric constant decreases monotonously from about 830 to 630 with increasing temperature ranging from 20/spl deg/C to 50/spl deg/C. Finally, it is found that the BTS/sub 15/ thin film shows a sufficient ferroelectricity and is an attractive material for functional ferroelectric devices, such as thermal-type infrared sensors.     

Magnetoresistance in magnetic tunnel junctions with amorphous electrodes

Magnetic tunnel junctions (MTJs) with amorphous CoFeB and Co/sub 2/MnSi electrodes were fabricated and examined. In the case of [Co/sub 90/Fe/sub 10/]/sub 100-x/B/sub x/, the x=32% boron addition reduces the magnetization by 30% compared to Co/sub 90/Fe/sub 10/, yet the reduction of the tunnel magnetoresistance (TMR) is over 95%. On the contrary, in the case of Co/sub (100-x-y)/Mn/sub x/Si/sub y/, although net magnetization is very small at room temperature, the TMR can be as large as 7%. The character of each metalloid (boron and silicon) could be responsible for the peculiar behavior to each system.     

Fabrication of resonant-tunneling diodes by Sb surfactant modified growth of Si films on CaF/sub 2//Si

Molecular beam epitaxy growth of Si thin films on CaF/sub 2//Si(111) substrates has been studied. A surfactant-modified solid-phase epitaxy method, where the room temperature Si deposition was followed by annealing under Sb flux, resulted in a continuous, smooth epitaxial crystalline Si film with a sharp (/spl radic/3/spl times//spl radic/3)R30/spl deg/ reconstruction and a surface roughness of 0.15-nm rms for a 2.8-nm Si thin film. This growth technique was used to fabricate CaF/sub 2//Si/CaF/sub 2/ double-barrier resonant tunneling diodes in SiO/sub 2/ windows patterned on Si(111) substrates. A negative differential resistance (NDR) peak was found at /spl sim/0.35 V at 77 K, and the current density at the NDR peak was estimated to be 3-4 orders of magnitude higher than in earlier reports.     

Nanofabrication of magnetic tunnel junctions by using side-edge thin film deposition

Nanostructured double ferromagnetic tunnel junctions (MTJs) are indispensable for investigation of spin-dependent single-electron transport at low temperature. A new fabrication process that enables us to reduce the size of MTJs down to nanometer scale by using the side edge of a patterned film were developed. The multilayers of MTJ partially replaced by thick Al₂O₃/Cu double layer were prepared by using electron beam lithography and lift-off, then Pt film was vacuum-evaporated onto the side edge of Al₂O₃/Cu film, which masked MTJ during following Ar ion milling. As a result, the double MTJs with the dimension of 10 nm £ 10 mm were formed beneath the Pt film. The large tunnel magnetoresistive ratio of 35% and symmetrical I–V characteristics were obtained at room temperature.