ARTICLE
Received 4 Apr 2013 | Accepted 16 Jul 2013 | Published 20 Aug 2013
P. Wadley1,2, V. Novk1, R.P. Campion2, C. Rinaldi1,3, X. Mart1,4,5, H. Reichlov1,4, J.elezn1, J. Gazquez6, M.A. Roldan7,8, M. Varela7,8, D. Khalyavin9, S. Langridge9, D. Kriegner10, F. Mca11, J. Maek11, R. Bertacco3,V. Hol4, A.W. Rushforth2, K.W. Edmonds2, B.L. Gallagher2, C.T. Foxon2, J. Wunderlich1,12 & T. Jungwirth1,2
Recent studies have demonstrated the potential of antiferromagnets as the active component in spintronic devices. This is in contrast to their current passive role as pinning layers in hard disk read heads and magnetic memories. Here we report the epitaxial growth of a new high-temperature antiferromagnetic material, tetragonal CuMnAs, which exhibits excellent crystal quality, chemical order and compatibility with existing semiconductor technologies. We demonstrate its growth on the IIIV semiconductors GaAs and GaP, and show that the structure is also lattice matched to Si. Neutron diffraction shows collinear antiferromagnetic order with a high Nel temperature. Combined with our demonstration of room-temperature-exchange coupling in a CuMnAs/Fe bilayer, we conclude that tetragonal CuMnAs lms are suitable candidate materials for antiferromagnetic spintronics.
DOI: 10.1038/ncomms3322
Tetragonal phase of epitaxial room-temperature antiferromagnet CuMnAs
1 Institute of Physics ASCR, v.v.i., Cukrovarnick 10, 162 53 Praha 6, Czech Republic. 2 School of Physics and Astronomy, University of Nottingham, Nottingham NG7 2RD, UK. 3 LNESS-Dipartimento di Fisica del Politecnico di Milano Via Anzani 42, 22100 Como, Italy. 4 Faculty of Mathematics and Physics, Charles University in Prague, Ke Karlovu 3, 121 16 Prague 2, Czech Republic. 5 Department of Materials Science and Engineering, University of California, Berkeley, California 94720, USA. 6 Institut de Cincia de Materials de Barcelona, ICMAB-CSIC E-08193, Bellaterra, Spain. 7 Departamento de Fisica Aplicada III, Universidad Compluense de Madrid, 28040 Madrid, Spain. 8 Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831-6071, USA. 9 ISIS, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Science and Technology Facilities Council, Oxon OX11 0QX, UK. 10 Institute of Semiconductor and Solid State Physics, University Linz, Altenbergerstrasse 69, A-4040 Linz, Austria. 11 Institute of Physics ASCR,v.v.i., Na Slovance 2, 182 21 Praha 8, Czech Republic. 12 Hitachi Cambridge Laboratory, Cambridge CB3 0HE, UK. Correspondence and requests for materials should be addressed to P.W. (email: mailto:[email protected]
Web End [email protected] ).
NATURE COMMUNICATIONS | 4:2322 | DOI: 10.1038/ncomms3322 | http://www.nature.com/naturecommunications
Web End =www.nature.com/naturecommunications 1
& 2013 Macmillan Publishers Limited. All rights reserved.
ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3322
Large and bistable magnetoresistance signals have been observed in tunnelling devices with an antiferromagnetic (AFM) IrMn layer on one side and a non-magnetic metal on
the other side of the tunnel barrier1,2. The work has experimentally demonstrated the feasibility of a spintronic concept35 in which the electronic device characteristics are governed by the staggered magnetization axis in an AFM. It has been shown that the AFM moments can be manipulated via an exchange-coupled ferromagnet (FM)1,2,6 and that the AFM magnetoresistance signals can persist to room temperature6. No stray elds and the relative insensitivity to external magnetic elds are among the features that make AFMs attractive complements to the conventionally utilized FMs in the design of spintronic devices, as highlighted in a recent study of AFM linear chains of a few Fe atoms7 and in the demonstration of the concept of an AFM memory8. The possibility to design spintronic elements based on AFMs becomes even more attractive in the context of magnetic counterparts of conventional compound semiconductors, which may enable new devices combining spintronic and nanoelectronic functionalities. In this paper, we report the discovery of a new member of this family: tetragonal epitaxial CuMnAs, a room-temperature AFM whose in-plane lattice constant matches GaP or Si.
Over the past two decades, the introduction of magnetism into common semiconductor hosts has driven a number of new research areas in spintronics. Inspired by spintronics research and applications based on transition metal ferromagnets (FMs), the focus has been on magnetic counterparts of semiconductors with the FM order. (Ga,Mn)As and related (III,Mn)V compounds911 have become archetypes among these materials, resulting in discoveries of new spin-related physical phenomena and device functionalities. For example, the understanding of spin-orbit-coupling phenomena has advanced because of experiments in (Ga,Mn)As from the ohmic transport regime to new realizations in tunnelling and Coulomb blockade devices12,13. Low Curie temperatures have prevented the direct integration of (III,Mn)V FM semiconductors into spintronic technologies. Nevertheless, new phenomena discovered in (Ga,Mn)As have been subsequently reported in the room-temperature metal FMs, relevant not only for basic science but also for practical spintronic applications1416.
Although a ferromagnetic ground state is rare within magnetic materials derived from semiconductor compounds and their Curie temperatures are below room temperature, high Nel temperature (TN) AFMs can be found, for example, among the magnetic counterparts of the IIIV semiconductors (see also Supplementary Table S1 and Supplementary Note 1)4,5. The structures of the non-magnetic semiconductors such as LiZnAs, NaZnAs, CuZnAs and AgZnAs are closely related to the IIIV zincblende structure, as shown in Fig. 1a,b. By splitting the group III atom into two elements from groups I and II, their combined valence equals that of the group III atom. One of the two elements resides on the zincblende site, whereas the other occupies one of the tetrahedral interstitial sites that is empty in the zincblende structure17. An extensively studied magnetic compound with the same lled zincblende (also called half-Heusler) crystal structure is CuMnSb (Fig. 1c)18,19. The AFM coupling of FM (111) planes of this cubic crystal has a frustration in the magnetic interactions, with half of the Mn nearest-neigbours coupled antiferromagnetically and half ferromagnetically20. This frustration leads to the relatively low TN 50 K of CuMnSb
and shows that keeping the same cubic structure as in the non-magnetic parent IIIV compound is unfavourable for robust antiferromagnetism. Moreover, lowering the symmetry from cubic to, for example, tetragonal enhances the magnetocrystalline anisotropy phenomena and is therefore favourable for the concept of AFM spintronics.
LiMnAs and NaMnAs are among the examples of AFM IIIV semiconductors4,2124, whose equilibrium crystal structure changes from the cubic half-Heusler lattice of their non-magnetic counterparts to a layered tetragonal structure (Fig. 1d). This more-anisotropic-crystal arrangement removes the frustration in the nearest-neighbour magnetic coupling, resulting in TNs far above the room temperature. Single-crystal thin lms of the LiMnAs AFM semiconductor were recently prepared by molecular beam epitaxy (MBE) on lattice-matched InAs substrate4,24,25. The inclusion of alkali metal elements represents, however, a challenge both in terms of the growth and the stability of devices. Group Ib transition metal elements may represent the solution to this problem: NaZnAs and AgZnAs are known to be twin compounds with identical crystal structure and lattice constants, and CuZnAs is also very similar17. This has motivated our interest in CuMnAs as a suitable IMnV AFM compound for spintronics20. The bulk equilibrium phase of CuMnAs displays room-temperature AFM ordering26, as conrmed in our recent study of chemically synthesized bulk samples20. However, the orthorhombic crystal structure (Fig. 1e)
IIIV IIIV
a b
CuMnSb
c LiMnAs
d
CuMnAs orthorhombic
e CuMnAs tetragonal
f
Figure 1 | Unit cell structures of non-magnetic semiconductors and their magnetic counterparts. (a) IIIV zincblende structure. (b) IIIV half-Heusler structure. (c) Half-Heusler CuMnSb. (d) Tetragonal LiMnAs.(e) Orthorhombic CuMnAs. (f) Tetragonal CuMnAs. The bonds in (c), highlighted in green and red, show the AFM and FM nearest-neighbour-exchange coupling of Mn present in the half-Heusler CuMnSb. The bonds in (f), highlighted in green, show that all Mn nearest neighbours are coupled antiferromagnetically in the tetragonal CuMnAs, which is favorable for high TN.
2 NATURE COMMUNICATIONS | 4:2322 | DOI: 10.1038/ncomms3322 | http://www.nature.com/naturecommunications
Web End =www.nature.com/naturecommunications
& 2013 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3322 ARTICLE
is not compatible with conventional compound semiconductor substrates.
In the present work, we demonstrate that CuMnAs lms can be prepared by MBE in the tetragonal form reminiscent of NaMnAs (Fig. 1f). In analogy to the IaMnV compounds, all nearest neighbours in the tetragonal CuMnAs lms couple antiferro-magnetically, resulting in a high TN. We demonstrate relaxed epilayers of the tetragonal phase of CuMnAs grown on GaAs substrate and fully strained CuMnAs lms grown on the closely lattice-matched GaP. The functionality of this new AFM IIIV compound is demonstrated in all-epitaxial CuMnAs/Fe AFM/FM bilayers, in which we observe large room-temperature-exchange bias effects.
ResultsSynthesis and structure of CuMnAs epilayers. To stabilize the tetragonal phase of CuMnAs, layers were grown on the zincblende IIIV semiconductor substrates GaAs(001) and GaP(001). In situ reection high-energy electron diffraction (RHEED) and ex situ X-ray diffraction (XRD) measurements, shown in Fig. 2, revealed a structure incompatible with the chemically synthesized bulk material studied by Mundelein and Schuster26. The space group of this structure was determined using a combined experimental and computational method that enables the precise determination of the atomic positions in a thin lm using conventional Cu Ka X-ray sources only27. The space group was found to be that of the tetragonal Cu2Sb family, P4/nmm. The lattice parameters of epitaxial CuMnAs were found to be a b 3.820 and
c 6.318 for the relaxed material grown on GaAs.
Figure 2c shows the unit cell of CuMnAs and Fig. 2d a birds-eye view of its registry with the substrate. The closest match to the
two substrates used, GaAs and GaP, is with the CuMnAs principal in-plane axis matching along the half diagonal of the GaAs/GaP unit cell, and this is indeed the orientation it robustly adopts for a range of temperatures and stoichiometries. In the case of the GaAs substrate, the match is only preserved for the rst few monolayers whereupon the layer relaxes, as evidenced by a dimming in the RHEED pattern. However, it continues to grow with the same relative orientation, and the RHEED pattern reappears several nanometres later. For the GaP substrate, a mismatch of B0.3% is observed along the same geometry and the layer remains strained up to the thickest layers grown so far (130 nm).
Figure 2e shows X-ray 2Y/o linescans and reciprocal space maps around the CuMnAs(003) diffraction peak for CuMnAs grown on GaAs(001) and GaP(001). The broadening of the reciprocal space map, as evidenced in Fig. 2e (left inset) of the CuMnAs(003), is attributed to mosaicity introduced by the poor lattice matching of CuMnAs to the GaAs substrate. The high strain and subsequent relaxation introduce defects, leading to mosaic blocks. This is supported by the tting of a mosaic block model to the CuMnAs/GaAs that shows good agreement with a model assuming ellipsoid blocks with lateral dimensions of 50 nm, vertical dimensions of 20 nm and RMS misalignment of1.5 (red line in Fig. 2e)28,29. The much sharper spot produced by the CuMnAs on GaP (right inset) indicates a more coherent layer that no longer ts a mosaic block model well.
The image shown in Fig. 2f is a Z-contrast scanning transmission electron microscopy (STEM) slice along the CuMnAs [100] direction. In the enlarged region shown in Fig. 2g, the brighter As atoms are clearly visible in a triangular arrangement that matches exactly to the X-ray-determined structural model along the same [100] direction, overlaid on
e 104
103
102
101
29 29.5
a b
Q z (nm1)
30
CuMnAs/GaAs CuMnAs/GaP
0.5 0 0.5 0.2 0.2Qx (nm1)
Intensity (cps)
29.6
Qx (nm1)
30 30.5
Qz (nm1)
c d f g
[001]
[010]
[001]
[010]
[100]
[100]
[010]
Figure 2 | Growth and structural characterization of CuMnAs. (a,b) RHEED images of the surface of a CuMnAs layer during growth on a GaP substrate taken along the substrate [110] and [ 110], respectively. (c) Diagram depicting the CuMnAs unit cell structure and spin arrangement, with Mn (purple), Cu(blue) and As(yellow). (d) A birds-eye view of how the layer grows on GaAs and GaP substrates, the green balls represent the As or P atoms. (e) X-ray 2Y/o scans of the CuMnAs (003) diffraction peak for layers grown on GaP and GaAs. The experimental data are shown as grey dots, whereas the red line is a mosaic block model tting for the layer grown on GaAs. This model is not applicable for the layers on GaP. The corresponding(003) reciprocal space maps are shown in the insets. (f,g) Z-contrast STEM image of CuMnAs along the [100] direction. The As positions are clearly visible as the brightest atoms, and intensity analysis along the rows reveal a highly ordered compound in complete agreement with the overlaid model structure in (g). The CuMnAs unit cell, as depicted in panel (c), is highlighted by a white dashed box in (g).
NATURE COMMUNICATIONS | 4:2322 | DOI: 10.1038/ncomms3322 | http://www.nature.com/naturecommunications
Web End =www.nature.com/naturecommunications 3
& 2013 Macmillan Publishers Limited. All rights reserved.
ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3322
the top right side of the image. The Cu and Mn, which are much closer in size, are not clearly distinguishable by eye; however, when the intensity is proled along the atomic planes, the Cu and Mn can be distinguished and they show a high degree of chemical order.
Magnetic characterization of CuMnAs. Magnetic properties of the CuMnAs layers were examined using a combination of neutron diffraction and superconducting quantum interference device magnetometry. Neutron diffraction measurements were taken using the WISH instrument at the ISIS neutron source. Two scattering geometries were used to access the (h00) and (00l) sets of reections and revealed the presence of the structurally forbidden (100) magnetic reection. The absence of this peak structurally was conrmed using in-plane XRD, which as expected reveals the presence of the (200) and (400) reections but not the forbidden (100) reection. Fig. 3a shows the (100) magnetic peak, which conrms the presence of long-range AFM order with the same dimensions as the structural unit cell. This peak is completely absent at 500 K, whereas the nuclear (200) peak (not shown) and the structural contribution of the (001) peak are still present (Fig. 3b), conrming that the layer has been neither destroyed nor undergone a phase change, but has lost long-range AFM order.
An analysis of the possible spin congurations, classied according to the irreducible representations associated with the G-point (k 0) of the P4/nmm space group, reveals that only
models involving basis functions of the bidimensional G 5 representation are consistent with the neutron-diffraction results.
These models imply AFM coupling of the two symmetry-related Mn sites, with spins conned to the (ab) plane (Fig. 2c). Precise determination of the direction of the spin axes within this plane is complicated by the expected magnetic domains. The room-temperature data normalized to a vanadium spectrum and scaled to the nuclear (200) peak allowed us to estimate the magnetic moments of Mn to be 3.6(2) mB, assuming that the possible magnetic domains are equally populated.
Superconducting quantum interference device magnetometry performed on stoichiometric CuMnAs layers revealed no ferroor paramagnetic response, consistent with a pure AFM. In order to provide further support for the magnetic properties of the samples, CuMnAs layers were grown with 3 nm of epitaxial Fe on top and capped to prevent oxidation. By eld-cooling these layers through 430 K, it is possible to induce an exchange bias shift at and above room temperature. This exchange bias is evident in the hysteresis loops shown in Fig. 3c, and is robust and reproducible across many samples (Supplementary Figs S1 and S2, and Supplementary Note 2). The effect remains present after training,
and there is also a large change in the coercive eld of the Fe layer compared with Fe on GaAs alone30. Heating above 440 K was found to damage the Fe/CuMnAs interface in a similar manner to that observed for Fe/GaAs heterostructures3032, and after this permanent damage it is no longer possible to induce exchange bias (Supplementary Fig. S2a). The permanent changes to the interface were conrmed using temperature-dependent X-ray reectivity and XRD, where roughening and density changes are observed in the interfacial region but the bulk crystal remains intact.
Transport measurements on CuMnAs. Transport measurements on stoichiometric CuMnAs samples are shown in Fig. 4. The resistivity at 4 K is about 90 mO cm rising to about 160 mO cm at 300 K. These values are compatible with the semimetallic-like band structure suggested by the GGA U calculations (detailed
in the next section), with strongly suppressed density of states around the Fermi energy. The measured positive Hall coefcient of 6 10 8 O cm T 1 interpreted in a single-carrier model
would give a carrier density of 1.1 1022 cm 3. However, as
discussed in Maca et al.20 for the orthorhombic bulk CuMnAs and conrmed by our calculations for the tetragonal CuMnAs presented below, the compounds electronic structure is at the transition from a semiconductor to a semimetal. The nature of electronic states near the Fermi energy may therefore be sensitive to relatively small changes of intrinsic and extrinsic parameters of the CuMnAs lms. In this situation, where the band structure is complex, the single-carrier interpretation is inappropriate and can greatly overestimate the number of carriers if (as the
a b
1.6104
1.4104
1.2104
1.0104
8.0105
0 75 150 225 5 0 5
4.0107
4.0107
0.0
[afii9845](cm)
[afii9845] H(cm)
T (K) Applied field (T)
Figure 4 | Transport in CuMnAs. (a) shows the temperature dependence of resistivity and (b) the Hall resistivity as a function of applied magnetic eld.
a b c
Integrated intensity
(a.u.)
Integrated intensity
(a.u.)
Moment (105 emu)
6.0 6.2 6.4 6.6
2
1
0
1
2
500 250 0 250 500 Field (Oe)
3.6 3.8 4.0d-spacing () d-spacing ()
Figure 3 | Magnetic characterization. (a) Neutron-diffraction data showing the structurally forbidden CuMnAs (100) diffraction peak at 300 K (lled symbols) and 500 K (open symbols). (b) Neutron-diffraction from the CuMnAs (001) peak measured at the same temperatures. At 300 K, this reection combines both nuclear and magnetic contributions. (c) Hysteresis loops performed on a 3-nm Fe lm on CuMnAs at 300 K after cooling in a 1-T eld from 430 K. A stable exchange bias is observed symmetrically for positive (blue) and negative (orange) eld cool directions.
4 NATURE COMMUNICATIONS | 4:2322 | DOI: 10.1038/ncomms3322 | http://www.nature.com/naturecommunications
Web End =www.nature.com/naturecommunications
& 2013 Macmillan Publishers Limited. All rights reserved.
NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3322 ARTICLE
a b
10
864202468108 6 4 2 0 2 4
EEF (eV)
DOS (states eV1 spin1 )
DOS (states eV1 spin1 )
10
8 6 4 2 0 2 4 6 8 10
8 6 4 2 0 2 4EEF (eV)
Figure 5 | Density of states calculations. GGA U-calculated density of states of tetragonal CuMnAs for (a) antiferromagnetic and (b) ferromagnetic
congurations. Upper and lower sections are for up and down spins, respectively. Blue and red lines in (a) are the local density of states for Mn in each sublattice. Blue lines in (b) are the local density of states of Mn. The black lines in both panels are the total density of states.
calculations indicate) the numbers of hole-like and electron-like carriers are comparable.
Calculations. From GGA U band-structure calculations, shown
in Fig. 5, we conrm that the AFM phase in CuMnAs has lower energy than the FM phase, and the difference is 109 meV f.u. 1.
For comparison, calculations for the cubic half-Heusler CuMnSb give the difference of only 4 meV f.u. 1. This suggests that the
Nel temperature of the tetragonal CuMnAs is much higher than the TN 50 K of CuMnSb (ref. 33), as indeed is observed in our
experiments. The robust AFM order is retained when the CuMnAs crystal transforms from the equilibrium bulk orthorhombic structure26 to the tetragonal structure stabilized in our thin lm epilayers.
The GGA U calculations show that tetragonal CuMnAs in
the AFM ground state has a strongly suppressed density of states around the Fermi energy (see Fig. 5a), indicating an electronic structure of a semimetal or a narrow bandgap semiconductor. This is in a contrast to the FM phase, which is strongly metallic (see Fig. 5b). Our results in CuMnAs illustrate the generic trend that AFMs are more compatible with semiconductor/semimetal electronic structure than FMs. We also performed relativistic GGA U calculations of magnetic anisotropy of the tetragonal
CuMnAs in the AFM ground state. Consistent with the experiment, we nd that the Mn moments, ordering ferromagnetically within the plane and antiferromagnetically between the planes, are oriented in the (ab) plane.
Finally, we note that the IaMnV compounds, NaMnAs and KMnAs, crystallize in a tetragonal structure very similarly to the structure of CuMnAs, with the only difference being that the group Ia element occupies the Mn position in the crystal structure of CuMnAs and Mn occupies the Cu position. For this reason, we compared total energies of CuMnAs when Cu and Mn switched places in the lattice. The lower energy state is observed for the conguration corresponding to the one inferred from our structural measurements of CuMnAs and shown in Fig. 2c, with the difference of 0.56 eV f.u. 1.
DiscussionThe results presented above demonstrate CuMnAs as a tetragonal room-temperature AFM with high crystalline quality and chemical delity. The exchange bias and broadening of the Fe hysteresis loop induced by CuMnAs provides not only additional evidence for the high-temperature AFM ordering in the tetragonal CuMnAs epilayers, but also clearly demonstrates the potential of this new material for AFM-based spintronic
functionalization. The same type of AFM/FM exchange-coupling phenomena was utilized in the demonstration of the rst AFM-tunnelling anisotropic magnetoresistance devices1,2,6.
Tunnelling anisotropic magnetoresistance is one of a family of spin-orbit-coupling phenomena in which electronic properties and spin can inuence each other. This is manifested in the realization of large magnetoresistances because of anisotropies in the density of states and chemical potential and in the realization of carrier-induced spin reorientation phenomena. Many of these relativistic spintronic effects were rst observed in the ferromagnetic Mn-doped zincblende GaAs12,13,34,35. CuMnAs shares the spin orbit, broken space-inversion symmetry character of the electronic structure with these magnetic zincblende compounds, and the tetragonal distortion of its lattice further enhances the magnetic anisotropy. The in-plane lattice parameter closely matches to GaP and Si. CuMnAs layers can be grown in a conventional IIIV MBE system and therefore can be readily combined with established semiconductor heterostructure technologies. All these characteristics, complemented by the room-temperature collinear magnetic order, make CuMnAs a favourable material candidate for exploring the phenomena and functionalities within the emerging concept of spintronics based on AFMs.
Methods
Growth of CuMnAs lms. The CuMnAs lms were grown in a Veeco GEN-III MBE system. Standard effusion cells were used as sources for elemental Mn and Cu, and a valved cracker cell (in the As4 regime) was used as the source of As. The epitaxial growths were carried out at a substrate temperature of 300 C, with the material uxes set to cover a range of ratios around the stoichiometric point of Cu:Mn:As 1:1:1. For growth on GaAs(001), after opening the cell shutters the
(2 4) RHEED image of the clean GaAs surface became diffuse within several
seconds. Typically, a new streaky (2 2) pattern emerged during the next 20 min
(corresponding to B10 nm of the epitaxial CuMnAs), which then remained stable till the end of the growth. In contrast, for growth on GaP(001), the transition period of the diffuse RHEED image was completely missing; instead, a (1 2)
pattern arose immediately after opening the shutters, transforming smoothly into the streaky (2 2) within the rst 5 min of growth (Fig. 2a,b).
Structural characterization. High-resolution XRD measurements to determine the lattice parameters were performed on a Panalytical Xpert Materials Research Diffractometer (MRD) equipped with a standard Cu X-ray tube, a parabolic X-ray mirror, a 4 220 Ge Bartels monochromator and a 3 220 Ge channel-cut crystal
analyser with point detector. For the space group renement, a combined experimental and computational procedure, which utilized a Bruker area detector in combination with the aforementioned MRD, was used. The details of this technique are published elsewhere27.
High-resolution aberration-corrected STEM was performed at Oak Ridge National Laboratory in a Nion UltraSTEM column, operated at 100 kV and equipped with a fth-order Nion aberration corrector. Samples were prepared by conventional thinning, grinding, dimpling and Ar ion milling.
NATURE COMMUNICATIONS | 4:2322 | DOI: 10.1038/ncomms3322 | http://www.nature.com/naturecommunications
Web End =www.nature.com/naturecommunications 5
& 2013 Macmillan Publishers Limited. All rights reserved.
ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms3322
Calculations. We used the full-potential linearized-augmented-plane-wave method (WIEN2k package36) to calculate the magnetic structure of the tetragonal CuMnAs. In all calculations we used the PBE-GGA exchange-correlation potential36. Plane wave cutoff was given by RMT kmax 7.5, where RMT is the
smallest mufn-tin radius. Brillouin zone was sampled by a mesh composed of up to 20,000 k-points. To describe the correlations of Mn 3d electrons, we employed the GGA U approximation with U 4.6 eV and J 0.5 eV. The lattice constants
and z positions of As and Mn were taken from the experiment.
References
1. Park, B. G. et al. A spin-valve-like magnetoresistance of an antiferromagnet-based tunnel junction. Nat. Mater. 10, 347351 (2011).
2. Mart, X. et al. Electrical measurement of antiferromagnetic moments in exchange-coupled IrMn/NiFe stacks. Phys. Rev. Lett. 108, 017201 (2012).
3. Shick, A. B., Khmelevskyi, S., Mryasov, O. N., Wunderlich, J. & Jungwirth, T. Spin-orbit coupling induced anisotropy effects in bimetallic antiferromagnets: A route towards antiferromagnetic spintronics. Phys. Rev. B 81, 212409 (2010).
4. Jungwirth, T. et al. Demonstration of molecular beam epitaxy and a semiconducting band structure for I-Mn-V compounds. Phys. Rev. B 83, 035321 (2011).
5. Cava, R. J. A useful pyramid scheme. Physics 4, 7 (2011).6. Wang, Y. Y. et al. Room-temperature perpendicular exchange coupling and tunnelling anisotropic magnetoresistance in an antiferromagnet-based tunnel junction. Phys. Rev. Lett. 109, 137201 (2012).
7. Loth, S., Baumann, S., Lutz, C. P., Eigler, D. M. & Heinrich, A. J. Bistability in atomic-scale antiferromagnets. Science 335, 196199 (2012).
8. Petti, D. et al. Storing magnetic information in IrMn/MgO/Ta tunnel junctions via eld-cooling. Appl. Phys. Lett. 102, 192404 (2013).
9. Ohno, H. Making nonmagnetic semiconductors magnetic. Science 281, 951955 (1998).
10. Jungwirth, T., Sinova, J., Maek, J., Kuera, J. & MacDonald, A. H. Theory of ferromagnetic (III,Mn)V semiconductors. Rev. Mod. Phys. 78, 809864 (2006).
11. Dietl, T., Awschalom, D. D., Kaminska, M. & Ohno, H. Spintronics. Semiconductors and Semimetals(Elsevier) 82, 135205 (2008).
12. Gould, C. et al. Tunnelling anisotropic magnetoresistance: A spin-valve like tunnel magnetoresistance using a single magnetic layer. Phys. Rev. Lett. 93, 117203 (2004).
13. Wunderlich, J. et al. Coulomb blockade anisotropic magnetoresistance effect in a (Ga,Mn)As single-electron transistor. Phys. Rev. Lett. 97, 077201 (2006).
14. Moser, J. et al. Tunnelling anisotropic magnetoresistance and spin-orbit coupling in Fe/GaAs/Au tunnel junctions. Phys. Rev. Lett. 99, 056601 (2007).
15. Gao, L. et al. Bias voltage dependence of tunneling anisotropic magnetoresistance in magnetic tunnel junctions with MgO and Al2O3 tunnel barriers. Phys. Rev. Lett. 99, 226602 (2007).
16. Park, B. G. et al. Tunnelling anisotropic magnetoresistance in multilayer-(Co/ Pt)/AlOx/Pt structures. Phys. Rev. Lett. 100, 087204 (2008).
17. Zunger, A., Wagner, S. & Petroff, P. M. New materials and structures for photovoltaics. J. Electron. Mater. 22, 316 (1993).
18. Forster, R. H., Johnston, G. B. & Wheeler, D. A. Studies on the heusler alloys-III. the antiferro-magnetic phase in the Cu-Mn-Sb system. J. Phys. Chem. Solids 29, 855861 (1968).
19. Endo, K. Magnetic studies of Clb-compounds CuMnSb, PdMnSb and Cu1-x (Ni or Pd)x MnSb. J. Phys. Soc. Jpn 29, 643649 (1970).
20. Maca, F. et al. Room-temperature antiferromagnetism in CuMnAs. J. Magn. Magn. Mater. 324, 16061612 (2012).
21. Bronger, W., Mller, P., Hppner, R. & Schuster, H. U. The magnetic properties of NaMnP, NaMnAs, NaMnSb, NaMnBi, LiMnAs, and KMnAs, characterized by neutron diffraction experiments. Z. Anorg. Allg. Chem. 539, 175182 (1986).
22. Muller, R., Kuckel, M., Schuster, H. U., Muller, P. & Bronger, W. Neue AMnX-verbindungen mit A-Rb, Cs und X-P, As, Sb, Bi: Struktur und magnetismu.J. Alloys Compnd. 176, 167172 (1991).23. Schucht, F. et al. The magnetic properties of the alkali metal manganese pnictides KMnP,RbMnP, CsMnP, RbMnAs, KMnSb, KMnBi, RbMnBi, and CsMnBineutron diffraction and susceptibility measurements. Z. Anorg. Allg. Chem. 625, 3136 (1999).
24. Wijnheijmer, A. P. et al. Scanning tunneling microscopy reveals LiMnAs is a room temperature anti-ferromagnetic semiconductor. Appl. Phys. Lett. 100, 112107 (2012).
25. Novk, V. et al. Molecular beam epitaxy of LiMnAs. J. Cryst. Growth 323,
348350 (2011).
26. Mndelein, J. & Schuster, H. U. Preparation and crystal structure of compounds MnCuX (X P, As, PxAs1 x). Z. Naturforsch. B 47, 925 (1992).
27. Wadley, P. et al. Solving and rening novel thin lm phases using Cu X-ray radiation: the epitaxy-induced CuMnAs tetragonal phase. Pre print http://arxiv.org/abs/1301.5227
Web End =http:// http://arxiv.org/abs/1301.5227
Web End =arxiv.org/abs/1301.5227 (2012).
28. Holy, V. et al. X-ray double and triple crystal diffractometry of mosaic structure in heteroepitaxial layers. J. Appl. Phys. 74, 17361743 (1993).
29. Hol, V., Wolf, K., Kastner, M., Stanzl, H. & Gebhardt, W. X-ray triple-crystal diffractometry of defects in epitaxic layers. J. Appl. Crystallogr. 27, 551557 (1994).
30. Wastlbauer, G. & Bland, J. A. C. Structural and magnetic properties of ultrathin epitaxial Fe lms on GaAs(001) and related semiconductor substrates. Adv. Phys. 54, 137219 (2005).
31. Deputier, S., Guerin, R., Lepine, B., Guivarch, A. & Jezequel, G. The ternary compound Fe3Ga2 xAsx: a promising candidate for epitaxial and
thermodynamically stable contacts on GaAs. J. Alloys Comp. 262-263, 416422 (1997).32. Deputier, S., Guerin, R. & Guivarch, A. Solid state phase equilibria in the Fe-Ga-As system. Eur. Phys. J. Appl. Phys. 2, 127133 (1998).
33. Endo, K. Magnetic studies of Clb-compounds CuMnSb, PdMnSb and Cu1 x
(Ni or Pd)x MnSb. J. Phys. Soc. Jpn 29, 643649 (1970).34. Chernyshov, A. et al. Evidence for reversible control of magnetization in a ferromagnetic material by means of spin-orbit magnetic eld. Nat. Phys. 5, 656659 (2009).
35. Ciccarelli, C. et al. Spin gating electrical current. Appl. Phys. Lett. 101, 122411 (2012).
36. Blaha, P., Schwarz, K., Madsen, G., Kvasnicka, D. & Luitz, J. Wien2k, An augmented plane wave local orbitals program for calculating crystal
properties Karlheinz Schwarz, Techn. Universitt Wien (http://www.wien2k.at/
Web End =http://www.wien2k.at/) (2001).
Acknowledgements
Research at UCM (M.A.R.) was supported by the ERC Starting Grant No. 23973. Research at ORNL was supported by the Materials Sciences and Engineering Division of the U.S. DOE (M.V.) and by ORNLs Shared Research Equipment (ShaRE) User Facility, which is sponsored by the Ofce of BES, U.S. DOE. J.R. C.F. acknowledges nancial support from Spanish Ministerio de Ciencia e Innovacin Tecnolgica (Projects MAT2009-07967, Consolider NANOSELECT CSD2007-00041) and the Generalitat de Catalunya.X.M. acknowledges the Czech Science Foundation (Project P204/11/P339). D.Kriegner acknowledges the support by the Austrian Academy of Sciences (DOC-Program). T.J. and V.N acknowledge the support from EU ERC Advanced Grant No. 268066 and from the Ministry of Education of the Czech Republic Grants No. LM2011026, and from the Academy of Sciences of the Czech Republic Preamium Academiae. R.B. and C.R. acknowledge nancial support from Fondazione Cariplo via the project EcoMag (Project No. 2010-0584). Experiments at the ISIS Pulsed Neutron and Muon Source were supported by a beamtime allocation from the Science and Technology Facilities Council. Research at the University of Nottingham was funded by EPSRC grant EP/K027808/1.
Author contributions
Proposal of the material: T.J., J.Z., J.M., B.L.G. and F.M.; Research Coordination: P.W.,X.M., R.P.C. and K.W.E.; Material growth and optimization: R.P.C., V.N., C.T.F and P.W.; Transport and Magnetization: C.R., H.R., J.W. and P.W.; X-ray diffraction: X.M.,V.H. and P.W.; STEM measurements and analysis: J.G., M.A.R., M.V and C.R.: Exchange bias heterostructure production: R.P.C. and A.W.R.; Temperature-dependent X-ray diffraction and X-ray reectivity: D.K.; Neutron diffraction and analysis: D.K., S.L., K.W.E. and P.W.; DFT calculations: T.J., J.Z., J.M. and F.M.: UV photoemission spectroscopy and inverse photoemission spectroscopy used to x the value of U in the GGA U calculations: R.B. and C.R.; Manuscript: P.W., T.J. and K.W.E.
Additional information
Supplementary Information accompanies this paper at http://www.nature.com/naturecommunications
Web End =http://www.nature.com/ http://www.nature.com/naturecommunications
Web End =naturecommunications
Competing nancial interests: The authors declare no competing nancial interests.
Reprints and permission information is available online at http://npg.nature.com/reprintsandpermissions/
Web End =http://npg.nature.com/ http://npg.nature.com/reprintsandpermissions/
Web End =reprintsandpermissions/
How to cite this article: Wadley, P. et al. Tetragonal phase of epitaxial room-temperature antiferromagnet CuMnAs. Nat. Commun. 4:2322 doi: 10.1038/ncomms3322 (2013).
6 NATURE COMMUNICATIONS | 4:2322 | DOI: 10.1038/ncomms3322 | http://www.nature.com/naturecommunications
Web End =www.nature.com/naturecommunications
& 2013 Macmillan Publishers Limited. All rights reserved.
You have requested "on-the-fly" machine translation of selected content from our databases. This functionality is provided solely for your convenience and is in no way intended to replace human translation. Show full disclaimer
Neither ProQuest nor its licensors make any representations or warranties with respect to the translations. The translations are automatically generated "AS IS" and "AS AVAILABLE" and are not retained in our systems. PROQUEST AND ITS LICENSORS SPECIFICALLY DISCLAIM ANY AND ALL EXPRESS OR IMPLIED WARRANTIES, INCLUDING WITHOUT LIMITATION, ANY WARRANTIES FOR AVAILABILITY, ACCURACY, TIMELINESS, COMPLETENESS, NON-INFRINGMENT, MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. Your use of the translations is subject to all use restrictions contained in your Electronic Products License Agreement and by using the translation functionality you agree to forgo any and all claims against ProQuest or its licensors for your use of the translation functionality and any output derived there from. Hide full disclaimer
Copyright Nature Publishing Group Aug 2013
Abstract
Recent studies have demonstrated the potential of antiferromagnets as the active component in spintronic devices. This is in contrast to their current passive role as pinning layers in hard disk read heads and magnetic memories. Here we report the epitaxial growth of a new high-temperature antiferromagnetic material, tetragonal CuMnAs, which exhibits excellent crystal quality, chemical order and compatibility with existing semiconductor technologies. We demonstrate its growth on the III-V semiconductors GaAs and GaP, and show that the structure is also lattice matched to Si. Neutron diffraction shows collinear antiferromagnetic order with a high Néel temperature. Combined with our demonstration of room-temperature-exchange coupling in a CuMnAs/Fe bilayer, we conclude that tetragonal CuMnAs films are suitable candidate materials for antiferromagnetic spintronics.
You have requested "on-the-fly" machine translation of selected content from our databases. This functionality is provided solely for your convenience and is in no way intended to replace human translation. Show full disclaimer
Neither ProQuest nor its licensors make any representations or warranties with respect to the translations. The translations are automatically generated "AS IS" and "AS AVAILABLE" and are not retained in our systems. PROQUEST AND ITS LICENSORS SPECIFICALLY DISCLAIM ANY AND ALL EXPRESS OR IMPLIED WARRANTIES, INCLUDING WITHOUT LIMITATION, ANY WARRANTIES FOR AVAILABILITY, ACCURACY, TIMELINESS, COMPLETENESS, NON-INFRINGMENT, MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE. Your use of the translations is subject to all use restrictions contained in your Electronic Products License Agreement and by using the translation functionality you agree to forgo any and all claims against ProQuest or its licensors for your use of the translation functionality and any output derived there from. Hide full disclaimer