# Publications

## Magnetic structures of the rare-earth quadruple perovskite manganites RMn7O12

PHYSICAL REVIEW B 98 (2018) ARTN 104423

RD Johnson, DD Khalyavin, P Manuel, L Zhang, K Yamaura, AA Belik

## Magnetic X-ray spectroscopy of two-dimensional CrI3 layers

MATERIALS LETTERS 232 (2018) 5-7

A Frisk, LB Duffy, S Zhang, G van der Laan, T Hesjedal

## Magneto-orbital texture in the perovskite modification of Mn2O3

PHYSICAL REVIEW B 98 (2018) ARTN 014426

DD Khalyavin, RD Johnson, P Manuel, AA Tsirlin, AM Abakumov, DP Kozlenko, Y Sun, L Dubrovinsky, SV Ovsyannikov

## Real-Space Observation of Skyrmionium in a Ferromagnet-Magnetic Topological Insulator Heterostructure.

Nano letters ACS 18 (2018) 1057-1063

S Zhang, F Kronast, G van der Laan, T Hesjedal

The combination of topological insulators, i.e., bulk insulators with gapless, topologically protected surface states, with magnetic order is a love-hate relationship that can unlock new quantum states and exotic physical phenomena, such as the quantum anomalous Hall effect and axion electrodynamics. Moreover, the unusual coupling between topological insulators and ferromagnets can also result in the formation of topological spin textures in the ferromagnetic layer. Skyrmions are topologically-protected magnetization swirls that are promising candidates for spintronics memory carriers. Here, we report on the observation of skyrmionium in thin ferromagnetic films coupled to a magnetic topological insulator. The occurrence of skyrmionium, which appears as a soliton composed of two skyrmions with opposite winding numbers, is tied to the ferromagnetic state of the topological insulator. Our work presents a new combination of two important classes of topological materials and may open the door to new topologically inspired information-storage concepts in the future.

## High-Pressure Synthesis, Structures, and Properties of Trivalent A-Site-Ordered Quadruple Perovskites RMn7O12 (R = Sm, Eu, Gd, and Tb).

Inorganic chemistry 57 (2018) 5987-5998

L Zhang, N Terada, RD Johnson, DD Khalyavin, P Manuel, Y Katsuya, M Tanaka, Y Matsushita, K Yamaura, AA Belik

A-site-ordered quadruple perovskites RMn7O12 with R = Sm, Eu, Gd, and Tb were synthesized at high pressure and high temperature (6 GPa and ∼1570 K), and their structural, magnetic, and dielectric properties are reported. They crystallize in space group I2/ m at room temperature. All four compounds exhibit a high-temperature phase transition to the cubic Im3̅ structure at ∼664 K (Sm), 663 K (Eu), 657 K (Gd), and 630 K (Tb). They all show one magnetic transition at TN1 ≈ 82-87 K at zero magnetic field, but additional magnetic transitions below TN2 ≈ 12 K were observed in SmMn7O12 and EuMn7O12 at high magnetic fields. Very weak kinklike dielectric anomalies were observed at TN1 in all compounds. We also observed pyroelectric current peaks near 14 K and frequency-dependent sharp steps in dielectric constant (near 18-35 K)-these anomalies are probably caused by dielectric relaxation, and they are not related to any ferroelectric transitions. TbMn7O12 shows signs of nonstoichiometry expressed as (Tb1- xMn x)Mn7O12, and these samples exhibit negative magnetization or magnetization reversal effects of an extrinsic origin on zero-field-cooled curves in intermediate temperature ranges. The crystal structures of SmMn7O12 and EuMn7O12 were refined from neutron powder diffraction data at 100 K, and the crystal structures of GdMn7O12 and (Tb0.88Mn0.12)Mn7O12 were studied by synchrotron X-ray powder diffraction at 295 K.

## Direct Observation of Twisted Surface skyrmions in Bulk Crystals.

Physical review letters 120 (2018) 227202-

SL Zhang, G van der Laan, WW Wang, AA Haghighirad, T Hesjedal

Magnetic skyrmions in noncentrosymmetric helimagnets with D_{n} symmetry are Bloch-type magnetization swirls with a helicity angle of ±90°. At the surface of helimagnetic thin films below a critical thickness, a twisted skyrmion state with an arbitrary helicity angle has been proposed; however, its direct experimental observation has remained elusive. Here, we show that circularly polarized resonant elastic x-ray scattering is able to unambiguously measure the helicity angle of surface skyrmions, providing direct experimental evidence that a twisted skyrmion surface state also exists in bulk systems. The exact surface helicity angles of twisted skyrmions for both left- and right-handed chiral bulk Cu_{2}OSeO_{3}, in the single as well as in the multidomain skyrmion lattice state, are determined, revealing their detailed internal structure. Our findings suggest that a skyrmion surface reconstruction is a universal phenomenon, stemming from the breaking of translational symmetry at the interface.

## THz carrier dynamics and magnetotransport study of topological surface states in thin film Bi<inf>2</inf>Se<inf>3</inf>

Proceedings of SPIE - The International Society for Optical Engineering 10531 (2018)

VS Kamboj, A Singh, T Ferrus, HE Beere, LB Duffy, T Hesjedal, CHW Barnes, DA Ritchie

© 2018 SPIE. The surface of a topological insulator harbors exotic topological states, protected against backscattering from disorder by time reversal symmetry. The study of these exotic quantum states not only provides an opportunity to explore fundamental phenomena in condensed matter physics, such as the spin Hall effect, but also lays the foundation for applications from quantum computing to spintronics. Conventional electrical measurements suffer from substantial bulk interference, making it difficult to clearly distinguish topological surface states from bulk states. Employing terahertz time-domain spectroscopy, we study the temperature-dependent optical behavior of a 23-quintuple-thick film of bismuth selenide (Bi2Se3) allowing for the deconvolution of the surface state response from the bulk. Our measurement of carrier dynamics give an optical mobility exceeding 2100 cm2/V•s at 4 K, indicative of a surface-dominated response, and a scattering lifetime of ∼0.18 ps and a carrier density of 6×1012cm-2at 4 K for the Bi2Se3film. The sample was further processed into a Hall bar device using two different etching techniques, a wet chemical etching and Ar+ion milling, which resulting in a reduced Hall mobility. Even so, the magneto-conductance transport reveals weak antilocalization behavior in our Bi2Se3 sample, consistent with the presence of a single topological surface state mode.

## Ab initio calculation of spin fluctuation spectra using time-dependent density functional perturbation theory, plane waves, and pseudopotentials

PHYSICAL REVIEW B 97 (2018) ARTN 024420

K Cao, H Lambert, PG Radaelli, F Giustino

We present an implementation of time-dependent density functional perturbation theory for spin fluctuations, based on plane waves and pseudopotentials. We compute the dynamic spin susceptibility self-consistently by solving the time-dependent Sternheimer equation, within the adiabatic local density approximation to the exchange and correlation kernel. We demonstrate our implementation by calculating the spin susceptibility of representative elemental transition metals, namely bcc Fe, fcc Ni, and bcc Cr. The calculated magnon dispersion relations of Fe and Ni are in agreement with previous work. The calculated spin susceptibility of Cr exhibits a soft-paramagnon instability, indicating the tendency of the Cr spins to condense in an incommensurate spin density wave phase, in agreement with experiment.

## Breaking Symmetry with Light: Ultra-Fast Ferroelectricity and Magnetism from Three-Phonon Coupling

Physical review B: Condensed matter and materials physics American Physical Society (2018)

A theory describing how ferroic properties can emerge transiently in the ultra-fast regime by breaking symmetry with light through three-phonon coupling is presented. Particular emphasis is placed on the special case when two exactly degenerate mid-infra-red or THz phonons are resonantly pumped, since this situation can give rise to an exactly rectified ferroic response with damping envelopes of ~ 1 ps or less. Light-induced ferroelectricity and ferromagnetism are discussed in this context, and a number of candidate materials that could display these phenomena are proposed. The same analysis is also applied to the interpretation of previous femto-magnetism experiments, performed in different frequency ranges (visible and near-infrared), but sharing similar symmetry characteristics.

## Electronic Structure and Enhanced Charge-Density Wave Order of Monolayer VSe2.

Nano letters 18 (2018) 4493-4499

J Feng, D Biswas, A Rajan, MD Watson, F Mazzola, OJ Clark, K Underwood, I Marković, M McLaren, A Hunter, DM Burn, LB Duffy, S Barua, G Balakrishnan, F Bertran, P Le Fèvre, TK Kim, G van der Laan, T Hesjedal, P Wahl, PDC King

How the interacting electronic states and phases of layered transition-metal dichalcogenides evolve when thinned to the single-layer limit is a key open question in the study of two-dimensional materials. Here, we use angle-resolved photoemission to investigate the electronic structure of monolayer VSe2 grown on bilayer graphene/SiC. While the global electronic structure is similar to that of bulk VSe2, we show that, for the monolayer, pronounced energy gaps develop over the entire Fermi surface with decreasing temperature below Tc = 140 ± 5 K, concomitant with the emergence of charge-order superstructures evident in low-energy electron diffraction. These observations point to a charge-density wave instability in the monolayer that is strongly enhanced over that of the bulk. Moreover, our measurements of both the electronic structure and of X-ray magnetic circular dichroism reveal no signatures of a ferromagnetic ordering, in contrast to the results of a recent experimental study as well as expectations from density functional theory. Our study thus points to a delicate balance that can be realized between competing interacting states and phases in monolayer transition-metal dichalcogenides.

## Evolution of Magneto-Orbital order Upon B-Site Electron Doping in Na_{1-x}Ca_{x}Mn_{7}O_{12} Quadruple Perovskite Manganites.

Physical review letters 120 (2018) 257202-

RD Johnson, F Mezzadri, P Manuel, DD Khalyavin, E Gilioli, PG Radaelli

We present the discovery and refinement by neutron powder diffraction of a new magnetic phase in the Na_{1-x}Ca_{x}Mn_{7}O_{12} quadruple perovskite phase diagram, which is the incommensurate analogue of the well-known pseudo-CE phase of the simple perovskite manganites. We demonstrate that incommensurate magnetic order arises in quadruple perovskites due to the exchange interactions between A and B sites. Furthermore, by constructing a simple mean field Heisenberg exchange model that generically describes both simple and quadruple perovskite systems, we show that this new magnetic phase unifies a picture of the interplay between charge, magnetic, and orbital ordering across a wide range of compounds.

## Evolution of magneto-orbital order upon B-site electron doping in Na1−xCaxMn7O12 quadruple perovskite manganites

Physical Review Letters American Physical Society (2018)

RD Johnson, F Mezzadri, P Manuel, DD Khalyavin, E Gilioli, PG Radaelli

## Spin-induced multiferroicity in the binary perovskite manganite Mn2O3.

Nature communications 9 (2018) 2996-

J Cong, K Zhai, Y Chai, D Shang, DD Khalyavin, RD Johnson, DP Kozlenko, SE Kichanov, AM Abakumov, AA Tsirlin, L Dubrovinsky, X Xu, Z Sheng, SV Ovsyannikov, Y Sun

The ABO3 perovskite oxides exhibit a wide range of interesting physical phenomena remaining in the focus of extensive scientific investigations and various industrial applications. In order to form a perovskite structure, the cations occupying the A and B positions in the lattice, as a rule, should be different. Nevertheless, the unique binary perovskite manganite Mn2O3 containing the same element in both A and B positions can be synthesized under high-pressure high-temperature conditions. Here, we show that this material exhibits magnetically driven ferroelectricity and a pronounced magnetoelectric effect at low temperatures. Neutron powder diffraction revealed two intricate antiferromagnetic structures below 100 K, driven by a strong interplay between spin, charge, and orbital degrees of freedom. The peculiar multiferroicity in the Mn2O3 perovskite is ascribed to a combined effect involving several mechanisms. Our work demonstrates the potential of binary perovskite oxides for creating materials with highly promising electric and magnetic properties.

## Reciprocal space tomography of 3D skyrmion lattice order in a chiral magnet.

Proceedings of the National Academy of Sciences of the United States of America 115 (2018) 6386-6391

S Zhang, G van der Laan, J Müller, L Heinen, M Garst, A Bauer, H Berger, C Pfleiderer, T Hesjedal

It is commonly assumed that surfaces modify the properties of stable materials within the top few atomic layers of a bulk specimen only. Exploiting the polarization dependence of resonant elastic X-ray scattering to go beyond conventional diffraction and imaging techniques, we have determined the depth dependence of the full 3D spin structure of skyrmions-that is, topologically nontrivial whirls of the magnetization-below the surface of a bulk sample of Cu2OSeO3 We found that the skyrmions change exponentially from pure Néel- to pure Bloch-twisting over a distance of several hundred nanometers between the surface and the bulk, respectively. Though qualitatively consistent with theory, the strength of the Néel-twisting at the surface and the length scale of the variation observed experimentally exceed material-specific modeling substantially. In view of the exceptionally complete quantitative theoretical account of the magnetic rigidities and associated static and dynamic properties of skyrmions in Cu2OSeO3 and related materials, we conclude that subtle changes of the materials properties must exist at distances up to several hundred atomic layers into the bulk, which originate in the presence of the surface. This has far-reaching implications for the creation of skyrmions in surface-dominated systems and identifies, more generally, surface-induced gradual variations deep within a bulk material and their impact on tailored functionalities as an unchartered scientific territory.

## Imposing long-range ferromagnetic order in rare-earth-doped magnetic topological-insulator heterostructures

PHYSICAL REVIEW MATERIALS 2 (2018) UNSP 054201

LB Duffy, A Frisk, DM Burn, N-J Steinke, J Herrero-Martin, A Ernst, G van der Laan, T Hesjedal

## Observation of magnetic vortex pairs at room temperature in a planar α-Fe2O3/Co heterostructure

Nature Materials Nature Publishing Group (2018)

FP Chmiel, N Waterfield Price, RD Johnson, AD Lamirand, J Schad, G van der Laan, DT Harris, MS Rzchowski, C-B Eom, PG Radaelli

## Observation of magnetic vortex pairs at room temperature in a planar α-Fe2O3/Co heterostructure

Nature Materials Nature Publishing Group (0)

FP Chmiel, NW Price, RD Johnson, AD Lamirand, J Schad, GVD Laan, DT Harris, J Irwin, MS Rzchowski, C-B Eom, PG Radaelli

Vortices are among the simplest topological structures, and occur whenever a flow field `whirls' around a one-dimensional core. They are ubiquitous to many branches of physics, from fluid dynamics to superconductivity and superfluidity, and are even predicted by some unified theories of particle interactions, where they might explain some of the largest-scale structures seen in today's Universe. In the crystalline state, vortex formation is rare, since it is generally hampered by long-range interactions: in ferroic materials (ferromagnetic and ferroelectric), vortices are only observed when the effects of the dipole-dipole interaction is modified by confinement at the nanoscale, or when the parameter associated with the vorticity does not couple directly with strain. Here, we present the discovery of a novel form of vortices in antiferromagnetic (AFM) hematite ($\alpha$-Fe$_2$O$_3$) epitaxial films, in which the primary whirling parameter is the staggered magnetisation. Remarkably, ferromagnetic (FM) topological objects with the same vorticity and winding number of the $\alpha$-Fe$_2$O$_3$ vortices are imprinted onto an ultra-thin Co ferromagnetic over-layer by interfacial exchange. Our data suggest that the ferromagnetic vortices may be merons (half-skyrmions, carrying an out-of-plane core magnetisation), and indicate that the vortex/meron pairs can be manipulated by the application of an in-plane magnetic field, H$_{\parallel}$, giving rise to large-scale vortex-antivortex annihilation.

## Intrinsic Triple Order in A-site Columnar-Ordered Quadruple Perovskites: Proof of Concept.

Chemphyschem : a European journal of chemical physics and physical chemistry (2018)

AA Belik, DD Khalyavin, L Zhang, Y Matsushita, Y Katsuya, M Tanaka, RD Johnson, K Yamaura

There is an emerging topic in the science of perovskite materials: A-site columnar-ordered A2 A'A''B4 O12 quadruple perovskites, which have an intrinsic triple order at the A sites. However, in many examples reported so far, A' and A'' cations are the same, and the intrinsic triple order is hidden. Here, we investigate structural properties of Dy2 CuMnMn4 O12 (1) and Ho2 MnGaMn4 O12 (2) by neutron and X-ray powder diffraction and prove the triple order at the A sites. The cation distributions determined are [Ho2 ]A [Mn]A' [Ga0.66 Mn0.34 ]A'' [Mn3.66 Ga0.34 ]B O12 and [Dy2 ]A [Cu0.73 Mn0.27 ]A' [Mn0.80 Dy0.20 ]A'' [Mn1.89 Cu0.11 ]B1 [Mn2 ]B2 O12 . There are clear signatures of Jahn-Teller distortions in 1 and 2, and the orbital pattern is combined with an original type of charge ordering in 1. Columnar-ordered quadruple perovskites represent a new playground to study complex interactions between different electronic degrees of freedom. No long-range magnetic order was found in 2 by neutron diffraction, and its magnetic properties in low fields are dominated by an impurity with negative magnetization or magnetization reversal. On the other hand, 1 shows three magnetic transitions at 21, 125, and 160 K.

## Manipulation of skyrmion motion by magnetic field gradients.

Nature communications 9 (2018) 2115-

SL Zhang, WW Wang, DM Burn, H Peng, H Berger, A Bauer, C Pfleiderer, G van der Laan, T Hesjedal

Magnetic skyrmions are particle-like, topologically protected magnetisation entities that are promising candidates as information carriers in racetrack memory. The transport of skyrmions in a shift-register-like fashion is crucial for their embodiment in practical devices. Here, we demonstrate that chiral skyrmions in Cu2OSeO3 can be effectively manipulated under the influence of a magnetic field gradient. In a radial field gradient, skyrmions were found to rotate collectively, following a given velocity-radius relationship. As a result of this relationship, and in competition with the elastic properties of the skyrmion lattice, the rotating ensemble disintegrates into a shell-like structure of discrete circular racetracks. Upon reversing the field direction, the rotation sense reverses. Field gradients therefore offer an effective handle for the fine control of skyrmion motion, which is inherently driven by magnon currents. In this scheme, no local electric currents are needed, thus presenting a different approach to shift-register-type operations based on spin transfer torque.

## Topological surface state of α-Sn on InSb(001) as studied by photoemission

Physical review B: Condensed matter and materials physics American Physical Society 97 (2018) 075101

MR Scholz, L Dudy, F Reis, F Adler, J Aulbach, LJ Collins-McIntyre, LB Duffy, HF Yang, YL Chen, T Hesjedal, ZK Liu, M Hoesch, S Muff, JH Dil, J Schaefer, R Claessen