Abstract
Since the discovery of the quantum anomalous Hall (QAH) effect in the magnetically doped topological insulators (MTI) Cr:(Bi,Sb)2Te3 and V:(Bi,Sb)2Te3, the search for the magnetic coupling mechanisms underlying the onset of ferromagnetism has been a central issue, and a variety of different scenarios have been put forward. By combining resonant photoemission, X-ray magnetic circular dichroism and density functional theory, we determine the local electronic and magnetic configurations of V and Cr impurities in (Bi,Sb)2Te3. State-of-the-art first-principles calculations find pronounced differences in their 3d densities of states, and show how these impurity states mediate characteristic short-range pd exchange interactions, whose strength sensitively varies with the position of the 3d states relative to the Fermi level. Measurements on films with varying host stoichiometry support this trend. Our results explain, in an unified picture, the origins of the observed magnetic properties, and establish the essential role of impurity-state-mediated exchange interactions in the magnetism of MTI.
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Introduction
Magnetically doped topological insulators (MTI) form a cornerstone in the field of topological quantum materials. Particularly in Cr-doped and V-doped (Bi,Sb)2Te3, the combination of ferromagnetism and a topologically non-trivial electronic band structure led to the discovery of the quantum anomalous Hall (QAH) effect1,2,3,4,5, i.e. a dissipationless quantised edge-state transport in the absence of external magnetic fields. These materials are now being widely utilised for possible realisations of topological superconductor6 and axion insulator states7, as well as in the context of metrology8 and spintronic functionalities9. However, despite the broad interest in these dilute MTI, controversy still remains as to the microscopic origin of the ferromagnetism and to the electronic states inducing the ferromagnetic (FM) coupling.
In a pioneering work, predicting the QAH effect in transition metal (TM)-based MTI, the FM state was proposed to arise from a van Vleck mechanism, as a result of strong spin–orbit coupling (SOC) and the topologically non-trivial band ordering in these materials10. Although some experimental support for this scenario has been reported2,11,12, more recent first-principles calculations find that the strength of the exchange interactions in Cr:(Bi,Sb)2Te3 and V:(Bi,Sb)2Te3 is, in fact, largely independent of SOC, suggesting that the van Vleck mechanism, in the form proposed in ref. 10, plays no decisive role13,14. Other theoretical works predict a dependence of the magnetic coupling on the precise configuration of the impurity 3d states13,14,15,16,17,18, as it is known in the context of dilute magnetic semiconductors19,20,21,22,23,24. Experimentally, the robustness of the FM state in Cr:(Bi,Sb)2Te3 and V:(Bi,Sb)2Te3 films was indeed found to vary substantially with dopant type and host stoichiometry3,25,26,27,28,29,30,31. It was speculated that these variations arise from differences in the electronic structure of the two systems3. So far, however, a comprehensive understanding of how this behaviour is related to the local impurity electronic structure is still absent. A realistic theory of the impurity 3d states in MTI shall not only explain the differences observed in the electronic and magnetic properties of these two coined QAH insulators, but also bring important insights for the physical description of other MTI, with possible implications to other TM-based van der Waals materials.
In this work, we present a combination of key experiments and theory that establishes the fundamental link between local impurity electronic structure and magnetic coupling in MTI. By means of X-ray magnetic circular dichroism (XMCD) and resonant photoelectron spectroscopy (resPES) we systematically probe the electronic and magnetic fingerprints of the 3d states of V and Cr impurities embedded in the bulk of (BixSb1−x)2Te3 thin films, as well as the effect of Bi/Sb substitution in the host. Supported by multiplet ligand field theory (MLFT) and ab initio density functional theory (DFT) calculations, our results unveil the essential role of impurity-state-mediated exchange interactions underlying the magnetic properties of V-doped and Cr-doped (Bi,Sb)2Te3 thin films, paving the way towards a more general theory of the magnetic interactions in MTI.
Results
Electronic and magnetic ground state of V and Cr impurities
We start by presenting in Fig. 1a, b the X-ray absorption (XAS) and XMCD spectra from V0.1(Bi0.32Sb0.68)1.9Te3 and Cr0.1(Bi0.1Sb0.9)1.9Te3, respectively, at the V and Cr L2,3 edges, measured at temperatures above (hollow circles) and below (full circles) the Curie temperature TC (Supplementary Fig. 1). No energy shifts or changes in the branching ratio are observed at the L2,3 edges with varying temperature across TC, contradicting recent reports where an apparent energy shift was interpreted as evidence of the van Vleck mechanism11. The XMCD spectra were measured under a small applied magnetic field of 10 mT (remanent state), oriented perpendicular to the surface, at 5 K. They confirm a persistent FM state at this temperature, with a sizable magnetic moment carried by the TM 3d states for both V-doped and Cr-doped (Bi,Sb)2Te3 systems.
A state-of-the-art MLFT analysis of the V and Cr L2,3 lineshapes has been performed (Supplementary Fig. 1) and described in detail elsewhere32. We find a strong deviation from the 3+ ionic (V d2, Cr d3) ground state25,29,30, with resulting d-shell occupations of d3.13 (mS = 2.33μB per atom) for V and d4.37 (mS = 3.32μB per atom) for Cr. Correspondingly, our first-principles calculations for single V and Cr impurities embedded in a quintuple layer of Sb2Te3, on an octahedral Sb site, find d3.35 (mS = 2.51μB per atom) and d4.40 (mS = 3.72μB per atom), (Supplementary Fig. 5 and below). This implies a substantial charge transfer (CT) from the ligand p states into the 3d impurity states as a result of strong pd hybridisation (Supplementary Fig. 4).
Fingerprint of the impurity 3d states
We next assess the contribution of the 3d states to the valence band (VB) by resPES at the V and Cr L3 edges. The data sets shown in Fig. 2a, b are obtained from the normalised difference between the on-resonant and off-resonant photoemission spectra, taken at 30 K (Supplementary Fig. 2), and represent the V and Cr 3d partial DOS. The data establish a remarkably pronounced difference in the character of the 3d DOS for V and Cr impurities. For V, the 3d states pile up predominantly in a narrow peak just below EF with the centre at EB = 170 meV. For Cr, on the other hand, the 3d states are broadly distributed over the host VB, with a maximum at EB = 1.71 eV and low spectral weight near EF. Our first-principles calculations nicely capture these main characteristics. Figure 2c shows the calculated spin-polarised 3d DOS and the corresponding integrated DOS for V (upper panel) and Cr (lower panel) impurities in Sb2Te3, which allow us to assign the experimentally observed states to majority-spin (spin-up) t2g states (Supplementary Fig. 6). The examination of the integrated 3d DOS at EF allows us to extract the predicted d-shell filling of d3.4 for V (red curve) and d4.4 for Cr (blue curve) impurities, in good agreement with our MLFT analysis. Furthermore, our calculations are able to reproduce our resPES data without self-interaction corrections, which suggests a minor role of the latter for the V and Cr occupied 3d states. While small self-interaction corrections tend to shift the 3d resonances deeper in the VB13,14,18,21, this is compensated by the natural charge doping of the host, as we discuss below. Our findings yet support previous resPES results33,34, and recent scanning tunnelling microscopy and spectroscopy studies of the electronic fingerprints of substitutional V and Cr impurities in Sb2Te318,35,36.
The presence of exchange-split 3d states at EF suscitate the emergence of localised magnetic moments and, possibly, long-range magnetic order. In order to study the effect of the impurity states on the magnetic coupling mechanism, we first consider the spin-up DOS of V and Cr impurities in Sb2Te3, calculated for different artificial EF shifts (ΔEF), i.e. different positions of EF with respect to the bulk VB and conduction band (CB) (Supplementary Fig. 3). This approach allows us to simulate the effect of n-type and p-type charge doping on the 3d states, i.e. the valence of the TM impurities37. The results for the spin-up V and Cr 3d DOS are shown in Fig. 3a, b, respectively. The grey-shaded areas correspond to the Sb2Te3 host total DOS, emphasising the position of the impurity states with respect to the bulk band gap, where the topological surface states (TSS) typically lie. We find that the position of the impurity states depends sensitively on the charge doping, shifting towards higher binding energies when going from p-type (dark-coloured curves) to n-type (light-coloured curves) doping. In particular, the narrow V 3d peak gradually moves away from EF. This trend is experimentally supported by our resPES data for (BixSb1−x)2Te3 films with different Bi concentrations x, which will be discussed later. For higher x, and thus higher n-doping3,15,16, the V 3d peak shifts to significantly higher binding energies.
Impurity-state-mediated magnetic exchange interactions
Based on our findings regarding the local electronic and magnetic impurity configurations, we now discuss their implications for the magnetic exchange interactions. In Fig. 4a, b we plot the calculated exchange-coupling constants Jij for different separation distances between two TM ions located in one atomic plane (intra-layer coupling, upper panels) and at neighbouring atomic planes within the same quintuple layer (inter-layer coupling, lower panels), using the same ΔEF values as in Fig. 3a, b (note the corresponding colour code). For both V and Cr, the interlayer coupling is dominant, in good agreement with ref. 17. Overall, at nearest-neighbour (NN) distances the calculated Jij contributions are larger for V, while at the second and third neighbour positions the Jij values for Cr are markedly larger. This behaviour follows the spatial decay of the calculated impurity-induced features in the 3d DOS (Supplementary Fig. 7). Most importantly, we find that Jij strongly varies with charge doping. Already small shifts of EF give rise to considerable changes in Jij, whose sign and strength are linked to characteristic features in the 3d DOS at EF. For V, Jij rapidly decreases in the n-doped regime, while for Cr the behaviour is more complex and depends more strongly on the relative impurity positions. Figure 4c, d show the energy dependence of Jij(E) for NN spins for ΔEF = −300 meV, which best corresponds to our experimental resPES data. The inter-layer and intra-layer components are, respectively, depicted as dashed and solid lines, and they exhibit qualitatively similar trends. In the same plots, the corresponding spin-up and spin-down 3d DOS are shown as shaded areas. For V, Jij(E) near EF consists of a sharp peak overlapping with a broad flat ridge that spans between the onsets of the t2g and eg peaks. Jij(E) is maximum when EF is positioned inside the V t2g manifold, and rapidly decreases otherwise. For Cr, the sharp peak in Jij(E) is absent, and only the broad ridge is seen. In sharp contrast to V, we find for Cr a maximal Jij(E) when EF lies in the gap between the t2g and eg peaks, where the 3d DOS is low. The calculated Jij(E) in Fig. 4d, thus, indicates a less pronounced dependence of the magnetic coupling on the EF position for Cr. This may explain the stronger gate-voltage dependence of the magnetic properties observed in V-doped3 as compared to Cr-doped films1,12,29. These distinct features in the V and Cr 3d DOS are fully in line with our resPES measurements in Fig. 2. In the context of dilute magnetic semiconductors, similar characteristics in the exchange coupling constants have been extensively discussed19,20,23,24,38,39,40. By comparison, we may tentatively associate the sharp peak in Jij(E) for V with the double-exchange mechanism14,17,19,20,22,24,31 and the broad ridge, found for both dopant types, with the FM superexchange mechanism13,19,23,38.
Effect of the host charge doping on the impurity 3d states
In order to verify the predicted trends of the impurity-mediated magnetic exchange interactions with the charge doping of the host, we now discuss the effect of the host stoichiometry on the local electronic and magnetic properties of V-doped (BixSb1−x)2Te3 via Bi/Sb substitution. Our resPES and XMCD data from V0.1(Bi0.32Sb0.68)1.9Te3 (dark red curve) and V0.1Bi1.9Te3 (light red curve) in Fig. 5 demonstrate the strong sensitivity of the magnetic coupling on the position of the V impurity states. The V 3d maximum in Fig. 5a is found at EB = 170 meV in the former, and at EB = 300 meV in the latter (EB = 130 meV for x = 0.24, as seen in Supplementary Fig. 2), confirming the trend predicted by our DFT calculations (Fig. 3). This may be attributed to the effect of CT from the Bi ions into the V impurities (Supplementary Fig. 4)15,16,41. Figure 5b shows a comparison of V L2,3 XMCD spectra for the same samples, measured at saturation (hollow circles) and in remanence (full circles) at 5 K. While in Sb-rich V:(Bi,Sb)2Te3 the remanent and saturated spectra almost coincide, in V0.1Bi1.9Te3 the remanent XMCD is critically lower than in saturation, demonstrating a suppression of FM interactions coinciding with the shift of the V states away from EF, as predicted in our theoretical calculations.
Discussion
The observed weakening of the ferromagnetism upon Bi doping in V:(Bi,Sb)2Te3 is in agreement with previous works3,28,31, as well reported for single-crystalline Cr:(Bi,Sb)2Te326. It is known from recent XMCD studies18,26,29,31,32 that the Sb ions become partially polarised in the presence of substitutional V or Cr, while Bi, on the other hand, does not. Thus, our findings are consistent with a scenario where loosely localised, spin-polarised holes in Sb ions facilitate a longer ranged magnetic coupling in both systems13,19,20,21,22. The substitution of Sb by Bi, thus, gradually disables the network of spin-polarised p orbitals that contribute to stabilise a more robust FM state.
Our results yet show that the sharp V and Cr resonances are mostly localised inside the bulk band gap (see Fig. 3), indicating a considerable overlap with the TSS. While the effect of the TSS on the magnetic interactions has not been explored here, our theory suggests that the scenario pictured in the bulk may possibly be affected by the presence of the Dirac electrons at the surface, potentially leading to modified magnetic properties as compared to the bulk.
In conclusion, our systematic experimental and theoretical results highlight the central role of impurity-state-mediated exchange coupling for the magnetism in the paradigmatic QAH insulators Cr:(Bi,Sb)2Te3 and V:(Bi,Sb)2Te3. The latter cannot be explained based solely on the van Vleck mechanism, bearing its origin on the topologically non-trivial band structure10,11,12. Instead, our theoretical calculations on the basis of pd hybridisation and exchange coupling unambiguously elucidate the experimental observations. They show that the nature and strength of the magnetic exchange coupling vary with the position of EF in the 3d DOS, i.e. with the occupation of the 3d states, thereby reconciling, in a unified theory, the differences observed between V and Cr doping of (BixSb1−x)2Te3 films, as well as unveiling the role of Sb in mediating a robust ferromagnetism in QAH insulators. The presence of the Dirac states might as well have further impact on the charge and magnetic ground states of 3d impurities in the vicinity of the surface and, consequently, on the pd magnetic interactions37. Conversely, the 3d impurity states may mediate spin scattering channels for the spin-momentum-locked Dirac electrons36. This advance in the knowledge on the microscopic electronic and magnetic properties in V-doped and Cr-doped (Bi,Sb)2Te3 may eventually facilitate an improved understanding of the microscopic origin of the QAH effect in these systems. Finally, the developed theory can be further applied to other instances of MTI for tailoring the properties of these materials in regard to potential spintronic applications.
Methods
Sample preparation, structural, transport and magnetic characterisation
Thin films (about 9–10 nm thick) of Crz(BixSb1−x)2−zTe3 and Vz(BixSb1−x)2−zTe3 were grown by molecular beam epitaxy (MBE) on hydrogen-passivated Si(111) substrates. The growth details and characterisation, e.g. by X-ray diffraction, atomic force microscopy and Hall magnetotransport, confirming the realisation of QAH effect in the V-doped samples (for x = 0.76−0.79 and z = 0.1–0.2), are published elsewhere5,28,42,43. After growth, the films were capped by a protective Te layer (~100 nm), which was mechanically removed in UHV conditions, prior to the spectroscopic measurements, revealing a chemically clean surface (Supplementary Fig. 8). Recent results have demonstrated the effectiveness of this decapping method on Bi2Te3 layers with high pristine quality44. The stoichiometries applied in this work are comparable to those that exhibited a stable and reproducible QAH effect.
XAS, XMCD and resPES
The XAS and XMCD data was acquired at the HECTOR endstation, located at BOREAS beamline of the ALBA storage ring (Barcelona, Spain)45. The measurements were performed in total electron yield mode, under magnetic fields of up to 6 T and temperatures down to 5 K. The resPES experiments were conducted at the ASPHERE III endstation located at beamline P04 of the PETRA III storage ring of DESY (Hamburg, Germany). The on-resonant and off-resonant VB photoemission spectra were taken at hνon = 514.8 eV and hνoff = 508 eV for V-doped samples, and at hνon = 575.6 eV and hνoff = 560 eV for Cr-doped ones, according to the respective XAS spectra in Fig. 1. The energy resolution of the resPES measurements was typically better than 67 meV. All experiments were performed in ultra-high vaccuum (UHV) at pressures below 3 × 10−10 mbar.
DFT calculations
The Sb2Te3 and Bi2Te3 bulk crystals were simulated using the experimental bulk lattice structure (see ref. 46 for Sb2Te3 and ref. 47 for Bi2Te3). The electronic structure was calculated within the local density approximation (LDA)48 to DFT by employing the full-potential relativistic Korringa–Kohn–Rostoker Green’s function method (KKR)49,50 with exact description of the atomic cells51,52. The truncation error arising from an \({\ell }_{\max }=3\) cutoff in the angular momentum expansion was corrected for using Lloyd’s formula53. The V and Cr defects, together with a charge-screening cluster comprising the first two shells of neighbouring atoms (consisting of about 20 surrounding scattering sites), were embedded self-consistently using the Dyson equation in the KKR method50 and have been chosen to occupy the substitutional Sb/Bi position in the quintuple layers and structural relaxations were neglected, while keeping the direction of the impurity’s magnetic moment fixed along the out-of-plane direction. The shift in the Fermi level occurring in (Bi,Sb)2Te3 was accounted for by adjusting the self-consistently computed Fermi level of the host systems in the impurity embedding step. The exchange interactions among two impurities were computed using the method of infinitesimal rotations54, which map the exchange interaction to the Heisenberg Hamiltonian \({\mathcal{H}}=-\frac{1}{2}{\sum }_{\left\langle ij\right\rangle }{J}_{ij}{\overrightarrow{s}}\!_{i}\cdot {\overrightarrow{s}}\!_{j}\).
MLFT calculations
Theoretical XAS and XMCD spectra for the L2,3 (2p → 3d) absorption edges of V and Cr ions were calculated by means of a configuration interaction (CI) cluster model, considering the central TM ion surrounded by six ligands (Te anions). We take into account all the 2p−3d and 3d−3d electronic Coulomb interactions, as well as the SOC on every open shell of the absorbing atom. We consider nominal 2p63dn (n = 2 for V3+and n = 3 for Cr3+) configurations and further include three more CT states \({d}^{n+1}{\underline{L}}^{1}\), \({d}^{n+2}{\underline{L}}^{2}\) and \({d}^{n+3}{\underline{L}}^{3}\) (\({\underline{L}}^{1}\) denotes a hole in the Te 5p orbitals) to account for hybridisation effects. To perform the CI calculation, the following fit parameters were introduced: scaling parameter β for the Hartree–Fock values of the Slater integrals, the CT energy Δ, the Coulomb interaction energy Udd between the 3d electrons, the hybridisation energy Veg and the octahedral crystal field parameter 10Dq. The simulations were performed using the Quanty software for quantum many-body calculations, developed by M. W. Haverkort et al.55. We assume V/Cr ions embedded in the cation sites and describe the crystal field in Oh symmetry, with C4 axes of the octahedron along the V–Te bonds. The spectral contributions from each of the split ground state terms to the absorption spectra were weighted by a Boltzmann factor. The calculated spectra were broadened by a Gaussian function to account for the instrumental broadening and by an energy-dependent Lorentzian profile for intrinsic lifetime broadening.
Data availability
The data published in this work can be made available by the authors upon justified request.
Code availability
The computer codes and algorithms used in this study can be provided by the authors upon justified request.
Change history
02 February 2021
A Correction to this paper has been published: https://doi.org/10.1038/s41535-021-00314-9
11 February 2021
A Correction to this paper has been published: https://doi.org/10.1038/s41535-021-00314-9
References
Chang, C.-Z., Zhang, J., Feng, X., Shen, J. & Zhang, Z. et al. Experimental observation of the quantum anomalous Hall effect in a magnetic topological insulator. Science 340, 167–170 (2013).
Kou, X., Fan, Y., Lang, M., Upadhyaya, P. & Wang, K. L. Magnetic topological insulators and quantum anomalous Hall effect. Solid State Commun. 215-216, 34–53 (2015).
Chang, C.-Z., Zhao, W., Kim, D. Y., Zhang, H. & Assaf, B. A. et al. High-precision realization of robust quantum anomalous Hall state in a hard ferromagnetic topological insulator. Nat. Mater. 14, 473–477 (2015).
Bestwick, A. J., Fox, E. J., Kou, X., Pan, L. & Wang, K. L. et al. Precise quantization of the anomalous Hall effect near zero magnetic field. Phys. Rev. Lett. 114, 187201 (2015).
Grauer, S., Schreyeck, S., Winnerlein, M., Brunner, K. & Gould, C. et al. Coincidence of superparamagnetism and perfect quantization in the quantum anomalous Hall state. Phys. Rev. B 92, 201304(R) (2015).
Tokura, Y., Yasuda, K. & Tsukazaki, A. Magnetic topological insulators. Nat. Rev. Phys. 1, 126–143 (2019).
Xiao, D., Jiang, J., Shin, J.-H., Wang, W. & Wang, F. et al. Realization of the axion insulator state in quantum anomalous Hall sandwich heterostructures. Phys. Rev. Lett. 120, 056801 (2018).
Götz, M., Fijalkowski, K. M., Pesel, E., Hartl, M. & Schreyeck, S. et al. Precision measurement of the quantized anomalous Hall resistance at zero magnetic field. Appl. Phys. Lett. 112, 072102 (2018).
Fan, Y., Upadhyaya, P., Kou, X., Lang, M. & Takei, S. et al. Magnetization switching through giant spin–orbit torque in a magnetically doped topological insulator heterostructure. Nat. Mater. 13, 699–704 (2014).
Yu, R., Zhang, W., Zhang, H.-J., Zhang, S.-C. & Dai, X. et al. Quantized anomalous Hall effect in magnetic topological insulators. Science 329, 61–64 (2010).
Li, M., Chang, C.-Z., Wu, L., Tao, J. & Zhao, W. et al. Experimental verification of the Van Vleck nature of long-range ferromagnetic order in the vanadium-doped three-dimensional topological insulator Sb2Te3. Phys. Rev. Lett. 114, 146802 (2015).
Chang, C.-Z., Zhang, J., Liu, M., Zhang, Z. & Feng, X. et al. Thin films of magnetically doped topological insulator with carrier-independent long-range ferromagnetic order. Adv. Mater. 25, 1065–1070 (2013).
Kim, J., Jhi, S.-H., MacDonald, A. H. & Wu, R. Ordering mechanism and quantum anomalous Hall effect of magnetically doped topological insulators. Phys. Rev. B 96, 140410(R) (2017).
Kim, J., Wang, H. & Wu, R. Importance of coulomb correlation on the quantum anomalous Hall effect in V-doped topological insulators. Phys. Rev. B 97, 125118 (2018).
Zhang, J.-M., Zhu, W., Zhang, Y., Xiao, D. & Yao, Y. Tailoring magnetic doping in the topological insulator Bi2Se3. Phys. Rev. Lett. 109, 266405 (2012).
Zhang, J.-M., Ming, W., Huang, Z., Liu, G.-B. & Kou, X. et al. Stability, electronic, and magnetic properties of the magnetically doped topological insulators Bi2Se3, Bi2Te3, and Sb2Te3. Phys. Rev. B 88, 235131 (2013).
Vergniory, M. G., Otrokov, M. M., Thonig, D., Hoffmann, M. & Maznichenko, I. V. et al. Exchange interaction and its tuning in magnetic binary chalcogenides. Phys. Rev. B 89, 165202 (2014).
Islam, M. F., Canali, C. M., Pertsova, A., Balatsky, A. & Mahatha, S. K. et al. Systematics of electronic and magnetic properties in the transition metal doped Sb2Te3 quantum anomalous Hall platform. Phys. Rev. B 97, 155429 (2018).
Kacman, P. Spin interactions in diluted magnetic semiconductors and magnetic semiconductor structures. Semicond. Sci. Technol. 16, R25–R39 (2001).
Sato, K., Dederichs, P. H., Katayama-Yoshida, H. & Kudrnovský, J. Exchange interactions in diluted magnetic semiconductors. J. Phys.: Cond. Matter 16, S5491–S5497 (2004).
Schulthess, T. C., Temmerman, W. M., Szotek, Z., Butler, W. H. & Malcolm Stocks, G. Electronic structure and exchange coupling of Mn impurities in III–V semiconductors. Nat. Mater. 4, 838–844 (2005).
Jungwirth, T., Sinova, J., Mašek, J., Kučera, J. & MacDonald, A. H. Theory of ferromagnetic (III,Mn)V semiconductors. Rev. Mod. Phys. 78, 809–864 (2006).
Sato, K., Bergqvist, L., Kudrnovský, J., Dederichs, P. H. & Eriksson, O. et al. First-principles theory of dilute magnetic semiconductors. Rev. Mod. Phys. 82, 1633–1690 (2010).
Dietl, T. & Ohno, H. Dilute ferromagnetic semiconductors: physics and spintronic structures. Rev. Mod. Phys. 86, 187–251 (2014).
Figueroa, A. I., van der Laan, G., Collins-McIntyre, L. J., Zhang, S.-L. & Baker, A. A. et al. Magnetic Cr doping of Bi2Se3: evidence for divalent Cr from x-ray spectroscopy. Phys. Rev. B 90, 134402 (2014).
Ye, M., Li, W., Zhu, S., Takeda, Y. & Saitoh, Y. et al. Carrier-mediated ferromagnetism in the magnetic topological insulator Cr-doped (Sb,Bi)2Te3. Nat. Comm. 6, 8913 (2015).
Gupta, S., Kanai, S., Matsukura, F. & Ohno, H. Magnetic and transport properties of Sb2Te3 doped with high concentration of Cr. Appl. Phys. Express 10, 103001 (2017).
Winnerlein, M., Grauer, S., Rosenberger, S., Fijalkowski, K. M. & Gould, C. et al. Epitaxy and structural properties of (V,Bi,Sb)2Te3 layers exhibiting the quantum anomalous hall effect. Phys. Rev. Mater. 1, 011201(R) (2017).
Duffy, L. B., Figueroa, A. I., Gładczuk, Ł., Steinke, N. J. & Kummer, K. et al. Magnetic proximity coupling to Cr-doped Sb2Te3 thin films. Phys. Rev. B 95, 224422 (2017).
Duffy, L. B., Figueroa, A. I., van der Laan, G. & Hesjedal, T. Codoping of Sb2Te3 thin films with V and Cr. Phys. Rev. Mater. 1, 064409 (2017).
Ye, M. et al. Negative Te spin polarization responsible for ferromagnetic order in the doped topological insulator V0.04(Sb1−xBix)1.96Te3. Phys. Rev. B 99, 144413 (2019).
Tcakaev, A., Zabolotnyy, V., Green, R. J., Peixoto, T. R. F. & Stier, F. et al. Comparing magnetic ground-state properties of the V- and Cr-doped topological insulator (Bi,Sb)2Te3. Phys. Rev. B 101, 045127 (2020).
Peixoto, T. R. F., Bentmann, H., Schreyeck, S., Winnerlein, M. & Seibel, C. et al. Impurity states in the magnetic topological insulator V:(Bi,Sb)2Te3. Phys. Rev. B 94, 195140 (2016).
Krieger, J. A., Chang, C. Z., Husanu, M.-A., Sostina, D. & Ernst, A. et al. Spectroscopic perspective on the interplay between electronic and magnetic properties of magnetically doped topological insulators. Phys. Rev. B 96, 184402 (2017).
Zhang, W., West, D., Lee, S. H., Qiu, Y. & Chang, C.-Z. et al. Electronic fingerprints of Cr and V dopants in the topological insulator Sb2Te3. Phys. Rev. B 98, 115165 (2018).
Sumida, K., Kakoki, M., Reinmann, J., Nurmamat, M. & Goto, S. et al. Magnetic-impurity-induced modifications to ultrafast carrier dynamics in the ferromagnetic topological insulators Sb2−xVxTe3. New J. Phys. 21, 093006 (2019).
Rüßmann, P., Mahatha, S. K., Sessi, P., Valbuena, M. A. & Bathon, T. et al. Towards microscopic control of the magnetic exchange coupling at the surface of a topological insulator. J. Phys. Mater. 1, 015002 (2018).
Belhadji, B., Bergqvist, L., Zeller, R., Dederichs, P. H. & Sato, K. et al. Trends of exchange interactions in dilute magnetic semiconductors. J. Phys.: Condens. Matter 19, 436227 (2007).
Larson, P. & Lambrecht, W. R. L. Electronic structure and magnetism in Bi2Te3, Bi2Se3, and Sb2Te3 doped with transition metals (Ti–Zn). Phys. Rev. B 78, 195207 (2008).
Dietl, T. A ten-year perspective on dilute magnetic semiconductors and oxides. Nat. Mater. 9, 965–974 (2010).
Zhang, J., Chang, C.-Z., Zhang, Z., Wen, J. & Feng, X. et al. Band structure engineering in (Bi1−xSbx)2Te3 ternary topological insulators. Nat. Commun. 2, 574 (2011).
Grauer, S., Fijalkowski, K. M., Schreyeck, S., Winnerlein, M. & Brunner, K. et al. Scaling of the quantum anomalous Hall effect as an indicator of axion electrodynamics. Phys. Rev. Lett. 118, 246801 (2017).
Tarakina, N. V., Schreyeck, S., Duchamp, M., Karczewski, G. & Gould, C. et al. Microstructural characterization of Cr-doped (Bi,Sb)2Te3 thin films. CrystEngComm 19, 3633–3639 (2017).
Fornari, C. I., Rappl, P. H. O., Morelhão, S. L., Peixoto, T. R. F. & Bentmann, H. et al. Preservation of pristine Bi2Te3 thin film topological insulator surface after ex situ mechanical removal of Te capping layer. APL Mater. 4, 106107 (2016).
Barla, A., Nicolás, J., Cocco, D., Valvidares, S. M. & Herrero-Martín, J. et al. Design and performance of BOREAS, the beamline for resonant X-ray absorption and scattering experiments at the ALBA synchrotron light source. J. Synchrotron Radiat. 23, 1507–1517 (2016).
Ullner, H.-A. Strukturuntersuchungen am System Sb2Te3−xSex (Halbleitereigenschaften von Telluriden. VIII). Ann. Phys. 476, 45–56 (1968).
Nakajima, S. The crystal structure of Bi2Te3−xSex. J. Phys. Chem. Solids 24, 479–485 (1963).
Vosko, S. H., Wilk, L. & Nusair, M. Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis. Can. J. Phys. 58, 1200–1211 (1980).
Ebert, H., Ködderitzsch, D. & Minár, J. Calculating condensed matter properties using the KKR-Green’s function method—recent developments and applications. Rep. Prog. Phys. 74, 096501 (2011).
Bauer, D. S. G. Development of a relativistic full-potential first-principles multiple scattering green function method applied to complex magnetic textures of nanostructures at surfaces. Ph.D. thesis (Forschungszentrum Jülich, RWTH Aachen University, Aachen, 2013).
Stefanou, N., Akai, H. & Zeller, R. An efficient numerical method to calculate shape truncation functions for Wigner–Seitz atomic polyhedra. Comput. Phys. Commun. 60, 231–238 (1990).
Stefanou, N. & Zeller, R. Calculation of shape-truncation functions for Voronoi polyhedra. J. Phys. Condens. Matter 3, 7599–7606 (1991).
Zeller, R. An elementary derivation of Lloyd’s formula valid for full-potential multiple-scattering theory. J. Phys. Condens. Matter 16, 6453–6468 (2004).
Liechtenstein, A., Katsnelson, M., Antropov, V. & Gubanov, V. Local spin density functional approach to the theory of exchange interactions in ferromagnetic metals and alloys. J. Magn. Magn. Mater. 67, 65–74 (1987).
Haverkort, M. W., Zwierzycki, M. & Andersen, O. K. Multiplet ligand-field theory using Wannier orbitals. Phys. Rev. B 85, 165113 (2012).
Acknowledgements
T.R.F.P. would like to thank Kai Fauth and Arthur Ernst for their collaboration at early phases of this study. H.B. would like to thank Ján Minár, and P.R. would like to thank Peter Dederichs for helpful discussions. P.R. and S.B. acknowledge funding from the Priority Programme SPP-1666 Topological Insulators of the Deutsche Forschungsgemeinschaft (DFG) (projects MA4637/3-1) and from the VITI Programme of the Helmholtz Association, as well as computing time granted by the JARA Vergabegremium and provided on the JARA Partition part of the supercomputer CLAIX at RWTH Aachen University. R.J.G. was supported by the Natural Sciences and Engineering Research Council of Canada. The experiments at the BOREAS beamline of ALBA Synchrotron were performed under the proposal-ID 2017082310, with the collaboration of ALBA staff. We acknowledge the financial support from the Deutsche Forschungsgemeinschaft (DFG) through the SFB1170 ‘ToCoTronics’ (project No. 258499086, projects A01, B01 and C06), and the Würzburg-Dresden Cluster of Excellence on Complexity and Topology in Quantum Matter - ct.qmat (EXC 2147, project-id 390858490). Funding for the photoemission spectroscopy instrument at beamline P04 (Contracts 05KS7FK2, 05K10FK1, 05K12FK1, and 05K13FK1 with Kiel University; 05KS7WW1 and 05K10WW2 with Würzburg University) by the Federal Ministry of Education and Research (BMBF) is gratefully acknowledged.
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T.R.F.P. wrote the paper, with support of H.B., P.R. and A.-V.T. M.W. and S. Schreyeck synthesised and characterised the samples under the supervision of C.G. and K.B. T.R.F.P., A.-V.T., R.C.V., S. Schatz, F.S., H.M. and A.B. performed the XAS and XMCD measurements. T.R.F.P., A.-V.T., V.Z. and A.B. analysed the XAS and XMCD data. A.-V.T., V.Z., R.J.G. and F.S. performed the MLFT calculations under the supervision of V.H. P.R. performed the DFT calculations under the supervision of S.B. T.R.F.P., H.B., S. Schatz, R.C.V., C.I.F. and C.H.M. performed the resPES experiments. T.R.F.P., R.C.V. and S. Schatz performed the resPES data analysis. A.B., H.B.V., P.G. and M.V. gave scientific and technical support during the XAS/XCMD experimental sessions at the BOREAS endstation, at ALBA. J.B., M.H., F.D., S.R. and M.K. gave scientific and technical support during the resPES experiments at the P04 beamline, at PETRA-III, DESY. K.R., S.B., V.H, L.W.M. and F.R. jointly supervised the work. All authors contributed in the discussions and interpretation of the results.
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Peixoto, T.R.F., Bentmann, H., Rüßmann, P. et al. Non-local effect of impurity states on the exchange coupling mechanism in magnetic topological insulators. npj Quantum Mater. 5, 87 (2020). https://doi.org/10.1038/s41535-020-00288-0
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DOI: https://doi.org/10.1038/s41535-020-00288-0
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