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The family of two-dimensional (2D) van der Waals (vdW) materials provides a playground for tuning structural and magnetic interactions to create a wide variety of spin textures. Of particular interest is the ferromagnetic compound Fe 5 GeTe 2 that we show displays a range of complex spin textures as well as complex crystal structures. Here, using a high-brailliance laboratory X-ray source, we show that the majority (1 × 1) Fe 5 GeTe 2 (FGT5) phase exhibits a structure that was previously considered as being centrosymmetric but rather lacks inversion symmetry. In addition, FGT5 exhibits a minority phase that exhibits a long-range ordered (√3 × √3)-R30° superstructure. This superstructure is highly interesting in that it is innately 2D without any lattice periodicity perpendicular to the vdW layers, and furthermore, the superstructure is a result of ordered Te vacancies in one of the topmost layers of the FGT5 sheets rather than being a result of vertical Fe ordering as earlier suggested. We show, from direct real-space magnetic imaging, evidence for three distinct magnetic ground states in lamellae of FGT5 that are stabilized with increasing lamella thickness, namely, a multidomain state, a stripe phase, and an unusual fractal state. In the stripe phase we also observe unconventional type-I and type-II bubbles where the spin texture in the central region of the bubbles is nonuniform, unlike conventional bubbles. In addition, we find a bobber or a cocoon-like spin texture in thick (∼170 μm) FGT5 that emerges from the fractal state in the presence of a magnetic field. Among all the 2D vdW magnets we have thus demonstrated that FGT5 hosts perhaps the richest variety of magnetic phases that, thereby, make it a highly interesting platform for the subtle tuning of magnetic interactions.

The niobium oxide polymorph T-Nb 2 O 5 has been extensively investigated in its bulk form especially for applications in fast-charging batteries and electrochemical (pseudo)capacitors. Its crystal structure, which has two-dimensional (2D) layers with very low steric hindrance, allows for fast Li-ion migration. However, since its discovery in 1941, the growth of single-crystalline thin films and its electronic applications have not yet been realized, probably due to its large orthorhombic unit cell along with the existence of many polymorphs. Here we demonstrate the epitaxial growth of single-crystalline T-Nb 2 O 5 thin films, critically with the ionic transport channels oriented perpendicular to the film's surface. These vertical 2D channels enable fast Li-ion migration, which we show gives rise to a colossal insulator-metal transition, where the resistivity drops by 11 orders of magnitude due to the population of the initially empty Nb 4d 0 states by electrons. Moreover, we reveal multiple unexplored phase transitions with distinct crystal and electronic structures over a wide range of Li-ion concentrations by comprehensive in situ experiments and theoretical calculations, which allow for the reversible and repeatable manipulation of these phases and their distinct electronic properties. This work paves the way for the exploration of novel thin films with ionic channels and their potential applications., (© 2023. The Author(s).)

Spin-triplet supercurrent spin valves are of practical importance for the realization of superconducting spintronic logic circuits. In ferromagnetic Josephson junctions, the magnetic-field-controlled non-collinearity between the spin-mixer and spin-rotator magnetizations switches the spin-polarized triplet supercurrents on and off. Here we report an antiferromagnetic equivalent of such spin-triplet supercurrent spin valves in chiral antiferromagnetic Josephson junctions as well as a direct-current superconducting quantum interference device. We employ the topological chiral antiferromagnet Mn 3 Ge, in which the Berry curvature of the band structure produces fictitious magnetic fields, and the non-collinear atomic-scale spin arrangement accommodates triplet Cooper pairing over long distances (>150 nm). We theoretically verify the observed supercurrent spin-valve behaviours under a small magnetic field of <2 mT for current-biased junctions and the direct-current superconducting quantum interference device functionality. Our calculations reproduce the observed hysteretic field interference of the Josephson critical current and link these to the magnetic-field-modulated antiferromagnetic texture that alters the Berry curvature. Our work employs band topology to control the pairing amplitude of spin-triplet Cooper pairs in a single chiral antiferromagnet., (© 2023. The Author(s).)

Antiferromagnets with non-collinear spin structures display various properties that make them attractive for spintronic devices. Some of the most interesting examples are an anomalous Hall effect despite negligible magnetization and a spin Hall effect with unusual spin polarization directions. However, these effects can only be observed when the sample is set predominantly into a single antiferromagnetic domain state. This can only be achieved when the compensated spin structure is perturbed and displays weak moments due to spin canting that allows for external domain control. In thin films of cubic non-collinear antiferromagnets, this imbalance is previously assumed to require tetragonal distortions induced by substrate strain. Here, it is shown that in Mn 3 SnN and Mn 3 GaN, spin canting is due to structural symmetry lowering induced by large displacements of the magnetic manganese atoms away from high-symmetry positions. These displacements remain hidden in X-ray diffraction when only probing the lattice metric and require measurement of a large set of scattering vectors to resolve the local atomic positions. In Mn 3 SnN, the induced net moments enable the observation of the anomalous Hall effect with an unusual temperature dependence, which is conjectured to result from a bulk-like temperature-dependent coherent spin rotation within the kagome plane., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Dodecagonal oxide quasicrystals are well established as examples of long-range aperiodic order in two dimensions. However, despite investigations by scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), low-energy electron microscopy (LEEM), photoemission spectroscopy as well as density functional theory (DFT), their structure is still controversial. Furthermore, the principles that guide the formation of quasicrystals (QCs) in oxides are elusive since the principles that are known to drive metallic QCs are expected to fail for oxides. Here we demonstrate the solution of the oxide QC structure by synchrotron-radiation based surface x-ray diffraction (SXRD) refinement of its largest-known approximant. The oxide QC formation is forced by large alkaline earth metal atoms and the reduction of their mutual electrostatic repulsion. It drives the n = 6 structure of the 2D Ti 2 O 3 honeycomb arrangement via Stone-Wales transformations into an ordered structure with empty n = 4, singly occupied n = 7 and doubly occupied n = 10 rings, as supported by DFT., (© 2022. The Author(s).)

Transition-metal dichalcogenides intercalated with 3d-transition metals within the van der Waals (vdW) gaps have been the focus of intense investigations owing to their fascinating structural and magnetic properties. At certain concentrations the intercalated atoms form ordered superstructures that exhibit ferromagnetic or anti-ferromagnetic ordering. Here we show that the self-intercalated compound Cr 1+δ Te 2 with δ ≈ 0.3 exhibits a new, so far unseen, three-dimensionally ordered (2×2×2) superstructure. Furthermore, high resolution X-ray diffraction reveals that there is an asymmetric occupation of the two inequivalent vdW gaps in the unit cell. The structure thus lacks inversion symmetry, which, thereby, allows for chiral non-collinear magnetic nanostructures. Indeed, Néel-type skyrmions are directly observed using Lorentz transmission electron microscopy. The skyrmions are stable within the accessible temperature range (100-200 K) as well as in zero magnetic field. The diameter of the Néel skyrmions increases with lamella thickness and varies with applied magnetic field, indicating the role of long-range dipole fields. Our studies show that self-intercalation in vdW materials is a novel route to the formation of synthetic non-collinear spin textures., (© 2022. The Author(s).)

Spin-momentum locking in topological insulators and materials with Rashba-type interactions is an extremely attractive feature for novel spintronic devices and is therefore under intense investigation. Significant efforts are underway to identify new material systems with spin-momentum locking, but also to create heterostructures with new spintronic functionalities. In the present study we address both subjects and investigate a van der Waals-type heterostructure consisting of the topological insulator Bi 2 Se 3 and a single Se-Ta-Se triple-layer (TL) of H-type TaSe 2 grown by a method which exploits an interface reaction between the adsorbed metal and selenium. We then show, using surface x-ray diffraction, that the symmetry of the TaSe 2 -like TL is reduced from D 3h to C 3v resulting from a vertical atomic shift of the tantalum atom. Spin- and momentum-resolved photoemission indicates that, owing to the symmetry lowering, the states at the Fermi surface acquire an in-plane spin component forming a surface contour with a helical Rashba-like spin texture, which is coupled to the Dirac cone of the substrate. Our approach provides a route to realize chiral two-dimensional electron systems via interface engineering in van der Waals epitaxy that do not exist in the corresponding bulk materials., (© 2022. The Author(s).)

Oxygen defects and their atomic arrangements play a significant role in the physical properties of many transition metal oxides. The exemplary perovskite SrCoO 3-δ ( P- SCO) is metallic and ferromagnetic. However, its daughter phase, the brownmillerite SrCoO 2.5 ( BM- SCO), is insulating and an antiferromagnet. Moreover, BM- SCO exhibits oxygen vacancy channels (OVCs) that in thin films can be oriented either horizontally ( H -SCO) or vertically ( V -SCO) to the film's surface. To date, the orientation of these OVCs has been manipulated by control of the thin film deposition parameters or by using a substrate-induced strain. Here, we present a method to electrically control the OVC ordering in thin layers via ionic liquid gating (ILG). We show that H -SCO (antiferromagnetic insulator, AFI) can be converted to P -SCO (ferromagnetic metal, FM) and subsequently to V -SCO (AFI) by the insertion and subtraction of oxygen throughout thick films via ILG. Moreover, these processes are independent of substrate-induced strain which favors formation of H -SCO in the as-deposited film. The electric-field control of the OVC channels is a path toward the creation of oxitronic devices.

There is considerable interest in van der Waals (vdW) materials as potential hosts for chiral skyrmionic spin textures. Of particular interest is the ferromagnetic, metallic compound Fe 3 GeTe 2 (FGT), which has a comparatively high Curie temperature (150-220 K). Several recent studies have reported the observation of chiral Néel skyrmions in this compound, which is inconsistent with its presumed centrosymmetric structure. Here the observation of Néel type skyrmions in single crystals of FGT via Lorentz transmission electron microscopy (LTEM) is reported. It is shown from detailed X-ray diffraction structure analysis that FGT lacks an inversion symmetry as a result of an asymmetric distribution of Fe vacancies. This vacancy-induced breaking of the inversion symmetry of this compound is a surprising and novel observation and is a prerequisite for a Dzyaloshinskii-Moriya vector exchange interaction which accounts for the chiral Néel skyrmion phase. This phenomenon is likely to be common to many 2D vdW materials and suggests a path to the preparation of many such acentric compounds. Furthermore, it is found that the skyrmion size in FGT is strongly dependent on its thickness: the skyrmion size increases from ≈100 to ≈750 nm as the thickness of the lamella is increased from ≈90 nm to ≈2 µm. This extreme size tunability is a feature common to many low symmetry ferro- and ferri-magnetic compounds., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

An advanced experimental and theoretical model to explain the correlation between the electronic and local structure of Eu[Formula: see text] in two different environments within a same compound, EuS, is presented. EuX monochalcogenides (X: O, S, Se, Te) exhibit anomalies in all their properties around 14 GPa with a semiconductor to metal transition. Although it is known that these changes are related to the [Formula: see text] [Formula: see text] [Formula: see text] electronic transition, no consistent model of the pressure-induced modifications of the electronic structure currently exists. We show, by optical and x-ray absorption spectroscopy, and by ab initio calculations up to 35 GPa, that the pressure evolution of the crystal field plays a major role in triggering the observed electronic transitions from semiconductor to the half-metal and finally to the metallic state., (© 2022. The Author(s).)

The proximity-coupling of a chiral non-collinear antiferromagnet (AFM) 1-5 with a singlet superconductor allows spin-unpolarized singlet Cooper pairs to be converted into spin-polarized triplet pairs 6-8 , thereby enabling non-dissipative, long-range spin correlations 9-14 . The mechanism of this conversion derives from fictitious magnetic fields that are created by a non-zero Berry phase 15 in AFMs with non-collinear atomic-scale spin arrangements 1-5 . Here we report long-ranged lateral Josephson supercurrents through an epitaxial thin film of the triangular chiral AFM Mn 3 Ge (refs. 3-5 ). The Josephson supercurrents in this chiral AFM decay by approximately one to two orders of magnitude slower than would be expected for singlet pair correlations 9-14 and their response to an external magnetic field reflects a clear spatial quantum interference. Given the long-range supercurrents present in both single- and mixed-phase Mn 3 Ge, but absent in a collinear AFM IrMn 16 , our results pave a way for the topological generation of spin-polarized triplet pairs 6-8 via Berry phase engineering 15 of the chiral AFMs., (© 2021. The Author(s).)

Magnetic nano-objects, namely antiskyrmions and Bloch skyrmions, have been found to coexist in single-crystalline lamellae formed from bulk crystals of inverse tetragonal Heusler compounds with D 2d symmetry. Here evidence is shown for magnetic nano-objects in epitaxial thin films of Mn 2 RhSn formed by magnetron sputtering. These nano-objects exhibit a wide range of sizes with stability with respect to magnetic field and temperature that is similar to single-crystalline lamellae. However, the nano-objects do not form well-defined arrays, nor is any evidence found for helical spin textures. This is speculated to likely be a consequence of the poorer homogeneity of chemical ordering in the thin films. However, evidence is found for elliptically distorted nano-objects along perpendicular crystallographic directions within the epitaxial films, which is consistent with elliptical Bloch skyrmions observed in single-crystalline lamellae. Thus, these measurements provide strong evidence for the formation of noncollinear spin textures in thin films of Mn 2 RhSn. Using these films, it is shown that individual nano-objects can be deleted using a local magnetic field from a magnetic tip and collections of nano-objects can be similarly written. These observations suggest a path toward the use of these objects in thin films with D 2d symmetry as magnetic memory elements., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Over the past decade the family of chiral noncollinear spin textures has continued to expand with the observation in metallic compounds of Bloch-like skyrmions in several B20 compounds, and antiskyrmions in a tetragonal inverse Heusler. Néel like skyrmions in bulk crystals with broken inversion symmetry have recently been seen in two distinct nonmetallic compounds, GaV 4 S 8 and VOSe 2 O 5 at low temperatures (below ≈13 K) only. Here, the first observation of bulk Néel skyrmions in a metallic compound PtMnGa and, moreover, at high temperatures up to ≈220 K is reported. Lorentz transmission electron microscopy reveals the chiral Néel character of the skyrmions. A strong variation is reported of the size of the skyrmions on the thickness of the lamella in which they are confined, varying by a factor of 7 as the thickness is varied from ≈90 nm to ≈4 µm. Moreover, the skyrmions are highly robust to in-plane magnetic fields and can be stabilized in a zero magnetic field using suitable field-cooling protocols over a very broad temperature range to as low as 5 K. These properties, together with the possibility of manipulating skyrmions in metallic PtMnGa via current induced spin-orbit torques, make them extremely exciting for future spintronic applications., (© 2019 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A stable BiI 3 monosheet has been grown for the first time on the (0001) surface of the topological insulator Bi 2 Se 3 as confirmed by scanning tunnelling microscopy, surface X-ray diffraction, and X-ray photoemision spectroscopy. BiI 3 is deposited by molecular beam epitaxy from the crystalline BiTeI precursor that undergoes decomposition sublimation. The key fragment of the bulk BiI 3 structure, [Formula: see text][I-Bi-I] layer of edge-sharing BiI 6 octahedra, is preserved in the ultra-thin film limit, but exhibits large atomic relaxations. The stacking sequence of the trilayers and alternations of the Bi-I distances in the monosheet are the same as in the bulk BiI 3 structure. Momentum resolved photoemission spectroscopy indicates a direct band gap of 1.2 eV. The Dirac surface state is completely destroyed and a new flat band appears in the band gap of the BiI 3 film that could be interpreted as an interface state.

A conducting 2D electron gas (2DEG) is formed at the interface between epitaxial LaFeO 3 layers >3 unit cells thick and the surface of SrTiO 3 single crystals. The 2DEG is exquisitely sensitive to cation intermixing and oxygen nonstoichiometry. It is shown that the latter thus allows the controllable formation of the 2DEG via ionic liquid gating, thereby forming a nonvolatile switch., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report on the first observation of an approximant structure to the recently discovered two-dimensional oxide quasicrystal. Using scanning tunneling microscopy, low-energy electron diffraction, and surface x-ray diffraction in combination with ab initio calculations, the atomic structure and the bonding scheme are determined. The oxide approximant follows a 3^{2}.4.3.4 Archimedean tiling. Ti atoms reside at the corners of each tiling element and are threefold coordinated to oxygen atoms. Ba atoms separate the TiO&#95;{3} clusters, leading to a fundamental edge length of the tiling 6.7 Å.

Angular resolved photoemission spectroscopy in combination with ab initio calculations show that trace amounts of carbon doping of the Bi&#95;{2}Se&#95;{3} surface allows the controlled shift of the Dirac point within the bulk band gap. In contrast to expectation, no Rashba-split two-dimensional electron gas states appear. This unique electronic modification is related to surface structural modification characterized by an expansion of the top Se-Bi spacing of ≈11% as evidenced by surface x-ray diffraction. Our results provide new ways to tune the surface band structure of topological insulators.

Using surface x-ray diffraction in combination with ab initio calculations, we demonstrate that the atomic structure of ultrathin BaTiO3 (BTO) films grown on Me(001) surfaces (Me=Fe, Pd, Pt) depends on subtle modifications of the interface chemical composition. A complete reversal of the surface termination from a BaO- [BTO on Fe(001)] to a TiO2-terminated film [BTO on Pt(001)] is observed which goes in parallel with the adsorption of submonolayer amounts of oxygen at metal hollow sites of the interface. Our results may suggest a new route to an overall control of both the surface and the interface geometry in BaTiO3/metal contacts.

The geometry of oxygen atoms in hollow sites of Fe nanoislands (⊘≈1-2  nm) on Fe(001) is modified by mesoscopic misfit-induced relaxations of the island atoms. Surface x-ray diffraction, scanning tunneling microscopy, and ab initio calculations indicate a 0.3 Å increased adsorption height [0.7 Å versus 0.4 Å in O/Fe(001)-p(1×1)] of O atoms going in parallel with a reduced Fe-Fe layer spacing inducing a reduction of the surface magnetic moment (2.85μ(B) versus 3.2μ(B)). Our results demonstrate the importance of the mesoscopic misfit for surface physical properties in general.

Using surface x-ray diffraction and ab initio calculations we present a model of the BaTiO3(001)-(2×1) surface structure, which has not been considered so far. While the crystal is terminated by two TiO2 layers similarly to SrTiO3(001)-(2×1), we find that one out of two surface layer Ti-atoms resides in a tetragonal pyramidal oxygen environment. This peculiar geometry leads to a metallic and magnetic surface involving local magnetic moments up to 2μ(B) in magnitude located at surface Ti and O atoms. Our results are important for the understanding of the intrinsic surface metallicity of insulating oxides in general.

Using scanning tunneling microscopy experiments in combination with first-principles calculations we have studied the geometric structure of the compressed c(7sqrt(2) × sqrt(2)) antiphase domain structure of CO on Cu(001). We find direct evidence for structural relaxations involving an inhomogeneous CO environment characterized by molecular tilting, bending, and nonterminal sites. Our analysis solves the long-standing problem of the adsorption structure of the compressed phase and is important for understanding the physical properties of this fundamental adsorption system.

We present an experimental and theoretical study of the geometric structure of ultrathin BaTiO(3) films grown on Fe(001). Surface x-ray diffraction reveals that the films are terminated by a BaO layer, while the TiO(2) layer is next to the top Fe layer. Cations in termination layers have incomplete oxygen shells inducing strong vertical relaxations. Onset of polarization is observed at a minimum thickness of two unit cells. Our findings are supported by first-principles calculations providing a quantitative insight into the multiferroic properties on the atomic scale., (© 2011 American Physical Society)

Using soft-x-ray resonant magnetic scattering in combination with first-principles calculations for noncollinear magnetic configurations we present a new model of the magnetism in ultrathin fcc Fe films on Cu(001). We find the presence of blocks with robust magnetic structure, while the relative directions of the moments of different blocks are sensitive to the detailed atomic structure and temperature. The magnetic noncollinearity is directly demonstrated, which has not been possible so far.

Surface x-ray diffraction experiments reveal that, in cobalt-doped ZnO films two to five monolayers thick, Wurtzite-type CoO nanocrystals are coherently embedded within a hexagonal boron-nitride- (h-BN)-type ZnO matrix, supporting the model of a phase separation. First-principles calculations confirm that, in contrast with ZnO, the formation of h-BN-type CoO is unfavorable in the ultrathin film limit. Our results are important for understanding magnetic properties of transition metal-doped semiconductors in general.

We present a quantitative surface x-ray analysis of the buried Ni/Cu(001) interface structure after deposition of 3 and 5 monolayers of Ni at room temperature. Interface mixing is found where 27+/-10% of top layer Cu atoms are exchanged by Ni. Atomic scale simulations reveal a kinetic pathway for the Ni/Cu-exchange process and explain the observed limited degree of intermixing. A disperse distribution of Ni within the Cu surface with a preferential Ni-Ni separation of 3-4 nearest neighbor distances is determined.

Surface x-ray diffraction in combination with scanning tunneling microscopy and molecular dynamics calculations provide first quantitative evidence for unusually large relaxations in nanometer-sized Co islands deposited on Cu(001) at 170 K. These lead to sharply reduced interatomic Co distances as low as 2.36 A as compared to bulk Co (2.51 A) involving low symmetry Co adsorption sites. Our results prove the validity of the concept of mesoscopic mismatch which governs the strain relaxation of nanosized islands in general.

The x-ray structure analysis of the oxygen-surfactant-mediated growth of Ni on Cu(001) identifies up to 0.15 monolayers of oxygen in subsurface octahedral sites. This questions the validity of the general view that surfactant oxygen floats on top of the growing Ni film. Rather, the surfactant action is ascribed to an oxygen-enriched zone extending over the two topmost layers. Surface stress measurements support this finding. Our results have important implications for the microscopic understanding of surfactant-mediated growth and the change of the magnetic anisotropy of the Ni films.

A novel nonpolar structure of 2 monolayer (ML) thick ZnO(0001) films grown on Ag(111) has been revealed, using surface x-ray diffraction and scanning tunneling microscopy. Zn and O atoms are arranged in planar sheets like in the hexagonal boron-nitride prototype structure. The observed depolarization is accompanied by a significant lateral 1.6% expansion of the lattice parameter and a 3% reduced Zn-O bond length within the sheets. The nonpolar structure stabilizes an atomically flat surface morphology unseen for ZnO surfaces thus far. The transition to the bulk wurtzite structure occurs in the 3-4 ML coverage range, connected to considerable roughening.

We present x-ray diffraction experiments and multiple-scattering calculations on the structure and transport properties of a Fe/MgO/Fe(001) magnetic tunnel junction (MTJ). Coherent growth of the top Fe electrode on the MgO spacer is observed only for Fe deposition in ambient oxygen atmosphere leading to a coherent and symmetric MTJ structure characterized by FeO layers at both interfaces. This goes in parallel with calculations indicating large positive tunnel magnetoresistance (TMR) values in such symmetric junctions. The results have important implications for achieving giant TMR values.

Using ab initio thermodynamics we compile a phase diagram for the surface of Fe3O4(001) as a function of temperature and oxygen pressures. A hitherto ignored polar termination with octahedral iron and oxygen forming a wavelike structure along the [110] direction is identified as the lowest energy configuration over a broad range of oxygen gas-phase conditions. This novel geometry is confirmed via x-ray diffraction analysis. The stabilization of the Fe3O4(001) surface goes together with dramatic changes in the electronic and magnetic properties, e.g., a half metal to metal transition.

The correlation between an ad-layer-induced spin reorientation transition (SRT) and the ad-layer-induced structural relaxation is investigated by combined in situ surface x-ray diffraction and magneto-optical Kerr-effect experiments on Ni/Fe/Ni(111) layers on W(110). The Fe-induced SRT from in-plane to out-of-plane, and the SRT back to in-plane upon subsequent coverage by Ni, are each accompanied by a small lattice relaxation of at most 0.002 A. Such a small strain variation excludes a magnetoelasticity driven SRT, and we suggest the interface anisotropy as a possible driving force.

The geometric structure of MgO deposited on Fe(001) in ultrahigh vacuum by electron evaporation was determined in detail by using surface x-ray diffraction. In contrast to the common belief that MgO grows in direct contact on the Fe(001) substrate, we find an FeO interface layer between the substrate and the growing MgO structure which has not been considered thus far. This result opens new perspectives for the understanding of the Fe/MgO/Fe(001) interface and the tunneling magnetoresistance effect in general.