arXiv subjects

Silvia Picozzi

Publications and source records attributed to Silvia Picozzi.

At least 19 recordsLinked to original sources

arXiv2026

The KNN rollercoaster: from bulk ceramics to phase engineered wafer-scale thin films

Since the initial disclosure of the extraordinary piezoelectric coefficients of Potassium sodium niobate (KNN) in near-equimolar bulk ceramics, its development trajectory has resembled a rollercoaster, with its integration into microelectronics severely lagging due to thermodynamic stability issues and poor planar process compatibility. In this work, we revisit the bulk-derived phase diagram for the specific case of thin films integrated on silicon. By systematically investigating Mn-doped K1-xNaxNbO3 films grown on 8-inch wafers, we demonstrate that the optimal stoichiometry for thin films fundamentally diverges from the bulk equimolar standard. A Na-rich composition (> 70 at.%) is required to overcome substrate-induced constraints, effectively suppressing pyrochlore formation and chemical phase segregation while promoting dense columnar growth with a complete (001) out-of-plane polar orientation. Consequently, Na-rich films deliver outstanding functional properties, reaching remanent polarizations up to 14 uC cm-2, with piezoelectric coefficients of d33f= 79 pm/V and e31f = 10 C/m2. Supported by Density Functional Theory simulations, we correlate this enhancement with improved stability and a strain-driven structural reorientation toward a lower-symmetry monoclinic phase with tilted polarization. By redefining the phase engineering rules for wafer-scale thin films, our results establish a clear route toward KNN integration in microsystems.

cond-mat.mtrl-sci↗

arXiv2026

Charge and spin photogalvanic effects in the p-wave magnet NiI2

NiI2 is an exotic van der Waals material in which a noncollinear spin spiral breaks spatial inversion symmetry without sizeable structural distortion, generating improper ferroelectric polarization, and stabilizing p-wave magnetic states with electron-volt-scale odd-parity spin splitting. Using first-principles calculations, here we establish that nonlinear optical transport can directly probe and separate these effects. Magnetically-induced inversion breaking associated with the spin spiral produces a photogalvanic shift current under linearly polarized light, with conductivities exceeding those of conventional ferroelectrics. In contrast, a large photogalvanic injection current under circularly polarized light originates from helicity-selective transitions between spin-split states at opposite crystal momenta, directly exposing the nonrelativistic p-wave spin texture. We further predict pure spin photocurrents whose flow direction exchanges with that of the charge current under linear and circular excitation. The ability to generate and control pure spin currents without accompanying charge currents makes NiI2 a promising material platform for all-optical spin injection in van der Waals heterostructures.

cond-mat.mtrl-sci↗

arXiv2026

Interplay between Relativistic Spin-Momentum Locking and Breaking of Inversion Symmetry: conditions for p-wave magnetism

We investigate the interplay between relativistic spin-momentum locking arising from altermagnetism and various forms of inversion symmetry breaking. Depending on the symmetry breaking, this can give rise to Rashba-type spin-orbit coupling (SOC), Weyl-type SOC, or the coexistence of two distinct spin-momentum lockings. We focus on the altermagnetic Ca2RuO4 as a testbed material. Our results reproduce the experimentally observed ground state, which is an A-centered magnetic order with the Neel vector along the b-axis, hosting spin cantings along the a- and c-axes but without weak ferromagnetism. Ca2RuO4 exhibits relativistic spin-momentum locking, with different even-parity wave orders for the three spin components. We interpret the experimental results on doped samples as evidence for a transition from a pure altermagnetic phase to a weak ferromagnetic phase. Under ferroelectric- and antiferroelectric-like distortions, there are no qualitative changes in the non-relativistic spin-momentum locking and in the weak ferromagnetism. However, we observe the rise of the Rashba or Weyl-type SOC. Using numerical and analytical models, we investigate which nodal planes persist when inversion symmetry is broken in the relativistic case. The spin-momentum locking of the other components adopt a p-wave character in the case of Rashba; in contrast, Weyl-type SOC disrupts all nodal planes, leaving only nodal lines. Finally, to simulate a stripe phase with structural distortions along the z-axis, we studied a modulated electric field inducing atomic displacements within one Ca2RuO4 layer. This produces a magnetic phase transition to an exotic altermagnetic state with two non-relativistic spin-momentum lockings hosting weak ferromagnetism. Our research presents a comprehensive analysis of various possible scenarios in altermagnets with breaking of inversion symmetries under relativistic effects

cond-mat.mtrl-sci↗

arXiv2025

Bulk photovoltaic effect in MoSe$_2$ and Janus MoSSe sliding ferroelectrics

We present a first-principles study of the nonlinear optical properties of sliding ferroelectric bilayers based on MoSe$_2$ and Janus MoSSe. Two Janus configurations are considered: i) one bilayer where the two intralayer polarizations caused by Janus chemical asymmetry cancel each other out, yielding photocurrent spectra comparable to pristine MoSe$_2$ bilayers; ii) another bilayer where the intralayer polarizations add up, for which the photoresponses are strongly enhanced. Our results show that photocurrent generation in the polar Janus structures is predominantly governed by vertical chemical asymmetry, with limited dependence on the sliding direction. These findings highlight complementary design strategies: interlayer sliding enables sensitivity to external tuning, while the Janus intralayer polarization enhances photoresponses in the visible range. The interplay between composition and stacking therefore provides a versatile platform for tailoring light-matter interactions in 2D ferroelectric materials.

cond-mat.mtrl-sci↗

arXiv2025

AMaRaNTA: Automated First-Principles Exchange Parameters In 2D Magnets

Two-dimensional (2D) magnets host a wide range of exotic magnetic textures, whose low-energy excitations and finite-temperature properties are typically described by effective spin models based on Heisenberg-like Hamiltonians. A key challenge in this framework is the reliable determination, from ab initio calculations, of exchange parameters and their anisotropic components, crucial for stabilising long-range order. Among the different strategies proposed for this task, the energy-mapping method -- based on total-energy calculations within Density Functional Theory (DFT) -- is the most widely adopted, but it typically requires laborious, multi-step procedures. To overcome this limitation, we introduce AMaRaNTA (Automating Magnetic paRAmeters iN a Tensorial Approach), a computational package that systematically automates the energy-mapping method, specifically through its ``four-state'' formulation, to extract exchange and anisotropy parameters in 2D magnets. In its current implementation, AMaRaNTA returns the nearest-neighbour exchange tensor, complemented by scalar parameters for second- and third-nearest-neighbour exchange interactions as well as single-ion anisotropy. Together, these provide a minimal yet sufficient set of parameters to capture magnetic frustration and anisotropies, essential for stabilising several observed magnetic states in 2D materials. Applied to a representative subset of the Materials Cloud 2D Structure database, AMaRaNTA demonstrates robust, automated and reproducible screening of magnetic interactions, with clear potential for high-throughput simulations.

cond-mat.mtrl-sci↗

arXiv2025

Hole doping as an efficient route to increase the Curie temperature in monolayer CrI$_3$

Two-dimensional van der Waals (vdW) magnets offer unprecedented opportunities to control magnetism at the atomic scale. Through charge carrier doping - realized by electrostatic gating, intercalation/adsorption, or interfacial charge transfer - one can efficiently tune exchange interactions and spin-orbit-induced effects in these systems. In this work, through a multi-scale theoretical framework combining density functional theory, spin Hamiltonian modeling, and Wannier-function analysis, we choose monolayer CrI$_3$ to unravel how carrier doping affects the isotropic as well as anisotropic exchange interactions in this prototypical vdW ferromagnet. The remarkable efficiency of hole doping in enhancing ferromagnetic exchange and magnetic anisotropy found in our study was explained through orbital-resolved analysis. Crucially, we demonstrated that unlike the undoped system - where isotropic exchange interactions govern magnetic long-range order - the hole-doped CrI$_3$ exhibits anisotropic terms comparable in magnitude to isotropic ones. Finally, we show that a high concentration of holes in a CrI$_3$ monolayer can increase its Curie temperature above 200 K. This work advances our understanding of doping-controlled magnetism in semiconducting 2D materials, demonstrating how anisotropy engineering can stabilize high-temperature magnetic order.

cond-mat.mtrl-sci↗

arXiv2025

Orbital mixing and strong Hund's coupling stabilize spin order in van der Waals ferromagnet CrI3

Recent years have seen a vast increase in research into van der Waals magnetic materials. In many of these systems, magnetism is introduced via light 3d-transition metal elements, combined with chalcogenides or halogens. Despite the high technological promise in the field of spintronics, the connection between the d-orbital configuration and the occurrence of low-dimensional magnetic order is currently unclear. Here we address the prototypical two-dimensional ferromagnet CrI3, via complementary spectroscopies and density functional theory calculations. We reveal the electronic structure and orbital character of bulk CrI3 in the paramagnetic and ferromagnetic phases, describing the couplings underpinning its energy diagram, and providing a robust experimental demonstration that the stabilization of ferromagnetism is attributable to orbital mixing between I p and Cr eg states, and to the presence of strong Hund's coupling. These findings reveal the microscopic connection between orbital and spin degrees of freedom, providing fundamental insights into the behavior of low-dimensional magnetic materials.

cond-mat.mtrl-sci↗

arXiv2025

Bulk photovoltaic effect in ferroelectric and antiferroelectric phases of antimony sulphoiodide investigated by means of ab-initio simulations

We employ first-principles calculations to investigate the ferroelectric properties and the bulk photovoltaic effect (BPVE) of antimony sulfur iodide (SbSI). The BPVE enables direct sunlight-to-electricity conversion in homogeneous materials and, in ferroelectric compounds, can be tuned via an electric field controlling the polarization. However, most ferroelectrics are oxides with large band gaps exceeding the energy of visible light, thereby limiting their photovoltaic performance. SbSI, featuring a visible-range band gap, combines remarkable photovoltaic capabilities with a spin-textured band structure, coupling charge and spin degrees of freedom. Our calculations predict ferroelectric and antiferroelectric phases with comparable band gaps but distinct spin textures, relevant for spintronics applications. The BPVE is driven by the linear and circular photogalvanic effects, exhibiting high photoconductivities under visible light. Furthermore, it serves as a diagnostic tool to identify the material phase, with the circular photogalvanic effect reflecting spin texture changes. Thanks to its multifunctional properties, SbSI emerges as a promising candidate for solar energy conversion and advanced electronics, with potential applications extending to spintronics.

cond-mat.mtrl-sci↗

arXiv2025

Electrical switching of an unconventional odd parity magnet

Magnetic states with zero magnetization but non-relativistic spin splitting are outstanding candidates for the next generation of spintronic devices. Their electron-volt (eV) scale spin splitting, ultrafast spin dynamics and nearly vanishing stray fields make them particularly promising for several applications. A variety of such magnetic states with nontrivial spin textures have been identified recently, including even-parity d, g, or i-wave altermagnets and odd-parity p-wave magnets. Achieving voltage-based control of the nonuniform spin polarization of these magnetic states is of great interest for realizing energyefficient and compact devices for information storage and processing. Spin-spiral type-II multiferroics are optimal candidates for such voltage-based control, as they exhibit an inversion-symmetry-breaking magnetic order which directly induces ferroelectric polarization, allowing for symmetry protected cross-control between spin chirality and polar order. Here we combine photocurrent measurements, first-principle calculations and group-theory analysis to provide direct evidence that the spin polarization of the spin-spiral type-II multiferroic NiI2 exhibits odd-parity character connected to the spiral chirality. The symmetry-protected coupling between chirality and polar order enables electrical control of a primarily non-relativistic spin polarization. Our findings represent the first direct observation of unconventional odd-parity magnetism in a spin-spiral type-II multiferroic, and open a new frontier of voltage-based switching of non-relativistic spin polarization in compensated magnets.

cond-mat.mes-hall↗

arXiv2025

Designing Non-Relativistic Spin Splitting in Oxide Perovskites

We investigate the role of atomic distortions in non-relativistic spin splitting in perovskite oxides with Pbnm symmetry. Using LaMnO3 as a representative material, we analyze its non-relativistic spin splitting through a combined phonon and multipolar analysis. Our study provides key insights into how structural distortions and magnetic ordering drive ferroically ordered magnetic multipoles, which, in turn, give rise to non-relativistic spin splitting. Based on these findings, we propose three strategies for engineering non-relativistic spin splitting: modifying the A-site cation size, strain engineering, and electric field control in superlattice structures. Our work establishes a framework for designing non-relativistic spin splitting in the Brillouin zone of oxide perovskites.

cond-mat.mtrl-sci↗

arXiv2025

Magnetoelectricity of Topological Solitons in 2D Magnets

We develop a multiscale approach to magnetoelectric effects, bridging atomistic and continuum models, with all parameters determined from ab initio electronic structure calculations. We show that the parameters of the model are equivalent to the electric field-induced Dzyaloshinski-Moriya interactions. After careful validation, we apply the models to study electric polarization and dipole moments carried by spin spirals and topological solitons, in the form of magnetic domain walls and Skyrmions, in the prototypical 2D magnet CrI$_3$. We show that the reduced symmetry of the material leads to additional magnetoelectric coupling terms, dominating over those expected in high symmetry (cubic) materials. An interesting consequence is that Skyrmions carry an out-of-plane electric dipole moment, while that of anti-Skyrmions is an order of magnitude larger and in-plane. Finally, we discuss the possibility to stabilize non-collinear spin states using electric fields.

cond-mat.mtrl-sci↗

arXiv2025

Giant non-reciprocal band structure effect in a multiferroic material

Multiferroic materials, characterized by the coexistence of ferroelectricity and ferromagnetism, may unveil band structures suggestive of complex phenomena and new functionalities. In this Letter, we analyze the band structure of EuO in its multiferroic phase. Using density functional theory calculations and detailed symmetry analysis, we reveal a previously overlooked non-reciprocal band structure effect, where the electronic energy bands exhibit asymmetry along opposite directions with respect to the special points in the Brillouin zone. This effect, which is enabled by spin-orbit coupling, is giant for the top valence Eu $4f$ bands, and can be switched by external electric or magnetic fields. Furthermore, this results in an enhanced bulk photovoltaic effect. Specifically, our predictions indicate the emergence of a large injection current response to linearly polarized light, resulting in a photoconductivity value several orders of magnitude higher than that reported in any other oxide material. Ultimately, this non-reciprocal band structure effect and the associated large bulk photovoltaic response may be general phenomena emerging not just in EuO but also in other multiferroics or magnetoelectrics, potentially providing new cross-functionalities.

cond-mat.mtrl-sci↗

arXiv2024

Avoided metallicity in a hole-doped Mott insulator on a triangular lattice

Doping of a Mott insulator gives rise to a wide variety of exotic emergent states, from high-temperature superconductivity to charge, spin, and orbital orders. The physics underpinning their evolution is, however, poorly understood. A major challenge is the chemical complexity associated with traditional routes to doping. Here, we study the Mott insulating CrO$_2$ layer of the delafossite PdCrO$_2$, where an intrinsic polar catastrophe provides a clean route to doping of the surface. From scanning tunnelling microscopy and angle-resolved photoemission, we find that the surface stays insulating accompanied by a short-range ordered state. From density functional theory, we demonstrate how the formation of charge disproportionation results in an insulating ground state of the surface that is disparate from the hidden Mott insulator in the bulk. We demonstrate that voltage pulses induce local modifications to this state which relax over tens of minutes, pointing to a glassy nature of the charge order.

cond-mat.str-el↗

arXiv2024

Emergence of Topological Bimerons in Monolayer CrSBr

The rich and fascinating physics of topological spin textures in van der Waals two-dimensional magnets has motivated recent growing interests, though a comprehensive understanding remains elusive. Here, in atomistic simulations on monolayer CrSBr, we find two magnetic phases emerging under non-equilibrium conditions at distinct temperatures, a standard ferromagnetic transition Tc and a lower temperature T*. Moreover, the real-space analysis of the spin texture reveals the emergence of metastable topological bimeron defects below T*, showing an algebraic-like decaying spin-spin correlation function. The Dzyaloshinskii-Moriya interaction, induced by the local site asymmetry in the centrosymmetric CrSBr monolayer, is proved to be the origin of the bimerons formation. Furthermore, the increasing bimerons density upon increasing the cooling rate follows a Kibble-Zurek behavior, suggesting a handle to drive and control topological bimerons below T*. Our results put forward CrSBr as an important candidate for the investigation of the dynamical behavior of bimerons in vdW magnets.

cond-mat.mtrl-sci↗

arXiv2024

Interplay of altermagnetism and weak ferromagnetism in two-dimensional RuF$_4$

Gaining growing attention in spintronics is a class of magnets displaying zero net magnetization and spin-split electronic bands called altermagnets. Here, by combining density functional theory and symmetry analysis, we show that RuF$_4$ monolayer is a two-dimensional $d$-wave altermagnet. Spin-orbit coupling leads to pronounced spin splitting of the electronic bands at the $Γ$ point by $\sim 100$ meV and turns the RuF$_4$ into a weak ferromagnet due to non trivial spin-momentum locking that cants the Ru magnetic moments. The net magnetic moment scales linearly with the spin-orbit coupling strength. Using group theory we derive an effective spin Hamiltonian capturing the spin-splitting and spin-momentum locking of the electronic bands. Disentanglement of the altermagnetic and spin-orbit coupling induced spin splitting uncovers to which extent the altermagnetic properties are affected by the spin-orbit coupling. Our results move the spotlight to the non trivial spin-momentum locking and weak ferromagnetism in the two-dimensional altermagnets relevant for novel venues in this emerging field of material science research.

cond-mat.mtrl-sci↗

arXiv2023

Charge doping into spin minority states mediates doubling of $T_\mathrm{C}$ in ferromagnetic CrGeTe$_3$

The recent discovery of the persistence of long-range magnetic order when van der Waals layered magnets are thinned towards the monolayer limit has provided a tunable platform for the engineering of novel magnetic structures and devices. Here, we study the evolution of the electronic structure of CrGeTe$_3$ as a function of electron doping in the surface layer. From angle-resolved photoemission spectroscopy, we observe spectroscopic fingerprints that this electron doping drives a marked increase in $T_\mathrm{C}$, reaching values more than double that of the undoped material, in agreement with recent studies using electrostatic gating. Together with density functional theory calculations and Monte Carlo simulations, we show that, surprisingly, the increased $T_\mathrm{C}$ is mediated by the population of spin-minority Cr $t_{2g}$ states, forming a half-metallic 2D electron gas at the surface. We show how this promotes a novel variant of double exchange, and unlocks a significant influence of the Ge -- which was previously thought to be electronically inert in this system -- in mediating Cr-Cr exchange.

cond-mat.mtrl-sci↗

arXiv2023

Delving into the anisotropic interlayer exchange in bilayer CrI$_3$

Bilayer CrI$_3$ attracted much attention owing to peculiar switching between the layered ferromagnetic and antiferromagnetic order upon stacking alternation. This finding pointed out the importance of the apparently small interlayer exchange, yet, existing literature addresses only its isotropic part. To fill this gap, we combine the density functional theory with Hamiltonian modeling to examine the anisotropic interlayer exchange in bilayer CrI$_3$ - Dzyaloshinskii-Moriya (DMI) and the Kitaev interaction (KI). We develop and apply a novel computational procedure that yields the off-diagonal exchange matrix elements with $μ$eV accuracy. Inspecting two types of bilayer stacking, we found a weak interlayer KI and much stronger DMI between the sublattices of monoclinic bilayer and their complete absence in rhombohedral bilayer. We show how these anisotropic interactions depend on the interlayer distance, stacking sequence, and the spin-orbit coupling strength and suggest the dominant superexchange processes at play. In addition, we demonstrate that the single-ion anisotropy largely depends on stacking, increasing by 50% from monoclinic to rhombohedral structure. Remarkably, our findings prove that iodines, owing to their spatially extended 5p orbitals featuring strong spin-orbit coupling, are extremely efficient in mediating DMI across the van der Waals gap in two-dimensional magnetic heterostructures. Given that similar findings were previously demonstrated only in metallic multilayers where the DMI shows a much longer range, our study gives promise that the chiral control of spin textures can be achieved in two-dimensional semiconducting magnetic bilayers whose ligands feature strong spin-orbit coupling.

cond-mat.mtrl-sci↗

arXiv2023

Covalency, correlations, and inter-layer interactions governing the magnetic and electronic structure of Mn$_3$Si$_2$Te$_6$

Mn$_3$Si$_2$Te$_6$ is a rare example of a layered ferrimagnet. It has recently been shown to host a colossal angular magnetoresistance as the spin orientation is rotated from the in- to out-of-plane direction, proposed to be underpinned by a topological nodal-line degeneracy in its electronic structure. Nonetheless, the origins of its ferrimagnetic structure remain controversial, while its experimental electronic structure, and the role of correlations in shaping this, are little explored to date. Here, we combine x-ray and photoemission-based spectroscopies with first-principles calculations, to probe the elemental-selective electronic structure and magnetic order in Mn$_3$Si$_2$Te$_6$. Through these, we identify a marked Mn-Te hybridisation, which weakens the electronic correlations and enhances the magnetic anisotropy. We demonstrate how this strengthens the magnetic frustration in Mn$_3$Si$_2$Te$_6$, which is key to stabilising its ferrimagnetic order, and find a crucial role of both exchange interactions extending beyond nearest-neighbours and anti-symmetric exchange in dictating its ordering temperature. Together, our results demonstrate a powerful methodology of using experimental electronic structure probes to constrain the parameter space for first-principles calculations of magnetic materials, and through this approach, reveal a pivotal role played by covalency in stabilising the ferrimagnetic order in Mn$_3$Si$_2$Te$_6$.

cond-mat.mtrl-sci↗