arXiv subjects

Javier Herrero-Martín

Publications and source records attributed to Javier Herrero-Martín.

13 recordsLinked to original sources

arXiv2026

Spin-orbit-entangled $J_{\rm eff}=\frac{1}{2}$ magnetism and unconventional spin freezing in the bond-disordered pyrochlore antiferromagnet NaCdCo$_2$F$_7$

Bond disorder in frustrated pyrochlore antiferromagnets can give rise to fundamentally different quantum ground states depending on the nature of the local magnetic moments. Here, we show that the bond-disordered $J_{\rm eff}=\frac{1}{2}$ pyrochlore antiferromagnet NaCdCo$_2$F$_7$ realizes an unconventional spin-glass-like state with continued dynamics, in stark contrast to its isostructural $S=\frac{1}{2}$ NaCdCu$_2$F$_7$ counterpart. High-field magnetization and Co $L_{2,3}$-edge XAS/XMCD establish spin-orbit-entangled $J_{\rm eff}=\frac{1}{2}$ Co$^{2+}$ moments with a substantial unquenched orbital contribution, consistent with local $XY$ anisotropy seen in the isostructural Na$A''$Co$_2$F$_7$ ($A''$ = Ca, Sr) analogues. $μ$SR and $^{23}$Na NMR measurements reveal progressive slowing of spin fluctuations below $\sim10$ K, culminating in a partially frozen state with persistent low-temperature dynamics that deviates from a canonical spin glass. Comparison with the isostructural bond-disordered pyrochlore NaCdCu$_2$F$_7$, which realizes a random-singlet state, reveals a fundamentally different response of spin-orbit-entangled Co$^{2+}$ moments to bond disorder. These results identify spin-orbit coupling as a key ingredient governing the fate of bond-disordered frustrated pyrochlore magnets.

cond-mat.str-el↗

arXiv2025

Carbon magneto-ionics: Control of magnetism through voltage-driven carbon transport

Control of magnetism through voltage-driven ionic processes (i.e., magneto-ionics) holds potential for next-generation memories and computing. This stems from its non-volatility, flexibility in adjusting the magnitude and speed of magnetic modulation, and energy efficiency. Since magneto-ionics depends on factors like ionic radius and electronegativity, identifying alternative mobile ions is crucial to embrace new phenomena and applications. Here, the feasibility of C as a prospective magneto-ionic ion is investigated in a Fe-C system by electrolyte gating. In contrast to most magneto-ionic systems, Fe-C presents a dual-ion mechanism: Fe and C act as cation and anion, respectively, moving uniformly in opposite directions under an applied electric field. This leads to a 7-fold increase in saturation magnetization with magneto-ionic rates larger than 1 emu cm-3 s-1, and a 25-fold increase in coercivity. Since carbides exhibit minimal cytotoxicity, this introduces a biocompatible dimension to magneto-ionics, paving the way for the convergence of spintronics and biotechnology.

cond-mat.mtrl-sci↗

arXiv2025

Charge-transfer-mediated boron magneto-ionics: Towards voltage-driven multi-ion transport

Voltage control of magnetism via magneto-ionics, where ion transport and/or redox processes drive magnetic modulation, holds great promise for next-generation memories and computing. This stems from its non-volatility and ability to precisely tune both the magnitude and speed of magnetic properties in an energy-efficient manner. However, expanding magneto-ionics to incorporate novel mobile ions or even multiple ion species is crucial for unlocking new phenomena and enabling multifunctional capabilities. Here, we demonstrate voltage-driven multi-ion transport in a FeBO system with increasing oxygen content, progressively transitioning from an electrostatic-like response to a more pronounced electrochemical (magneto-ionic) behavior. The voltage-driven transport of both B and Fe is activated by oxidation state tuning, owing to the larger electronegativity of oxygen. Such charge-transfer effects allow multi-ion magneto-ionics, where O ions move oppositely to Fe and B ions. These results pave the way for programmable functionalities by leveraging elements with different electron affinities through charge-transfer engineering.

cond-mat.mtrl-sci↗

arXiv2023

Design and processing as ultrathin films of a sublimable Iron(II) spin crossover material exhibiting efficient and fast light-induced spin transition

Materials based on spin crossover (SCO) molecules have centred the attention in Molecular Magnetism for more than forty years as they provide unique examples of multifunctional and stimuli-responsive materials, which can be then integrated into electronic devices to exploit their molecular bistability. This process often requires the preparation of thermally stable SCO molecules that can sublime and remain intact in contact with surfaces. However, the number of robust sublimable SCO molecules is still very scarce. Here we report a novel example of this kind. It is based on a neutral iron (II) coordination complex formulated as [FeII(neoim)2], where neoimH is the ionogenic ligand 2-(1H-imidazol-2-yl)-9-methyl-1,10-phenanthroline. In the first part a comprehensive study, which covers the synthesis and magneto-structural characterization of the [FeII(neoim)2] complex as a bulk microcrystalline material, is reported. Then, in the second part we investigate the suitability of this material to form thin films through high vacuum (HV) sublimation. Finally, the retainment of all present SCO capabilities in the bulk when the material is processed is thoroughly studied by means of X-ray absorption spectroscopy. In particular, a very efficient and fast light-induced spin transition (LIESST effect) has been observed, even for ultrathin films of 15 nm.

cond-mat.mtrl-sci↗

arXiv2023

Wireless magneto-ionics: voltage control of magnetism by bipolar electrochemistry

Modulation of magnetic properties through voltage-driven ion motion and redox processes, i.e., magneto-ionics, is a unique approach to control magnetism with electric field for low-power memory and spintronic applications. So far, magneto-ionics has been achieved through direct electrical connections to the actuated material. Here we evidence that an alternative way to reach such control exists in a wireless manner. Induced polarization in the conducting material immersed in the electrolyte, without direct wire contact, promotes wireless bipolar electrochemistry, an alternative pathway to achieve voltage-driven control of magnetism based on the same electrochemical processes involved in direct-contact magneto-ionics. A significant tunability of magnetization is accomplished for cobalt nitride thin films, including transitions between paramagnetic and ferromagnetic states. Such effects can be either volatile or non-volatile depending on the electrochemical cell configuration. These results represent a fundamental breakthrough that may inspire future device designs for applications in bioelectronics, catalysis, neuromorphic computing, or wireless communications.

cond-mat.mtrl-sci↗

arXiv2022

Sublimable complexes with spin switching: Chemical design, processing as thin films and integration in graphene-based devices

Among the different types of switchable molecular compounds, sublimable Fe(II) SCO molecules provide a suitable platform to develop smart devices that respond to external stimuli. Here we report the synthesis, crystallographic structure and magnetic properties of three new neutral Fe(II) SCO molecules belonging to the {Fe[H2B(pz)2]2(L)} family with bidentate-alpha-diimine ligands L = 3-(pyridin-2-yl)-[1,2,3]triazolo[1,5-a]pyridine (tzpy), 5,5,6,6-tetrahydro-4H,4H-2,2-bi(1,3-thiazine) (btz) and 4,4,5,5-tetrahydro-2,2-bithiazole (bt) (1, 2 and 3, respectively), as well as two solvated forms of 1 and 3. All three desolvated compounds present thermal- and light-induced SCO transitions with different degrees of cooperativity and effectiveness. Furthermore, 1 and 2 are demonstrated to be sublimable under HV conditions affording homogeneous thin films 200 nm thick (TF1 and TF2) that retain the chemical integrity of the original molecules regardless the deposition surface. The SCO behaviour of the films is characterized by XAS technique revealing the partial retainment of both thermal- and light-induced spin transitions, yet losing the cooperativity. Finally, SCO/2D horizontal hybrid devices based on CVD-graphene are produced using these films. Being the first ones of this type utilizing molecules of {Fe[H2B(pz)2]2(L)} family, with L = tzpy and btz, the devices have allowed the successful detection of the thermal SCO transition through the electric properties of the CVD-graphene.

cond-mat.mtrl-sci↗

arXiv2022

Electrical sensing of the thermal and light induced spin transition in robust contactless spin-crossover/graphene hybrid devices

Hybrid devices based on spin-crossover (SCO)/2D heterostructures grant a highly sensitive platform to detect the spin transition in the molecular SCO component and tune the properties of the 2D material. However, the fragility of the SCO materials upon thermal treatment, light irradiation or contact with surfaces and the methodologies used for their processing have limited their applicability. Here, we report an easily processable and robust SCO/2D hybrid device with outstanding performance based on the sublimable SCO [Fe(Pyrz)2] molecule deposited over CVD-graphene, which is fully compatible with electronics industry protocols. Thus, a novel methodology based on growing an elusive polymorph of [Fe(Pyrz)2] (tetragonal phase) over graphene is developed that allows us to electrically detect a fast and effective light-induced spin transition in the devices (~50% yield in 5 minutes). Such performance can be enhanced even more when a flexible polymeric layer of PMMA is inserted in between the two active components in a contactless configuration, reaching a ~100 % yield in 5 minutes.

cond-mat.mtrl-sci↗

arXiv2021

Magnetic properties of a highly ordered single crystal of the layered perovskite YBaCuFe$_{0.95}$Mn$_{0.05}$O$_5$

The layered perovskite YBaCuFeO5 (YBCFO) is able to adopt chiral magnetic order up to unexpectedly high temperatures, paving the way to strong magnetoelectric coupling at room temperature. In this perovskite A-site cations are fully ordered whereas the occupancy of the B-sites strongly depend on the preparation process. Though the structure is not geometrically frustrated, the presence of partial Fe3+/Cu2+ disorder at the B-sites produces magnetic frustration. In an effort to increase the spin-orbit coupling in the system, we have synthesized and studied YBaCuFe0.95Mn0.05O5 in single crystal form, where the highly symmetric Fe3+ ions (3d5) are partially substituted with Jahn-Teller active 3d4 Mn3+ ions. We report the structural and magnetic properties of a highly ordered single crystal of this layered perovskite, which are presented in comparison with a polycrystalline specimen (three times more disordered). Single-crystal neutron diffraction measurements reveal two collinear magnetic phases and the lack of incommensurate spiral order. The magnetic phases and transitions found in the crystal grown by the traveling solvent floating zone (TSFZ) method are fully described and analyzed in the light of its high level of Fe/Cu cationic order (~90%).

cond-mat.mtrl-sci↗

arXiv2021

Magnetic Frustration in a Zeolite

Zeolites are so well known in real world applications and after decades of scientific study that they hardly need any intro-duction: their importance in chemistry cannot be overemphasized. Here we add to the remarkable properties that they dis-play by reporting our discovery that the simplest zeolite, sodalite, when doped with Cr3+ in the \b{eta}-cage, is a frustrated magnet. Soft X-ray absorption spectroscopy and magnetic measurements reveal that the Cr present is Cr(III). Cr(III), with its isotropic 3d3 valence electron configuration, is well-known as the basis for many geometrically frustrated magnets, but it is especially surprising that a material like the Ca8Al12Cr2O29 zeolite is a frustrated magnet. This finding illustrates the value of exploring the properties of even well-known materials families.

cond-mat.mtrl-sci↗

arXiv2021

Ferromagnetic metallic Sr-rich Ln$_{1/2}$A$_{1/2}$CoO$_3$ cobaltites with spontaneous spin rotation

The Pr$_{0.50}$Sr$_{0.5}$0CoO$_3$ perovskite exhibits unique magnetostructural properties among the rest of ferromagnetic/metallic Ln$_{0.50}$Sr$_{0.50}$CoO$_3$ compounds. The sudden orthorhombic-tetragonal (Imma $\to$ I4/mcm) structural transition produces an unusual magnetic behavior versus temperature and external magnetic fields. In particular, the symmetry change is responsible for a spontaneous spin rotation in this metallic oxide. We have studied half-doped Ln$_{0.50}$(Sr$_{1-x}$A$_x$)$_{0.50}$CoO$_3$ cobaltites varying the ionic radius rA of A-site cations (divalent cations and lanthanides) in order to complete the T-rA phase diagram. The influence of the structural distortion and the A-cations size for the occurrence of a spontaneous spin reorientation in the metallic state has been investigated. As the reorientation of the magnetization is driven by the temperature induced collapse of the orthorhombic distortion, a careful investigation of the structural symmetry is presented varying the structural distortion of the Sr-rich half-doped cobaltites by means of both compositional and temperature changes. The region in the phase diagram of these perovskites where the phase of magnetic symmetry Fm'm'm replaces that of Im'm'a symmetry was determined in this family of ferromagnetic/metallic cobaltites. In that region the magnetization direction has rotated 45 degrees within the a-b plane with respect to the second.

cond-mat.mtrl-sci↗

arXiv2018

Synthetic antiferromagnetic coupling between ultra-thin insulating garnets

The use of magnetic insulators is attracting a lot of interest due to a rich variety of spin-dependent phenomena with potential applications to spintronic devices. Here we report ultra-thin yttrium iron garnet (YIG) / gadolinium iron garnet (GdIG) insulating bilayers on gadolinium iron garnet (GGG). From spin Hall magnetoresistance (SMR) and X-ray magnetic circular dichroism measurements, we show that the YIG and GdIG magnetically couple antiparallel even in moderate in-plane magnetic fields. The results demonstrate an all-insulating equivalent of a synthetic antiferromagnet in a garnet-based thin film heterostructure and could open new venues for insulators in magnetic devices. As an example, we demonstrate a memory element with orthogonal magnetization switching that can be read by SMR.

cond-mat.mtrl-sci↗

arXiv2017

Magnetic anisotropy and valence states in La$_2$Co$_{1-x}$Mn$_{1+x}$O$_6$ ($x\approx 0.23$) thin films studied by X-ray absorption spectroscopy techniques

X-ray absorption spectroscopy was used to determine the valence state in La$_2$Co$_{1-x}$Mn$_{1+x}$O$_6$ ($x\approx 0.23$) thin films. We found that in spite of the non-stoichiometry, Co is in a divalent state while Mn ions show a mixed valence state. The relation of this finding with the magnetic properties of the films is discussed. X-ray magnetic circular dichroism measurements prove that magnetic anisotropy originates from Co spin-orbit coupling and it is strain-dependent: a strong increase of the angular contribution to the magnetic moment is found when in-plane (out-of-plane) and cell parameters get expanded (compressed). This behavior is reproduced by first order perturbation theory calculations.

cond-mat.mtrl-sci↗

arXiv2016

Magnetostructural coupling, magnetic ordering and cobalt spin reorientation in metallic Pr0.50Sr0.50CoO3 cobaltite

In half-doped Pr0.50A0.50CoO3 metallic perovskites, the spin-lattice coupling brings about distinct magnetostructural transitions for A=Ca and A=Sr at temperatures close to 100 K. However, the ground magnetic properties of Pr0.50Sr0.50CoO3 (PSCO) strongly differ from Pr0.50Ca0.50CoO3 ones, where a partial Pr3+ to Pr4+ valence shift and Co spin transition makes the system insulating below the transition. This work investigates and describes the relationship between the Imma-to-I4/mcm symmetry change [Padilla-Pantoja et al, Inorg. Chem. 53, 12297 (2014)] and the original magnetic behavior of PSCO versus temperature and external magnetic fields. The FM1 and FM2 ferromagnetic phases, above and below the magnetostructural transition (TS1=120 K) have been investigated. The FM2 phase of PSCO is composed of [100] FM domains, with magnetic symmetry Im'm'a (mz=0). The magnetic space group of the FM1 phase is Fm'm'm (with mx=my). Neutron data analyses in combination with magnetometry and earlier reports results agrees with a reorientation of the magnetization axis by 45 deg within the a-b plane across the transition, in which the system retains its metallic character. The presence below TS1 of conjugated magnetic domains, both of Fm'm'm symmetry but having perpendicular spin orientations along the diagonals in the xy-plane of the tetragonal unit cell, is at the origin of the anomalies observed in the macroscopic magnetization. A relatively small field m0H > 30 mT is able to reorient the magnetization within the a-b plane, whereas a higher field (m0H,[H//z] >1.2 T at 2K) is necessary to align the Co moments perpendicular to a-b plane. Such a spin reorientation, in which the orbital and spin components of the Co moment rotate joined by 45deg, was not observed with other lanthanides different to praseodymium.

cond-mat.mtrl-sci↗