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Georgeta Salvan

Publications and source records attributed to Georgeta Salvan.

14 recordsLinked to original sources

Chiral Spinterfaces as an Overlooked Component of the Chiral-Induced Spin Selectivity Effect

The chiral-induced spin selectivity (CISS) effect is generally attributed to spin-selective transport through chiral molecules, while the role of the molecule-electrode interface remains largely unexplored. Here, we show that adsorption of chiral amino acid derived molecules on ferromagnetic Ni thin films generates a remanent chirality-dependent magneto-optical response that is localized to the molecule-Ni/NiO interface and can be reversibly switched by an external magnetic field, demonstrating its genuine magnetic character. A comprehensive series of control experiments establishes that the response originates from the interfacial region rather than from the molecular layer or the bulk ferromagnet. First-principles calculations reveal that Boc-methionine adsorption proceeds through energetically accessible sulfur- and carboxyl-bound configurations that produce distinct molecular orientations and ligand-p/Ni-d hybridization, thereby defining structurally and electronically distinct interfaces. Together, the experimental and theoretical results support the formation of chiral spinterfaces, identifying the molecule-ferromagnet interface as an active and previously overlooked component of CISS systems. These findings broaden the microscopic picture of CISS beyond the chiral molecule itself and reveals interface electronic structure as a key design parameter for spin-selective molecular devices.

cond-mat.mtrl-sci

Microscopic and macroscopic characterization: MBE-grown versus sputter-deposited Au/Co/Au thin films for CISS and MIPAC effect studies

Chirality-induced spin selectivity (CISS) enables spin-dependent transport at chiral molecule/Au(111) interfaces and is used in spintronics when combined with ferromagnetic thin films in spin-valve-type hybrids. However, the influence of substrate microstructure on CISS and the related magnetization induced by the proximity of adsorbed chiral molecules (MIPAC) effect is still not well understood. In this study, we compare the effects of the adsorption of L-chiral alpha-helical alanine-rich peptides on Au/Co/Au ferromagnetic thin films fabricated by molecular beam epitaxy (MBE) and magnetron sputtering. X-ray reflectivity and X-ray diffraction show sharper interfaces and a narrower Au(111) rocking-curve width for the MBE-grown sample. However, atomic force microscopy and scanning tunneling microscopy images reveal that both sample types have locally smooth Au(111) surface regions suitable for peptide adsorption, despite clear differences in larger-scale morphology. Microscopic scanning tunneling spectroscopy after peptide exposure yields similar magnetization-direction-dependent tunneling currents in both sample types, confirming a similar magnitude CISS effect on the molecular scale. In contrast, macroscopic magneto-optical Kerr effect hysteresis loops and effect microscopy reveals that only sputter-deposited samples show slight coercivity enhancements and a consistent reduction in domain wall velocity after peptide exposure. These results suggest that microscopic CISS signatures are robust for both sample types, whereas macroscopic MIPAC-type magnetic responses are more sensitive to the substrate microstructure.

cond-mat.mtrl-sci

A step-by-step workflow to extract the genuine circular dichroism of thin films

Circular Dichroism (CD) spectroscopy has evolved from a purely solution based method towards a powerful tool in the analysis of chiral thin films. Although a straightforward technique, the genuine CD signal is often accompanied by artifacts arising from optical anisotropy and instrumental imperfections. This tutorial presents a two-step workflow that reliably isolates the orientation invariant CD response for anisotropic thin films by combining azimuthal sample rotation with sample flipping. For this purpose, a home-built sample stage was developed, which enables systematic suppression of many anisotropy-induced artifacts in commercial CD spectrophotometers. Both a detailed description of the setup itself as well as the needed python script are provided. The reliability of the workflow is demonstrated on two selected samples from different research fields: chiral molecules attached to metallic surfaces as well as metal halide perovskites incorporating chiral spacer molecules

cond-mat.mtrl-sci

Chiral-Induced Spin Selectivity Effect in a 1 nm Thin 1,1'-Binaphthyl-2,2'-diyl Hydrogenphosphate Self-Assembled Monolayer on Nickel Oxide

The chiral-induced spin selectivity (CISS) effect describes an observed correlation between the orientation of an electron spin transported or transferred through a molecule and that molecule's chirality. Suitable molecules are usually arranged as self-assembled monolayers (SAMs), and the primary CISS systems are based on multiple nanometer-long biomolecules exhibiting helical chirality. Aside from these typically thiolate-anchored molecules, phosphonic and phosphoric acid SAMs may well become significant for those CISS applications that require a more robust molecular coupling to metal oxide surfaces. In this work, we report on our studies, employing the aromatic, low-molecular-mass, axially chiral organophosphoric acid derivative 1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (BNP). Grown as a roughly 1 nm thin SAM on top of a NiOx/Ni substrate, a strong circular dichroism signal indicates that the thin films preserved chirality. The CISS response exhibits a high magnetoresistance with a spin polarization of 50-80% when measured using magnetic-conductive atomic force microscopy. For biases above 0.5 V, the magnetoresistance curves could be well fitted to the Fowler-Nordheim (FN) tunneling model. Using a minimal FN model, we determined that, depending on the magnetization direction and the handedness of the molecules, electrons of a certain spin direction face an effective tunneling barrier at high bias, which is either 80 % higher or 40 % lower compared to the barrier for electrons of the opposite spin direction. Due to the small size of the molecules, their compatibility with oxide materials, and their commercial availability, they are excellent candidates for the realization of novel (nanoscale) organic spintronic devices.

cond-mat.mtrl-sci

Organic Hydrogen Sensors for Potential Use in Safety-Critical Environments

Accurate monitoring of the hydrogen concentration is critical for optimizing fuel cell performance, minimizing purge losses, and reducing long-term degradation. Conventional hydrogen sensors often rely on catalytic materials and face limitations such as the need of oxygen purging when operated in fuel cell environments. Here, we report the discovery of a novel hydrogen-sensing mechanism based on organic molecules, without the use of catalytic metals. The sensor is based on a typical vertical stack geometry, containing $\mathrm{Alq_3}$ as active organic material. Upon exposure to hydrogen, the device shows an increase in resistivity, yielding a reliable sensor signal that varies linearly with hydrogen concentration, temperature, and humidity, and exhibits a relative response of up to 3.5 % at 100 %vol hydrogen. By exposing the sensor to an external magnetic field, the rise and fall times of the sensor response were found to be tunable. This novel organic sensor demonstrates sensitivity across a wide range of hydrogen concentrations under fuel cell-relevant conditions and beyond. This new class of hydrogen sensors with high miniaturization potential and cost efficiency paves the way for real-time hydrogen monitoring and advanced control strategies in fuel cells, the chemical industry, or energy storage applications.

physics.app-ph

Unlocking Spin Dynamics: Spin-Orbit Coupling Driven Spin State Interconversion in Carbazole-Containing TADF Emitters

The determination of transport mechanisms in organic light-emitting diodes (OLEDs) is crucial for optimizing device performance. Magnetic field measurements enable the differentiation of spin state interconversion mechanisms, but data interpretation remains challenging. Here, experimental and theoretical investigations were combined to provide a comprehensive understanding of the underlying processes. This study systematically compares three cyanoarene-based emitters with different singlet-triplet gaps to explore factors influencing reverse intersystem crossing (RISC). The comparison of all-$^1$H and all-$^2$H 4CzIPN isotopologues confirms that RISC is governed by spin-orbit coupling (SOC) rather than hyperfine interactions. Magnetic field-dependent measurements reveal that charge transport in OLED devices is driven by triplet-charge annihilation in 3CzClIPN and 4CzIPN, while triplet-triplet annihilation dominates for 5CzBN. Theoretical calculations further indicate that SOC-mediated RISC in 3CzClIPN and 4CzIPN can additionally occur via a $T_2$ intermediate state with an activation energy distinct from the singlet-triplet energy gap. A temperature-dependent analysis of the devices was conducted to quantify this activation energy and compare it with the computational findings. These findings establish key correlations between activation energy, spin dynamics, and magnetic field effects in TADF emitters, advancing our understanding of excitonic processes in OLEDs.

physics.app-ph

Exciplex-driven blue OLEDs: unlocking multifunctionality applications

We present the development of multifunctional blue-emission organic light-emitting diodes (OLEDs) using TADF-exciplex materials. These OLEDs exhibit sensitivity to external stimuli and achieve a maximum external quantum efficiency (EQE) of 11.6 % through partly liquid processing. This technique allows for large-scale production on arbitrary geometries. The potential multifunctionality of the devices arises from their response to low external magnetic fields (up to 100 mT) with an efficiency up to 2.5 % for magnetoconductance, while maximum magneto-electroluminescence effects of 4.1 % were detected. We investigated novel aspects, including the utilization of two organic materials without further doping and the investigation of the impact of 2,2',2''-(1,3,5-Benzinetriyl)-tris(1phenyl-1-H-benzimidazole) (TPBi) processing in liquid and vapor form. The insights gained provide a fundamental understanding regarding the applicability of exciplex (EX) materials for fully solution-processed OLEDs through a deliberate omission of doping. Our work represents a significant advancement on the path towards multifunctional OLED technology, with potential applications in cost-efficient, scalable organic full-color displays and advanced sensing system

physics.app-ph

Probing magnetic ordering in air stable iron-rich van der Waals minerals

In the rapidly expanding field of two-dimensional materials, magnetic monolayers show great promise for the future applications in nanoelectronics, data storage, and sensing. The research in intrinsically magnetic two-dimensional materials mainly focuses on synthetic iodide and telluride based compounds, which inherently suffer from the lack of ambient stability. So far, naturally occurring layered magnetic materials have been vastly overlooked. These minerals offer a unique opportunity to explore air-stable complex layered systems with high concentration of local moment bearing ions. We demonstrate magnetic ordering in iron-rich two-dimensional phyllosilicates, focusing on mineral species of minnesotaite, annite, and biotite. These are naturally occurring van der Waals magnetic materials which integrate local moment baring ions of iron via magnesium/aluminium substitution in their octahedral sites. Due to self-inherent capping by silicate/aluminate tetrahedral groups, ultra-thin layers are air-stable. Chemical characterization, quantitative elemental analysis, and iron oxidation states were determined via Raman spectroscopy, wavelength disperse X-ray spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. Superconducting quantum interference device magnetometry measurements were performed to examine the magnetic ordering. These layered materials exhibit paramagnetic or superparamagnetic characteristics at room temperature. At low temperature ferrimagnetic or antiferromagnetic ordering occurs, with the critical ordering temperature of 38.7 K for minnesotaite, 36.1 K for annite, and 4.9 K for biotite. In-field magnetic force microscopy on iron bearing phyllosilicates confirmed the paramagnetic response at room temperature, present down to monolayers.

cond-mat.mtrl-sci

Deposition of nanosized amino acid functionalized bismuth oxido clusters on gold surfaces

Bismuth compounds are of growing interest with regard to potential applications in catalysis, medicine and electronics, for which their environmentally benign nature is one of the key factors. The most common starting material is bismuth nitrate, which easily hydrolyses to give a large number of condensation products. The so-called bismuth subnitrates are composed of bismuth oxido clusters of varying composition and nuclearity. One reason that hampers the further development of bismuth oxido-based materials, however is the low solubility of the subnitrates, which makes targeted immobilisation on substrates challenging. We present an approach towards solubilisation of bismuth oxido clusters by introducing an amino carboxylate as functional group and a study of the growth mode of these atom-precise nanoclusters on gold surfaces. For this purpose the bismuth oxido cluster [Bi38O45(NO3)20(dmso)28](NO3)4*4dmso (dmso=dimethyl sulfoxide) was reacted with the sodium salt of tert-butyloxycabonyl(Boc)-protected phenylalanine (Phe) to give the soluble and chiral nanocluster [Bi38O45(Boc-Phe)24(dmso)9]. The hydrodynamic diameter of the cluster was estimated with (1.4-1.6) nm (in CH3CN) and (2.2 nm-2.9) nm (in Ethanol) based on dynamic light scattering (DLS). The full exchange of the nitrates by the amino carboxylates was proven by NMR and FTIR as well as elemental analysis (EA) and XPS. The solubility of the bismuth oxido cluster in a protic as well as an aprotic polar organic solvent and the growth mode of the clusters on Au upon spin-, dip-, and drop-coating on gold surfaces were studied. Successful deposition of bismuth oxido cluster was proven by powder XRD, FTIR, and XPS while the microstructure of the resulting films was investigated as a function of the deposition method and the solvent used by SEM, AFM, and optical microscopy.

cond-mat.mtrl-sci

Highly Tunable Magnetic and Magnetotransport Properties of Exchange Coupled Ferromagnet/Antiferromagnet-based Heterostructures

Antiferromagnets (AFMs) with zero net magnetization are proposed as active elements in future spintronic devices. Depending on the critical thickness of the AFM thin films and the measurement temperature, bimetallic Mn-based alloys and transition metal oxide-based AFMs can host various coexisting ordered, disordered, and frustrated AFM phases. Such coexisting phases in the exchange coupled ferromagnetic (FM)/AFM-based heterostructures can result in unusual magnetic and magnetotransport phenomena. Here, we integrate chemically disordered AFM IrMn3 thin films with coexisting AFM phases into complex exchange coupled MgO(001)/Ni3Fe/IrMn3/Ni3Fe/CoO heterostructures and study the structural, magnetic, and magnetotransport properties in various magnetic field cooling states. In particular, we unveil the impact of rotating the relative orientation of the disordered and reversible AFM moments with respect to the irreversible AFM moments on the magnetic and magnetoresistance properties of the exchange coupled heterostructures. We further found that the persistence of AFM grains with thermally disordered and reversible AFM order is crucial for achieving highly tunable magnetic properties and multi-level magnetoresistance states. We anticipate that the introduced approach and the heterostructure architecture can be utilized in future spintronic devices to manipulate the thermally disordered and reversible AFM order at the nanoscale.

cond-mat.mtrl-sci

Terahertz charge and spin transport in metallic ferromagnets: the role of crystalline and magnetic order

We study the charge and spin dependent scattering in a set of CoFeB thin films whose crystalline order is systematically enhanced and controlled by annealing at increasingly higher temperatures. Terahertz conductivity measurements reveal that charge transport closely follows the development of the crystalline phase, with increasing structural order leading to higher conductivity. The terahertz-induced ultrafast demagnetization, driven by spin-flip scattering mediated by the spin-orbit interaction, is measurable in the pristine amorphous sample and much reduced in the sample with highest crystalline order. Surprisingly, the largest demagnetization is observed at intermediate annealing temperatures, where the enhancement in spin-flip probability is not associated with an increased charge scattering. We are able to correlate the demagnetization amplitude with the magnitude of the in-plane magnetic anisotropy, which we characterize independently, suggesting a magnetoresistance-like description of the phenomenon.

cond-mat.mes-hall

Radiative Decay of Dark Exciton Related Emission in a Sandwiched Monolayer WSe2 Revealed by Room Temperature Micro and Nano Photoluminescence

TMDCs have attracted a lot of attention in recent years due to their unique indirect to direct band gap transition from bulk to monolayer thickness. Strong confinement in the out-of-plane direction enhances the Coulomb potential between the charged particles (e-h pairs) and thus increases the exciton binding energy dramatically. The lattice inversion asymmetry in a monolayer creates two non-equivalent (but degenerate in energy) band edges protected by time reversal polarisation via pseudo-spin. However, the presence of strong spin-orbit coupling in the valence band and weak spin-splitting in the conduction band results in the lowest lying exciton in WX2 (X = S, Se) being spin forbidden and optically dark. Because of their long life times, dark excitons (XD) are highly attractive for quantum optics and optoelectronic applications. To date studying XD emission is limited to cryogenic temperature or required very complex experimental configurations to observe them at room temperature (RT). Here, we demonstrate a novel approach of radiative decay of XD related emissions in 1L-WSe2 studied by micro and nano PL at RT. 1L-WSe2 flakes were sandwiched by noble metal (Au or Ag) substrates and PDMS nano-patches providing a strong local out-of-plane dipole moment with respect to the 2D plane. This strong dipole moment not only enhances the XD in WSe2, it also produces bound excitons due to extrinsic charge defects visible at RT. The spatial distributions of these XD related emissions were studied by TEPL with a spatial resolution < 10 nm confirming the confinement of these excitons within the PDMS nano-patches. Finally, by removing the nano-patches from the top of the flakes we are able to recover the bright excitons in the 1L-WSe2. Our approach paves the way for deep understanding and to harness excitonic properties in low dimensional semiconductors, thus offering a platform towards quantum optics.

cond-mat.mes-hall

Transport band gap opening at metal-organic interfaces

The interface formation between copper phthalocyanine (CuPc) and two representative metal substrates, i.e., Au and Co, was investigated by the combination of ultraviolet photoelectron spectroscopy and inverse photoelectron spectroscopy. The occupied and unoccupied molecular orbitals and thus the transport band gap of CuPc are highly influenced by film thickness, i.e., molecule-substrate distance. Due to the image charge potential given by the metallic substrates the transport band gap of CuPc "opens" from $(1.4 \pm 0.3)$ eV for 1 nm thickness to $(2.2 \pm 0.3)$ eV, and saturates at this value above 10 nm CuPc thickness. The interface dipoles with values of 1.2 eV and 1.0 eV for Au and Co substrates, respectively, predominantly depend on the metal substrate work functions. X-ray photoelectron spectroscopy measurements using synchrotron radiation provide detailed information on the interaction between CuPc and the two metal substrates. While charge transfer from the Au or Co substrate to the Cu metal center is present only at sub-monolayer coverages, the authors observe a net charge transfer from the molecule to the Co substrate for films in the nm range. Consequently, the Fermi level is shifted as in the case of a p-type doping of the molecule. This is, however, a competing phenomenon to the energy band shifts due to the image charge potential.

physics.chem-ph

Comparative Study of Optical and Magneto-Optical Properties of Normal, Disordered and Inverse Spinel Type Oxides

Co$_3$O$_4$, ZnFe$_2$O$_4$, CoFe$_2$O$_4$, ZnCo$_2$O$_4$, and Fe$_3$O$_4$ thin films were fabricated by pulsed laser deposition at high and low temperatures resulting in crystalline single-phase normal, inverse, as well as disordered spinel oxide thin films with smooth surface morphology. The dielectric function, determined by spectroscopic ellipsometry in a wide spectral range from 0.5 eV to 8.5 eV, is compared with the magneto-optical response of the dielectric tensor, investigated by magneto-optical Kerr effect (MOKE) spectroscopy in the spectral range from 1.7 eV to 5.5 eV with an applied magnetic field of 1.7 T. Crystal field, inter-valence and inter-sublattice charge transfer transitions, and transitions from O$_{2p}$ to metal cation 3d or 4s bands are identified in both the principal diagonal elements and the magneto-optically active off-diagonal elements of the dielectric tensor. Depending on the degree of cation disorder, resulting in local symmetry distortion, the magneto-optical response is found to be strongest for high crystal quality inverse spinels and for disordered normal spinel structure, contrary to the first principle studies of CoFe$_2$O$_4$ and ZnFe$_2$O$_4$. The results presented provide a basis for deeper understanding of light-matter interaction in this material system that is of vital importance for device-related phenomena and engineering.

cond-mat.mtrl-sci