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We report on the magnetic properties of Dy atoms adsorbed on the (001) surface of SrTiO3. X-ray magnetic circular dichroism reveals slow relaxation of the Dy magnetization on a time scale of about 800 s at 2.5 K, unusually associated with an easy-plane magnetic anisotropy. We attribute these properties to Dy atoms occupying hollow adsorption sites on the TiO2-terminated surface. Conversely, Ho atoms adsorbed on the same surface show paramagnetic behavior down to 2.5 K. With the help of atomic multiplet simulations and first-principles calculations, we establish that Dy populates also the top-O and bridge sites on the coexisting SrO-terminated surface. A simple magnetization relaxation model predicts these two sites to have an even longer magnetization lifetime than the hollow site. Moreover, the adsorption of Dy on the insulating SrTiO3 crystal leads, regardless of the surface termination, to the formation of a spin-polarized two-dimensional electron gas of Ti 3d(xy) character, together with an antiferromagnetic Dy-Ti coupling. Our findings support the feasibility of tuning the magnetic properties of the rare-earth atoms by acting on the substrate electronic gas with electric fields., ACS Nano, 16 (7), ISSN:1936-0851, ISSN:1936-086X

The fabrication of complex low-dimensional quantum devices requires the control of the heteroepitaxial growth at the subnanometer scale. This is particularly challenging when the total thickness of stacked layers of device-active material becomes extremely large and exceeds the multi-μm limit, as in the case of quantum cascade structures. Here, we use the ultrahigh-vacuum chemical vapor deposition technique for the growth of multi-μm-thick stacks of high Gecontent strain-balanced Ge/SiGe tunneling heterostructures on Si substrates, designed to serve as the active material in a THz quantum cascade laser. By combining thorough structural investigation with THz spectroscopy absorption experiments and numerical simulations we show that the optimized deposition process can produce state-of-the-art threading dislocation density, ultrasharp interfaces, control of dopant atom position at the nanoscale, and reproducibility within 1% of the layer thickness and composition within the whole multilayer. We show that by using ultrahigh-vacuum chemical vapor deposition one achieves simultaneously a control of the epitaxy down to the sub-nm scale typical of the molecular beam epitaxy, and the high growth rate and technological relevance of chemical vapor deposition. Thus, this technique is a key enabler for the deposition of integrated THz devices and other complex quantum structures based on the Ge/SiGe material system.

Acinetobacter baumanni, is an opportunistic nosocomial multi-drug resistant bacterium, which represents a threat for human health. This pathogen is able to persist in intensive care units thanks to its extraordinary resistance towards dehydration, whose mechanisms are unknown and enable it to easily spread through surfaces, contaminating also medical devices. In this article we reveal, with a multimodal approach, based on μ-R Spectroscopy, Gas Chromatography coupled to Mass Spectroscopy, Atomic Force Microscopy and Fluorescence Recovery After Photobleaching, the bio-physical mechanisms that the membrane of two A. baumannii strains undergoes during dehydration. Showing a substantial decoupling of the phase transition from liquid crystalline to gel phase from evidence of cell lysis. Such decoupling may be the core of the resistance of A. baumannii against dehydration and highlights the different ability to resist to drought between strains.

Mechanical robustness, biocompatibility, and antibacterial performances are key features for materials suitable to be used in tissue engineering applications. In this work, we investigated the link existing between structural and functional properties of TiCu(Ag) thin films deposited by physical vapor deposition magnetron sputtering on Si substrates. The thin films were characterized by X-ray diffraction (XRD), nanoindentation, atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The TiCu(Ag) thin films showed complete amorphous structure and improved mechanical properties in comparison with pure Ti films. However, for contents in excess of 20% Ag, we observed the appearance of nanometric Ag crystallite. The TiCu(Ag) thin films displayed excellent biocompatibility properties, allowing adhesion and proliferation of the human fibroblasts MRC-5 cell line. Moreover, all the investigated TiCu(Ag) alloy display bactericidal properties, preventing the growth of both Pseudomonas aeruginosa and Staphylococcus aureus. Results obtained from biological tests have been correlated to the surface structure and microstructure of films. The excellent biocompatibility and bactericidal properties of these multifunctional thin films opens to their use in tissue engineering applications.

Abstract A challenging topic in surface engineering is predicting the wetting properties of soft interfaces with different liquids. However, a robust computational protocol suitable for predicting wettability with molecular precision is still lacking. In this article, we propose a workflow based on molecular dynamics simulations to predict the wettability of polymer surfaces and test it against the experimental contact angle of several polar and nonpolar liquids, namely water, formamide, toluene, and hexane. The specific case study addressed here focuses on a poly(lactic-co-glycolic acid) (PLGA) flat surface, but the proposed experimental-modeling protocol may have broader fields of application. The structural properties of PLGA slabs have been modeled on the surface roughness determined with microscopy measurements, while the computed surface tensions and contact angles were validated against standardized characterization tests, reaching a discrepancy of less than 3% in the case of water. Overall, this work represents the initial step toward an integrated multiscale framework for predicting the wettability of more complex soft interfaces, which will eventually take into account the effect of surface topology at higher scales and synergically be employed with experimental characterization techniques. Impact statement Controlling the wettability of surfaces has important implications for energy (e.g., self-cleaning solar panels), mechanical (e.g., enhanced heat transfer), chemical (e.g., fluids separation), and biomedical (e.g., implants biocompatibility) industries. Wetting properties arise from a combination of chemical and physical features of surfaces, which are inherently intertwined and multiscale. Therefore, tailoring wettability to target functionalities is a time-intensive process, especially if relying on a trial-and-error approach only. This becomes even more challenging with soft materials, since their surface configuration depends on the solid-liquid interactions at the molecular level and could not be defined a priori. The improved accuracy of atomistic models allows detailing how the effective properties of materials arise from their nanoscale features. In this article, we propose and validate a new molecular dynamics protocol for assessing the wettability of soft interfaces with polar and nonpolar liquids. The prediction capabilities of simulations are augmented by a close comparison with microscopy and contact angle experiments. Since smooth copolymer surfaces are considered, here the effort mainly focuses on the effect of chemical features on wettability. In perspective, the proposed atomistic in silico approach could be coupled with computational models at higher scales to include the effect of surface microstructures, eventually easing the development of multi-scale surfaces with tunable wettability. Graphical abstract

Single atom magnets offer the possibility of magnetic information storage in the most fundamental unit of matter. Identifying the parameters that control the stability of their magnetic states is crucial to design novel quantum magnets with tailored properties. Here, we use X-ray absorption spectroscopy to show that the electronic configuration of dysprosium atoms on MgO(100) thin films can be tuned by the proximity of the metal Ag(100) substrate onto which the MgO films are grown. Increasing the MgO thickness from 2.5 to 9 monolayers induces a change in the dysprosium electronic configuration from 4f(9) to 4f(10). Hysteresis loops indicate long magnetic lifetimes for both configurations, however, with a different field-dependent magnetic stability. Combining these measurements with scanning tunneling microscopy, density functional theory, and multiplet calculations unveils the role of the adsorption site and charge transfer to the substrate in determining the stability of quantum states in dysprosium single atom magnets.

High-quality n-type continuously graded Ge-rich Si1−xGex parabolic quantum wells with different doping level were grown by using ultrahigh-vacuum chemical vapor deposition on Si(001) substrates. A thorough structural characterization highlights an ideal parabolic compositional profile. THz intersubband absorption has been investigated in modulation-doped samples and samples directly doped in the wells. The comparison of experimental absorption data and theoretical calculations allowed us to quantify the impact of electron correlation effects on the absorption resonances in the different doping conditions and for electron sheet densities in the (1÷6)×1011 cm−2 range. A single optical resonance is present in modulation doped samples. Its peak energy and line-shape is independent of temperature-induced variations of the electron distribution in the subbands up to 300 K, in agreement with the generalized Kohn theorem. This achievement represents a relevant step-forward for the development of CMOS compatible optoelectronic devices in the THz spectral range, where thermal charge fluctuations play a key role.

© 2021 Author(s). We report electroluminescence originating from L-valley transitions in n-type Ge/Si0.15Ge0.85 quantum cascade structures centered at 3.4 and 4.9 THz with a line broadening of Δ f / f ≈ 0.2. Three strain-compensated heterostructures, grown on a Si substrate by ultrahigh vacuum chemical vapor deposition, have been investigated. The design is based on a single quantum well active region employing a vertical optical transition, and the observed spectral features are well described by non-equilibrium Green's function calculations. The presence of two peaks highlights a suboptimal injection in the upper state of the radiative transition. Comparison of the electroluminescence spectra with a similar GaAs/AlGaAs structure yields one order of magnitude lower emission efficiency. ISSN:0003-6951 ISSN:1077-3118

Acinetobacter baumannii has emerged as a major bacterial pathogen during the past three decades. The majority of the A. baumannii infections occur in hospitals and are caused by strains endowed with high desiccation tolerance, which represents an essential feature for the adaptation to the nosocomial environment. This work aims at investigating the desiccation response of the multidrug-resistant A. baumannii strain ACICU as a function of the bacterial growth phase and oxygen availability, by correlating bacterial survival with shape alterations. The three-dimensional morphological analysis of bacteria was carried out by atomic force microscopy (AFM), following the evolution of bacterial shape descriptors, such as the area, volume, roughness of individual cell membranes, and the cell cluster roughness, which exhibited peculiar and distinctive behavior as a function of the growth conditions. AFM images of A. baumannii ACICU cells revealed the prevalence of the coccoid morphology at all growth stages, with a tendency to reduce their size in the stationary phase, accompanied by a higher survival rate to air-drying. Moreover, cells harvested from the logarithmic phase featured a larger volume and resulted to be more sensitive to desiccation compared to the cells harvested at later growth stages. In addition, oxygen deprivation caused a significant decrease in cellular size and was associated with the formation of pores in the cell membrane, accompanied by a relative reduction in culturability after desiccation. Morphological plasticity and multidrug resistance may contribute to desiccation tolerance and therefore to persistence in the hospital setting.

Combining scanning tunneling microscopy and angle-resolved photoemission spectroscopy, we demonstrate how to tune the doping of epitaxial graphene from p to n by exploiting the structural changes that occur spontaneously on the Ge surface upon thermal annealing. Furthermore, using first-principle calculations, we build a model that successfully reproduces the experimental observations. Since the ability to modify graphene electronic properties is of fundamental importance when it comes to applications, our results provide an important contribution toward the integration of graphene with conventional semiconductors.

n-type Ge/SiGe asymmetric coupled quantum wells represent the building block of a variety of nanoscale quantum devices, including recently proposed designs for a silicon-based THz quantum cascade laser. In this paper, we combine structural and spectroscopic experiments on 20-module superstructures, each featuring two Ge wells coupled through a Ge-rich SiGe tunnel barrier, as a function of the geometry parameters of the design and the P dopant concentration. Through a comparison of THz spectroscopic data with numerical calculations of intersubband optical absorption resonances, we demonstrated that it is possible to tune, by design, the energy and the spatial overlap of quantum confined subbands in the conduction band of the heterostructures. The high structural/interface quality of the samples and the control achieved on subband hybridization are promising starting points towards a working electrically pumped light-emitting device.

n-type doped Ge quantum wells with SiGe barriers represent a promising heterostructure system for the development of radiation emitters in the terahertz range such as electrically pumped quantum cascade lasers and optically pumped quantum fountain lasers. The nonpolar lattice of Ge and SiGe provides electron&ndash, phonon scattering rates that are one order of magnitude lower than polar GaAs. We have developed a self-consistent numerical energy-balance model based on a rate equation approach which includes inelastic and elastic inter- and intra-subband scattering events and takes into account a realistic two-dimensional electron gas distribution in all the subband states of the Ge/SiGe quantum wells by considering subband-dependent electronic temperatures and chemical potentials. This full-subband model is compared here to the standard discrete-energy-level model, in which the material parameters are limited to few input values (scattering rates and radiative cross sections). To provide an experimental case study, we have epitaxially grown samples consisting of two asymmetric coupled quantum wells forming a three-level system, which we optically pump with a free electron laser. The benchmark quantity selected for model testing purposes is the saturation intensity at the 1&rarr, 3 intersubband transition. The numerical quantum model prediction is in reasonable agreement with the experiments and therefore outperforms the discrete-energy-level analytical model, of which the prediction of the saturation intensity is off by a factor 3.

We study radiative relaxation at terahertz frequencies in n-type Ge/SiGe quantum wells, optically pumped with a terahertz free electron laser. Two wells coupled through a tunneling barrier are designed to operate as a three-level laser system with non-equilibrium population generated by optical pumping around the 1→3 intersubband transition at 10 THz. The non-equilibrium subband population dynamics are studied by absorption-saturation measurements and compared to a numerical model. In the emission spectroscopy experiment, we observed a photoluminescence peak at 4 THz, which can be attributed to the 3→2 intersubband transition with possible contribution from the 2→1 intersubband transition. These results represent a step towards silicon-based integrated terahertz emitters.

The research and the individuation of tumour markers in biological fluids are currently one of the main tools to support diagnosis, prognosis, and monitoring of the therapeutic response in oncology. Although the identification of tumour markers in asymptomatic patients is crucial for early diagnosis, its application is still limited by the relatively low sensitivity and the complexity of existing methods (i.e. ELISA, mass spectrometry). We developed an easy, fast, and ultrasensitive surface-enhanced Raman scattering (SERS)–based system, for the detection and quantitation of the LGALS3BP (90K) biomarker that was used as a model, based on the development of antibody-functionalized nanostructured gold surfaces. The detection system was effective for the ultrasensitive detection and characterization of samples of different biochemical compositions. In conclusion, this work could provide the foundation for the development of a medical diagnostic device with the highest predictive power when compared with the methods currently used in cancer diagnostics. Electronic supplementary material The online version of this article (10.1007/s00216-020-02903-2) contains supplementary material, which is available to authorized users.

Exploiting intersubband transitions in Ge/SiGe quantum cascade devices provides a way to integrate terahertz light emitters into silicon-based technology. With the view to realizing a Ge/SiGe Quantum Cascade Laser, we present the optical and structural properties of n-type strain-symmetrized Ge/SiGe asymmetric coupled quantum wells grown on Si(001) substrates by means of ultrahigh vacuum chemical vapor deposition. We demonstrate high material quality of strain-symmetrized structures and heterointerfaces as well as control over inter-well coupling and electron tunneling. Motivated by the promising results obtained on ACQWs, which are the basic building block of a cascade structure, we investigate, both experimentally and theoretically, a Ge/SiGe THz QCL design, optimized through a non-equilibrium Green’s function formalism

The imaging and sensing technology operating in the THz region of the electromagnetic spectrum has a number of applications, with demonstrator products already available on the market for oncology imaging, production monitoring, and non-destructive test [1]. However, the THz sources now at hand are still bulky and too expensive for expanding this technology to other proposed applications, which also include, among other, THz bandwidth photonics and security imaging. A higher level of integration with control electronics, a lower production cost, and a broader wavelength range of emission towards the far-infrared, are all desirable features to expand the fields of application of THz radiation. N-type Ge/SiGe quantum cascade structures grown on top of a Si(001) substrate are particularly promising for realizing a Si based THz source [2]. The low effective mass and long non-radiative relaxation times due to the non-polar nature of the material, are expected to i) provide gain values close to those demonstrated in III-V quantum cascade structures at 4 K, and ii) to potentially enable 300 K operation. In this presentation we will discuss the optical and structural properties of n-type s-Ge/SiGe multi-quantum wells and asymmetric coupled quantum wells grown on Si(001) substrates by means of ultrahigh vacuum chemical vapor deposition [3]. Extensive structural characterization obtained by scanning transmission electron microscopy (STEM), atomic probe tomography (APT) and X-ray diffraction shows the high material quality of strain-symmetrized structures (up to 5 micron active region thickness) and heterointerfaces (featuring interface roughness below 0.2 nm), down to the ultrathin barrier limit (about 1 nm). By performing THz absorption spectroscopy measurements combined to theoretical modeling on different asymmetric coupled quantum well systems (with varying large-well width or barrier thickness), we unambiguously demonstrated inter-well coupling and wavefunction tunneling [3]. The agreement between experimental data and simulations allowed us to characterize the tunneling barrier parameters and, in turn, achieve a highly-controlled engineering of the electronic structure in forthcoming unipolar cascade systems based on n-type Ge/SiGe multi quantum-wells. Furthermore, by pump-and-probe, and time domain spectroscopic data with a thorough theoretical modeling, we will show that this material system is indeed promising as active material in quantum cascade lasers (QCL). We found i) narrow intersubband (ISB) absorption lines; ii) relatively long non-radiative ISB relaxation times at high temperature; iii) relaxation times for different ISB transitions favorable to population inversion. Leveraging on the promising results obtained by spectroscopy experiments, we theoretically investigate an electrically-pumped Ge/SiGe THz QCL through a non-Equilibrium Green Function formalism (nextnano.QCL), using as material parameters to model the scattering processes the values estimated from the analysis of the optical experimental data [4]. As expected, due to the weaker interaction with the phonon field with respect to III-V based devices, we find a lower impact of the temperature on the gain spectrum. In addition, simulations show that the interface roughness values measured on our samples allows to achieve gain overcoming the losses of double-metal waveguides at room temperature. We believe that the present results will motivate new experimental efforts aimed at demonstrating room-temperature operation in group IV QCL THz devices. References [1] D. J. Paul, Laser Photon. Rev. 4, 610 (2010). [2] K. Driscoll, and R. Paiella, J. Appl. Phys. 102, 093103 (2007). [3] C. Ciano, M. Virgilio, M. Montanari, L. Persichetti, L. Di Gaspare, M. Ortolani, L. Baldassarre, M. H. Zollner, O. Skibitzki, G.Scalari, J. Faist, D. J. Paul, M. Scuderi, G. Nicotra, T. Grange, S. Birner, G. Capellini, and M. De Seta, Accepted in Phys. Rev. Appl., 11, 014003 (2019). [4] T. Grange, D. Stark, G. Scalari, J. Faist, L. Persichetti, L. Di Gaspare, M. De Seta, M. Ortolani, D.J. Paul, G. Capellini, S. Birner and M. Virgilio, Submitted to Applied Physics Letters. Preprint available at https://arxiv.org/pdf/1811.12879.pdf.

The efficient integration of electronic and optoelectronic functions on a single chip within a CMOS-compatible material and technology platform is witnessing the next disruptive innovation in the microelectronics industry. Among the proposed approaches to “siliconize” photonics, the most ambitious is to develop a monolithic Si-based light source. The main challenge is the indirect bandgap of Si which hinders efficient light emission. A number of different solutions has been suggested to break down this material limitation, and the optimal strategy depends on the specific spectral range of application. In the THz range, quantum cascade laser (QCL) architectures based on the Group-IV material system have been predicted as viable potential sources up to room temperature1-3, by exploiting intersubband (ISB) transitions in the conduction band of n-type, Ge-rich Ge/SiGe multi-quantum well (MQW) heterostructures3. In this paper, we will show that the interface quality and threading dislocation density4 in this material system have finally reached the level required for possibly enabling, within a wide temperature range, a material gain larger than the cavity losses5. From the structural standpoint, we report on the growth by ultra-high-vacuum chemical vapor deposition (UHV-CVD) of strain-compensated QCL stacks with a thickness up to 10 µm, demonstrating by X-ray diffraction and scanning transmission electron microscopy their high crystalline quality and remarkable growth reproducibility [Fig. 1(a)]. We will also describe optimized designs obtained in waveguide modelling with which waveguide losses comparable to III-V architectures are achieved6. In the model system of n-type Ge-rich asymmetric coupled quantum wells (ACQWs)7,8, being the building block of a QCL structure, we will prove a high degree of control on the engineering at the nanoscale the intersubband electronic spectrum and the wavefunctions relevant for tunneling processes, which allowed us the observation of photoluminescence at 4 THz after optical excitation using a free-electron laser (FEL)9. In addition, we will present a systematic calibration study of the material parameters controlling the interface roughness (IFR) and electron-phonon scatterings in n-type Ge/SiGe MQWs by combining experimental pump-probe data with a numerical model of ISB carrier dynamics including inelastic and elastic scattering channels. The time evolution of subband populations after FEL optical pumping is investigated as a function of the MQW design geometry, comparing symmetric and stepwise configurations, and analyzed by varying the subband energy spacing changing the well width. As a matter of fact, these material parameters critically affect the outcomes of the non-equilibrium Green’s function calculations widely used for predicting quantum transport and, ultimately optical gain of QCL devices10,11 and so to guide the optimization of proposed device designs. Hitherto, however, in most cases, the adopted values for these material parameters were not calibrated against experiments. For a proper calibration of the deformation potentials, we studied the non-radiative lifetimes as a function of the subband spacing on a set of symmetric MQWs of different Ge well widths. The corresponding α2D absorption spectra are reported in the left panels Fig. 1(b-d). Differential transmission spectra from single-color pump-probe experiments and model simulations indicate [Fig. 1(e-g)] that the electron-phonon coupling is much less effective than that expected from the bulk deformation potentials reported by Jacoboni et al.12. In particular, we found that the relaxation mediated by the emission of intervalley OPs is suppressed in low-dimensional multilayer structures while the intravalley OP scattering is described by a reduced effective deformation potential, thus explaining the observation of relaxation times larger than 10 ps above both the OP energy thresholds in single-color pump probe spectroscopy experiments. These results are crucial for developing adequate simulation frameworks and specific design approaches for achieving optical gain in silicon-compatible quantum cascade emitters. [1] K. Driscoll et al., Appl. Phys. Lett. 89, 191110 (2006). [2] K. Driscoll et al., J. Appl. Phys. 102, 093103 (2007). [3] D. J. Paul, Laser & Photonics Reviews 4, 610 (2010). [4] T. Grange et al., Physical Review Applied 13, 044062 (2020). [5] T. Grange et al., Appl. Phys. Lett. 114, 111102 (2019). [6] K. Gallacher et al., Opt. Express 28, 4786 (2020). [7] C. Ciano et al., Physical Review Applied 11, 014003 (2019). [8] L. Persichetti et al., Crystals 10, 179 (2020). [9] C. Ciano et al., Opt. Express 28, 7245 (2020). [10] A. Valavanis et al., Phys. Rev. B 83, 195321 (2011). [11] C. Jirauschek et al., Applied Physics Reviews 1, 011307 (2014). [12] C. Jacoboni et al., Phys. Rev. B 24, 1014 (1981). Figure 1

n-type Ge/SiGe terahertz quantum cascade laser are investigated using non-equilibrium Green's functions calculations. We compare the temperature dependence of the terahertz gain properties with an equivalent GaAs/AlGaAs QCL design. In the Ge/SiGe case, the gain is found to be much more robust to temperature increase, enabling operation up to room temperature. The better temperature robustness with respect to III-V is attributed to the much weaker interaction with optical phonons. The effect of lower interface quality is investigated and can be partly overcome by engineering smoother quantum confinement via multiple barrier heights., 5 pages, 5 figures

This article belongs to the Special Issue Electronic Structure Calculations Applied to Magnetic Phenomena., The magnetic anisotropy and exchange coupling between spins localized at the positions of 3d transition metal atoms forming two-dimensional metal–organic coordination networks (MOCNs) grown on a Au(111) metal surface are studied. In particular, we consider MOCNs made of Ni or Mn metal centers linked by 7,7,8,8-tetracyanoquinodimethane (TCNQ) organic ligands, which form rectangular networks with 1:1 stoichiometry. Based on the analysis of X-ray magnetic circular dichroism (XMCD) data taken at T = 2.5 K, we find that Ni atoms in the Ni–TCNQ MOCNs are coupled ferromagnetically and do not show any significant magnetic anisotropy, while Mn atoms in the Mn–TCNQ MOCNs are coupled antiferromagnetically and do show a weak magnetic anisotropy with in-plane magnetization. We explain these observations using both a model Hamiltonian based on mean-field Weiss theory and density functional theory calculations that include spin–orbit coupling. Our main conclusion is that the antiferromagnetic coupling between Mn spins and the in-plane magnetization of the Mn spins can be explained by neglecting effects due to the presence of the Au(111) surface, while for Ni–TCNQ the metal surface plays a role in determining the absence of magnetic anisotropy in the system., We thank MINECO and the University of the Basque Country (UPV/EHU) for partial financial support, with grant numbers FIS2016-75862-P and IT-756-13, respectively, the former covering costs to publish in open access journals. MMO acknowledges the support by the Tomsk State University competitiveness improvement programme (project No. 8.1.01.2017) and the Saint Petersburg State University grant for scientific investigation (No. 15.61.202.2015).

We report x-ray absorption spectroscopy and x-ray magnetic circular dichroism measurements as well as multiplet calculations for Dy, Ho, Er, and Tm atoms adsorbed on Pt(111), Cu(111), Ag(100), and Ag(111). In the gas phase, all four elements are divalent and we label their $4f$ occupancy as $4{f}^{n}$. Upon surface adsorption, and depending on the substrate, the atoms either remain in that state or become trivalent with $4{f}^{n\ensuremath{-}1}$ configuration. The trivalent state is realized when the sum of the atomic correction energies ($4f$\ensuremath{\rightarrow}$5d$ promotion energy ${E}_{fd}\phantom{\rule{0.16em}{0ex}}+$ intershell coupling energy $\ensuremath{\delta}{E}_{c}$) is low and the surface binding energy is large. The latter correlates with a high substrate density of states at the Fermi level. The magnetocrystalline anisotropy of trivalent RE atoms is larger than the one of divalent RE atoms. We ascribe this to the significantly smaller covalent radius of the trivalent state compared to the divalent one for a given RE element. For a given valency of the RE atom, the anisotropy is determined by the overlap between the $spd$ states of the RE and the $d$ states of the surface. For all investigated systems, the magnetization curves recorded at 2.5 K show absence of hysteresis indicating that magnetic relaxation is faster than about 10 s.

We report on the magnetic coupling between isolated Co atoms as well as small Co islands and Ni(111) mediated by an epitaxial graphene layer. X-ray magnetic circular dichroism and scanning tunneling microscopy combined with density functional theory calculations reveal that Co atoms occupy two distinct adsorption sites, with different magnetic coupling to the underlying Ni(111) surface. We further report a transition from an antiferromagnetic to a ferromagnetic coupling with increasing Co cluster size. Our results highlight the extreme, sensitivity of the exchange interaction mediated by graphene to the adsorption site and to the in-plane coordination of the magnetic atoms.