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Atomically thin two-dimensional (2D) layered semiconductors such as transition metal dichalcogenides have attracted considerable attention due to their tunable band gap, intriguing spin-valley physics, piezoelectric effects and potential device applications. Here we study the electronic properties of a single layer WS

In atomically thin transition metal dichalcogenide semiconductors, there is a crossover from indirect to direct band gap as the thickness drops to one monolayer, which comes with a fast increase of the photoluminescence signal. Here, we show that for different alloy compositions of WS2(1−x)Se2x this trend may be significantly affected by the alloy content and we demonstrate that the sample with the highest Se ratio presents a strongly reduced effect. The highest micro-PL intensity is found for bilayer WS2(1−x)Se2x (x = 0.8) with a decrease of its maximum value by only a factor of 2 when passing from mono-layer to bi-layer. To better understand this factor and explore the layer-dependent band structure evolution of WS2(1−x)Se2x, we performed a nano-angle-resolved photoemission spectroscopy study coupled with first-principles calculations. We find that the high micro-PL value for bilayer WS2(1−x)Se2x (x = 0.8) is due to the overlay of direct and indirect optical transitions. This peculiar high PL intensity in WS2(1−x)Se2x opens the way for spectrally tunable light-emitting devices.

International audience; Two-dimensional materials (2D) arranged in hybrid van der Waals (vdW) heterostructures provide a route toward the assembly of 2D and conventional III–V semiconductors. Here{,} we report the structural and electronic properties of single layer WSe2 grown by molecular beam epitaxy on Se-terminated GaAs(111)B. Reflection high-energy electron diffraction images exhibit sharp streaky features indicative of a high-quality WSe2 layer produced via vdW epitaxy. This is confirmed by in-plane X-ray diffraction. The single layer of WSe2 and the absence of interdiffusion at the interface are confirmed by high resolution X-ray photoemission spectroscopy and high-resolution transmission microscopy. Angle-resolved photoemission investigation revealed a well-defined WSe2 band dispersion and a high p-doping coming from the charge transfer between the WSe2 monolayer and the Se-terminated GaAs substrate. By comparing our results with local and hybrid functionals theoretical calculation{,} we find that the top of the valence band of the experimental heterostructure is close to the calculations for free standing single layer WSe2. Our experiments demonstrate that the proximity of the Se-terminated GaAs substrate can significantly tune the electronic properties of WSe2. The valence band maximum (VBM{,} located at the K point of the Brillouin zone) presents an upshift of about 0.56 eV toward the Fermi level with respect to the VBM of the WSe2 on graphene layer{,} which is indicative of high p-type doping and a key feature for applications in nanoelectronics and optoelectronics.

Atomically thin two-dimensional (2D) layered semiconductors such as transition metal dichalcogenides (TMDs) have attracted considerable attention due to their tunable band gap, intriguing spin-valley physics, piezoelectric effects and potential device applications. Here we study the electronic properties of a single layer WS$_{1.4}$Se$_{0.6}$ alloys. The electronic structure of this alloy, explored using angle resolved photoemission spectroscopy, shows a clear valence band structure anisotropy characterized by two paraboloids shifted in one direction of the k-space by a constant in-plane vector. This band splitting is a signature of a unidirectional Rashba spin splitting with a related giant Rashba parameter of 2.8 0.7 eV . The combination of angle resolved photoemission spectroscopy with piezo force microscopy highlights the link between this giant unidirectional Rashba spin splitting and an in-plane polarization present in the alloy. These peculiar anisotropic properties of the WS$_{1.4}$Se$_{0.6}$ alloy can be related to local atomic orders induced during the growth process due the different size and electronegativity between S and Se atoms. This distorted crystal structure combined to the observed macroscopic tensile strain, as evidenced by photoluminescence, displays electric dipoles with a strong in-plane component, as shown by piezoelectric microscopy. The interplay between semiconducting properties, in-plane spontaneous polarization and giant out-of-plane Rashba spin-splitting in this two-dimensional material has potential for a wide range of applications in next-generation electronics, piezotronics and spintronics devices., Comment: Nanotechnology (2022)

International audience; In atomically thin transition metal dichalcogenide semiconductors, there is a crossover from indirect to direct band gap as the thickness drops to one monolayer, which comes with a fast increase of the photoluminescence signal. Here, we show that for different alloy compositions of WS 2(1-x) Se 2x this trend may be significantly affected by the alloy content and we demonstrate that the sample with the highest Se ratio presents a strongly reduced effect. The highest micro-PL intensity is found for bilayer WS 2(1-x) Se 2x (x = 0.8) with a decrease of its maximum value by only a factor of 2 when passing from mono-to bi-layer. To better understand this factor and explore the layer-dependent band structure evolution of WS 2(1-x) Se 2x , we performed a nano-angle resolved photoemission spectroscopy study coupled with first-principles calculations. We find that the high micro-PL value for bilayer WS 2(1-x) Se 2x (x = 0.8) is due to the overlay of direct and indirect optical transitions. This peculiar high PL intensity in WS 2(1-x) Se 2x opens the way for spectrally tunable light-emitting devices.

International audience; van der Waals materials offer a large variety of electronic properties depending on chemical composition, number of layers, and stacking order. Among them, As2Te3 has attracted attention due to the promise of outstanding electronic properties, and high photo-response. Precise experimental determinations of the electronic properties of As2Te3 are yet sorely needed for better understanding of potential properties and device applications. Here, we study the structural and electronic properties of α-As2Te3. Scanning transmission electron microscopy coupled to energy X-ray dispersion (STEM-EDX), and micro-Raman spectroscopy all confirm that our specimens correspond to α-As2Te3. Scanning tunneling spectroscopy (STS) at 4.2K demonstrates that α-As2Te3 exhibits an electronic band gap of about 0.4 eV. The material can be exfoliated, revealing the (100) anisotropic surface. Transport measurements on a thick exfoliated sample (bulk-like) confirm the STS results. These findings allows for a deeper understanding of the As2Te3 electronic properties, underlying the potential of V-VI semiconductors for electronic and photonic technologies.

The angle-resolved photoemission spectra of the superconductor (Ba$_{1-x}$K$_x$)Fe$_2$As$_2$ have been investigated both experimentally and theoretically. Our results explain the previously obscured origins of all salient features of the ARPES response of this paradigm pnictide compound and reveal the origin of the Lifshitz transition. Comparison of calculated ARPES spectra with the underlying DMFT band structure shows an important impact of final state effects, which results for three-dimensional states in a deviation of the ARPES spectra from the true spectral function. In particular, the apparent effective mass enhancement seen in the ARPES response is not an entirely intrinsic property of the quasiparticle valence bands but may have a significant extrinsic contribution from the photoemission process and thus differ from its true value. Because this effect is more pronounced for low photoexcitation energies, soft-X-ray ARPES delivers more accurate values of the mass enhancement due to a sharp definition of the 3D electron momentum., Comment: including Supplemental Material

Electronic phase separation is crucial for the fascinating macroscopic properties of the ${\mathrm{LaAlO}}_{3}/{\mathrm{SrTiO}}_{3}$ (LAO/STO) paradigm oxide interface, including the coexistence of superconductivity and ferromagnetism. We investigate this phenomenon using angle-resolved photoelectron spectroscopy (ARPES) in the soft-x-ray energy range, where the enhanced probing depth combined with resonant photoexcitation allow us access to fundamental electronic structure characteristics -- momentum-resolved spectral function, dispersions and ordering of energy bands, Fermi surface -- of buried interfaces. Our experiment uses x-ray irradiation of the LAO/STO interface to tune its oxygen deficiency, building up a dichotomic system where mobile weakly correlated $\mathrm{Ti}\phantom{\rule{0.28em}{0ex}}{t}_{2\mathrm{g}}$ electrons coexist with localized strongly correlated $\mathrm{Ti}\phantom{\rule{0.28em}{0ex}}{e}_{\mathrm{g}}$ ones. The ARPES spectra dynamics under x-ray irradiation shows a gradual intensity increase under constant Luttinger count of the Fermi surface. This fact identifies electronic phase separation (EPS) where the mobile electrons accumulate in conducting puddles with fixed electronic structure embedded in an insulating host phase, and allows us to estimate the lateral fraction of these puddles. We discuss the physics of EPS invoking a theoretical picture of oxygen-vacancy clustering, promoted by the magnetism of the localized $\mathrm{Ti}\phantom{\rule{0.28em}{0ex}}{e}_{\mathrm{g}}$ electrons, and repelling of the mobile ${t}_{2\mathrm{g}}$ electrons from these clusters. Our results on the irradiation-tuned EPS elucidate the intrinsic one taking place at the stoichiometric LAO/STO interfaces.

Metal mono-chalcogenide compounds offer a large variety of electronic properties depending on chemical composition, number of layers and stacking-order. Among them, the InSe has attracted much attention due to the promise of outstanding electronic properties, attractive quantum physics, and high photo-response. Metal mono-chalcogenide compounds offer a large variety of electronic properties depending on chemical composition, number of layers and stacking-order. Among them, the InSe has attracted much attention due to the promise of outstanding electronic properties, attractive quantum physics, and high photo-response. Precise experimental determination of the electronic structure of InSe is sorely needed for better understanding of potential properties and device applications. Here, combining scanning tunneling spectroscopy (STS) and two-photon photoemission spectroscopy (2PPE), we demonstrate that InSe exhibits a direct band gap of about 1.25 eV located at the Gamma point of the Brillouin zone (BZ). STS measurements underline the presence of a finite and almost constant density of states (DOS) near the conduction band minimum (CBM) and a very sharp one near the maximum of the valence band (VMB). This particular DOS is generated by a poorly dispersive nature of the top valence band, as shown by angle resolved photoemission spectroscopy (ARPES) investigation. technologies. In fact, a hole effective mass of about m/m0 = -0.95 gammaK direction) was measured. Moreover, using ARPES measurements a spin-orbit splitting of the deeper-lying bands of about 0.35 eV was evidenced. These findings allow a deeper understanding of the InSe electronic properties underlying the potential of III-VI semiconductors for electronic and photonic

Rational design of low-dimensional electronic phenomena at oxide interfaces is currently considered to be one of the most promising schemes for realizing new energy-efficient logic and memory devices. An atomically abrupt interface between paramagnetic $\mathrm{LaNi}{\mathrm{O}}_{3}$ and antiferromagnetic $\mathrm{CaMn}{\mathrm{O}}_{3}$ exhibits interfacial ferromagnetism, which can be tuned via a thickness-dependent metal-insulator transition in $\mathrm{LaNi}{\mathrm{O}}_{3}$. Once fully understood, such emergent functionality could turn this archetypal Mott-interface system into a key building block for the above-mentioned future devices. Here, we use depth-resolved standing-wave photoemission spectroscopy in conjunction with scanning transmission electron microscopy and x-ray absorption spectroscopy, to demonstrate a depth-dependent charge reconstruction at the $\mathrm{LaNi}{\mathrm{O}}_{3}/\mathrm{CaMn}{\mathrm{O}}_{3}$ interface. Our measurements reveal an increased concentration of $\mathrm{M}{\mathrm{n}}^{3+}$ and $\mathrm{N}{\mathrm{i}}^{2+}$ cations at the interface, which create an electronic environment favorable for the emergence of interfacial ferromagnetism mediated via the $\mathrm{M}{\mathrm{n}}^{4+}\ensuremath{-}\mathrm{M}{\mathrm{n}}^{3+}$ ferromagnetic double exchange and $\mathrm{N}{\mathrm{i}}^{2+}\ensuremath{-}\mathrm{O}\ensuremath{-}\mathrm{M}{\mathrm{n}}^{4+}$ superexchange mechanisms. Our findings suggest a strategy for designing functional Mott oxide heterostructures by tuning the interfacial cation characteristics via controlled manipulation of thickness, strain, and ionic defect states.

A key issue in heavy fermion research is how subtle changes in the hybridization between the $4f$ ($5f$) and conduction electrons can result in fundamentally different ground states. ${\mathrm{CeRhIn}}_{5}$ stands out as a particularly notable example: when replacing Rh with either Co or Ir, antiferromagnetism gives way to superconductivity. In this photoemission study of ${\mathrm{CeRhIn}}_{5}$, we demonstrate that the use of resonant angle-resolved photoemission spectroscopy with polarized light allows us to extract detailed information on the $4f$ crystal field states and details on the $4f$ and conduction electron hybridization, which together determine the ground state. We directly observe weakly dispersive Kondo resonances of $f$ electrons and identify two of the three Ce $4{f}_{5/2}^{1}$ crystal-electric-field levels and band-dependent hybridization, which signals that the hybridization occurs primarily between the Ce $4f$ states in the ${\mathrm{CeIn}}_{3}$ layer and two more three-dimensional bands composed of the Rh $4d$ and In $5p$ orbitals in the ${\mathrm{RhIn}}_{2}$ layer. Our results allow us to connect the properties observed at elevated temperatures with the unusual low-temperature properties of this enigmatic heavy fermion compound.

We report on the fabrication, the morphological, structural, and chemical characterization, and the study of the electrical response to NO 2 and other gases of resistive type gas sensors based on liquid chemically exfoliated (in N-methyl pyrrolidone, NMP) MoS 2 flakes annealed in air either at 150 °C or at 250 °C. The active material has been analyzed by scanning electron microscopy (SEM), and micro Raman and X-ray core level photoemission spectroscopies. SEM shows that MoS 2 exfoliated flakes are interconnected between electrodes of the sensing device to form percolation paths. Raman spectroscopy of the flakes before annealing demonstrates that the flakes are constituted by crystalline MoS 2 , while, annealing at 250 °C, does not introduce a detectable bulk contamination in the expected form of MoO 3 . The sensor obtained by thermal annealing in air at 150 °C exhibits a peculiar p -type response under exposure to NO 2 . In line with core level spectroscopy evidences, this behavior is potentially ascribed to nitrogen substitutional doping of S vacancies in the MoS 2 surface (nitrogen atoms being likely provided by the intercalated NMP). Thermal annealing the MoS 2 flakes in air at 250 °C irreversibly sets an n -type behavior of the gas sensing device, with a NO 2 detection limit of 20 ppb. This behavior is assigned, in line with core level spectroscopy data, to a significant presence of S vacancies in the MoS 2 annealed flakes and to the surface co-existence of MoO 3 arising from the partial oxidation of the flakes surface. Both p- and n -type sensors have been demonstrated to be sensitive also to relative humidity. The n -type sensor shows good electrical response under H 2 exposure.

Half-metals such as chromium dioxide behave as metals in one spin orientation and insulators or semiconductors in the opposite one. New measurements of the electronic structure of CrO${}_{2}$ provide clear insight, for the first time, into the role that electronic correlations play in affecting this behavior.

While the bonding of molecular adsorbates to graphene has so far been characterized as physisorption, our study of adsorbed ammonia and water using near-edge X-ray absorption spectroscopy provides unambiguous evidence for a chemical contribution to the adsorption bond. We use the situation, unique to graphene, to characterize the unoccupied valence band states of the partners in the bond on the basis of the complementary adsorbate and substrate X-ray absorption K edges. New adsorbate-induced features on the substrate (carbon) K edge are interpreted as hybrid states in terms of a simple model of chemical interaction.

Heavy-fermion systems share some of the strange metal phenomenology seen in other unconventional superconductors, providing a unique opportunity to set strange metals in a broader context. Central to understanding heavy-fermion systems is the interplay of localization and itinerancy. These materials acquire high electronic masses and a concomitant Fermi volume increase as the $f$ electrons delocalize at low temperatures. However, despite the wide-spread acceptance of this view, a direct microscopic verification has been lacking. Here we report high-resolution angle-resolved photoemission measurements on ${\mathrm{CeCoIn}}_{5}$, a prototypical heavy-fermion compound, which spectroscopically resolve the development of band hybridization and the Fermi surface expansion over a wide temperature region. Unexpectedly, the localized-to-itinerant transition occurs at surprisingly high temperatures, yet $f$ electrons are still largely localized even at the lowest temperature. These findings point to an unanticipated role played by crystal-field excitations in the strange metal behavior of ${\mathrm{CeCoIn}}_{5}$. Our results offer a comprehensive experimental picture of the heavy-fermion formation, setting the stage for understanding the emergent properties, including unconventional superconductivity, in this and related materials.

Applied Physics Letters, 110 (13), ISSN:0003-6951, ISSN:1077-3118

The Weyl semimetal phase is a recently discovered topological quantum state of matter characterized by the presence of topologically protected degeneracies near the Fermi level. These degeneracies are the source of exotic phenomena, including the realization of chiral Weyl fermions as quasiparticles in the bulk and the formation of Fermi arc states on the surfaces. Here, we demonstrate that these two key signatures show distinct evolutions with the bulk band topology by performing angle-resolved photoemission spectroscopy, supported by first-principle calculations, on transition-metal monophosphides. While Weyl fermion quasiparticles exist only when the chemical potential is located between two saddle points of the Weyl cone features, the Fermi arc states extend in a larger energy scale and are robust across the bulk Lifshitz transitions associated with the recombination of two non-trivial Fermi surfaces enclosing one Weyl point into a single trivial Fermi surface enclosing two Weyl points of opposite chirality. Therefore, in some systems (e.g. NbP), topological Fermi arc states are preserved even if Weyl fermion quasiparticles are absent in the bulk. Our findings not only provide insight into the relationship between the exotic physical phenomena and the intrinsic bulk band topology in Weyl semimetals, but also resolve the apparent puzzle of the different magneto-transport properties observed in TaAs, TaP and NbP, where the Fermi arc states are similar., Comment: To appear in Physical Review Letters

Semiconductor spintronics provides a framework for hybrid devices combining logic, communication and storage, circumventing limitations of the current electronics, especially with respect to the energy efficiency. Enormous efforts have been invested worldwide into the development of spintronics based on Si, the mainstream semiconductor platform. Notwithstanding remarkable pace, Si spintronics still experiences a technological bottleneck – creation of significant spin polarization in nonmagnetic Si. An emerging approach based on direct electrical spin injection from a ferromagnetic semiconductor – EuO being the prime choice – avoids problems inherent to metallic injectors. The functionality of the EuO/Si spin contact is controlled by the interface band alignment. To be competitive with charge electronics, the EuO/Si interface should exhibit a band offset which falls within the 0.5–2 eV range. We employ a soft-X-ray ARPES technique, using synchrotron radiation with photon energies around 1 keV, to probe the electronic structure of the buried EuO/Si interface with momentum resolution and chemical specificity. The band structure reveals a conduction band offset of 1.0 eV attesting the technological potential of the EuO/Si system.

Identifikace bulkových a povrchových Rashba stavů v ferroelektrickém GeTe Macroscopic ferroelectric order in α-GeTe with its noncentrosymmetric lattice structure leads to a giant Rashba spin splitting in the bulk bands due to strong spin-orbit interaction. Direct measurements of the bulk band structure using soft x-ray angle-resolved photoemission (ARPES) reveals the three-dimensional electronic structure with spindle torus shape. By combining high-resolution and spin-resolved ARPES as well as photoemission calculations, the bulk electronic structure is disentangled from the two-dimensional surface electronic structure by means of surface capping, which quenches the complex surface electronic structure. This unravels the bulk Rashba-split states in the ferroelectric Rashba α-GeTe(111) semiconductor exhibiting a giant spin splitting with Rashba parameter αR around 4.2 eV A°, the highest of so-far known materials.

The interplay between electronic eigenstates, spin, and orbital degrees of freedom, combined with fundamental breaking of symmetries is currently one of the most exciting fields of research. Multiferroics such as (GeMn)Te fulfill these requirements providing unusual physical properties due to the coexistence and coupling between ferromagnetic and ferroelectric order in one and the same system. Here we show that multiferroic (GeMn)Te inherits from its parent ferroelectric {\alpha}-GeTe compound a giant Rashba splitting of three-dimensional bulk states which competes with the Zeeman spin splitting induced by the magnetic exchange interactions. The collinear alignment of ferroelectric and ferromagnetic polarization leads to an opening of a tunable Zeeman gap of up to 100 meV around the Dirac point of the Rashba bands, coupled with a change in spin texture by entanglement of magnetic and spin-orbit order. Through applications of magnetic fields, we demonstrate manipulation of spin- texture by spin resolved photoemission experiments, which is also expected for electric fields based on the multiferroic coupling. The control of spin helicity of the bands and its locking to ferromagnetic and ferroelectric order opens fascinating new avenues for highly multifunctional multiferroic Rashba devices suited for reprogrammable logic and/or nonvolatile memory applications., Comment: 10 pages, 4 figures

In the studies of iron pnictides, a key question is whether their bad-metal state from which the superconductivity emerges lies in close proximity with a magnetically ordered insulating phase. Recently, it was found that at low temperatures, the heavily Cu-doped ${\mathrm{NaFe}}_{1\ensuremath{-}x}{\mathrm{Cu}}_{x}\mathrm{As}$ ($xg0.3$) iron pnictide is an insulator with long-range antiferromagnetic order, similar to the parent compound of cuprates but distinct from all other iron pnictides. Using angle-resolved photoemission spectroscopy, we determined the momentum-resolved electronic structure of ${\mathrm{NaFe}}_{1\ensuremath{-}x}{\mathrm{Cu}}_{x}\mathrm{As}$ ($x=0.44$) and identified that its ground state is a narrow-gap insulator. Combining the experimental results with density functional theory (DFT) and $\mathrm{DFT}+U$ calculations, our analysis reveals that the on-site Coulombic (Hubbard) and Hund's coupling energies play crucial roles in the formation of the band gap about the chemical potential. We propose that at finite temperatures, charge carriers are thermally excited from the Cu-As-like valence band into the conduction band, which is of Fe $3d$-like character. With increasing temperature, the number of electrons in the conduction band becomes larger and the hopping energy between Fe sites increases, and finally the long-range antiferromagnetic order is destroyed at $Tg{T}_{N}$. Our study provides a basis for investigating the evolution of the electronic structure of a Mott insulator transforming into a bad metallic phase and eventually forming a superconducting state in iron pnictides.

The complex electronic properties of ${\mathrm{ZrTe}}_{5}$ have recently stimulated in-depth investigations that assigned this material to either a topological insulator or a 3D Dirac semimetal phase. Here we report a comprehensive experimental and theoretical study of both electronic and structural properties of ${\mathrm{ZrTe}}_{5}$, revealing that the bulk material is a strong topological insulator (STI). By means of angle-resolved photoelectron spectroscopy, we identify at the top of the valence band both a surface and a bulk state. The dispersion of these bands is well captured by ab initio calculations for the STI case, for the specific interlayer distance measured in our x-ray diffraction study. Furthermore, these findings are supported by scanning tunneling spectroscopy revealing the metallic character of the sample surface, thus confirming the strong topological nature of ${\mathrm{ZrTe}}_{5}$.

In 1929, H. Weyl proposed that the massless solution of Dirac equation represents a pair of new type particles, the so-called Weyl fermions [1]. However the existence of them in particle physics remains elusive for more than eight decades. Recently, significant advances in both topological insulators and topological semimetals have provided an alternative way to realize Weyl fermions in condensed matter as an emergent phenomenon: when two non-degenerate bands in the three-dimensional momentum space cross in the vicinity of Fermi energy (called as Weyl nodes), the low energy excitation behaves exactly the same as Weyl fermions. Here, by performing soft x-ray angle-resolved photoemission spectroscopy measurements which mainly probe bulk band structure, we directly observe the long-sought-after Weyl nodes for the first time in TaAs, whose projected locations on the (001) surface match well to the Fermi arcs, providing undisputable experimental evidence of existence of Weyl fermion quasiparticles in TaAs., Comment: 10 pages, 4 figures, see also related papers on TaAs arXiv:1501.00060, arXiv:1502.04684

Graphene formation on top of SiC(0001) by decoupling the carbon buffer layer through lithium intercalation is investigated. Low-energy electron diffraction and core-level photoemission spectroscopy results show that graphene formation already occurs at room temperature, and that the interface morphology is improved after thermal annealing. Angle-resolved photoemission spectroscopy (ARPES) shows that the resulting graphene layer is strongly $n$-type doped, and in spite of the decoupling by lithium intercalation, a persistent interaction with the substrate imposes a superperiodicity on the graphene band structure that modulates the $\ensuremath{\pi}$ band intensity and gives rise to quasi-$(2\ifmmode\times\else\texttimes\fi{}2) \ensuremath{\pi}$ replica bands. Through a comparison of the ARPES-derived band structure with density-functional-theory calculations, we assign the observed bands to SiC-derived states and interface-related ones; this assignment permits us to establish that the intercalated lithium occupies the T4 site on the topmost SiC layer.

A novel technique to lithograph the MoS2 surface is described here. Mechanically exfoliated MoS2 flakes have been patterned with an atomic force microscope tip. After the patterning process, the lithographed areas have been removed by selective chemical etching. The electronic properties of the MoS2 flakes have been analyzed with spatially resolved photoelectron spectroscopy, with tunable incident photon energy, provided by a synchrotron light source. Tens of meV core level shifts can be recorded in relation to the flakes edges, coming from both the exfoliation and from the lithography.

The electronic structures of three new synthesised tetrakis Erbium(III) quinolinate complexes (Na[ErQ4], Na[Er(Q57Br)4] and Na[Er(Q57I)4]) have been studied by means of photoemission and absorption spectroscopies and compared with corresponding experimental data of Tris(8-hydroxyquinolinate)Erbium(III) (ErQ3). Core level and valence band spectra of Na[ErQ4] are very similar to ErQ3 ones apart from a slight modification in the O 1s core level. The fundamental physical parameters for optical device applications as ionization energy and optical gap are the same, corresponding to 5.2 eV and 2.9 eV respectively. For the other two molecules, the introduction of halogens (Br, I) in the ligands leads to a reduction of 0.2 eV for the optical gap and to an increase of 0.5 eV for the ionization energy with respect to ErQ3.

We report an optical contrast study of graphene oxide on 72 nm Al2O3/Si(100) and 300 nm SiO2/Si(100) as a function of its reduction degree. The reduction has been performed by means of ultrahigh vacuum thermal annealing from 25 degrees C (pristine graphene oxide) to 670 degrees C. In parallel to the optical contrast investigation, performed with optical microscopy, the graphene oxide films have been characterized with core level X-ray photoemission spectroscopy and micro-Raman spectroscopy. The optical contrast of graphene oxide (normalized to the one measured for pure graphene) on both substrates ranges from similar to 0.4 to 1.0 for pristine and 670 degrees C annealed graphene oxide, respectively. Optical microscopy and X-ray photoemission spectroscopy data have been cross-correlated, leading to calibration graphs that demonstrate that just by simply measuring the optical contrast of graphene oxide one can determine with very good approximation the fraction of sp(2) hybridized carbon.

The effects of thermal annealing in ultra-high vacuum on the electronic structures of bulk and liquid exfoliated MoS 2 have been studied by core level and valence band X-ray photoemission spectroscopy. A quantitative analysis of core level spectra demonstrates, in the case of exfoliated MoS 2 , that, upon annealing above 200 °C, defect formation occurs in the form of sulfur single and double vacancies. Sulfur vacancies introduce surface states in the band gap (determined by the analysis of the valence band spectra). This determines a rigid shift of the core levels to lower binding energies, as a consequence of an upward band bending.

The ability to pattern graphene over large areas with nanometer resolution is the current request for nanodevice fabrication at the industrial scale. Existing methods do not match high throughput with nanometer resolution. We propose a high-throughput resistless extreme-UV (EUV) photolithographic approach operating with sub-micrometer resolution on large area (~10 mm(2)) graphene oxide (GO) films via spatially resolved photoreduction. The efficiency of EUV photoreduction is tested with 46.9 nm coherent light produced by a table top capillary discharge plasma source. Irradiated samples are studied by X-ray photoemission spectroscopy (XPS) and micro-Raman Spectroscopy (μRS). XPS data show that 200 mJ/cm(2) EUV dose produces, onto pristine GO, a 6% increase of sp(2) carbon bonds and a 20% decrease of C-O bonds. μRS data demonstrate a photoreduction efficiency 2 orders of magnitude higher than the one reported in the literature for UV-assisted photoreduction. GO patterning is obtained modulating the EUV dose with a Lloyd's interferometer. The lithographic features consist of GO stripes with modulated reduction degree. Such modulation is investigated and demonstrated by μRS on patterns with 2 μm periodicity.

Films of 6,13-pentacenequinone (PQ, C22H12O2) of nominal thicknesses 5 and 30 nm grown in high vacuum onto SiO2 have been UV (325 nm) excited and their photoluminescence (PL) response has been investigated with the support of parallel scanning electron microscopy (FE-SEM) and x-ray diffraction (XRD) experiments. The photoluminescence spectra typically show a multiplet structure that can be ultimately assigned to the sum of the emission spectra from two different crystal phases, namely the “bulk” and the “thin film” phase, emitting respectively in the 500–600 nm and 600–750 nm spectral ranges. The assignment is done via the systematic parallel SEM and XRD investigation of the samples. Data are also discussed in comparison with PL spectra of PQ reported in the literature. The blue shift of the “bulk” phase PL spectrum is assigned to its smaller (about 9% less than in the “thin film” phase) molecular packing density in the ab-plane, and accordingly, to a decreased π–π orbital overlap.

The electronic properties of tris(8-hydroxyquinolinato)aluminium(III) (AlQ${}_{3}$) have been revisited using the screened hybrid Heyd-Scuseria-Ernzerhof density functional theory. We show that such approach very well accounts for the experimental occupied (valence band spectrum) and unoccupied (inverse photoemission spectrum) states. Furthermore, the density of states projected onto nitrogen, oxygen, and carbon are compared with soft x-ray adsorption and emission spectroscopy, showing a very good agreement between theory and experiments. Finally, a fully theoretical interpretation of the carbon $1s$ core level is proposed.

The electronic structure of Croconic Acid in the condensed phase has been studied by comparing core level and valence band x-ray photoelectron spectroscopy experiments and first principles density functional theory calculations using the Heyd-Scuseria-Ernzerhof screened hybrid functional and the GW approximation. By exploring the photoemission spectra for different deposition thicknesses, we show how the formation of the hydrogen bond network modifies the O 1s core level lineshape. Moreover, the valence band can be explained only if the intermolecular interactions are taken into account in the theoretical approach.

A distributed feedback (DFB) waveguide cavity with erbium-tris(8-hydroxyquinoline) has been fabricated by X-ray interference lithography in a laboratory-scale apparatus. The DFB cavity consists of a large area ( ∼ 8 mm 2 ) one-dimensional grating of polymethylmethacrylate on Si (1 0 0). Structural, morphological and optical properties of the device have been studied. On-grating narrowing of the photoluminescence emission has been observed for the 492 nm grating period in correspondence to the 4f–4f Er band peak (at 1530 nm), indicating the possibility of optical gain for applications in the telecommunications.

6,13 Pentacenequinone (PQ) ultrathin films (3 and 5 nm nominal thickness) have been grown by means of ultrahigh vacuum deposition onto 100 nm thick SiO2/Si(100). The structure and morphology of the thin films have been studied with field emission-scanning electron microscopy, tapping mode atomic force microscopy, and x-ray diffraction. The growth begins with PQ molecules standing almost upright (with respect to the substrate) and aggregating into two-dimensional 3.62 nm thick pseudodendritic islands. The islands are characterized by two preferential growth directions (at 117°), a clear evidence of a chiral growth. The thickness of the islands and the angle formed by the two directions of preferential growth, allow a straightforward assignment to a PQ initial growth in the “bulk” phase. Above the critical thickness of 3.62 nm the PQ growth proceeds in a Stranski−Krastanov mode, with the formation of “bulk” and “thin-film” phase crystallites.

Quasicrystals (QCs) are intermetallic alloys that have excellent long-range order but lack translational symmetry in at least one dimension. The valence band electronic structure near the Fermi energy EF in such materials is of special interest since it has a direct relation to their unusual physical properties. However, the Fermi surface (FS) topology as well as the mechanism of QC structure stabilization are still under debate. Here we report the first observation of the three-dimensional FS and valence band dispersions near EF in decagonal Al70Ni20Co10 (d-AlNiCo) QCs using soft X-ray angle-resolved photoemission spectroscopy. We show that the FS, formed by dispersive Al sp-states, has a multicomponent character due to a large contribution from high-order bands. Moreover, we discover that the magnitude of the gap at the FS related to the interaction with Brillouin zone boundary (Hume–Rothery gap) critically differs for the periodic and quasiperiodic directions., Quasicrystals show long-range order but lack the symmetry of conventional crystals. Here, the authors study the bulk electronic structure of quasicrystals and their three-dimensional Fermi surface topology, providing links to the structural stability of these materials.

SiO2 and Al2O3 surfaces exposed to periodically modulated extreme ultraviolet (EUV) light (λ = 46.9 nm) have been investigated at the μm scale by optical microscopy, scanning electron microscopy, scanning Auger microscopy, atomic force microscopy, and Kelvin probe force microscopy. The formation of a carbon contamination layer preserving the same periodical modulation of the EUV dose has been observed. The mechanisms of hydrocarbon molecules deposition have been studied with the help of correlation plots between the modulated Auger signal and the corresponding EUV dose. A surface-dependent secondary-electron-based model has been proposed.

A Weyl semimetal possesses spin-polarized band-crossings, called Weyl nodes, connected by topological surface arcs. The low-energy excitations near the crossing points behave the same as massless Weyl fermions, leading to exotic properties like chiral anomaly. To have the transport properties dominated by Weyl fermions, Weyl nodes need to locate nearly at the chemical potential and enclosed by pairs of individual Fermi surfaces with non-zero Fermi Chern numbers. Combining angle-resolved photoemission spectroscopy and first-principles calculation, here we show that TaP is a Weyl semimetal with only a single type of Weyl fermions, topologically distinguished from TaAs where two types of Weyl fermions contribute to the low-energy physical properties. The simple Weyl fermions in TaP are not only of fundamental interests but also of great potential for future applications. Fermi arcs on the Ta-terminated surface are observed, which appear in a different pattern from that on the As-termination in TaAs and NbAs., Weyl semimetals exhibit exotic properties owing to the presence of Weyl fermions. Here, Xu et al. show that tantalum phosphide is an ideal platform for studying the transport properties of these particles because its low-energy properties are dominated by a single type of Weyl fermion.