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The interface of manganese(II) phtalocyanine (MnPc) with an α-RuCl3 single crystal is studied by means of photoelectron spectroscopy. The organic molecule was evaporated on top of an in situ cleaved α-RuCl3 bulk crystal in steps. The work function and electron affinity of α-RuCl3 is determined to be 6.3 and 5.4 eV, respectively, in line with common fluorinated acceptor molecules, but with the potential to absorb more electrons per area at interfaces with other materials. These favorable electronic properties lead to a charge transfer from MnPc to α-RuCl3 which manifests itself mainly in peak shape changes of core level photoemission spectra and further filling of Ru 4d states as revealed by valence band photoemission. This work demonstrates the promising potential of α-RuCl3 as a strong acceptor material for interfaces in general, and for organic molecules in particular.

Their exceptional optical properties are a driving force for the persistent interest in atomically thin transition metal dichalcogenides such as MoS2. The optical response is dominated by excitons. Apart from the bright excitons, which directly couple to light, it has been realized that dark excitons, where photon absorption or emission is inhibited by the spin state or momentum mismatch, are decisive for many optical properties. However, in particular the momentum dependence is difficult to assess experimentally and often remains elusive or is investigated by indirect means. Here we study the momentum dependent electronic structure experimentally and theoretically. We use angle-resolved photoemission as a one-particle probe of the occupied valence band structure and electron energy loss spectroscopy as a two-particle probe of electronic transitions across the gap to benchmark a single-particle model of the dielectric function $$\epsilon ({\bf{q}},\omega )$$ ϵ(q,ω) against momentum dependent experimental measurements. This ansatz captures key aspects of the data surprisingly well. In particular, the energy region where substantial nesting occurs, which is at the origin of the strong light–matter interaction of thin transition metal dichalcogenides and crucial for the prominent C-exciton, is described well and spans a more complex exciton landscape than previously anticipated. Its local maxima in $$({\bf{q}}\ \ne \ 0,\omega )$$ (q≠0,ω) space can be considered as dark excitons and might be relevant for higher order optical processes. Our study may lead to a more complete understanding of the optical properties of atomically thin transition metal dichalcogenides.

Investigation of the influence of the nanocrystal (NC) surface chemistry on the (opto)electronic properties of NC-based thin films is of paramount importance for their further application in variou...

In this work, we present a new synthetic approach to colloidal PbS nanoplatelets (NPLs) utilizing a cation exchange (CE) strategy starting from CuS NPLs synthesized via the hot-injection method. Whereas the thickness of the resulting CuS NPLs was fixed at approx. 5 nm, the lateral size could be tuned by varying the reaction conditions, such as time from 6 to 16 h, the reaction temperature (120 °C, 140 °C), and the amount of copper precursor. In a second step, Cu+ cations were replaced with Pb2+ ions within the crystal lattice via CE. While the shape and the size of parental CuS platelets were preserved, the crystal structure was rearranged from hexagonal covellite to PbS galena, accompanied by the fragmentation of the monocrystalline phase into polycrystalline one. Afterwards a halide mediated ligand exchange (LE) was carried out in order to remove insulating oleic acid residues from the PbS NPL surface and to form stable dispersions in polar organic solvents enabling thin-film fabrication. Both CE and LE processes were monitored by several characterization techniques. Furthermore, we measured the electrical conductivity of the resulting PbS NPL-based films before and after LE and compared the processing in ambient to inert atmosphere. Finally, we fabricated field-effect transistors with an on/off ratio of up to 60 and linear charge carrier mobility for holes of 0.02 cm2 V−1 s−1.

Conducting domain walls (CDWs) in ferroelectric materials are promising candidates for applications in a manifold of nanoscale, optoelectronic devices. Characterization of their microscopic properties, however, remains challenging due to their small dimension and highly insulating environment. Here, we inspect individual CDWs in single-crystalline LiNbO3 by the combination of photoemission electron microscopy (PEEM) and second harmonic generation (SHG) microscopy. While SHG unveils the overall domain wall inclination angle α, PEEM is sensitive to local conductance variations, both at and away from the domain wall. Thus, the two imaging techniques deliver complementary information over a large field of view. In agreement with earlier theoretical predictions we find that the local conductance is dictated by α and reveal a quantitative connection between them. Our results help to elucidate the electronic structure of CDWs and underline the value of PEEM as a non-contact characterization tool for mapping local conductance variations in highly resistive environments.

Quasi-two-dimensional (2D) CdSe nanoplatelets (NPLs) are distinguished by their unique optical properties in comparison to classical semiconductor nanocrystals, such as extremely narrow emission line widths, reduced Auger recombination, and relatively high absorption cross sections. Inherent to their anisotropic 2D structure, however, is the loss of continuous tunability of their photoluminescence (PL) properties due to stepwise growth. On top of that, limited experimental availability of NPLs of different thicknesses and ultimately the bulk band gap of CdSe constrain the achievable PL wavelengths. Here, we report on the doping of CdSe NPLs with mercury, which gives rise to additional PL in the red region of the visible spectrum and in the near-infrared region. We employ a seeded-growth method with injection solutions containing cadmium, selenium, and mercury. The resulting NPLs retain their anisotropic structure, are uniform in size and shape, and present significantly altered spectroscopic characteristics due to the existence of additional energetic states. We conclude that doping takes place by employing elemental analysis in combination with PL excitation spectroscopy, X-ray photoelectron spectroscopy, and single-particle fluorescence spectroscopy, confirming single emitters being responsible for multiple distinct emission signals.

Semimetallic ${\mathrm{MoTe}}_{2}$ has recently generated enormous attention due to its topological properties, large magnetoresistance, superconductivity, suitability for homojunction phase patterning, and, in particular, metal-insulator transition of thin layers, possibly indicating a quantum spin hall state. These observations prove the potential of ${\mathrm{MoTe}}_{2}$ for thin film applications and call for systematic investigations of the thickness dependent electronic structure. Here we apply angle-resolved photoemission spectroscopy supported by band structure calculations to elucidate the electronic structure of exfoliated $1{\mathrm{T}}^{\ensuremath{'}}\text{\ensuremath{-}}{\mathrm{MoTe}}_{2}$. Electron and hole pockets of the inverted conduction and valence bands near $\mathrm{\ensuremath{\Gamma}}$ are resolved down to the monolayer. The Fermi level of exfoliated $1{\mathrm{T}}^{\ensuremath{'}}\text{\ensuremath{-}}{\mathrm{MoTe}}_{2}$ monolayers lays within the electron pockets indicating intrinsic $n$-type doping. ${E}_{F}$ shifts downward with increasing thickness consistent with a surface driven mechanism. Our study provides insight on the electronic properties of semimetallic $1{\mathrm{T}}^{\ensuremath{'}}\text{\ensuremath{-}}{\mathrm{MoTe}}_{2}$ as an indispensable ingredient for future thin film functionalization.

The long search for materials carrying quantum spin liquid states has recently led to $\ensuremath{\alpha}$-RuCl${}_{3}$, a layered honeycomb Mott insulator with substantial spin-orbit coupling. Often, controlled doping of materials with strong 2D character generates new exotic properties as well as a better understanding of the parent compound. This paper shows that the intercalation compound K${}_{0.5}$RuCl${}_{3}$ sustains a peculiar charge disproportionation into formally Ru${}^{2+}$ and Ru${}^{3+}$. Every Ru${}^{3+}$ with one hole in the t${}_{2g}$ shell is surrounded by Ru${}^{2+}$ where the t${}_{2g}$ level is full and magnetically inert. Thus each type of Ru sites forms a triangular lattice and nearest-neighbor interactions of the original honeycomb are blocked.

Kitaev-type interactions between neighbouring magnetic moments emerge in the honeycomb material ${\alpha}$-RuCl3. It is debated however whether these Kitaev interactions are ferromagnetic or antiferromagnetic. With electron energy loss spectroscopy (EELS) we study the lowest excitation across the Mott-Hubbard gap, which involves a d4 triplet in the final state and therefore is sensitive to nearest-neighbor spin-spin correlations. At low temperature the spectral weight of these triplets is strongly enhanced, in accordance with optical data. We show that the magnetic correlation function that determines this EELS spectral weight is directly related to a Kitaev-type spin-spin correlator and that the temperature dependence agrees very well with the results of a microscopic magnetic Hamiltonian for ${\alpha}$-RuCl3 with ferromagnetic Kitaev coupling., Comment: 5 pages, 3 figures

Combining dissimilar transition metal oxides (TMOs) into artificial heterostructures enables to create electronic interface systems with new electronic properties that do not exist in bulk. A detailed understanding of how such interfaces can be used to tailor physical properties requires characterization techniques capable to yield interface sensitive spectroscopic information with monolayer resolution. In this regard resonant x-ray reflectivity (RXR) provides a unique experimental tool to achieve exactly this. It yields the element specific electronic depth profiles in a non-destructive manner. Here, using a YBa2Cu3O7−δ (YBCO) thin film, we demonstrate that RXR is further capable to deliver site selectivity. By applying a new analysis scheme to RXR, which takes the atomic structure of the material into account, together with information of the local charge anisotropy of the resonant ions, we obtained spectroscopic information from the different Cu sites (e.g., chain and plane) throughout the film profile. While most of the film behaves bulk-like, we observe that the Cu-chains at the surface show characteristics of electron doping, whereas the Cu-planes closest to the surface exhibit an orbital reconstruction similar to that observed at La1−x Ca x MnO3/YBCO interfaces.

Novel ground states might be realized in honeycomb lattices with strong spin-orbit coupling. Here we study the electronic structure of α-RuCl_{3}, in which the Ru ions are in a d^{5} configuration and form a honeycomb lattice, by angle-resolved photoemission, x-ray photoemission, and electron energy loss spectroscopy supported by density functional theory and multiplet calculations. We find that α-RuCl_{3} is a Mott insulator with significant spin-orbit coupling, whose low energy electronic structure is naturally mapped onto J_{eff} states. This makes α-RuCl_{3} a promising candidate for the realization of Kitaev physics. Relevant electronic parameters such as the Hubbard energy U, the crystal field splitting 10 Dq, and the charge transfer energy Δ are evaluated.

Some heavy fermion materials show so-called hidden-order phases which are invisible to many characterization techniques and whose microscopic origin remained controversial for decades. Among such hidden-order compounds, CeB6 is of model character due to its simple electronic configuration and crystal structure. Apart from more conventional antiferromagnetism, it shows an elusive phase at low temperatures, which is commonly associated with multipolar order. Here we show that this phase roots in a Fermi surface instability. This conclusion is based on a full 3D tomographic sampling of the electronic structure by angle-resolved photoemission and comparison with inelastic neutron scattering data. The hidden order is mediated by itinerant electrons. Our measurements will serve as a paradigm for the investigation of hidden-order phases in f-electron systems, but also generally for situations where the itinerant electrons drive orbital or spin order., In compounds containing 4f and 5f elements, hidden-order phases exist which are undetectable by many methods, the origins of which are debated. Here, the authors use photoemission and neutron scattering methods to show how such a multipolar-ordered phase emerges due to Fermi surface instability in CeB6.