Ultrafast creation of a light-induced semimetallic state in strongly excited 1T-TiSe2.

Screening, a ubiquitous phenomenon associated with the shielding of electric fields by surrounding charges, has been widely adopted as a means to modify a material's properties. While most studies have relied on static changes of screening through doping or gating thus far, here we demonstrate that screening can also drive the onset of distinct quantum states on the ultrafast timescale. By using time- and angle-resolved photoemission spectroscopy, we show that intense optical excitation can drive 1T-TiSe2, a prototypical charge density wave material, almost instantly from a gapped into a semimetallic state. By systematically comparing changes in band structure over time and excitation strength with theoretical calculations, we find that the appearance of this state is likely caused by a dramatic reduction of the screening length. In summary, this work showcases how optical excitation enables the screening-driven design of a nonequilibrium semimetallic phase in TiSe2, possibly providing a general pathway into highly screened phases in other strongly correlated materials.

Tunable Van Hove Singularity without Structural Instability in Kagome Metal CsTi_{3}Bi_{5}.

In kagome metal CsV_{3}Sb_{5}, multiple intertwined orders are accompanied by both electronic and structural instabilities. These exotic orders have attracted much recent attention, but their origins remain elusive. The newly discovered CsTi_{3}Bi_{5} is a Ti-based kagome metal to parallel CsV_{3}Sb_{5}. Here, we report angle-resolved photoemission experiments and first-principles calculations on pristine and Cs-doped CsTi_{3}Bi_{5} samples. Our results reveal that the van Hove singularity (vHS) in CsTi_{3}Bi_{5} can be tuned in a large energy range without structural instability, different from that in CsV_{3}Sb_{5}. As such, CsTi_{3}Bi_{5} provides a complementary platform to disentangle and investigate the electronic instability with a tunable vHS in kagome metals.

Visualizing Orbital Content of Electronic Bands in Anisotropic 2D Semiconducting ReSe2.

Many properties of layered materials change as they are thinned from their bulk forms down to single layers, with examples including indirect-to-direct band gap transition in 2H semiconducting transition metal dichalcogenides as well as thickness-dependent changes in the valence band structure in post-transition-metal monochalcogenides and black phosphorus. Here, we use angle-resolved photoemission spectroscopy to study the electronic band structure of monolayer ReSe2, a semiconductor with a distorted 1T structure and in-plane anisotropy. By changing the polarization of incoming photons, we demonstrate that for ReSe2, in contrast to the 2H materials, the out-of-plane transition metal dz2 and chalcogen pz orbitals do not contribute significantly to the top of the valence band, which explains the reported weak changes in the electronic structure of this compound as a function of layer number. We estimate a band gap of 1.7 eV in pristine ReSe2 using scanning tunneling spectroscopy and explore the implications on the gap following surface doping with potassium. A lower bound of 1.4 eV is estimated for the gap in the fully doped case, suggesting that doping-dependent many-body effects significantly affect the electronic properties of ReSe2. Our results, supported by density functional theory calculations, provide insight into the mechanisms behind polarization-dependent optical properties of rhenium dichalcogenides and highlight their place among two-dimensional crystals.

How Indium Nitride Senses Water.

The unique electronic band structure of indium nitride InN, part of the industrially significant III-N class of semiconductors, offers charge transport properties with great application potential due to its robust n-type conductivity. Here, we explore the water sensing mechanism of InN thin films. Using angle-resolved photoemission spectroscopy, core level spectroscopy, and theory, we derive the charge carrier density and electrical potential of a two-dimensional electron gas, 2DEG, at the InN surface and monitor its electronic properties upon in situ modulation of adsorbed water. An electric dipole layer formed by water molecules raises the surface potential and accumulates charge in the 2DEG, enhancing surface conductivity. Our intuitive model provides a novel route toward understanding the water sensing mechanism in InN and, more generally, for understanding sensing material systems beyond InN.

Universal Mechanism of Band-Gap Engineering in Transition-Metal Dichalcogenides.

van der Waals two-dimensional (2D) semiconductors have emerged as a class of materials with promising device characteristics owing to the intrinsic band gap. For realistic applications, the ideal is to modify the band gap in a controlled manner by a mechanism that can be generally applied to this class of materials. Here, we report the observation of a universally tunable band gap in the family of bulk 2H transition metal dichalcogenides (TMDs) by in situ surface doping of Rb atoms. A series of angle-resolved photoemission spectra unexceptionally shows that the band gap of TMDs at the zone corners is modulated in the range of 0.8-2.0 eV, which covers a wide spectral range from visible to near-infrared, with a tendency from indirect to direct band gap. A key clue to understanding the mechanism of this band-gap engineering is provided by the spectroscopic signature of symmetry breaking and resultant spin-splitting, which can be explained by the formation of 2D electric dipole layers within the surface bilayer of TMDs. Our results establish the surface Stark effect as a universal mechanism of band-gap engineering on the basis of the strong 2D nature of van der Waals semiconductors.

Sublattice Interference as the Origin of σ Band Kinks in Graphene.

Kinks near the Fermi level observed in angle-resolved photoemission spectroscopy (ARPES) have been widely accepted to represent electronic coupling to collective excitations, but kinks at higher energies have eluded a unified description. We identify the mechanism leading to such kink features by means of ARPES and tight-binding band calculations on σ bands of graphene, where anomalous kinks at energies as high as ∼4 eV were reported recently [Phys. Rev. Lett. 111, 216806 (2013)]. We found that two σ bands show a strong intensity modulation with abruptly vanishing intensity near the kink features, which is due to sublattice interference. The interference induced local singularity in the matrix element is a critical factor that gives rise to apparent kink features, as confirmed by our spectral simulations without involving any coupling to collective excitations.

A novel quasi-one-dimensional topological insulator in bismuth iodide ß-Bi4I4.

Recent progress in the field of topological states of matter has largely been initiated by the discovery of bismuth and antimony chalcogenide bulk topological insulators (TIs; refs ,,,), followed by closely related ternary compounds and predictions of several weak TIs (refs ,,). However, both the conceptual richness of Z2 classification of TIs as well as their structural and compositional diversity are far from being fully exploited. Here, a new Z2 topological insulator is theoretically predicted and experimentally confirmed in the ß-phase of quasi-one-dimensional bismuth iodide Bi4I4. The electronic structure of ß-Bi4I4, characterized by Z2 invariants (1;110), is in proximity of both the weak TI phase (0;001) and the trivial insulator phase (0;000). Our angle-resolved photoemission spectroscopy measurements performed on the (001) surface reveal a highly anisotropic band-crossing feature located at the  point of the surface Brillouin zone and showing no dispersion with the photon energy, thus being fully consistent with the theoretical prediction.

Latent instabilities in metallic LaNiO3 films by strain control of Fermi-surface topology.

Strain control is one of the most promising avenues to search for new emergent phenomena in transition-metal-oxide films. Here, we investigate the strain-induced changes of electronic structures in strongly correlated LaNiO3 (LNO) films, using angle-resolved photoemission spectroscopy and the dynamical mean-field theory. The strongly renormalized eg-orbital bands are systematically rearranged by misfit strain to change its fermiology. As tensile strain increases, the hole pocket centered at the A point elongates along the kz-axis and seems to become open, thus changing Fermi-surface (FS) topology from three- to quasi-two-dimensional. Concomitantly, the FS shape becomes flattened to enhance FS nesting. A FS superstructure with Q1 = (1/2,1/2,1/2) appears in all LNO films, while a tensile-strained LNO film has an additional Q2 = (1/4,1/4,1/4) modulation, indicating that some instabilities are present in metallic LNO films. Charge disproportionation and spin-density-wave fluctuations observed in other nickelates might be their most probable origins.

Luminescence, patterned metallic regions, and photon-mediated electronic changes in single-sided fluorinated graphene sheets.

Single-sided fluorination has been predicted to open an electronic band gap in graphene and to exhibit unique electronic and magnetic properties; however, this has not been substantiated by experimental reports. Our comprehensive experimental and theoretical study of this material on a SiC(0001) substrate shows that single-sided fluorographene exhibits two phases, a stable one with a band gap of ∼6 eV and a metastable one, induced by UV irradiation, with a band gap of ∼2.5 eV. The metastable structure, which reverts to the stable "ground-state" phase upon annealing under emission of blue light, in our view is induced by defect states, based on the observation of a nondispersive electronic state at the top of the valence band, not unlike that found in organic molecular layers. Our structural data show that the stable C2F ground state has a "boat" structure, in agreement with our X-ray magnetic circular dichroism data, which show the absence of an ordered magnetic phase. A high flux of UV or X-ray photons removes the fluorine atoms, demonstrating the possibility of lithographically patterning conducting regions into an otherwise semiconducting 2D material.

Layer-by-layer evolution of a two-dimensional electron gas near an oxide interface.

We report the momentum-resolved measurement of a two-dimensional electron gas at the LaTiO(3)/SrTiO(3) interface by angle-resolved photoemission spectroscopy (ARPES). Thanks to an advanced sample preparation technique, the orbital character of the conduction electrons and the electronic correlations can be accessed quantitatively as each unit cell layer is added. We find that all of these quantities change dramatically with distance from the interface. These findings open the way to analogous studies on other heterostructures, which are traditionally a forbidden field for ARPES.

Coexisting massive and massless Dirac fermions in symmetry-broken bilayer graphene.

Charge carriers in bilayer graphene are widely believed to be massive Dirac fermions that have a bandgap tunable by a transverse electric field. However, a full transport gap, despite its importance for device applications, has not been clearly observed in gated bilayer graphene, a long-standing puzzle. Moreover, the low-energy electronic structure of bilayer graphene is widely held to be unstable towards symmetry breaking either by structural distortions, such as twist, strain, or electronic interactions that can lead to various ground states. Which effect dominates the physics at low energies is hotly debated. Here we show both by direct band-structure measurements and by calculations that a native imperfection of bilayer graphene, a distribution of twists whose size is as small as ~0.1°, is sufficient to generate a completely new electronic spectrum consisting of massive and massless Dirac fermions. The massless spectrum is robust against strong electric fields, and has a unusual topology in momentum space consisting of closed arcs having an exotic chiral pseudospin texture, which can be tuned by varying the charge density. The discovery of this unusual Dirac spectrum not only complements the framework of massive Dirac fermions, widely relevant to charge transport in bilayer graphene, but also supports the possibility of valley Hall transport.

Fluorographene: a wide bandgap semiconductor with ultraviolet luminescence.

The manipulation of the bandgap of graphene by various means has stirred great interest for potential applications. Here we show that treatment of graphene with xenon difluoride produces a partially fluorinated graphene (fluorographene) with covalent C-F bonding and local sp(3)-carbon hybridization. The material was characterized by Fourier transform infrared spectroscopy, Raman spectroscopy, electron energy loss spectroscopy, photoluminescence spectroscopy, and near edge X-ray absorption spectroscopy. These results confirm the structural features of the fluorographane with a bandgap of 3.8 eV, close to that calculated for fluorinated single layer graphene, (CF)(n). The material luminesces broadly in the UV and visible light regions, and has optical properties resembling diamond, with both excitonic and direct optical absorption and emission features. These results suggest the use of fluorographane as a new, readily prepared material for electronic, optoelectronic applications, and energy harvesting applications.

Giant spin splitting through surface alloying.

The long-range ordered surface alloy Bi/Ag(111) is found to exhibit a giant spin splitting of its surface electronic structure due to spin-orbit coupling, as is determined by angle-resolved photoelectron spectroscopy. First-principles electronic structure calculations fully confirm the experimental findings. The effect is brought about by a strong in-plane gradient of the crystal potential in the surface layer, in interplay with the structural asymmetry due to the surface-potential barrier. As a result, the spin polarization of the surface states is considerably rotated out of the surface plane.