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By adjusting the incidence angle of incoming X-ray near the critical angle of X-ray total reflection, the photoelectron intensity is strongly modulated due to the variation of X-ray penetration depth. Photoelectron spectroscopy (PES) combining with near total reflection (NTR) exhibit tunable surface sensitivity, providing depth-resolved information. In this review article, we first describe the experimental setup and specific data analysis process. We then review three different examples which show the broad application of this method. The emphasis is on its applications to correlated oxide heterostructures, especially quantitative depth analyses of compositions and electronic states. In a last part, we discussed the limitations of this technique, mostly in terms of range of samples which can be studied., Comment: 28 pages, 5 figures, review paper on NTR HAXPES

One way to induce insulator to metal transitions in the spin-orbit Mott insulator Sr2IrO4 is to substitute iridium with transition metals (Ru, Rh). However, this creates intriguing inhomogeneous metallic states, which cannot be described by a simple doping effect. We detail the electronic structure of the Ru-doped case with angle-resolved photoemission and show that, contrary to Rh, it cannot be connected to the undoped case by a rigid shift. We further identify bands below $E_F$ coexisting with the metallic ones that we assign to non-bonding Ir sites. We rationalize the differences between Rh and Ru by a different hybridization with oxygen, which mediates the coupling to Ir and sensitively affects the effective doping. We argue that the spin-orbit coupling does not control neither the charge transfer nor the transition threshold.

Sr2IrO4 is characterized by a large spin-orbit coupling, which gives rise to bands with strongly entangled spin and orbital characters, called J=1/2 and J=3/2. We use light-polarization dependent ARPES to study directly the orbital character of these bands and fully map out their dispersion. We observe bands in very good agreement with our cluster dynamical mean-field theory calculations. We show that the J=1/2 band, the closest to the Fermi level Ef, is dominated by dxz character along kx and dyz along ky. This is actually in agreement with an isotropic J=1/2 character on average, but this large orbital dependence in k-space was mostly overlooked before. It gives rise to strong modulations of the ARPES intensity that we explain and carefully take into account to compare dispersions in equivalent directions of the Brillouin zone. Although the latter dispersions look different at first, suggesting possible symmetry breakings, they are found essentially similar, once corrected for these intensity variations. In particular, the pseudogap-like features close to the $X$ point appearing in the nearly metallic 15% Rh-doped Sr2IrO4 strongly depend on experimental conditions. We reveal that there is nevertheless an energy scale of 30meV below which spectral weight is suppressed, independent of the experimental conditions, which gives a reliable basis to analyze this behavior. We suggest it is caused by disorder.

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

We report on the controlled growth of h-BN/graphite by means of molecular beam epitaxy (MBE). X-ray photoelectron spectroscopy (XPS) suggests an interface without any reaction or intermixing, while the angle resolved photoemission spectroscopy (ARPES) measurements show that the h-BN layers are epitaxially aligned with graphite. A well-defined band structure is revealed by ARPES measurement, reflecting the high quality of the h-BN films. The measured valence band maximum (VBM) located at 2.8 eV below the Fermi level reveals the presence of undoped h-BN films (band gap ~ 6 eV). These results demonstrate that, although only weak van der Waals interactions are present between h-BN and graphite, a long range ordering of h-BN can be obtained even on polycrystalline graphite via van der Waals epitaxy, offering the prospect of large area, single layer h-BN., Comment: 9 pages, 4 figures SI 5 pages 2 figures

Combining single-layer two-dimensional semiconducting transition metal dichalcogenides (TMDs) with graphene layer in van der Waals heterostructures offers an intriguing means of controlling the electronic properties through these heterostructures. Here, we report the electronic and structural properties of transferred single layer WS2 on epitaxial graphene using micro-Raman spectroscopy, angle-resolved photoemission spectroscopy measurements (ARPES) and Density Functional Theory (DFT) calculations. The results show good electronic properties as well as well-defined band arising from the strong splitting of the single layer WS2 valence band at K points, with a maximum splitting of 0.44 eV. By comparing our DFT results with local and hybrid functionals, we find the top valence band of the experimental heterostructure is close to the calculations for suspended single layer WS2. . Our results provide an important reference for future studies of electronic properties of WS2 and its applications in valleytronic devices., Comment: 11 pages, 3 figures + SI 7 pages 8 figures

We have studied the chemical and electronic properties of LaAlO3/SrVO3 ultrathin films by combining hard x-ray photoemission spectroscopy and transport measurements. We compare single SrVO3 (SVO) ultrathin films and SrVO3 buried below a polar LaAlO3 (LAO) thin layer, both epitaxially grown on SrTiO3. While ultrathin films (4 unit cells) of SVO do show insulating behavior over the entire temperature range, the LAO/SVO interface has a resistivity minimum at 250 K. When increasing the SVO layer thickness, the minimum is observed to shift to higher temperatures, but the resistivity stays always smaller than that of comparable SVO single films. Hard x-ray photoemission spectroscopy reveals a surface or interface related V5+ component in the V 2p spectra for SVO films and LAO/SVO heterostructures, respectively, attributed to a strongly oxidized component. This chemical reconstruction is weaker in LAO/SVO heterostructures compared to single SVO films. We show that this dead layer in SVO ultrathin films has to be considered when the film thickness reaches the few unit-cells limit and propose solutions on how to prevent this detrimental effect., Comment: 15 pages, 4 figures + SI 2 pages, 1 figure

Hybrid heterostructures based on bulk GaN and two-dimensional (2D) materials offer novel paths toward nanoelectronic devices with engineered features. Here, we study the electronic properties of a mixed-dimensional heterostructure composed of intrinsic n-doped MoS2 flakes transferred on p-doped GaN(0001) layers. Based on angle-resolved photoemission spectroscopy (ARPES) and high resolution X-ray photoemission spectroscopy (HR-XPS), we investigate the electronic structure modification induced by the interlayer interactions in MoS2/GaN heterostructure. In particular, a shift of the valence band with respect to the Fermi level for MoS2/GaN heterostructure is observed; which is the signature of a charge transfer from the 2D monolayer MoS2 to GaN. ARPES and HR-XPS revealed an interface dipole associated with local charge transfer from the GaN layer to the MoS2 monolayer. Valence and conduction band offsets between MoS2 and GaN are determined to be 0.77 and -0.51 eV, respectively. Based on the measured work functions and band bendings, we establish the formation of an interface dipole between GaN and MoS2 of 0.2 eV., Comment: 13 pages, 5 figures + SI 2 pages, 2 figures

Structural defects in the molybdenum disulfide (MoS2) monolayer are widely known for strongly altering its properties. Therefore, a deep understanding of these structural defects and how they affect MoS2 electronic properties is of fundamental importance. Here, we report on the incorporation of atomic hydrogen in mono-layered MoS2 to tune its structural defects. We demonstrate that the electronic properties of single layer MoS2 can be tuned from the intrinsic electron (n) to hole (p) doping via controlled exposure to atomic hydrogen at room temperature. Moreover, this hydrogenation process represents a viable technique to completely saturate the sulfur vacancies present in the MoS2 flakes. The successful incorporation of hydrogen in MoS2 leads to the modification of the electronic properties as evidenced by high resolution X-ray photoemission spectroscopy and density functional theory calculations. Micro-Raman spectroscopy and angle resolved photoemission spectroscopy measurements show the high quality of the hydrogenated MoS2 confirming the efficiency of our hydrogenation process. These results demonstrate that the MoS2 hydrogenation could be a significant and efficient way to achieve tunable doping of transition metal dichalcogenides (TMD) materials with non-TMD elements., Comment: 15 pages, 6 figures + SI 3 pages 3 figures. Pre-print published with the authorization of ACS Publications

LaCrO$_3$ (LCO) / SrTiO$_3$ (STO) heterojunctions are intriguing due to a polar discontinuity along (001), two distinct and controllable interface structures [(LaO)$^+$/(TiO$_2$)$^0$ and (SrO)$^0$/(CrO$_2$)$^-$], and interface-induced polarization. In this study, we have used soft- and hard x-ray standing-wave excited photoemission spectroscopy (SW-XPS) to generate a quantitative determination of the elemental depth profiles and interface properties, band alignments, and the depth distribution of the interface-induced built-in potentials in the two constituent oxides. We observe an alternating charged interface configuration: a positively charged (LaO)$^+$/(TiO$_2$)$^0$ intermediate layer at the LCO$_\textbf{top}$/STO$_\textbf{bottom}$ interface and a negatively charged (SrO)$^0$/(CrO$_2$)$^-$ intermediate layer at the STO$_\textbf{top}$/LCO$_\textbf{bottom}$ interface. Using core-level SW data, we have determined the depth distribution of species, including through the interfaces, and these results are in excellent agreement with scanning transmission electron microscopy and electron energy loss spectroscopy (STEM-EELS) mapping of local structure and composition. SW-XPS also enabled deconvolution of the LCO-contributed and STO- contributed matrix-element-weighted density of states (MEWDOSs) from the valence band (VB) spectra for the LCO/STO superlattice (SL). Monitoring the VB edges of the deconvoluted MEWDOS shifts with a change in probing profile, the alternating charge- induced built-in potentials are observed in both constituent oxides. Finally, using a two-step simulation approach involving first core-level binding energy shifts and then valence-band modeling, the built-in potential gradients across the SL are resolved in detail and represented by the depth distribution of VB edges., Comment: Main text: 29 pages, 5 figures; Supplementary Information: 20 pages, 10 figures

A major remaining challenge in the superconducting cuprates is the unambiguous differentiation of the composition and electronic structure of the CuO$_2$ layers and those of the intermediate layers. The large c axis for these materials permits employing soft x-ray (930.3 eV) standing wave (SW) excitation in photoemission that yields atomic layer-by-atomic layer depth resolution of these properties. Applying SW photoemission to Bi$_2$Sr$_2$CaCu$_2$O$_{8+\delta}$ yields the depth distribution of atomic composition and the layer-resolved densities of states. We detect significant Ca presence in the SrO layers and oxygen bonding to three different cations. The layer-resolved valence electronic structure is found to be strongly influenced by the supermodulation structure--as determined by comparison to DFT calculations, by Ca-Sr intermixing, and by the Cu 3d-3d Coulomb interaction, further clarifying the complex interactions in this prototypical cuprate. Measurements of this type for other quasi-two-dimensional materials with large-c represent a promising future direction., Comment: 22 pages, 5 figures, plus Supplemental Material (15 pages)

We have investigated the electronic structure of the dilute magnetic semiconductor (DMS) $Ga_{0.98}Mn_{0.02}P$ and compared it to that of an undoped $GaP$ reference sample, using hard X-ray photoelectron spectroscopy (HXPS) and hard X-ray angle-resolved photoemission spectroscopy (HARPES) at energies of about 3 keV. We present experimental data, as well as theoretical calculations, in order to understand the role of the Mn dopant in the emergence of ferromagnetism in this material. Both core-level spectra and angle-resolved or angle-integrated valence spectra are discussed. In particular, the HARPES experimental data are compared to free-electron final-state model calculations and to more accurate one-step photoemission theory. The experimental results show differences between $Ga_{0.98}Mn_{0.02}P$ and $GaP$ in both angle-resolved and angle-integrated valence spectra. The $Ga_{0.98}Mn_{0.02}P$ bands are broadened due to the presence of Mn impurities that disturb the long-range translational order of the host $GaP$ crystal. Mn-induced changes of the electronic structure are observed over the entire valence band range, including the presence of a distinct impurity band close to the valence-band maximum of the DMS. These experimental results are in good agreement with the one-step photoemission calculations, and a prior HARPES study of $Ga_{0.97}Mn_{0.03}As$ and $GaAs$ (Gray et al. Nature Materials 11, 957 (2012)), demonstrating the strong similarity between these two materials. The Mn 2p and 3s core-level spectra also reveal an essentially identical state in doping both $GaAs$ and $GaP$., Comment: 37 pages (double spaced) 10 figures

It has recently been proposed that electronic band structures in crystals give rise to a previously overlooked type of Weyl fermion, which violates Lorentz invariance and, consequently, is forbidden in particle physics. It was further predicted that Mo$_x$W$_{1-x}$Te$_2$ may realize such a Type II Weyl fermion. One crucial challenge is that the Weyl points in Mo$_x$W$_{1-x}$Te$_2$ are predicted to lie above the Fermi level. Here, by studying a simple model for a Type II Weyl cone, we clarify the importance of accessing the unoccupied band structure to demonstrate that Mo$_x$W$_{1-x}$Te$_2$ is a Weyl semimetal. Then, we use pump-probe angle-resolved photoemission spectroscopy (pump-probe ARPES) to directly observe the unoccupied band structure of Mo$_x$W$_{1-x}$Te$_2$. For the first time, we directly access states $> 0.2$ eV above the Fermi level. By comparing our results with $\textit{ab initio}$ calculations, we conclude that we directly observe the surface state containing the topological Fermi arc. Our work opens the way to studying the unoccupied band structure as well as the time-domain relaxation dynamics of Mo$_x$W$_{1-x}$Te$_2$ and related transition metal dichalcogenides., Comment: Incorporates earlier results presented in arXiv:1512.09099, by the same authors