Photoemission Measurements Research Articles

Development of a laser-based angle-resolved-photoemission spectrometer with sub-micrometer spatial resolution and high-efficiency spin detection.

Angle-resolved photoemission spectroscopy with sub-micrometer spatial resolution (μ-ARPES), has become a powerful tool for studying quantum materials. To achieve sub-micrometer or even nanometer-scale spatial resolution, it is important to focus the incident light beam (usually from synchrotron radiation) using x-ray optics, such as the zone plate or ellipsoidal capillary mirrors. Recently, we developed a laser-based μ-ARPES with spin-resolution (LMS-ARPES). The 177nm laser beam is achieved by frequency-doubling a 355nm beam using a KBBF crystal and subsequently focused using an optical lens with a focal length of about 16mm. By characterizing the focused spot size using different methods and performing spatial-scanning photoemission measurement, we confirm the sub-micron spatial resolution of the system. Compared with the μ-ARPES facilities based on the synchrotron radiation, our LMS-ARPES system is not only more economical and convenient, but also with higher photon flux (>5 × 1013 photons/s), thus enabling the high-resolution and high-statistics measurements. Moreover, the system is equipped with a two-dimensional spin detector based on exchange scattering at a surface-passivated iron film grown on a W(100) substrate. We investigate the spin structure of the prototype topological insulator Bi2Se3 and reveal a high spin-polarization rate, confirming its spin-momentum locking property. This lab-based LMS-ARPES will be a powerful research tool for studying the local fine electronic structures of different condensed matter systems, including topological quantum materials, mesoscopic materials and structures, and phase-separated materials.

Observation of spin-polarized surface states in the nodal-line semimetal SnTaS2

The superconductor ${\mathrm{SnTaS}}_{2}$ is theoretically predicted to be an intriguing topological nodal line semimetal without consideration of spin-orbit coupling. By carrying out angle-resolved photoemission (ARPES) and spin-resolved ARPES measurements combined with band structure calculations, we have provided a complete picture of the electronic structure and spin polarization property for the prominent surface states of ${\mathrm{SnTaS}}_{2}$. The low-energy electronic states are dominated by surface states; two of them are from the S-terminated surface, while four of them are from the Sn-terminated surface. These give rise to interesting Fermi surface topology of ${\mathrm{SnTaS}}_{2}$: three pockets located at $\overline{\mathrm{\ensuremath{\Gamma}}}, \overline{M}$ and $\overline{K}$ for the S-terminated surface and two pockets surrounding $\overline{\mathrm{\ensuremath{\Gamma}}}$ and $\overline{K}$ for the Sn-terminated surface. We further reveal that two surface states that cross the Fermi level are spin-polarized. Since ${\mathrm{SnTaS}}_{2}$ is also a superconductor, our observations indicate that it may provide a new platform to explore topological superconductivity and other exotic properties.

Evidence of symmetry breaking in a Gd2 di-nuclear molecular polymer.

A chiral 3D coordination compound, [Gd2(L)2(ox)2(H2O)2], arranged around a dinuclear Gd unit has been characterized by X-ray photoemission and X-ray absorption measurements in the context of density functional theory studies. Core level photoemission of the Gd 5p multiplet splittings indicates that spin orbit coupling dominates over j-J coupling evident in the 5p core level spectra of Gd metal. Indications of spin-orbit coupling are consistent with the absence of inversion symmetry due to the ligand field. Density functional theory predicts antiferromagnet alignment of the Gd2 dimers and a band gap of the compound consistent with optical absorption.

Insight into the electronic structure of the centrosymmetric skyrmion magnet GdRu2Si2.

The discovery of a square magnetic-skyrmion lattice in GdRu2Si2, with the smallest so far found skyrmion size and without a geometrically frustrated lattice, has attracted significant attention. In this work, we present a comprehensive study of surface and bulk electronic structures of GdRu2Si2 by utilizing momentum-resolved photoemission (ARPES) measurements and first-principles calculations. We show how the electronic structure evolves during the antiferromagnetic transition when a peculiar helical order of 4f magnetic moments within the Gd layers sets in. A nice agreement of the ARPES-derived electronic structure with the calculated one has allowed us to characterize the features of the Fermi surface (FS), unveil the nested region along kz at the corner of the 3D FS, and reveal their orbital compositions. Our findings suggest that the Ruderman-Kittel-Kasuya-Yosida interaction plays a decisive role in stabilizing the spiral-like order of Gd 4f moments responsible for the skyrmion physics in GdRu2Si2. Our results provide a deeper understanding of electronic and magnetic properties of this material, which is crucial for predicting and developing novel skyrmion-based systems.

Surface doping of rubrene single crystals by molecular electron donors and acceptors.

The surface molecular doping of organic semiconductors can play an important role in the development of organic electronic or optoelectronic devices. Single-crystal rubrene remains a leading molecular candidate for applications in electronics due to its high hole mobility. In parallel, intensive research into the fabrication of flexible organic electronics requires the careful design of functional interfaces to enable optimal device characteristics. To this end, the present work seeks to understand the effect of surface molecular doping on the electronic band structure of rubrene single crystals. Our angle-resolved photoemission measurements reveal that the Fermi level moves in the band gap of rubrene depending on the direction of surface electron-transfer reactions with the molecular dopants, yet the valence band dispersion remains essentially unperturbed. This indicates that surface electron-transfer doping of a molecular single crystal can effectively modify the near-surface charge density, while retaining good charge-carrier mobility.

High p doped and robust band structure in Mg-doped hexagonal boron nitride.

In two dimensional materials, substitutional doping during growth can be used to alter the electronic properties. Here, we report on the stable growth of p-type hexagonal boron nitride (h-BN) using Mg-atoms as substitutional impurities in the h-BN honeycomb lattice. We use micro-Raman spectroscopy, angle-resolved photoemission measurements (nano-ARPES) and Kelvin probe force microscopy (KPFM) to study the electronic properties of Mg-doped h-BN grown by solidification from a ternary Mg-B-N system. Besides the observation of a new Raman line at ∼1347 cm-1 in Mg-doped h-BN, nano-ARPES reveals p-type carrier concentration. Our nano-ARPES experiments demonstrate that the Mg dopants can significantly alter the electronic properties of h-BN by shifting the valence band maximum about 150 meV toward higher binding energies with respect to pristine h-BN. We further show that, Mg doped h-BN exhibits a robust, almost unaltered, band structure compared to pristine h-BN, with no significant deformation. Kelvin probe force microscopy (KPFM) confirms the p-type doping, with a reduced Fermi level difference between pristine and Mg-doped h-BN crystals. Our findings demonstrate that conventional semiconductor doping by Mg as substitutional impurities is a promising route to high-quality p-type doped h-BN films. Such stable p-type doping of large band h-BN is a key feature for 2D materials applications in deep ultra-violet light emitting diodes or wide bandgap optoelectronic devices.

Inside a nanocrystal-based photodiode using photoemission microscopy.

As nanocrystal-based devices gain maturity, a comprehensive understanding of their electronic structure is necessary for further optimization. Most spectroscopic techniques typically examine pristine materials and disregard the coupling of the active material to its actual environment, the influence of an applied electric field, and possible illumination effects. Therefore, it is critical to develop tools that can probe device in situ and operando. Here, we explore photoemission microscopy as a tool to unveil the energy landscape of a HgTe NC-based photodiode. We propose a planar diode stack to facilitate surface-sensitive photoemission measurements. We demonstrate that the method gives direct quantification of the diode's built-in voltage. Furthermore, we discuss how it is affected by particle size and illumination. We show that combining SnO2 and Ag2Te as electron and hole transport layers is better suited for extended-short-wave infrared materials than materials with larger bandgaps. We also identify the effect of photodoping over the SnO2 layer and propose a strategy to overcome it. Given its simplicity, the method appears to be of utmost interest for screening diode design strategies.

Extremely Shallow Valence Band in Lanthanum Trihydride.

Hydride ions (H-) in solvents are chemically active anions with strong electron-donating ability and are used as reducing agents in organic chemistry. Here, we evaluate the energy level of 1s-electrons in H- accommodated in solid lanthanum hydrides, LaHx (2 ≤ x ≤ 3), by photoemission (ultraviolet photoelectron and photoelectron yield spectroscopies) measurements and density functional theory calculations. We show that a very shallow valance band maximum with an ionization potential of 3.8 eV is attained in LaH3 and that the primary cause is attributed to the small electronegativity of hydrogen and the significant bonding-antibonding interaction between neighboring H-s with a close separation originating from the H-stuffed fluorite-related structure. These results encourage the challenge for p-type conduction in hydride semiconductors and provide a clue to the chemical understanding of polyhydride superconductors.

Tailoring the Optical and Electronic Properties of 2D Hybrid Dion–Jacobson Copper Chloride Perovskites

The upsurge of low-dimensional Dion–Jacobson (DJ) phase perovskites has brought significant interest in view of their appealing stability against harsh environmental conditions as well as their promising performance in optoelectronic applications. Few reports to date have concentrated on the fundamental relationship of fine-tuning the control of diamine-based perovskite single crystals toward their electronic properties and optical behaviors. Here, we demonstrate that cationic control is proposed to regulate the role of hydrogen bonding of organic ligands with the edge-sharing [CuCl6]4– octahedral layers, leading to strong differences in the material excitonic profile and tunability of their electronic properties. Interestingly, we observe a significant reduction of photoluminescence intensity upon controlling the Cu2+/Cu+ proportion in this hybrid system. According to the photoemission measurements, variation in the oxidation states of Cu cations plays a crucial role in stabilizing the diammonium-based perovskite geometric structure. Interestingly, we find that the electronic signatures of the singlet spin-state and high-energy region transition are not influenced by the thermal effect, as probed by temperature-dependent X-ray absorption spectroscopy (XAS) at elevated temperature. Density functional calculations suggest that such an electronic difference originates from the hydrogen bonding reduction that altered the magnitude of the octahedral distortion within the DJ layered structure. As a result, the 3+NHC4H9NH3+ conformation produces a non-negligible interaction toward tuning the optical and electronic properties of DJ copper-based perovskites.

Structure and electronic properties of stable facets in the 2D material hexagonal boron nitride (hBN) on curved platinum

<h2>Abstract</h2> A hexagonal boron nitride (hBN) monolayer was grown on a curved crystal c-Pt(331) substrate including all vicinal surfaces between Pt(111) and Pt(110) faces. The surface structure has been studied by a combination of low-energy electron diffraction (LEED) and scanning tunnelling microscopy (STM). We observed that the hBN monolayer covers the entire curved crystal, but induces a faceting subsequent to the growth. We encountered (111), (221), (441), (991), and (110) as stable facets. We assign this faceting to two factors i) a better lattice coincidence and ii) the existence of local covalent bonds and non-local Van der Waals interactions. The electronic structure was characterized by near-edge x-ray absorption fine structure (NEXAFS), X-ray photoemission spectroscopy and angle-resolved photoemission spectroscopy (ARPES). The hBN/Pt(111) has the weakest interacting overlayer system, while the hBN on vicinal surfaces is more strongly bound to the Pt substrate. Additionally, we determined using angle-resolved photoemission measurements (ARPES) that the π band shifts downward when going away from the hBN/Pt(111) surface towards hBN/Pt(110). In the latter case, the π band shift is the largest.

Fine details of sixfold Dirac fermions in pyrite-structured PdSb2

We report detailed angle-resolved photoemission measurements on the electronic structure of an unconventional multifold Dirac fermionic semimetal ${\mathrm{PdSb}}_{2}$ with a pyrite structure. By exploiting the photon energy and polarization dependence of the matrix element in photoemission intensity and by comparing photoemission data with ab initio band calculations, we experimentally identify the exact electronic structure, including the orbital characters of the electron pockets at the $R$ point in the Brillouin zone of ${\mathrm{PdSb}}_{2}$. Each electron pocket and hole-pocket-like structure consists of three doubly degenerate parabolic bands, respectively, which cross one another at the $R$ point, forming a sixfold Dirac fermion. The overall electronic structure is consistent with the band calculations, but the gap size between two sextuple points is very sensitive to the Wyckoff position of Sb atoms, which is a result of the competition between the band energies and crystal symmetries.

Polarization dependent photoemission as a probe of the magnetic ground state in the van der Waals ferromagnet VI3

Van der Waals ferromagnets are thrilling materials from both a fundamental and technological point of view. VI3 is an interesting example, with a complex magnetism that differentiates it from the first reported Cr based layered ferromagnets. Here, we show in an indirect way through angle resolved photoemission spectroscopy experiments, the importance of spin–orbit coupling setting the electronic properties of this material. Our light polarized photoemission measurements point to a ground state with a half-filled e±′ doublet, where a gap opening is triggered by spin–orbit coupling enhanced by electronic correlations.

Fermi surface of LaSb2 and direct observation of a CDW transition

We have studied the temperature-dependent electronic structure of the light rare-earth antimonide LaSb2 by combining angle-resolved photoemission (ARPES) measurements and density functional theory (DFT) calculations. ARPES measurements show the appearance of band replicas in the low-temperature Fermi surface with q = 0.25 ± 0.02 A−1 and a band folding of the same periodicity with a considerable spectral weight in the folded band. From our calculations we elucidate that the folded band exhibiting the new periodicity is associated with the La-Sb layer. We propose that an in-plane distortion, probably affecting the whole unit cell, is the structural modification related to the electronic changes. All these results converge to support that a charge density wave is stabilized in LaSb2 at low temperature.

Quasiparticle characteristics of the weakly ferromagnetic Hund metal MnSi

Hund's metals are multi-orbital systems with $3d$ or $4d$ electrons exhibiting both itinerant character and local moments, and they feature Kondo-like screenings of local orbital and spin moments, with suppressed coherence temperature driven by Hund's coupling $J_H$. They often exhibit magnetic order at low temperature, but how the interaction between the Kondo-like screening and long-range magnetic order is manifested in the quasiparticle spectrum remains an open question. Here we present spectroscopic signature of such interaction in a Hund's metal candidate MnSi exhibiting weak ferromagnetism. Our photoemission measurements reveal renormalized quasiparticle bands near the Fermi level with strong momentum dependence: the ferromagnetism manifests through possibly exchange-split bands (Q1) below $T_C$ , while the spin/orbital screenings lead to gradual development of quasiparticles (Q2) upon cooling. Our results demonstrate how the characteristic spin/orbital coherence in a Hund's metal could coexist and compete with the magnetic order to form a weak itinerant ferromagnet, via quasiparticle bands that are well separated in momentum space and exhibit distinct temperature dependence. Our results imply that the competition between the spin/orbital screening and the magnetic order in a Hund's metal bears intriguing similarity to the Kondo lattice systems.

Crystal electric field and properties of 4f magnetic moments at the surface of the rare-earth compound TbRh2Si2

By means of 4$f$ photoemission measurements and first-principles calculations, the authors demonstrate here how the crystal electric field (CEF) and related magnetic properties can be modified at the surface of rare-earth materials. For TbRh${}_{2}$Si${}_{2}$, CEF at the Tb surface makes the 4$f$ moments orthogonal to those in the bulk. For the Tb layer below the Si termination, the temperature-dependent photoemission data reveal larger CEF splitting relative to the bulk. The methodology used here can facilitate unveiling of the surface magnetic properties of layered 4$f$ systems.

Uniaxial ferromagnetism in the kagome metal TbV6Sn6

The synthesis and characterization of the vanadium-based kagome metal TbV${_6}$Sn${_6}$ is presented. X-ray measurements confirm this material forms with the same crystal structure type as the recently investigated kagome metals GdV$_6$Sn$_6$ and YV$_6$Sn$_6$, with space group symmetry P6/mmm. A signature of a phase transition at 4.1K is observed in heat capacity, resistivity, and magnetic susceptibility measurements, and both resistivity and magnetization measurements exhibit hysteresis in magnetic field. Furthermore, a strikingly large anisotropy in the magnetic susceptibility was observed, with the c-axis susceptibility nearly 100 times the ab plane susceptibility at 2K. This is highly suggestive of uniaxial ferromagnetism, and the large size of 9.4$\mu_b$/f.u. indicates the Tb$^{3+}$ $4f$ electronic moments cooperatively align perpendicular to the V kagome lattice plane. The entropy at the phase transition is nearly Rln(2), indicating that the CEF ground state of the Tb$^{3+}$ ion is a doublet, and therefore the sublattice of $4f$ electrons in this material can be shown to map at low temperatures to the Ising model in a D$_{6h}$ symmetry environment. Hall measurements at temperatures from 300K to 1.7K can be described by two-band carrier transport at temperatures below around 150K, with a large increase in both hole and electron mobilities, similar to YV$_6$Sn$_6$, and an anomalous Hall effect is seen below the ordering temperature. Angle-resolved photoemission measurements above the magnetic ordering temperature reveal typical kagome dispersions. Our study presents TbV${_6}$Sn${_6}$ as an ideal system to study the interplay between Ising ferromagnetism and non-trivial electronic states emerging from a kagome lattice.

Giant and reversible electronic structure evolution in a magnetic topological material EuCd2As2

The electronic structure and the physical properties of quantum materials can be significantly altered by charge carrier doping and magnetic state transition. Here we report a discovery of a giant and reversible electronic structure evolution with doping in a magnetic topological material. By performing high-resolution angle-resolved photoemission measurements on EuCd2As2,we found that a huge amount of hole doping can be introduced into the sample surface due to surface absorption. The electronic structure exhibits a dramatic change with the hole doping which can not be described by a rigid band shift. Prominent band splitting is observed at high doping which corresponds to a doping-induced magnetic transition at low temperature (below -15 K) from an antiferromagnetic state to a ferromagnetic state. These results have established a detailed electronic phase diagram of EuCd2As2 where the electronic structure and the magnetic structure change systematically and dramatically with the doping level. They further suggest that the transport, magnetic and topological properties of EuCd2As2 can be greatly modified by doping. These work will stimulate further investigations to explore for new phenomena and properties in doping this magnetic topological material.

A Novel 19$\sqrt {19} $ × 19$\sqrt {19} $ Superstructure in Epitaxially Grown 1T‐TaTe2

The spontaneous formation of electronic orders is a crucial element for understanding complex quantum states and engineering heterostructures in 2D materials. A novel × charge order in few-layer-thick 1T-TaTe2 transition metal dichalcogenide films grown by molecular beam epitaxy, which has not been realized, is report. The photoemission and scanning probe measurements demonstrate that monolayer 1T-TaTe2 exhibits a variety of metastable charge density wave orders, including the × superstructure, which can be selectively stabilized by controlling the post-growth annealing temperature. Moreover, it is found that only the × order persists in 1T-TaTe2 films thicker than a monolayer, up to 8 layers. The findings identify the previously unrealized novel electronic order in a much-studied transition metal dichalcogenide and provide a viable route to control it within the epitaxial growth process.

CsCu2I3 Nanoparticles Incorporated within a Mesoporous Metal-Organic Porphyrin Framework as a Catalyst for One-Pot Click Cycloaddition and Oxidation/Knoevenagel Tandem Reaction.

Metal-organic frameworks (MOFs) and metal halide perovskites are currently under much investigation due to their unique properties and applications. Herein, an innovative strategy has been developed combining an iron-porphyrin MOF, PCN-222(Fe), and an in situ-grown CsCu2I3 nontoxic lead-free halide perovskite based on an earth-abundant metal that becomes incorporated within the MOF channels [CsCu2I3@PCN-222(Fe)]. Encapsulation was designed to decrease and control the particle size and increase the stability of CsCu2I3. The hybrid materials were characterized by various techniques including FE-SEM, elemental mapping and line scanning EDX, TEM, PXRD, UV-Vis DRS, BET surface area, XPS, and photoemission measurements. Hybrid CsCu2I3@PCN-222(Fe) materials were examined as heterogeneous multifunctional (photo)catalysts for copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) and one-pot selective photo-oxidation/Knoevenagel condensation cascade reaction. Interestingly, CsCu2I3@PCN-222(Fe) outperforms not only its individual components CsCu2I3 and PCN-222(Fe) but also other reported (photo)catalysts for these transformations. This is attributed to cooperation and synergistic effects of the PCN-222(Fe) host and CsCu2I3 nanocrystals. To understand the catalytic and photocatalytic mechanisms, control and inhibition experiments, electron paramagnetic resonance (EPR) measurements, and time-resolved phosphorescence were performed, revealing the main role of active species of Cu(I) in the click reaction and the superoxide ion (O2•-) and singlet oxygen (1O2) in the photocatalytic reaction.

Mott versus Hybridization Gap in the Low-Temperature Phase of 1T-TaS_{2}.

We address the long-standing problem of the ground state of 1T-TaS_{2} by computing the correlated electronic structure of stacked bilayers using the GW+EDMFT method. Depending on the surface termination, the semi-infinite uncorrelated system is either band insulating or exhibits a metallic surface state. For realistic values of the on-site and inter-site interactions, a Mott gap opens in the surface state, but it is smaller than the gap originating from the bilayer structure. Our results are consistent with recent scanning tunneling spectroscopy measurements for different terminating layers, and with our own photoemission measurements, which indicate the coexistence of spatial regions with different gaps in the electronic spectrum. By comparison to exact diagonalization data, we clarify the interplay between Mott insulating and band insulating behavior in this archetypal layered system.