通过掺杂对二维（2D）材料的电子能带结构进行可控调制，对器件制造至关重要。例如，掺杂石墨烯已被设想用于传感器、超级电容器、晶体管、p-n 结、光电探测器等多种应用。目前已发展出许多不同技术来在二维材料中实现所需掺杂，如化学掺杂、静电掺杂、衬底掺杂等。在本研究中，我们将空间电荷掺杂与空间和角分辨光电子能谱（nano-ARPES）相结合，以直接观察微米尺寸单层和双层石墨烯薄片上的费米能级调制。掺杂水平可以受控方式调节，这使我们能够直接观察费米能级调谐。在实验中，我们成功地用 p 型和 n 型载流子（空穴/电子）对石墨烯进行掺杂，并通过 ARPES 测量中的能带移动直接观察到这些载流子。双层石墨烯观察到的能带移动约为 250 meV，单层石墨烯约为 500 meV。我们的实验结果推动了空间电荷掺杂技术和 nano-ARPES 应用于二维半导体和超导体等其他材料，从而直接观察带隙转变和相变等随载流子掺杂变化的物理现象。
英文摘要：
Controlled modulation of electronic band structure in two-dimensional (2D) materials via doping is crucial for devices fabrication. For instance doped graphene has been envisaged for various applications like sensors, super-capacitors, transistors, p-n junctions, photo-detectors, etc. Many different techniques have been developed to achieve desired doping in 2D materials, like chemical doping, electrostatic doping, substrate doping, etc. Here, we have combined space charge doping with space and angle resolved photoemission (nano-ARPES), in order to directly observe the Fermi level modulation on micron-sized flakes of monolayer and bilayer graphene. The doping level can be tuned in a controlled manner, which allows us to directly observe the Fermi level tuning. In our experiment we successfully doped the graphene with p- and n-type carriers (holes/electrons) which are directly observed through band shift in ARPES measurements. The observed band shift is $\sim$250 meV for bilayer and $\sim$500 meV for monolayer graphene. The results from our experiment promote the space charge doping technique and nano-ARPES into other materials such as 2D semiconductors and superconductors, in order to directly observe the physical phenomena such as band gap transition and phase transition as function of carrier doping.
We have performed scanning angle-resolved photoemission spectroscopy with a nanometer-sized beam spot (nano-ARPES) on the cleaved surface of Pb5Bi24Se41, which is a member of the (PbSe)5(Bi2Se3)3m homologous series (PSBS) with m = 4 consisting of alternate stacking of the topologically-trivial insulator PbSe bilayer and four quintuple layers (QLs) of the topological insulator Bi2Se3. This allows us to visualize a mosaic of topological Dirac states at a nanometer scale coming from the variable thickness of the Bi2Se3 nano-islands (1-3 QLs) that remain on top of the PbSe layer after cleaving the…
The structural and electronic properties of thermally reduced SrTiO3(100) single crystals have been investigated using a probe with real- and reciprocal-space sensitivity: a synchrotron radiation microsopic setup which offers the possibility of Scanning Photoemission Microscopy and Angle Resolved Photoelectron Spectroscopy (ARPES) down to the nanometric scale. We have spectroscopically imaged the chemical composition of samples which present reproducible and suitable low-energy electron diffraction patterns after following well-established thermal reduction protocols. At the micrometric scale,…
Free-standing exfoliated monolayer graphene is an ultra-thin flexible membrane, which exhibits out of plane deformation or corrugation. In this paper, a technique is described to measure the band structure of such free-standing graphene by angle-resolved photoemission. Our results show that photoelectron coherence is limited by the crystal corrugation. However, by combining surface morphology measurements of the graphene roughness with angle-resolved photoemission, energy dependent quasiparticle lifetime and bandstructure measurements can be extracted. Our measurements rely on our development …
Two-dimensional crystals of semimetallic van der Waals materials hold much potential for the realization of novel phases, as exemplified by the recent discoveries of a polar metal in few layer 1T'-WTe$_2$ and of a quantum spin Hall state in monolayers of the same material. Understanding these phases is particularly challenging because little is known from experiment about the momentum space electronic structure of ultrathin crystals. Here, we report direct electronic structure measurements of exfoliated mono-, bi-, and few-layer 1T'-WTe$_2$ by laser-based micro-focus angle resolved photoemissi…
In van der Waals heterostructures, the periodic potential from the Moiré superlattice can be used as a control knob to modulate the electronic structure of the constituent materials. Here we present a nanoscale angle-resolved photoemission spectroscopy (Nano-ARPES) study of transferred graphene/h-BN heterostructures with two different stacking angles of 2.4° and 4.3° respectively. Our measurements reveal six replicas of graphene Dirac cones at the superlattice Brillouin zone (SBZ) centers. The size of the SBZ and its relative rotation angle to the graphene BZ are in good agreement with Moiré s…
Transport experiments in twisted bilayer graphene revealed multiple superconducting domes separated by correlated insulating states. These properties are generally associated with strongly correlated states in a flat mini-band of the hexagonal moiré superlattice as it was predicted by band structure calculations. Evidence for such a flat band comes from local tunneling spectroscopy and electronic compressibility measurements, reporting two or more sharp peaks in the density of states that may be associated with closely spaced van Hove singularities. Direct momentum resolved measurements proved…
We investigated the electronic structure of monolayer VTe2 grown on bilayer graphene by angle-resolved photoemission spectroscopy (ARPES). We found that monolayer VTe2 takes the octahedral 1T structure in contrast to the monoclinic one in the bulk, as evidenced by the good agreement in the Fermi-surface topology between ARPES results and first-principles band calculations for octahedral monolayer 1T-VTe2. We have revealed that monolayer 1T-VTe2 at low temperature is characterized by a metallic state whereas the nesting condition is better than that of isostructural monolayer VSe2 which undergo…
The crystallographic stacking order in multilayer graphene plays an important role in determining its electronic structure. In trilayer graphene, rhombohedral stacking (ABC) is particularly intriguing, exhibiting a flat band with an electric-field tunable band gap. Such electronic structure is distinct from simple hexagonal stacking (AAA) or typical Bernal stacking (ABA), and is promising for nanoscale electronics, optoelectronics applications. So far clean experimental electronic spectra on the first two stackings are missing because the samples are usually too small in size (um or nm scale) …
Altermagnetism, ARPES, symmetry, non-relativistic band splitting
Shanghai Institute of Microsystem and Information Technology, Chinese Academy of Sciences（中国科学院上海微系统与信息技术研究所）；University of Chinese Academy of Sciences（中国科学院大学）；National Synchrotron Radiation Laboratory and School of Nuclear Science and Technology, University of Science and Technology of China（中国科学技术大学核科学与技术学院及国家同步辐射实验室）；Shanghai Synchrotron Radiation Facility, Shanghai Advanced Research Institute（上海先进应用研究院上海同步辐射光源）
Atomically thin films of III-VI post-transition metal chalcogenides (InSe and GaSe) form an interesting class of two-dimensional semiconductor that feature strong variations of their band gap as a function of the number of layers in the crystal [1-4] and, specifically for InSe, an earlier predicted crossover from a direct gap in the bulk [5,6] to a weakly indirect band gap in monolayers and bilayers [7-11]. Here, we apply angle resolved photoemission spectroscopy with submicrometer spatial resolution ($μ$ARPES) to visualise the layer-dependent valence band structure of mechanically exfoliated …
Monolayer MX$_2$ (M = Mo, W; X = S, Se) has drawn much attention recently for its possible application possibilities for optoelectronics, spintronics, and valleytronics. Its exotic optical and electronic properties include a direct band gap, circular polarization dependent optical transitions, and valence band (VB) spin band splitting at the $K$ and $-K$ points. These properties can be described within a minimal model, called the massive Dirac fermion model for which the parameters need to be experimentally determined. We propose that the parameters can be obtained from angle resolved photoemi…
For solid-state materials, the electronic structure, E(k), is critical in determining a crystal's physical properties. By experimentally detecting the electronic structure, the fundamental physics can be revealed. Angle-resolved photoemission spectroscopy (ARPES) is a powerful technique for directly observing the electronic structure with energy- and momentum-resolved information. Over the past decades, major improvements in the energy and momentum resolution, alongside the extension of ARPES observables to spin (SpinARPES), micrometer or nanometer lateral dimensions (MicroARPES/NanoARPES), an…
Hexagonal boron nitride (hBN) is the supporting substrate of choice for two-dimensional material devices because it is atomically flat and chemically inert. However, due to the small size of mechanically exfoliated hBN flakes, electronic structure studies of 2D materials supported by hBN using angle-resolved photoemission spectroscopy (ARPES) are challenging. Here we investigate the electronic band structure of a Bernal-stacked bilayer graphene sheet on a hexagonal boron nitride (BLG/hBN) flake using nanospot ARPES (nanoARPES). By fitting high-resolution energy vs. momentum electronic band spe…
We present a novel theoretical approach to simulate spin, time and angular-resolved photoelectron spectroscopy (ARPES) from first principles that is applicable to surfaces, thin films, few layer systems, and low-dimensional nanostructures. The method is based on a general formulation in the framework of time-dependent density functional theory (TDDFT) to describe the real time-evolution of electrons escaping from a surface under the effect of any external (arbitrary) laser field. By extending the so called t-SURFF method to periodic systems one can calculate the final photoelectron spectrum by…
ARPES signatures of trions in van der Waals materials
Philipps-Universität Marburg（马尔堡菲利普斯大学）；mar.quest | Marburg Center for Quantum Materials and Sustainable Technologies（mar.quest | 马尔堡量子材料与可持续技术中心）；Stockholm University（斯德哥尔摩大学）；Georg-August-Universität Göttingen（格奥尔格·奥古斯特哥廷根大学）
The dynamics of photo-generated electron-hole pairs in solids are dictated by many-body interactions such as electron-electron and electron-phonon scattering. Hence, understanding and controlling these scattering channels is crucial for many optoelectronic applications, ranging from light harvesting to optical amplification. Here we measure the formation and relaxation of the photo-generated non-thermal carrier distribution in monolayer graphene with time- and angle-resolved photoemission spectroscopy. Using sub 10fs pulses we identify impact ionization as the primary scattering channel, which…
The recent demonstration of saturable absorption and negative optical conductivity in the Terahertz range in graphene has opened up new opportunities for optoelectronic applications based on this and other low dimensional materials. Recently, population inversion across the Dirac point has been observed directly by time- and angle-resolved photoemission spectroscopy (tr-ARPES), revealing a relaxation time of only ~ 130 femtoseconds. This severely limits the applicability of single layer graphene to, for example, Terahertz light amplification. Here we use tr-ARPES to demonstrate long-lived popu…
We employ angle-resolved photoemission spectroscopy (ARPES) to investigate the electronic structures of two rotational variants of epitaxial, single-layer graphene on Ir(111). As grown, the more-abundant R0 variant is nearly charge-neutral, with strong hybridization between graphene and Ir bands near the Fermi level. The graphene Fermi surface and its replicas exactly coincide with Van Hove singularities in the Ir Fermi surface. Sublattice symmetry breaking introduces a small gap-inducing potential at the Dirac crossing, which is revealed by n-doping the graphene using K atoms. The energy gaps…
The dosing of layered materials with alkali metals has become a commonly used strategy in ARPES experiments. However, precisely what occurs under such conditions, both structurally and electronically, has remained a matter of debate. Here we perform a systematic study of 1T-HfTe$_2$, a prototypical semimetal of the transition metal dichalcogenide family. By utilizing photon energy-dependent angle-resolved photoemission spectroscopy (ARPES), we have investigated the electronic structure of this material as a function of Potassium (K) deposition. From the k$_z$ maps, we observe the appearance of…
The millimeter sized monolayer and bilayer 2H-MoTe2 single crystal samples are prepared by a new mechanical exfoliation method. Based on such high-quality samples, we report the first direct electronic structure study on them, using standard high resolution angle-resolved photoemission spectroscopy (ARPES). A direct band gap of 0.924eV is found at K in the rubidium-doped monolayer MoTe2. Similar valence band alignment is also observed in bilayer MoTe2,supporting an assumption of a analogous direct gap semiconductor on it. Our measurements indicate a rather large band splitting of 212meV at the…
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 the 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 177 nm laser beam is achieved by frequency doubling a 355 nm beam using a KBBF crystal and subsequently focused using an optical l…
Searching for new quantum spin Hall insulators with large fully opened energy gap to overcome the thermal disturbance at room temperature has attracted tremendous attention due to the one-dimensional (1D) spin-momentum locked topological edge states serving as dissipationless channels for the practical applications in low consumption electronics and high performance spintronics. Here, we report the investigation of topological nature of monolayer Bi4Br4 by the techniques of scanning tunneling microscopy and angle-resolved photoemission spectroscopy (ARPES). The topological non-triviality of 1D…
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 …
Cutting-edge research in the band engineering of nanowires at the ultimate fine scale is related to the minimum scale of a nanowire-based device. The fundamental issue at the subnanometre scale is whether angle-resolved photoemission spectroscopy (ARPES) can be used to directly measure the momentum-resolved electronic structure of a single wire because of the difficulty associated with assembling single wire into an ordered array for such measurements. Here, we demonstrated that the one-dimensional (1D) confinement of electrons, which are transferred from external dopants, within a single subn…
Time-resolved, angle-resolved photoemission spectroscopy (TR-ARPES) is a one-particle spectroscopic technique that can probe excitons (two-particle excitations) in momentum space. We present an ab initio, time-domain GW approach to TR-ARPES and apply it to monolayer MoS$_2$. We show that photoexcited excitons may be measured and quantified as satellite bands, as well as leading to the renormalization of the quasiparticle bands. These features are explained in terms of an exciton- Floquet phenomenon induced by an exciton time-dependent bosonic field, which is orders of magnitude stronger than l…
We have conducted temperature dependent Angle Resolved Photoemission Spectroscopy (ARPES) study of the electronic structures of PbTe, PbSe and PbS. Our ARPES data provide direct evidence for the \emph{light} hole upper valence bands (UVBs) and hitherto undetected \emph{heavy} hole lower valence bands (LVBs) in these materials. An unusual temperature dependent relative movement between these bands leads to a monotonic decrease in the energy separation between their maxima with increasing temperature, which is referred as band convergence and has long been believed to be the driving factor behin…
2D materials have intriguing quantum phenomena that are distinctively different from their bulk counterparts. Recently, epitaxially synthesized wafer-scale 2D metals, composed of elemental atoms, are attracting attention not only for their potential applications but also for exotic quantum effects such as superconductivity. By mapping momentum-resolved electronic states using time-resolved and angle-resolved photoemission spectroscopy (ARPES), we reveal that monolayer Ag confined between bilayer graphene and SiC is a large gap (> 1 eV) 2D semiconductor, consistent with GW-corrected density fun…
