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Systematic studies of the effect of the electron concentration on the Raman spectra of single-layer graphene films have been carried out. The samples were grown by thermal destruction of the Si-face of the 4H-SiC substrate. Analysis of the results led us to the conclusion that for the correct estimation of the electron concentration and strain values in graphene using Raman spectroscopy data it is necessary to take into account the value of the Fermi velocity in the graphene layer. This conclusion is valid for graphene on any other substrate as well, since the Fermi velocity in graphene depends on the dielectric constant of the substrate.

The structural and electronic characteristics of epitaxial graphene films grown by thermal decomposition of the Si face of a semi-insulating 4H-SiC substrate in an argon environment have been studied by a large set of analytical techniques. It is shown that the results of a complex study make it possible to optimize the growth parameters and develop a reliable technology for the growth of high-quality single-layer graphene films. The charge-carrier concentration in the graphene layer was within 7 × 1011–1 × 1012 cm–2, and the maximum mobility of electrons at room temperature approached 6000 cm2/(V s).

We present a combined experimental and theoretical study of the two-dimensional electron states at the iridium-silicide surface of the antiferromagnet GdIr2Si2 above and below the Neel temperature. Using angle-resolved photoemission spectroscopy (ARPES) we find a significant spin-orbit splitting of the surface states in the paramagnetic phase. By means of ab initio density-functional-theory (DFT) calculations we establish that the surface electron states that reside in the projected band gap around the M¯ point exhibit very different spin structures which are governed by the conventional and the cubic Rashba effect. The latter is reflected in a triple spin winding, i.e., the surface electron spin reveals three complete rotations upon moving once around the constant energy contours. Below the Neel temperature, our ARPES measurements show an intricate photoemission intensity picture characteristic of a complex magnetic domain structure. The orientation of the domains, however, can be clarified from a comparative analysis of the ARPES data and their DFT modeling. To characterize a single magnetic domain picture, we resort to the calculations and scrutinize the interplay of the Rashba spin-orbit coupling field with the in-plane exchange field, provided by the ferromagnetically ordered 4f moments of the near-surface Gd layer. (Less)

Discovered in 1962, the divalent ferromagnetic semiconductor EuS (TC = 16.5 K, Eg = 1.65 eV) has remained constantly relevant to the engineering of novel magnetically active interfaces, heterostructures, and multilayer sequences and to combination with topological materials. Because detailed information on the electronic structure of EuS and, in particular, its evolution across TC is not well-represented in the literature but is essential for the development of new functional systems, the present work aims at filling this gap. Our angle-resolved photoemission measurements complemented with first-principles calculations demonstrate how the electronic structure of EuS evolves across a paramagnetic–ferromagnetic transition. Our results emphasize the importance of the strong Eu 4f–S 3p mixing for exchange-magnetic splittings of the sulfur-derived bands as well as coupling between f and d orbitals of neighboring Eu atoms to derive the value of TC accurately. The 4f–3p mixing facilitates the coupling between 4f and 5d orbitals of neighboring Eu atoms, which mainly governs the exchange interaction in EuS., This work was supported by the German Research Foundation (DFG) through Grant No. KR3831/5-1, No. LA655/20-1, No. SFB1143 (Project No. 247310070), and No. TRR288 (422213477, project A03). We acknowledge support from the Russian Foundation for Basic Research (Grant No. 20-32-70127) and Saint-Petersburg State University (Grant No. ID 73028629). S.V.E. acknowledges support from a government research assignment for ISPMS SB RAS (Project FWRW-2019-0032). We acknowledge MAX-IV Laboratory for time on the Bloch Beamline under Proposal 20190824. Research conducted at MAX IV, a Swedish national user facility, is supported by the Swedish Research council under contract 2018-07152, the Swedish Governmental Agency for Innovation Systems under contract 2018-04969, and Formas under contract 2019-02496. The research has also been supported by the project CALIPSO plus under Grant Agreement 730872 from the EU Framework Programme for Research and Innovation HORIZON 2020.

We present and discuss the methodology for modeling $4f$ photoemission spectra, $4f$ photoelectron diffraction (PED) patterns, and magnetic dichroism effects for rare-earth-based materials. Using PED and magnetic dichroism in photoemission, we explore the electronic and magnetic properties of the near-surface region of the valence-fluctuating material ${\mathrm{EuIr}}_{2}{\mathrm{Si}}_{2}$. For the Eu-terminated surface, we found that the topmost Eu layer is divalent and exhibits a ferromagnetic order below 10 K. The valency of the next Eu layer, that is the fifth atomic layer, is about 2.8 at low temperature that is close to the valency in the bulk. The properties of the Si-terminated surface are drastically different. The first subsurface Eu layer (fourth atomic layer below the surface) behaves divalently and orders ferromagnetically below 48 K. Experimental data indicate, however, that there is an admixture of trivalent Eu in this layer, resulting in its valency of about 2.1. The next deeper lying Eu layer (eighth atomic layer below the surface) behaves mixed valently, but the estimated valency of 2.4 is notably lower than the value in the bulk. The presented approach and obtained results create a background for further studies of exotic surface properties of $4f$-based materials, and allow us to derive information related to valency and magnetism of individual rare-earth layers in a rather extended area near the surface.

Spin-orbit interaction and structure inversion asymmetry in combination with magnetic ordering is a promising route to novel materials with highly mobile spin-polarized carriers at the surface. Spin-resolved measurements of the photoemission current from the Si-terminated surface of the antiferromagnet TbRh2Si2 and their analysis within an ab initio one-step theory unveil an unusual triple winding of the electron spin along the fourfold-symmetric constant energy contours of the surface states. A two-band k⋅p model is presented that yields the triple winding as a cubic Rashba effect. The curious in-plane spin-momentum locking is remarkably robust and remains intact across a paramagnetic-antiferromagnetic transition in spite of spin-orbit interaction on Rh atoms being considerably weaker than the out-of-plane exchange field due to the Tb 4f moments., This work was supported by the German Research Foundation (Grants No. KR-3831/5-1, No. LA655/20-1, GRK1621, Fermi-NESt No. ANR-16-CE92-0018, and SFB1143, project-id 247310070) and the Spanish Ministry of Science, Innovation, and Universities (Grant Nos. FIS2016-76617-P and MAT-2017-88374-P). We also acknowledge funding from the Department of Education of the Basque government (Grant No. IT1164-19), St. Petersburg State University (Project ID 51126254), and the Russian Foundation for Basic Research (Grant No. 20-32-70127). The SR-ARPES experiments at HiSOR were performed with the approval of the Proposal Assessing Committee of the Hiroshima Synchrotron Radiation Center (Proposal No. 18BG023). We also acknowledge the Impuls-und Vernetzungsfonds der Helmholtz Gemeinschaft (Grant No. HRSF-0067)

The emergence of ferromagnetism in Rashba systems, where the evolving exchange interaction enters into competition with spin-orbit coupling, leads to a nontrivial spin-polarized electronic landscape with an intricate momentum-dependent spin structure, which is challenging to unveil. Here, we show a way to disentangle the contributions from the effective spin-orbit and exchange fields and thus to gain knowledge of the spin structure in ferromagnetic Rashba materials, which is required for spintronic applications. Our approach is based exclusively on spin-integrated photoemission measurements combined with a two-band modeling. As an example, we consider the mixed-valent material EuIr2Si2 which, while being nonmagnetic in the bulk, reveals strong ferromagnetism at the iridium-silicide surface where both spin-orbit and exchange magnetic interactions coexist. The combined effect of these interactions causes a complex band dispersion of the surface state which can be observed in photoemission experiments. Our method allows us to comprehensively unravel the surface-state spin structure driven by spin-orbit coupling at the ferromagnetic surface. This approach opens up opportunities to characterize the spin structure of ferromagnetic Rashba materials, especially where dedicated spin-resolved measurements remain challenging., This work was supported by Saint Petersburg State University (Grant No. ID 51126254) and the Russian Foundation for Basic Research (Grant No. 20-32-70127). We acknowledge financial support from the Spanish Ministry of Economy (No. MAT-2017-88374-P) and the German Research Foundation (DFG) through Grants No. LA655/20-1, No. KR3831/5-1, and Fermi-NEst. We acknowledge Diamond Light Source for access to beamline I05 (Proposals No. SI18844-1 and No. SI17761-1).

The structural, chemical, and electronic properties of epitaxial graphene films grown by thermal decomposition of the Si-face of a semi-insulating 6H-SiC substrate in an argon environment are studied by Raman spectroscopy, atomic-force microscopy, the low-energy electron diffraction method, X-ray photoelectron spectroscopy, angle-resolved photoemission spectroscopy and X-ray absorption spectroscopy at the carbon K edge. It is shown that the results of a systematic integrated study make it possible to optimize the growth parameters and develop a reliable technology for the growth of high-quality single-layer graphene films with a small fraction of bilayer graphene inclusions.

A new method for synthesis of graphene-protected iron silicides has been tested, which consists in formation of graphene on Ni(111) followed by two-step intercalation of the system with Fe and Si. Characterization of the samples was performed in situ by low-energy electron diffraction, angular-resolved photoelectron spectroscopy, core-level photoelectron spectroscopy with synchrotron radiation and magnetic linear dichroism in photoemission of Fe 3p electrons. It is shown, that at 400 °C the intercalation of graphene/Ni(111) with iron occurs in a range up to 14 ML. The graphene layer strongly interacts with the topmost Fe atoms and stabilizes the fcc structure of the film. The in-plane ferromagnetic ordering of the film has a threshold nature and arises after the intercalation of 5 ML Fe due to the thickness-driven spin reorientation transition. Subsequent intercalation of graphene/Fe/Ni(111) with Si leads to the formation of the inhomogeneous system consisted of intercalated and nonintercalated areas. The intercalated islands coalesce at 2 ML Si when a Fe-Si solid solution covered with the Fe3Si surface silicide is formed. The Fe3Si silicide is ferromagnetic and has an ordered (√3 × √3)R30° structure. The graphene layer is weakly electronically coupled to the silicide phase keeping its remarkable properties ready for use.

The structural and electronic properties of hexagonal boron nitride (hBN) grown on stepped Ni surfaces are systematically investigated using a cylindrical Ni crystal as a tunable substrate. Our experiments reveal homogeneous hBN monolayer coating of the entire Ni curved surface, which in turn undergoes an overall faceting. The faceted system is defined by step-free hBN/Ni(1 1 1) terraces alternating with strongly tilted hBN/Ni(1 1 5) or hBN/Ni(1 1 0) nanostripes, depending on whether we have A-type or B-type vicinal surfaces, respectively. Such deep substrate self-organization is explained by both the rigidity of the hBN lattice and the lack of registry with Ni crystal planes in the vicinity of the (1 1 1) surface. The analysis of the electronic properties by photoemission and absorption spectroscopies reveal a weaker hBN/Ni interaction in (1 1 0)- and (1 1 5)-oriented facets, as well as an upward shift of the valence band with respect to the band position at the hBN/Ni(1 1 1) terrace., We acknowledge financial support from the Deutsches Forschungsgemein chaft DFG (Grants LA655-17/1 and LA655-19/1), the Spanish Ministry of Economy (Grants MAT-2016-78293-C6, MAT-2017-88374-P), the Basque Government (Grant IT-1255-19), the Helmholtz-Zentrum Berlin für Materialien und Energie for support within the bilateral RussianGerman Laboratory program as well as from the joint project of the Russian Science Foundation (project 16-42-01093) and DFG (Grant No. LA655-17/1). DYuU acknowledges St. Petersburg State University for research Grant No. 11.65.42.2017 and Russian Foundation for Basic Research RFBR (Project No. 17-02-00427).

The structural, chemical, and electronic characteristics of graphene grown by thermal decomposition of a singlecrystal SiC substrate in Ar atmosphere are presented. It is shown that this technology allows the creation of high-quality monolayer graphene films with a small fraction of bilayer graphene inclusions. The performance of graphene on SiC as a gas sensor or a biosensor was tested. The sensitivity of gas sensors to NO2 on the order of 1 ppb and that of biosensors to fluorescein with concentration on the order of 1 ng/mL and to bovine serum albumin-fluorescein conjugate with concentration on the order of 1 ng/mL were determined.

The intercalation of silicon under graphene on the Co(0001) surface, which is accompanied by the formation of a silicon solid solution in cobalt and by the formation of a surface crystalline Co2Si phase, has been investigated using photoelectron spectroscopy. It has been shown that the formation of cobalt silicide leads to a substantial weakening of the hybridization of electronic states of graphene and cobalt and to the recovery of the Dirac spectrum of electronic states of graphene near the Fermi level. This has made it possible to investigate the electron doping of graphene on the cobalt silicide substrate upon deposition of lithium on its surface. It has been found that doping with lithium leads to a significant charge transfer onto graphene, and the electron concentration reaches 3.1 × 1014 cm−2. Moreover, the specific form of the Fermi surface creates favorable conditions for the enhancement of the electron-phonon coupling. As a result, the formed system can be considered as a candidate for the creation of superconductivity in single-layer graphene.

Comprehensive study of high-quality monolayer graphene samples grown by thermal destruction of the Si-face of the 4H-SiC substrate was carried out. Analysis of the data obtained by Raman spectroscopy and angle-resolved photoemission spectroscopy suggest the need to use the Fermi velocity in the graphene layer under study to obtain a correct estimate of the electron concentration and strain values using Raman data. This statement is valid not only for graphene on the SiC substrate, but for graphene on any other substrate as well, since the Fermi velocity in graphene depends on the dielectric constant of the substrate.

The crystalline and electronic structure of nitrogen-doped graphene (N-graphene) has been studied by photoelectron spectroscopy and scanning tunneling microscopy. Synthesis of N-graphene from triazine molecules on Ni(111) surface results in incorporation into graphene of nitrogen atoms primarily in the pyridinic configuration. It has been found that inclusions of nitrogen enhance significantly thermal stability of graphene on nickel. An analysis of the electronic structure of N-graphene intercalated by gold atoms has revealed that the pyridinic nitrogen culminates in weak p-type doping, in full agreement with theoretical predictions. Subsequent thermal treatment makes possible conversion of the major part of nitrogen atoms into the substitutional configuration, which involves n-type doping. It has been shown that the crystalline structure of the N graphene thus obtained reveals local distortions presumably caused by inhomogeneous distribution of impurities in the layer. The results obtained have demonstrated a promising application potential of this approach for development of electronic devices based on graphene with controllable type of conduction and carrier concentration.

This paper reports on a study of the process of Al intercalation underneath a graphene monolayer formed on the Ni(111) surface by propylene cracking. Graphene formed on Ni(111) is known to be strongly coupled to the substrate; however, we have been able to show that Al intercalation underneath a graphene monolayer eventually results in blocking of this interaction and the formation of an electronic structure similar to that of quasi-freestanding graphene. As a result, the dispersion relation of the π states of graphene is linear at the К point of the Brillouin zone, with the Dirac point located in the region of the Fermi level. Thereat, an energy gap opens at the Fermi level near the K¯ point between the cones of occupied π and unoccupied π* states of graphene. There are no features in the spectra that would signal a partial filling of the π* states and clearly detectable charge transfer between the graphene and the intercalated Al. A detailed analysis of the process by which Al intercalates underneath the graphene monolayer revealed that intercalation of Al differs somewhat from that of other (for instance, noble) metals. The intercalated Al is observed to dissolve and subsequently, alloy with the Ni substrate. Only if the concentration of Al intercalated underneath the graphene is high enough, will it accumulate on the interface directly under the graphene monolayer and form, in the near-surface region, an alloy with a prevalent concentration of Al; the stage at which the strong binding of graphene to the Ni substrate becomes blocked.

The paper reports on a study of the electronic structure of binary homogeneous alloys Ti55Ni45, Ti50Ni50, and Ti45Ni55 by X-ray photoelectron and near-edge X-ray absorption spectroscopies. The experimental data obtained were used to derive the occupied and unoccupied d-states density redistribution upon formation of the Ti–Ni alloys. The Ti and Ni L2,3 X-ray absorption edge intensity measured permitted calculation of the variation of the titanium and nickel d-shell occupancy induced by formation of the Ti50Ni50, Ti55Ni45 and Ti45Ni55 alloys. It is shown that the occupation of the nickel d-band decreases by 0.13 el./atom in formation of the above alloys and practically does not depend on the ratio of the constituent elements, whereas that of the titanium d-shell is strongly dependent on the atomic composition of the alloy. The charge transfer between the components was found to be insignificant; this implies that the change in occupancy of the nickel and titanium d-shells originates from intratomic redistribution of electron density between the d- and sp-states. The Ti50Ni50 equiatomic alloy is unique in that it has the lowest titanium d-shell occupancy and, hence, the largest number of sp-electrons. It is shown that the increasing Ni content in the TiNi alloys leads to a noticeable gain of titanium d-electrons. It is assumed that the additional d-electrons can form a direct bonds, which increases the elastic moduli and, consequently, reduce the temperature of martensitic transformation in Ni-rich TiNi alloys.

The structure of graphene on Ni(110) was studied using scanning tunneling microscopy (STM) and low-energy electron diffraction spectroscopy. STM images show a Moire structure, depending on the orientation of the domains making up the graphene layer. A simple model has been proposed which permits prediction of the Moire structure and interpretation of STM images based on calculation of the distances between the nearest neighbor carbon and nickel atoms. Our theoretical calculation suggests that the final orientation of graphene domains forming in the course of synthesis is defined by the angle of rotation of small clusters in the initial stages of growth.

The chemical composition of the surface of TiNi-based alloys in the form of ribbons produced by rapid melt quenching in oxygen-containing environment has been investigated. It is shown that titanium oxide is formed on the Ti50Ni25Cu25 alloy surface, while on the Ti39.2Ni24.8Cu25Hf11 alloy surface titanium and hafnium oxides are formed. Atomic-force microscope images reveal crystalline structures of titanium oxide with sizes of up to 500 × 500 nm2 on the surface of the Ti50Ni25Cu25 sample. After removing the surface oxide layer by ion etching, the ratio of elements becomes close to the stoichiometric composition.

The substrate-induced spin-orbit splitting of interface and quantum-well states formed in Au, Ag, and Cu layers on W(110) and Mo(110) surfaces has been revealed using angle- and spin-resolved photoelectron spectroscopy. It has been shown that the magnitude of the splitting depends noticeably on the atomic number of the substrate material and is markedly larger for layers of these metals on W(110), i.e., on the surface of a metal with a larger atomic number (Z W = 74), than on the surface of Mo(110), i.e., an element with a smaller atomic number (Z Mo = 42), while depending only weakly on the atomic number of the adsorbed metal. Measurements of the dispersion of the formed quantum-well states have shown that the substrate-induced spin-orbit splitting increases with increasing parallel component of the photoelectron momentum (which correlates with the Rashba model) for all thicknesses of deposited films (up to 10 ML). The magnitude of induced spin-orbit splitting of the interface states evolving in monolayer Au, Ag, and Cu coatings on W(110) and Mo(110) decreases with increasing parallel component of the excited photoelectron momentum.

Quantum well states of sp-type in thin metal layers of aluminum on the W(110) surface were experimentally studied by angle-resolved photoelectron spectroscopy depending on the layer thickness in a range of about 1–15 monolayers. It is shown that the aluminum layer is formed in accordance with the Kurdyumov-Sachs orientation relationship. Modification of the quantum well state spectra is observed with the increase in the layer thickness. The changes of the energy of quantum well states with the formation of each new monolayer have a stepwise character. This behavior can be used to calibrate the thickness of the deposited film with an accuracy within fractions of a monolayer. To confirm the reliability of the calibration, the thickness of the formed layers was tested using the attenuation of the W4f7/2 peak intensity.

The conditions of the formation of different carbon surface phases on nickel substrates by the example of a planar Ni( 110) surface and a stepped Ni(771 ) surface similar in structure were determined. The structure of the phases was investigated by means of scanning tunneling microscopy (STM), and the influence of carbon on the structure of the nickel surface was demonstrated. The process of graphene synthesis by propylene cracking is described. A method for forming graphene islands on nickel is proposed. A variety of phase transitions between the carbon surface phases (e.g., surface carbide, graphene, and graphene islands) and the reasons for their irreversibility are discussed. The relation between the structures of the surface carbide phases and the crystal structures of the initial surfaces for two different substrates is shown.

Experimental investigation and computer simulation of a graphite monolayer (graphene) on different Ni single-crystal surfaces have been performed. In contrast to graphene on Ni(111), which forms a solid coating with a (1 × 1) structure, graphene on Ni(110) forms a complex crystal structure which is substantially distorted by interaction with the substrate. The calculations showed that the strong chemical interaction of carbon with nickel leads to a significant bending of the graphene layer (up to few angstroms). The calculated model made it possible to predict the main result of studying graphene on faceted surfaces, which revealed the graphene ability to coat geometrically nonuniform surfaces with a curved continuous film.

Under the terms of the Creative Commons Attribution License 3.0 (CC-BY).-- et al., The modification of the graphene spin structure is of interest for novel possibilities of application of graphene in spintronics. The most exciting of them demand not only high value of spin-orbit splitting of the graphene states, but non-Rashba behavior of the splitting and spatial modulation of the spin-orbit interaction. In this work we study the spin and electronic structure of graphene on Ir(111) with intercalated Pt monolayer. Pt interlayer does not change the 9.3×9.3 superlattice of graphene, while the spin structure of the Dirac cone becomes modified. It is shown that the Rashba splitting of the π state is reduced, while hybridization of the graphene and substrate states leads to a spin-dependent avoided-crossing effect near the Fermi level. Such a variation of spin-orbit interaction combined with the superlattice effects can induce a topological phase in graphene., The work was partially supported by grants of Saint Petersburg State University for scientific investigations (Grants No. 11.38.271.2014, No. 15.61.202.2015 and No. 11.37.634.2013) and Russian Foundation for Basic Research (RFBR) projects (No. 13-02-91327). We acknowledge the financial support of the University of Basque Country UPV/EHU (Grant No. GIC07-IT-756-13), the Departamento de Educacion del Gobierno Vasco, and the Spanish Ministerio de Ciencia e Innovacion (Grant No. FIS2010-19609-C02-01), the Spanish Ministry of Economy and Competitiveness MINECO (Grant No. FIS2013-48286-C2-1-P), and the Tomsk State University Competitiveness Improvement Program.

It has been shown that low size dispersion systems of carbon nanoclusters can be fabricated by ion irradiation of fullerite C60 film through a special mask. As the mask, lavsan track membrane with more or less equal pinholes of diameter of about 60 nm was used. STM study showed that fabricated clusters have a form of the cone‐like island with average diameter of about 60 nm and height of about 5 nm.

Atomic force microscopy (AFM) and electron backscatter diffraction were used to study formation of the low-carbon steel surface relief upon chemical etching with nital. The combination of these techniques allowed quantitative characterization of the iron etch depth dependence on the crystallographic orientation of individual ferrite grains. The obtained results demonstrate high potential of AFM for quantitative metallography.

We investigate the N = 9 atoms wide armchair-type graphene nanoribbons (9-AGNRs) by performing a comprehensive spectroscopic and microscopic characterization of this novel material. In particular, we use X-ray photoelectron, near edge X-ray absorption fine structure, scanning tunneling, polarized Raman and angle-resolved photoemission (ARPES) spectroscopies. The ARPES measurements are aided by calculations of the photoemission matrix elements which yield the position in k space having the strongest photoemission cross section. Comparison with well-studied narrow N = 7 AGNRs shows that the effective electron mass in 9-AGNRs is reduced by two times and the valence band maximum is shifted to lower binding energy by ∼0.6 eV. In polarized Raman measurements of the aligned 9-AGNR, we reveal anisotropic signal depending upon the phonon symmetry. Our results indicate the 9-AGNRs are a novel 1D semiconductor with a high potential in nanoelectronic applications.

Two-dimensional superconductivity in alkali- and alkaline-Earth-metal doped monolayer graphene has been explained in the framework of electron–phonon coupling (EPC) and experiments yielded superconducting transition temperatures (T C ) up to 6 K. In contrast to bulk graphite intercalation compounds, the interface of doped graphene with its environment affects its physical properties. Here we present a novel and well-defined BaC8 interface structure in Ba-doped single-layer graphene on Au and Ge substrates. We use angle-resolved photoemission spectroscopy in combination with ab initio modelling to extract the Eliashberg function and EPC for both substrates. This allows us to quantitatively assess the environmental effects for both Au and Ge substrates on superconductivity in graphene. We show that for semiconducting Ge substrates, the doping level and EPC are higher. Our study highlights that both dopant order and the metallicity of the substrate can be used to control EPC and hence superconductivity.

First principles calculations demonstrate the metallization of phosphorene by means of Li doping filling the unoccupied antibonding pz states. The electron–phonon coupling in the metallic phase is strong enough to eventually lead to a superconducting phase at Tc= 17 K for LiP8 stoichiometry. Using angle-resolved photoemission spectroscopy we confirm that the surface of black phosphorus can be chemically functionalized using Li atoms which donate their 2s electron to the conduction band. The combined theoretical and experimental study demonstrates the semiconductor-metal transition indicating a feasible way to induce a superconducting phase in phosphorene and few-layer black phosphorus.