Showing papers on "Photoemission spectroscopy published in 2014"

Direct observation of the transition from indirect to direct bandgap in atomically thin epitaxial MoSe2

Abstract: The transition from an indirect to direct bandgap in transition metal dichalcogenides has been observed in samples with thicknesses ranging from 8 to 1 monolayers by angle-resolved photoemission spectroscopy.

Interfacial mode coupling as the origin of the enhancement of T(c) in FeSe films on SrTiO3.

Abstract: High-resolution angle-resolved photoemission spectroscopy reveals bosonic modes in a SrTiO3 substrate coupling to electrons in an FeSe overlayer to facilitate high-temperature superconductivity. Bulk iron selenide (FeSe) is a superconductor with a critical temperature Tc = 8 K, but superconductivity is substantially enhanced in single-unit cell films of FeSe grown on strontium titanate (SrTiO3 or STO) substrates, where superconducting energy gaps open at temperatures close to the boiling point of liquid nitrogen (77 K). This raises the question of whether the substrate has a contributory role in this enhancement. Zhi-Xun Shen and colleagues report high-resolution angle-resolved photoemission spectroscopy (ARPES) results that reveal bosonic modes (thought to be oxygen optical phonons) in the SrTiO3 substrate coupling to electrons in the FeSe overlayer to facilitate high-temperature superconductivity. Such coupling helps superconductivity in most channels, so the pairing enhancement described here may well work for other superconducting materials, as well as for FeSe. Films of iron selenide (FeSe) one unit cell thick grown on strontium titanate (SrTiO3 or STO) substrates have recently shown1,2,3,4 superconducting energy gaps opening at temperatures close to the boiling point of liquid nitrogen (77 kelvin), which is a record for the iron-based superconductors. The gap opening temperature usually sets the superconducting transition temperature Tc, as the gap signals the formation of Cooper pairs, the bound electron states responsible for superconductivity. To understand why Cooper pairs form at such high temperatures, we examine the role of the SrTiO3 substrate. Here we report high-resolution angle-resolved photoemission spectroscopy results that reveal an unexpected characteristic of the single-unit-cell FeSe/SrTiO3 system: shake-off bands suggesting the presence of bosonic modes, most probably oxygen optical phonons in SrTiO3 (refs 5, 6, 7), which couple to the FeSe electrons with only a small momentum transfer. Such interfacial coupling assists superconductivity in most channels, including those mediated by spin fluctuations8,9,10,11,12,13,14. Our calculations suggest that this coupling is responsible for raising the superconducting gap opening temperature in single-unit-cell FeSe/SrTiO3.

Valley-dependent spin polarization in bulk MoS2 with broken inversion symmetry

Abstract: The valley degree of freedom of electrons is attracting growing interest as a carrier of information in various materials, including graphene, diamond and monolayer transition-metal dichalcogenides. The monolayer transition-metal dichalcogenides are semiconducting and are unique due to the coupling between the spin and valley degrees of freedom originating from the relativistic spin-orbit interaction. Here, we report the direct observation of valley-dependent out-of-plane spin polarization in an archetypal transition-metal dichalcogenide--MoS2--using spin- and angle-resolved photoemission spectroscopy. The result is in fair agreement with a first-principles theoretical prediction. This was made possible by choosing a 3R polytype crystal, which has a non-centrosymmetric structure, rather than the conventional centrosymmetric 2H form. We also confirm robust valley polarization in the 3R form by means of circularly polarized photoluminescence spectroscopy. Non-centrosymmetric transition-metal dichalcogenide crystals may provide a firm basis for the development of magnetic and electric manipulation of spin/valley degrees of freedom.

Direct observation of half-metallicity in the Heusler compound Co2MnSi

Abstract: Ferromagnetic thin films of Heusler compounds are highly relevant for spintronic applications owing to their predicted half-metallicity, that is, 100% spin polarization at the Fermi energy. However, experimental evidence for this property is scarce. Here we investigate epitaxial thin films of the compound Co2MnSi in situ by ultraviolet-photoemission spectroscopy, taking advantage of a novel multi-channel spin filter. By this surface sensitive method, an exceptionally large spin polarization of (93(-11)(+7)) % at room temperature is observed directly. As a more bulk sensitive method, additional ex situ spin-integrated high energy X-ray photoemission spectroscopy experiments are performed. All experimental results are compared with advanced band structure and photoemission calculations which include surface effects. Excellent agreement is obtained with calculations, which show a highly spin polarized bulk-like surface resonance ingrained in a half metallic bulk band structure.

A Direct and Polymer-Free Method for Transferring Graphene Grown by Chemical Vapor Deposition to Any Substrate

Abstract: We demonstrate a polymer-free method that can routinely transfer relatively large-area graphene to any substrate with advanced electrical properties and superior atomic and chemical structures as compared to the graphene sheets transferred with conventional polymer-assisted methods. The graphene films that are transferred with polymer-free method show high electrical conductance and excellent optical transmittance. Raman spectroscopy and X-ray/ultraviolet photoelectron spectroscopy also confirm the presence of high quality graphene sheets with little contamination after transfer. Atom-resolved images can be obtained using scanning tunneling microscope on as-transferred graphene sheets without additional cleaning process. The mobility of the polymer-free graphene monolayer is as high as 63 000 cm2 V–1 s–1, which is 50% higher than the similar sample transferred with the conventional method. More importantly, this method allows us to place graphene directly on top of devices made of soft materials, such as ...

Iron-based high transition temperature superconductors

Abstract: In a superconductor electrons form pairs and electric transport becomes dissipation-less at low temperatures. Recently discovered iron-based superconductors have the highest superconducting transition temperature next to copper oxides. In this article, we review material aspects and physical properties of iron-based superconductors. We discuss the dependence of transition temperature on the crystal structure, the interplay between antiferromagnetism and superconductivity by examining neutron scattering experiments, and the electronic properties of these compounds obtained by angle-resolved photoemission spectroscopy in link with some results from scanning tunneling microscopy/spectroscopy measurements. Possible microscopic model for this class of compounds is discussed from a strong coupling point of view.

Spin-Orbital Entanglement and the Breakdown of Singlets and Triplets in Sr 2 RuO 4 Revealed by Spin- and Angle-Resolved Photoemission Spectroscopy

Abstract: Spin-orbit coupling has been conjectured to play a key role in the low-energy electronic structure of Sr2RuO4. By using circularly polarized light combined with spin- and angle-resolved photoemission spectroscopy, we directly measure the value of the effective spin-orbit coupling to be 130 � 30 meV. This is even larger than theoretically predicted and comparable to the energy splitting of the dxy and dxz;yz orbitals around the Fermi surface, resulting in a strongly momentum-dependent entanglement of spin and orbital character in the electronic wavefunction. As demonstrated by the spin expectation value h sk · s−ki calculated for a pair of electrons with zero total momentum, the classification of the Cooper pairs in terms of pure singlets or triplets fundamentally breaks down, necessitating a description of the unconventional superconducting state of Sr2RuO4 in terms of these newly found spin-orbital entangled eigenstates.

Distinguishing bulk and surface electron-phonon coupling in the topological insulator Bi(2)Se(3) using time-resolved photoemission spectroscopy.

Abstract: We report time- and angle-resolved photoemission spectroscopy measurements on the topological insulator Bi(2)Se(3). We observe oscillatory modulations of the electronic structure of both the bulk and surface states at a frequency of 2.23 THz due to coherent excitation of an A(1g) phonon mode. A distinct, additional frequency of 2.05 THz is observed in the surface state only. The lower phonon frequency at the surface is attributed to the termination of the crystal and thus reduction of interlayer van der Waals forces, which serve as restorative forces for out-of-plane lattice distortions. Density functional theory calculations quantitatively reproduce the magnitude of the surface phonon softening. These results represent the first band-resolved evidence of the A(1g) phonon mode coupling to the surface state in a topological insulator.

Chemical-potential-dependent gap opening at the Dirac surface states of Bi2Se3 induced by aggregated substitutional Cr atoms.

Abstract: With angle-resolved photoemission spectroscopy, gap opening is resolved at up to room temperature in the Dirac surface states of molecular beam epitaxy grown Cr-doped Bi2Se3 topological insulator films, which, however, show no long-range ferromagnetic order down to 1.5 K. The gap size is found decreasing with increasing electron-doping level. Scanning tunneling microscopy and first-principles calculations demonstrate that substitutional Cr atoms aggregate into superparamagnetic multimers in the Bi2Se3 matrix, which contribute to the observed chemical-potential-dependent gap opening in the Dirac surface states without long-range ferromagnetic order.

Concentration and chemical-state profiles at heterogeneous interfaces with sub-nm accuracy from standing-wave ambient-pressure photoemission

Abstract: Heterogeneous processes at solid/gas, liquid/gas and solid/liquid interfaces are ubiquitous in modern devices and technologies but often difficult to study quantitatively. Full characterization requires measuring the depth profiles of chemical composition and state with enhanced sensitivity to narrow interfacial regions of a few to several nm in extent over those originating from the bulk phases on either side of the interface. We show for a model system of NaOH and CsOH in an ~1-nm thick hydrated layer on α-Fe2O3 (haematite) that combining ambient-pressure X-ray photoelectron spectroscopy and standing-wave photoemission spectroscopy provides the spatial arrangement of the bulk and interface chemical species, as well as local potential energy variations, along the direction perpendicular to the interface with sub-nm accuracy. Standing-wave ambient-pressure photoemission spectroscopy is thus a very promising technique for measuring such important interfaces, with relevance to energy research, heterogeneous catalysis, electrochemistry, and atmospheric and environmental science.

Valence to Core X‐ray Emission Spectroscopy

Abstract: This Progress Report discusses the chemical sensitivity of Kβ valence to core X-ray emission spectroscopy (vtc-XES) and its applications for investigating 3d-transition-metal based materials. Vtc-XES can be used for ligand identification and for the characterization of the valence electronic levels. The technique provides information that is similar to valence band photoemission spectroscopy but the sample environment can be chosen freely and thus allows measurements in presence of gases and liquids and it can be applied for measurements under in situ/operando or extreme conditions. The theoretical basis of the technique is presented using a one-electron approach and the vtc-XES spectral features are interpreted using ground state density functional theory calculations. Some recent results obtained by vtc-XES in various scientific fields are discussed to demonstrate the potential and future applications of this technique. Resonant X-ray emission spectroscopy is briefly introduced with some applications for the study of 3d and 5d-transition-metal based systems.

Anisotropic two-dimensional electron gas at SrTiO3(110)

Abstract: Two-dimensional electron gases (2DEGs) at oxide heterostructures are attracting considerable attention, as these might one day substitute conventional semiconductors at least for some functionalities. Here we present a minimal setup for such a 2DEG––the SrTiO3(110)-(4 × 1) surface, natively terminated with one monolayer of tetrahedrally coordinated titania. Oxygen vacancies induced by synchrotron radiation migrate underneath this overlayer; this leads to a confining potential and electron doping such that a 2DEG develops. Our angle-resolved photoemission spectroscopy and theoretical results show that confinement along (110) is strikingly different from the (001) crystal orientation. In particular, the quantized subbands show a surprising “semiheavy” band, in contrast with the analog in the bulk, and a high electronic anisotropy. This anisotropy and even the effective mass of the (110) 2DEG is tunable by doping, offering a high flexibility to engineer the properties of this system.

Effective attenuation length of an electron in liquid water between 10 and 600 eV.

Abstract: The absolute values of the effective attenuation length of an electron in liquid water are determined using soft x-ray $\mathrm{O}1s$ photoemission spectroscopy of a liquid beam of water without employing any theoretical estimation or computationally obtained value. The effective attenuation length is greater than 1 nm in the entire electron kinetic energy region and exhibits very flat energy dependence in the 10--100 eV region.

Mixed dimensionality of confined conducting electrons in the surface region of SrTiO3.

Abstract: Using angle-resolved photoemission spectroscopy, we show that the recently discovered surface state on SrTiO3 consists of nondegenerate t(2g) states with different dimensional characters. While the d(xy) bands have quasi-2D dispersions with weak k(z) dependence, the lifted d(xz)/d(yz) bands show 3D dispersions that differ significantly from bulk expectations and signal that electrons associated with those orbitals permeate the near-surface region. Like their more 2D counterparts, the size and character of the d(xz)/d(yz) Fermi surface components are essentially the same for different sample preparations. Irradiating SrTiO3 in ultrahigh vacuum is one method observed so far to induce the "universal" surface metallic state. We reveal that during this process, changes in the oxygen valence band spectral weight that coincide with the emergence of surface conductivity are disproportionate to any change in the total intensity of the O 1s core level spectrum. This signifies that the formation of the metallic surface goes beyond a straightforward chemical doping scenario and occurs in conjunction with profound changes in the initial states and/or spatial distribution of near-E-F electrons in the surface region.

Probing the mechanism for graphene nanoribbon formation on gold surfaces through X-ray spectroscopy

Abstract: We studied the formation of graphene nanoribbons (GNRs) via the self-assembly of 10,10′-dibromo-9,9′-bianthryl precursor molecules on gold surfaces with different synchrotron spectroscopies. Through X-ray photoemission spectroscopy core-level shifts, we followed each step of the synthetic process, and could show that the Br–C bonds of the precursors cleave at temperatures as low as 100 °C on both Au(111) and Au(110). We established that the resulting radicals bind to Au, forming Au–C and Au–Br bonds. We show that the polymerization of the precursors follows Br desorption from Au, suggesting that the presence of halogens is the limiting factor in this step. Finally, with angle-resolved ultraviolet photoemission spectroscopy and density functional theory we show that the GNR/Au interaction results in an upshift of the Shockley surface state of Au(111) by ∼0.14 eV, together with an increased electron effective mass.

Experimental and theoretical electronic structure of quinacridone

Abstract: The energy positions of frontier orbitals in organic electronic materials are often studied experimentally by (inverse) photoemission spectroscopy and theoretically within density functional theory. However, standard exchange-correlation functionals often result in too small fundamental gaps, may lead to wrong orbital energy ordering, and do not capture polarization-induced gap renormalization. Here we examine these issues and a strategy for overcoming them by studying the gas phase and bulk electronic structure of the organic molecule quinacridone (5Q), a promising material with many interesting properties for organic devices. Experimentally we perform angle-resolved photoemission spectroscopy (ARUPS) on thin films of the crystalline $\ensuremath{\beta}$ phase of 5Q. Theoretically we employ an optimally tuned range-separated hybrid functional (OT-RSH) within density functional theory. For the gas phase molecule, our OT-RSH result for the ionization potential (IP) represents a substantial improvement over the semilocal PBE and the PBE0 hybrid functional results, producing an IP in quantitative agreement with experiment. For the bulk crystal we take into account the correct screening in the bulk, using the recently developed optimally tuned screened range-separated hybrid (OT-SRSH) approach, while retaining the optimally tuned parameters for the range separation and the short-range Fock exchange. This leads to a band gap narrowing due to polarization effects and results in a valence band spectrum in excellent agreement with experimental ARUPS data, with respect to both peak positions and heights. Finally, full-frequency ${G}_{0}{W}_{0}$ results based on a hybrid functional starting point are shown to agree with the OT-SRSH approach, improving substantially on the PBE-starting point.

Valence-band density of states and surface electron accumulation in epitaxial SnO2 films

Abstract: The surface band bending and electronic properties of SnO2(101) films grown on r-sapphire by plasma-assisted molecular beam epitaxy have been studied by Fourier-transform infrared spectroscopy (FTIR), x-ray photoemission spectroscopy (XPS), Hall effect, and electrochemical capacitance-voltage measurements. The XPS results were correlated with density functional theory calculation of the partial density of states in the valence-band and semicore levels. Good agreement was found between theory and experiment with a small offset of the Sn 4d levels. Homogeneous Sb-doped SnO2 films allowed for the calculation of the bulk Fermi level with respect to the conduction-band minimum within the k⋅p carrier statistics model. The band bending and carrier concentration as a function of depth were obtained from the capacitance-voltage characteristics and model space charge calculations of the Mott-Schottky plots at the surface of Sb-doped SnO2 films. It was quantitatively demonstrated that SnO2 films have downward band bending and surface electron accumulation. The surface band bending, unoccupied donor surface-state density, and width of the accumulation region all decrease with increasing Sb concentration.

Observation of topological crystalline insulator surface states on (111)-oriented Pb1-xSnxSe films

Abstract: We present angle-resolved photoemission spectroscopy measurements of the surface states on in-situ grown (111) oriented films of Pb1-xSnxSe, a three-dimensional topological crystalline insulator. We observe surface states with Dirac-like dispersion at (Gamma) over bar and (M) over bar in the surface Brillouin zone, supporting recent theoretical predictions for this family of materials. We study the parallel dispersion isotropy and Dirac-point binding energy of the surface states, and perform tight-binding calculations to support our findings. The relative simplicity of the growth technique is encouraging, and suggests a clear path for future investigations into the role of strain, vicinality, and alternative surface orientations in (Pb,Sn)Se solid solutions.

In Situ XANES/XPS Investigation of Doped Manganese Perovskite Catalysts

Abstract: Studying catalysts in situ is of high interest for understanding their surface structure and electronic states in operation. Herein, we present a study of epitaxial manganite perovskite thin films (Pr1−xCaxMnO3) active for the oxygen evolution reaction (OER) from electro-catalytic water splitting. X-ray absorption near-edge spectroscopy (XANES) at the Mn L- and O K-edges, as well as X-ray photoemission spectroscopy (XPS) of the O 1s and Ca 2p states have been performed in ultra-high vacuum and in water vapor under positive applied bias at room temperature. It is shown that under the oxidizing conditions of the OER a reduced Mn2+ species is generated at the catalyst surface. The Mn valence shift is accompanied by the formation of surface oxygen vacancies. Annealing of the catalysts in O2 atmosphere at 120 °C restores the virgin surfaces.

Epitaxial growth of CeO2(111) film on Ru(0001): Scanning tunneling microscopy (STM) and x-ray photoemission spectroscopy (XPS) study

Abstract: We formed an epitaxial film of CeO2(111) by sublimating Ce atoms on Ru(0001) surface kept at elevated temperature in an oxygen ambient. X-ray photoemission spectroscopy measurement revealed a decrease of Ce4+/Ce3+ ratio in a small temperature window of the growth temperature between 1070 and 1096 K, which corresponds to the reduction of the CeO2(111). Scanning tunneling microscope image showed that a film with a wide terrace and a sharp step edge was obtained when the film was grown at the temperatures close to the reduction temperature, and the terrace width observed on the sample grown at 1060 K was more than twice of that grown at 1040 K. On the surface grown above the reduction temperature, the surface with a wide terrace and a sharp step was confirmed, but small dots were also seen in the terrace part, which are considerably Ce atoms adsorbed at the oxygen vacancies on the reduced surface. This experiment demonstrated that it is required to use the substrate temperature close to the reduction temperature to obtain CeO2(111) with wide terrace width and sharp step edges.

NiOX/MoO3 Bi-Layers as Efficient Hole Extraction Contacts in Organic Solar Cells

Abstract: The electronic structure of a bi-layer hole extraction contact consisting of nickel oxide (NiO x ) and molybdenum trioxide (MoO 3 ) is determined via ultraviolet and X-ray photoemission spectroscopy. The bi-layer presents ideal energetics for the extraction of holes and suppression of carrier recombination at the interface. The application of the NiO x /MoO 3 bi-layer as the anode of organic bulk heterojunction solar cells based on PCDTBT/PC 71 BM leads to improved device performance, which is explained by an intricate charge transfer process across the interface.

X-ray absorption spectroscopy studies of electronic structure recovery and nitrogen local structure upon thermal reduction of graphene oxide in an ammonia environment

Abstract: Annealing graphene oxide under an ammonia environment provides a facile approach to defunctionalise this material while simultaneously enabling nitrogen incorporation en route to the preparation of chemically derived graphene. Here, we use X-ray photoemission spectroscopy (XPS) in conjunction with near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy to probe both the global recovery of electronic structure in this material as well as to monitor evolution of the local structure of incorporated nitrogen atoms when graphene oxide is reduced under an ammonia gas environment at ambient and low pressures in the temperature range between 250 and 1000 °C. The local structure and extent of recovery of the π-conjugated framework is correlated to electrical conductivity measurements. Angle-resolved C K-edge NEXAFS spectra along with O K-edge NEXAFS and C 1s high-resolution XPS spectra suggest that hydroxyl and epoxide functional groups on the basal plane of graphene oxide are eliminated upon annealing to a temperature of 250 °C, bringing about substantial restoration of the π-conjugated framework of graphene. Furthermore, an increase in the in-plane orientation of constituent graphene oxide flakes is observed up to a temperature of 750 °C for annealing under both sets of conditions and is manifested as a greater spread in the intensity of the C K-edge π* resonance as a function of angle of incidence of the X-ray beam. Angle-resolved N K-edge NEXAFS spectra and high-resolution N 1s XPS spectra supplement the global view of recovery of π-conjugation with a local perspective of the chemical bonding environments of incorporated nitrogen atoms. Three distinct modes of nitrogen incorporation are evidenced: amine or nitrile like (N1), pyridinic (N2), and substitutional/graphitic (N3). The data suggest that nitrogen is initially incorporated as nitrile like functionalities at lower temperatures with these moieties protruding above and below the graphene basal plane; however, the nitrile and amine groups are subsequently transformed at higher temperatures through the elimination of oxygenated functional groups and reconstitution of the sp2-hybridized network to in-plane pyridinic and graphitic moieties. The latter two configurations are seen to substantially enhance the conductivity of reduced graphene oxide.

Orientational tuning of the Fermi sea of confined electrons at the SrTiO3 (110) and (111) surfaces

Abstract: We report the existence of confined electronic states at the (110) and (111) surfaces of SrTiO3. Using angle-resolved photoemission spectroscopy, we find that the corresponding Fermi surfaces, subband masses, and orbital ordering are different from the ones at the (001) surface of SrTiO3. This occurs because the crystallographic symmetries of the surface and sub-surface planes, and the electron effective masses along the confinement direction, influence the symmetry of the electronic structure and the orbital ordering of the t2g manifold. Remarkably, our analysis of the data also reveals that the carrier concentration and thickness are similar for all three surface orientations, despite their different polarities. The orientational tuning of the microscopic properties of two-dimensional electron states at the surface of SrTiO3 echoes the tailoring of macroscopic (e.g. transport) properties reported recently in LaAlO3/SrTiO3 (110) and (111) interfaces, and is promising for searching new types of 2D electronic states in correlated-electron oxides.

Effect of dynamical spectral weight redistribution on effective interactions in time-resolved spectroscopy

Abstract: The redistribution of electrons in an ultrafast pump-probe experiment causes significant changes to the spectral distribution of the retarded interaction between electrons and bosonic modes. We study the influence of these changes on pump-probe photoemission spectroscopy for a model electron-phonon coupled system using the nonequilibrium Keldysh formalism. We show that spectral rearrangement due to the driving field preserves an overall sum rule for the electronic self-energy, but modifies the effective electron-phonon scattering as a function of energy. Experimentally, this pump-modified scattering can be tracked by analyzing the fluence or excitation energy dependence of population decay rates and transient changes in dispersion kinks.

High concentration of nitrogen doped into graphene using N2 plasma with an aluminum oxide buffer layer

Abstract: We performed plasma doping of nitrogen into single-layer graphene on SiO2. Using aluminum oxide as a buffer layer to reduce the plasma damage, up to 19.7% nitrogen was substitutionally doped into graphene. The nitrogen doping of graphene was confirmed by Raman and X-ray photoemission spectroscopy analyses. The n-doping property of the N-doped graphene was measured by Raman spectroscopy. Raman mapping was carried out to statistically confirm the Dirac cone shift of graphene resulting from the N-doping. The Dirac cone shift was directly measured by ultraviolet photoemission spectroscopy (UPS). The UPS result was consistent with the value calculated from the Raman G peak shift.

Time- and angle-resolved photoemission spectroscopy of hydrated electrons near a liquid water surface.

Abstract: We present time- and angle-resolved photoemission spectroscopy of trapped electrons near liquid surfaces. Photoemission from the ground state of a hydrated electron at 260 nm is found to be isotropic, while anisotropic photoemission is observed for the excited states of 1,4-diazabicyclo[2,2,2]octane and ${\mathrm{I}}^{\ensuremath{-}}$ in aqueous solutions. Our results indicate that surface and subsurface species create hydrated electrons in the bulk side. No signature of a surface-bound electron has been observed.

Effects of Oxygen Adsorption on the Surface State of Epitaxial Silicene on Ag(111)

Abstract: Epitaxial silicene, which is one single layer of silicon atoms packed in a honeycomb structure, demonstrates a strong interaction with the substrate that dramatically affects its electronic structure. The role of electronic coupling in the chemical reactivity between the silicene and the substrate is still unclear so far, which is of great importance for functionalization of silicene layers. Here, we report the reconstructions and hybridized electronic structures of epitaxial 4x4 silicene on Ag(111), which are revealed by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. The hybridization between Si and Ag results in a metallic surface state, which can gradually decay due to oxygen adsorption. X-ray photoemission spectroscopy confirms the decoupling of Si-Ag bonds after oxygen treatment as well as the relatively oxygen resistance of Ag(111) surface, in contrast to 4x4 silicene [with respect to Ag(111)]. First-principles calculations have confirmed the evolution of the electronic structure of silicene during oxidation. It has been verified experimentally and theoretically that the high chemical activity of 4x4 silicene is attributable to the Si pz state, while the Ag(111) substrate exhibits relatively inert chemical behavior.