Tunable two-dimensional electron system at the (110) surface of SnO$_2$
J. Dai, E. Frantzeskakis, F. Fortuna, P. Lömker, R. Yukawa, M. Thees, S. Sengupta, P. Le Fèvre, F. Bertran, J. E. Rault, K. Horiba, M. Müller, H. Kumigashira, A. F. Santander-Syro
We report the observation of a two-dimensional electron system (2DES) at the $(110)$ surface of the transparent bulk insulator SnO$_2$, and the tunability of its carrier density by means of temperature or Eu deposition. The 2DES is insensitive to surface reconstructions and, surprisingly, it survives even after exposure to ambient conditions --an extraordinary fact recalling the well known catalytic properties SnO$_2$. Our data show that surface oxygen vacancies are at the origin of such 2DES, providing key information about the long-debated origin of $n$-type conductivity in SnO$_2$, at the basis of a wide range of applications. Furthermore, our study shows that the emergence of a 2DES in a given oxide depends on a delicate interplay between its crystal structure and the orbital character of its conduction band.
BaSnO$_3$ exhibits the highest carrier mobility among perovskite oxides, making it ideal for oxide electronics. Collective charge carrier oscillations, plasmons, are expected to arise in this material, thus providing a tool to control the nanoscale optical field for optoelectronics applications. Here, we demonstrate the existence of relatively long-lived plasmons supported by high-mobility charge carriers in La-doped BaSnO$_3$ (BLSO). By exploiting the high spatial and energy resolution of electron energy-loss spectroscopy with a focused beam in a scanning transmission electron microscope, we …
Motivated by the excellent electronic and optoelectronic properties of two-dimensional (2D) tin oxides, we systematically investigated the thermal conductivity of monolayer SnO and SnO2by the first-principles calculations. The room-temperature thermal conductivity of monolayer SnO and SnO2reaches 9.6 W/(mK) and 98.8 W/(mK), respectively. The size effect is much weaker for monolayer SnO than for monolayer SnO2, due to the coexistence of size dependent and independent component in the thermal conductivity of monolayer SnO. The large difference between the thermal conductivity of 2D tin oxides ca…
In this study, the structural, electronic and optical properties of Pb doped rutile SnO$_2$ were investigated using the range separated hybrid exchange-correlation functional method. In the calculations, LDA functional was used instead of PBE functional. The electronic structure of SnO$_2$ obtained by this method is quite compatible with the experimental data. The SnO$_2$ has an important usage area in optoelectronic devices due to its transparent and conductive nature. One of these important areas is the use of SnO$_2$ as an electron transport layer (ETL) in perovskite solar cells. Therefore,…
In this paper we use an ab-initio quantum transport approach to study the electron current flowing through lithiated SnO anodes for potential applications in Li-ion batteries. By investigating a set of lithiated structures with varying lithium concentrations, it is revealed that LixSnO can be a good conductor, with values comparable to bulk $β$-Sn and Li. A deeper insight into the current distribution indicates that electrons preferably follow specific trajectories, which offer superior conducting properties than others. These channels have been identified and it is shown here how they can enh…
Oxide two-dimensional electron gases (2DEGs) promise high charge carrier concentrations and low-loss electronic transport in semiconductors such as BaSnO$_{3}$ (BSO). ACBN0 computations for BSO/SrNbO$_{3}$ (SNO) interfaces show Nb-4$\textit{d}$ electron injection into extended Sn-5$\textit{s}$ electronic states. The conduction band minimum consists of Sn-5$\textit{s}$ states ~1.2 eV below the Fermi level for intermediate thickness 6-unit cell BSO/6-unit cell SNO superlattices, corresponding to an electron density in BSO of ~10$^{21}$ cm$^{-3}$. Experimental studies of analogous SNO/BSO interfa…
Both the semi-classical and quantum transport properties of F-doped SnO$_2$ thick films ($\sim$1\,$μ$m) were investigated experimentally. It is found that the resistivity caused by the thermal phonons obeys Bloch-Grüneisen law from $\sim$90 to 300\,K, while only the diffusive thermopower, which varies linearly with temperature from 300 down to 10\,K, can be observed.The phonon-drag thermopower is completely suppressed due to the long electron-phonon relaxation time in the compound. These observations, together with the temperature independent characteristic of carrier concentration, indicate t…
Based on the dimension of degeneracy, topological electronic systems can roughly be divided into three parts: nodal point, line and surface materials corresponding to zero-, one- and two-dimensional degeneracy, respectively. In parallel to electronic systems, the concept of topology was extended to phonons, promoting the birth of topological phonons. Till date, few nodal point, line and surface phonons candidates have been predicted in solid-state materials. In this study, based on symmetry analysis and first-principles calculation, for the first time, we prove that zero-, one- and two-dimensi…
ASnO3 (A=Ba, Sr) are unique perovskite oxides in that they have superior electron conductivity despite their wide optical band gaps. Using first-principles band structure calculations, we show that the small electron effective masses, thus, good electron conductivity of ASnO3 can be attributed to the large size of Sn in this system that gives the conduction band edge with antibonding Sn and O s characters. Moreover, we show that ASnO3 can be easily doped by La with shallow LaA(+/0) donor level. Our results, therefore, explained why the perovskite BaSnO3, SrSnO3, and their alloys are promising …
In this paper we investigate the effect of Cd doping at ultra-low concentrations in SnO$_2$ both experimentally, by measuring the temperature dependence of the electric quadrupole hyperfine interactions with time-differential perturbed angular correlation (TDPAC) spectroscopy using $^{111}$Cd as probe nuclei, and theoretically, by performing first-principles calculations based on the density functional theory. TDPAC spectra were successfully analyzed with a time-dependent on-off model for the perturbation factor. These results show combined dynamic plus static interactions whose electric-field…
High value of magnetic moment 0.08 emu/g at room temperature for SnO_2 nanoparticles (NPs) was observed. Surface functionalization with octadecyltrichlorosilane (OTS) enhanced the saturation magnetic moment of NPs to an anomalously high value of 0.187 emu/g by altering the electronic configuration on NPs surface. Surface functionalization also suppressed photoluminescence (PL) peaks arising from oxygen defects around 2 eV and caused an increase in the intensities of two peaks near violet region (2.6 - 3 eV). PL studies under uniform external magnetic field enriched understanding of the role of…
We present an approach to monitor and control the strength of the hybridization between electronic states of graphene and metal surfaces. Inspecting the distribution of the $π$ band in a high-quality graphene layer synthesized on Ni(111) by angle-resolved photoemission, we observe a new "kink" feature which indicates a strong hybridization between $π$ and \textit{d} states of graphene and nickel, respectively. Upon deposition and gradual intercalation of potassium atoms into the graphene/Ni(111) interface, the "kink" feature becomes less pronounced pointing at potassium mediated attenuation of…
Oxygen vacancies at the SnO2(110) and (101) surface and subsurface sites have been studied in the framework of density functional theory by using both all-electron Gaussian and pseudopotential plane-wave methods. The all-electron calculations have been performed using the B3LYP exchange-correlation functional with accurate estimations of energy gaps and density of states. We show that bulk oxygen vacancies are responsible for the appearance of a fully occupied flat energy level lying at about 1 eV above the top valence band, and an empty level resonant with the conduction band. Surface oxygen …
Using LDA+$U$, we investigate Li-doped rutile SnO$_2$(001) surface. The surface defect formation energy shows that it is easier for Li to be doped at surface Sn site than bulk Sn site in SnO$_2$. Li at surface and sub-surface Sn sites has a magnetic ground state, and the induced magnetic moments are not localized at Li site, but spread over Sn and O sites. The surface electronic structures show that Li at surface Sn site shows $100%$ spin-polarization (half metallic), whereas Li at sub-surface Sn site does not have half metallic state due to Li-Sn hybridized orbitals. The spin-polarized surfac…
Highly conducting $SnO_{2}$ thin films were prepared by chemical spray pyrolysis technique. One set of as-deposited films were annealed in air for 2 h at 850$^{o}$C. These as-deposited and annealed films were irradiated using $Au^{9+}$ ions with energy of 120 MeV at different fluences ranging from $1\times10^{11}$ to $3\times10^{13}$ $ions/cm^{2}$. Electrical measurement shows that as-deposited $SnO_{2}$ films are in conducting state with n = $3.164 \times 10^{20}$ $cm^{-3}$ and annealed $SnO_{2}$ films are in insulating state. The amorphized latent tracks are created only above a certain thre…
We report, for the first time, the luminescence property of the hydroxyl group surface functionalized quantum dots (QDs) and nanoparticles (NPs) of SnO_2 using low energy excitations of 2.54 eV (488 nm) and 2.42 eV (514.5 nm). This luminescence is in addition to generally observed luminescence from 'O' defects. The as-prepared SnO_2 quantum dots (QDs) are annealed at different temperatures in ambient conditions to create varied NPs in size. Subsequently, average size of the NPs is calculated from the acoustic vibrations observed at low frequencies in the Raman spectra and by the transmission e…
Compared with direct-gap semiconductors, the valley degeneracy of silicon and germanium opens up new channels for spin relaxation that counteract the spin degeneracy of the inversion-symmetric system. Here the symmetries of the electron-phonon interaction for silicon and germanium are identified and the resulting spin lifetimes are calculated. Room-temperature spin lifetimes of electrons in silicon are found to be comparable to those in gallium arsenide, however, the spin lifetimes in silicon or germanium can be tuned by reducing the valley degeneracy through strain or quantum confinement. The…
We present a new way to tune the electron-phonon coupling (EPC) in graphene by changing the deformation potential with electron/hole doping. We show the EPC for highest optical branch at the high symmetry point K, acquires a strong dependency on the doping level due to electron-electron correlation not accounted in mean-field approaches. Such a dependency influences the dispersion (with respect to the laser energy) of the Raman D and 2D lines and the splitting of the 2D peak in multi-layer graphene. Finally this doping dependence opens the possibility to construct tunable electronic devices th…
Tin monoxide is an interesting two-dimensional material because of the rare oxide semiconductor with bipolar conductivity. However, the lower room temperature mobility limits the applications of SnO in the future. Thus, we systematically investigate the effects of the different layer structures and strains on the electron-phonon coupling and phonon-limited mobility of SnO. The A2u phonon mode in the high frequency region is the main contributor coupling with electron for the different layer structures. And the orbital hybridization of Sn atoms existing only in bilayer structure changes the con…
We propose a novel class of two-dimensional (2D) Dirac materials in the MX family (M=Be, Mg, Zn and Cd, X = Cl, Br and I), which exhibit graphene-like band structures with linearly-dispersing Dirac-cone states over large energy scales (0.8~1.8 eV) and ultra-high Fermi velocities comparable to graphene. The electronic and topological properties are found to be highly tunable and amenable to effective modulation via anion-layer substitution and vertical electric field. The electronic structures of several members of the family are shown to host a Van-Hove singularity (VHS) close to the energy of…
For the purpose of elucidating the gas sensing mechanism of SnO$_2$ for NO and NO$_2$ gases, we calculate the phase diagram of SnO$_2$(110) surface in contact with an O$_2$ and NO gas environment by means of {\it ab initio} thermodynamic method. Firstly we build a range of surface slab models of oxygen pre-adsorbed SnO$_2$(110) surfaces using (1$\times$1) and (2$\times$1) surface unit cells and calculate their Gibbs free energies considering only oxygen chemical potential. The fully reduced surface containing the bridging and in-plane oxygen vacancies in the oxygen-poor condition, while the fu…
It is investigated that the lateral shifts of the ballistic electrons transmitted through a semiconductor quantum slabs can be negative as well as positive, which are analogous to the anomalous lateral shifts of the transmitted light beam through a dielectric slab. The necessary condition for the shift to be negative is advanced. It is shown that the lateral shifts depend not only on the structure parameters of semiconductor quantum slab, but also on the incidence angle and the incident energy. Numerical calculations further indicate that the lateral shifts can be tuned from negative to positi…
We report on a theoretical study of collective electronic excitations in single-layer antimony crystals (antimonene), a novel two-dimensional semiconductor with strong spin-orbit coupling. Based on a tight-binding model, we consider electron-doped antimonene and demonstrate that the combination of spin-orbit effects with external bias gives rise to peculiar plasmon excitations in the mid-infrared spectral range. These excitations are characterized by low losses and negative dispersion at frequencies effectively tunable by doping and bias voltage. The observed behavior is attributed to the spin…
The honeycomb lattice of graphene is a unique two-dimensional (2D) system where the quantum mechanics of electrons is equivalent to that of relativistic Dirac fermions. Novel nanometer-scale behavior in this material, including electronic scattering, spin-based phenomena, and collective excitations, is predicted to be sensitive to charge carrier density. In order to probe local, carrier-density dependent properties in graphene we have performed atomically-resolved scanning tunneling spectroscopy measurements on mechanically cleaved graphene flake devices equipped with tunable back-gate electro…
We report the discovery of two-dimensional electron gas (2DEG) at the surface of thermoelectric material In$_4$Se$_3$ by angle-resolved photoemission spectroscopy. The observed 2DEG exhibits a nearly isotropic band dispersion with a considerably small effective mass of m* = 0.16 m_0, and its carrier density shows a significant temperature dependence, leading to unconventional metal-semiconductor transition at the surface. The observed wide-range thermal tunability of 2DEG in In$_4$Se$_3$ gives rise to additional degrees of freedom to better control the surface carriers of semiconductors.
The electron spins of semiconductor defects can have complex interactions with their host, particularly in polar materials like SiC where electrical and mechanical variables are intertwined. By combining pulsed spin resonance with ab-initio simulations, we show that spin-spin interactions within SiC neutral divacancies give rise to spin states with an enhanced Stark effect, sub-10**-6 strain sensitivity, and highly spin-dependent photoluminescence with intensity contrasts of 15-36%. These results establish SiC color centers as compelling systems for sensing nanoscale fields.
