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At least 1,387 records · Page 77

Spectroscopic evidence of highly correlated electrons in $\mathrm{VSe_2}$

We present detailed high-resolution angle-resolved photoemission experiments on $\mathrm{VSe_2}$ grown under various conditions. The surface electronic structure optimally grown samples can host high-temperature spectral kink, quasiparticle peak, and the Fermi gap. Collective observation of these electronic features refers to the strong electronic correlation and is usually attributed to the characteristics of superconductors. Temperature evolution of the quasiparticle peak and the Fermi gap also follow the trend observed in high-$T_c$ superconductors as progressive quenching of the quasiparticle peak at a lower temperature than the complete Fermi gap closing. As a result, the quasiparticle peak can be observed up to 100 ± 5 K while the Fermi gap persists up to ~ 150 K. Importantly, these realizations can guide future studies to induce high-temperature superconductivity in transition metal dichalcogenides as well as understand the physics behind high-$T_c$ superconductors.

36 MATERIALS SCIENCE↗

$N$-Type Surface Doping of MAPbI 3 via Charge Transfer from Small Molecules

Organic hole and electron transport materials are regularly employed as electron- and hole-blocking layers in perovskite thin-film solar cells. In order to optimize charge-extraction in the device, these organic layers can be doped using organic small molecules. However, to date there has been little work carried out on direct doping of perovskite surfaces. In this report, we study the change in electrical properties of thin films of MAPbI 3 by surface doping the film with an organic dopant molecule: cobaltocene (Co(C 5 H 5 ) 2 ). By varying the quantity of cobaltocene deposited, the conductivity of MAPbI3 thin films are observed to be tunable over several orders of magnitude. We observe a tunable shift in the Fermi level illustrating that charge transfer doping enables control over the interfacial energy levels. An increase in photoconductivity is seen at intermediate doping levels, indicating passivation of surface traps confirmed by increased photolumeniscence. In conclusion, this model system provides a means to understand more complex heterointerfaces of doped organic blends at perovskite surfaces.

36 MATERIALS SCIENCE↗

A study of the characteristics of indium tin oxide after chlorine electro-chemical treatment

Graphical abstract: The presence of Chlorine in the outer surface resulted in a highly electro-negative surface states and an increase in the vacuum energy level. - Highlights: • We investigated the influence of chlorine surface treatment on ITO properties. • Chlorination induced the change of the electro-static potential in the outer surface. • Chlorine electro-chemical treatment of ITO is a simple, fast and effective technique. - Abstract: In this work, we investigate the influence of a chlorine-based electro-chemical surface treatment on the characteristics of indium tin oxide (ITO) including the work function, chemical composition, and phase transition. The treated ITOs were characterized using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), 4-point probe measurements, and grazing incidence X-ray diffraction (GI-XRD). We confirmed a change of the chemical composition in the near-surface region of the ITO and the formation of indium-chlorine (In-Cl) bonds and surface dipoles (via XPS). In particular, the change of the electro-static potential in the outer surface was caused by chlorination. Due to the vacuum-level shift after the electro-chemical treatment in a dilute hydrochloric acid, the ITO work function was increased by ∼0.43 eV (via UPS); furthermore, the electro-negativity of the chlorine anions attracted electrons to emit them from the hole transport layer (HTL) to the ITO anodes, resulting in an increase of the hole-injection efficiency.

36 MATERIALS SCIENCE↗

Designing Passivating, Carrier-Selective Contacts for Photovoltaic Devices

"The first step towards building a high-efficiency solar cell is to develop an absorber with few recombination-active defects. Many photovoltaic technologies have already achieved this (monocrystalline Si, III-V materials grown on lattice-matched substrates, perovskites, polycrystalline CdTe and CIGS); those that have not (a-Si:H, organics) have been limited to low open-circuit voltage. The second step is to develop contacts that both inhibit surface recombination and allow for low-resistance collection of either only electrons or only holes. For most photovoltaic technologies, this step is both more difficult and less explored than the first, and we are unaware of a prescribed methodology for selecting materials for contacts to solar cells. We elucidate a unified, conceptual understanding of contacts within which existing contacting schemes can be interpreted and future contacting schemes can be imagined. Whereas a split of the quasi-Fermi levels of holes and electrons is required in the absorber of any solar cell to generate a voltage, carriers are eventually collected through a metallic wire in which no such quasi-Fermi-level split exists. We define a contact to be all layers between the bulk of the absorber and the recombination-active interface through which carriers are extracted. The quasi-Fermi levels must necessarily collapse at this interface, and thus the transition between maximal quasi-Fermi-level splitting (in the absorber) and no splitting occurs entirely in the contact. Depending on the solar cell architecture, the contact will usually extend from the surface of the absorber to the surface of a metal or transparent conductive oxide layer, and may include deposited or diffused doped layers (e.g., as in crystalline and thin-film Si cells) and heterostructure buffer layers (e.g., the CdS layer in a CdTe device). We further define a passivating contact as one that enables high quasi-Fermi-level splitting in the absorber (large “internal” voltage), where “high” is relative to the splitting dictated by bulk recombination. Finally, we define a carrier-selective contact as one that enables a high “external” voltage measured across the contacts, where “high” is relative to the internal voltage. With these definitions, passivating contacts are those that allow only electrons, only holes, or neither electrons or holes to transport from the absorber to any position in the contact that has recombination-active defects. An excellent example of this is a SiNx layer on a Si wafer: the layer removes dangling bonds at the wafer surface (where there are both electrons and holes) and does not allow either carrier type to travel to its outermost surface, where there are undoubtedly defects. Carrier-selective contacts are then passivating contacts that also allow for low-impedance flow of either electrons or holes (but not both) to the recombination-active, extracting interface. The most common example is a heavily doped layer that establishes an electric field at the absorber surface, which then “filters” the carriers that may pass to the contact according to the sign of their charge.

14 SOLAR ENERGY↗

Quasi one-dimensional band dispersion and surface metallization in long-range ordered polymeric wires

We study the electronic structure of an ordered array of poly(para-phenylene) chains produced by surface-catalyzed dehalogenative polymerization of 1,4-dibromobenzene on copper (110). The quantization of unoccupied molecular states is measured as a function of oligomer length by scanning tunnelling spectroscopy, with Fermi level crossings observed for chains longer than ten phenyl rings. Angle-resolved photoelectron spectroscopy reveals a quasi-one-dimensional valence band as well as a direct gap of 1.15 eV, as the conduction band is partially filled through adsorption on the surface. Tight-binding modelling and ab initio density functional theory calculations lead to a full description of the organic band-structure, including the k-dispersion, the gap size and electron charge transfer mechanisms, highlighting a strong substrate-molecule interaction that drives the system into a metallic behaviour. In summary, we have fully characterized the band structure of a carbon-based conducting wire. This model system may be considered as a fingerprint of -conjugation of surface organic frameworks.

36 MATERIALS SCIENCE↗

Structural, electronic and magnetic properties of the MnGa(111)-1 $\times$ 2 and 2 $\times$ 2 reconstructions: Spin polarized first principles total energy calculations

In this work, using first principles total energy calculations within the periodic spin polarized density functional theory, we have investigated the structural, electronic, and magnetic properties of manganese gallium (MnGa) alloys. Specifically, we explore the MnGa(111)-1 $\times$ 2 and 2 $\times$ 2 reconstructions. The surface formation energies reveal that selected substitutions occur under Mn (Ga) rich growth conditions. Structures with top layers missing all Mn (Ga) atoms and two layers deep substitutions are also investigated. However, the formation energy shows that these structures are less favorable. For the stable structures, the magnetic properties per layer are proportional to the Mn:Ga ratio. Also, the density of states shows that the MnGa surfaces are metallic. The projected density of states shows that the electronic states in the vicinity of the Fermi level are due mainly to the manganese 3d orbitals. However charge density plots reveal that Mn 3d electrons are closer to the nucleus than Ga sp electrons. Consequently, experimental scanning tunneling microscopy images reveal periodically-arranged bright features, corresponding to the Ga atoms.

36 MATERIALS SCIENCE↗

Charge Transport at Ti-Doped Hematite (001)/Aqueous Interfaces

Solid-state transport and electrochemical properties of Ti-doped hematite (001) epitaxial thin films (6.0, 8.3, and 16.6 at% Ti) were probed to achieve a better understanding of doped hematite for photoelectrochemical (PEC) applications. Room temperature resistivity measurements predict a resistivity minimum near 10 at% Ti doping, which can be rationalized as maximizing charge compensating Fe2+ concentration and Fe3+ electron accepting percolation pathways simultaneously. Temperature dependent resistivity data are consistent with small polaron hopping, revealing an activation energy that is Ti concentration dependent and commensurate with previously reported values (≈ 0.11 eV). In contact with inert electrolyte, linear Mott-Schottky data at various pH values indicate that there is predominantly a single donor for Ti-doped hematite at 6.0 at% Ti and 16.6 at% Ti concentrations. Two slope Mott-Schottky data at pH extremes indicate the presence of a second donor or surface state in the 8.3 at% Ti-doped film, with an energy level ≈ 0.7 eV below the Fermi level. Mott-Schottky plots indicate pH and Ti concentration dependent flatband potentials of -0.4 to -1.1 V vs. Ag/AgCl, commensurate with previously reported data. Flatband potentials exhibited super-Nernstian pH dependence ranging from -69.1 to -101.0 mV/pH. Carrier concentration data indicate that the Fermi energy of the Ti-doped system is Ti concentration dependent, with a minimum of 0.15 eV near 10 at% Ti. These energy level data allow us to construct an energy band diagram for Ti-doped hematite electrode/electrolyte interfaces, and to determine a Ti-doping concentration t

Environmental Molecular Sciences Laboratory↗

Modeling surface roughness scattering in metallic nanowires

Ando's model provides a rigorous quantum-mechanical framework for electron-surface roughness scattering, based on the detailed roughness structure. We apply this method to metallic nanowires and improve the model introducing surface roughness distribution functions on a finite domain with analytical expressions for the average surface roughness matrix elements. This approach is valid for any roughness size and extends beyond the commonly used Prange-Nee approximation. The resistivity scaling is obtained from the self-consistent relaxation time solution of the Boltzmann transport equation and is compared to Prange-Nee's approach and other known methods. The results show that a substantial drop in resistivity can be obtained for certain diameters by achieving a large momentum gap between Fermi level states with positive and negative momentum in the transport direction.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Epitaxial growth and electronic properties of mixed valence YbAl{sub 3} thin films

We report the growth of thin films of the mixed valence compound YbAl{sub 3} on MgO using molecular-beam epitaxy. Employing an aluminum buffer layer, epitaxial (001) films can be grown with sub-nm surface roughness. Using x-ray diffraction, in situ low-energy electron diffraction, and aberration-corrected scanning transmission electron microscopy, we establish that the films are ordered in the bulk as well as at the surface. Our films show a coherence temperature of 37 K, comparable to that reported for bulk single crystals. Photoelectron spectroscopy reveals contributions from both f{sup 13} and f{sup 12} final states establishing that YbAl{sub 3} is a mixed valence compound and shows the presence of a Kondo Resonance peak near the Fermi-level.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

FERMI Observations of Gamma -Ray Emission From the Moon

We report on the detection of high-energy γ -ray emission from the Moon during the first 24 months of observations by the Fermi Large Area Telescope (LAT). This emission comes from particle cascades produced by cosmicray (CR) nuclei and electrons interacting with the lunar surface. The differential spectrum of the Moon is soft and can be described as a log-parabolic function with an effective cutoff at 2-3 GeV, while the average integral flux measured with the LAT from the beginning of observations in 2008 August to the end of 2010 August is F(greater than100 MeV) = (1.04 plus or minus 0.01 [statistical error] plus or minus 0.1 [systematic error]) × 10(sup −6) cm(sup −2) s(sup −1). This flux is about a factor 2-3 higher than that observed between 1991 and 1994 by the EGRET experiment on board the Compton Gamma Ray Observatory, F(greater than100 MeV)≈5×10(sup −7) cm(sup −2) s(sup −1), when solar activity was relatively high. The higher gamma -ray flux measured by Fermi is consistent with the deep solar minimum conditions during the first 24 months of the mission, which reduced effects of heliospheric modulation, and thus increased the heliospheric flux of Galactic CRs. A detailed comparison of the light curve with McMurdo Neutron Monitor rates suggests a correlation of the trends. The Moon and the Sun are so far the only known bright emitters of gamma-rays with fast celestial motion. Their paths across the sky are projected onto the Galactic center and high Galactic latitudes as well as onto other areas crowded with high-energy gamma-ray sources. Analysis of the lunar and solar emission may thus be important for studies of weak and transient sources near the ecliptic.

fermi↗

Deposition-Dependent Coverage and Performance of Phosphonic Acid Interface Modifiers in Halide Perovskite Optoelectronics

In this work, we study the effect of various deposition methods for phosphonic acid interface modifiers commonly pursued as self-assembled monolayers in high-performance metal halide perovskite photovoltaics and light-emitting diodes. We compare the deposition of (2-(3,6-diiodo-9H-carbazol-9-yl)ethyl)phosphonic acid onto indium tin oxide (ITO) bottom contacts by varying three parameters: the method of deposition, specifically spin coating or prolonged dip coating; ITO surface treatment via HCl/FeCl3 etching; and use in combination with a second modifier, 1,6-hexylenediphosphonic acid. We demonstrate that varying these modification protocols can impact time-resolved photoluminescence carrier lifetimes and quasi-Fermi level splitting of perovskite films deposited onto the phosphonic acid-modified ITO. Ultraviolet photoelectron spectroscopy shows an increase in the effective work function after phosphonic acid modification and clear evidence for photoemission from carbazole functional groups at the ITO surface. We used X-ray photoelectron spectroscopy to probe differences in phosphonic acid coverage on the metal oxide contact and show that perovskite samples grown on ITO with the highest phosphonic acid coverage exhibit the longest carrier lifetimes. Finally, we establish that device performance follows these same trends. These results indicate that the reactivity, heterogeneity, and composition of the bottom contact help to control recombination rates and therefore power conversion efficiencies. ITO etching, prolonged deposition times for phosphonic acids via dip coating, and the use of a secondary, more hydrophilic bisphosphonic acid all contribute to improvements in surface coverage, carrier lifetime, and device efficiency. Furthermore, these improvements each have a positive impact, and we achieve the best results when all three strategies are implemented.

contact engineering↗

Giant Valley Splitting and Valley Polarized Plasmonics in Group V Transition-Metal Dichalcogenide Monolayers

Two-dimensional group VI transition-metal dichalcogenides (TMDs) provide a promising platform to encode and manipulate quantum information in the valleytronics. However, the two valleys are energetically degenerate, protected by time-reversal symmetry (TRS). To lift this degeneracy, one needs to break the TRS by either applying an external magnetic field or using a magnetic rare-earth oxide substrate. Here, we predict a different strategy to achieve this goal. We propose that the ferromagnetic group V TMD monolayer, in which the TRS is intrinsically broken, can produce a larger valley and spin splitting. A polarized ZnS(0001) surface is also used as a substrate, which shifts the valleys to the low-energy regime (near the Fermi level). Moreover, by calculating its collective electronic excitation behaviors, we show that such a system hosts a giant valley polarized terahertz plasmonics. Our results demonstrate a new way to design and use valleytronic devices, which are both fundamentally and technologically significant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Weyl semimetal in the rare-earth hexaboride family supporting a pseudonodal surface and a giant anomalous Hall effect

Rare-earth hexaborides offer a rich tapestry for exploring the interplay of topological orders, magnetism, and electron-correlation effects associated with protected quantum phenomena. Using first-principles modeling, we identify in cerium hexaboride (CeB 6 ) a topological state that harbors a pseudonodal surface (PNS) along with double-Weyl fermions. An analysis of the electronic states in the vicinity of the Fermi level reveals the presence of M z -mirror-symmetry-protected band crossings that involve itinerant (d) and localized (f) states of Ce. These band crossings are found to remain nearly gapless as one goes away from the mirror plane, driving the formation of PNS states. We also demonstrate the presence of coexisting double-Weyl fermions with chiral charges of ±2 on the C 4z rotational axis. By analyzing the Berry curvature field associated with the topological states, we predict that CeB 6 supports a giant anomalous Hall conductivity of -1840Ω -1 cm -1 in the slightly electron-doped regime, which would be larger than the values reported to date in magnetic Weyl semimetals. Our study thus indicates that CeB 6 , which combines ferromagnetic order with topological physics in a heavy-fermion matrix, would provide a promising playground for investigating topological magnetic states with giant anomalous Hall responses.

36 MATERIALS SCIENCE↗

Effects of the surface termination and the oxygen vacancy position on LaNiO 3 ultra-thin films: First-principles study

In this study, while ultra-thin layers of the LaNiO 3 film exhibit a remarkable metal-insulator transition as the film thickness becomes smaller than a few unit cell (u.c.), the formation of possible oxygen vacancies and their effects on the correlated electronic structure have been rarely studied using first principles. Here, we investigate the effects of the surface termination and the oxygen vacancy position on the electronic properties and vacancy energetics of LaNiO 3 ultra-thin films under the compressive strain using density functional theory plus U (DFT + U). We find that oxygen vacancies can be easily formed in the Ni layers with the NiO 2 terminated surface (0.5 u.c. and 1.5 u.c. thickness) compared to the structures with the LaO terminated surface and the in-plane vacancy is energetically favored than the out-of-plane vacancy. When two vacancy sites are allowed, the Ni square plane geometry is energetically more stable in most cases as two oxygen vacancies tend to stay near a Ni ion. Strong anisotropy between the in-plane and out-of-plane vacancy formation as well as the layer and orbital dependent electronic structure occur due to strain, surface termination, charge reconstruction, and quantum confinement effects. The in-plane vacancy of the NiO 2 terminated structure is favored since the released charge due to the oxygen vacancy can be easily accommodated in the d x 2 -y 2 orbital, which is less occupied than the d z 2 orbital. Remarkably, the oxygen vacancy structure containing the Ni square-plane geometry becomes an insulating state in DFT + U with a sizable band gap of 1.2 eV because the large crystal field splitting between d z 2 and d x 2 -y 2 orbitals in the square-plane favors an insulating state and the Mott insulating state is induced in other Ni sites due to strong electronic correlations. In the thin-film structure without oxygen vacancies, the strong correlation effect in DFT + U drives a pseudogap ground state at the Fermi energy, similarly as the experimental photo-emission spectra; however, the variation of the DFT + U electronic structure depending on the surface termination becomes weaker compared to those obtained in DFT.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Stoichiometry-dependent surface electronic structure of SrTiO3 films grown by hybrid molecular beam epitaxy

We investigate the surface electronic structure of SrTiO3 (STO) films grown by a hybrid molecular beam epitaxy that are both stoichiometric and nonstoichiometric by means of x-ray photoelectron spectroscopy and electron energy loss spectroscopy. Increasing the fraction of the surface that is terminated with an SrO layer is correlated with a decrease in the chemical potential whereby the valence band maximum moves closer to the Fermi level, but without a significant change in the bandgap. Inasmuch as SrO-terminated STO (001) has previously been shown to act as an electron scavenger in which carriers from the bulk are trapped, we argue that the high fraction of SrO in the terminal layer is what lowers the chemical potential in Sr-rich STO. Our experimental results provide important insights into various physical phenomena that can occur on STO (001) surfaces and their effect on bulk electronic properties.

Lee, Dooyong (ORCID:0000000175361677)↗

Evidence for nitrogen binding to surface defects for topological insulator Bi 2 Se 3

Using scanning tunneling spectroscopy and theoretical simulations we have studied the effects of nitrogen gas exposure on the electronic density of states of Bi 2 Se 3 , a well-studied topological insulator. In carefully controlled measurements, Bi 2 Se 3 crystals were initially cleaved in a helium gas environment and then exposed to a 22 SCFH flow of ultra-high purity N 2 gas. We observe a resulting change in the spectral curves, with the exposure effect saturating after approximately 50 min, ultimately bringing the Dirac point about 50 meV closer to the Fermi level. Furthermore, these results are compared to density functional theory calculations, which support a picture of N 2 molecules physisorbing near Se vacancies. Furthermore, ab initio molecular dynamics simulations aided by a Blue Moon ensemble method reveal the dissociative adsorption of N 2 molecules which then bind strongly to Se vacancies at the surface. In this scenario, the binding of the N atom to a Se vacancy site removes the surface defect state created by the vacancy and changes the position of the Fermi energy with respect to the Dirac point.

36 MATERIALS SCIENCE↗

Comparative operando XPS studies of quasi-Fermi level splitting and open-circuit voltage in CZTSe/CdS and CIGS/CdS junctions and device structures

This contribution describes operando x-ray photoelectron spectroscopy (opXPS) studies of Cu(In,Ga)Se 2 (CIGS) and Cu 2 ZnSnSe 4 (CZTSe) absorber layers and device structures. X-ray-excited valence-band and core-level spectra were acquired on bare absorber surfaces and after CdS and ZnO:Al depositions in standard absorber/CdS/ZnO/ZnO:Al device stacks. OpXPS data sets were acquired at various x-ray fluxes, with and without white-light illumination. From these measurements, quasi-Fermi level splitting (ΔE F ) values in the absorber/CdS junctions were measured directly as a function of excitation conditions. For both CIGS and CZTSe, results show that ..delta..EF proportional to the full open-circuit voltage (V OC ) of the completed devices is present after the deposition of the CdS layer - i.e., E F = qV OC - demonstrating that the so-called V OC deficit in CZTSe solar cells is also present at this stage of processing. The authors find that photoexcitation due to x-rays or stray visible light during XPS or similar measurements can produce measurable photovoltages in materials, absorber/CdS junctions, and finished devices. In situ current density versus voltage measurements on a typical CIGS device reveal that x-ray-induced photoexcitation associated with typical XPS measurement conditions is equivalent to ~3 x 10 -3 suns, which in this study produced V OC = 440 mV. These findings demonstrate that accounting for photoexcitation conditions during XPS or similar measurements can improve band-offset determinations and produce more reliable values for the junction built-in voltage. The implications of the study findings on the CZTSe V OC deficit and device performance are discussed.

36 MATERIALS SCIENCE↗

Stretching Epitaxial La 0.6 Sr 0.4 CoO 3–δ for Fast Oxygen Reduction

The slow kinetics of the oxygen reduction reaction (ORR) is one of the key challenges in developing high performance energy devices, such as solid oxide fuel cells. Straining a film by growing on a lattice-mismatched substrate has been a conventional approach to enhance the ORR activity. However, due to the limited choice of electrolyte substrates to alter the degree of strain, a systematic study in various materials has been a challenge. Here, we explore the strain modulation of the ORR kinetics by growing epitaxial La 0.6 Sr 0.4 CoO 3-δ (LSCO) films on yttria-stabilized zirconia substrates with the film thickness below and above the critical thickness for strain relaxation. Two orders of magnitude higher ORR kinetics is achieved in an ultrathin film with ~0.8% tensile strain as compared to unstrained films. Time-of-flight secondary ion mass spectrometry depth profiling confirms that the Sr surface segregation is not responsible for the enhanced ORR in strained films. Here, we attribute this enhancement of ORR kinetics to the increase in oxygen vacancy concentration in the tensile-strained LSCO film owing to the reduced activation barrier for oxygen surface exchange kinetics. Density functional theory calculations reveal an upshift of the oxygen 2p-band center relative to the Fermi level by tensile strain, indicating the origin of the enhanced ORR kinetics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗