Iori Tanabe

The Complete In-Gap Electronic Structure of Colloidal Quantum Dot Solids and Its Correlation with Electronic Transport and Photovoltaic Performance

The direct observation of the complete electronic band structure of a family of PbS CQD solids via photoelectron spectroscopy is reported. We investigate how materials processing strategies, such as the latest passivation methods that produce record-performance photovoltaics, achieve their performance advances. Halide passivated films show a drastic reduction in states in the midgap, contributing to a marked improvement in the device performance.

Spin-orbit coupling in the band structure of monolayer WSe2.

We used angle-resolved photoemission spectroscopy (ARPES) to map out the band structure of single-layer WSe2. The splitting of the top of the valence band because of spin-orbit coupling is 513 ± 10 meV, in general agreement with theoretical predictions and in the same range as that of bulk WSe2. Overall, our density functional theory (DFT) calculations of the band structure are in excellent agreement with the ARPES results. We have verified that the few discrepancies between theory and experiment are not due to the effect of strain. The differences between the DFT-calculated band structure using local density approximation (LDA) and that using the generalized gradient approximation (GGA), for single-layer WSe2, are caused mainly by differences in the respective charge densities.

Band structure characterization of WS2 grown by chemical vapor deposition

Growth by chemical vapor deposition (CVD) leads to multilayer WS2 of very high quality, based on high-resolution angle-resolved photoemission spectroscopy. The experimental valence band electronic structure is considered to be in good agreement with that obtained from density functional theory calculations. We find the spin-orbit splitting at the K¯ point to be 420  ± 20 meV with a hole effective mass of −0.35  ± 0.02 me for the upper spin-orbit component (the branch closer to the Fermi level) and −0.43  ± 0.07 me for the lower spin-orbit component. As predicted by theory, a thickness-dependent increase of bandwidth is observed at the top of the valence band, in the region of the Brillouin zone center. The top of the valence band of the CVD-prepared films exhibits a substantial binding energy, consistent with n-type behavior, and in agreement with transistor characteristics acquired using devices incorporating the same WS2 material.

Atomic layer-by-layer deposition of h-BN(0001) on cobalt: a building block for spintronics and graphene electronics

X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and Raman measurements demonstrate that macroscopically continuous hexagonal BN(0001) (h-BN) multilayer layer films can be grown by atomic layer deposition on Co(0001) substrates. The growth procedure involves alternating exposures of BCl3 and NH3 at 550 K, followed by annealing in ultrahigh vacuum above 700 K to induce long-range order. XPS data demonstrate that the films have a consistent B:N atomic ratio of 1:1. LEED data show that the BN layers are azimuthally in registry, with an estimated domain size of ~170 A. The films are continuous over a macroscopic (1 cm × 1 cm) area as demonstrated by the fact that exposure of a h-BN(0001) bi-layer film to ambient at room temperature yields no observable Co oxidation, although some N oxidation is observed, and long range order is lost. The ability to grow large area, continuous multilayer BN films on Co, with atomic level control of film thickness, makes possible an array of magnetic tunnel junction and spin filter applications.

Influence of steric hindrance on the molecular packing and the anchoring of quinonoid zwitterions on gold surfaces

Driven by the huge potential of engineering the molecular band offset with highly dipolar molecules for improving charge injection into organic electrics, the anchoring of various N-alkyl substituted quinonoid zwitterions of formula (R = iPr, Cy, CH2CH(Et)CH2CH2CH2CH3,…) on gold surfaces is studied. The N–Au interactions result in an orthogonal arrangement of the zwitterions cores with respect to the surface, and stabilize adsorbed compact rows of molecules. IR spectroscopy is used as a straightforward diagnostic tool to validate the presence of ultra-thin molecular films. When combined with computational studies, IR measurements indicate that the presence of a CH2 group in α position to the nitrogen atom is important for a successful anchoring through N–Au interactions. The presence of such a flexible CH2 spacer, or of aryl groups, enables π-interactions with the surface, making possible the anchoring of enantiopure or sterically-hindered zwitterions. X-ray diffraction analyses indicate that the intermolecular spacing within a row of molecules can be modulated by the nature of the alkyl substituent R. This modulation is directly relevant to the electronic properties of the corresponding molecular films since these zwitterions are expected to form rows on gold surfaces similar to those observed in the bulk crystalline state.

Adsorbate doping of MoS2 and WSe2: the influence of Na and Co

We have investigated the influence of metal adsorbates (sodium and cobalt) on the occupied and unoccupied electronic structure of MoS2(0 0 0 1) and WSe2(0 0 0 1), through a combination of both photoemission and inverse photoemission. The electronic structure is rigidly shifted in both the WSe2 and MoS2 systems, with either Na or Co adsorption, generally as predicted by accompanying density functional theory based calculations. Na adsorption is found to behave as an electron donor (n-type) in MoS2, while Co adsorption acts as an electron acceptor (p-type) in WSe2. The n-type transition metal dichalcogenide (MoS2) is easily doped more n-type with Na deposition while the p-type transition metal dichalcogenide (WSe2) is easily doped more p-type with Co deposition. The binding energy shifts have some correlation with the work function differences between the metallic adlayer and the transition metal dichalcogenide substrate.

Low temperature growth of cobalt on Cr2O3(0 0 0 1)

The thickness and temperature dependence of in situ grown cobalt thin films on Cr2O3(0 0 0 1) single crystalline substrate has been studied by low energy electron microscopy (LEEM). The LEEM images indicate that growth of thin Co films (⩽5 monolayers) on chromia at 100 K tends to be continuous and flat with suppressed island growth compared to films grown on chromia at room temperature and above (to ~440 K). Low energy electron diffraction indicates that disorder builds and crystallinity of the cobalt thin film decreases with increased film thickness. Compared with cobalt thin films on Al2O3(0 0 0 1) single crystalline substrate, cobalt thin films on Cr2O3(0 0 0 1) show larger magnetic contrast in magnetic force microscopy indicating enhancement of perpendicular anisotropy induced by Cr2O3.

The symmetry-resolved electronic structure of 2H-WSe2(0 0 0 1)

The orbital symmetry of the band structure of 2H-WSe2(0 0 0 1) has been investigated by means of angle-resolved photoelectron spectroscopy (ARPES) and density functional theory (DFT). The WSe2(0 0 0 1) experimental band structure is found, by ARPES, to be significantly different for states of even and odd reflection parities along both the [Formula: see text]-[Formula: see text] and [Formula: see text]-[Formula: see text] lines, in good agreement with results obtained from DFT. The light polarization dependence of the photoemission intensities from the top of the valence band for bulk WSe2(0 0 0 1) is explained by the dominance of W 5[Formula: see text] states around the [Formula: see text]-point and W 5d xy states around the [Formula: see text]-point, thus dominated, respectively, by states of even and odd symmetry, with respect to the [Formula: see text]-[Formula: see text] line. The splitting of the topmost valence band at [Formula: see text], due to spin-orbit coupling, is measured to be 0.49  ±  0.01 eV, in agreement with the 0.48 eV value from DFT, and prior measurements for the bulk single crystal WSe2(0 0 0 1), albeit slightly smaller than the 0.513  ±  0.01 eV observed for monolayer WSe2.

Multi-layer graphene on Co(0001) by ethanol chemical vapor deposition

N layer (1 ≤ N ≤ 10) monolayer films of graphene were formed by the chemical vapor deposition of ethanol on either clean or oxidized Co(0001) substrates at 1000 K, with no evidence of either interfacial oxide formation or graphene/substrate charge transfer. Low energy electron diffraction data indicate that the graphene layers or domains are azimuthally rotated, but otherwise show the characteristics of graphene with a Raman spectra D/G intensity ratio of 0.25 or less, and a C 1s binding energy of 284.5 eV with an observable π → π* transition. Magneto optic Kerr effect spectra indicate only the ferromagnetic hysteresis with high remanence, with no evidence of Co/graphene exchange bias. This is very different from the negligible remanent magnetization of graphene/Co3O4/Co trilayer structures.

Changes in molecular film metallicity with minor modifications of the constitutive quinonoid zwitterions

Molecular films of quinonoid zwitterions, of the general formula C6H2(O)2(NHR)2, have been shown to display electronic properties highly dependent on the nature of the N-substituent R when deposited on gold substrates. The different spacing and organization of the molecules can lead to molecular films with semi-metal or dielectric behavior. With the long term goal to establish how packing effects in the solid state correlate with properties as thin films, we first attempted to identify by X-ray diffraction analysis candidate molecules showing suitable packing arrangements in the crystalline state. To this end, we have prepared a series of new functionalized, enantiopure or sterically-hindered quinonoid zwitterions and established the crystal structure of those with R = CH2–CH2–Ph (6), CH2–CH2–CH2–Ph (7), CH2–CH2–CH2–CH2–Ph (8), CH2–CH2–CH(Ph)–Ph (9), CH(CH3)–Ph (12), CH(CH2–CH3)–Ph (13), CH2–((4–CH3)–C6H4) (15), CH2–((4–NH2)–C6H4) (19) and CH2–CH2–((3,4–(OCH3)2)–C6H3) (24). An analysis of the crystal packing of three molecules, 5, 13 and 15, selected as illustrative examples for comparisons, was carried out and it was unexpectedly found that these chemically very similar molecules gave rise to different packing in the bulk, with resulting thin films showing different electronic properties. Various methods have been used for the characterization of the films, such as synchrotron radiation-based FTIR spatial spectra-microscopy, which provided an anchoring map of zwitterion 15 on a patterned substrate (Au/SiO2) showing its selective anchoring on gold. This is one of the best examples of preferential anchoring of a zwitterion and the sole example of spatial localization for a quinonoid zwitterion thin film. We have also used combined photoemission and inverse photoemission spectra and the data were compared to occupied and unoccupied DFT density state calculations.