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Photocurrent production in the quasi-one-dimensional transition metal trichalcogenides, TiS3(001) and ZrS3(001), was exam-ined using polarization dependent scanning photocurrent microscopy. The pho...

We find that a five-phase (substrate, mixed native oxide and roughness interface layer, metal oxide thin film layer, surface ligand layer, ambient) model with two-dynamic (metal oxide thin film layer thickness and surface ligand layer void fraction) parameters (dynamic dual box model) is sufficient to explain in-situ spectroscopic ellipsometry data measured within and across multiple cycles during plasma-enhanced atomic layer deposition of metal oxide thin films. We demonstrate our dynamic dual box model for analysis of in-situ spectroscopic ellipsometry data in the photon energy range of 0.7-3.4eV measured with time resolution of few seconds over large numbers of cycles during the growth of titanium oxide (TiO2) and tungsten oxide (WO3) thin films, as examples. We observe cyclic surface roughening with fast kinetics and subsequent roughness reduction with slow kinetics, upon cyclic exposure to precursor materials, leading to oscillations of the metal thin film thickness with small but positive growth per cycle. We explain the cyclic surface roughening by precursor-surface interactions leading to defect creation, and subsequent surface restructuring. Atomic force microscopic images before and after growth, x-ray photoelectron spectroscopy, and x-ray diffraction investigations confirm structural and chemical properties of our thin films. Our proposed dynamic dual box model may be generally applicable to monitor and control metal oxide growth in atomic layer deposition, and we include data for SiO2 and Al2O3 as further examples. Funding Agencies|National Science Foundation (NSF) through the Nebraska Materials Research Science and Engineering Center (MRSEC)National Science Foundation (NSF) [DMR-1420645, CMMI 1337856, DMR 1808715]; Air Force Research Office [FA9550-18-1-0360]; American Chemical SocietyAmerican Chemical Society [ACS PRF 59374-ND5]; University of Nebraska-Lincoln; J. A. Woollam Co., Inc.; J. A. Woollam Foundation

In this chapter, we introduce the efficacy of photoemission and inverse photoemission in determining the interactions of adsorbates with a substrate, with an emphasis on simple adsorbates on various metallic and oxide surfaces. We cover symmetry and selection rules, and how hybridization, bonding, and molecular orientation affect x-ray photoemission (XPS), angle resolved photoemission (ARPES), and angle resolved inverse photoemission (ARIPES). The application of ARPES and ARIPES in the determination of the orientation of molecular adsorbates and the wave vector dependence of the adsorbate molecular orbitals is addressed. We also address some of the difficulties associated with photoemission data interpretation as they relate to initial states and screened and unscreened final states, surface-to-bulk core level shifts, and core level satellites. This chapter isintended to help those new to photoemission spectroscopy with a basic understanding of the photoemission phenomenon and the associated intricacies that will be encountered in an experimental setting.

We have used X-ray photoemission spectroscopy to study the interaction of gold (Au) with novel boron carbide-based semiconductors grown by plasma-enhanced chemical vapor deposition (PECVD). Both n- and p-type films have been investigated and the PECVD boron carbides are compared to those containing aromatic compounds. In the case of the p-type semiconducting PECVD hydrogenated boron carbide samples, the binding energy of the B(1s) core level shows a shift to higher binding energies as the Au is deposited, an indication of band bending and possibly Schottky barrier formation. In the case of the n-type boron carbide semiconductors the interaction at the interface is more typical of an ohmic contact. Addition of the aromatic compounds increases the change in binding energies on both n-type and p-type PECVD boron carbide semiconductors, and the gold appears to diffuse into the PECVD boron carbides alloyed with aromatic moieties.

The tuning of the photoresponse and electronic structure for ion induced graphene quantum dots (I-GQDs), through variations in the ion irradiation processing of monolayer graphene, is demonstrated. Synthesis of nano-dimensional quantum dots (3–9 nm) was observed for graphene after irradiation in the ion energy range of 100–250 eV. Remarkably, the photo-response from these GQDs can be manipulated and significantly enhanced simply with the change of ion energy. Changes to the photo-response are reflected in the appearance of an optical mode near 560 nm, and the enhancement of UV-regime absorbance by nearly 70%. The results display a method that can be useful in designing graphene quantum dot based photodetectors, in a single step process with ion irradiation, without incorporation of any metal-nanoparticles or hybrid-metal platforms. Changes in the UV absorbance are of immense significance having many potential applications in UV based detectors.

Here we describe some preliminary device results from field effect transistors made from metal trichalcogenides. Although not much investigated, is both promise and room for improvement. Improvements could come from better contacts and lower semiconductor channel defect densities, in metal trichalcogenides transistors. Devices with ohmic contacts have now been fabricated, and the surface termination of these materials modeled by density functional theory.

We find that a five-phase (substrate, mixed native oxide and roughness interface layer, metal oxide thin film layer, surface ligand layer, ambient) model with two-dynamic (metal oxide thin film layer thickness and surface ligand layer void fraction) parameters (dynamic dual box model) is sufficient to explain in-situ spectroscopic ellipsometry data measured within and across multiple cycles during plasma-enhanced atomic layer deposition of metal oxide thin films. We demonstrate our dynamic dual box model for analysis of in-situ spectroscopic ellipsometry data in the photon energy range of 0.7-3.4 eV measured with time resolution of few seconds over large numbers of cycles during the growth of titanium oxide (TiO

The surface termination of In4Se3(001) and the interface of this layered trichalcogenide, with Au, was examined using x-ray photoemission spectroscopy. Low energy electron diffraction indicates that the surface is highly crystalline, but suggests an absence of C2v mirror plane symmetry. The surface termination of the In4Se3(001) is found, by angle-resolved x-ray photoemission spectroscopy, to be In, which is consistent with the observed Schottky barrier formation found with this n-type semiconductor. Transistor measurements confirm earlier results from photoemission, suggesting that In4Se3(001) is an n-type semiconductor, so that Schottky barrier formation with a large work function metal, such as Au, is expected. The measured low carrier mobilities could be the result of the contacts and would be consistent with Schottky barrier formation.

The band structure of the quasi-one-dimensional transition metal trichalcogenide ZrS3(001) was investigated using nanospot angle resolved photoemission spectroscopy (nanoARPES) and shown to have many similarities with the band structure of TiS3(001). We find that ZrS3, like TiS3, is strongly n-type with the top of the valence band ∼1.9 eV below the Fermi level, at the center of the surface Brillouin zone. The nanoARPES spectra indicate that the top of the valence band of the ZrS3(001) is located at [Formula: see text]. The band structure of both TiS3 and ZrS3 exhibit strong in-plane anisotropy, which results in a larger hole effective mass along the quasi-one-dimensional chains than perpendicular to them.

In the present study, carbon nanotube (CNT), thermally reduced graphite oxide (TRGO), and CNT-TRGO were functionalized with p-sulfonatocalix[4]arene (SC4) and then investigated for fluorescent detection of cholesterol in the presence of rhodamine 6G (R6G). All of the composite samples show effective quenching of R6G fluorescent intensity without cholesterol, but the fluorescence intensity significantly increases with the addition of cholesterol. The results indicate a strong interaction between SC4 composites and cholesterol rather than between the SC4 composites and R6G, increasing R6G fluorescence intensity in the presence of cholesterol due to the release of R6G from the SC4 composites. Formation of the complex, made of the SC4 composite plus the cholesterol, enables the detection of cholesterol in the wide range of cholesterol concentration up to 109 µM. The binding constant between SC4 and cholesterol has been calculated, indicating that the SC4 composites display the maximum binding constant of 1.9 × 104 M−1 with cholesterol.

The interfaces of layered trichalcogenide TiS3(001), with metals Au and Pt, were examined using X-ray photoemission spectroscopy. In spite of the fact that both Au and Pt are large work function metals, no evidence of Schottky barrier formation was found with this n-type semiconductor. Two- and four-terminal field-effect transistor measurements performed on exfoliated few-nm-thick TiS3 crystals using pure Au contacts indicate that Au forms an Ohmic contact on TiS3(001), with negligible contact resistance. The absence of appreciable Schottky barrier formation is attributed to strong interactions with sulfur at the metal-semiconductor interface.

The experimental mapping of the band structure of TiS3(001), by momentum resolution nanospot angle resolved photoemission, is presented. The experimental band structure, derived from angle-resolved photoemission, confirms that the top of the valence band is at the center of the Brillouin zone. This trichalcogenide has a rectangular surface Brillouin zone where the effective hole mass along the chain direction is −0.95 ± 0.09 me, while perpendicular to the chain direction, the magnitude of the effective hole mass is much lower at −0.37 ± 0.1 me. The placement of the valence band well below the Fermi level suggests that this is an n-type semiconductor.

Recent discovery of a new class of materials, spin-gapless semiconductors (SGS), has attracted considerable attention in the last few years, primarily due to potential applications in the emerging field of spin-based electronics (spintronics). Here, we investigate structural, electronic, and magnetic properties of one potential SGS compound, MnCrVAl, using various experimental and theoretical techniques. Our calculations show that this material exhibits ≈ 0.5 eV band gap for the majority-spin states, while for the minority-spin it is nearly gapless. The calculated magnetic moment for the completely ordered structure is 2.9 μB/f.u., which is different from our experimentally measured value of almost zero. This discrepancy is explained by the structural disorder. In particular, A2 type disorder, where Mn or Cr atoms exchange their positions with Al atoms, results in induced antiferromagnetic exchange coupling, which, at a certain level of disorder, effectively reduces the total magnetic moment to zero. This is consistent with our x-ray diffraction measurements which indicate the presence of A2 disorder in all of our samples. In addition, we also show that B2 disorder does not result in antiferromagnetic exchange coupling and therefore does not significantly reduce the total magnetic moment.

Disordered CoFeCrAl and CoFeCrSi0.5Al0.5 alloys have been investigated experimentally and by first-principle calculations. The melt-spun and annealed samples all exhibit Heusler-type superlattice peaks, but the peak intensities indicate a substantial degree of B2-type chemical disorder. Si substitution reduces the degree of this disorder. Our theoretical analysis also considers several types of antisite disorder (Fe-Co, Fe-Cr, Co-Cr) in Y-ordered CoFeCrAl and partial substitution of Si for Al. The substitution transforms the spin-gapless semiconductor CoFeCrAl into a half-metallic ferrimagnet and increases the half-metallic band gap by 0.12 eV. Compared CoFeCrAl, the moment of CoFeCrSi0.5Al0.5 is predicted to increase from 2.01 μB to 2.50 μB per formula unit, in good agreement with experiment.

The increasing interest in spin-based electronics has led to a vigorous search for new materials that can provide a high degree of spin polarization in electron transport. An ideal candidate would act as an insulator for one spin channel and a conductor or semiconductor for the opposite spin channel, corresponding to the respective cases of half-metallicity and spin-gapless semiconductivity. Our first-principle electronic-structure calculations indicate that the metallic Heusler compound Ti2MnAl becomes half-metallic and spin-gapless semiconducting if half of the Al atoms are replaced by Sn and In, respectively. These electronic structures are associated with structural transitions from the regular cubic Heusler structure to the inverted cubic Heusler structure.

Structural, electronic, and magnetic properties of a Heusler-type CoFeCrAl alloy have been investigated experimentally and by model calculations, with a focus on the alloy's spin-gapless semiconductivity. The as-quenched samples are ferrimagnetic at room temperature with a Curie temperature of about 456 K, which increases to 540 K after vacuum annealing at 600 °C for 2 h. The saturation magnetizations of the as-quenched and 600 °C-annealed samples are 1.9 µB/f.u. and 2.1 µB/f.u., respectively, which are very close to the value predicted by the Slater–Pauling curve. The resistivity shows a nearly linear decrease with increasing temperature, from about 930 µΩ cm at 5 K to about 820 µΩ cm at 250 K, with dρ/dT of about −5 × 10−7 Ω cm K−1. We explain this high resistivity and its temperature dependence as imperfect spin-gapless semiconducting behavior, with a negative band-gap parameter of 0.2 eV.