Enhanced Electron Emission Performance and Air-Surface Stability in ScO-Terminated Diamond for Thermionic Energy Converters.

Diamond with negative electron affinity (NEA) and low work function surfaces are suggested as a suitable material for electron-generation applications in vacuum, in particular, as the emitter electrode in thermionic energy converters. Such NEA surfaces can be fabricated by evaporating and then annealing submonolayers of a suitable metal in vacuo onto bare or oxidized diamond. Among the metals studied, scandium termination of bare diamond (100) and (111) surfaces is recently reported to give the largest NEA values reported to date for a metal-diamond system, as well as being thermally stable to 900 °C. It is now shown that preoxidized (100) diamond functionalized with 0.25 monolayers of Sc also produces a large NEA value of -1.02 eV with low work functions (<3.63 eV). Moreover, this surface is thermally stable to 700 °C and can withstand exposure to air for extended periods. Here, the structural and electronic properties of this Sc─O-functionalized diamond surface are characterized in detail using a variety of surface-science techniques. The results suggest that this material may be the ideal candidate for the fabrication of commercial thermionic energy conversion devices, e.g., for solar-power generation, as well as for various other electronic devices that rely upon electron emission.

Versatile Method for Preparing Two-Dimensional Metal Dihalides.

Ever since the ground-breaking isolation of graphene, numerous two-dimensional (2D) materials have emerged with 2D metal dihalides gaining significant attention due to their intriguing electrical and magnetic properties. In this study, we introduce an innovative approach via anhydrous solvent-induced recrystallization of bulk powders to obtain crystals of metal dihalides (MX2, with M = Cu, Ni, Co and X = Br, Cl, I), which can be exfoliated to 2D flakes. We demonstrate the effectiveness of our method using CuBr2 as an example, which forms large layered crystals. We investigate the structural properties of both the bulk and 2D CuBr2 using X-ray diffraction, along with Raman scattering and optical spectroscopy, revealing its quasi-1D chain structure, which translates to distinct emission and scattering characteristics. Furthermore, microultraviolet photoemission spectroscopy and electronic transport reveal the electronic properties of CuBr2 flakes, including their valence band structure. We extend our methodology to other metal halides and assess the stability of the metal halide flakes in controlled environments. We show that optical contrast can be used to characterize the flake thicknesses for these materials. Our findings demonstrate the versatility and potential applications of the proposed methodology for preparing and studying 2D metal halide flakes.

Ex situ Ge-doping of CZTS nanocrystals and CZTSSe solar absorber films.

Cu2ZnSn(S,Se)4 (CZTSSe) is a promising material for thin-film photovoltaics, however, the open-circuit voltage (VOC) deficit of CZTSSe prevents the device performance from exceeding 13% conversion efficiency. CZTSSe is a heavily compensated material that is rich in point defects and prone to the formation of secondary phases. The landscape of these defects is complex and some mitigation is possible by employing non-stoichiometric conditions. Another route used to reduce the effects of undesirable defects is the doping and alloying of the material to suppress certain defects and improve crystallization, such as with germanium. The majority of works deposit Ge adjacent to a stacked metallic precursor deposited by physical vapour deposition before annealing in a selenium rich atmosphere. Here, we use an established hot-injection process to synthesise Cu2ZnSnS4 nanocrystals of a pre-determined composition, which are subsequently doped with Ge during selenisation to aid recrystallisation and reduce the effects of Sn species. Through Ge incorporation, we demonstrate structural changes with a negligible change in the energy bandgap but substantial increases in the crystallinity and grain morphology, which are associated with a Ge-Se growth mechanism, and gains in both the VOC and conversion efficiency. We use surface energy-filtered photoelectron emission microscopy (EF-PEEM) to map the surface work function terrains and show an improved electronic landscape, which we attribute to a reduction in the segregation of low local effective work function (LEWF) Sn(II) chalcogenide phases.

Mapping the Energetics of Defect States in Cu2ZnSnS4 films and the Impact of Sb Doping.

The sub-bandgap levels associated with defect states in Cu2ZnSnS4 (CZTS) thin films are investigated by correlating the temperature dependence of the absorber photoluminescence (PL) with the device admittance spectroscopy. CZTS thin films are prepared by thermolysis of molecular precursors incorporating chloride salts of the cations and thiourea. Na and Sb are introduced as dopants in the precursor layers to assess their impact on Cu/Zn and Sn site disorder, respectively. Systematic analysis of PL spectra as a function of excitation power and temperature show that radiative recombination is dominated by quasi-donor-acceptor pairs (QDAP) with a maximum between 1.03 and 1.18 eV. It is noteworthy that Sb doping leads to a transition from localized to delocalized QDAP. The activation energies obtained associated with QDAP emission closely correlate with the activation energies of the admittance responses in a temperature range between 150 K and room temperature in films with or without added dopants. Admittance data of CZTS films with no added dopants also have a strong contribution from a deeper state associated with Sn disorder. The ensemble of PL and admittance data, in addition to energy-filtered photoemission of electron microscopy (EF-PEEM), shows a detailed picture of the distribution of sub-bandgap states in CZTS and the impact of doping on their energetics and device performance.

Correlating Thermionic Emission with Specific Surface Reconstructions in a <100> Hydrogenated Single-Crystal Diamond.

Thermionic emission relies on the low work function and negative electron affinity of the, often functionalized, surface of the emitting material. However, there is little understanding of the interplay between thermionic emission and temperature-driven dynamic surface transformation processes as these are not represented on the traditional Richardson-Dushman equation for thermionic emission. Here, we show a new model for thermionic emission that can reproduce the effect of dynamic surface changes on the electron emission and correlate the components of the thermionic emission with specific surface reconstruction phases on the surface of the emitter. We use hydrogenated <100> single-crystal and polycrystalline diamonds as thermionic emitters to validate our model, which shows excellent agreement with the experimental data and could be applicable to other emitting materials. Furthermore, we find that tailoring the coverage of specific structures of the C(100)-(2 × 1):H surface reconstruction could increase the thermionic emission of diamond by several orders of magnitude.

Characterisation of thermionic emission current with a laser-heated system.

Thermionic emitting materials are relevant for several technological applications like electron guns, X-ray sources, or thermionic energy converters. As new materials and surface functionalisations that enable thermionic emission are developed, it is essential to be able to test them in a repeatable and reliable manner. Here, we present a CO2 laser-heated system for thermionic tests that can be used to test the thermionic emission current of different materials regardless of the optical properties or form factor. Our system can reach sample temperatures of T ≈ 1000 °C and can follow pre-programmed heating profiles. Additionally, a double thermo-electrical decoupling provides a very low electrical noise environment while keeping the sample heat loss to a minimum. Experimental data on sample temperature and thermionic current from a hydrogen terminated single crystal diamond are presented and discussed.

Anodization study of epitaxial graphene: insights on the oxygen evolution reaction of graphitic materials.

The photoemission electron microscopy and x-ray photoemission spectroscopy were utilized for the study of anodized epitaxial graphene (EG) on silicon carbide as a fundamental aspect of the oxygen evolution reaction on graphitic materials. The high-resolution analysis of surface morphology and composition quantified the material transformation during the anodization. We investigated the surface with lateral resolution <150 nm, revealing significant transformations on the EG and the role of multilayer edges in increasing the film capacitance.

Electrochemical Modification and Characterization of Topological Insulator Single Crystals.

We compare electrochemically modified or thiol-functionalized single-crystal samples of the topological insulator (TI) Bi2Te0.9Se2.1 to freshly cleaved/air-exposed control samples and use X-ray photoelectron spectroscopy (XPS) to investigate the extent of any surface oxidation. XPS spectra for a TI sample maintained at an appropriate potential for 2 h demonstrate the feasibility of protecting the TI surface from oxidation while working in an electrochemical environment. Deliberate electrochemical oxidation, in contrast, generates prominent Bi, Te, and Se peaks associated with oxidation. However, this change is reversible, as further XPS spectra following electrochemical reduction are similar to those measured for an in situ cleaved sample. XPS also shows that adsorption of pentanedithiol (PDT) protects the TI surface from oxidation. Cyclic voltammetry shows that PDT adsorption suppresses electrochemical oxidation and reduction, while electrochemical impedance spectroscopy shows that it increases the charge transfer resistance significantly. Our work demonstrates the ability to control and characterize the surface chemistry of single-crystal TIs in an electrochemical environment for the first time.

Mapping Shunting Paths at the Surface of Cu2ZnSn(S,Se)4 Films via Energy-Filtered Photoemission Microscopy.

The performance of Cu2ZnSn(S,Se)4 thin-film solar cells, commonly referred to as kesterite or CZTSSe, is limited by open-circuit voltage (VOC) values less than 60% of the maximum theoretical limit. In the present study, we employ energy-filtered photoemission microscopy to visualize nanoscale shunting paths in solution-processed CZTSSe films, which limit the VOC of cells to approximately 400 mV. These studies unveil areas of local effective work function (LEWF) narrowly distributed around 4.9 eV, whereas other portions show hotspots with LEWF as low as 4.2 eV. Localized valence band spectra and density functional theory calculations allow rationalizing the LEWF maps in terms of the CZTSSe effective work function broadened by potential energy fluctuations and nanoscale Sn(S,Se) phases.

A theoretical study of substitutional boron-nitrogen clusters in diamond.

Substitutional clusters of multiple light element dopants are a promising route to the elusive shallow donor in diamond. To understand the behaviour of co-dopants, this report presents an extensive first principles study of possible clusters of boron and nitrogen. We use periodic hybrid density functional calculations to predict the geometry, stability and electronic excitation energies of a range of clusters containing up to five N and/or B atoms. Excitation energies from hybrid calculations are compared to those from the empirical marker method, and are in good agreement. When a boron-rich or nitrogen-rich cluster consists of three to five atoms, the minority dopant element-a nitrogen or boron atom respectively-can be in either a central or peripheral position. We find B-rich clusters are most stable when N sits centrally, whereas N-rich clusters are most stable with B in a peripheral position. In the former case, excitation energies mimic those of the single boron acceptor, while the latter produce deep levels in the band-gap. Implications for probable clusters that would arise in high-pressure high-temperature co-doped diamond and their properties are discussed.

A Perspective on the Application of Spatially Resolved ARPES for 2D Materials.

In this paper, a perspective on the application of Spatially- and Angle-Resolved PhotoEmission Spectroscopy (ARPES) for the study of two-dimensional (2D) materials is presented. ARPES allows the direct measurement of the electronic band structure of materials generating extremely useful insights into their electronic properties. The possibility to apply this technique to 2D materials is of paramount importance because these ultrathin layers are considered fundamental for future electronic, photonic and spintronic devices. In this review an overview of the technical aspects of spatially localized ARPES is given along with a description of the most advanced setups for laboratory and synchrotron-based equipment. This technique is sensitive to the lateral dimensions of the sample. Therefore, a discussion on the preparation methods of 2D material is presented. Some of the most interesting results obtained by ARPES are reported in three sections including: graphene, transition metal dichalcogenides (TMDCs) and 2D heterostructures. Graphene has played a key role in ARPES studies because it inspired the use of this technique with other 2D materials. TMDCs are presented for their peculiar transport, optical and spin properties. Finally, the section featuring heterostructures highlights a future direction for research into 2D material structures.

Comprehending Sentences With the Body: Action Compatibility in British Sign Language?

Previous studies show that reading sentences about actions leads to specific motor activity associated with actually performing those actions. We investigate how sign language input may modulate motor activation, using British Sign Language (BSL) sentences, some of which explicitly encode direction of motion, versus written English, where motion is only implied. We find no evidence of action simulation in BSL comprehension (Experiments 1-3), but we find effects of action simulation in comprehension of written English sentences by deaf native BSL signers (Experiment 4). These results provide constraints on the nature of mental simulations involved in comprehending action sentences referring to transfer events, suggesting that the richer contextual information provided by BSL sentences versus written or spoken English may reduce the need for action simulation in comprehension, at least when the event described does not map completely onto the signer's own body.

Processing advantage for emotional words in bilingual speakers.

Effects of emotion on word processing are well established in monolingual speakers. However, studies that have assessed whether affective features of words undergo the same processing in a native and nonnative language have provided mixed results: Studies that have found differences between native language (L1) and second language (L2) processing attributed the difference to the fact that L2 learned late in life would not be processed affectively, because affective associations are established during childhood. Other studies suggest that adult learners show similar effects of emotional features in L1 and L2. Differences in affective processing of L2 words can be linked to age and context of learning, proficiency, language dominance, and degree of similarity between L2 and L1. Here, in a lexical decision task on tightly matched negative, positive, and neutral words, highly proficient English speakers from typologically different L1s showed the same facilitation in processing emotionally valenced words as native English speakers, regardless of their L1, the age of English acquisition, or the frequency and context of English use.

Imaging the Predicted Isomerism of Oligo(aniline)s: A Scanning Tunneling Microscopy Study.

The self-assembly of two emeraldine base tetra(aniline) derivatives is investigated using scanning tunneling microscopy. A combination of the scanning tunneling microscopy data and calculations reveals the presence of predicted cis/trans isomerism in this oxidation state. This isomerism is shown to hinder self-assembly into ordered structures, and provides indications as to why the properties of these materials, and their parent polymer, polyaniline, remain unfulfilled.

Electrochemical properties of two dimensional assemblies of insulating diamond particles.

The electrochemical properties of two-dimensional assemblies of 500 nm type Ib diamond particles are investigated as a function of their surface oxidation state. High Pressure High Temperature particles are sequentially exposed to a hot strong acid bath and to H(2) plasma in order to generate oxygen (ODP) and hydrogen surface terminations (HDP). Changes in the surface composition following the chemical treatments are confirmed by FTIR. Electrophoretic mobility measurements show that the diamond particles exhibit a negative surface charge at pH above 7 independently of the surface termination. Oxidation in the acid bath and subsequent reduction in the H(2) plasma only affects about 30% of the particle surface charge. The intrinsic negative charge allows the formation of 2D assemblies by electrostatic adsorption on poly(diallyldimethylammonium chloride) (PDADMAC) modified In-doped SnO(2) electrodes (ITO). The particle number density in the assembly was controlled by the adsorption time up to a maximum coverage of ca. 40%. Cyclic voltammetry in the absence of redox species in solution show that the acid treatment effectively removes responses associated with sp(2) carbon impurities, resulting in a potential independent capacitive signal. On the other hand, HDP assemblies are characterized by a charging process at a potential above 0.1 V vs Ag/AgCl. These responses are associated with hole-injection into the valence band edge which is shifted to approximately -4.75 eV vs vacuum upon hydrogenation. Information concerning the position of the valence band edge as well as hole number density at the HDP surface as a function of the applied potential are extracted from the electrochemical analysis.

The hands and mouth do not always slip together in British sign language: dissociating articulatory channels in the lexicon.

In contrast to the single-articulatory system of spoken languages, sign languages employ multiple articulators, including the hands and the mouth. We asked whether manual components and mouthing patterns of lexical signs share a semantic representation, and whether their relationship is affected by the differing language experience of deaf and hearing native signers. We used picture-naming tasks and word-translation tasks to assess whether the same semantic effects occur in manual production and mouthing production. Semantic errors on the hands were more common in the English-translation task than in the picture-naming task, but errors in mouthing patterns showed a different trend. We conclude that mouthing is represented and accessed through a largely separable channel, rather than being bundled with manual components in the sign lexicon. Results were comparable for deaf and hearing signers; differences in language experience did not play a role. These results provide novel insight into coordinating different modalities in language production.

Through-mask anodization of titania dot- and pillar-like nanostructures on bulk Ti substrates using a nanoporous anodic alumina mask.

Nanosized surface topography on an implant material has the capability of stimulating the acceptance of the material in its host surrounding. Fine-tuning of nanotopography feature size has been shown to trigger differentiation of mesenchymal stem cells into bone cells in vitro. For this purpose we have created well defined nanosized titania dot- and pillar-like structures on mechanically polished Ti substrates using a through-mask anodization technique with an anodic porous alumina template. The anodization technique allowed the titania structure dimensions to be precisely tuned in the range 15-140 nm in a single electrolyte system. The fabricated surfaces serve as good model surfaces for precise studies of in vitro cell behaviour. The through-mask anodization technique was used directly on bulk Ti surfaces, thus demonstrating a potential application for patterning of actual Ti implant surfaces.

Experimental and modeling studies of B atom number density distributions in hot filament activated B2H6/H2 and B2H6/CH4/H2 gas mixtures.

Experimental and modeling studies of the gas-phase chemistry occurring in dilute, hot filament (HF) activated B2H6/H2 and B2H6/CH4/H2 gas mixtures are reported. Spatially resolved relative number densities of B (and H) atoms have been measured by resonance enhanced multiphoton ionization methods, as a function of process conditions (e.g. the HF material and its temperature, the B2H6/H2 mixing ratio, and the presence (or not) of added CH4). Three-dimensional modeling of the H/B chemistry prevailing in such HF activated gas mixtures using a simplified representation of the gas phase chemistry succeeds in reproducing all of the experimentally observed trends, and in illustrating the key role of the "H-shifting" reactions BHx + H <= => BHx-1 + H2 (x = 1-3) in enabling rapid interconversion between the various BHx (x = 0-3) species. CH4 addition, at partial pressures appropriate for growth of boron-doped diamond by chemical vapor deposition methods, leads to approximately 30% reduction in the measured B atom signal near the HF. The modeling suggests that this is mainly due to concomitant H atom depletion near the HF, but it also allows us a first assessment of the possible contributions from B/C coupling reactions upon CH4 addition to HF activated B2H6/H2 gas mixtures.