Lithium-Induced Reorientation of Few-Layer MoS2 Films.

Molybdenum disulfide (MoS2) few-layer films have gained considerable attention for their possible applications in electronics and optics and also as a promising material for energy conversion and storage. Intercalating alkali metals, such as lithium, offers the opportunity to engineer the electronic properties of MoS2. However, the influence of lithium on the growth of MoS2 layers has not been fully explored. Here, we have studied how lithium affects the structural and optical properties of the MoS2 few-layer films prepared using a new method based on one-zone sulfurization with Li2S as a source of lithium. This method enables incorporation of Li into octahedral and tetrahedral sites of the already prepared MoS2 films or during MoS2 formation. Our results discover an important effect of lithium promoting the epitaxial growth and horizontal alignment of the films. Moreover, we have observed a vertical-to-horizontal reorientation in vertically aligned MoS2 films upon lithiation. The measurements show long-term stability and preserved chemical composition of the horizontally aligned Li-doped MoS2.

Physical Delithiation of Epitaxial LiCoO2 Battery Cathodes as a Platform for Surface Electronic Structure Investigation.

We report a novel delithiation process for epitaxial thin films of LiCoO2(001) cathodes using only physical methods, based on ion sputtering and annealing cycles. Preferential Li sputtering followed by annealing produces a surface layer with a Li molar fraction in the range 0.5 < x < 1, characterized by good crystalline quality. This delithiation procedure allows the unambiguous identification of the effects of Li extraction without chemical byproducts and experimental complications caused by electrolyte interaction with the LiCoO2 surface. An analysis by X-ray photoelectron spectroscopy (XPS) and X-ray absorption spectroscopy (XAS) provides a detailed description of the delithiation process and the role of O and Co atoms in charge compensation. We observe the simultaneous formation of Co4+ ions and of holes localized near O atoms upon Li removal, while the surface shows a (2 × 1) reconstruction. The delithiation method described here can be applied to other crystalline battery elements and provide information on their properties that is otherwise difficult to obtain.

A ferromagnetic Eu-Pt surface compound grown below hexagonal boron nitride.

One of the fundamental applications for monolayer-thick 2D materials is their use as protective layers of metal surfaces and in situ intercalated reactive materials in ambient conditions. Here we investigate the structural, electronic, and magnetic properties, as well as the chemical stability in air of a very reactive metal, Europium, after intercalation between a hexagonal boron nitride (hBN) layer and a Pt substrate. We demonstrate that Eu intercalation leads to a hBN-covered ferromagnetic EuPt2 surface alloy with divalent Eu2+ atoms at the interface. We expose the system to ambient conditions and find a partial conservation of the di-valent signal and hence the Eu-Pt interface. The use of a curved Pt substrate allows us to explore the changes in the Eu valence state and the ambient pressure protection at different substrate planes. The interfacial EuPt2 surface alloy formation remains the same, but the resistance of the protecting hBN layer to ambient conditions is reduced, likely due to a rougher surface and a more discontinuous hBN coating.

On-Surface Synthesis of Unsaturated Hydrocarbon Chains through C-S Activation.

We use an on-surface synthesis approach to drive the homocoupling reaction of a simple dithiophenyl-functionalized precursor on Cu(111). The C-S activation reaction is initiated at low annealing temperature and yields unsaturated hydrocarbon chains interconnected in a fully conjugated reticulated network. High-resolution atomic force microscopy imaging reveals the opening of the thiophenyl rings and the presence of trans- and cis-oligoacetylene chains as well as pentalene units. The chemical transformations were studied by C 1s and S 2p core level photoemission spectroscopy and supported by theoretical calculations. At higher annealing temperature, additional cyclization reactions take place, leading to the formation of small graphene flakes.

Energy Level Alignment at the Cobalt Phosphate/Electrolyte Interface: Intrinsic Stability vs Interfacial Chemical Reactions in 5 V Lithium Ion Batteries.

The intrinsic stability of the 5 V LiCoPO4-LiCo2P3O10 thin-film (carbon-free) cathode material coated with MoO3 thin layer is studied using a comprehensive synchrotron electron spectroscopy in situ approach combined with first-principle calculations. The atomic-molecular level study demonstrates fully reversible electronic properties of the cathode after the first electrochemical cycle. The polyanionic oxide is not involved in chemical reactions with the fluoroethylene-containing liquid electrolyte even when charged to 5.1 V vs Li+/Li. The high stability of the cathode is explained on the basis of the developed energy level model. In contrast, the chemical composition of the cathode-electrolyte interface evolves continuously by involving MoO3 in the decomposition reaction with consequent leaching of oxide from the surface. The proposed mechanisms of chemical reactions are attributed to external electrolyte oxidation via charge transfer from the relevant electron level to the MoO3 valence band state and internal electrolyte oxidation via proton transfer to the solvents. This study provides a deeper insight into the development of both a doping strategy to enhance the electronic conductivity of high-voltage cathode materials and an efficient surface coating against unfavorable interfacial chemical reactions.

Modular Assembly of Vibrationally and Electronically Coupled Rhenium Bipyridine Carbonyl Complexes on Silicon.

Hybrid inorganic/organic heterointerfaces are promising systems for next-generation photocatalytic, photovoltaic, and chemical-sensing applications. Their performance relies strongly on the development of robust and reliable surface passivation and functionalization protocols with (sub)molecular control. The structure, stability, and chemistry of the semiconductor surface determine the functionality of the hybrid assembly. Generally, these modification schemes have to be laboriously developed to satisfy the specific chemical demands of the semiconductor surface. The implementation of a chemically independent, yet highly selective, standardized surface functionalization scheme, compatible with nanoelectronic device fabrication, is of utmost technological relevance. Here, we introduce a modular surface assembly (MSA) approach that allows the covalent anchoring of molecular transition-metal complexes with sub-nanometer precision on any solid material by combining atomic layer deposition (ALD) and selectively self-assembled monolayers of phosphonic acids. ALD, as an essential tool in semiconductor device fabrication, is used to grow conformal aluminum oxide activation coatings, down to sub-nanometer thicknesses, on silicon surfaces to enable a selective step-by-step layer assembly of rhenium(I) bipyridine tricarbonyl molecular complexes. The modular surface assembly of molecular complexes generates precisely structured spatial ensembles with strong intermolecular vibrational and electronic coupling, as demonstrated by infrared spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy analysis. The structure of the MSA can be chosen to avoid electronic interactions with the semiconductor substrate to exclusively investigate the electronic interactions between the surface-immobilized molecular complexes.

Atomically-Precise Texturing of Hexagonal Boron Nitride Nanostripes.

Monolayer hexagonal boron nitride (hBN) is attracting considerable attention because of its potential applications in areas such as nano- and opto-electronics, quantum optics and nanomagnetism. However, the implementation of such functional hBN demands precise lateral nanostructuration and integration with other two-dimensional materials, and hence, novel routes of synthesis beyond exfoliation. Here, a disruptive approach is demonstrated, namely, imprinting the lateral pattern of an atomically stepped one-dimensional template into a hBN monolayer. Specifically, hBN is epitaxially grown on vicinal Rhodium (Rh) surfaces using a Rh curved crystal for a systematic exploration, which produces a periodically textured, nanostriped hBN carpet that coats Rh(111)-oriented terraces and lattice-matched Rh(337) facets with tunable width. The electronic structure reveals a nanoscale periodic modulation of the hBN atomic potential that leads to an effective lateral semiconductor multi-stripe. The potential of such atomically thin hBN heterostructure for future applications is discussed.

Turning Low-Nanoscale Intrinsic Silicon Highly Electron-Conductive by SiO2 Coating.

Impurity doping in silicon (Si) ultra-large-scale integration is one of the key challenges which prevent further device miniaturization. Using ultraviolet photoelectron spectroscopy and X-ray absorption spectroscopy in the total fluorescence yield mode, we show that the lowest unoccupied and highest occupied electronic states of ≤3 nm thick SiO2-coated Si nanowells shift by up to 0.2 eV below the conduction band and ca. 0.7 eV below the valence band edge of bulk silicon, respectively. This nanoscale electronic structure shift induced by anions at surfaces (NESSIAS) provides the means for low-nanoscale intrinsic Si (i-Si) to be flooded by electrons from an external (bigger, metallic) reservoir, thereby getting highly electron- (n-) conductive. While our findings deviate from the behavior commonly believed to govern the properties of silicon nanowells, they are further confirmed by the fundamental energy gap as per nanowell thickness when compared against published experimental data. Supporting our findings further with hybrid density functional theory calculations, we show that other group IV semiconductors (diamond, Ge) do respond to the NESSIAS effect in accord with Si. We predict adequate nanowire cross-sections (X-sections) from experimental nanowell data with a recently established crystallographic analysis, paving the way to undoped ultrasmall silicon electronic devices with significantly reduced gate lengths, using complementary metal-oxide-semiconductor-compatible materials.

Morphological characterization and electronic properties of pristine and oxygen-exposed graphene nanoribbons on Ag(110).

Graphene nanoribbons (GNRs) are at the frontier of research on graphene materials since the 1D quantum confinement of electrons allows for the opening of an energy gap. GNRs of uniform and well-defined size and shape can be grown using the bottom-up approach, i.e. by surface assisted polymerization of aromatic hydrocarbons. Since the electronic properties of the nanostructures depend on their width and on their edge states, by careful choice of the precursor molecule it is possible to design GNRs with tailored properties. A key issue for their application in nanoelectronics is their stability under operative conditions. Here, we characterize pristine and oxygen-exposed 1.0 nm wide GNRs with a well-defined mixed edge-site sequence (two zig-zag and one armchair) synthesized on Ag(110) from 1,6-dibromo-pyrene precursors. The energy gap and the presence of quantum confined states are investigated by scanning tunneling spectroscopy. The effect of oxygen exposure under ultra-high vacuum conditions is inferred from scanning tunneling microscopy images and photoemission spectra. Our results demonstrate that oxygen exposure deeply affects the overall system by interacting both with the nanoribbons and with the substrate; this factor must be considered for supported GNRs under operative conditions.

Electronic properties of carbon nanotubes as detected by photoemission and inverse photoemission.

The relation between morphology and energy level alignment in carbon nanotubes (CNT) is a crucial information for the optimization of applications in nanoelectronics, optics, mechanics and (bio)chemistry. Here we present a study of the relation between the electronic properties and the morphology of single wall CNT (SWCNT), aligned multi wall CNT (MWCNT) and unaligned MWCNT. The CNT were synthesized via catalytic chemical vapor deposition in ultra-high vacuum conditions. Combined ultraviolet photoemission and inverse photoemission (IPES) spectra reveal a high sensitivity to the nanotube morphology. In the case of unaligned SWCNT the distinctive unoccupied Van Hove singularities (vHs) features are observed in the high resolution IPES spectra. Those features are assigned to semiconducting and metallic SWCNT states, according to calculated vHs DOS. The two MWCNT samples are similar in the diameter of the tube (about 15 nm) and present similar filled and empty electronic states, although the measured features in the aligned MWCNT are more defined. Noteworthy, interlayer states are also revealed. Their intensities are directly related to the MWCNT alignment. Focussing and geometrical effects associated to the MWCNT alignment are discussed to account the spectral differences.

Tuning the charge carrier mobility in few-layer PtSe2 films by Se : Pt ratio.

Recently, few-layer PtSe2 films have attracted significant attention due to their properties and promising applications in high-speed electronics, spintronics and optoelectronics. Until now, the transport properties of this material have not reached the theoretically predicted values, especially with regard to carrier mobility. In addition, it is not yet known which growth parameters (if any) can experimentally affect the carrier mobility value. This work presents the fabrication of horizontally aligned PtSe2 films using one-zone selenization of pre-deposited platinum layers. We have identified the Se : Pt ratio as a parameter controlling the charge carrier mobility in the thin films. The mobility increases more than twice as the ratio changes in a narrow interval around a value of 2. A simultaneous reduction of the carrier concentration suggests that ionized impurity scattering is responsible for the observed mobility behaviour. This significant finding may help to better understand the transport properties of few-layer PtSe2 films.

Correction: Tuning the charge carrier mobility in few-layer PtSe2 films by Se : Pt ratio.

[This corrects the article DOI: 10.1039/D1RA04507E.].

Hydrogen Bonding of Ammonia with (H,OH)-Si(001) Revealed by Experimental and Ab Initio Photoelectron Spectroscopy.

Combining experimental and ab initio core-level photoelectron spectroscopy (periodic DFT and quantum chemistry calculations), we elucidated how ammonia molecules bond to the hydroxyls of the (H,OH)-Si(001) model surface at a temperature of 130 K. Indeed, theory evaluated the magnitude and direction of the N 1s (and O 1s) chemical shifts according to the nature (acceptor or donor) of the hydrogen bond and, when confronted to experiment, showed unambiguously that the probe molecule makes one acceptor and one donor bond with a pair of hydroxyls. The consistency of our approach was proved by the fact that the identified adsorption geometries are precisely those that have the largest binding strength to the surface, as calculated by periodic DFT. Real-time core-level photoemission enabled measurement of the adsorption kinetics of H-bonded ammonia and its maximum coverage (0.37 ML) under 1.5 × 10-9 mbar. Experimental desorption free energies were compared to the magnitude of the adsorption energies provided by periodic DFT calculations. Minority species were also detected on the surface. As in the case of H-bonded ammonia, DFT core-level calculations were instrumental to attribute these minority species to datively bonded ammonia molecules, associated with isolated dangling bonds remaining on the surface, and to dissociated ammonia molecules, resulting largely from beam damage.

Electronic Structures of the Vanadium-Intercalated and Substitutionally Doped Transition-Metal Dichalcogenides TixVySe2.

The electronic structures of V-intercalated TiSe2 and substitutionally doped dichalcogenides Ti1-xVxSe2 have been studied using soft X-ray photoelectron, resonant photoelectron, and absorption spectroscopies. In the case of the substitution of Ti by V, the formation of coherently oriented structural fragments VSe2 and TiSe2 is observed and a small charge transfer between these fragments is found. Intercalation of the V atoms into TiSe2 leads to charge transfer from the V atoms to the Ti atoms with the formation of covalent complexes Ti-Se3-V-Se3-Ti.

Surface effects on a photochromic spin-crossover iron(ii) molecular switch adsorbed on highly oriented pyrolytic graphite.

Thin films of an iron(ii) complex with a photochromic diarylethene-based ligand and featuring a spin-crossover behaviour have been grown by sublimation in ultra-high vacuum on highly oriented pyrolytic graphite and spectroscopically characterized through high-resolution X-ray and ultraviolet photoemission, as well as via X-ray absorption. Temperature-dependent studies demonstrated that the thermally induced spin-crossover is preserved at a sub-monolayer (0.7 ML) coverage. Although the photochromic ligand ad hoc integrated into the complex allows the photo-switching of the spin state of the complex at room temperature both in bulk and for a thick film on highly oriented pyrolytic graphite, this photomagnetic effect is not observed in sub-monolayer deposits. Ab initio calculations justify this behaviour as the result of specific adsorbate-substrate interactions leading to the stabilization of the photoinactive form of the diarylethene ligand over photoactive one on the surface.

Highly Hydrophilic Gold Nanoparticles as Carrier for Anticancer Copper(I) Complexes: Loading and Release Studies for Biomedical Applications.

Gold nanoparticles (AuNPs), which are strongly hydrophilic and dimensionally suitable for drug delivery, were used in loading and release studies of two different copper(I)-based antitumor complexes, namely [Cu(PTA)4]+ [BF4]- (A; PTA = 1, 3, 5-triaza-7-phosphadamantane) and [HB(pz)3Cu(PCN)] (B; HB(pz)3 = tris(pyrazolyl)borate, PCN = tris(cyanoethyl)phosphane). In the homoleptic, water-soluble compound A, the metal is tetrahedrally arranged in a cationic moiety. Compound B is instead a mixed-ligand (scorpionate/phosphane), neutral complex insoluble in water. In this work, the loading procedures and the loading efficiency of A and B complexes on the AuNPs were investigated, with the aim to improve their bioavailability and to obtain a controlled release. The non-covalent interactions of A and B with the AuNPs surface were studied by means of dynamic light scattering (DLS), UV-Vis, FT-IR and high-resolution x-ray photoelectron spectroscopy (HR-XPS) measurements. As a result, the AuNPs-A system proved to be more stable and efficient than the AuNPs-B system. In fact, for AuNPs-A the drug loading reached 90%, whereas for AuNPs-B it reached 65%. For AuNPs-A conjugated systems, a release study in water solution was performed over 4 days, showing a slow release up to 10%.

Under-cover stabilization and reactivity of a dense carbon monoxide layer on Pt(111).

The space between a metal surface and a two-dimensional cover can be regarded as a nanoreactor, where confined molecule adsorption and surface reactions may occur. In this work, we report CO intercalation and reactivity between a graphene-hexagonal boron nitride (h-BNG) heterostructure and Pt(111). By employing high resolution X-ray photoemission spectroscopy (XPS) we demonstrate the molecular intercalation of the full h-BNG overlayer and stabilization of a dense R23.4°-13CO layer on Pt(111) under ultra-high vacuum at room temperature. We provide experimental evidence of a weakened CO-metal bond due to the confinement effects of the 2D cover. Temperature-programmed XPS results reveal that CO desorption is kinetically delayed and occurs at a higher temperature than on bare Pt(111). Moreover, CO partially reacts with the h-BNG layer to form boron-oxide species, which affect repeated CO intercalation. Finally, we found that the properties of the system towards interaction with CO can be considerably recovered using high temperature treatment.

Synthesis of corrugated C-based nanostructures by Br-corannulene oligomerization.

The structure and electronic properties of carbon-based nanostructures obtained by metal surface assisted synthesis is highly dependent on the nature of the precursor molecule. Here, we report on a combined scanning tunneling microscopy, soft X-ray spectroscopy and density functional theory investigation on the surface assisted polymerization of Br-corannulene at Ag(110) and on the possibility of building a mesh of π-conjugated polymers starting from buckyball shaped molecules. Indeed, the corannulene units form one-molecule-wide ribbons in which the natural concavity of the precursor molecule is maintained. These C-based nanostructures are corrugated and merge into a covalent network on the surface.

Guest-Host Chemical Bonding and Possibility of Ordering of Intercalated Metals in Transition-Metal Dichalcogenides.

The comparison of the specifics of the guest-host chemical bonding in the materials with (Fe xTiSe2) and without (Fe xTiTe2) ordering of the iron atoms was performed. For this purpose the electronic structure of the materials were studied using X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, resonant X-ray photoelectron spectroscopy, and theoretical calculations (total density of states, partial density of states, and multiplet calculations). For the iron-intercalated TiTe2 compound iron-chalcogen bonds are formed, whereas the formation of iron-iron bonds is most typical for the iron-intercalated TiSe2 compound. This leads to an increase in the lifetime of electrons on the titanium atoms and does not allow the formation of atomic chains of intercalated metal.

How a tertiary diamine molecule chelates the silicon dimers of the Si(001) surface: a real-time scanning tunneling microscopy study.

The patterning of silicon surfaces by organic molecules emerges as an original way to fabricate innovative nanoelectronic devices. In this regard, we have studied how a diamine, N,N,N',N'-tetramethylethylenediamine (TMEDA, (CH3)2N-[CH2]2-N(CH3)2), chelates the silicon dimers of the Si(001)-2 × 1 surface. Starting from very low coverage to surface saturation (at 300 K), we used real-time scanning tunneling microscopy (STM) in a scanning-while-dosing approach. The images show that the molecules can adopt two bonding configurations: the cross-trench (CT) configuration by bridging two adjacent dimer rows, and the end-bridge (EB) configuration by chelating two adjacent dimers in the same row. However, while CT dominates over EB at low coverage, the percentage of EB adducts steadily increases, until it becomes largely dominant at high molecular coverage. Above a critical coverage θmol of ∼0.13 monolayer (ML), a sudden change in the molecular imprints is seen, likely due to a change in the tunneling conditions. The EB stapling of two adjacent dimers in a row via a dual-dative bond (as shown by XPS) is achieved efficiently by the TMEDA molecule with a very high chemical selectivity. The EB is a unique configuration in amine adsorption chemistry, as it leads to the formation of a pair of first-neighbor, doubly-occupied dangling bonds. Further reactivity of the EB site with other molecules remains to be explored, and possible reaction schemes are envisaged.