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Surface-supported molecular overlayers have demonstrated versatility as platforms for fundamental research and a broad range of applications, from atomic-scale quantum phenomena to potential for electronic, optoelectronic and catalytic technologies. Here, we report a structural and electronic characterisation of self-assembled magnesium phthalocyanine (MgPc) mono and bilayers on the Ag(100) surface, via low-temperature scanning tunneling microscopy and spectroscopy, angle-resolved photoelectron spectroscopy (ARPES), density functional theory (DFT) and tight-binding (TB) modeling. These crystalline close-packed molecular overlayers consist of a square lattice with a basis composed of a single, flat-adsorbed MgPc molecule. Remarkably, ARPES measurements at room temperature on the monolayer reveal a momentum-resolved, two-dimensional (2D) electronic energy band, 1.27 eV below the Fermi level, with a width of ∼20 meV. This 2D band results from in-plane hybridization of highest occupied molecular orbitals of adjacent, weakly interacting MgPc's, consistent with our TB model and with DFT-derived nearest-neighbor hopping energies. This work opens the door to quantitative characterisation – as well as control and harnessing – of subtle electronic interactions between molecules in functional organic nanofilms.

Deoxyribonucleic acid (DNA) has been hypothesized to act as a molecular wire due to the presence of an extended π-stack between base pairs, but the factors that are detrimental in the mechanism of charge transport (CT) across tunnel junctions with DNA are still unclear. Here we systematically investigate CT across dense DNA monolayers in large-area biomolecular tunnel junctions to determine when intrachain or interchain CT dominates and under which conditions the mechanism of CT becomes thermally activated. In our junctions, double-stranded DNA (dsDNA) is 30-fold more conductive than single-stranded DNA (ssDNA). The main reason for this large change in conductivity is that dsDNA forms ordered monolayers where intrachain tunneling dominates, resulting in high CT rates. By varying the temperature T and the length of the DNA fragments in the junctions, which determines the tunneling distance, we reveal a complex interplay between T, the length of DNA, and structural order on the mechanism of charge transport. Both the increase in the tunneling distance and the decrease in structural order result in a change in the mechanism of CT from coherent tunneling to incoherent tunneling (hopping). Our results highlight the importance of the interplay between structural order, tunneling distance, and temperature on the CT mechanism across DNA in molecular junctions.

Intrinsic magnetic topological insulators offer low disorder and large magnetic bandgaps for robust magnetic topological phases operating at higher temperatures. By controlling the layer thickness, emergent phenomena such as the Quantum Anomalous Hall (QAH) effect and axion insulator phases have been realised. These observations occur at temperatures significantly lower than the Neel temperature of bulk MnBi2Te4, and measurement of the magnetic energy gap at the Dirac point in ultra-thin MnBi2Te4 has yet to be achieved. Critical to achieving the promise of this system is a direct measurement of the layer-dependent energy gap and verifying whether the gap is magnetic in the QAH phase. Here we utilise temperature dependent angle-resolved photoemission spectroscopy to study epitaxial ultra-thin MnBi2Te4. We directly observe a layer dependent crossover from a 2D ferromagnetic insulator with a bandgap greater than 780 meV in one septuple layer (1 SL) to a QAH insulator with a large energy gap (>100 meV) at 8 K in 3 and 5 SL MnBi2Te4. The QAH gap is confirmed to be magnetic in origin, as it abruptly diminishes with increasing temperature above 8 K. The direct observation of a large magnetic energy gap in the QAH phase of few-SL MnBi2Te4 is promising for further increasing the operating temperature of QAH materials.

Porous metal-organic frameworks (MOFs) have become one of the fastest growing fields with broad applications due to the presence of various active sites (e.g., cavities, metal nodes, and organic linkers). Notably, an on-surface synthesis represents a facile method for the fabrication of two-dimensional (2D) MOFs, where the substrate not only supports and dictates the symmetry of the surface nanostructures but also provides the metal atoms to form the metal nodes. However, the realization of on-surface synthesized 2D metal-inorganic porous networks is rarely explored, except for a recently reported gold-phosphorus network. Here, we integrate one more dimension into the growth process (activated gas phase atoms) and demonstrate the on-surface synthesis of ternary metal-inorganic gold-phosphorus-nitrogen porous networks on Au(111). The atomic structure is precisely identified through a combination of low-temperature scanning tunneling microscopy, density functional theory calculations, and X-ray photoelectron spectroscopy. Using the thermal energy from the heated Au(111) substrate, the phosphorus precursor can simultaneously grab gold atoms from the surface and nitrogen atoms from activated nitrogen gas to build up a long-range ordered 2D surface porous structure. Our study opens a completely new platform for the on-surface synthesis of tailored metal-inorganic frameworks.

We demonstrate locally the coherent formation of silicon carbide (SiC) on diamond, a rare example of heteroepitaxy with a lattice mismatch that exceeds 20%. High-resolution transmission electron mi...

Understanding the air stability of MnBi

Detonation nanodiamonds (DNDs) are becoming increasingly important in science and technology with applications from drug delivery to tribology. DNDs are known to self-assemble into fractal-like aggregates in water, but their colloidal properties remain poorly understood. Here, the effect of salt and particle concentration on the size and shape of these aggregates is investigated using dynamic light scattering and small-angle X-ray scattering. Our results suggest the existence of two particle aggregate populations with diameters on the scale of 50 nm and 300 nm, respectively. The concentration of NaCl, in the range 0.005–1 mM, does not have a significant effect on the size or shape of the particle aggregates. The hydrodynamic radius of both aggregate populations decreases as the DND concentration increases from 0.01 to 2 mg mL−1. At the same time, the particle aggregates become denser and their overall shape changes from disk-like to rod-like with increasing DND concentration. We identify unexpected similarities between the aggregate structures observed for DNDs and those commonly observed for concentrated colloidal particles in high salt environments, described by classical colloid aggregation theories. Our results contribute to the fundamental understanding of the colloidal properties of DNDs and pave the way for the engineering of novel nanoparticle-based systems that make use of DNDs’ unique colloidal properties for future applications.

Perovskite transition metal oxides are promising non-precious metal electrocatalysts for promoting the oxygen evolution reaction (OER) in many electrochemical energy conversion devices. This work reports a systematic study of the relation between the electronic structure and OER performance of perovskite La1−xSrxFeO3 (0 ≤ x ≤ 1). The partial substitution of La for Sr in LaFeO3 results in the oxidation of Fe3+ to Fe4+ and substantially enhances OER activity. A comprehensive X-ray spectroscopic study reveals a strong correlation of the enhanced OER activity with these Fe4+ states. The presence of Fe4+ leads to a stronger Fe–O bond due to stronger Fe 3d–O 2p orbital hybridization and shifts the energy position of the valence band (VB) to EF. Such an electronic modulation optimizes the surface adsorption energetics of *OH intermediates, contributing to faster OER kinetics. Furthermore, a new unoccupied state is created at ∼0.9 eV below the conduction band. This hole state reduces the energy barrier for electron transfer from 1.34 eV to 0.44 eV, thereby facilitating charge transfer at the interface. The Fe4+-induced electronic states responsible for higher OER activity have implications for the understanding of structure–activity relationships in other Fe-based electrocatalysts such as highly active Fe-doped NiOOH.

Broadband photodetectors are essential for various applications including spectroscopy, communication, imaging and sensing. Even though few materials show broadband photodetection, they are only capable of detecting light in limited spectral ranges from infrared (IR) to ultraviolet (UV) wavelengths. However, their functionalities at much shorter wavelengths such as ionizing radiation still present a challenge because of the limitations from the material properties. Here we demonstrate a room temperature, high performance broadband photodetector based on van der Waals (vdWs) magnetic material CrSiTe3 (CST) that can efficiently detect both soft X-rays and light in the near-infrared (NIR) and visible wavelength ranges. The CrSiTe3 based device can work with a high sensitivity (≈463 μC Gyair−1 cm−2) under synchrotron soft X-rays, which is more than twenty times more sensitive than the conventional α-Se device. In the NIR range, the device can achieve a maximum responsivity of around 206 A W−1 at 785 nm, an extremely high external quantum efficiency (EQE) of 32 600%, a detectivity of 1.25 × 1012 cm Hz1/2 W−1 and a relatively fast photoresponse time (rise time ∼43 ms under X-rays, 17 ms under a 785 nm laser). Together these results demonstrate a high-performance broadband photo and X-ray detector, offering intriguing opportunities for novel optoelectronic applications.

Being a metallic transition-metal dichalcogenide, monolayer vanadium diselenide (VSe2) exhibits many novel properties, such as charge density waves and magnetism. Its interfaces with other materials can potentially be used in device applications as well as for manipulating its intrinsic properties. Here, we present a scanning tunneling microscopy and synchrotron-based X-ray photoemission spectroscopy study of the surface charge-transfer doping using efficient electron-withdrawing and electron-donating materials, that is, molybdenum trioxide (MoO3) and potassium (K), on the molecular beam epitaxy-grown monolayer VSe2 on highly oriented pyrolytic graphite (HOPG). We demonstrate that monolayer VSe2 is immune to MoO3- and K-doping effects. However, at the monolayer edges where the local chemical reactivity is higher because of Se deficiency, MoO3 is seen to react with VSe2 to form molybdenum dioxide (MoO2) and vanadium dioxide (VO2). Compared to the obvious charge-transfer doping effects of MoO3 and K on HOPG, the electronic structure of monolayer VSe2 is barely perturbed. This is attributed to the large density of states at the Fermi level of monolayer VSe2 carrying the metallic character. This work provides new insights into the chemical and electronic properties of monolayer VSe2, important for future VSe2-based electronic device design.

A detailed understanding of the bonding and molecular geometry characteristics of amino acids on chiral surfaces is vital toward discovering new pathways in chiral chemistry. Saturated layers of d-...

Practical applications of two-dimensional (2D) black phosphorus (BP) are limited by its fast degradation under ambient conditions, for which many different mechanisms have been proposed; however, an atomic level understanding of the degradation process is still hindered by the absence of bottom-up methods for the growth of large-scale few-layer black phosphorus. Recent experimental success in the fabrication of single-layer blue phosphorus provides a model system to probe the oxidation mechanism of two-dimensional (2D) phosphorene down to single-layer thicknesses. Here, we report an atomic-scale investigation of the interaction between molecular oxygen and blue phosphorus. The atomic structure of blue phosphorus and the local binding sites of oxygen have been precisely identified using qPlus-based noncontact atomic force microscopy. A combination of low-temperature scanning tunneling microscopy and X-ray photoelectron spectroscopy measurements reveal a thermally reversible oxidation process of blue phosphorus in a pure oxygen atmosphere. Our study clearly demonstrates the essential role of oxygen in the initial oxidation process, and it sheds further light on the fundamental pathways of the degradation mechanism.

Intrinsic magnetic topological insulators offer low disorder and large magnetic band gaps for robust magnetic topological phases operating at higher temperatures. By controlling the layer thickness, emergent phenomena such as the quantum anomalous Hall (QAH) effect and axion insulator phases have been realized. These observations occur at temperatures significantly lower than the Néel temperature of bulk MnBi

This paper describes the transition from the normal to inverted Marcus region in solid-state tunnel junctions consisting of self-assembled monolayers of benzotetrathiafulvalene (BTTF), and how this transition determines the performance of a molecular diode. Temperature-dependent normalized differential conductance analyses indicate the participation of the HOMO (highest occupied molecular orbital) at large negative bias, which follows typical thermally activated hopping behavior associated with the normal Marcus regime. In contrast, hopping involving the HOMO dominates the mechanism of charge transport at positive bias, yet it is nearly activationless indicating the junction operates in the inverted Marcus region. Thus, within the same junction it is possible to switch between Marcus and inverted Marcus regimes by changing the bias polarity. Consequently, the current only decreases with decreasing temperature at negative bias when hopping is “frozen out,” but not at positive bias resulting in a 30-fold increase in the molecular rectification efficiency. These results indicate that the charge transport in the inverted Marcus region is readily accessible in junctions with redox molecules in the weak coupling regime and control over different hopping regimes can be used to improve junction performance., Y.H., C.N., M.S.M., and S.K.K. contributed equally to this work. The authors acknowledge the Ministry of Education (MOE) for supporting this research under award no. MOE2019-T2-1-137. Prime Minister's Office, Singapore under its Medium sized centre program is also acknowledged for supporting this research. The authors also gratefully acknowledge the Australian Synchrotron (ANSTO) soft X-ray spectroscopy beamline where the SAM characterization was conducted. C.N. and E.d.B. acknowledge support from the US National Science Foundation (grant no. ECCS#1916874). D.Q. acknowledges the support of the Australian Research Council (Grant No. FT160100207). Authors also acknowledge the Marie-Sklodowska-Curie project ITN iSwitch (GA-642196), Spanish Ministry of Economy and Competitiveness (project FANCY CTQ2016-80030-R, GENESIS PID2019-111682RB-I00 and Severo Ochoa programme for Centers of excellence in R&D (SEV-2015-0496)). J.C. is a research director of the Belgian National Fund for Scientific Research (FNRS).

Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction. The junction is constructed from [FeIII(qsal-I)2]NTf2 (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate) molecules self-assembled on graphene surfaces with conductance switching of one order of magnitude associated with the high and low spin states of the SCO complex. Normalized conductance analysis of the current–voltage characteristics as a function of temperature reveals that charge transport across the SCO molecule is dominated by coherent tunnelling. Temperature-dependent X-ray absorption spectroscopy and density functional theory confirm the SCO complex retains its SCO functionality on the surface implying that van der Waals molecule—electrode interfaces provide a good trade-off between junction stability while retaining SCO switching capability. These results provide new insights and may aid in the design of other types of molecular devices based on SCO compounds., Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction.

Tunnel junctions based on Fe storing globular proteins are an interesting class of biomolecular tunnel junctions due to their tunable Fe ion loading, symmetrical structure and thermal stability, and are therefore attractive to study the mechanisms of charge transport (CT) at the molecular level. This paper describes a temperature-induced change in the CT mechanism across junctions with large globular (similar to 25 nm in diameter) E2-proteins bioengineered with Fe-binding peptides from ferritin (E2-LFtn) to mineralise Fe ions in the form of iron oxide nanoparticles (NPs) inside the protein's cavity. The iron oxide NPs provide accessible energy states that support high CT rates and shallow activation barriers. Interestingly, the CT mechanism changes abruptly, but reversibly, from incoherent tunnelling (which is thermally activated) to coherent tunnelling (which is activationless) across the E2-LFtn-based tunnel junctions with the highest Fe ion loading at a temperature of 220-240 K. During this transition the current density across the junctions increases by a factor of 13 at an applied voltage of V = -0.8 V. X-ray absorption spectroscopy indicates that the iron oxide NPs inside the E2-LFtn cages undergo a reversible phase transition; this phase transition opens up new a tunnelling pathway changing the mechanism of CT from thermally activated to activationless tunnelling despite the large size of the E2-LFtn and associated distance for tunnelling. Ministry of Education (MOE) Published version D. Q. acknowledges the support of the Australian Research Council (Grant No. FT160100207). We acknowledge the Ministry of Education (MOE) for supporting this research under award no. MOE2019-T2-1-137. Prime Minister’s Office, Singapore, under its Medium-sized centre program is also acknowledged for supporting this research.

The large-scale formation of patterned, quasi-freestanding graphene structures supported on a dielectric has so far been limited by the need to transfer the graphene onto a suitable substrate and contamination from the associated processing steps. We report μm scale, few-layer graphene structures formed at moderate temperatures (600–700 °C) and supported directly on an interfacial dielectric formed by oxidizing Si layers at the graphene/substrate interface. We show that the thickness of this underlying dielectric support can be tailored further by an additional Si intercalation of the graphene prior to oxidation. This produces quasi-freestanding, patterned graphene on dielectric SiO2 with a tunable thickness on demand, thus facilitating a new pathway to integrated graphene microelectronics.

Understanding the air-stability of MnBi$_2$Te$_4$ thin films is crucial for the development and long-term operation of electronic devices based around magnetic topological insulators. In the present work, we study MnBi$_2$Te$_4$ thin films upon exposure to atmosphere using a combination of synchrotron-based photoelectron spectroscopy, room temperature electrical transport and atomic force microscopy to determine the oxidation process. After 2 days air exposure a 2 nm thick oxide passivates the surface, corresponding to oxidation of only the top two surface layers, with the underlying layers preserved. This protective oxide layer results in samples that still exhibit metallic conduction even after several days air exposure. Furthermore, the work function decreases from 4.4 eV for pristine MnBi$_2$Te$_4$ to 4.0 eV after the formation of the oxide, along with only a small shift in the core levels indicating minimal doping as a result of air exposure. With the oxide confined to the top surface layers, and the underlying layers preserved, it may be possible to explore new avenues in how to handle, prepare and passivate future MnBi$_2$Te$_4$ devices.

The industrial realization of graphene has so far been limited by challenges related to the quality, reproducibility, and high process temperatures required to manufacture graphene on suitable substrates. We demonstrate that epitaxial graphene can be grown on transition metal treated 6H-SiC(0001) surfaces, with an onset of graphitization starting around $450-500^\circ\text{C}$. From the chemical reaction between SiC and thin films of Fe or Ru, $\text{sp}^{3}$ carbon is liberated from the SiC crystal and converted to $\text{sp}^{2}$ carbon at the surface. The quality of the graphene is demonstrated using angle-resolved photoemission spectroscopy and low-energy electron diffraction. Furthermore, the orientation and placement of the graphene layers relative to the SiC substrate is verified using angle-resolved absorption spectroscopy and energy-dependent photoelectron spectroscopy, respectively. With subsequent thermal treatments to higher temperatures, a steerable diffusion of the metal layers into the bulk SiC is achieved. The result is graphene supported on magnetic silicide or optionally, directly on semiconductor, at temperatures ideal for further large-scale processing into graphene based device structures., 10 pages, 4 figures, 51 references

Materials with flat bands are considered as ideal platforms to explore strongly correlated physics such as the fractional quantum hall effect, high-temperature superconductivity, and more. In theory, a Kagome lattice with only nearest-neighbor hopping can give rise to a flat band. However, the successful fabrication of Kagome lattices is still very limited. Here, we provide a new design principle to construct the Kagome lattice by trapping atoms into Kagome arrays of potential valleys, which can be realized on a potassium-decorated phosphorus-gold surface alloy. Theoretical calculations show that the flat band is less correlated with the neighboring trivial electronic bands, which can be further isolated and dominate around the Fermi energy with increased Kagome lattice parameters of potassium atoms. Our results provide a new strategy for constructing Kagome lattices, which serve as an ideal platform to study topological and more general flat band phenomena.

We use angle-resolved photoemission spectroscopy to investigate the electronic structure of bilayer graphene at high n-doping and extreme displacement fields, created by intercalating epitaxial monolayer graphene on silicon carbide with magnesium to form quasi-freestanding bilayer graphene on magnesium-terminated silicon carbide. Angle-resolved photoemission spectroscopy reveals that upon magnesium intercalation, the single massless Dirac band of epitaxial monolayer graphene is transformed into the characteristic massive double-band Dirac spectrum of quasi-freestanding bilayer graphene. Analysis of the spectrum using a simple tight binding model indicates that magnesium intercalation results in an n-type doping of 2.1 $\times$ 10$^{14}$ cm$^{-2}$, creates an extremely high displacement field of 2.6 V/nm, opening a considerable gap of 0.36 eV at the Dirac point. This is further confirmed by density-functional theory calculations for quasi-freestanding bilayer graphene on magnesium-terminated silicon carbide, which show a similar doping level, displacement field and bandgap. Finally, magnesium-intercalated samples are surprisingly robust to ambient conditions; no significant changes in the electronic structure are observed after 30 minutes exposure in air., 46 pages including supporting information, 4 figures in the main paper and 9 figures in the supporting information

Hydrogenated detonation nanodiamonds are of great interest for emerging applications in areas from biology and medicine to lubrication. Here, we compare the two main hydrogenation techniques&mdash, annealing in hydrogen and plasma-assisted hydrogenation&mdash, for the creation of detonation nanodiamonds with a hydrogen terminated surface from the same starting material. Synchrotron-based soft X-ray spectroscopy, infrared absorption spectroscopy, and electron energy loss spectroscopy were employed to quantify diamond and non-diamond carbon contents and determine the surface chemistries of all samples. Dynamic light scattering was used to study the particles&rsquo, colloidal properties in water. For the first time, steady-state and time-resolved fluorescence spectroscopy analysis at temperatures from room temperature down to 10 K was performed to investigate the particles&rsquo, fluorescence properties. Our results show that both hydrogenation techniques produce hydrogenated detonation nanodiamonds with overall similar physico-chemical and fluorescence properties.

Transition metal oxides are being actively pursued as low-cost electrocatalysts for the oxygen evolution reaction (OER) in many electrochemical energy devices. A fundamental understanding of the oxide electronic structures, along with the ability to rationally tune them, is a key step toward designing of highly active catalysts. Here, we report the tuning of the electronic structure of NiO via Li doping (LixNi1–xO) to enhance the OER activities. We identified that Li0.5Ni0.5O (LiNiO2) has the highest OER activity, comparable to or exceeding that of the benchmark perovskite Ba0.5Sr0.5Co0.8Fe0.2O3−δ and LaNiO3. More importantly, a synergistic combination of synchrotron-based photoemission spectroscopy, X-ray absorption spectroscopy, and density functional theory was used to unravel the electronic structure of LixNi1–xO with unprecedented accuracy, thus providing deep insight into the origin of the enhanced catalytic activity. The results unambiguously reveal the creation of a new hole state at 1.1 eV above the Fermi level and an enhanced degree of O 2p–Ni 3d hybridization induced by Li doping optimize the adsorption energetics of OH intermediates and thereby facilitate the fast kinetics for the OER. The LixNi1–xO would serve as a new platform to study the relationship of composition–electronic structure–activity for OER electrocatalysts, beyond the extensively studied Co-based perovskites.

The electric-field-induced quantum phase transition from topological to conventional insulator has been proposed as the basis of a topological field effect transistor1-4. In this scheme, 'on' is the ballistic flow of charge and spin along dissipationless edges of a two-dimensional quantum spin Hall insulator5-9, and 'off' is produced by applying an electric field that converts the exotic insulator to a conventional insulator with no conductive channels. Such a topological transistor is promising for low-energy logic circuits4, which would necessitate electric-field-switched materials with conventional and topological bandgaps much greater than the thermal energy at room temperature, substantially greater than proposed so far6-8. Topological Dirac semimetals are promising systems in which to look for topological field-effect switching, as they lie at the boundary between conventional and topological phases3,10-16. Here we use scanning tunnelling microscopy and spectroscopy and angle-resolved photoelectron spectroscopy to show that mono- and bilayer films of the topological Dirac semimetal3,17 Na3Bi are two-dimensional topological insulators with bulk bandgaps greater than 300millielectronvolts owing to quantum confinement in the absence of electric field. On application of electric field by doping with potassium or by close approach of the scanning tunnelling microscope tip, the Stark effect completely closes the bandgap and re-opens it as a conventional gap of 90millielectronvolts. The large bandgaps in both the conventional and quantum spin Hall phases, much greater than the thermal energy at room temperature (25millielectronvolts), suggest that ultrathin Na3Bi is suitable for room-temperature topological transistor operation.

We report on a study using a combination of XPS/NEXAFS and conductivity measurements to develop a fundamental understanding of how dipolar molecules interact with the heterostructure device surface and affect the device conductivity of AlGaN/GaN heterostructure-based transistors. In such structures, which are increasingly being investigated for chemical and biological sensing, a 2-dimensional electron gas spontaneously forms at the layer interface that is sensitive to the charge characteristics of the exposed surface. Glycine, chosen for this study because it is the simplest of the amino acids and is known to form a zwitterionic configuration when stabilized through intermolecular interactions, was evaporated under ultra-high vacuum conditions onto the device surface and subsequently both XPS/NEXAFS and conductivity measurements were conducted. NEXAFS spectra show a preferential orientation for the Glycine molecules on the surface and evidence for both neutral and zwitterionic species on the surface. In situ conductivity measurements suggest that the negatively charged carboxylate group is closest to the surface. These results are a unique and pivotal contribution to the previous and at times conflicting literature on the zwitterionic nature of Glycine.

Carbon-free production of hydrogen from renewable energy sources is readily attainable via electrochemical water splitting. Increasing the fraction of H2 generated by such environmentally friendly routes requires, however, further progress in electrode design to overcome the limited stability and activity of earth-abundant electrocatalysts. Herein, we report the multiscale engineering of the properties of Co3O4 electrocatalysts for oxygen evolution reaction (OER), revealing insights into the close interplay between activity and stability. The surface chemistry and physical properties of Co3O4 electrodes such as Co2+/Co3+ ratio, fractal features, and electron conductivity are modulated by a highly scalable one-step hot-aerosol synthesis. Optimized Co3O4 electrodes are obtained with a high mass-specific current density for OER of 642 A g−1 at 400 mV overpotential, which can be boosted to 1947 A g−1 at industrially-relevant elevated electrolyte temperature of 80 °C. Through operando Raman measurements, we reveal the in-situ transformation of the as-synthesized cobalt oxide moieties to oxyhydroxide species, identifying their role as catalytic active sites for OER. The potential of these earth-abundant electrocatalysts and their scalable preparation approach are demonstrated with a custom-designed electrolyzer, achieving a very high mass-specific current density of 800 A g−1 at 400 mV overpotential and more than 12 h stable operation.

The intercalation of epitaxial graphene on SiC(0001) with Ca has been studied extensively, yet precisely where the Ca resides remains elusive. Furthermore, the intercalation of Mg underneath epitaxial graphene on SiC(0001) has not been reported. Here, we use low energy electron diffraction, x-ray photoelectron spectroscopy, secondary electron cut-off photoemission and scanning tunneling microscopy to elucidate the physical and electronic structure of both Ca- and Mg-intercalated epitaxial graphene on 6H-SiC(0001). We find that Ca intercalates underneath the buffer layer and bonds to the Si-terminated SiC surface, breaking the C-Si bonds of the buffer layer i.e. 'freestanding' the buffer layer to form Ca-intercalated quasi-freestanding bilayer graphene (Ca-QFSBLG). The situation is similar for the Mg-intercalation of epitaxial graphene on SiC(0001), where an ordered Mg-terminated reconstruction at the SiC surface and Mg bonds to the Si-terminated SiC surface are formed, resulting in Mg-intercalated quasi-freestanding bilayer graphene (Mg-QFSBLG). Ca-intercalation underneath the buffer layer has not been considered in previous studies of Ca-intercalated epitaxial graphene. Furthermore, we find no evidence that either Ca or Mg intercalates between graphene layers. However, we do find that both Ca-QFSBLG and Mg-QFSBLG exhibit very low workfunctions of 3.68 and 3.78 eV, respectively, indicating high n-type doping. Upon exposure to ambient conditions, we find Ca-QFSBLG degrades rapidly, whereas Mg-QFSBLG remains remarkably stable., 58 pages, 10 figures, 4 tables. Revised text and figures

Being a metallic transition-metal dichalcogenide, monolayer vanadium diselenide (VSe

Layered indium selenides ($In_{2}Se_{3}$) have recently been discovered to host robust out-of-plane and in-plane ferroelectricity in the $\alpha$ and $\beta$' phases, respectively. In this work, we utilise angle-resolved photoelectron spectroscopy to directly measure the electronic bandstructure of $\beta '-In_{2}Se_{3}$, and compare to hybrid density functional theory (DFT) calculations. In agreement with DFT, we find the band structure is highly two-dimensional, with negligible dispersion along the c-axis. Due to n-type doping we are able to observe the conduction band minima, and directly measure the minimum indirect (0.97 eV) and direct (1.46 eV) bandgaps. We find the Fermi surface in the conduction band is characterized by anisotropic electron pockets with sharp in-plane dispersion about the $\overline{M}$ points, yielding effective masses of 0.21 $m_{0}$ along $\overline{KM}$ and 0.33 $m_{0}$ along $\overline{\Gamma M}$. The measured band structure is well supported by hybrid density functional theory calculations. The highly two-dimensional (2D) bandstructure with moderate bandgap and small effective mass suggest that $\beta'-In_{2}Se_{3}$ is a potentially useful new van der Waals semiconductor. This together with its ferroelectricity makes it a viable material for high-mobility ferroelectric-photovoltaic devices, with applications in non-volatile memory switching and renewable energy technologies., Comment: 19 pages, 4 + 1 figures; typos corrected;added references; updated figures & discussion to reflect changes in model

This work reports a fundamental study on the electronic structure, optical properties, and defect chemistry of a series of Co-based spinel oxide ( Co 3 O 4 , ZnCo 2 O 4 , and CoAl 2 O 4 ) epitaxial thin films using x-ray photoemission and absorption spectroscopies, optical spectroscopy, transport measurements, and density functional theory. We demonstrate that ZnCo 2 O 4 has a fundamental bandgap of 1.3 eV, much smaller than the generally accepted values, which range from 2.26 to 2.8 eV. The valence band edge mainly consists of occupied Co 3 d t 2 g 6 with some hybridization with O 2 p /Zn 3 d , and the conduction band edge of unoccupied e g * state. However, optical transition between the two band edges is dipole forbidden. Strong absorption occurs at photon energies above 2.6 eV, explaining the reasonable transparency of ZnCo 2 O 4 . A detailed defect chemistry study indicates that Zn vacancies formed at high oxygen pressure are the origin of a high p -type conductivity of ZnCo 2 O 4 , and the hole conduction mechanism is described by small-polaron hoping model. The high p -type conductivity, reasonable transparency, and large work function make ZnCo 2 O 4 a desirable p -type transparent semiconductor for various optoelectronic applications. Using the same method, the bandgap of Co 3 O 4 is further proved to be ∼0.8 eV arising from the tetrahedrally coordinated Co 2 + cations. Our work advances the fundamental understanding of these materials and provides significant guidance for their use in catalysis, electronic, and solar applications.

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution- and solid-phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom-up on-surface synthesis of well-defined nanostructures. We report an internal strain-induced skeletal rearrangement of one-dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu-catalyzed debromination of organic monomers to generate 1,5-dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond-resolved non-contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate-induced internal strain drives the skeletal rearrangement of MOCs via 1,3-H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain-induced structural rearrangement in 1D systems will enrich the toolbox for on-surface synthesis of novel functional materials and quantum nanostructures.

CuWO 4 is an n-type oxide semiconductor with a bandgap of 2.2 eV which exhibits great potential for photoelectrochemical (PEC) conversion of solar energy into chemical fuels. However, the photocurrent achieved so far is limited to ∼0.3 mA cm -2 at +1.23 V vs. reversible hydrogen electrode (RHE). Possible limiting factors include slow surface reaction kinetics, poor charge carrier mobility and/or presence of surface defect states. A detailed understanding of the fundamental electronic structure and its correlation with PEC activity is of significant importance for devising strategies for further improvements. In this work, we have synthesized CuWO 4 thin films showing a record photocurrent density of 0.50 mA cm -2 at +1.23 V vs. RHE. Importantly, we have used a synergistic combination of photoemission spectroscopy, X-ray absorption spectroscopy and density functional theory (DFT) to unravel the electronic structure of CuWO 4 . Our results show that the valence band (VB) consists of strongly hybridized states of O 2p 6 and Cu 3d 9 , while the bottom of the conduction band (CB) is primarily composed of unoccupied Cu 3d states. The localized nature of the Cu 3d state leads to the low charge carrier mobility and the localization of the photo-excited electrons to the CB. The combined experimental and theoretical results also indicate that CuWO 4 is better described as having a direct but d-d forbidden optical bandgap, leading to a low absorption coefficient for visible light. Furthermore, the implication of the electronic structure on its PEC characteristics and strategies for further improvements by adding Co 3 O 4 as a co-catalyst or surface layer to increase the interfacial band bending to facilitate photo-carriers transport, are discussed.

We report a detailed investigation of elementary catalytic decomposition of ammonia on the Pt-Ni-Pt(111) bimetallic surface using in situ near ambient pressure X-ray photoelectron spectroscopy. Under the near ambient pressure (0.6 mbar) reaction conditions, a different dehydrogenation pathway with a reduced activation energy barrier for recombinative nitrogen desorption on the Pt-Ni-Pt(111) bimetallic surface is observed. The unique surface catalytic activity is correlated with the downward shift of the Pt 5d band states induced by the Ni subsurface atoms via charge redistribution of the topmost Pt layer. Our results provide a practical understanding of the unique chemistry of bimetallic catalysts for facile ammonia decomposition under realistic reaction conditions.

Chiral separation using heterogeneous methods has long been sought after. Chiral metal surfaces have the potential to make it possible to model these systems using small amino acids, the building blocks for proteins. A comparison of submonolayer concentrations of alanine enantiomers adsorbed onto Cu{421}R has revealed a large geometrical differences between the two molecules as compared to the saturated coverage. Large differences were observed in HR-XPS and NEXAFS and complemented by theoretical DFT calculations. At approximately one third of a monolayer a comparison of the C1s XPS signal showed a shift in the methyl group of more than 300 meV indicating that the two enantiomers are in different chemical environments. NEXAFS spectroscopy confirmed the XPS variations and showed large differences in the orientation of the adsorbed molecules. Our DFT results show that the l-enantiomer is energetically the most stable in the {311} microfacet configuration. In contrast to the full monolayer coverage, these lower coverages showed enhanced selectivity.

Enhancing the efficiency of upconversion nanoparticles (UCNPs) and therefore their brightness is the critical goal for this emerging material to meet growing demands in many potential applications including sensing, imaging, solar energy conversion and photonics. The distribution of the photon sensitizer and activator ions that form a network of energy transfer systems within each single UCNP is vital for understanding and optimizing their optical properties. Here we employ synchrotron-based X-ray Photoelectron Spectroscopy (XPS) to characterize the depth distribution of Yb3+ sensitizer ions in host NaYF4 nanoparticles and systematically correlate the structure with the optical properties for a range of UCNPs with different sizes and doping concentrations. We find a radial gradient distribution of Yb3+ from the core to the surface of the NaYF4 nanoparticles, regardless of their size or the sensitizer's concentration. Energy dispersive X-ray Spectroscopy (EDX) was also used to further confirm the distribution of the sensitizer ions in the host matrix. These results have profound implications for the upconversion optical property variations.

We studied the long-range average and short-range local structures in Y2Ti2–xHfxO7 (x = 0–2.0) using diffraction and spectroscopy techniques, respectively. Both neutron and synchrotron X-ray powder diffraction data show a clear phase transition of the average structure from ordered pyrochlore to disordered defect-fluorite at x ≈ 1.6; the long-range anion disorder appears to develop gradually throughout the entire pyrochlore region in contrast to the rapid loss of cation ordering from x = 1.4 to 1.6. The commonly observed two-phase region around the pyrochlore/defect-fluorite phase boundary is absent in this system, demonstrating high sample quality. X-ray absorption near-edge structure (XANES) results at the Y L2-, Ti K- and L3,2-, Hf L3-, and O K-edges indicate a gradual local structural evolution across the whole compositional range; the Y coordination number (CN) decreases and the CN around Ti and Hf increases with increasing Hf content (x). The spectroscopic results suggest that the local disorder occ...

Topological Dirac semimetals (TDS) are three-dimensional analogues of graphene, with linear electronic dispersions in three dimensions. Nanoscale confinement of TDSs in thin films is a necessary step toward observing the conventional-to-topological quantum phase transition (QPT) with increasing film thickness, gated devices for electric-field control of topological states, and devices with surface-state-dominated transport phenomena. Thin films can also be interfaced with superconductors (realizing a host for Majorana Fermions) or ferromagnets (realizing Weyl Fermions or T-broken topological states). Here we report structural and electrical characterization of large-area epitaxial thin films of TDS Na3Bi on single crystal Al2O3[0001] substrates. Charge carrier mobilities exceeding 6,000 cm(2)/(V s) and carrier densities below 1 × 10(18) cm(-3) are comparable to the best single crystal values. Perpendicular magnetoresistance at low field shows the perfect weak antilocalization behavior expected for Dirac Fermions in the absence of intervalley scattering. At higher fields up to 0.5 T anomalously large quadratic magnetoresistance is observed, indicating that some aspects of the low field magnetotransport (μB1) in this TDS are yet to be explained.

Chromium nitride (CrN)-based materials display broad applications as protective coatings for automotive, power generation and aerospace industries, in which surfaces are often subjected to wear and corrosion. By using an appropriate choice of dopant, one can further increase the mechanical hardness, corrosion and oxidation resistance of these coatings. In order to identify the effect of dopants on the structural evolution and surface electronic properties of CrN coatings, Cr1-z(Al/Si)zN coatings were prepared by magnetron sputtering and then characterized via X-ray diffraction (XRD) and soft X-ray synchrotron radiation Near-edge X-ray Absorption Fine Structure (NEXAFS) studies around N K-edge. Higher degree of crystallinity of the coatings were identified through XRD studies. The bonding structure, of the doped CrN coating, was analyzed by Near-edge X-ray Absorption Fine Structure (NEXAFS) measurements performed around the N K-edge (390–450 eV) in the Auger electron yield (AEY) and total fluorescence yield (TFY) modes. NEXAFS analysis revealed Cr3d(Al3p/Si3p)N2p hybridizations in Cr1-z(Al/Si)zN compositions and complex structure splitting via spin–orbit interaction of the Cr3d levels.

The electric-field-induced quantum phase transition from topological to conventional insulator has been proposed as the basis of a topological field effect transistor