Benzene-1,4-Di(dithiocarboxylate) Linker-Based Coordination Polymers of Mn2+, Zn2+, and Mixed-Valence Fe2+/3.

Three new coordination polymers (CPs) constructed from the linker 1,4-di(dithiocarboxylate) (BDDTC2-)─the sulfur-analog of 1,4-benzenedicarboxylate (BDC2-)─together with Mn-, Zn-, and Fe-based inorganic SBUs are reported with description of their structural and electronic properties. Single-crystal X-ray diffraction revealed structural diversity ranging from one-dimensional chains in [Mn(BDDTC)(DMF)2] (1) to two-dimensional (2D) honeycomb sheets observed for [Zn2(BDDTC)3][Zn(DMF)5(H2O)] (2). Gas adsorption experiments confirmed a 3D porous structure for the mixed-valent material [Fe2(BDDTC)2(OH)] (3). 3 contains a 1:1 ratio of Fe2+/3+ ions, as evidenced by 57Fe Mössbauer, X-band EPR, and X-ray absorption spectroscopy. Its empirical formula was established by elemental analysis, thermal gravimetric analysis, infrared vibrational spectroscopy, and X-ray absorption spectroscopy in lieu of elusive single-crystal X-ray diffraction data. In contrast to the Mn- and Zn-based compounds 1 and 2, the Fe2+/3+ CP 3 showed remarkably high electrical conductivity of 5 × 10-3 S cm-1 (according to van der Pauw measurements), which is within the range of semiconducting materials. Overall, our study confirms that sulfur derivatives of typical carboxylate linkers (e.g., BDC) are suitable for the construction of electrically conducting CPs, due to acceptedly higher covalency in metal-ligand bonding compared to the electrically insulating carboxylate CPs or metal-organic frameworks. At the same time, the direct comparison between insulating CPs 1 and 2 with CP 3 emphasizes that the electronic structure of the metal is likewise a crucial aspect to construct electrically conductive materials.

CO2 reduction on pure Cu produces only H2 after subsurface O is depleted: Theory and experiment.

We elucidate the role of subsurface oxygen on the production of C2 products from CO2 reduction over Cu electrocatalysts using the newly developed grand canonical potential kinetics density functional theory method, which predicts that the rate of C2 production on pure Cu with no O is ∼500 times slower than H2 evolution. In contrast, starting with Cu2O, the rate of C2 production is >5,000 times faster than pure Cu(111) and comparable to H2 production. To validate these predictions experimentally, we combined time-dependent product detection with multiple characterization techniques to show that ethylene production decreases substantially with time and that a sufficiently prolonged reaction time (up to 20 h) leads only to H2 evolution with ethylene production ∼1,000 times slower, in agreement with theory. This result shows that maintaining substantial subsurface oxygen is essential for long-term C2 production with Cu catalysts.

Revealing Nanoscale Chemical Heterogeneities in Polycrystalline Mo-BiVO4 Thin Films.

The activity of polycrystalline thin film photoelectrodes is impacted by local variations of the material properties due to the exposure of different crystal facets and the presence of grain/domain boundaries. Here a multi-modal approach is applied to correlate nanoscale heterogeneities in chemical composition and electronic structure with nanoscale morphology in polycrystalline Mo-BiVO4 . By using scanning transmission X-ray microscopy, the characteristic structure of polycrystalline film is used to disentangle the different X-ray absorption spectra corresponding to grain centers and grain boundaries. Comparing both spectra reveals phase segregation of V2 O5 at grain boundaries of Mo-BiVO4 thin films, which is further supported by X-ray photoelectron spectroscopy and many-body density functional theory calculations. Theoretical calculations also enable to predict the X-ray absorption spectral fingerprint of polarons in Mo-BiVO4 . After photo-electrochemical operation, the degraded Mo-BiVO4 films show similar grain center and grain boundary spectra indicating V2 O5 dissolution in the course of the reaction. Overall, these findings provide valuable insights into the degradation mechanism and the impact of material heterogeneities on the material performance and stability of polycrystalline photoelectrodes.

Post-Synthetic Decoupling of On-Surface-Synthesized Covalent Nanostructures from Ag(111).

The on-surface synthesis of covalent organic nanosheets driven by reactive metal surfaces leads to strongly adsorbed organic nanostructures, which conceals their intrinsic properties. Hence, reducing the electronic coupling between the organic networks and commonly used metal surfaces is an important step towards characterization of the true material. We demonstrate that post-synthetic exposure to iodine vapor leads to the intercalation of an iodine monolayer between covalent polyphenylene networks and Ag(111) surfaces. The experimentally observed changes from surface-bound to detached nanosheets are reproduced by DFT simulations. These findings suggest that the intercalation of iodine provides a material that shows geometric and electronic properties substantially closer to those of the freestanding network.

Zirconium Oxynitride Thin Films for Photoelectrochemical Water Splitting.

Transition metal oxynitrides are a promising class of functional materials for photoelectrochemical (PEC) applications. Although these compounds are most commonly synthesized via ammonolysis of oxide precursors, such synthetic routes often lead to poorly controlled oxygen-to-nitrogen anion ratios, and the harsh nitridation conditions are incompatible with many substrates, including transparent conductive oxides. Here, we report direct reactive sputter deposition of a family of zirconium oxynitride thin films and the comprehensive characterization of their tunable structural, optical, and functional PEC properties. Systematic increases of the oxygen content in the reactive sputter gas mixture enable access to different crystalline structures within the zirconium oxynitride family. Increasing oxygen contents lead to a transition from metallic to semiconducting to insulating phases. In particular, crystalline Zr2ON2-like films have band gaps in the UV-visible range and are n-type semiconductors. These properties, together with a valence band maximum position located favorably relative to the water oxidation potential, make them viable photoanode candidates. Using chopped linear sweep voltammetry, we indeed confirm that our Zr2ON2 films are PEC-active for the oxygen evolution reaction in alkaline electrolytes. We further show that high-vacuum annealing boosts their PEC performance characteristics. Although the observed photocurrents are low compared to state-of-the-art photoanodes, these dense and planar thin films can offer a valuable platform for studying oxynitride photoelectrodes, as well as for future nanostructuring, band gap engineering, and defect engineering efforts.

Microstrain and Crystal Orientation Variation within Naked Triple-Cation Mixed Halide Perovskites under Heat, UV, and Visible Light Exposure.

The instability of perovskite absorbers under various environmental stressors is the most significant obstacle to widespread commercialization of perovskite solar cells. Herein, we study the evolution of crystal structure and microstrain present in naked triple-cation mixed CsMAFA-based perovskite films under heat, UV, and visible light (1 Sun) conditions by grazing-incidence wide-angle X-ray scattering (GIWAXS). We find that the microstrain is gradient distributed along the surface normal of the films, decreasing from the upper surface to regions deeper within the film. Moreover, heat, UV, and visible light treatments do not interfere with the crystalline orientations within annealed polycrystalline films. However, when subjected to heat, the naked perovskite films exhibit a rapid component decomposition, induced by phase separation and ion migration. Conversely, under exposure to UV and 1 Sun light soaking, the naked perovskite films undergo a self-optimization structure evolution during degradation and develop into smoother films with reduced surface potential fluctuations.

Solution-based synthesis of wafer-scale epitaxial BiVO4 thin films exhibiting high structural and optoelectronic quality.

We demonstrate a facile approach to solution-based synthesis of wafer-scale epitaxial bismuth vanadate (BiVO4) thin films by spin-coating on yttria-stabilized zirconia. Epitaxial growth proceeds via solid-state transformation of initially formed polycrystalline films, driven by interface energy minimization. The (010)-oriented BiVO4 films are smooth and compact, possessing remarkably high structural quality across complete 2'' wafers. Optical absorption is characterized by a sharp onset with a low sub-band gap response, confirming that the structural order of the films results in correspondingly high optoelectronic quality. This combination of structural and optoelectronic quality enables measurements that reveal a strong optical anisotropy of BiVO4, which leads to significantly increased in-plane optical constants near the fundamental band edge that are of particular importance for maximizing light harvesting in semiconductor photoanodes. Temperature-dependent transport measurements confirm a thermally activated hopping barrier of ∼570 meV, consistent with small electron polaron conduction. This simple approach for synthesis of high-quality epitaxial BiVO4, without the need for complex deposition equipment, enables a broadly accessible materials base to accelerate research aimed at understanding and optimizing photoelectrochemical energy conversion mechanisms.

Real-Time Investigation of Sulfur Vacancy Generation and Passivation in Monolayer Molybdenum Disulfide via in situ X-ray Photoelectron Spectromicroscopy.

Understanding the chemical and electronic properties of point defects in two-dimensional materials, as well as their generation and passivation, is essential for the development of functional systems, spanning from next-generation optoelectronic devices to advanced catalysis. Here, we use synchrotron-based X-ray photoelectron spectroscopy (XPS) with submicron spatial resolution to create sulfur vacancies (SVs) in monolayer MoS2 and monitor their chemical and electronic properties in situ during the defect creation process. X-ray irradiation leads to the emergence of a distinct Mo 3d spectral feature associated with undercoordinated Mo atoms. Real-time analysis of the evolution of this feature, along with the decrease of S content, reveals predominant monosulfur vacancy generation at low doses and preferential disulfur vacancy generation at high doses. Formation of these defects leads to a shift of the Fermi level toward the valence band (VB) edge, introduction of electronic states within the VB, and formation of lateral pn junctions. These findings are consistent with theoretical predictions that SVs serve as deep acceptors and are not responsible for the ubiquitous n-type conductivity of MoS2. In addition, we find that these defects are metastable upon short-term exposure to ambient air. By contrast, in situ oxygen exposure during XPS measurements enables passivation of SVs, resulting in partial elimination of undercoordinated Mo sites and reduction of SV-related states near the VB edge. Correlative Raman spectroscopy and photoluminescence measurements confirm our findings of localized SV generation and passivation, thereby demonstrating the connection between chemical, structural, and optoelectronic properties of SVs in MoS2.

The Influence of CsBr on Crystal Orientation and Optoelectronic Properties of MAPbI3-Based Solar Cells.

Crystal orientations are closely related to the behavior of photogenerated charge carriers and are vital for controlling the optoelectronic properties of perovskite solar cells. Herein, we propose a facile approach to reveal the effect of lattice plane orientation distribution on the charge carrier kinetics via constructing CsBr-doped mixed cation perovskite phases. With grazing-incidence wide-angle X-ray scattering measurements, we investigate the crystallographic properties of mixed perovskite films at the microscopic scale and reveal the effect of the extrinsic CsBr doping on the stacking behavior of the lattice planes. Combined with transient photocurrent, transient photovoltage, and space-charge-limited current measurements, the transport dynamics and recombination of the photogenerated charge carriers are characterized. It is demonstrated that CsBr compositional engineering can significantly affect the perovskite crystal structure in terms of the orientation distribution of crystal planes and passivation of trap-state densities, as well as simultaneously facilitate the photogenerated charge carrier transport across the absorber and its interfaces. This strategy provides unique insight into the underlying relationship between the stacking pattern of crystal planes, photogenerated charge carrier transport, and optoelectronic properties of solar cells.

Nanoscale Heterogeneities and Composition-Reactivity Relationships in Copper Vanadate Photoanodes.

The photoelectrochemical performance of thin film photoelectrodes can be impacted by deviations from the stoichiometric composition, both at the macroscale and at the nanoscale. This issue is especially pronounced for the class of ternary compounds that are currently investigated for simultaneously achieving the optoelectronic characteristics and chemical stability required for solar fuel generation. Here, we combine macroscopic photoelectrochemical testing with atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM) to reveal relationships between photoelectrochemical activity, nanoscale morphology, and local chemical composition in copper vanadate (CVO) thin films as a model system. For films with varying Cu/(Cu + V) ratios around the ideal stoichiometry of stoiberite Cu5V2O10, AFM resolves submicrometer morphology variations, which correlate with variations of the Cu content resolved by STXM. Both stoichiometric and Cu-deficient films exhibit a clear photoresponse, which indicates electronic tolerance to reduced Cu content. While both films exhibit homogeneous O and V content, they are also characterized by local regions of Cu enrichment and depletion that extend beyond individual grains. By contrast, Cu-rich photoelectrodes exhibit a tendency toward CuO secondary phase formation and a significantly reduced photoelectrochemical activity, indicating a significantly poor electronic tolerance to Cu-enrichment. These findings highlight that the average film composition at the macroscale is insufficient for defining structure-function relationships in complex ternary compounds. Rather, correlating microscopic variations in chemical composition to macroscopic photoelectrochemical performance provides insights into photocatalytic activity and stability that are otherwise not apparent from pure macroscopic characterization.

Indirect bandgap, optoelectronic properties, and photoelectrochemical characteristics of high-purity Ta3N5 photoelectrodes.

The (opto)electronic properties of Ta3N5 photoelectrodes are often dominated by defects, such as oxygen impurities, nitrogen vacancies, and low-valent Ta cations, impeding fundamental studies of its electronic structure, chemical stability, and photocarrier transport. Here, we explore the role of ammonia annealing following direct reactive magnetron sputtering of tantalum nitride thin films, achieving near-ideal stoichiometry, with significantly reduced native defect and oxygen impurity concentrations. By analyzing structural, optical, and photoelectrochemical properties as a function of ammonia annealing temperature, we provide new insights into the basic semiconductor properties of Ta3N5, as well as the role of defects on its optoelectronic characteristics. Both the crystallinity and material quality improve up to 940 °C, due to elimination of oxygen impurities. Even higher annealing temperatures cause material decomposition and introduce additional disorder within the Ta3N5 lattice, leading to reduced photoelectrochemical performance. Overall, the high material quality enables us to unambiguously identify the nature of the Ta3N5 bandgap as indirect, thereby resolving a long-standing controversy regarding the most fundamental characteristic of this material as a semiconductor. The compact morphology, low defect content, and high optoelectronic quality of these films provide a basis for further optimization of photoanodes and may open up further application opportunities beyond photoelectrochemical energy conversion.

Metastable Ta2N3 with highly tunable electrical conductivity via oxygen incorporation.

The binary Ta-N chemical system includes several compounds with notable prospects in microelectronics, solar energy harvesting, and catalysis. Among these, metallic TaN and semiconducting Ta3N5 have garnered significant interest, in part due to their synthetic accessibility. However, tantalum sesquinitride (Ta2N3) possesses an intermediate composition and largely unknown physical properties owing to its metastable nature. Herein, Ta2N3 is directly deposited by reactive magnetron sputtering and its optoelectronic properties are characterized. Combining these results with density functional theory provides insights into the critical role of oxygen in both synthesis and electronic structure. While the inclusion of oxygen in the process gas is critical to Ta2N3 formation, the resulting oxygen incorporation in structural vacancies drastically modifies the free electron concentration in the as-grown material, thus leading to a semiconducting character with a 1.9 eV bandgap. Reducing the oxygen impurity concentration via post-synthetic ammonia annealing increases the conductivity by seven orders of magnitude and yields the metallic characteristics of a degenerate semiconductor, consistent with theoretical predictions. Thus, this inverse oxygen doping approach - by which the carrier concentration is reduced by the oxygen impurity - offers a unique opportunity to tailor the optoelectronic properties of Ta2N3 for applications ranging from photochemical energy conversion to advanced photonics.

Effects of Defects on Band Structure and Excitons in WS2 Revealed by Nanoscale Photoemission Spectroscopy.

Two-dimensional materials with engineered composition and structure will provide designer materials beyond conventional semiconductors. However, the potentials of defect engineering remain largely untapped, because it hinges on a precise understanding of electronic structure and excitonic properties, which are not yet predictable by theory alone. Here, we utilize correlative, nanoscale photoemission spectroscopy to visualize how local introduction of defects modifies electronic and excitonic properties of two-dimensional materials at the nanoscale. As a model system, we study chemical vapor deposition grown monolayer WS2, a prototypical, direct gap, two-dimensional semiconductor. By cross-correlating nanoscale angle-resolved photoemission spectroscopy, core level spectroscopy, and photoluminescence, we unravel how local variations in defect density influence electronic structure, lateral band alignment, and excitonic phenomena in synthetic WS2 monolayers.

Disentangling the Role of Surface Chemical Interactions on Interfacial Charge Transport at BiVO4 Photoanodes.

Chemical transformations that occur on photoactive materials, such as photoelectrochemical water splitting, are strongly influenced by the surface properties as well as by the surrounding environment. Herein, we elucidate the effects of oxygen and water surface adsorption on band alignment, interfacial charge transfer, and charge-carrier transport by using complementary Kelvin probe measurements and photoconductive atomic force microscopy on bismuth vanadate. By observing variations in surface potential, we show that adsorbed oxygen acts as an electron-trap state at the surface of bismuth vanadate, whereas adsorbed water results in formation of a dipole layer without inducing interfacial charge transfer. The apparent change of trap state density under dry or humid nitrogen, as well as under oxygen-rich atmosphere, proves that surface adsorbates influence charge-carrier transport properties in the material. The finding that oxygen introduces electronically active states on the surface of bismuth vanadate may have important implications for understanding functional characteristics of water splitting photoanodes, devising strategies to passivate interfacial trap states, and elucidating important couplings between energetics and charge transport in reaction environments.

Nanoscale imaging of charge carrier transport in water splitting photoanodes.

The performance of energy materials hinges on the presence of structural defects and heterogeneity over different length scales. Here we map the correlation between morphological and functional heterogeneity in bismuth vanadate, a promising metal oxide photoanode for photoelectrochemical water splitting, by photoconductive atomic force microscopy. We demonstrate that contrast in mapping electrical conductance depends on charge transport limitations, and on the contact at the sample/probe interface. Using temperature and illumination intensity-dependent current-voltage spectroscopy, we find that the transport mechanism in bismuth vanadate can be attributed to space charge-limited current in the presence of trap states. We observe no additional recombination sites at grain boundaries, which indicates high defect tolerance in bismuth vanadate. These findings support the fabrication of highly efficient bismuth vanadate nanostructures and provide insights into how local functionality affects the macroscopic performance.

Remote functionalization in surface-assisted dehalogenation by conformational mechanics: organometallic self-assembly of 3,3',5,5'-tetrabromo-2,2',4,4',6,6'-hexafluorobiphenyl on Ag(111).

Even though the surface-assisted dehalogenative coupling constitutes the most abundant protocol in on-surface synthesis, its full potential will only become visible if selectivity issues with polybrominated precursors are comprehensively understood, opening new venues for both organometallic self-assembly and on-surface polymerization. Using the 3,3',5,5'-tetrabromo-2,2',4,4',6,6'-hexafluorobiphenyl (Br4F6BP) at Ag(111), we demonstrate a remote site-selective functionalization at room temperature and a marked temperature difference in double- vs. quadruple activation, both phenomena caused by conformational mechanical effects of the precursor-surface ensemble. The submolecularly resolved structural characterization was achieved by Scanning Tunneling Microscopy, the chemical state was quantitatively assessed by X-ray Photoelectron Spectroscopy, and the analysis of the experimental signatures was supported through first-principles Density-Functional Theory calculations. The non-planarity of the various structures at the surface was specifically probed by additional Near Edge X-ray Absorption Fine Structure experiments. Upon progressive heating, Br4F6BP on Ag(111) shows the following unprecedented phenomena: (1) formation of regular organometallic 1D chains via remote site-selective 3,5'-didebromination; (2) a marked temperature difference in double- vs. quadruple activation; (3) an organometallic self-assembly based on reversibility of C-Ag-C linkages with a thus far unknown polymorphism affording both hexagonal and rectangular 2D networks; (4) extraordinary thermal stability of the organometallic networks. Controlled covalent coupling at the previously Br-functionalized sites was not achieved for the Br4F6BP precursor, in contrast to the comparatively studied non-fluorinated analogue.

Reversible intercalation of iodine monolayers between on-surface synthesised covalent polyphenylene networks and Au(111).

We report on post-synthetic decoupling of covalent polyphenylene networks from Au(111) by intercalation of a chemisorbed iodine monolayer. The covalent networks were synthesised by on-surface Ullmann polymerization of 1,3-bis(p-bromophenyl)-5-(p-iodophenyl)benzene precursors on Au(111) under ultra-high vacuum conditions. The present study relates to previous work, where successful detachment was demonstrated on Ag(111) by a combination of microscopic and spectroscopic techniques. On the more reactive Ag(111) surfaces, intercalation was readily accomplished by exposing the samples to iodine vapour at room temperature. On more noble Au(111), however, STM, XPS and NEXAFS consistently indicate that the same protocol merely results in co-adsorption of iodine on uncovered surface areas, whereas the covalent networks remain adsorbed on the metal. Yet, performing the iodine exposure at elevated surface temperatures similarly results in detachment of the organic networks via intercalation of an iodine monolayer also on Au(111) as evidenced by characteristic changes in STM. In addition, owing to the high thermal stability of the covalent networks and the comparatively low iodine desorption temperature, the reversibility of the process is demonstrated: sample annealing at 400 °C results in complete desorption of the iodine monolayer, whereby the covalent networks re-adsorb directly on Au(111).

From Au-Thiolate Chains to Thioether Sierpinski Triangles: The Versatile Surface Chemistry of 1,3,5-Tris(4-mercaptophenyl)benzene on Au(111).

Self-assembly of 1,3,5-tris(4-mercaptophenyl)benzene (TMB), a 3-fold symmetric, thiol-functionalized aromatic molecule, was studied on Au(111) with the aim of realizing extended Au-thiolate-linked molecular architectures. The focus lay on resolving thermally activated structural and chemical changes by a combination of microscopy and spectroscopy. Thus, scanning tunneling microscopy (STM) provided submolecularly resolved structural information, while the chemical state of sulfur was assessed by X-ray photoelectron spectroscopy (XPS). Directly after room-temperature deposition, only less well ordered structures were observed. Mild annealing promoted the first structural transition into ordered molecular chains, partly organized in homochiral molecular braids. Further annealing led to self-similar Sierpinski triangles, while annealing at even higher temperatures again resulted in mostly disordered structures. Both the irregular aggregates observed at room temperature and the chains were identified as metal-organic assemblies, whereby two out of the three intermolecular binding motifs are energetically equivalent according to density functional theory (DFT) simulations. The emergence of Sierpinski triangles is driven by a chemical transformation, i.e., the conversion of coordinative Au-thiolate to covalent thioether linkages, and can be further understood by Monte Carlo simulations. The great structural variance of TMB on Au(111) can on one hand be explained by the energetic equivalence of two binding motifs. On the other hand, the unexpected chemical transition even enhances the structural variance and results in thiol-derived covalent molecular architectures.

On-surface Ullmann coupling: the influence of kinetic reaction parameters on the morphology and quality of covalent networks.

On-surface Ullmann coupling is a versatile and appropriate approach for the bottom-up fabrication of covalent organic nanostructures. In two-dimensional networks, however, the kinetically controlled and irreversible coupling leads to high defect densities and a lack of long-range order. To derive general guidelines for optimizing reaction parameters, the structural quality of 2D porous covalent networks was evaluated for different preparation protocols. For this purpose, polymerization of an iodine- and bromine-functionalized precursor was studied on Au(111) by scanning tunneling microscopy under ultrahigh vacuum conditions. By taking advantage of the vastly different temperature thresholds for C-Br and C-I cleavage, two different polymerization routes were compared - hierarchical and direct polymerization. The structural quality of the covalent networks was evaluated for different reaction parameters, such as surface temperatures, heating rates, and deposition rates by statistical analysis of STM data. Experimental results are compared to Monte Carlo simulations.

On-surface Ullmann polymerization via intermediate organometallic networks on Ag(111).

The role of organometallic intermediates during on-surface polymerization via Ullmann coupling was studied on Ag(111). The polymerization progress was monitored by X-ray photoelectron spectroscopy (XPS). Scanning Tunneling Microscopy (STM) was used to characterize organometallic and covalent networks and to identify the temperature regimes for organometallic and covalent bond formation.