Ultrahigh Vacuum Conditions Research Articles

Production of linear alkanes via the solid-state hydrogenation of interstellar polyynes

Highly unsaturated carbon chains, including polyynes, have been detected in many astronomical regions and planetary systems. With the success of the QUIJOTE survey of the Taurus Molecular Cloud-1 (TMC-1), the community has seen a "boom" in the number of detected carbon chains. On the other hand, the Rosetta mission revealed the release of fully saturated hydrocarbons, C_3H_8, C_4H_10, C_5H_12, and (under specific conditions) C_6H_14 with C_7H_16, from the comet 67P/Churyumov-Gerasimenko. The detection of the latter two is attributed to dust-rich events. Similarly, the analysis of samples returned from asteroid Ryugu by Hayabusa2 mission indicates the presence of long saturated aliphatic chains in Ryugu's organic matter. The surface chemistry of unsaturated carbon chains under conditions resembling those of molecular clouds can provide a possible link among these independent observations. However, laboratory-based investigations to validate such a chemistry is still lacking. In the present study, we aim to experimentally verify the formation of fully saturated hydrocarbons by the surface hydrogenation of C_2nH_2 (n>1) polyynes under ultra-high vacuum conditions at 10 K. We undertook a two-step experimental technique. First, a thin layer of C_2H_2 ice was irradiated by UV-photons (≥ 121 nm) to achieve a partial conversion of C_2H_2 into larger polyynes: C_4H_2 and C_6H_2. Afterwards, the obtained photoprocessed ice was exposed to H atoms to verify the formation of various saturated hydrocarbons. In addition to C_2H_6, which was investigated previously, the formation of larger alkanes, including C_4H_10 and (tentatively) C_6H_14, is confirmed by our study. A qualitative analysis of the obtained kinetic data indicates that hydrogenation of HCCH and HCCCCH triple bonds proceeds at comparable rates, given a surface temperature of 10 K. This can occur on the timescales typical for the dark cloud stage. A general pathway resulting in formation of other various aliphatic organic compounds by surface hydrogenation of N- and O-bearing polyynes is also proposed. We also discuss the astrobiological implications and the possibility of identifying alkanes with JWST.

The Impact of Carbon on Electronic Structure of N-Doped ZnO Films: Scanning Photoelectron Microscopy Study and DFT Calculations.

A Scanning Photoelectron Microscopy (SPEM) experiment has been applied to ZnO:N films deposited by Atomic Layer Deposition (ALD) under O-rich conditions and post-growth annealed in oxygen at 800 °C. State-of-the-Art spatial resolution (130 nm) allows for probing the electronic structure of single column of growth. The samples were cleaved under ultra-high vacuum (UHV) conditions to open atomically clean cross-sectional areas for SPEM experiment. It has been shown that different columns reveal considerably different shape of the valence band (VB) photoemission spectra and that some of them are shifted towards the bandgap. The shift of the VB maximum, which is associated with hybridization with acceptor states, was found to be correlated with carbon content measured as a relative intensity of the C1s and Zn3d core levels. Generalized Gradient Approximation (GGA) supplemented by +U correction was applied to both Zn3d and O2p orbitals for calculation of the VZn migration properties by the Nudged Elastic Band (NEB) method. The results suggest that interstitial -CHx groups facilitate the formation of acceptor complexes due to additional lattice perturbation.

Flexible Pressure Sensors Based on Laser-Induced Graphene

Graphene, with its remarkable attributes such as zero bandgap, broad-spectrum optical absorption, high carrier mobility, mechanical strength, and exceptional electrical conductivity, has gained significant interest across various fields including wearable technology, semiconductor components, and sensor technology. In 2009, Li et al. advanced the use of the chemical vapor deposition (CVD) technique, which is favored for its capability to produce high-quality graphene over large areas. This process involves introducing carbon-containing gases into a controlled environment within a chamber. However, the CVD method is hampered by its complex production scaling and the need for subsequent transfer of graphene to the desired substrate. An alternative approach, the SiC epitaxial growth method developed by Heer et al. in 2006, uses single-crystal silicon carbide as a substrate to synthesize graphene under ultra-high vacuum conditions (10-9torr) and at temperatures around 1300 ℃. Although this method has high potential for producing high-quality graphene, its high cost and significant safety concerns have limited its commercial viability. A more recent innovation is the development of laser-induced graphene (LIG) by Tour et al. in 2014. This technique allows for the rapid production of graphene with high porosity (340 m2/g), excellent thermal stability (up to 900℃), and impressive electrical conductivity (25 S/cm). LIG is created through laser irradiation that induces lattice vibrations and localized heating, causing covalent bonds to break and gases to be released, ultimately forming porous graphene structures. The process is rapid, does not require masks, and is environmentally friendly, making it particularly appealing for applications in flexible electronics and as an eco-friendly alternative. LIG's versatility has been demonstrated in a range of applications, from wearable electronics to supercapacitors, heaters, and biosensors. It can be synthesized on various substrates including polyimide films, plant material, paper, textiles, and other carbon-based materials. This method significantly broadens the range of material choices and facilitates modifications of substrate properties—from hydrophilicity to superhydrophobicity—through doping or control of processing parameters.Sensitive pressure sensors trends favor compact, highly sensitive sensors that meet the requirements of personal wearable devices, robotic technology, military applications, and sports equipment. Electronic textiles, which provide superior tensile performance, are often combined with small-scale sensors to enhance functionality. Currently, products in this category typically suffer from limited design flexibility and involve complex manufacturing processes. However, textile electronic products created using LIG has great potential due to their ability to be mass-produced and intricately patterned. This patterning is achieved with high precision directly through the computer software controlling the laser machine, offering significant advantages in terms of production efficiency and scalability.In the study, the fabrication of LIG into a flexible pressure sensor and evaluating its performance is reported. We use a 10.6 µm continuous-wave (CW) CO2 laser to fabricate LIG on carbon fiber substrates, with the aim of developing flexible strain sensors. This fabrication process is designed to not only enhance the mechanical strength of carbon fiber but also to impart electronic functionality. The study primarily focuses on adjusting three specific parameters: pulse per inch (PPI), power, and image density, with the finding that power significantly affects graphene formation more than the other variables. Through the optimization of these parameters, we have successfully produced high-density and high-quality graphene, achieving a reduction in sheet resistance by over 50% post-LIG formation, thereby enhancing the electronic performance of the materials. Additionally, variations in the contact angle among different types of laser-induced graphene samples illustrate differences in hydrophilicity and hydrophobicity, highlighting the functional versatility of LIG. The device also shows prompt response times and high sensitivity, enduring continuous bending without loss of functionality, which underscores its reliability. Experimental results further demonstrate that the sensor can detect cylinders of different radii, proving its potential in applications requiring flexibility and elasticity.

Role of Metal-Oxide Interfaces in Methanol Decomposition: Reaction of Methanol on CeO2/Ag(111) Inverse Model Catalysts.

Metal-oxide interfaces play a critical role in catalytic processes, such as methanol adsorption and decomposition reactions. In this work, we investigated methanol reactions on the inverse model CeO2/Ag(111) catalyst surfaces, i.e., submonolayer CeO2 films on Ag(111), under ultrahigh vacuum (UHV) conditions to specially address the role of CeO2-Ag interface in the catalytic methanol decomposition reactions. Using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and synchrotron radiation photoemission spectroscopy (SRPES), we found that, at the submonolayer ceria coverages, the CeO2 nanoislands exhibit a hexagonal CeO2(111) lattice with fully oxidized Ce4+ on Ag(111). At higher ceria coverages, multilayer ceria nanoislands form on the Ag(111) surface instead of a well-ordered film. A combination of temperature-programmed desorption (TPD) and SRPES reveals that methanol adsorbs dissociatively on the CeO2/Ag(111) surfaces at 110 K, resulting in the formation of methoxy groups. These methoxy groups subsequently decompose via two pathways: (i) interaction with lattice oxygen to produce formate species at 230 K, which then decompose to CO, and (ii) direct dehydrogenation of methoxy to formaldehyde. Notably, the surface with submonolayer CeO2 film on Ag(111) demonstrates low-temperature reactivity (440 K) for methoxy dehydrogenation to formaldehyde, which occurs at a much lower temperature, compared to the surface of multilayer CeO2 on Ag(111) surface (530 K). This finding emphasizes that the CeO2-Ag(111) interfaces provide unique active sites for methoxy dehydrogenation reactions.

Advancements in π-Magnetism and Precision Engineering of Carbon-Based Nanostructures.

The emergence of π-magnetism in low-dimensional carbon-based nanostructures, such as nanographenes (NGs), has captured significant attention due to their unique properties and potential applications in spintronics and quantum technologies. Recent advancements in on-surface synthesis under ultra-high vacuum conditions have enabled the atomically precise engineering of these nanostructures, effectively overcoming the challenges posed by their inherent strong chemical reactivity. This review highlights the essential concepts and synthesis methods used in studying NGs. It also outlines the remarkable progress made in understanding and controlling their magnetic properties. Advanced characterization techniques, such as scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM), have been instrumental in visualizing and manipulating these nanostructures, which highlighting their critical role in the field. The review underscores the versatility of carbon-based π-magnetic materials and their potential for integration into next-generation electronic devices. It also outlines future research directions aimed at optimizing their synthesis and exploring applications in cutting-edge technologies.

Directing Organometallic Ring-Chain Equilibrium by Electrostatic Interactions.

Dynamic chemistry, which falls into the realm of both supramolecular and covalent chemistry, enables intriguing properties, such as structural diversity, self-healing, and adaptability. Due to robustness of covalent bonds compared to noncovalent ones, dynamic covalent chemistry has been exploited to synthesize complex molecular nanostructures at solid/liquid interfaces under ambient conditions, generally responsive to internal factors that directly regulate intermolecular covalent bonds. However, directing dynamics of covalent nanostructures, e.g., the typical ring-chain equilibria, on surface by extrinsic interactions remains elusive and challenging. Herein, we have controllably directed the ring-chain equilibrium of covalent organometallic structures by regulating intermolecular electrostatic interactions, thus achieving on-surface dynamic covalent chemistry under ultrahigh vacuum conditions. Our findings unravel the dynamic mechanism of covalent polymers governed by weak intermolecular interactions at the submolecular level, which not only bridges the gap between supramolecular and covalent chemistry but also offers great opportunities for the fabrication of adaptive polymeric nanostructures that respond to different conditions.

Surface Structure and Chemistry of CeO2 Powder Catalysts Determined by Surface-Ligand Infrared Spectroscopy (SLIR).

ConspectusCerium is the most abundant rare earth element in the Earth's crust. Its most stable oxide, cerium dioxide (CeO2, ceria), is increasingly utilized in the field of catalysis. It can catalyze redox and acid-base reactions, and serve as a component of electrocatalysts and even photocatalysts. As one of the most commonly used in situ/operando characterization methods in catalysis, infrared (IR) spectroscopy is routinely employed to monitor reaction intermediates on the surface of solid catalysts, offering profound insight into reaction mechanisms. Additionally, IR vibrational frequencies of probe molecules adsorbed on solid catalysts provide detailed information about their structure and chemical states. Numerous studies in the literature have utilized carbon monoxide and methanol as IR probe molecules on ceria particles. However, assigning their vibrational frequencies is often highly controversial due to the great complexity of the actual surface of ceria particles, which include differently oriented crystal facets, reconstructions, defects, and other structural variations. In our laboratory, taking bulk ceria single crystals with distinct orientations as model systems, we employed a highly sensitive ultrahigh vacuum (UHV) infrared spectroscopy system (THEO) to study the adsorption of CO and methanol. It turns out that the theoretical calculations adopting hybrid functionals (HSE06) can bring the theoretical predictions into agreement with the experimental results for the CO frequencies on ceria single crystal surfaces. The obtained frequencies serve as reliable references to resolve the long-standing controversial assignments for the IR bands of CO and methanol adsorbed on ceria particles. Furthermore, these characteristic frequencies allow for the determination of orientations, oxidation states and restructuring of exposed crystal facets of ceria nanoparticles, which is applicable from UHV conditions to industrially relevant pressures of up to 1 bar, and from low temperatures (∼65 K) to high temperatures (∼1000 K). We also used molecular oxygen as a probe molecule to investigate its interaction with the ceria surface, crucial for understanding ceria's redox properties. Our findings reveal that the localization of oxygen vacancies and the mechanism of dioxygen activation are highly sensitive to surface orientations. We provided the first spectroscopic evidence showing that the oxygen vacancies on ceria (111) surfaces tend to localize in deep layers. In addition, we employed N2O as a probe molecule to elucidate the origin of the photocatalytic activity of ceria and showed that the photocatalytic activity is highly sensitive to the surface orientation (i.e., surface coordination structure). This Account shows that probe-molecule infrared spectroscopy serves as a powerful in situ/operando tool for studying the surface structure and chemistry of solid catalysts, and the knowledge gained through the "Surface Science" approach is essential as a crucial benchmark.

Solution Versus On-Surface Synthesis of Peripherally Oxygen-Annulated Porphyrins through C-O Bond Formation.

This study investigates the synthesis of tetra- and octa-O-fused porphyrinoids employing an oxidative O-annulation approach through C-H activation. Despite encountering challenges such as overoxidation and instability in conventional solution protocols, successful synthesis was achieved on Au(111) surfaces under ultra-high vacuum (UHV) conditions. X-ray photoelectron spectroscopy, scanning tunneling microscopy, and non-contact atomic force microscopy elucidated the preferential formation of pyran moieties via C-O bond formation and subsequent self-assembly driven by C-H⋅⋅⋅O interactions. Furthermore, the O-annulation process was found to reduce the HOMO-LUMO gap by lifting the HOMO energy level, with the effect rising upon increasing the number of embedded O-atoms.

2M NaCl by XPS using monochromatic Al K α x rays

Cryo-XPS enables the study of many substances that are unsuitable for standard XPS analysis, such as moderately volatile liquids, biological samples, porous materials, and polymeric materials that may outgas significantly under ultrahigh vacuum conditions. In this article, XPS spectra of a 50 μl frozen droplet of 2M sodium chloride solution (NaCl) in Millipore water purified to 18.2 MΩ cm at 25 °C were obtained using an Al Kα (1486.6 eV) source with a quartz (1010) crystal monochromator through first order diffraction and irradiating the sample at 54.7° to the surface normal. The sample was sputter cleaned using a Gas Cluster Ion Source pre-acquisition to remove the minor layer of adventitious carbon contamination on the surface. Spectra of the principal lines include Na 1s, O 1s, and Cl 2p. Spectra of O KLL, Na KLL, Cl 2s, Na 2s, Na 2p, O 2s, and valence band were also acquired.

Step-by-step silicon carbide graphitisation process study in terms of time and temperature parameters

This work investigates the temperature and time as key parameters for graphene formation on the silicon carbide surface during the high thermal decomposition process. Measurements were performed using various experimental techniques under ultra-high vacuum conditions. The graphitisation process was divided into various stages, after which the surface chemical composition and atomic structures were analysed in detail. It has been shown that despite the known theory of graphitisation mechanism and initial condition for occurrence of this process, the application of different temperatures and heating times affect the quality and quantity of formed graphene layers. Applying a temperature too low or annealing the sample for a too short time led to an inefficient silicon sublimation process. On the other hand, too high temperature during flashing modifies the visibility of surface structures, which may be crucial for other investigations and potential applications of such systems.

Synthesis and electrical transport properties of superconducting platinum silicide thin films and devices

We evaluate the material characteristics of superconducting platinum silicide (PtSi) thin films as candidate materials for superconducting quantum information devices compatible with silicon technology. These films were synthesized using magnetron sputtering under ultrahigh vacuum conditions, followed by rapid thermal annealing. Polycrystalline PtSi films synthesized by this method have the favorable properties of superconducting critical temperature of 0.95 K and relatively long zero-temperature Ginzburg-Landau coherence length of 76 nm. We further studied coplanar microbridge devices fabricated by electron beam lithography and chlorine-free reactive ion etching, finding that the temperature-dependent critical current density follows the Ginzburg Landau depairing mechanism.

Determining the carbon detection limit with magnetic sector dynamic secondary ion mass spectrometry (SIMS)

Dynamic SIMS is often used to evaluate the concentration of impurities in solids because of its high sensitivity, depth profiling capabilities, good depth resolution, and high throughput. Continuous ion beam sputtering with a high-density primary beam provides high sensitivity and reduces the background contribution from residual gases within the analytical chamber. Dynamic SIMS experiments performed with several magnetic sector instruments using various sputtering rate conditions demonstrated a slow decrease of the carbon detection limit with the increase of sputtering rate (SR), when it was varied by changing the sputtering beam density. The dependence data, within the scatter limits, can be fit by a power function of SR with the exponent of about −1/2. The observed detection-limit-dependence curve is common for magnetic sector SIMS instruments, owing to contamination and the design of the analytical chamber. The depth resolution of light-element SIMS analysis (except for oxygen) performed using Cs+ sputtering is limited and cannot be improved by reducing the impact energy of the sputtering beam. A segregation-type depth profile with a long trailing edge was observed in the B, C, and N depth profiles when Cs+ sputtering was employed under ultra-high vacuum conditions. This effect is plausibly associated with preferential sputtering owing to the difference in the surface binding energy, along with the large difference in the mass of the interacting atoms within the collision cascade during sputtering. The depth resolution improved with surface oxidation when Cs + sputtering was combined with backfilling of the analytical chamber using O2. The analytical chamber backfilled with oxygen can be sufficiently replaced with a very low-impact energy-focused oxygen beam, enabling simultaneous oxygen and cesium co-sputtering SIMS analysis. The practical feasibility of using a co-sputtering with focused Cs+ and O2+ sputtering beams to achieve a high depth-resolution for carbon analysis under ultrahigh vacuum conditions was demonstrated.

In-situ observation of recrystallization of K-doped tungsten sheets using laser reflection

The microstructure of (doped) tungsten sheets is crucial for their mechanical behavior. Within this study, a new method, based on laser reflection, is proposed to in-situ determine the process of (secondary) recrystallization and the resulting grain size of (doped) tungsten sheets under ultra high vacuum conditions. The system introduced here allows to position the reflection setup at a reasonable distance from the sample to further observe the sample temperature via a pyrometer. The main signals of interest are the reflection intensity, the resulting distribution, and changes thereof. Furthermore, the proposed method can be carried out on polished and as rolled surfaces likewise. This novel method makes it possible to determine the secondary recrystallization temperature (TRx) in rolled (K-)doped tungsten sheets within a single non-isothermal annealing procedure. The average surface grain size during isothermal annealing procedures can be evaluated as well. Even though the observations are generally restricted to the surface, in the case of tungsten sheets a sufficient determination of bulk recrystallization kinetics is possible as well. Furthermore, the obtained results show, that the recrystallization temperature can serve as a sufficient measure to describe the recrystallized microstructure. Even for different sample strains, TRx correctly predicts the average grain size resulting for various temperature increase rates. The proposed method provides a simple, coherent, and robust method to evaluate the recrystallization properties of (doped) tungsten sheets within a single measurement.

Stability and dissolution of single-crystalline iron oxide thin films in electrochemical environments

The stability of single-crystalline monolayer FeO(111) and 10 nm thin Fe3O4(111) films on Pt(111) upon exposure to environments of increasing chemical complexity has been studied with X-ray photoelectron spectroscopy, temperature-programmed desorption, in-situ scanning tunneling microscopy, and cyclic voltammetry. The well-defined oxide films, which were prepared under ultrahigh-vacuum conditions, were exposed to aqueous solutions of different pH and electrochemical cycling in pure and catechol-containing electrolyte. The films are stable in neutral (pH 7) and alkaline (pH 13) solutions both at open circuit conditions and during electrochemical cycling within the limits of hydrogen and oxygen evolution potentials. Also in strongly acidic (pH 1) perchlorate solution the films remain intact under open circuit conditions, but they quickly dissolve on application of electrochemical potential. Especially for the ultrathin FeO(111) films, catechol enhances the dissolution at neutral pH during electrochemical cycling. A comparison of Pt(111), FeO(111) and Fe3O4(111) substrates in the electrochemical catechol oxidation reaction reveals enhanced and sustained activity of FeO in alkaline environment, while strong deactivation occurs on Pt(111) and Fe3O4(111). This is explained by the weaker interaction between catechol and FeO(111) compared to the other substrates, which hampers the formation of a barrier layer on the electrode surface.

Generation of ultrashort ion pulses from ultrafast electron-stimulated desorption

We present an efficient method to produce laser-triggered proton pulses well below 500 ps pulse width at keV energies. We use femtosecond photoelectron pulses emitted from a cathode to enable ultrafast electron-stimulated desorption of adsorbates on a stainless steel plate under ultrahigh vacuum conditions. While direct photoionization of atoms to form well-timed ion pulses can suffer from a laser-focus-limited large starting volume, in our method the two-dimensional starting plane of the ions is defined with nanometer precision at a solid surface. We clearly outline how the method could be used in the future to efficiently produce ion beam pulses in the (sub)picosecond range for pump-probe experiments with ions. Published by the American Physical Society 2024

Thermal stability of gold films on titanium-adhered silicon substrate

In this study, thermally induced changes in the surface of a thin gold film deposited on Si(100) with a 5 nm thick titanium adhesion layer were investigated. The analysis involved X-ray photoelectron spectroscopy, low-energy electron diffraction, and scanning tunnelling microscopy. The sample was subjected to stepwise annealing under ultra-high vacuum conditions at temperatures ranging from 430 to 1330 K. Low-temperature annealing up to 450 K did not alter the morphology but improved the cleanliness of the gold film surface. Annealing between 530 and 930 K resulted in the disintegration of the gold film, along with mixing and interaction between the sample components. Annealing the sample at 980 K led to the emergence of a gold silicide surface on Si(100) exhibiting the (5 × 3.2)R5.7° reconstruction.

Reconstruction of calcite (10.4) manifests itself in the tip-assisted diffusion of water

Calcite (calcium carbonate) is the most abundant carbonate in the Earth's crust. Due to its omnipresence it plays a prominent role in fields such as geochemistry, biomineralization and industrial processes. Moreover, the interaction of water with the most stable cleavage plane, calcite (10.4), has been studied intensively, elucidating atomic-scale details of water binding and structure formation on this surface. Interestingly, calcite (10.4) reconstructs under ultrahigh vacuum conditions, exhibiting a (2 × 1) surface unit cell. Although first indications of this reconstruction have been presented more than 20 years ago, a clear confirmation of the existence has been provided only very recently. Here, we study the tip-assisted diffusion of water molecules on calcite (10.4) under ultrahigh vacuum conditions. By recording images series using dynamic atomic force microscopy we follow the movement of water molecules on the surface kept at 140 K. Analyzing the change in consecutive images allows for elucidating details of the molecular movement on the surface. Most notably, the analysis reveals that water molecules occupy one type of adsorption position exclusively, while the other type is not adopted. Our analysis thus demonstrates that the (2 × 1) reconstruction manifests itself in the movement of single water molecules on this surface.

Role of graphene substrate in the formation of MoS2-based nanoparticles with improved sensitivity to NO2 gas

MoS2 coatings were formed on surface-oxidized silicon, chemical vapor deposition (CVD)-grown graphene, and reduced fluorinated graphene (rFG) from ammonium tetrathiomolybdate. The samples were annealed under ultra-high vacuum conditions at a temperature of 1000 °C. Analysis of X-ray photoelectron and X-ray absorption spectra revealed a bonding between MoS2 and the supporting material that was particularly strong for CVD-graphene. Uniform covering of the flat CVD-graphene surface with MoS2 nanoparticles and numerous contacts between them promoted the removal of sulfur and the formation of exposed molybdenum edges. A cracked MoS2 coating consisting of dense domains was formed on the wrinkled rFG surface. The study of samples as NO2 gas sensors revealed the best performance of MoS2/CVD-graphene. The sensor detected NO2 in air below 50 ppb at room temperature, had good response and recovery, operated in humid air, and demonstrated excellent NO2 selectivity. The other two sensors gave signals at elevated temperatures. The advantage of MoS2/CVD-graphene is due to improved electron transport in the hybrid, accessibility of small MoS2 nanoparticles to the analyte, and passivation of high-energy molybdenum sites by oxygen, which improves NO2 desorption.

Scanning Probe Microscopy Characterization of Biomolecules enabled by Mass-Selective, Soft-landing Electrospray Ion Beam Deposition.

Scanning probe microscopy (SPM), in particular at low temperature (LT) under ultra-high vacuum (UHV) conditions, offers the possibility of real-space imaging with resolution reaching the atomic level. However, its potential for the analysis of complex biological molecules has been hampered by requirements imposed by sample preparation. Transferring molecules onto surfaces in UHV is typically accomplished by thermal sublimation in vacuum. This approach however is limited by the thermal stability of the molecules, i. e. not possible for biological molecules with low vapour pressure. Bypassing this limitation, electrospray ionisation offers an alternative method to transfer molecules from solution to the gas-phase as intact molecular ions. In soft-landing electrospray ion beam deposition (ESIBD), these molecular ions are subsequently mass-selected and gently landed on surfaces which permits large and thermally fragile molecules to be analyzed by LT-UHV SPM. In this concept, we discuss how ESIBD+SPM prepares samples of complex biological molecules at a surface, offering controls of the molecular structural integrity, three-dimensional shape, and purity. These achievements unlock the analytical potential of SPM which is showcased by imaging proteins, peptides, DNA, glycans, and conjugates of these molecules, revealing details of their connectivity, conformation, and interaction that could not be accessed by any other technique.

Zinc blende ZnS (001) surface structure investigated by XPS, LEED, and DFT

The formation and stability of the zinc blende ZnS (001) single crystal surface have been examined by x-ray photoemission spectroscopy (XPS), low-energy electron diffraction (LEED), and density-functional theory (DFT) calculations. LEED patterns obtained from the ZnS (001) surface prepared in ultrahigh vacuum conditions at 1420 K reveal the formation of a (1 × 2) reconstructed structure. Surface chemical characterization performed by XPS indicates that the surface region consists of a Zn-deficient (sulfur-rich) phase. Our DFT theoretical calculations confirm that the ZnS (001) (1x2) surface structure is energetically favorable and consists of a Zn-terminated topmost surface layer stabilized by Zn-vacancies. The calculations also suggest that the remaining Zn-cations on the surface are displaced inward, driven by surface energy minimization related to zinc-blend ZnS (001) polar nature. Notably, the observed surface structural modifications have potential implications for the ZnS physical and chemical properties.