Infrared reflection absorption spectroscopy setup with incidence angle selection for surfaces of non-metals.

Infrared Reflection Absorption Spectroscopy (IRAS) on dielectric single crystals is challenging because the optimal incidence angles for light-adsorbate interaction coincide with regions of low IR reflectivity. Here, we introduce an optimized IRAS setup that maximizes the signal-to-noise ratio for non-metals. This is achieved by maximizing light throughput and by selecting optimal incidence angles that directly impact the peak heights in the spectra. The setup uses a commercial Fourier transform infrared spectrometer and is usable in ultra-high vacuum (UHV). Specifically, the optical design features sample illumination and collection mirrors with a high numerical aperture inside the UHV system and adjustable apertures to select the incidence angle range on the sample. This is important for p-polarized measurements on dielectrics because the peaks in the spectra reverse the direction at the Brewster angle (band inversion). The system components are connected precisely via a single flange, ensuring long-term stability. We studied the signal-to-noise ratio (SNR) variation in p-polarized IRAS spectra for one monolayer of CO on TiO2(110) as a function of incidence angle range, where a maximum SNR of 70 was achieved at 4 cm-1 resolution in a measurement time of 5 min. The capabilities for s polarization are demonstrated by measuring one monolayer D2O adsorbed on a TiO2(110) surface, where a SNR of 65 was achieved at a peak height ΔR/R0 of 1.4 × 10-4 in 20 min.

NH3 adsorption and competition with H2O on a hydroxylated aluminosilicate surface.

The interaction between ammonia (NH3) and (alumino)silicates is of fundamental and applied importance, yet the specifics of NH3 adsorption on silicate surfaces remain largely unexplored, mainly because of experimental challenges related to their electrically insulating nature. An example of this knowledge gap is evident in the context of ice nucleation on silicate dust, wherein the role of NH3 for ice nucleation remains debated. This study explores the fundamentals of the interaction between NH3 and microcline feldspar (KAlSi3O8), a common aluminosilicate with outstanding ice nucleation abilities. Atomically resolved non-contact atomic force microscopy, x-ray photoelectron spectroscopy, and density functional theory-based calculations elucidate the adsorption geometry of NH3 on the lowest-energy surface of microcline, the (001) facet, and its interplay with surface hydroxyls and molecular water. NH3 and H2O are found to adsorb molecularly in the same adsorption sites, creating H-bonds with the proximate surface silanol (Si-OH) and aluminol (Al-OH) groups. Despite the closely matched adsorption energies of the two molecules, NH3 readily yields to replacement by H2O, challenging the notion that ice nucleation on microcline proceeds via the creation of an ordered H2O layer atop pre-adsorbed NH3 molecules.

High-κ Wide-Gap Layered Dielectric for Two-Dimensional van der Waals Heterostructures.

van der Waals heterostructures of two-dimensional materials have unveiled frontiers in condensed matter physics, unlocking unexplored possibilities in electronic and photonic device applications. However, the investigation of wide-gap, high-κ layered dielectrics for devices based on van der Waals structures has been relatively limited. In this work, we demonstrate an easily reproducible synthesis method for the rare-earth oxyhalide LaOBr, and we exfoliate it as a 2D layered material with a measured static dielectric constant of 9 and a wide bandgap of 5.3 eV. Furthermore, our research demonstrates that LaOBr can be used as a high-κ dielectric in van der Waals field-effect transistors with high performance and low interface defect concentrations. Additionally, it proves to be an attractive choice for electrical gating in excitonic devices based on 2D materials. Our work demonstrates the versatile realization and functionality of 2D systems with wide-gap and high-κ van der Waals dielectric environments.

CO-Induced Dimer Decay Responsible for Gem-Dicarbonyl Formation on a Model Single-Atom Catalyst.

The ability to coordinate multiple reactants at the same active site is important for the wide-spread applicability of single-atom catalysis. Model catalysts are ideal to investigate the link between active site geometry and reactant binding, because the structure of single-crystal surfaces can be precisely determined, the adsorbates imaged by scanning tunneling microscopy (STM), and direct comparisons made to density functional theory. In this study, we follow the evolution of Rh1 adatoms and minority Rh2 dimers on Fe3O4(001) during exposure to CO using time-lapse STM at room temperature. CO adsorption at Rh1 sites results exclusively in stable Rh1CO monocarbonyls, because the Rh atom adapts its coordination to create a stable pseudo-square planar environment. Rh1(CO)2 gem-dicarbonyl species are also observed, but these form exclusively through the breakup of Rh2 dimers via an unstable Rh2(CO)3 intermediate. Overall, our results illustrate how minority species invisible to area-averaging spectra can play an important role in catalytic systems, and show that the decomposition of dimers or small clusters can be an avenue to produce reactive, metastable configurations in single-atom catalysis.

Interaction of surface cations of cleaved mica with water in vapor and liquid forms.

Natural minerals contain ions that become hydrated when they come into contact with water in vapor and liquid forms. Muscovite mica - a common phyllosilicate with perfect cleavage planes - is an ideal system to investigate the details of ion hydration. The cleaved mica surface is decorated by an array of K+ ions that can be easily exchanged with other ions or protons when immersed in an aqueous solution. Despite the vast interest in the atomic-scale hydration processes of these K+ ions, experimental data under controlled conditions have remained elusive. Here, atomically resolved non-contact atomic force microscopy (nc-AFM) is combined with X-ray photoelectron spectroscopy (XPS) to investigate the cation hydration upon dosing water vapor at 100 K in ultra-high vacuum (UHV). The cleaved surface is further exposed to ultra-clean liquid water at room temperature, which promotes ion mobility and partial ion-to-proton substitution. The results offer the first direct experimental views of the interaction of water with muscovite mica under UHV. The findings are in line with previous theoretical predictions.

How Water Binds to Microcline Feldspar (001).

Microcline feldspar (KAlSi3O8) is a common mineral with important roles in Earth's ecological balance. It participates in carbon, potassium, and water cycles, contributing to CO2 sequestration, soil formation, and atmospheric ice nucleation. To understand the fundamentals of these processes, it is essential to establish microcline's surface atomic structure and its interaction with the omnipresent water molecules. This work presents atomic-scale results on microcline's lowest-energy surface and its interaction with water, combining ultrahigh vacuum investigations by noncontact atomic force microscopy and X-ray photoelectron spectroscopy with density functional theory calculations. An ordered array of hydroxyls bonded to silicon or aluminum readily forms on the cleaved surface at room temperature. The distinct proton affinities of these hydroxyls influence the arrangement and orientation of the first water molecules binding to the surface, holding potential implications for the subsequent condensation of water.

Evolution of the surface atomic structure of multielement oxide films: curse or blessing?

Atomically resolved scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) are used to gain atomic-scale insights into the heteroepitaxy of lanthanum-strontium manganite (LSMO, La1-xSrxMnO3-δ, x ≈ 0.2) on SrTiO3(110). LSMO is a perovskite oxide characterized by several composition-dependent surface reconstructions. The flexibility of the surface allows it to incorporate nonstoichiometries during growth, which causes the structure of the surface to evolve accordingly. This happens up to a critical point, where phase separation occurs, clusters rich in the excess cations form at the surface, and films show a rough morphology. To limit the nonstoichiometry introduced by non-optimal growth conditions, it proves useful to monitor the changes in surface atomic structures as a function of the PLD parameters and tune the latter accordingly.

Effect of Different In2O3(111) Surface Terminations on CO2 Adsorption.

In2O3-based catalysts have shown high activity and selectivity for CO2 hydrogenation to methanol; however, the origin of the high performance of In2O3 is still unclear. To elucidate the initial steps of CO2 hydrogenation over In2O3, we have combined X-ray photoelectron spectroscopy and density functional theory calculations to study the adsorption of CO2 on the In2O3(111) crystalline surface with different terminations, namely, the stoichiometric, reduced, and hydroxylated surface. The combined approach confirms that the reduction of the surface results in the formation of In adatoms and that water dissociates on the surface at room temperature. A comparison of the experimental spectra and the computed core-level shifts (using methanol and formic acid as benchmark molecules) suggests that CO2 adsorbs as a carbonate on all three surface terminations. We find that the adsorption of CO2 is hindered by hydroxyl groups on the hydroxylated surface.

A Multitechnique Study of C2H4 Adsorption on Fe3O4(001).

The adsorption/desorption of ethene (C2H4), also commonly known as ethylene, on Fe3O4(001) was studied under ultrahigh vacuum conditions using temperature-programmed desorption (TPD), scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT)-based computations. To interpret the TPD data, we have employed a new analysis method based on equilibrium thermodynamics. C2H4 adsorbs intact at all coverages and interacts most strongly with surface defects such as antiphase domain boundaries and Fe adatoms. On the regular surface, C2H4 binds atop surface Fe sites up to a coverage of 2 molecules per (√2 × âˆš2)R45° unit cell, with every second Fe occupied. A desorption energy of 0.36 eV is determined by analysis of the TPD spectra at this coverage, which is approximately 0.1-0.2 eV lower than the value calculated by DFT + U with van der Waals corrections. Additional molecules are accommodated in between the Fe rows. These are stabilized by attractive interactions with the molecules adsorbed at Fe sites. The total capacity of the surface for C2H4 adsorption is found to be close to 4 molecules per (√2 × âˆš2)R45° unit cell.

Correction to "Why and How Savitzky-Golay Filters Should Be Replaced".

[This corrects the article DOI: 10.1021/acsmeasuresciau.1c00054.].

Oxygen-Terminated (1 × 1) Reconstruction of Reduced Magnetite Fe3O4(111).

The (111) facet of magnetite (Fe3O4) has been studied extensively by experimental and theoretical methods, but controversy remains regarding the structure of its low-energy surface terminations. Using density functional theory (DFT) computations, we demonstrate three reconstructions that are more favorable than the accepted Feoct2 termination under reducing conditions. All three structures change the coordination of iron in the kagome Feoct1 layer to be tetrahedral. With atomically resolved microscopy techniques, we show that the termination that coexists with the Fetet1 termination consists of tetrahedral iron capped by 3-fold coordinated oxygen atoms. This structure explains the inert nature of the reduced patches.

Resolving the intrinsic short-range ordering of K+ ions on cleaved muscovite mica.

Muscovite mica, KAl2(Si3Al)O10(OH)2, is a common layered phyllosilicate with perfect cleavage planes. The atomically flat surfaces obtained through cleaving lend themselves to scanning probe techniques with atomic resolution and are ideal to model minerals and clays. Despite the importance of the cleaved mica surfaces, several questions remain unresolved. It is established that K+ ions decorate the cleaved surface, but their intrinsic ordering - unaffected by the interaction with the environment - is not known. This work presents clear images of the K+ distribution of cleaved mica obtained with low-temperature non-contact atomic force microscopy (AFM) under ultra-high vacuum (UHV) conditions. The data unveil the presence of short-range ordering, contrasting previous assumptions of random or fully ordered distributions. Density functional theory (DFT) calculations and Monte Carlo simulations show that the substitutional subsurface Al3+ ions have an important role for the surface K+ ion arrangement.

Analysis of Temperature-Programmed Desorption via Equilibrium Thermodynamics.

Temperature-programmed desorption (TPD) experiments in surface science are usually analyzed using the Polanyi-Wigner equation and/or transition-state theory. These methods are far from straightforward, and the determination of the pre-exponential factor is often problematic. We present a different method based on equilibrium thermodynamics, which builds on an approach previously used for TPD by Kreuzer et al. (Surf. Sci. 1988). Equations for the desorption rate are presented for three different types of surface-adsorbate interactions: (i) a 2D ideal hard-sphere gas with a negligible diffusion barrier, (ii) an ideal lattice gas, that is, fixed adsorption sites without interaction between the adsorbates, and (iii) a lattice gas with a distribution of (site-dependent) adsorption energies. We show that the coverage dependence of the sticking coefficient for adsorption at the desorption temperature determines whether the desorption process can be described by first- or second-order kinetics. The sticking coefficient at the desorption temperature must also be known for a quantitative determination of the adsorption energy, but it has a rather weak influence (like the pre-exponential factor in a traditional TPD analysis). Quantitative analysis is also influenced by the vibrational contributions to the energy and entropy. For the case of a single adsorption energy, we provide equations to directly convert peak temperatures into adsorption energies. These equations also provide an approximation of the desorption energy in cases that cannot be described by a fixed pre-exponential factor. For the case of a distribution of adsorption energies, the desorption spectra cannot be considered a superposition of desorption spectra corresponding to the different energies. Nevertheless, we present a method to extract the distribution of adsorption energies from TPD spectra, and we rationalize the energy resolution of TPD experiments. The analytical results are complemented by a program for simulation and analysis of TPD data.

Water Structures Reveal Local Hydrophobicity on the In2O3(111) Surface.

Clean oxide surfaces are generally hydrophilic. Water molecules anchor at undercoordinated surface metal atoms that act as Lewis acid sites, and they are stabilized by H bonds to undercoordinated surface oxygens. The large unit cell of In2O3(111) provides surface atoms in various configurations, which leads to chemical heterogeneity and a local deviation from this general rule. Experiments (TPD, XPS, nc-AFM) agree quantitatively with DFT calculations and show a series of distinct phases. The first three water molecules dissociate at one specific area of the unit cell and desorb above room temperature. The next three adsorb as molecules in the adjacent region. Three more water molecules rearrange this structure and an additional nine pile up above the OH groups. Despite offering undercoordinated In and O sites, the rest of the unit cell is unfavorable for adsorption and remains water-free. The first water layer thus shows ordering into nanoscopic 3D water clusters separated by hydrophobic pockets.

Surface chemistry on a polarizable surface: Coupling of CO with KTaO3(001).

Polarizable materials attract attention in catalysis because they have a free parameter for tuning chemical reactivity. Their surfaces entangle the dielectric polarization with surface polarity, excess charge, and orbital hybridization. How this affects individual adsorbed molecules is shown for the incipient ferroelectric perovskite KTaO3. This intrinsically polar material cleaves along (001) into KO- and TaO2-terminated surface domains. At TaO2 terraces, the polarity-compensating excess electrons form a two-dimensional electron gas and can also localize by coupling to ferroelectric distortions. TaO2 terraces host two distinct types of CO molecules, adsorbed at equivalent lattice sites but charged differently as seen in atomic force microscopy/scanning tunneling microscopy. Temperature-programmed desorption shows substantially stronger binding of the charged CO; in density functional theory calculations, the excess charge favors a bipolaronic configuration coupled to the CO. These results pinpoint how adsorption states couple to ferroelectric polarization.

Competing electronic states emerging on polar surfaces.

Excess charge on polar surfaces of ionic compounds is commonly described by the two-dimensional electron gas (2DEG) model, a homogeneous distribution of charge, spatially-confined in a few atomic layers. Here, by combining scanning probe microscopy with density functional theory calculations, we show that excess charge on the polar TaO2 termination of KTaO3(001) forms more complex electronic states with different degrees of spatial and electronic localization: charge density waves (CDW) coexist with strongly-localized electron polarons and bipolarons. These surface electronic reconstructions, originating from the combined action of electron-lattice interaction and electronic correlation, are energetically more favorable than the 2DEG solution. They exhibit distinct spectroscopy signals and impact on the surface properties, as manifested by a local suppression of ferroelectric distortions.

Why and How Savitzky-Golay Filters Should Be Replaced.

Savitzky-Golay (SG) filtering, based on local least-squares fitting of the data by polynomials, is a popular method for smoothing data and calculations of derivatives of noisy data. At frequencies above the cutoff, SG filters have poor noise suppression; this unnecessarily reduces the signal-to-noise ratio, especially when calculating derivatives of the data. In addition, SG filtering near the boundaries of the data range is prone to artifacts, which are especially strong when using SG filters for calculating derivatives of the data. We show how these disadvantages can be avoided while keeping the advantageous properties of SG filters. We present two classes of finite impulse response (FIR) filters with substantially improved frequency response: (i) SG filters with fitting weights in the shape of a window function and (ii) convolution kernels based on the sinc function with a Gaussian-like window function and additional corrections for improving the frequency response in the passband (modified sinc kernel). Compared with standard SG filters, the only price to pay for the improvement is a moderate increase in the kernel size. Smoothing at the boundaries of the data can be improved with a non-FIR method, the Whittaker-Henderson smoother, or by linear extrapolation of the data, followed by convolution with a modified sinc kernel, and we show that the latter is preferable in most cases. We provide computer programs and equations for the smoothing parameters of these smoothers when used as plug-in replacements for SG filters and describe how to choose smoothing parameters to preserve peak heights in spectra.