Stability of Iridium Single Atoms on Fe3O4(001) in the mbar Pressure Range.

Stable single metal adatoms on oxide surfaces are of great interest for future applications in the field of catalysis. We studied iridium single atoms (Ir1) supported on a Fe3O4(001) single crystal, a model system previously only studied in ultra-high vacuum, to explore their behavior upon exposure to several gases in the millibar range (up to 20 mbar) utilizing ambient-pressure X-ray photoelectron spectroscopy. The Ir1 single adatoms appear stable upon exposure to a variety of common gases at room temperature, including oxygen (O2), hydrogen (H2), nitrogen (N2), carbon monoxide (CO), argon (Ar), and water vapor. Changes in the Ir 4f binding energy suggest that Ir1 interacts not only with adsorbed and dissociated molecules but also with water/OH groups and adventitious carbon species deposited inevitably under these pressure conditions. At higher temperatures (473 K), iridium adatom encapsulation takes place in an oxidizing environment (a partial O2 pressure of 0.1 mbar). We attribute this phenomenon to magnetite growth caused by the enhanced diffusion of iron cations near the surface. These findings provide an initial understanding of the behavior of single atoms on metal oxides outside the UHV regime.

Dynamic Equilibrium at the HCOOH-Saturated TiO2(110)-Water Interface.

Carboxylic acids bind to titanium dioxide (TiO2) dissociatively, forming surface superstructures that give rise to a (2 × 1) pattern detected by low-energy electron diffraction. Exposing this system to water, however, leads to a loss of the highly ordered surface structure. The formate-covered surface was investigated by a combination of diffraction and spectroscopy techniques, together with static and dynamic ab initio simulations, with the conclusion that a dynamic equilibrium exists between adsorbed formic acid and water molecules. This equilibrium process is an important factor for obtaining a better understanding of controlling the self-cleaning properties of TiO2, because the formic acid monolayer is responsible for the amphiphilic character of the surface.

Amorphization mechanism of SrIrO3 electrocatalyst: How oxygen redox initiates ionic diffusion and structural reorganization.

The use of renewable electricity to prepare materials and fuels from abundant molecules offers a tantalizing opportunity to address concerns over energy and materials sustainability. The oxygen evolution reaction (OER) is integral to nearly all material and fuel electrosyntheses. However, very little is known about the structural evolution of the OER electrocatalyst, especially the amorphous layer that forms from the crystalline structure. Here, we investigate the interfacial transformation of the SrIrO3 OER electrocatalyst. The SrIrO3 amorphization is initiated by the lattice oxygen redox, a step that allows Sr2+ to diffuse and O2- to reorganize the SrIrO3 structure. This activation turns SrIrO3 into a highly disordered Ir octahedral network with Ir square-planar motif. The final Sr y IrO x exhibits a greater degree of disorder than IrO x made from other processing methods. Our results demonstrate that the structural reorganization facilitated by coupled ionic diffusions is essential to the disordered structure of the SrIrO3 electrocatalyst.

Surface chemistry of 2-propanol and O2 mixtures on SnO2(110) studied with ambient-pressure x-ray photoelectron spectroscopy.

Tin dioxide (SnO2) has various applications due to its unique surface and electronic properties. These properties are strongly influenced by Sn oxidation states and associated defect chemistries. Recently, the oxidation of volatile organic compounds (VOCs) into less harmful molecules has been demonstrated using SnO2 catalysts. A common VOC, 2-propanol (isopropyl alcohol, IPA), has been used as a model compound to better understand SnO2 reaction kinetics. We have used ambient-pressure x-ray photoelectron spectroscopy (AP-XPS) to characterize the surface chemistry of IPA and O2 mixtures on stoichiometric, unreconstructed SnO2(110)-(1 × 1) surfaces. AP-XPS experiments were performed for IPA pressures ≤3 mbar, various IPA/O2 ratios, and several reaction temperatures. These measurements allowed us to determine the chemical states of adsorbed species on SnO2(110)-(1 × 1) under numerous experimental conditions. We found that both the IPA/O2 ratio and sample temperature strongly influence reaction chemistries. AP-XPS valence-band spectra indicate that the surface was partially reduced from Sn4+ to Sn2+ during reactions with IPA. In situ mass spectrometry and gas-phase AP-XPS results indicate that the main reaction product was acetone under these conditions. For O2 and IPA mixtures, the reaction kinetics substantially increased and the surface remained solely Sn4+. We believe that O2 replenished surface oxygen vacancies and that SnO2 bridging and in-plane oxygen are likely the active oxygen species. Moreover, addition of O2 to the reaction results in a reduction in formation of acetone and an increase in formation of CO2 and H2O. Based on these studies, we have developed a reaction model that describes the catalytic oxidation of IPA on stoichiometric SnO2(110)-(1 × 1) surfaces.

Effect of Oxygen on Thermal and Radiation-Induced Chemistries in a Model Organotin Photoresist.

Organotin photoresists have shown promise for next-generation lithography because of their high extreme ultraviolet (EUV) absorption cross sections, their radiation sensitive chemistries, and their ability to enable high-resolution patterning. To better understand both temperature- and radiation-induced reaction mechanisms, we have studied a model EUV photoresist, which consists of a charge-neutral butyl-tin cluster. Temperature-programmed desorption (TPD) showed very little outgassing of the butyl-tin resist in ultrahigh vacuum and excellent thermal stability of the butyl groups. TPD results indicated that decomposition of the butyl-tin resist was first order with a fairly constant decomposition energy between 2.4 and 3.0 eV, which was determined by butyl group desorption. Electron-stimulated desorption (ESD) showed that butyl groups were the primary decomposition product for electron kinetic energies expected during EUV exposures. X-ray photoelectron spectroscopy was performed before and after low-energy electron exposure to evaluate the compositional and chemical changes in the butyl-tin resists after interaction with radiation. The effect of molecular oxygen during ESD experiments was evaluated, and it was found to enhance butyl group desorption during exposure and resulted in a significant increase in the ESD cross section by over 20%. These results provide mechanistic information that can be applied to organotin EUV photoresists, where a significant increase in photoresist sensitivity may be obtained by varying the ambient conditions during EUV exposures.

Ambient-Pressure X-ray Photoelectron Spectroscopy Characterization of Radiation-Induced Chemistries of Organotin Clusters.

Advances in extreme ultraviolet (EUV) photolithography require the development of next-generation resists that allow high-volume nanomanufacturing with a single nanometer patterning resolution. Organotin-based photoresists have demonstrated nanopatterning with high resolution, high sensitivity, and low-line edge roughness. However, very little is known regarding the detailed reaction mechanisms that lead to radiation-induced solubility transitions. In this study, we investigate the interaction of soft X-ray radiation with organotin clusters to better understand radiation-induced chemistries associated with EUV lithography. Butyltin Keggin clusters (ß-NaSn13) were used as a model organotin photoresist, and characterization was performed using ambient-pressure X-ray photoelectron spectroscopy. The changes in relative atomic concentrations and associated chemical states in ß-NaSn13 resists were evaluated after exposure to radiation for a range of ambient conditions and photon energies. A significant reduction in the C 1s signal versus exposure time was observed, which corresponds to the radiation-induced homolytic cleavage of the butyltin bond in the ß-NaSn13 clusters. To improve the resist sensitivity, we evaluated the effect of oxygen partial pressure during radiation exposures. We found that both photon energy and oxygen partial pressure had a strong influence on the butyl group desorption rate. These studies advance the understanding of radiation-induced processes in ß-NaSn13 photoresists and provide mechanistic insights for EUV photolithography.

Alkyltin Keggin Clusters Templated by Sodium.

Dodecameric (Sn12 ) and hexameric topologies dominate monoalkyltin-oxo cluster chemistry. Their condensation, triggered by radiation exposure, recently produced unprecedented patterning performance in EUV lithography. A new cluster topology was crystallized from industrial n-BuSnOOH, and additional characterization techniques indicate other clusters are present. Single-crystal X-ray analysis reveals a ß-Keggin cluster, which is known but less common than other Keggin isomers in polyoxometalate and polyoxocation chemistry. The structure is formulated [NaO4 (BuSn)12 (OH)3 (O)9 (OCH3 )12 (Sn(H2 O)2 )] (ß-NaSn13 ). SAXS, NMR, and ESI MS differentiate ß-NaSn13 , Sn12 , and other clusters present in crude "n-BuSnOOH" and highlight the role of Na as a template for alkyltin Keggin clusters. Unlike other alkyltin clusters that are cationic, ß-NaSn13 is neutral. Consequently, it stands as a unique model system, absent of counterions, to study the transformation of clusters to films and nanopatterns.