HIPPIE is a soft X-ray beamline on the 3 GeV electron storage ring of the MAX IV Laboratory, equipped with a novel ambient-pressure X-ray photoelectron spectroscopy (APXPS) instrument. The endstation is dedicated to performing in situ and operando X-ray photoelectron spectroscopy experiments in the presence of a controlled gaseous atmosphere at pressures up to 30 mbar [1 mbar = 100 Pa] as well as under ultra-high-vacuum conditions. The photon energy range is 250 to 2200 eV in planar polarization and with photon fluxes >1012 photons s−1 (500 mA ring current) at a resolving power of greater than 10000 and up to a maximum of 32000. The endstation currently provides two sample environments: a catalysis cell and an electrochemical/liquid cell. The former allows APXPS measurements of solid samples in the presence of a gaseous atmosphere (with a mixture of up to eight gases and a vapour of a liquid) and simultaneous analysis of the inlet/outlet gas composition by online mass spectrometry. The latter is a more versatile setup primarily designed for APXPS at the solid–liquid (dip-and-pull setup) or liquid–gas (liquid microjet) interfaces under full electrochemical control, and it can also be used as an open port for ad hoc-designed non-standard APXPS experiments with different sample environments. The catalysis cell can be further equipped with an IR reflection–absorption spectrometer, allowing for simultaneous APXPS and IR spectroscopy of the samples. The endstation is set up to easily accommodate further sample environments.

Heterogeneous catalyst surfaces are dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts’ action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the timescales of the dynamic changes. Here we use the CO oxidation reaction and a Pd(100) model catalyst to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy. Central elements of the method are cyclic gas pulsing and software-based event-averaging by image recognition of spectral features. A key finding is that at 3.2 mbar total pressure a metallic, predominantly CO-covered metallic surface turns highly active for a few seconds once the O2:CO ratio becomes high enough to lift the CO poisoning effect before mass transport limitations triggers formation of a √5 oxide.

III−V semiconductors, such as InAs, with an ultrathin high-κ oxide layer have attracted a lot of interests in recent years as potential next-generation metal−oxide− semiconductor field-effect transistors, with increased speed and reduced power consumption. The deposition of the high-κ oxides is nowadays based on atomic layer deposition (ALD), which guarantees atomic precision and control over the dimensions. However, the chemistry and the reaction mechanism involved are still partially unknown. This study reports a detailed time-resolved analysis of the ALD of high-κ hafnium oxide (HfO x ) on InAs(100). We use ambient pressure X-ray photoemission spectroscopy and monitor the surface chemistry during the first ALD half-cycle, i.e., during the deposition of the metalorganic precursor. The removal of In and As native oxides, the adsorption of the Hf-containing precursor molecule, and the formation of HfO x are investigated simultaneously and quantitatively. In particular, we find that the generally used ligand exchange model has to be extended to a two-step model to properly describe the first half-cycle in ALD, which is crucial for the whole process. The observed reactions lead to a complete removal of the native oxide and the formation of a full monolayer of HfO x already during the first ALD half-cycle, with an interface consisting of In−O bonds. We demonstrate that a sufficiently long duration of the first half-cycle is essential for obtaining a high-quality InAs/HfO 2 interface.

Heterogeneous catalyst surfaces are highly dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts’ action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the time scales of the dynamic changes. Here we use the CO oxidation reaction over a Pd(100) surface exposed to pressures of 3 and 100 mbar of a CO + O2 gas mixture to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy. Central elements of the method are cyclic gas pulsing and software-based event-averaging by image recognition of spectral features. For the CO oxidation reaction over Pd(100) our main finding is that that all surface phases – the CO-covered Pd surface, a surface oxide and a thick PdOx phase – catalyse the CO oxidation reaction, in dependence on the supply of gas phase reactants.

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