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The influence of microgeometries on the Secondary Electron Yield (SEY) of surfaces is investigated. Laser written structures of different aspect ratio (height to width) on a copper surface tuned the SEY of the surface and reduced its value to less than unity. The aspect ratio of microstructures was methodically controlled by varying the laser parameters. The results obtained corroborate a recent theoretical model of SEY reduction as a function of the aspect ratio of microstructures. Nanostructures - which are formed inside the microstructures during the interaction with the laser beam - provided further reduction in SEY comparable to that obtained in the simulation of structures which were coated with an absorptive layer suppressing secondary electron emission.

Electron cooling is a fundamental process to guarantee the beam quality in low energy antimatter facilities. In extra low energy antiproton, the electron cooler reduces the emittance blowup of the antiproton beam and thus delivers a focused and bright beam to the experiments at the unprecedentedly low kinetic energy of 100 keV. In order to achieve a cold beam at this low energy, the electron gun of the cooler must emit a monoenergetic and relatively intense electron beam. An optimization of the extra low energy antiproton electron cooler gun involving a cold cathode is studied, with the aim of investigating the feasibility of using carbon nanotubes (CNTs) as cold electron field emitters. CNTs are considered among the most promising field emitting material. However, stability data for emission operation over hundreds of hours, as well as lifetime and conditioning process studies to ensure optimal performance, are still incomplete or missing, especially if the purpose is to use them in operation in a machine such as extra low energy antiproton. This manuscript reports experiments that characterize these properties and ascertain whether CNTs are reliable enough to be used as cold electron field emitters for many hundreds of hours.

Cost-effective thick film manufacturing offers a wide material portfolio for sensor solutions. Low Temperature Cofired Ceramic (LTCC) technology as thick film based multilayer manufacturing process enables the design of complex fluid reactors used in versatile application scenarios. The technology meets the requirements for the design of 3-dimensional electrode arrays, which are essential for impedance monitoring in 3D cell cultures. Since the miniaturization of gold electrodes is limited, electrode functionalization is necessary for achieving high spatial resolution in sensor arrays. Coating of thick film gold electrodes with electropolymerized poly-3,4-ethylenedioxythiophene can significantly decrease the impedance. This work optimizes the coating process applying design of experiments. Electrode topography, chemical composition and electrochemical properties of coated and uncoated electrodes are compared and scaling effects are discussed based on fit parameters obtained from impedance spectroscopy. In addition to a reduction of impedance by two orders of magnitude, poly-3,4-ethylenedioxythiophene coating induces a reduction of size effects and a significant decrease of the variation. The scaling-down capability of electrodes achieves herewith dimensions of several tens of μm. The results evince an approach for sensor array integration with high spatial resolution providing increased measurement certainty for impedance monitoring in ceramic fluid systems and 3-dimensional bioreactors.

Preparation of rectifying Schottky contacts on n-type oxide semiconductors, such as indium oxide (In2O3), is often challenged by the presence of a distinct surface electron accumulation layer. We investigated the material properties and electrical transport characteristics of platinum contact/indium oxide heterojunctions to define routines for the preparation of high-performance Schottky diodes on n-type oxide semiconductors. Combining the evaluation of different Pt deposition methods, such as electron-beam evaporation and (reactive) sputtering in an (O and) Ar atmosphere, with oxygen plasma interface treatments, we identify key parameters to obtain Schottky-type contacts with high electronic barrier height and high rectification ratio. Different photoelectron spectroscopy approaches are compared to characterize the chemical properties of the contact layers and the interface region toward In2O3, to analyze charge transfer and plasma oxidation processes as well as to evaluate the precision and limits of different methodologies to determine heterointerface energy barriers. An oxygen-plasma-induced passivation of the semiconductor surface, which induces electron depletion and generates an intrinsic interface energy barrier, is found to be not sufficient to generate rectifying platinum contacts. The dissolution of the functional interface oxide layer within the Pt film results in an energy barrier of ∼0.5 eV, which is too low for an In2O3 electron concentration of ∼1018 cm-3. A reactive sputter process in an Ar and O atmosphere is required to fabricate rectifying contacts that are composed of platinum oxide (PtOx). Combining oxygen plasma interface oxidation of the semiconductor surface with reactive sputtering of PtOx layers results in the generation of a high Schottky barrier of ∼0.9 eV and a rectification ratio of up to 106. An additional oxygen plasma treatment after contact deposition further reduced the reverse leakage current, likely by eliminating a surface conduction path between the coplanar Ohmic and Schottky contacts. We conclude that processes that allow us to increase the oxygen content in the interface and contact region are essential for fabrication of device-quality-rectifying contacts on various oxide semiconductors.

Electrochemical quartz crystal microbalance (EQCM) with damping monitoring is applied for real-time analysis of solid-electrolyte interphase (SEI) formation in diphenyl octyl phosphate (DPOP) and vinylene carbonate (VC) modified electrolytes. Fast SEI formation is observed for the DPOP containing electrolyte, whereas slow growth is detected in VC-modified and reference electrolytes. QCM measurements in a dry state show considerable reduction of the mass quantity for DPOP and reference samples and minor mass decrease for the SEI layer formed in the presence of VC. The results indicate that VC enhances SEI stability, whereas the addition of DPOP or no additive results in incorporation of loosely attached species, leadubg to SEI instability. Resonance frequency damping, Δw, and dissipation factor, D, are used for analyzing mechanical properties of the SEI layers. The apparent increase of Δw and D during SEI formation in presence of DPOP suggests a pronounced viscoelasticity of the layer. QCM results are compared with surface morphology and chemical composition, revealing excellent agreement of the applied characterization approaches.

Energy-resolved secondary electron spectroscopy has been performed on air-exposed standard Cu samples and modified Cu surfaces that are tested and possibly applied to efficiently suppress electron cloud formation in the high-luminosity upgrade of the Large Hadron Collider at CERN. The Cu samples comprise pristine oxygen-free, carbon-coated and laser-structured surfaces, which were characterized prior to and after electron irradiation and rare-gas ion bombardment. Secondary-electron and reflected-electron yields measured with low charge dose of the samples exhibit a universal dependence on the energy of the primary impinging electrons. State-of-the-art models can successfully be used to describe the spectroscopic data. The supplied spectral dependence of electron emission and integrated electron yield as well as the derived parametrization can serve as a basis for forthcoming simulations of electron cloud formation and multipacting.

${\mathrm{In}}_{2}{\mathrm{O}}_{3}$ is an $n$-type transparent semiconducting oxide possessing a surface electron accumulation layer (SEAL) like several other relevant semiconductors, such as InAs, InN, ${\mathrm{SnO}}_{2}$, and ZnO. Even though the SEAL is within the core of the application of ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$ in conductometric gas sensors, a consistent set of transport properties of this two-dimensional electron gas (2DEG) is missing in the present literature. To this end, we investigate high-quality single-crystalline as well as textured doped and undoped ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$(111) films grown by plasma-assisted molecular beam epitaxy to extract transport properties of the SEAL by means of Hall effect measurements at room temperature while controlling the oxygen adsorbate coverage via illumination. The resulting sheet electron concentration and mobility of the SEAL are $\ensuremath{\approx}1.5\ifmmode\times\else\texttimes\fi{}{10}^{13}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$ and $\ensuremath{\approx}150\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{2}/\mathrm{Vs}$, respectively, both of which are strongly reduced by oxygen-related surface adsorbates from the ambient air. Our transport measurements further demonstrate a systematic reduction of the SEAL by doping ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$ with the deep compensating bulk acceptors Ni or Mg. This finding is supported by x-ray photoelectron spectroscopy (XPS) measurements of the surface band bending and SEAL electron emission. Quantitative analyses of these XPS results using self-consistent, coupled Schr\"odinger-Poisson calculations indicate the simultaneous formation of compensating bulk donor defects (likely oxygen vacancies), which almost completely compensate the bulk acceptors. Finally, an enhancement of the thermopower by reduced dimensionality is demonstrated in ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$: Seebeck coefficient measurements of the surface 2DEG with partially reduced sheet electron concentrations between $3\ifmmode\times\else\texttimes\fi{}{10}^{12}$ and $7\ifmmode\times\else\texttimes\fi{}{10}^{12}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}2}$ (corresponding average volume electron concentration between $1\ifmmode\times\else\texttimes\fi{}{10}^{19}$ and $2.3\ifmmode\times\else\texttimes\fi{}{10}^{19}\phantom{\rule{4pt}{0ex}}{\mathrm{cm}}^{\ensuremath{-}3}$) indicate a value enhanced by $\ensuremath{\approx}80%$ compared to that of bulk Sn-doped ${\mathrm{In}}_{2}{\mathrm{O}}_{3}$ with comparable volume electron concentration.

The interaction of n-type GaN(0001) surfaces with potassium and water is investigated using photoelectron spectroscopy, with special focus on adsorbate–substrate charge-transfer processes and water dissociation. Potassium atoms adsorb at the surface, forming a distinct surface dipole layer. For very low K coverage, the attached ionized K adsorbates result in a drop of the work function and the released electrons induce a reduction of the initial upward band bending. After stabilization of both quantities in the sub-monolayer regime, a reverse effect is observed for higher K coverage up to one monolayer (ML), exceeding the upward band bending of the clean surface. If the K-covered surface is exposed to water, hydroxyl groups are formed, whereas during long K and H2O coadsorption, a potassium hydroxide film grows. In both cases, a further reduction of the work function and an abrupt change in the surface depletion layer is recorded. For the coadsorption, initially an electron accumulation layer forms at the...

This paper describes the deposition of superconductive Nb-N thin films in a metal-organic plasma-enhanced atomic layer deposition process using (tert-butylimido)-tris (diethylamino)-niobium and hydrogen plasma as precursors. In extension of our previous work, which investigated the possibility to deposit superconducting Nb-N, we systematically investigated the influence of different plasma parameters on superconducting and morphological properties of the niobium nitride thin film formed during the process. An initial increase of the duration of the plasma dose led to higher transitions temperatures and critical current densities, the optimum being a plasma dose time of 50 s. By decreasing plasma pressure, the resistivity at room temperature decreased, while the transition temperature increased. In addition, Nb-N thin films were deposited onto several substrates such as silicon, thermally grown silica, magnesium oxide (MgO), and r-plane sapphire. ${\rm{T}}_{{\rm{C}}}$ values from 6.2 K up to 14 K were achieved independently of the substrate materials. However, films deposited on MgO showed lower ${\rm{T}}_{{\rm{C}}}$ values. X-ray photoelectron spectroscopy measurement revealed the presence of niobium nitride but also of niobium oxide and oxy-nitride components in the films as well as the existence of a high amount of incorporated carbon impurities. X-ray diffraction measurements revealed two significant reflexes, which could be attributed to niobium nitride only. No crystalline niobium oxide or niobium oxynitride was detected. Thus, the films consisted of a matrix of polycrystalline Nb-N and amorphous or microcrystalline grains of different niobium oxide and oxynitride phases. Due to the fact that the deposited material showed superconductivity especially for ultrathin layers with thicknesses in the nanometer range, these films may be suitable for superconducting nanowire single photon detectors.

Gallium oxide nanowires were grown on different substrates using a corona plasma assisted vapor phase epitaxy process and gold catalyst. It is shown that the silicon carbide pseudo substrate in combination with the plasma excitation of the gas phase supports the growth of the gallium oxide nanowires. Analyzing the orientation of the nanowires with respect to the growth surface, it is concluded that the nanowires growth proceed along the fast growth direction of gallium oxide.

The vacuum/liquid interface of ionic liquid/metal salt binary mixtures was investigated under ultra-high vacuum conditions using photoelectron spectroscopy. In this study we compare two ionic liquids 1- B utyl-1- m ethyl- p yrrolidinium-bis( t ri f luoromethylsulfonyl)-imide, [BMP][Tf 2 N] and 1- P ropyl-3- m ethyl- im idazolium- bis( t ri f luoromethyl-sulfonyl)-imide [PMIm][Tf 2 N] – in combination with two fluoride salts – TaF 5 and NbF 5 – at different concentrations. The results show a clearly different behavior for samples, which were in contact with ambient conditions and those being kept in inert conditions. Under inert atmosphere, the experimental results suggest rather equal anion and cation concentration of the IL constituents in the near surface region. At ambient conditions and high MF 5 (M = Ta, Nb) concentration, a strong deviation from the expected stoichiometry in the near surface region was observed, obviously caused by chemical reactions of the IL/salt system with the atmospheric environment. It is expected, that these reactions have also impact on the quality of electrodeposited metal films from these solutions.

The surface resistance of copper samples with an amorphous carbon (a-C) coating or with laser surface structuring, the surface treatments of choice for electron cloud suppression in critical cryogenic sectors of the high-luminosity upgrade of the Large Hadron Collider (HL-LHC), has been measured for the first time at a cryogenic temperature using the quadrupole resonator at CERN. Three different frequencies of relevance for evaluating beam impedance effects, namely, 400, 800, and 1200 MHz, have been investigated. No significant increase in surface resistance is observed for the a-C coating, compared to plain copper. In the case of laser structuring, the surface resistance depends on the direction of the surface currents relative to the laser-engraved groove pattern. The increase is minimal for parallel patterns, but in the perpendicular case the surface resistance increases considerably. Radio frequency (rf) heating from wake losses would then also increase in the HL-LHC case; however, the reduction in the power deposited onto the cold surfaces thanks to electron cloud suppression would still outweigh this effect.

Amorphous carbon thin films were prepared by direct current hollow cathode sputter deposition in Ar discharge with the injection of small amounts of H2 and/or N2. The influence of these additives on the film properties with particular focus on the application as a coating for electron cloud mitigation in particle accelerators is characterized by optical spectroscopy, X-ray photoelectron spectroscopy, and secondary electron yield (SEY) measurements. The SEY maximum increased from initially 0.98 with pure Ar in the gas discharge up to 1.38 at 0.5% H2 while the addition of 1% of pure N2 enabled to reduce it to 0.88. The simultaneous addition of N2 to the H2 containing discharge allowed an average SEY maximum reduction of 20%. The optical bandgap revealed a correlation between the increase/decrease of the bandgap and the SEY increment/reduction for H2/N2 addition. The surface composition changes and the resulting modification of the sp2/sp3 ratio correlate with the changes in SEY and optical properties. The obtained results highlight the potential of intentionally injected N2 to counteract the detrimental effect of the inevitable H2 partial pressure in the coating systems during the production of amorphous carbon thin films for anti-multipacting applications in particle accelerators.

Controlling the surface formation of the group-V face of (1 1 1)-oriented III-V semiconductors is crucial for subsequent successful growth of III-V nanowires for electronic and optoelectronic applications. With a view to preparing GaP/Si(1 1 1) virtual substrates, we investigate the atomic structure of the MOVPE (metalorganic vapor phase epitaxy)-prepared GaP(1 1 1)B surface (phosphorus face). We find that upon high-temperature annealing in the H2-based MOVPE process ambience, the surface is phosphorus-depleted, as evidenced by X-ray photoemission spectroscopy (XPS). However, a combination of density functional theory calculations and scanning tunneling microscopy (STM) suggests the formation of a partially H-terminated phosphorus surface, where the STM contrast is due to electrons tunneling from non-terminated dangling bonds of the phosphorus face. Atomic force microscopy (AFM) reveals that a high proportion of the surface is covered by islands, which are confirmed as Ga-rich by Auger electron spectroscopy (AES). We conclude that the STM images of the samples after high-temperature annealing only reflect the flat regions of the partially H-terminated phosphorus face, whereas an increasing coverage with Ga-rich islands, as detected by AFM and AES, forms upon annealing and underlies the higher proportion of Ga in the XPS measurements.

Single crystalline and textured In2O3 thin films with (1 1 1) surface orientation, grown by plasma-assisted molecular beam epitaxy, were used as a model system to study the role of bulk and surface electron accumulation layer conductance for ozone sensing. Both conductance contributions, which add to the total film conductance, were systematically varied. The resulting ozone sensitivity was determined by total conductance measurements in synthetic air with defined ozone concentration using UV irradiation instead of heating to regenerate the In2O3 surface. Depletion of the surface electron accumulation by an oxygen plasma treatment, confirmed by X-ray photoelectron spectroscopy, rendered the films ozone insensitive. The ozone response of films with an accumulation layer was increased by thickness reduction or by designing the bulk of the film semi-insulating using deep acceptor doping by Mg. Our results of using electron accumulation layers for gas sensing and bulk doping by deep acceptors to increase sensitivity can be generalized to other gas sensing materials. The use of single crystalline films allows selecting the most sensitive crystallographic surface orientation and may have further advantages over polycrystalline films, such as increased stability and sensing speed.

authoren The interaction of defect-rich nanocrystalline indium oxide films, which have previously shown to exhibit excellent ozone sensing properties, with O3, O2, and H2O molecules is investigated using ultra-violet and X-ray photoelectron spectroscopy. The investigated samples are grown by metalorganic chemical vapor deposition at low temperatures resulting in high oxygen deficiency and high defect density. The ozone-induced surface oxidation and UV-induced photoreduction mechanisms of the ozone sensor active material are evaluated with respect to surface stoichiometry and electronic properties including adsorbate features, band bending and surface dipole formation. A strong interaction with ozone and water is found, whereas the interaction with O2 is relatively weak. In all cases the interaction results in the same negatively charged oxygen adsorbate species, which can either be removed by UV light or by annealing resulting in the capability of these films to be used in reversible adsorption induced oxidation and UV/thermal reduction cycles.

We report the design of a low-temperature liquid metal battery (LMB). Li and Ga as the negative and positive electrode, respectively, are used in combination with a room temperature ionic liquid as an electrolyte. 1 mol/L lithium bis(trifluoromethylsulfonyl)imide (Li[TFSI]) in 1-butyl-1-methylpyrrolidinium bis (trifluoromethylsulfonyl)imide ([BMP][TFSI]) is chosen as electrolyte. The battery operates at 220 °C which is a relatively low temperature for a LMB and shows good electrochemical performance at low current density. The cells were cycled for more than 600 h and achieved a round-trip Coulombic efficiency close to 100% and an average voltage efficiency of 66% resulting in an overall energy efficiency of 65%. At higher current densities, however, the system showed up to 75% irreversible capacity loss after three cycles. To understand the origin of this strong deterioration, we characterized the surface and the bulk properties of the Ga cathode using X-ray Photoelectron Spectroscopy. Especially at higher current densities a decomposition of the electrolyte was found. The chemical changes that occurred and the elemental distribution at the Ga cathode are analyzed based on XPS measurements at different stages of the battery charge/discharge cycling.

The adsorption of hydrogen at nonpolar $\mathrm{GaN}(1\overline{1}00)$ surfaces and its impact on the electronic and vibrational properties is investigated using surface electron spectroscopy in combination with density functional theory (DFT) calculations. For the surface mediated dissociation of ${\mathrm{H}}_{2}$ and the subsequent adsorption of H, an energy barrier of 0.55 eV has to be overcome. The calculated kinetic surface phase diagram indicates that the reaction is kinetically hindered at low pressures and low temperatures. At higher temperatures ab initio thermodynamics show, that the H-free surface is energetically favored. To validate these theoretical predictions experiments at room temperature and under ultrahigh vacuum conditions were performed. They reveal that molecular hydrogen does not dissociatively adsorb at the $\mathrm{GaN}(1\overline{1}00)$ surface. Only activated atomic hydrogen atoms attach to the surface. At temperatures above 820 K, the attached hydrogen gets desorbed. The adsorbed hydrogen atoms saturate the dangling bonds of the gallium and nitrogen surface atoms and result in an inversion of the Ga--N surface dimer buckling. The signatures of the Ga--H and N--H vibrational modes on the H-covered surface have experimentally been identified and are in good agreement with the DFT calculations of the surface phonon modes. Both theory and experiment show that H adsorption results in a removal of occupied and unoccupied intragap electron states of the clean $\mathrm{GaN}(1\overline{1}00)$ surface and a reduction of the surface upward band bending by 0.4 eV. The latter mechanism largely reduces surface electron depletion.

We report the room-temperature anisotropic dielectric functions (DFs), refractive indices, and absorption coefficients as well as birefringence and dichroism of wurtzite GaN in the spectral range between 0.6 eV and 6 eV. They have been determined by combined spectroscopic ellipsometry, optical retardation, and transmission measurements on a series of m- and c-plane bulk substrates prepared from crystals grown by hydride vapor phase epitaxy. The accuracy of the derived DFs is estimated by investigation of the role of mosaicity-related crystal imperfections, self-consistency test based on a Kramers-Kronig analysis, and examination of the influence of kind of overlayer. We also briefly discuss optical properties of a highly defective near-surface layer of GaN crystals introduced by their mechanical polishing.

The influence of oxygen plasma treatments on the surface chemistry and electronic properties of unintentionally doped and Mg-doped In2O3(111) films grown by plasma-assisted molecular beam epitaxy or metal-organic chemical vapor deposition is studied by photoelectron spectroscopy. We evaluate the impact of semiconductor processing technology relevant treatments by an inductively coupled oxygen plasma on the electronic surface properties. In order to determine the underlying reaction processes and chemical changes during film surface–oxygen plasma interaction and to identify reasons for the induced electron depletion, in situ characterization was performed implementing a dielectric barrier discharge oxygen plasma as well as vacuum annealing. The strong depletion of the initial surface electron accumulation layer is identified to be caused by adsorption of reactive oxygen species, which induce an electron transfer from the semiconductor to localized adsorbate states. The chemical modification is found to be ...

The intermediate layer (IL) between glass substrate and silicon plays a significant role in the optimization of multicrystalline liquid phase crystallized silicon thin film solar cells on glass. This study deals with the influence of the IL on the surface condition and the required chemical surface treatment of the crystallized silicon (mc-Si), which is of particular interest for a-Si:H heterojunction thin film solar cells. Two types of IL were investigated: sputtered silicon nitride (SiN) and a layer stack consisting of silicon nitride and silicon oxide (SiN/SiO). X-ray photoelectron spectroscopy measurements revealed the formation of silicon oxynitride (SiOxNy) or silicon oxide (SiO2) layers at the surface of the mc-Si after liquid phase crystallization on SiN or SiN/SiO, respectively. We propose that SiOxNy formation is governed by dissolving nitrogen from the SiN layer in the silicon melt, which segregates at the crystallization front during crystallization. This process is successfully hindered, when additional SiO layers are introduced into the IL. In order to achieve solar cell open circuit voltages above 500 mV, a removal of the formed SiOxNy top layer is required using sophisticated cleaning of the crystallized silicon prior to a-Si:H deposition. However, solar cells crystallized on SiN/SiO yield high open circuit voltage even when a simple wet chemical surface treatment is applied. The implementation of SiN/SiO intermediate layers facilitates the production of mesa type solar cells with open circuit voltages above 600 mV and a power conversion efficiency of 10%.