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The processes at the interface between ionic liquids (ILs) and metals are a key factor for understanding especially in electrochemical deposition, nanoscale tribology applications and batteries. In the present work, the interfaces of 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([Py1,4]TFSI) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]TFSI) and platinum and aluminum were investigated by depositing thin IL films and studying them with X-ray photoelectron spectroscopy (XPS) in ultrahigh vacuum. It is found that there is no evidence of a decomposition reaction of either IL on platinum; however, the imidazolium cation of [EMIm]TFSI shows a strong interaction with the surface in the monolayer regime. In contrast, [Py1,4]TFSI and [EMIm]TFSI show massive decomposition on the aluminum surface without applying any electrochemical potential. The spectra for the [TFSI]− anion components show cleavage of C-F or N-S bonds in both cases. Both cleavage of a single fluorine atom and complete cleavage were observed, leading to further decomposition reactions of the anion. Consequently, new components such as AlOOH, Al(OH)3, Al2S3, Al2(SO4)3 and AlF3 appear at the interface. In addition, there is also evidence of decomposition of the cation by the splitting off hydrogen atoms or parts of the alkyl chain in both ILs.

The application of ionic liquids in ultra-high vacuum opens new opportunities to investigate the electrochemical reactions and interfacial properties by in situ electrochemical X-ray photoelectron ...

Cyanoacrylates are an extremely reactive class of adhesives. Despite their commercial use as instant adhesives, the adhesion mechanism, especially to technically relevant oxidized metal surfaces, has not yet been sufficiently investigated. In the present work, ultra-thin ethyl cyanoacrylate films are deposited on copper oxide and aluminum oxide by spin coating and cured there. Various surface sensitive spectroscopy methods are used to identify possible interactions.

Plastics are artificial synthetic organic polymers that have been used in every area of daily life. However, because of their slow degradation rate, their use is contentious. The treatment of the surface of the sample is considered necessary as enzymatic or bacterial attach is not possible if the plastic surface environment is not ideal. The main topic of this work is the investigation of the effect of different advanced oxidation processes (AOP) on the near surface structure of polylactic acid (PLA) samples, which, in turn, can promote the adhesion of enzymes or bacteria for further biodegradation. The Advanced Oxidation Processes that have been used are Ultrasonication, UV photodegradation and Dielectric Barrier Discharge (DBD) plasma. After the treatments, the surfaces were characterized by Infrared Spectroscopy (IR), Drop Contact Angle (DCA), Confocal Laser Scanning Microscopy (CLSM) and X-ray Photoelectron Spectroscopy (XPS). Both ultrasonic and UV treatments have a significant impact on the surface properties of immersed PLA by removing the oxygen-containing groups of the polymer chain, albeit in different ways, while plasma tends to uncover oxygen groups on the surface. The influence of the pre-treatment on improving the adhesion of bacteria on the PLA surface has been proven using a pseudomonas knackmussii strain.

The tunicate species Ciona intestinalis is a fast-growing marine invertebrate animal that contains cellulose in its outer part—the tunic. The high crystallinity and microfibril aspect ratio of tunicate cellulose make it an excellent starting material for the isolation of nanocellulose. In the present work, tunic from C. intestinalis was subjected to organosolv pretreatment followed by bleaching and acid-hydrolysis steps for the isolation of nanocrystals. Applying an intermediate enzymatic treatment step with a lytic polysaccharide monooxygenase (LPMO) from the thermophilic fungus Thermothelomyces thermophila was proved to facilitate the isolation of nanocellulose and to improve the overall process yield, even when the bleaching step was omitted. LPMOs are able to oxidatively cleave the glycosidic bonds of a polysaccharide substrate, either at the C1 and/or C4 position, with the former leading to introduction of carboxylate moieties. X-ray photoelectron spectroscopy analysis showed a significant increase in the atomic percentage of the C═O/O–C–O and O–C═O bonds upon the addition of LPMO, while the obtained nanocrystals exhibited higher thermal stability compared to the untreated ones. Moreover, an enzymatic post-treatment with LPMOs was performed to additionally functionalize the cellulose nanocrystals. Our results demonstrate that LPMOs are promising candidates for the enzymatic modification of cellulose fibers, including the preparation of oxidized-nanocellulose, and offer great perspectives for the production of novel biobased nanomaterials.

Graphical abstract, Highlights • We present pre-treatment processes for the microplastics management. • AOPs are suitable for minimizing microplastics in the environment. • These processes make plastics digestion by bacteria and enzymes feasible. • Synergy of AOPs and biotechnology can boost the concept of Bioeconomy of polymers., New biotechnological processes using microorganisms and/or enzymes to convert carbonaceous resources, either biomass or depolymerized plastics into a broad range of different bioproducts are recognized for their high potential for reduced energy consumption and reduced GHG emissions. However, the hydrophobicity, high molecular weight, chemical and structural composition of most of them hinders their biodegradation. A solution to reduce the impact of non-biodegradable polymers spread in the environment would be to make them biodegradable. Different approaches are evaluated for enhancing their biodegradation. The aim of this work is to develop and optimize the ultrasonication (US) and UV photodegradation and their combination as well as dielectric barrier discharge (DBD) plasma as pre‐treatment technologies, which change surface properties and enhance the biodegradation of plastic by surface oxidation and thus helping bacteria to dock on them. Polylactic acid (PLA) has been chosen as a model polymer to investigate its surface degradation by US, UV, and DBD plasma using surface characterization methods like X-ray Photoelectron Spectroscopy (XPS) and Confocal Laser Microscopy (CLSM), Atomic Force Microscopy (AFM) as well as FT-IR and drop contour analysis. Both US and UV affect the surface properties substantially by eliminating the oxygen content of the polymer but in a different way, while plasma oxidizes the surface.

Copyright © 2021 The Author(s). Electrochemical energy storage with lignin-based composite electrodes offers a cheap and renewable source for batteries. Lignin composites have mainly been used in supercapacitors and little has been investigated related to applying these composites in batteries. Here we show a biodegradable hybrid Zn-ion battery with a polymer/lignin composite electrode as a cathode, a Zn anode and bio-ionic liquid electrolytes. Interestingly, the polymer/lignin composite cathode led to a higher discharge capacity compared to the charge capacity over the entire 100 charge/discharge cycling process. It was observed that the lignin concentration in the composite polymer electrode was crucial in obtaining such a phenomenon. Using SEM, electrochemical analysis and NMR, we showed that lignin electrocatalytically oxidizes during battery charging, which produced the extra energy. This results in obtaining a higher discharge capacity compared to the charge capacity. It is anticipated that such an electrocatalytic technique can be extended to other battery systems to harness clean electrochemical energy from biomass. BMBF project ZIB 03XP0204C

The adsorption behavior of thin films of 4-alkoxybenzoic acids (with either hydroxy-, methoxy-, propoxy-, pentoxy- and decoxy-chains) and terephthalic acid, evaporated on a Highly Oriented Pyrolytic Graphite (HOPG) surface was studied. The orientation of the molecules was characterized by Metastable Induced Electron Spectroscopy (MIES) and Ultraviolet Photoelectron Spectroscopy (UPS(HeI)). On HOPG the 4-alkoxybenzoic acids and the terephthalic acid show a layer like growth at the beginning. Since the MIE spectra for the molecules on HOPG show all molecular orbitals, especially the π orbitals of the phenyl ring, a flat laying orientation on the graphite surface is assumed. The only exception is observed for 4-decoxy-benzoic acid. After a coverage of approximately 1 monolayer (ML) the spectrum is dominated by the spectral features of the alkyl structures.

In this paper, we have investigated the performance and solid electrolyte interphase formation (SEI) of a hybrid polymer gel electrolyte based on poly(vinylidene fluoride)-co-hexafluoropropylene, 1...

A comparative study of the chemical reactions of three different ionic liquids prepared by physical vapor deposition on a Li/Cu surface was performed. In this investigation, the ionic liquids 1-butyl-1-methylpyrrolidinium bis[fluorosulfonyl]imide ([Py1,4]FSI), 1-butyl-1-methylpyrrolidinium bis[trifluoromethylsulfonyl]imide ([Py1,4]TFSI), and 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([OMIm]TFSI) were characterized by monochromatic X-ray photoelectron spectroscopy after adsorption on Li/Cu. All spectra prove the formation of LiF and Li2O, which verifies the partial decomposition of the anions. This is found to be much less intense for [Py1,4]TFSI than for [Py1,4]FSI, indicating a more rapid decomposition of the FSI anion in the presence of lithium. In addition, changes of the cation structure, as well as changes of the anion/cation ratio, were observed in the spectra. In summary, cations were most likely displaced from the Li/Cu surface and were partially decomposed, especially in case ...

In the plastic-processing industry, the formation of unknown deposits at the interface between polymer melt and steel surfaces can pose major challenges, which occurs especially on screws, barrels, and tools. These deposits will detach during production and lead to quality restrictions mostly as spots in the products. We investigated the interactions between tool steel and polymer melt, especially polycarbonate, in the early stages of deposit formation. Steel-polymer-composite samples are prepared close to the realistic conditions in the plastic-processing industry. To get further insight, thin polymer films on tool steel specimens and its alloy elements, representing model systems, are prepared. X-ray-photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) are used to characterize the interfaces chemically. Additionally, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used. We found iron and chromium diffusion into the polycarbonate melt induced by polymer metal interaction. Iron and polymer chains are immobilized at the interface by a chemical interaction, while chromium does not chemically interact with the polymer melt. Basing on these results, we propose a mechanism for deposit formation in plastic-processing machines and tools.

The adsorption behavior of thin films of terephthalic acid (TPA) evaporated on a gold surface as well as on an aluminum foil was studied. The orientation of the molecules was characterized by metastable induced electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS). To make sure that the evaporation of TPA is nondestructive, additional X-ray photoelectron spectroscopy (XPS) was performed. These measurements also exclude any radiation damage. TPA on the gold surface shows a well-ordered layer growth up to 7.5 nm. Since the MIES spectra show both the acid structure and the phenyl group, a flat-laying orientation is assumed. In contrast, the phenylic carbon structure could not be observed while evaporating TPA on the oxidized aluminum foil. The MIES/UPS spectra only show the COOH group. To exclude a random arrangement of the molecules we also performed low temperature measurements. It can be concluded from these measurements, in addition to the fact that the work function increases during the evaporation, that TPA has a perpendicular arrangement on the aluminum foil.

The deposition behavior of bisphenol A polycarbonate (BPA-PC) on a Au(111) single crystal has been studied. Thin films of PC were prepared by in situ evaporation of PC pellets under UHV conditions. The resulting PC/Au(111) interfaces were characterized by means of Ultraviolet Photoelectron Spectroscopy (UPS), X-ray Photoelectron Spectroscopy (XPS) and Scanning Tunneling Microscopy (STM). XPS and UPS revealed that no decomposition of the polymer takes place during evaporation. The C 1s and O 1s XPS core level analysis as well as the UPS spectra show distinct features which can be attributed to chemical bonding states of the PC molecule. Therefore, we conclude that the molecular structure within the monomeric unit remains intact after evaporation. Furthermore, STM measurements in the submonolayer regime revealed a self-assembly of small polymer chains of 2-4 monomeric units on the Au(111) surface.

The metastable induced electron spectroscopy (MIES), in combination with photoelectron spectroscopies, is a powerful tool to analyze the molecular arrangement at surfaces due to its high surface sensitivity. In this contribution MIES is applied to analyze structural changes at the surface of [EMIm]Tf2N and [OMIm]Tf2N films on two different substrates, Highly Ordered Pyrolytic Graphite (HOPG) and Au(111), as a function of the film thickness, starting from submonolayer coverage up to multilayers. The discussion is based on previous MIES studies of the vacuum–liquid interface of ionic liquids with imidazolium cations and on available DFT calculations. The presented data indicate that – in contrast to multilayers where the surface is dominated by the alkyl chains of the imidazolium cations – the structure of the first adlayer of [XMIm]Tf2N molecules on solid surfaces depends on the strength of their interaction with the surface resulting in alkyl chains aligned parallel or oblique to the substrate surface.

The highly ordered pyrolytic graphite (HOPG)/1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([OMIm]Tf2N) interface is examined by ultrahigh vacuum scanning tunneling microscopy (UHV-STM), atomic force microscopy (UHV-AFM) (and as a function of potential by in situ scanning tunneling microscopy (STM)), in situ atomic force microscopy (AFM), and density functional theory (DFT) calculations. In situ STM and AFM results reveal that multiple ionic liquid (IL) layers are present at the HOPG/electrode interface at all potentials. At open-circuit potential (OCP), attractions between the cation alkyl chain and the HOPG surface result in the ion layer bound to the surface being cation rich. As the potential is varied, the relative concentrations of cations and anions in the surface layer change: as the potential is made more positive, anions are preferentially adsorbed at the surface, while at negative potentials the surface layer is cation rich. At −2 V an unusual overstructure forms. STM images and...

In this paper an overview will be given about the generation of metal and semiconductor nanoparticles with plasma electrochemistry using the example of the plasma electrochemistry project in the DFG framework of SPP1191. After an introduction in nanoparticle synthesis and plasma electrochemistry in ionic liquids, we focus on our own results on the synthesis of silver, copper, germanium and silicon nanoparticles. We will present the results in chronological order to exemplify the assumptions, the difficulties and consequences. At the end we will give first indications for the particle forming process during plasma electrochemistry.

Metastable Induced Electron Spectroscopy, Ultraviolet Photoelectron Spectroscopy (He I), X-ray Photoelectron Spectroscopy, and Quadrupole Mass Spectrometry are employed to study the interaction of water with Ag nanoparticles on cinnamyl alcohol films. The films have been prepared on Au(111) substrates by thermal evaporation. The water adsorption does not result in any chemical interaction with the silver nanoparticles at all, but the cinnamyl alcohol changes its chemical structure significantly. While water molecules induce a reduction of the organic groups, the film thickness seems to decrease. Thus, a decomposition of the cinnamyl alcohol films is proposed. Since no effects are observed during water interaction with pure cinnamyl alcohol films at all, a catalytic reaction appears to take place. No decomposition is found for cinnamyl alcohol adsorbed on a closed silver film, indicating that Ag nanoparticles are required for this catalytical decomposition. The MIES and UPS spectra indicate the existence of a closed metallic film directly after silver adsorption on cinnamyl alcohol, while they suggest the presence of silver nanoparticles after the exposure to water. The formation of silver nanoparticles therefore seems to happen concurrently to the catalytic decomposition of cinnamyl alcohol.

In this article, we investigated the electrodeposition of SixGe1–x from 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide containing different molar concentrations of SiCl4 and GeCl4. Upon the deposition of SixGe1–x using a 1:1 molar ratio of SiCl4 and GeCl4, a color change of the deposit from red to green was observed during the cyclic voltammetric scan. On increasing the concentration of SiCl4, only a reddish deposit could be seen during cyclic voltammetry. When the concentration of GeCl4 was increased, only a black deposit was obtained. Constant potential electrodeposition showed the formation of SixGe1–x with varying proportions of Si to Ge on changing the molar ratio in the solution. To further evaluate the reaction mechanism of the electrodeposition process, in situ UV visible spectroelectrochemistry was performed. From the changes in the UV spectra combined with XPS and SEM observations, a layered growth process has been proposed during the formation of SixGe1–x.

We report on in situ UV–vis spectroscopic measurement during the electrodeposition of silicon, germanium, and silicon–germanium alloys from an ionic liquid. From the spectroscopic analysis, the potential-dependent formation and growth of Ge, Si, and SixGe1–x nanoparticles were evaluated. The possible formation of adlayers and an underpotential deposition of Si on Ge during silicon and germanium electrodeposition are also discussed.

The lipids of the stratum corneum comprise the most important components of the skin barrier. In patients with ichthyoses or atopic dermatitis, the composition of the skin barrier lipids is disturbed resulting in dry, scaly, itching erythematous skin. Using the latest X-Ray Photoelectron Spectroscopy (XPS) technology, we investigated the physiological skin lipid composition of human skin and the effects of cold atmospheric plasma treatment on the lipid composition. Skin lipids were stripped off forearms of six healthy volunteers using the cyanoacrylate glue technique, plasma treated or not and then subjected to detailed XPS analysis. We found that the human lipid skin barrier consisted of 84.4% carbon (+1.3 SEM%), 10.8% oxygen (+1.0 SEM%) and 4.8% nitrogen (+0.3 SEM%). The composition of physiological skin lipids was not different in males and females. Plasma treatment resulted in significant changes in skin barrier lipid stoichiometry. The total carbon amount was reduced to 76.7%, and the oxygen amount increased to 16.5%. There was also a slight increase in nitrogen to 6.8%. These changes could be attributed to reduced C-C bonds and increased C-O, C=O, C-N and N-C-O bonds. The moderate increase in nitrogen was caused by an increase in C-N and N-C-O bonds. Our results show for the first time that plasma treatment leads to considerable changes in the human skin lipid barrier. Our proof of principle investigations established the technical means to analyse, if plasma-induced skin lipid barrier changes may be beneficial in the treatment of ichthyotic or eczematous skin.

In this paper we report on recent results from our group, namely on the interface ionic liquid/electrode, plasma electrochemistry and electrodeposition of selenium and of macroporous structures. Ionic liquids show an interesting and liquid dependent surface chemistry: in some liquids the long range “herringbone” superstructure of Au(1 1 1) is visible, in others it is not. Glow discharge plasmas can be employed as a contact free electrode to make nanoparticles in solutions, e.g. nanoparticles of germanium. Selenium can be electrodeposited from ionic liquids under environmental conditions in an open cell and both the red and the grey phases of selenium are feasible. With the help of self organized opal structures of polystyrene spheres macroporous materials of Ag, Al and conducting polymers can be made. The prospects and limits of ionic liquids in surface electrochemistry and electrodeposition are shortly discussed.

Radiation induced degradation effects are studied for a model ionic liquid (IL)--[EMIm]Tf(2)N--in order to distinguish in which way the results of X-ray based material analysis methods can be falsified by the radiation supplied by typical X-ray sources itself. Photoelectron spectroscopy is commonly used for determining the electronic structure of ionic liquids. Degradation effects, which often occur e.g. in organic materials during X-ray or electron irradiation, are potentially critical for the interpretation of data obtained from ionic liquids. The changes of the chemical composition as well as the radiation-induced desorption of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm]Tf(2)N) fragments are analysed by X-ray photoelectron spectroscopy (XPS) as well as quadrupole mass spectroscopy (QMS) upon exposure to monochromated or non-monochromated AlKα X-rays from typical laboratory sources. During the irradiation of [EMIm]Tf(2)N, an increasing carbon concentration is observed in both cases and especially the [Tf(2)N](-) ion is strongly altered. This observation is supported by the results from the QMS analysis which revealed a variety of different IL fragments that are desorbed during X-ray irradiation. It is shown that the decomposition rate is directly linked to the photon flux on the sample and hence has to be considered when planning an XPS experiment. However, for typical experiments on this particular IL the measurements suggest that the changes are on a larger time scale as typically required for spectra acquisition, in particular if monochromated X-ray sources are used.

We report on the reaction of CuCl and CuCl 2 , each dissolved in 1-butyl-3-methylimidazolium dicyanamide ([BMIm]dca), with a glow discharge argon plasma. The interaction of the plasma with the solutions exhibits a strong reaction with gas evolution and the growth of copper nanoparticles. The particle size was determined with transmission electron microscopy (from the particle/ionic liquid, IL solution). The chemical composition was investigated by ex situ X-ray photoelectron spectroscopy (XPS). We found that the mean diameter of the copper particles produced in CuCl/[BMIm]dca and CuCl 2 /[BMIm]dca was in the same order of magnitude (between 2 and 10 nm). Despite the strong reaction we found no hints for IL degradation products in the liquids with infrared spectroscopy. XPS showed that ex situ treatment of the particles leads to the formation of CuO.

Subjecting drying latex films, the water phase of which contains metal ions, to a reducing, low-temperature atmospheric pressure plasma results in the formation of metal (nano-)particles or a metal film. The process is demonstrated with gold and silver. A continuous metal layer forms on top of the film, when the salt concentration is high enough. At lower concentrations, particles are created inside the film. In the case of gold these are mostly nanoparticles, which are enriched at the top. The reduction drives an auto-stratification process.

We have measured the bulk and surface electronic structure of several ionic liquids of alkyl-imidazolium cations with different alkyl chains (EMIm, BMIm, HMIm, OMIm) and bis(trifluoromethylsulfonyl)imide anions (Tf2N) by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS He I and He II) as well as metastable induced electron spectroscopy (MIES). The results are compared with the densities of states (DOS) calculated by density functional theory (DFT). By XPS we found the stoichiometry of the respective ILs reproduced, and different carbon atom positions reflected by the splitting of the C(1s) - from the trifluor-methyl groups (CF3) of the anion with highest binding energy to the alkyl chains of the cation with the lowest one. Furthermore with increasing alkyl chain length the peak related to the alkyl group appears at slightly lower binding energy. The more bulk-sensitive XPS spectra reveal only minor differences in the valence band structure for the studied ionic liquids, whereas the more surface-sensitive methods UPS and especially MIES display distinct changes in the peak-intensities for varying the alkyl chain length. This is a strong indication for either a non-stoichiometric composition of the upmost molecular layer of the IL-surface and/or a reorientation of the cations, probably turning the alkyl chains to the surface. [DOI: 10.1380/ejssnt.2010.241]

In the present paper the electrodeposition of Ga on Au(1 1 1) from 0.5 mol L −1 GaCl 3 in the air- and water-stable ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide, [Py 1,4 ]TFSA, has been investigated by in situ scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and cyclic voltammetry (CV). The CV shows two redox processes: the one at −0.3 V vs . Pt is attributed to a Ga deposition on a Ga layer formed during an electroless deposition process at OCP and/or to the formation of a Au–Ga alloy; the other one at −0.9 V is due to the bulk deposition of Ga. The XPS measurement reveals that there is an oxide layer on the top of the gallium electrodeposit due to exposure to air. In situ STM measurements show that the first layer of the Ga deposit consists of islands of 10–30 nm in width and several nanometers in height surprisingly the result of an electroless deposition at the OCP. If the electrode potential is further reduced the bulk deposition of Ga sets in.

The valence band of lignin and sputtered lignin was studied by X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS) and metastable induced electron spectroscopy (MIES). The corresponding spectra were compared with those from fingerprint molecules, representing the various chemical groups of lignin. The results of this analysis show that valence band spectroscopy, in particular a combination of XPS, UPS and MIES, allows an identification of hydroxyl, methoxy and phenyl groups at the lignin surface.

Time-of-flight secondary ion mass spectroscopy (TOF-SIMS) has been used to investigate the surface structural transformation of room temperature ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imid ([EMIM][Tf 2 N]), in the temperature range between 300 and 160 K. The intensity of the [EMIM] + cation from the crystal surface becomes about twice as large as that from the glassy and liquid surfaces, whereas the fragment ions from the [Tf 2 N] − moiety are almost unchanged upon crystallization. This phenomenon can be ascribed to the steric effect of the cation relative to the counter anion at the topmost surface layer rather than their surface compositions: a specific layered structure of the crystal surface, in which the imidazolium ring of [EMIM] + is aligned parallel to the surface plane, is thought to be responsible for the enhancement of the [EMIM] + ion emission. The smaller [EMIM] + intensity from the glassy and liquid films evidences that the imidazolium ring is not parallel to the surface.

The reflection-absorption infrared (RAIRS) spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]Tf(2)N) are presented for liquid as well as for amorphous and crystalline solid films. The liquid and amorphous films show rather similar spectra, indicating that the film structure is similar in both cases. On the other hand, these spectra differ considerably from those of crystalline films, indicating that the film structure is different for liquid and crystalline films. There are however indications that in all of the studied phases, including the crystalline state, the cation interaction with the SO(2) groups of the anion dominates.

The reflection-absorption infrared (RAIRS) spectra of 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM]Tf 2N) are presented as a function of temperature between 114 and 292 K. A comparison is made with the corresponding infrared spectra (obtained with transmission spectroscopy) from bulk [EMIM]Tf 2N. The liquid and amorphous films show rather similar spectra, indicating that the film structure is similar in both cases. On the other hand, these spectra differ considerably from those of crystalline films. Characteristic differences seen between the film and bulk spectra are attributed to the different structures of the respective networks. There are, however, indications that under all studied conditions the cation-anion interaction is between the C-H groups of the [EMIM] ring and the SO 2 groups of the anion.

We present a spectroscopic and microscopic study of nanoscale Al and Si films electrodeposited in water- and air-stable ionic liquids. The choice of cations for such ionic liquids has previously been shown to have a significant effect on the crystallite size of electrodeposited Al or Si films. We found that the deposits are generally uniform, dense, metallic bright, and adherent with crystallite sizes in the nanometer range. The nanocrystalline films were characterized using X-ray Photoelectron Spectroscopy (XPS) and High-Resolution Scanning Electron Microscopy (HRSEM). The XPS results show that the surface of both films is oxidized although the deposition was done in an inert gas glove box. Furthermore our results suggest that as a consequence of oxygen attack the nanoparticles are composed of a metallic core surrounded by a thin oxidic shell. Our XPS study also shows that neither the cation nor the anion of the ionic liquid is entrapped in the deposit. Thus, electrodeposition in ionic liquids delivers pure materials.

Metastable induced electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) were applied to study the interaction of Ti metal atoms with spruce surfaces. Spruce surfaces were produced by planing splints from a spruce bar. Ti atoms were adsorbed from a metal evaporator under ultra-high vacuum conditions. The amount adsorbed corresponds to 10 monolayer equivalents. Strong interactions between the spruce surface and metals atoms occurred. Impinging Ti atoms were oxidized by the spruce surface. No Ti agglomeration or particle formation was observed. The surface was smoothed by the Ti applied and was completely covered by a titanium oxide film.

The near-surface electronic structure of the room-temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide has been investigated with ultraviolet and X-ray photoelectron spectroscopy as well as metastable induced electron spectroscopy. The results have been compared with density functional theory calculations. The good agreement between the experimental and theoretical data provides detailed insight into the origin of the observed spectral features. In particular, we found that a simple composition of the spectra of the isolated ions does not suffice to fit to the experimental results, but interionic interactions have to be considered.

Ultrathin MgO films were grown on a W(1 1 0) substrate while metastable impact electron (MIES) and photoelectron (UPS) spectra were measured in situ; apart from the valence band emission, no additional spectral features were detected. The oxide surface was exposed to metal atoms (Cu, Pd) at RT. A comparison with the DOS extracted from first-principles DFT calculations shows that the metal-induced intensity developing above the top of the O 2p valence band in the UP spectra under Cu(Pd) exposure is caused by Cu 3d (Pd 4d) emission. The emission seen in the MIES spectra is attributed to the ionization of Cu 3d and 4s states of adsorbed neutral Cu atoms in an Auger process, Auger neutralization, involving two electrons from the surface, at least one of them from the metal adsorbate. The shape of the MIES spectra suggests metallic island growth even at the lowest studied exposures, which is supported by the firstprinciples calculations. 2006 Elsevier B.V. All rights reserved.

The interaction of NaI with amorphous solid water (ASW) and methanol (MeOH) has been investigated with metastable impact electron spectroscopy (MIES), UPS(HeI), and temperature programmed desorption (TPD). We have studied the electron emission from the ionization of the highest-lying states of H(2)O, CH(3)OH, and of 5pI. We have prepared NaI layers on ASW (MeOH) films at about 105 K and annealed them up to about 200 K. Surface segregation of iodide is observed in ASW, as predicted for NaI aqueous solutions. On the other hand, surface segregation is not observed in MeOH, again as predicted for the interaction of NaI with liquid methanol. Electronic properties (ionization potentials, optical band gaps) and water binding energies are reported and are analyzed on the basis of available DFT results for hydrated NaI clusters.

The near-surface electronic structure of the room-temperature ionic liquid (RT-IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf(2)N]) has been investigated with the combination of the electron spectroscopies metastable impact electron spectroscopy (MIES), ultraviolet photoelectron spectroscopy (UPS (HeI and HeII)), and monochromatized X-ray photoelectron spectroscopy (XPS). We find that the top of the valence band states originates from states of the cation (see also ref 1). The ultimately surface-sensitive technique MIES proves that the surface layer consists of both cations and anions. The temperature dependence of the spectra has been measured between about 160 and 610 K. Information on the glass transition and the possibility for low-temperature distillation of [EMIM][Tf(2)N] at reduced pressures is derived from the present results.

Surface segregation of iodide, but not of fluoride or cesium ions, is observed by a combination of metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy (UPS(HeI)) of amorphous solid water exposed to CsI or CsF vapor. The same surface ionic behavior is also derived from molecular dynamics (MD) simulations of the corresponding aqueous salt solutions. The MIES results show the propensity of iodide, but not fluoride, for the surface of the amorphous solid water film, providing thus strong evidence for the suggested presence of heavier halides (iodide, bromide, and to a lesser extent chloride) at the topmost layer of aqueous surfaces. In contrast, no appreciable surface segregation of ions is observed in methanol, neither in the experiment nor in the simulation. Furthermore, the present results indicate that, as far as the thermodynamic aspects of solvation of alkali halides are concerned, amorphous solid water and methanol surfaces behave similarly as surfaces of the corresponding liquids.

The interaction of CsF with multilayered water has been investigated with metastable impact electron spectroscopy (MIES) and ultraviolet photoelectron spectroscopy with HeI (UPS(HeI)). We have studied the emission from the ionization of H2O states 1b1, 3a1, and 1b2; of Cs5p and of F2p. We have prepared CsF-H2O interfaces, namely, CsF layers on thin films of multilayered water and vice versa; they were annealed between 80 and about 280 K. Up to about 100 K, a closed CsF layer can be deposited on H2O and vice versa; no interpenetration of the two components H2O and CsF could be observed. Above 110 K, CsF (H2O) layers deposited on thin H2O (CsF) films (stoichiometry CsF.1.5H2O) gradually transform into a mixed layer containing F, Cs, and H2O species. When annealing, H2O molecules can be detected up to 200 K from the mixed F-Cs-H2O layer (while for pure H2O desorption is essentially complete at 165 K); a water network is not formed under these conditions, and all H2O molecules are involved in bonding with Cs+ and F- ions. When CsF is deposited at 120 K on sufficiently thick water multilayers, full solvation of both F and Cs takes place, even for the species closest to the surface, as long as the stoichiometry remains CsF.(H2O)n with n > 3.

We report studies of the interaction (80–200 K) of atoms and molecules with ice films, deposited on tungsten, by combining photoelectron spectroscopy, UPS with HeI and II, metastable impact electron spectroscopy (MIES), and temperature programmed desorption (TPD). The focus is on the following issues: (1) Interaction of Na Atoms with films of solid NH3 and CH3OH: the delocalization of the 3sNa electrons and their role in the deprotonation of ice molecules (seen for CH3OH, but not for NH3) is studied. DOS (density of states) information from density functional theory (DFT) is compared with the MIES spectra. It is concluded that the 3s electron, delocalized from its Na core and trapped between the core and surrounding molecules, triggers the CH3OH deprotonation; for NH3, Na dimers appear to play an important role in the delocalization process. (2) Interaction of salt (NaCl) and acid (HCOOH) molecules with H2O ice: neither NaCl nor HCOOH penetrate into the ice film during adsorption below 90 K. However, ionic dissociation of NaCl occurs as a consequence of the NaCl–ice interaction. At 105 K the solvation of ionic species becomes significant. The desorption of H2O from the mixed film takes place between 145 and 170 K; those species bound to Na+ and Cl− are removed last. No dissociation of HCOOH is observed as a consequence of the interaction with ice. Partial solvation of formic acid species takes place above about 120 K whereby these species become embedded into the rim of the water film. However, no deeper penetration of formic acid molecules into the water film can be detected before H2O desorption becomes significant. The TPD spectra of HCOOH display structure, around 160 K, close to or coinciding with the sublimation temperature of water, and around 180 K, caused by species chemisorbed on the tungsten substrate supporting the ice film. The interaction of both NaCl and HCOOH with ice is discussed on the basis of qualitative free energy profiles.