Physical chemistry chemical physics : PCCP, Jan 21, 2014
In this experimental investigation the interaction of lithium with 1-octyl-3-methylimidazolium bi... more In this experimental investigation the interaction of lithium with 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([OMIm]Tf2N) is shown. For this purpose thin films of lithium and [OMIm]Tf2N were successively vapor deposited on a copper substrate and analyzed by X-ray Photoelectron Spectroscopy (XPS) as well as by Ultraviolet Photoelectron Spectroscopy (UPS). When [OMIm]Tf2N is evaporated on top of a thin lithium film a chemical shift analysis of XPS spectra shows a variety of reaction products like LiF, Li2O and LixCHy which reveals the instability of the IL against lithium. Time resolved XPS spectra were discussed to distinguish cation reactions from beam damage effects. In a second step lithium is deposited on a [OMIm]Tf2N layer. The XPS spectra are in agreement with the results of the previous step, but show some differences concerning the [OMIm] cation. In a third step [OMIm]Tf2N has been deposited on a passivated lithium layer. XPS results show nearly unaffected...
ABSTRACT The adsorption behavior of thin films of terephthalic acid (TPA) evaporated on a gold su... more ABSTRACT 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.
Self-assembling systems of colloidal spheres are widely used as templates for the structured depo... more Self-assembling systems of colloidal spheres are widely used as templates for the structured deposition of metals and semiconductors. Multilayer samples of ordered polystyrene spheres are prepared by a flow induced process. The subsequent surface activation by a dielectric barrier discharge in oxygen is followed by the fabrication of protecting polysiloxane layers. Electrochemical deposition of copper is used to test the stability of the pre-treated colloidal crystal. The arrangement of the spheres is preserved during the deposition process, due to the polysiloxane layer. The results of the consecutive preparation steps are investigated concerning topographical and chemical changes by atomic force microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy.
The interaction of H2O and CO2 with bare and alkali (Li, Na, K, Cs) pre-covered TiO2 surfaces was... more The interaction of H2O and CO2 with bare and alkali (Li, Na, K, Cs) pre-covered TiO2 surfaces was investigated (130 and 300 K). Metastable impact electron spectroscopy and ultraviolet photoelectron spectroscopy (HeI and II) spectra were collected in situ during the exposure procedure. For H2O at 130 K on bare TiO2 an eventual initial dissociative adsorption at defect sites is
We report on the synthesis of copper nanoparticles in two different water- and air-stable ionic l... more We report on the synthesis of copper nanoparticles in two different water- and air-stable ionic liquids using plasma electrochemical deposition. The copper nanoparticles were deposited in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIm]Tf(2)N). To get information on the dimensions of the particles made, we have applied in situ transmission electron microscopy (TEM) (particles in ionic liquid). The chemical composition was investigated by ex situ X-ray photoelectron spectroscopy (XPS). We found that the copper particles produced in [Py(1,4)]Tf(2)N were larger in size compared to the particles obtained in [EMIm] Tf(2)N (roughly 20 vs. 10 nm). The chemical composition of the particle surface differs too. In both cases the particles are partly oxidised leading to a CuO shell, but the particles obtained in [Py(1,4)]Tf(2)N carry a lot of residues from the ionic liquid.
Radiation induced degradation effects are studied for a model ionic liquid (IL)--[EMIm]Tf(2)N--in... more 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.
Physical chemistry chemical physics : PCCP, Jan 21, 2014
In this experimental investigation the interaction of lithium with 1-octyl-3-methylimidazolium bi... more In this experimental investigation the interaction of lithium with 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([OMIm]Tf2N) is shown. For this purpose thin films of lithium and [OMIm]Tf2N were successively vapor deposited on a copper substrate and analyzed by X-ray Photoelectron Spectroscopy (XPS) as well as by Ultraviolet Photoelectron Spectroscopy (UPS). When [OMIm]Tf2N is evaporated on top of a thin lithium film a chemical shift analysis of XPS spectra shows a variety of reaction products like LiF, Li2O and LixCHy which reveals the instability of the IL against lithium. Time resolved XPS spectra were discussed to distinguish cation reactions from beam damage effects. In a second step lithium is deposited on a [OMIm]Tf2N layer. The XPS spectra are in agreement with the results of the previous step, but show some differences concerning the [OMIm] cation. In a third step [OMIm]Tf2N has been deposited on a passivated lithium layer. XPS results show nearly unaffected...
ABSTRACT The adsorption behavior of thin films of terephthalic acid (TPA) evaporated on a gold su... more ABSTRACT 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.
Self-assembling systems of colloidal spheres are widely used as templates for the structured depo... more Self-assembling systems of colloidal spheres are widely used as templates for the structured deposition of metals and semiconductors. Multilayer samples of ordered polystyrene spheres are prepared by a flow induced process. The subsequent surface activation by a dielectric barrier discharge in oxygen is followed by the fabrication of protecting polysiloxane layers. Electrochemical deposition of copper is used to test the stability of the pre-treated colloidal crystal. The arrangement of the spheres is preserved during the deposition process, due to the polysiloxane layer. The results of the consecutive preparation steps are investigated concerning topographical and chemical changes by atomic force microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy.
The interaction of H2O and CO2 with bare and alkali (Li, Na, K, Cs) pre-covered TiO2 surfaces was... more The interaction of H2O and CO2 with bare and alkali (Li, Na, K, Cs) pre-covered TiO2 surfaces was investigated (130 and 300 K). Metastable impact electron spectroscopy and ultraviolet photoelectron spectroscopy (HeI and II) spectra were collected in situ during the exposure procedure. For H2O at 130 K on bare TiO2 an eventual initial dissociative adsorption at defect sites is
We report on the synthesis of copper nanoparticles in two different water- and air-stable ionic l... more We report on the synthesis of copper nanoparticles in two different water- and air-stable ionic liquids using plasma electrochemical deposition. The copper nanoparticles were deposited in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py(1,4)]Tf(2)N) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide ([EMIm]Tf(2)N). To get information on the dimensions of the particles made, we have applied in situ transmission electron microscopy (TEM) (particles in ionic liquid). The chemical composition was investigated by ex situ X-ray photoelectron spectroscopy (XPS). We found that the copper particles produced in [Py(1,4)]Tf(2)N were larger in size compared to the particles obtained in [EMIm] Tf(2)N (roughly 20 vs. 10 nm). The chemical composition of the particle surface differs too. In both cases the particles are partly oxidised leading to a CuO shell, but the particles obtained in [Py(1,4)]Tf(2)N carry a lot of residues from the ionic liquid.
Radiation induced degradation effects are studied for a model ionic liquid (IL)--[EMIm]Tf(2)N--in... more 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.
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