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- X-ray photoelectron spectroscopy (XPS) (20)
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Institute
Photo-Emission-Electron-Microscopy for Characterization of an Operating Organic Electronic Device
(2006)
In this contribution we report on investigations of the electronic structure and composition of regioregular poly(3-hexylthiophene) (P3HT) and phenyl-C61-butyric acid methyl ester (PCBM) based films by using Near Edge X-Ray Absorption Fine Structure (NEXAFS). The measurements were done at the U49/2-PGM2 beam line of BESSY II, Berlin using TEY (total electron yield) and TFY (total fluorescence yield) detection. The samples were produced by spin casting a mixture of P3HT (dissolved in chloroform) and PCBM (dissolved in chlorobenzene) on ITO (indium tin oxide) coated glass slides. Measurements of pure P3HT and PCBM show all typical excitations, whereas the blended system is a weighted superposition of the related peaks. Analyzing these weighted superposition, we observe in the surface sensitive TEY data an accumulation of P3HT, whereas in the bulk sensitive TFY signal an as expected mixture is found. We also show angular dependent NEXAFS measurements of the P3HT/PCBM blend in order to measure the orientation and distribution of the P3HT polymer. Additionally, we will show a new approach for organic solar cell application by introducing ferroelectric nanoparticles into the mixture.
Replacing Co by large amounts of Ni is considered to reduce costs in Li-Ion-Batteries while maintaining their performance. We are interested in whether this replacement causes changes in the valence band (VB) and conduction band (CB) states or not.
Samples were prepared as thin films from nitrate solutions on metal substrates and annealed in air and UHV. The Co to Ni ratio was varied from 50/50 over 40/60 and 30/70 up to 20/80. The results are compared to the pure Co-oxide. Experiments were carried out at the U49/2 beamline at BESSYII, Berlin.
XPS of the TM2p states reveals the existence of charge transfer ground states and different oxidation states. NEXAS at the Co2p, Ni2p and O1s edges projects the density of unoccupied states while resonant PES at these edges provides the related partial density of states (pDOS) and thus can be used to distinguish between the different contributions of TM3d and O2p states in the valence band region.
We find systematic variation of the VB structure, the valence band maximum and a shift at the O1s absorption edge while the TM2p XPS and absorption spectra do not seem to be affected by the mixing.
We investigated several layered perovskite derivatives of the family AnBnO3n+2, such as LaTiO3.41, CaNbO3.41 and SrNbO3.41, which can be considered as a stacking of blocks consisting of 5 perovskite layers. Electric transport across these layers takes place via intrinsic tunnelling. Mesa devices with a cross-sectional area of 50 to 200 µm2 and a height between 30 and 500 nm were fabricated by electron-beam lithography and ion-beam etching. Both dc I-V characteristics and pulsed current injection have shown switching between different resistive states in these materials. The resistive states have long-term stability, which makes them interesting for memory applications. The transport experiments suggest that switching and resistive memory are controlled by trapping and release of charge carriers. Furthermore, photoelectron and NEXAFS spectroscopy of cleaved LaTiO3.41 surfaces have been performed. The results are compared to recent correlated band theory (LDA+U) calculations.
Scanning Kelvin probe and photoemission electron microscopy of organic source-drain structures
(2004)
The TiO2 films are prepared by atomic layer deposition (ALD) method using titanium
isopropoxide precursors at 250 °C and analyzed using resonant photoemission spectroscopy (resPES). We report on the Ti2p and O1s core levels, on the valence band (VB) spectra and
x-ray absorption spectroscopy (XAS) data, and on the resonant photoelectron spectroscopy (resPES) profiles at the O1s and the Ti3p absorption edges. We determine the elemental
abundance, the position of the VB maxima, the partial density of states (PDOS) in the VB and in the conduction band (CB) and collect these data in a band scheme. In addition, we analyze the band-gap states as well as the intrinsic states due to polarons and charge-transfer
excitations. These states are found to cause multiple Auger decay processes upon resonant
excitation. We identify several of these processes and determine their relative contribution to the Auger signal quantitatively. As our resPES data allow a quantitative analysis of these defect states, we determine the relative abundance of the PDOS in the VB and in CB and also the charge neutrality level.
The anatase and rutile polymorphs of TiO2 are analyzed in the same way as the TiO2 ALD layer. The electronic properties of the TiO2ALD layer are compared with the anatase and rutile polymorphs of TiO2. In our comparative study, we find that ALD has its own
characteristic electronic structure that is distinct from that of anatase and rutile. However, many details of the electronic structure are comparable and we benefit from our spectroscopic
data and our careful analysis to find these differences. These can be attributed to a stronger hybridization of the O2p and Ti3d4s states for the ALD films when compared to the anatase and rutile polymorphs.
Wir haben CuInS2 (CIS) unterschiedlicher Herstellung (Koverdampfung, Sputtern, Pulsed Laser Deposition, CIS auf Kupferband aufgebracht) untersucht. Neben Tiefenprofilen (durch Sputtern) der Elementverteilung dieser Proben wurden der Einfluss der Temperatur, von aufgedampftem Kupfer und Indium, ebenfalls bei verschiedenen Temperaturen, auf das Verhalten der Stöchiometrie mit spektroskopischen Methoden (XPS, UPS) studiert. Parallel dazu wurde das Verhalten von im Vakuum aufgedampften ZnS und die entsprechenden Oberflächenreaktionen in Abhängigkeit von der Temperatur untersucht und charakterisiert, so dass Aussagen über die Optimierung und Anpassung von Präparationsbedingungen und Parametern zur Herstellung von erstens reinem CIS und zweitens von Mischkristallen des Typs Zn2-xCuxInxS2 möglich werden. Zwischen den beiden Endgliedern ZnS und CuInS2 besteht bis auf einen Phasenübergang bei etwa 80% CIS lückenlose Mischbarkeit gemäss Zn2-xCuxInxS2 (Bente: Chem.Erde (1991)). Die elektronische Bandlücke dieser Mischkristalle lässt sich im Vergleich zu reinem CuInS2 in einem Bereich von 3,67 eV (ZnS) bis 1,55 eV (CuInS2) variieren. Damit besteht die Möglichkeit, durch kontrollierte Änderung der Zusammensetzung der Schichten die Effizienz von Solarzellen aus diesem Material zu optimieren.
Due to the growing range of applications for organic materials considerable interest has been focused on the controlled growth of films on silicon substrates. Recently, it has been shown that ultra-thin oligimide films can be grown on Si(100)-2x1 with a direct Si-C linkage to the substrate. In this study, we have focused on the chemisorption of maleic anhydride (C4O3H2) on Si(100)-2x1. The combined HREELS data indicate that the adsorption of maleic anhydride on Si(100)-2x1 at low dosages occurs mainly through cycloaddition of the C=C bond to the dangling bonds of the Si-Si dimer analogous to the behaviour of ethene. The Si-Si dimer bonds are not involved in the chemisorption, as the continued observation of a 2x1 pattern in LEED shows. In the NEXAFS spectra, a π* resonance indicative of a C=C bond is absent upon exposure of the silicon substrate to maleic anhydride. At higher dosages, we observe chemisorbed maleic anhydride species, which are bonded to the Si surface atoms via a single Si-C linkage with preservation of the C=C double bond. In this case, the dissociated hydrogen bonds to one of the neighbouring Si atoms. Possible adsorption geometries will be discussed.
Es werden spektro-mikroskopische Untersuchungen an multikristallinem Silizium (mc-Si) vorgestellt, einem aussichtsreichen Material für die Herstellung preiswerter Solarzellen. Dazu wird ein Photoemissions- Elektronenmikroskop (PEEM) ausgestattet mit einem zusätzlichen Energieanalysator für Elektronen (µESCA) genutzt. Bei Verwendung eines Synchrotrons als Anregungsquelle ist es so möglich, sowohl Absorbtions-Spektren (NEXAFS) als auch Photoelektronen-Spektren (PES) mit Ortsauflösung zu erhalten.
Dabei wird gezeigt, dass das natürliche Oxid zur Untersuchung der morphologie-abhängigen Oberflächenpotentiale nicht entfernt werden muss. Des Weiteren wird die Verteilung von Ca- und Na-Ausscheidungen, die auf dem mc-Si gefunden wurden, durch ortsaufgelöstes NEXAFS bzw. PES dargestellt.
Für den Photoemissions-Prozess des mc-Si im PEEM wird ein Modell aufgestellt, welches Photoemission mit einer Quecksilberdampflampe (hνmax = 4,9 eV) erklärt.
Conducting Polypyrrole doped with Phthalocyaninesulfonates - new materials for chemical sensors
(2000)
Polypyrrole - a conducting polymer - is used as an active electrode of a quartz micro ballance and considered as a gate electrode in all-polymer field effect transistors used as chemical sensor. We use substituted phthalocyanines as dopants of polypyrrole as they offer the possibility to enhance the dopant concentration as well as to include functionalized groups. We studied these films by photoelectron spectroscopy, NEXAFS, PEEM, and TEM. These investigations revealed that the electronic structure as well as the morphology are highly dependent on the dopant’s structure. We suggest a new charge transport model for 5-ring heterocycle conductive polymers. Whereas in the standard model only the carbon backbone is considered for the charge transport, we found by NEXAFS investigations that the heteroatom has a considerable high participation in the gap states, which are responsible for the charge transport. The dopants π-interactions force the nitrogen lone pair wave functions to contribute to the conducting polymer π-system. This is a novel approach concerning the application as chemical sensors since the reversible interaction of the analyte modifies the dopant and not the matrix.