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Photoemission studies of very thin (<10nm) silicon oxynitride (SiOxNy) layers formed by PECVD
(2004)
The "ITRS Roadmap" suggests the necessity of working out the processing methods allowing formation of ultrathin dielectric layers with higher values of the dielectric permittivity than for silicon dioxide. The silicon oxynitride layers (SiOxNy) seem to be the most natural compromise. But still none of high temperature methods used for its formation can be seriously considered as final solution for future ULSI-CMOS ICs production due to the inevitable formation of nitride monolayers just at the silicon-insulator interface. The main scope of this investigation is to check if this is true.
Ultra-thin homogeneous oxynitride films are prepared on Si(001). The Si surface is cleaned in UHV by heating (flashing) and is exposed to different pressures of N2Oat altered temperatures. Thus oxynitride layers of different thickness and different properties are grown depending on the N2O pressure and the Si temperature. This isillustrated by a schematic diagram. The properties of the different oxynitride layers were studied by a combined photoemission electron microscopy (PEEM) andphotoelectron spectroscopy (PES) investigation using highly monochromatic synchrotron radiation. The amount of oxygen and nitrogen incorporated in the oxynitridelayers is determined from the PES measurements. The typical surface morphology for different preparation conditions is shown in PEEM images.
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.
Es werden Untersuchungen an als Hochtemperatur-Sensoren arbeitenden Schottky-Dioden mit dem Aufbau Metall-Oxidschicht-Siliziumkarbid vorgestellt. Dazu wurden Tiefenprofile mit XPS durch abwechselndes Abtragen durch Sputtern und Messen erstellt. Die Messungen erfolgten an thermisch unterschiedlich vorbehandelten Proben. Dabei konnten dipol-bedingte Verschiebungen der Bindungsenergie von Rumpfniveaus beobachtet werden. Das dazu notwendige Dipol-Moment wird durch das Entstehen von mit einer Oxidschicht überzogenen Nanoteilchen erklärt. Die unterschiedlich ausgeprägten Dipol-Verschiebungen auf den einzelnen Proben erlaubten eine Erklärung der thermischen Vorbehandlung, die bei Weglassen zu „frischen“ und je nach Temperatur zu „aktivierten“ oder „toten“ Sensoren führte.
Untersuchungen des metallischen Kontaktes von Silber auf tosylat- und phthalocyanindotiertem Polypyrrol wurden mittels XPS- und µ-NEXAFS vorgenommen. Es wurde festgestellt, daß Silber mit dem Polypyrrol keine Verbindung eingeht. Daraus kann geschlossen werden, daß sowohl das leitfähige Polymer, als auch das Silber ihren Leitfähigkeitsmechanismus beibehalten. Es konnte gezeigt werden, daß bei steigender Silberbelegung die Intensität der Polaronenzustände des Polypyrrol in stärkerem Maße abnimmt, als die Intensität der unbesetzten Zustände. Das läßt darauf schließen, daß Silber die Grenzfläche stabilisiert.
Molybdänditellurid (MoTe2) gehört zu den Schichtgitterverbindung und ist im allgemeinen durch den Herstellungsprozeß n-dotiert. Proben dieses MoTe2 wurden im Ultrahochvakuum gespalten und die so erhaltenen sauberen (0001)-Spaltflächen mit einem Photoemissions-Elektronenmikroskop (PEEM) untersucht. Diese Untersuchung erbrachte nebeneinander auf den Proben- oberflächen liegende stark kontrastierte helle und dunkle Bereiche. Da das PEEM Austrittsarbeitsunterschiede als Kontrast darstellt, können diese hellen und dunklen Bereiche auf lokale Unterschiede in der Austrittsarbeit zurückgeführt werden. Weiterhin wird über den Versuch berichtet, eine Zuordnung zwischen dem Kontrast und dem Unterschied in der Austrittsarbeit mit Hilfe eines Elektronenenergie-Analysators (micro-ESCA) zu treffen.
The interface region of friction-welded joints Al-Fe samples is investigated by scanning Auger Spectroscopy, Electron Probe Micro-analysis (EPMA), X-ray Photoelectron spectroscopy, and Photoemission Electron Microscopy, performed at the synchrotron light source (BESSY). We investigated polished samples cut to obtain a cross-section of the Al-Fe joints. At the Al-Fe interface there is a small number of Fe teeth protuding into the adjacent Al-matrix. Beside this mechanical interlock mechanism we identify an Fe-Al alloy which is formed in an almost homogeneous interface layer of approximately 80 micron thickness. We determine the valence band spectra within that layer and notice that the alloying formation is limited to the interface region. In addition, the profile of both, the Fe and O distribution within the Al next to that interface is determined. A model of the friction-welding mechanism is derived and discussed in terms of the ability of achieving low temperature Fe-Al joints.
Photoelectron spectroscopy utilizing synchrotron radiation of high energetic resolution (more than E/ΔE=3000) was used to record the Si2p emission signal of Si, SiC, SiGe, and SiGeC samples. The spectra exhibit signals of the elemental silicon as well as of fully oxidised silicon. Upon variing the photon energy, and therefore the escape depth of the photoelectrons, we find an oxidic silicon signal which is only half oxidized. This half oxidized silicon is located to be at the interface of the bulk material with the oxide. We determine the thickness of the surface oxide from the total ratio of oxidic and elemental silicon. We find differences between the interface and bulk oxides regarding their elemental composition. The line width of the elemental Si2p-signal exhibits a broadening of approximately 200meV while variing the photoelectron escape depth. This behaviour is interpreted as caused by surface stress.
To determine the depth structure of samples various destructive (SIMS, depth profiling with sputtering and AES or XPS) and non-destructive techniques (RBS - Rutherford-Back-Scattering) are available. But all methods are less suitable for investigating especially ultrathin (<5nm) layers: While the destructive techniques suffer from Ion-mixing the RBS can not deliver chemical information.
Due to the depth-dependent attenuation of photo-electrons XPS also contains depth information. As XPS gives only a sum signal across the layer one needs to modify the Inelastic Mean Free Path (IMFP) of the photo-electrons to vary the depth information in the photo-electron spectra. This can be done by changing the kinetic energy with the use of different excitation energies delivered from a Synchrotron.
Using this method we were able to investigate the chemical depth structure of silicon oxynitride layers. The layers were grown on Si(111) by a N2O-treatment. The depth profile of that layer shows a silicon nitride layer forming the interface between the silicon substrate and the oxynitride.
Si(001) surface oxidation
(2001)
A Si(001) surface is cleaned in UHV by heating (flashing) and is exposed to different pressures of N2O at altered temperatures. Oxynitride layers of different thicknesses and different properties are grown depending on the N2O-pressure and the Si- temperature. This is illustrated by a schematic diagram.
The properties of the different Oxynitride layers were studied by a combined PEEM- and PES-investigation using highly monochromatised synchrotron radiation. The amount of Oxygen and Nitrogen incorporated in the Oxynitride layers is determined from the PES measurements. The typical surface morphology for different preparation conditions is shown in PEEM images.
A model based on differently established dipole layers in the Oxynitride layers is proposed. This model is capable of interpreting the features appearing in the PE-spectra. This model can also be applied to the interface of Si/SiO2.
Oxynitride layers are grown on 4H-SiC(0001) by a thermal treatment in N2O. The nitrogen content is controlled by varying the growth conditions (N2O pressure and substrate temperature) and the nitrogen incorporation is found to be stronger for higher substrate temperatures and lower N2O pressures.
Excess carbon is generated due to SiC decomposition under such growth conditions (high temperature and low N2O pressure) which leads to unwanted high interface state density and has to be avoided. Our approach is to prepare a Si-rich or even Si-covered SiC surface by Si evaporation. Upon oxidation in N2O the additional silicon is expected to compensate the loss of silicon from the SiC while preparation.
The Si-rich SiC surface as well as the grown layers were investigated by photoelectron spectroscopy (XPS) for chemical analysis and by AFM/STM for analysis of the surface morphology. Concerning the chemical analysis we focus on the total nitrogen content, on the amount of silicon nitride Si3N4 and of silicon oxynitride SiOxNy, and on the existence of sub-oxides which build the interface between SiC and the oxynitride layers.
It will be reported on the growth of oxynitride thin layers (≤10nm) on (0001)-oriented 4H-SiC surfaces. The oxynitride layers were grown by a thermal treatment of the samples in low pressure N2O ambient. By varying the growth conditions (N2O pressure, sample temperature, growth time) different layers were made.
The grown layers were investigated by photoelectron spectroscopy (XPS) for chemical analysis and by AFM/STM for analysis of the surface morphology. Concerning the chemical analysis it will be discussed the general nitrogen content of the samples, the composition of the films (e.g. content of silicon nitride Si3N4 and silicon oxynitride SiOxNy) and the sub-oxides which build the interface between SiC and the oxynitride layers. Concerning the surface morphology mainly the roughness will be discussed.
The so obtained results for oxynitride thin films on 4H-SiC will be compared to similarly prepared oxynitride layers on Si(111) investigated in the past.
We introduce a recently developed novel polypyrrole-based coating, which can be formed on the aluminium surface from an aqueous pyrrole solution of fluorozirconic and fluorotitanic acid neutralised with zinc oxide. The composite layer consists of polypyrrole (Ppy) chemisorbed on titanium and zinc oxides and exhibits advanced corrosion resistance. For the investigation of the structure and the corrosion mechanism of the composite corrosion resistant layer we use a photo-electron emission microscope (PEEM). PEEM is especially suitable because it can deliver topographic contrast as well as elemental contrast and chemical information in connection with a variable X-ray source. Additionally, in order to investigate further the corrosion mechanism, but also the role of the alloy in the corrosion process, we examine the aluminium samples with SEM/EDX. The structure of the corrosion resistant layer was investigated before and after accelerated corrosion tests. Our results pointed out the important role of titanium oxide and zinc in the corrosion resistance of our Ppy coating on aluminium.
The quality of the SiO2/Si interface is of crucial importance in the development and performance of sub 0.1 small mu, Greekm technologies. The knowledge of the chemical composition of the interface is an important piece of information in the preparation of ultra-thin oxides and high-k dielectrics, in order to maintain a high-quality interface and channel mobility. Here we report on investigations of 2 nm oxide layers formed by a RTP process under various gas mixtures containing N2O and NH3 at different concentrations. We studied the SiO2/Si(001) interface by a non-destructive depth profiling using Synchrotron radiation photoelectron spectroscopy. We determine the thickness of the oxide layer, the relative content and chemical state of nitrogen within the oxide, the thickness of the interface layer, and the relative abundance of Si intermediate oxides within. In all systems we find the thickness of the intermediate layer to be approximately 0.17 nm. The intermediate layer contains Si atoms in the oxidation states +1, +2 and +3 with similar relative abundance. Nitrogen is found predominantly close to the intermediate layer forming Si---N as well as Si---N---O bonds. Within the oxide there are only spurious nitrogen content with predominately Si---N---O bonds. Our method is able to detect a nitrogen content within the intermediate layer as low as approximately 5%.
Aluminium is a material of everyday use in many applications,like automobile,aero-space or cookware,due to its specialproperties (low density,low weight,strength,easy to form and cast,abundance etc).Although aluminium is a reactive metal,italso has a significant corrosion resistance because of a thin,protective oxide layer which is generally stable in air and aqueous solutions.However,pores within the oxide film and other defects caused from alloying elements can lead to local corrosion and the formation of pits.
The surface condition of electrochemically H-terminated Si is compared with the situation at the first photocurrent maximum in dilute acidic ammonium fluoride solution where the divalent dissolution converts into the four-valence process. The first high spectral-resolution photoelectron spectroscopy data using synchrotron radiation of electrochemically hydrogenated Si are presented. A combined electrochemistry/ultrahigh vacuum surface analysis system, attached to the U 49/2 beamline at the synchrotron Bessy II, is used for photoelectron spectroscopy (PES) of the electrochemically conditioned samples. We analyze the Si 2p, O 1s, and F 1s core levels. A comparison of a density functional theory calculation of the reaction sequence, proposed in the dissolution model of Gerischer and co-workers, with the PES results supports this model. The anodized sample is characterized by a residual H coverage of 0.35 monolayers evidenced by a surface core level shift, Si-OH and Si-Fx species, F-, and a higher oxidized Si species. SiO2 is not found. Even on very well H-terminated surfaces, we find residual Si-OH complexes, fluoride and water. In situ atomic force microscopy shows a roughening with a root mean square roughness parameter of 2.6 nm. %A92003 The Electrochemical Society. All rights reserved.
N2O-Oxidation of Si(100)
(2001)
The CO oxidation reaction on Iridium(111) surfaces shows bistability in a limited range of the CO fraction of the reactant gas flux Y and a wide range of temperatures T. The two branches are characterized by their reactivity for CO2 formation. The upper rate (high CO2 formation) rate is related to high oxygen coverage on the surface, the lower rate (little CO2 formation) to high CO coverage. Quadrupol mass spectroscopy and PEEM (photoelectron emission microscopy) was employed to study the influence of a noisy reactant gas flux composition on the spatio-temporal pattern development in the CO oxidation reaction on flat Ir(111) and stepped Ir(977) surfaces. PEEM shows nucleation and growth of few oxygen resp. CO islands at small noise amplitudes. Anisotropic diffusion of CO parallel and normal to the steps causes elliptic shapes of large islands. The long axes of the ellipses are aligned along the steps. At increased noise amplitudes the density of islands becomes larger. 2D modeling of the phenomena based on reaction-diffusion differential equations reproduces the experimental findings quite nicely.
Oxynitride on 4H-SiC (0001)
(2005)
It will be reported on the growth of oxynitride ultra-thin layers (<2 nm) on (0 0 0 1)-oriented 4H-SiC surfaces. The oxynitride layers were grown by a thermal treatment of the samples in low pressure (up to 1000 Pa) N2O ambient. By varying the growth conditions (N2O pressure, sample temperature, growth time) different layers were made. The highest nitrogen incorporation was found to be at high temperatures and low N2O pressures.The grown layers were investigated by photoelectron spectroscopy (XPS) for chemical analysis. Concerning the chemical analysis, the general nitrogen content of the samples is compared at different preparation conditions. The films are found to consist mainly of SiO2 and small fraction of silicon nitride. Only a tenth of the nitrogen was incorporated as oxynitride. The results obtained for oxynitride thin films on 4H-SiC are compared to similarly prepared oxynitride layers on Si(1 1 1) investigated in the past. Furthermore, an additional source of nitrogen due to dopand diffusion in the SiC single crystal is reported.
A spectro-microscopic approach to study the morphology and elemental distribution of mc-Si surfaces
(1999)
The initial stages of porous Si formation on Si(111) in dilute ammonium fluoride solution are analysed by photoelectron spectroscopy using synchrotron radiation (SRPES). The PES results in the por-Si formation regime partly support a recent dissolution model. The contribution from the Si 2p surface core level shift shows that 0.35 ML of the surface is still H-terminated after interruption of the conditioning process at the first photocurrent maximum. Two signals shifted in binding energy by 0.8 and 1 eV, respectively, are attributed to reaction intermediates expected from the proposed reaction mechanism and from theoretical calculations using density functional theory (DFT). A distinct roughening is found in in-situ AFM measurements, with a calculated RMS roughness parameter of 2.6 nm.
The oxide of Si(111) formed by electropolishing in dilute ammonium fluoride solution is analysed by photoelectron spectroscopy using synchrotron radiation. The oxidiclayer is about 3.1 nm thick and contains Si-F-x species as well as oxyfluorides. The oxyfluorides are found preferentially at the electropolishing layer surface. SiOHspecies are concentrated at the oxidic film/substrate interface. The full width half maximum of the Si 2p line indicates that the Si/electropolishing oxide interface issmoother than the Si/natural oxide interface.
We have studied the surface chemistry of 6H-SiC(0001) and 6H-SiC (000 (1) over bar) after wet-chemical treatment using photoelectron spectroscopy (PES) andlow-energy electron diffraction (LEED). The origin of chemically shifted components in the Si2p and C1s spectra is discussed in the light of previous studies onwet-chemically prepared surfaces and on silicate adlayer reconstructed surfaces. On 6H-SiC(0001) an ordered silicate adlayer was prepared by etching the surface withsulfuric acid based agents.
We studied two novel electrochemical treatments of CuInS2 solar-cell absorber films, introduced to remove the deleterious segregated CuS phase. Their influence onsurface topography, chemistry and electronic properties was investigated using in situ atomic force microscopy (AFM) and photoclectron spectroscopy, performed inpart at the U49/2 undulator beam line at BESSY II. The results are examined in order to develop an improved understanding of the chemical-electrochemical surfacetransformation processes.
The photo emission electron microscope (PEEM) with its direct imaging of the sample surface is a convenient tool for fast evaluation of large sample areas. It is possibleto handle samples with a size of 30 mm x 30 mm.With PEEM it is possible to visualise grain boundaries and crystal displacements without removing the native oxide. No special sample treatment is needed exceptchemical polishing of the sample surface and a HF-dip to obtain a thin (1 ... 2 nm) oxide layer.The quality of that oxide was proofed by high resolution photo electron spectroscopy (PES) at a synchrotron. The results were compared to native oxide onsingle-crystalline Si and no suboxides (e.g. SiO) were found. Our spectromicroscopic PEEM measurements show no difference in the oxide qualities of different grainsand on grain boundaries or crystal displacements. Furthermore no difference in the binding energy of Si2p core levels were found.In addition to grain boundaries other spot-like features were found on the sample surface. These could be identified in some cases as precipitation of Ca underneath thenative oxide.
The composition of CuInS2-films tends to differ from the ideal ratio of 1:1:2. A molecularlyvariation of dm=[Cu]/[In]-1 not equal 0 occurs due to the formation of binary phases as segregation's at the surface, as crystallites in the bulk of the film or at the surface of grains [1]. Furthermore, the range of homogeneity of the phase CuInS2 is relatively large caused by a low enthalpy of formation of defects like Cu-vacancies [2]. Segregation's at surfaces can be removed by KCN etching or by an electrochemical process [3, 4] We investigated the effect of an in-situ-heat-treatment of samples, prepared in the Cu-rich regime with additional amounts of copper, deposited on the surface of the Cu-In-S-films.We used Cu-In-S-films on molybdenum, prepared from precursors of Cu/In and a following reactive annealing-process in a sulphur-atmosphere. The experiments were performed as follows: The surface of the films was cleaned in situ to remove CuS-Phases by Argon-bombardment. The thin layers of additional Copper were prepared by evaporation of copper metal in Knudsen-cells. The thickness of this copper-films is in the range of monolayers, revealed by a calibration with copper on iron-substrates. After this deposition the samples were heated up to several temperatures (up to 550 ºC) for ten minutes, respectively. Here the molybdenum back-contact was used as electrical heater.
Zwei Schwingquarzsensoren mit gleicher sensitiver Beschichtung wurden zur Messung von CO2-Konzentrationen bei variierenden Luftfeuchten genutzt. Die Daten wurden neuronalen Netzen mit unterschiedlicher Architektur trainiert. Zwei Netze wurden auf ihre Generalisierungsfähigkeit getestet und miteinander verglichen. Für ein einstufiges Netz konnten Ergebnisse mit Fehlern kleiner 12% für die CO2-Konzentration und kleiner 5% für die Luftfeuchte erzielt werden. Ein zweistufiges Netz erkannte Kategorien der Luftfeuchte 100%-ig, für die CO2-Konzentration wurden Fehler kleiner 9% erreicht, wobei eine deutlich bessere Generalisierungsfähigkeit dieses Netzes im Vergleich zum einstufigen Netz zu verzeichnen ist.
Aluminium and Stainless Steel bi-metal material is extremely versatile and is used in a wide range of products; from cooking utensils to high technology applications such as automobile manufacture and Synchrotron radiation instrumentation. As a consequence of this wide range of applications the study of the formation of Aluminium Steel junctions and the bonding mechanism is of considerable industrialimportance [1-3].In a previous publication [4] evidence for a chemical bond, alloying at the interface was found. As the monochromator focus and welded region are similar in size about 200 µm (the actual interface from SEM is an order of magnitude smaller) a simple photoemission experiment of translating the sample perpendicular (vertically, weld horizontal) to the weld and measuring spectra was performed.
The use of low dielectric constant materials in the on-chip interconnect process reduces interconnect delay, power dissipation and crosstalk noise. In CVD deposited organo-silicate glass (OSG) the substitution of oxygen in SiO2 by methyl groups (-CH3) reduces the permittivity significantly
(from 4.0 in SiO2 to 2.6-3.3 in the OSG). However, plasma processing removes C and H containing molecular groups. Therefore, compositional
analysis and chemical bonding characterization of structured films with
nanometer resolution is necessary. OSG thin films as-deposited and after
plasma treatment are studied using XAS and EELS. In both techniques, the fine structure near the C1s edge allows to identify C-H, C-C, and C-O bonds. XAS spectra have been recorded for non-patterned films and EELS spectra for patterned structures. The chemical bonding is compared for as-deposited and plasma-treated low-k materials. The flu-orescence and the electron yield recorded while XAS measurement are compared. Examination of the C 1s near-edge structures reveal a mod-ified bonding of the remaining C atoms in the plasma-treated sample regions.