An experimental apparatus has been constructed to investigate ionisation mechanisms of complex molecules and nanoparticles after femtosecond and/or picosecond laser excitation. The photoproducts are detected by time-of-flight mass spectrometry and velocity-map imaging (VMI) photoelectron spectroscopy. Test measurements on C60 and Xe have successfully reproduced previously published work indicating that the setup is working in a satisfactory manner. New detailed investigations of mass spectra and angle resolved photoelectron spectra (PES) have been carried out as a function of laser intensity, wavelength and pulse duration for C60 and C70, providing new insights into the electronic structure and ionisation mechanisms of these molecules. For 400 nm, 130 fs laser excitation, an isotropic contribution from thermally emitted electrons is found. A series of peaks are seen superimposed on the thermal background with binding energies in agreement with the recently discovered superatom molecular orbitals (SAMOs) of C60 [Feng et.al. Science 320 (2008) p. 359]. Furthermore, the angular dependence of the peak in the PES corresponding to the s-SAMO is in agreement with this assignment. To confirm the assignment of the other observed peaks it is concluded that the measured photoelectron angular distributions (PADs) need to be compared to calculated angular distributions. Measurements have also been made with the same wavelength but with a pulse duration of about 5 ps. Mass spectra, PES and PADs for these measurements show that the main ionisation mechanism for these laser conditions is delayed (thermionic) ionisation. For 800 nm, 130 and 180 fs laser excitation, thermally emitted electrons are observed. In contrast to the 400 nm measurements, the PADs show an asymmetry with higher apparent temperatures along the laser polarisation direction. Measurements were also made for longer pulse durations (1.0 – 3.8 ps). For pulse durations above 1 ps the asymmetry is gradually reduced while the delayed ionisation component in the mass spectrum increases with increasing pulse duration. The asymmetry is compared to calculations made assuming a field-assisted thermal electron emission. Similarly to the 400 nm experiments, a series of peaks are seen superimposed on the thermal background. PADs are presented for these peaks. PADs for peaks with the same binding energy as peaks seen in the 400 nm experiments follow the same trend. Isotropic PADs after ns laser excitation are also presented confirming delayed ionisation for these pulse durations.

SiGe 25% substrates were treated with aqueous solutions of ammonium sulfide with and without added acid to understand the adsorption of sulfur on the surface. X-ray photoelectron spectroscopy showed no sulfide layer was deposited from aqueous (NH4)(2)S alone and instead both Si and Ge oxides formed during immersion in the sulfur solution. The addition of hydrofluoric and hydrochloric acids dropped the pH from 10 to 8 and deposited sulfides, yet increased the oxide coverage on the surface and preferentially formed Ge oxides. The sulfur coverage grew with increasing concentrations of acid in the aqueous (NH4)(2)S. The simultaneous deposition of O and S is suspected to be the result of oxidized sulfur species in solution. Metal-insulator-semiconductor capacitor (MISCAP) devices were fabricated to test the electrical consequences of aqueous ammonium sulfide wet chemistries on SiGe. MISCAPs treated with acidic ammonium sulfide solutions contained fewer interface defects in the valence band region. The defect density (D-it) was on the order of 10(+12) cm(-2) eV(-1). The flat band voltage shift was lower after the acidic ammonium sulfide treatment, despite the presence of surface oxides. Adsorption of S and potentially O improved the stability of the surface and made it less electrically active. (C) 2017 American Vacuum Society.

by Ka-wai Wong. / Thesis (M.Phil.)--Chinese University of Hong Kong, 1995. / Includes bibliographical references (leaves 106-109). / TABLE OF CONTENTS --- p.i / ABSTRACT --- p.v / LIST OF FIGURES --- p.vi / LIST OF TABLES --- p.xi / LIST OF ABBREVIATIONS --- p.x / Chapter Chapter 1 --- Research Background --- p.1 / Chapter 1.1 --- Introduction --- p.1 / Chapter 1.2 --- The effect of solid acceptance angle --- p.2 / Chapter 1.3 --- Research goals --- p.4 / Chapter 1.3.1 --- Determination of the electron spectrometer transmission function --- p.4 / Chapter 1.3.2 --- Novel depth profiling technique by adjusting the solid acceptance angle --- p.6 / Chapter 1.3.3 --- Correction to conventional ARXPS --- p.8 / Chapter 1.4 --- Thesis Structure --- p.8 / Chapter Chapter 2 --- Fundamentals of X-ray Photoelectron Spectroscopy --- p.9 / Chapter 2.1 --- Introduction --- p.9 / Chapter 2.2 --- X-ray Photoelectron Spectroscopy (XPS) --- p.9 / Chapter 2.2.1 --- Basic principles --- p.9 / Chapter 2.2.2 --- Surface sensitivity --- p.11 / Chapter 2.2.3 --- A typical XPS spectrum --- p.13 / Chapter 2.3 --- Qualitative analysis --- p.16 / Chapter 2.3.1 --- Binding energy --- p.16 / Chapter 2.3.2 --- Chemical state information --- p.17 / Chapter 2.4 --- Quantitative analysis --- p.20 / Chapter 2.4.1 --- Factors affecting intensity --- p.20 / Chapter 2.4.2 --- Homogeneous materials --- p.22 / Chapter 2.4.3 --- Layer structure --- p.23 / Chapter Chapter 3 --- Instrumentation --- p.26 / Chapter 3.1 --- XPS spectrometer --- p.26 / Chapter 3.1.1 --- Magnetic immersion lens system --- p.26 / Chapter 3.1.2 --- Tunable iris --- p.29 / Chapter 3.1.3 --- Scan plates --- p.29 / Chapter 3.1.4 --- Input lens aperture --- p.32 / Chapter 3.2 --- Calibration of the iris --- p.32 / Chapter 3.3 --- Applications --- p.35 / Chapter 3.3.1 --- Two dimensional XPS imaging --- p.35 / Chapter 3.3.2 --- ARXPS --- p.37 / Chapter 3.4 --- Summary --- p.37 / Chapter Chapter 4 --- Determination of electron spectrometer transmission function --- p.38 / Chapter 4.1 --- Introduction --- p.38 / Chapter 4.2 --- Traditional method of determination --- p.39 / Chapter 4.3 --- Methodology of the novel approach --- p.40 / Chapter 4.4 --- Calculation Procedures and Results --- p.48 / Chapter 4.5 --- Results and Discussions --- p.50 / Chapter 4.6 --- Conclusions --- p.57 / Chapter Chapter 5 --- "Depth Profiling by Adjusting the Solid Acceptance Angle: a Starting Point to “ Three-Dimensional Imaging""" --- p.59 / Chapter 5.1 --- Introduction --- p.59 / Chapter 5.2 --- Theoretical Background --- p.60 / Chapter 5.2.1 --- Quantification of Intensity --- p.60 / Chapter 5.3 --- Experimental --- p.69 / Chapter 5.3.1 --- Operation --- p.69 / Chapter 5.3.2 --- Calibration of iris --- p.70 / Chapter 5.3.3 --- Novel depth profile by adjusting the solid acceptance angle --- p.71 / Chapter 5.4 --- Results and Discussions --- p.71 / Chapter 5.4.1 --- Depth Profiles --- p.71 / Chapter 5.4.2 --- "Concept of ""Three-Dimensional XPS Imaging""" --- p.72 / Chapter 5.5 --- Conclusions --- p.76 / Chapter Chapter 6 --- Correction to Quantitative X-ray Photoelectron Spectroscopy with Consideration of the Solid Acceptance Angle --- p.79 / Chapter 6.1 --- Introduction --- p.79 / Chapter 6.2 --- The effect of the solid acceptance angle --- p.80 / Chapter 6.3 --- Theoretical Background --- p.83 / Chapter 6.4 --- Results and Discussions --- p.87 / Chapter 6.4.1 --- Homogeneous Sample --- p.87 / Chapter 6.4.2 --- Layer structure --- p.90 / Chapter 6.4.3 --- Simulation plots and further investigation --- p.92 / Chapter 6.5 --- Conclusions --- p.101 / Chapter Chapter 7 --- Conclusion --- p.103 / Acknowledgment --- p.105 / References --- p.106

<p>This report presents a model to determine the solar Extreme UltraViolet (EUV) intensity and the ion flux in the vicinity of Saturn, by using measurements from the Langmuir probe, a plasma investigation instrument, of the Cassini satellite. The model is based on in situ measurements and does therefore provide an improved estimation of the wanted parameters compared to previously used calculations based only on the EUV flux measured near Earth. The solar EUV and ion flux were determined by analysing and processing the current measurements from the Cassini Langmuir probe in several steps. Initially the time intervals where the measured current were expected to be due only to the photoelectron current was extracted. The photoelectron current is the part of the measured probe current that is only due to electrons ejected from the probe by photons coming from the Sun. The measurements showed a periodic behaviour which was concluded to be due to the attitude of the satellite. This interfering effect was corrected for and the data was then plotted against an EUV index, estimated from a traditionally used proxy of the EUV flux near Earth; the F10.7 solar radio flux index. In agreement with the theory of the photoelectric effect a linear relationship between the EUV flux and the photoelectron current <em>m_ph</em> was expected. A least square linear fit to the extracted photoelectron current data provided the relation, for the Langmuir probe on Cassini, in the form of the equation <em>m_ph</em>=0.1842<em>EUV</em>+0.2405, where <em>m_ph</em> is the photoelectron current in nA and <em>EUV</em> is the EUV index in W/Hzm^2. The derived equation is the result of the study, showing how to estimate the solar EUV flux using the Langmuir probe current measurements. This result was used to derive the other wanted parameter, the ion flux. The derivation was done by calculating the photoelectron current <em>m_ph </em>at all time and subtracting the result from the total current. The retrieved difference gives the magnitude of the ion current for every measurement.</p>

<p>In order to develop blood biocompatible materials a heparin surface and a phosphorylcholine (PC) functionalized polymer surface were characterized using photoelectron spectroscopy (PES). The formation of the heparin surface was studied by quartz crystal microbalance with dissipation monitoring (QCM-D). This heparin surface consists of heparin conjugates deposited on a conditioning layer, applied once or twice. The PC functionalized polymer, poly(trimethylene carbonate), was linked to a silicon substrate through 3-amino- propyltrimethoxysilane (APTMS), also studied using PES. </p><p>Synchrotron radiation based PES showed that the thicker heparin film resulted in complete coverage of the substrate, while the thinner did not. This could explain the difference in blood biocompatibility between the two films, as observed by others. It was also found that the heparin chains bend down towards the substrate (under vacuum). </p><p>For the thinner heparin film the modifications, resulting from extensive irradiation of the sample, were studied with synchrotron radiation based PES. This was done at a pressure of about 10^-7 mbar and in 0.5 mbar water vapor. It was found that the modification is slower under water vapor than at low pressures and that the damaged film incorporates water upon exposure.</p><p>The heparin coating was found to be stable and wear resistant enough to still be present on artificial heart valves after three weeks testing in circulating plasma. It then had about the same antithrombin uptake as a non-tested surface. The film was, however, partly destroyed by the durability test and plasma proteins were deposited. </p><p>The PC functionalized, APTMS linked polymer was found to be much shorter than could be expected from random reactions. One plausible explanation is an interaction between the PC group and the silane surface, favoring aminolysis close to the PC group. This is consistent with our finding that the PC group bends down towards the surface.</p>

In order to develop blood biocompatible materials a heparin surface and a phosphorylcholine (PC) functionalized polymer surface were characterized using photoelectron spectroscopy (PES). The formation of the heparin surface was studied by quartz crystal microbalance with dissipation monitoring (QCM-D). This heparin surface consists of heparin conjugates deposited on a conditioning layer, applied once or twice. The PC functionalized polymer, poly(trimethylene carbonate), was linked to a silicon substrate through 3-amino- propyltrimethoxysilane (APTMS), also studied using PES. Synchrotron radiation based PES showed that the thicker heparin film resulted in complete coverage of the substrate, while the thinner did not. This could explain the difference in blood biocompatibility between the two films, as observed by others. It was also found that the heparin chains bend down towards the substrate (under vacuum). For the thinner heparin film the modifications, resulting from extensive irradiation of the sample, were studied with synchrotron radiation based PES. This was done at a pressure of about 10-7 mbar and in 0.5 mbar water vapor. It was found that the modification is slower under water vapor than at low pressures and that the damaged film incorporates water upon exposure. The heparin coating was found to be stable and wear resistant enough to still be present on artificial heart valves after three weeks testing in circulating plasma. It then had about the same antithrombin uptake as a non-tested surface. The film was, however, partly destroyed by the durability test and plasma proteins were deposited. The PC functionalized, APTMS linked polymer was found to be much shorter than could be expected from random reactions. One plausible explanation is an interaction between the PC group and the silane surface, favoring aminolysis close to the PC group. This is consistent with our finding that the PC group bends down towards the surface.

This report presents a model to determine the solar Extreme UltraViolet (EUV) intensity and the ion flux in the vicinity of Saturn, by using measurements from the Langmuir probe, a plasma investigation instrument, of the Cassini satellite. The model is based on in situ measurements and does therefore provide an improved estimation of the wanted parameters compared to previously used calculations based only on the EUV flux measured near Earth. The solar EUV and ion flux were determined by analysing and processing the current measurements from the Cassini Langmuir probe in several steps. Initially the time intervals where the measured current were expected to be due only to the photoelectron current was extracted. The photoelectron current is the part of the measured probe current that is only due to electrons ejected from the probe by photons coming from the Sun. The measurements showed a periodic behaviour which was concluded to be due to the attitude of the satellite. This interfering effect was corrected for and the data was then plotted against an EUV index, estimated from a traditionally used proxy of the EUV flux near Earth; the F10.7 solar radio flux index. In agreement with the theory of the photoelectric effect a linear relationship between the EUV flux and the photoelectron current mph was expected. A least square linear fit to the extracted photoelectron current data provided the relation, for the Langmuir probe on Cassini, in the form of the equation mph=0.1842EUV+0.2405, where mph is the photoelectron current in nA and EUV is the EUV index in W/Hzm^2. The derived equation is the result of the study, showing how to estimate the solar EUV flux using the Langmuir probe current measurements. This result was used to derive the other wanted parameter, the ion flux. The derivation was done by calculating the photoelectron current mph at all time and subtracting the result from the total current. The retrieved difference gives the magnitude of the ion current for every measurement.

This work is to study the interface properties of Gallium-Gadolinium oxide / GaAs structures. The samples we probed were produced by depositing oxide films in situ on freshly grown n type GaAs (100) surface. Three different oxides were deposited : Ga2O3, Gd2O3, and (Ga2O3-Gd2O3) oxide mixture. Structural properties of the interfaces have been investigated by X-ray photoelectron spectroscopy (XPS). Using Ar+ sputtering to remove the oxide layer step by step, we are able to observe the depth profiles of these samples. No Asenic or Asenic oxides are observed at the interfaces of these samples. The Ga(3d) of Ga2O3 / GaAs interface shows three different oxidation states, whose binding energies are 21.5eV, 21.0eV and 20.3eV, respectively. The binding energy of O (1s) core level is about at 530eV. For (Ga2O3-Gd2O3) / GaAs, Ga(3d) peaks exhibit at 21.0eV and 20.3eV. Also, two O (1s) peaks were clearly observed: one is Ga-O at 532.2eV and the other is Gd-O at 530.1eV. For the Gd2O3 / GaAs, only one Ga(3d) peak shows at 20.3eV, and the O (1s) spectra exhibit two peaks related to Ga-O at 532eV and Gd-O at 530eV, similar to the data of (Ga2O3-Gd2O3) sample. In conclusion, the Ga2O3 / GaAs interface has a Ga2O3 and two non-fully oxidized GaxOy states (i.e. Ga+1, Ga+2). The (Ga2O3-Gd2O3) layer consists two non-fully oxidized GaxOy states. For the Gd2O3 / GaAs interface, the GaxOy (Ga+1) state is formed possibly by the competitive oxidation of Ga, which diffused from the GaAs substrate, with the Gd2O3.

The purpose of this thesis is to probe microscopic compositions and electronic structures at the high-£edielectric-semiconductor interfaces. The samples are prepared by electron beam evaporation, including Y2O3/Si, (Ga2O3-Gd2O3)/GaAs, Gd2O3/GaAs, Gd2O3/GaN and (Ga2O3-Gd2O3)/GaN. The thermal annealing effects on the interfacial properties have been investigated by depth-profiling X-ray photoelectron spectroscopy (XPS) with synchrotron radiation beam. The depth-profiling XPS data show the O-H bonding in all the measured oxide layers. For Y2O3/Si, the hydroxide can be removed by surface desorption at 300¢J, while a Y-Si-O-H state maintained at the interface. The data suggests that the Y-Si-O-H state is possibly formed in the deposition process. For (Ga2O3-Gd2O3)/GaAs, the hydroxide can be removed by surface desorption at 100¢J, and GaOx and GaOy intermediary states have been observed. For Gd2O3/GaAs, the hydroxide can be removed by surface desorption at 250¢J, and a GaOx intermediary state has been observed, and no arsenic oxides have been detected. For Gd2O3/GaN and (Ga2O3-Gd2O3)/GaN, a GaOx intermediary state and little N-O bonding have been observed. Comparing the XPS relative intensity of the N 1s states, (Ga2O3-Gd2O3)/GaN shows a more stable interface than Gd2O3/GaN.

Thesis (Ph. D.)--University of Texas at Austin, 2001. / Vita. Includes bibliographical references. Available also from UMI Company.