Dr. Costel Cotirlan

Hafnium oxide (HfO2) thin films were deposited on n-type gallium arsenide (GaAs) substrates by Oxide-Molecular Beam Epitaxy (Oxide-MBE) method using Hafnium (Hf) metallic flow in an oxidizing atmosphere of 10-6 mbar molecular oxygen. The Hf metallic flow was provided by an e-beam evaporator and a deposition rate 10 nm/h was established. Semiconductor surface preparation was done prior to deposition, beginning with chemical wet etching and aggressively adjusted by in treatments until a desired stoichiometry was reached. Heterojunctions with HfO2 thin layers of 1 nm, 3 nm, 10 nm and 20 nm were fabricated. X-Ray Photoelectron Spectroscopy (XPS) and ARXPS(Angle Resolved XPS) in-situ analyses provided a clear picture of the structure of the interfaces, the chemical bonds and composition. The interfaces are chemically stable and abrupt. A small amount of Ga2O3 provides a passivating effect of the semiconductor surface. The electrical properties of the heterostructures were determined using the Kraut method and Reflection Electron Energy Loss Spectroscopy (REELS) technique. Band offsets Delta EC=1.75 eV and Delta EV=2.62 eV confirm a high application potential. Additionally, data on the morphology and continuity of the layers were obtained by Atomic Force Microscopy (AFM) technique while the amorphous growth was monitored by XRD(X-ray Diffraction), GIXRD (Grazing Incidence XRD) and XRR(X-ray Reflectivity) measurements. The dielectric layers showed values of the constant k in the range of 19-22, established by electrical measurements on MOS capacitors.

InGeNi ohmic contacts on n-type semi-insulating GaAs(110) cleaved surfaces were fabricated. Cleaving semiconductor single crystal ensures the obtaining of semiconductor surfaces almost ideal in terms of chemical purity and stoichiometry. The chemical depth profile of metallic layer was investigated and revealed through multiple alternating steps of Ar+ etchings and XPS (x-ray photoelectron spectroscopy) measurements. The metallic layers made of alloy of Ge, In and Ni (60 nm Ge, 60 nm In and 10 nm Ni), were obtained by thermal evaporation on cleaved surfaces in a high vacuum facility, followed by a thermal annealing at 430-450 degrees C for 5 min. Twelve etching sessions were required until the metal/semiconductor interface has been reached. A total of 14 etchings steps were performed during the experiment, a layer with a thickness of 140 nm being removed from the surface. The atomic concentrations of the constituent chemical elements were determined. In3d, In4d, Ga3d, Ga2p, As3d, As2p, Ni2p(3/2), Ge3d, O1s and C1s spectral lines were recorded and chemical bonds within the layer were analyzed from the fittings. The formation of InxGa1-xAs type compounds and of an intermediate semiconductor layer rich in Ge atoms at the interface was highlighted. X-ray detectors InGeNi/GaAs/Al and InGeNi/GaAs/Ti were fabricated with ohmic contacts based on this contacting scheme and Schottky interfaces prepared also by evaporation on cleaved edges. Electrical characteristics have been investigated and key diode parameters determined - ideality factor, Schottky barrier height, series resistance. Detection capabilities of these devices were studied in an x-rays flux, provided by a Co anode x-ray source.

The depth composition of the thin layer alloy, AuGeNi, devoted to acting as an ohmic contact on n-GaAs(110) has been investigated by in situ XPS combined with Argon ion sputtering techniques. The fresh cleaved surfaces, supposed to be free of oxygen, were usually deposited with a 200nm metallic layer in high vacuum conditions (better than 10(-7) torr), by thermal evaporation, and annealed at a 430-450 degrees Celsius temperature for 5 minutes. About 18 sessions of ion Ar surfaces etching and intermediate XPS measurements were performed in order to reveal the border of the metal/semiconductor interface. The atomic concentrations of the chemical elements have been approximated. Au4f, Ga3d, Ga2p, As3d, As2p, Ni2p(3/2), Ge3d, O1s, and C1s spectral lines were recorded. The Au, Ge, and Ni have a homogenous distribution while Ga and As tend to diffuse to the surface. Oxygen is present in the first layers of the surface while carbon completely disappears after the second etching step. The existence of an Au-Ga alloy was detected and XPS spectra show only metal Ni and Ge within the layer and at the interface. We tried to perform a study about the depth chemical composition profile analysis of AuGeNi layer on cleaved n-GaAs(110) by X-Ray Photoelectron Spectroscopy (XPS) technique.

Gallium antimonide (GaSb) is the basis of the most photovoltaic and thermophotovoltaic (TPV) systems and its innovative technological aspects based on modern ultra-high vacuum techniques are in trend for device achievement. The real surface of GaSb is modified by technological processes that can conduce to problems related to the reproducible control of its surface properties. The GaSb surface is reactive in atmosphere due to oxygen presence and exhibits a native oxide layer. The evolution of native oxides during the ion sputtering, chemical etching and thermal annealing processes for preparing the surface is presented in detailed way. Ratios of surface constituents are obtained by Angle Resolved X-ray Photoelectron Spectroscopy (ARXPS). Moreover, Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDS), Atomic Force Microscopy (AFM) and Low-Energy Electron Diffraction (LEED) are used for characterization. The surface stoichiometry is changed using a specific etchant (e.g. citric acid) at different etching time and is analyzed by ARXPS, SEM, EDS and AFM methods. The experimental results provide useful information regarding surface native oxides characteristics on n-GaSb(100) to be taken into account for development of low resistance contacts for TPV devices based on GaSb alloy. (C) 2015 Elsevier B.V. All rights reserved.

A genuine GaAs surface is covered with a relatively thick layer (similar to 10 nm) of native oxide pinning the surface Fermi level within the band gap of semiconductor. The method presented in this work is related to the sulphur passivation by treating n-GaAs(100) and (110) in sulphide solutions (e.g pure ammonium sulphide and sulphur monochloride) that combines both chemical electronic passivation by reducing the surface state density. The effects of passivation were put into evidence by Photoluminescence measurements where it was observed the variation of state density. The presence of sulphur dipoles at surface was presented in a diagram of Second Harmonic Generation analysis and the general aspect of sulphur compound was identified by SEM images. The presence of the covalent bond Ga-S and the variation of surface barrier as well as the effect of crystal orientation were put into evidence by micro-Raman Spectroscopy. At the surface of n-GaAs it is developed an adherent layer of sulphur compound as a resul of chemical interaction of sulphur ions with n-GaAs surface.

A genuine GaAs surface is covered with a layer (similar to few nm) of native oxide pinning the surface Fermi level within the band gap of semiconductor. In this work is presented a study of GaAs surface passivation by sulfur compounds inorganic and organic (alkane thiols), a method that combines both chemical and electronic passivation. At the surface of GaAs it is developed an adherent layer of sulfur compound as a result of chemical interaction of sulfur ions with GaAs surface, a compound putted into evidence by scanning electron microscopy (SEM) images, photoluminescence analysis, second harmonic generation (SHG) measurement and Raman spectroscopy. Using X-ray photoelectron spectroscopy (XPS) it is putted into evidence the presence of covalent bonds Ga-S and AsS as a result of chemical interaction with sulf ions. Electrical characteristic of AuGeNi/thiol/GaAs structure is presented in I (V) recorded in the region of small currents.

A genuine GaAs surface is covered with a relatively thick layer (similar to nm) of native oxide pinning the Surface Fermi level within the band gap of semiconductor. The method presented in this work is related to sulfur passivation by treating n-GaAs in different solutions of alkane thiols. At the surface of GaAs it is developed an adherent layer of sulfur compound as a result of chemical interaction of sulfur ions with GaAs(100) face, that are putted in evidence by scanning electron microscopy (SEM) images and second harmonic generation (SHG) analysis. Using X-ray photoelectron spectroscopy (XPS) is presented a detailed analysis of XPS data at the surface of thiols on GaAs together with the presence of the covalent bond As-S. The electric characteristics of the AuGeNi/Thiol/GaAs structure are presented in I (V) curves recorded in the region of small currents.

A new method, that involves Evanescent-Wave Cavity Ring-Down Spectroscopy (EW-CRDS), is presented. This method is useful for the study of thin films on optical solid surfaces. The new design of experimental set-up incorporates a semicylindrical prism with a plane surface where the Total Internal Reflection (TIR) effect appears. The antireflex (AR) coated cylindrical surface of the prism induces the stability of resonant cavity. The evanescent wave generated at the plane surface of the prism probes the absorption by matter in the vicinity of the prism. A general discussion of design criteria is presented to quantify intrinsic losses, and then absorption spectra for Rhodamine chloride R590 from 555 to 560 nm are presented to demonstrate the sensitivity of the system. The layer of R590 on BK7 surfaces is deposited from a solution of R590 in ethanol (92% purity) with 51 mg/l concentration. After vaporization of the ethanol the dye layer on surfaces is supposed to be uniform. This implementation of TIR surface in a resonant cavity provides a powerful new spectroscopic tool especially to angle-resolved diagnostic for interfaces and thin-films. The loss spectrum can be obtained for an angular range from the TIR critical angle to a maximum angle when the resonance of system is lost.

The to study of the total oxide (SiO2+SiOx) thickness, SiO2 and SiOx (e.g. Si2O, SiO, Si2O3) thicknesses on Si(100) crystalline substrate with take-off angles ranging from 30 degrees to 80 degrees has been carried out by spectrometric method. The d(s) X-ray Photoelectron Spectroscopy (XPS) thicknesses were compared with d(EL) thicknesses obtained by fitting the Spectroscopic Ellipsometry (SE) spectra. A qualitatively good correlation is revealed. However, from these estimations of film thicknesses it results that ellipsometry analysis cannot be as accurate as in XPS evaluation. This is due to uncertainty of used optical constants as well due to very thin oxide films used in this work.

The obtaining of a good ohmic contacts on the semiconductor material surfaces is strongly depending on the ability of the cleaning procedures to remove the native oxides and also, in the case of the compounds, to keep the surface stoichiometry. In this work, the XPS technique has been used in order to compare the efficiency of both, chemical etching and the Ar+ ion sputtering methods as to be suitable cleaning procedures in the case of n-GaP semiconductor compound surfaces preparation for the optoelectronic devices obtaining. The results have revealed some differences in the final surface composition/stoichiometry. The atomic ratio P/Ga within the outer layer of the single crystalline sample (similar to 100 angstrom) has been evaluated. The presence of residual of surface oxides was recorded after performing the chemical cleaning.

Angle-resolved X-ray Photoelectron Spectroscopy (ARXPS) has been performed on (100) Si surfaces in different conditions as regards the oxides nature - native oxides, thermally formed oxides, and also after a cleaning procedure by Ar+ ion sputtering (e.g. E= 2 keV). The most sensitive angle to surface oxidation states (Si1+, Si2+, Si3+, Si4+) was the take-off-angle (TOA): 25 degrees. Native oxides and thermally oxide phases on Si surfaces consists in a mixture of Si2O, SiO, Si2O3 and SiO2. The XPS measurements have putted into evidence a higher concentration of suboxides in high oxidation state (Si3+) on naturally oxidized Si substrates. The thermally oxidized Silicon surfaces contain suboxides in a low oxidation state (Si1+). The Ar+ ion sputtering removed rapidly the superficial silicon oxides. The analysis and computation of SiO2 film thickness on crystalline Silicon was done in the frame of modified Bethe equation for Electron inelastic mean free path (IMFP) and taking into account the intensity of SiO2 peak and Si peak together with the TOA in the XPS measurement. Native oxide thickness for SiO2 was d(oxy) similar to 24 angstrom and for thermally oxidized sample was d(oxy) similar to 27 angstrom. Due to the slightly difference in the nature oxidation states it is suggested that the silicon dioxide appeared from two different kinetics in the oxidation processes.

Angle-resolved X-ray photoelectron spectroscopy (ARXPS) analysis has been performed on GaAs (10 0) surfaces in different conditions as naturally oxidized, Ar+ ion sputtering (E = 1-5 keV) and chemical etching in H2SO4/H2O2/H2O(3: 1: 1). The most sensitive angle to the surface compositional changes was the take-off angle (TOA): 25 degrees. Native oxide phases on GaAs consist of a mixture of Ga2O3, As2O3 and As2O5. Ar+ ion sputtering procedure modifies the surface composition, in the altered layer where the concentration ratio C-Ga/C-As tends to 1.5-1.6. Wet chemical etching removes the oxide layer and the As-rich region from the surface. In the experiment combining chemical etching with Ar+ ion sputtering for cleaning purpose, the native oxides are removed from the surface and C-Ga/C-As tends to stoichiometry. The experiment on native oxide reconstruction after storage in high-vacuum conditions (P similar to 10(-8) Torr) provides evidence of the high reactivity of GaAs (10 0) surfaces. We have observed the presence of an As oxide (BE = 43 eV) within a concentration range of 2-3%. (C) 2007 Elsevier B.V. All rights reserved.

For the fabrication of the rectifying contact, respectively the Schottky diode structure on semi-insulating GaAs (100) oriented, Cr-doped, with a resistivity of rho similar to 10(6) - 10(7) Omega cm we have used Au-Ti contact. The Ti contact was deposited on a plasma etched GaAs surface in high vacuum (10(-8) torr), Au was deposited in medium vacuum (10(-6) torr) and the Au-Ti/GaAs interface was formed by a rapid thermal annealing procedure at T = 320 - 360 degrees C in low vacuum (10(-1) torr). The representative I-V characteristics in dark and under illumination at different power levels are presented. It is worth to mention that we estimate a barrier height of Phi(B) similar to 0.84 V (in the frame of thermionic emission model). The spectral response at two operating points and at different temperatures is presented. The signal has a maximum in the Delta lambda range (850-950) nm, which corresponds to the generation of photo-carriers due to a band-to-band direct transition. (c) 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Titanium dioxide thin films prepared by sol-gel method and deposited on p-Si (111), n-GaAs (100) and glass have been investigated by Raman spectrometry and photoluminescence analysis. The films were annealed in the temperature range (500-800)degrees C in air. Raman scattering studies reveal the presence of Raman active modes in the calcinated TiO2 films related to anatase phase of titania. The photo luminescence spectrum presents prominent red shifted peaks (e.g. at 400 nm for TiO2/glass), where the maximum is related to the presence in titania films of defect levels corresponding to oxygen vacancies.