Surface segregation in HAYNES 230 alloy

The surface segregation in the Ni-based alloy HAYNES 230 was studied by Auger Electron Spectroscopy and X-ray Photoelectron Spectroscopy between 400 and 1100 °C. The qualitative variations of the surface contents of S, P, W, Mo, N, Si, and Mn were determined as a function of annealing temperature and time. It was found that at 925 °C the maximum coverage of sulphur at the alloy surface is in the range 0.06-0.15 monolayers. Chromium evaporation from the HAYNES 230 surface under UHV conditions is clearly evidenced for annealing at 1100 °C.     

La1−xCaxCoO3 perovskite-type oxides: Identification of the surface oxygen species by XPS

A detailed study of the La_1−xCa_xCoO₃ perovskites surface by XPS was carried out since this is a potentially useful tool to identify the oxygen species involved in the catalytic reaction and discriminate them. Mainly, the concentration of surface oxygen vacancies (λ′) can be estimated from the XPS atomic ratio.     

Electrical characterization and carrier transportation in Hf-silicate dielectrics using ALD gate stacks for 90 nm node MOSFETs

Metal-oxide-semiconductor capacitors (MOSCs) and metal-oxide-semiconductor field-effect transistors (MOSFETs) incorporating hafnium silicate (Hf-silicate) dielectrics were fabricated by using atomic layer deposition (ALD). The electrical properties of these Hf-silicate thin films with various postnitridation annealing (PNA) temperatures were then examined to find the best nitridation condition. It is found that the best conditions to achieve the lowest gate leakage current and best equivalent oxide thickness (EOT) are when PNA is performed at 800 °C in NH₃ ambient for 60 s. To understand the obtained film, carrier transportation mechanisms, the temperature dependence of the leakage current was measured from 300 K to 500 K for both gate injection and substrate injection. The result reveals that the leakage mechanisms involve Schottky emission at high temperature and low electrical field and Poole-Frenkle emission at low temperature and high electrical field. The barrier heights of poly-Si/Hf-silicate and Hf-silicate/Si interfaces extracted from Schottky emission are 1.1 eV and 1.04 eV, respectively. The interface traps per unit area, the mean density of interface traps per area and energy and the mean capture cross-section are determined about 8.1 × 10¹⁰ cm⁻², 2.7 × 10¹¹ cm⁻² eV⁻¹ and 6.4 × 10⁻¹⁵ cm⁻² using charge pumping method.     

Investigation of Oxygen Vacancy and Interstitial Oxygen Defects in ZnO Films by Photoluminescence and X-Ray Photoelectron Spectroscopy

ZnO films prepared at different temperatures and annealed at 900^o C in oxygen are studied by photoluminescence （PL） and x-ray photoelectron spectroscopy （XPS）. It is observed that in the PL of the as-grown films the green luminescence （GL） and the yellow luminescence （YL） are related, and after annealing the GL is restrained and the YL is enhanced. The 0 ls XPS results also show the coexistence of oxygen vacancy （Vo） and interstitial oxygen （Oi） before annealing and the quenching of the Vo after annealing. By combining the two results it is deduced that the GL and YL are related to the Vo and Oi defects, respectively.     

An XPS study of CrOx on a thin alumina film and in alumina supported catalysts

We have investigated chromium layers evaporated onto a thin alumina film at room temperature. The oxidation and reduction behavior of this model catalyst was compared to atomic layer deposition (ALD) and impregnated alumina supported catalysts using X-ray photoelectron spectroscopy (XPS) with a detailed analysis method utilizing asymmetric peak shapes to represent both metallic and oxidic states. The ALD and impregnated catalysts were measured after calcination in air and after reduction with several gases at 850 K. Both catalysts show Cr³⁺ and Cr⁶⁺ species after calcination and mostly Cr³⁺ after reduction. The chromium layers deposited in vacuum show initially small partial oxidation due to the interaction with the oxygen terminated alumina film. These model catalysts can be oxidized in vacuum to Cr³⁺ species but not to higher oxidation states. The model catalysts were also subjected to calcination and reduction treatments after deposition in vacuum. Under these conditions the model systems exhibit similar oxidation/reduction behavior as the supported catalysts. Photoreduction of Cr⁶⁺ during the measurements was also studied and found to be very slow having a negligible effect on the results.     

Auger electron spectroscopy of Au/NiOx contacts on p-GaN annealed in N2 and O2 + N2 ambients

We have designed a promising contact scheme to p-GaN. Au/NiO_x layers with a low concentration of O in NiO_x are deposited on p-GaN by reactive dc magnetron sputtering and annealed in N₂ and in a mixture of O₂ + N₂ to produce low resistivity ohmic contacts. Annealing has been studied of NiO_x layers with various contents of oxygen upon the electrical properties of Au/NiO_x/p-GaN. It has been found that the Au/NiO_x/p-GaN structure with a low content of oxygen in NiO_x layer provides a low resistivity ohmic contact even after subsequent annealing in N₂ or O₂ + N₂ ambient at 500 °C for 2 min.Auger depth profiles and transmission electron microscopy (TEM) micrographs reveal that while annealing in O₂ + N₂ ambient results in reconstruction of the initial deposited Au/NiO_x/p-GaN contact structure into a Au/p-NiO/p-GaN structure, annealing in N₂ brings about reconstruction into Au/p-NiO/p-GaN and Ni/p-NiO/p-GaN structures. Hence, in both cases, after annealing in N₂ as well as in O₂ + N₂ ambient, the ohmic properties of the contacts are determined by creation of a thin oxide layer (p-NiO) on the metal/p-GaN interface. Higher contact resistivities in the samples annealed in O₂ + N₂ ambient are most likely caused by a smaller effective area of the contact due to creation of voids.     

Behavior of N atoms in atomic-order nitrided Si0.5Ge0.5(1 0 0)

Behavior of N atoms in atomic-order nitrided Si_0.5Ge_0.5(1 0 0) by heat treatment in Ar at 600 °C was investigated by X-ray photoelectron spectroscopy (XPS). For thermal nitridation by NH₃ at 400 °C, nitridation of surface Si atoms tends to proceed preferentially over nitridation of surface Ge atoms. It is also clear that, with the heat treatment, nitridation of Si atoms proceeds by transfer of N atoms from Ge atoms. Angle-resolved XPS results show that Ge fraction beneath the surface nitrided layer increases significantly at 600 °C compared to the initial surface. These results indicate that preferential nitridation of Si atoms at surface over Ge atoms induces Ge segregation beneath the surface nitrided layer at higher temperatures above 400 °C.     

Scanning tunneling microscopy on self-assembled calix[4]resorcinarene monolayer adsorbates on Au(111)

Self-assembled Monolayers of calix[4]resorcinarene receptor molecules on Au(111) were studied by UHV scanning tunneling microscopy and X-ray photoelectron spectroscopy. Highly ordered monolayers were observed with domains oriented at an angle of 60° relative to each other. Molecularly resolved images were investigated and lattice constants found which depended on the preparation solvent. The STM images of two samples, one prepared in 1 mM chloroform/ethyl alcohol adsorbate solution and one in 1 mM hexane adsorbate solution are consistent with having a ×2 and 4×2 lattice, respectively. Received: 22 September 1999 / Accepted: 28 March 2000 / Published online: 11 May 2000     

Growth of a Novel Periodic Structure of SiC/AIN Multilayers by Low Pressure Chemical Vapour Deposition

A novel lO-period SiC/A1N multilayered structure with a SiC cap layer is prepared by low pressure chemical vapour deposition （LPCVD）. The structure with total film thickness of about 1.45~m is deposited on a Si （111） substrate and shows good surface morphology with a smaller rms surface roughness of f.3 nm. According to the secondary ion mass spectroscopy results, good interface of the 10 period SiC/A1N structure and periodic changes of depth profiles of C, Si, A1, N components are obtained by controlling the growth procedure. The structure exhibits the peak reflectivity close to 30% near the wavelength of 322 nm. To the best of our knowledge, this is the first report of growth of the SiC/AIN periodic structure using the home-made LPCVD system.     

XPS and LEED study of Pd and Au growth on alumina/Cu-Al surface

Metal-insulator-metal system was prepared using the single-crystalline Cu-9at.% Al(1 1 1) support. Oxidation of the substrate under well-controlled conditions at elevated temperature leads to the formation of well-ordered aluminium oxide layer. The Pd-Au topmost layer was prepared by a step-by-step deposition of both metals afterwards on the oxide layer at room temperature. Low energy electron diffraction (LEED) measurement did not confirm epitaxial growth of the metal overlayer and gave only a rise of diffuse background after each deposition step. The growth of Pd-Au overlayer exhibited Stranski-Krastanov mode influenced by intermetallic interaction between those metals. No binding energy shifts were visible for the core-level photoelectron peaks of the substrate and the oxide using X-ray photoelectron spectroscopy (XPS). In contrast, the binding energy shifts of Pd 3d and Au 4f photoelectron levels in both directions were observed during all depositions. Bimetallic interactions between the metals as well as size effects are further discussed.     

Photoluminescence and X-Ray Photoelectron Spectroscopy of p-Type Phosphorus-Doped ZnO Films Prepared by MOCVD

Reproducible p-type phosphorus-doped ZnO （p-ZnO：P） films are prepared on semi-insulating InP substrates by metal-organic chemical vapour deposition technology. The electrical properties of these films show a hole concentration of 9.02 × 10^17 cm ^-3, a mobifity of 1.05 cm^2 /Vs, and a resistivity of 6.6 Ω.cm. Obvious acceptorbound-exciton-related emission and P-induced zinc vacancy （Vzn） emission are observed by low-temperature photoluminescence spectra of the films, and the acceptor binding energy is estimated to be about 125meV. The local chemical bonding environments of the phosphorus atoms in the ZnO are also identified by x-ray photoelectron spectra. Our results show direct experimental evidence that Pzn-2Vzn shallow acceptor complex most likely contributes to the p-type conductivity of ZnO：P films.     

Desorption of chemisorbed Carbon on Mo(1 0 0) by noble gas ion sputtering: Validation of ground test measurements of ion engine lifetimes

We report desorption cross section measurements for one monolayer of chemisorbed carbon on a Mo(1 0 0) surface induced by sputtering with noble gas ions (Ne⁺, Ar⁺, Xe⁺) at different incident angles, ion energies, and substrate temperatures. Desorption cross sections were determined by using low-energy ion scattering (LEIS) to monitor the increase of the signal from the Mo substrate. A monolayer of p(1 × 1) carbon adatoms on the Mo(1 0 0) surface was created by dosing ethylene (C₂H₄) to the substrate at 800 K, and characterized by Auger electron spectroscopy (AES) and low energy electron diffraction (LEED). We find that the carbon desorption cross section increases with increasing mass and energy of the impinging ions, and there is a maximum value for the desorption cross section at an incident angle for the ions of 30° from the surface plane. The desorption cross section also increases up to a substrate temperature of 300 °C. Values for the carbon desorption cross section for carbon adatoms on Mo(1 0 0) by 400-eV Xe⁺ ion sputtering are about 2 × 10⁻¹⁵ cm², which is one order of magnitude higher than those for bulk carbon samples. This information is particularly important for evaluation of ion-engine lifetimes from ground-test measurements in which contaminant carbon is deposited on Mo accelerator grids, potentially altering the sputtering rate of the Mo. Our measurements show that monolayer amounts of carbon on Mo have desorption cross sections that are two orders of magnitude higher than estimates of what would be required to reduce the Mo erosion rate, and thus ground-test measurements can be used with confidence to predict ion-engine wear in space, from this perspective.     

Low-macroscopic field emission from silicon-incorporated diamond-like carbon film synthesized by dc PECVD

Silicon-incorporated diamond-like carbon (Si-DLC) films were deposited via dc plasma-enhanced chemical vapor deposition (PECVD), on glass and alumina substrates at a substrate temperature 300 °C. The precursor gas used was acetylene and for Si incorporation, tetraethyl orthosilicate dissolved in methanol was used. Si atomic percentage in the films was varied from 0% to 19.3% as measured from energy-dispersive X-ray analysis (EDX). The binding energies of C 1s, Si 2s and Si 2p were determined from X-ray photoelectron spectroscopic studies. We have observed low-macroscopic field electron emission from Si-DLC thin films deposited on glass substrates. The emission properties have been studied for a fixed anode-sample separation of 80 μm for different Si atomic percentages in the films. The turn-on field was also found to vary from 16.19 to 3.61 V/μm for a fixed anode-sample separation of 80 μm with a variation of silicon atomic percentage in the films 0% to 19.3%. The turn-on field and approximate work function are calculated and we have tried to explain the emission mechanism there from. It was found that the turn-on field and effective emission barrier were reduced by Si incorporation than undoped DLC.     

Photoemission studies of oxygen adsorbed on a LiAl(1 1 0) alloy surface: Role of Li segregation

We investigated that the effect of the number of segregated Li atoms on the rate of oxidation on a LiAl alloy surface. Oxygen molecules adsorbed on the LiAl alloy react with the surface atoms to form stable oxides. The segregated Li atoms at reconstructed surfaces (c(2×2) and (2×1)) enhance the oxidation rate and form stable LiAlO_x and Li₂O. The degree of enhancement of oxidation by segregated Li atoms varies as a function of O₂ exposure and annealing temperature, where the latter is directly related to the mode of surface reconstruction by Li segregation.     

Photocatalytic oxidation of natural organic adsorbates on anatase TiO2 films observed by infrared adsorption spectroscopy with a multiple internal reflection geometry

Photocatalytic oxidation of organic adsorbates on anatase TiO₂ films has been examined in different atmospheres of humid air, dry air and vacuum. The photocatalytic oxidation was observed by IR absorption spectroscopy (IRAS) with a multiple-internal-reflection (MIR) geometry. The photocatalytic oxidation is the fastest in the air at a humidity of 70% where oxygen and water vapor are consuming to produce OH radicals and O₂⁻ anions on the TiO₂ surface with the UV exposure. In the dry air, a rate of the photocatalytic oxidation is almost 30% of that in the humid air, where only O₂⁻ anions oxidize the organic adsorbates. In vacuum, on the other hand, it is negligible, which suggests that adsorbed H₂O molecules do not play an important role in the photocatalytic reaction. It is suggested that an addition of the water vapor is necessary to achieve the higher catalytic activity.     

The role of atomic hydrogen in pre-epitaxial silicon substrate cleaning

The cleaning of silicon (Si) surfaces is a very important issue for the fabrication of novel semiconductor devices on the nanoscale. Established methods for the removal of organic impurities and the native or chemical oxide are often combined with high temperature desorption steps. However, devices with small feature sizes will be unfunctional if, for example, out-diffusion of dopants is not prevented. In this paper we present two possible processes for low-temperature cleaning: an atomic hydrogen source, based on dissociative adsorption of hydrogen at a heated tantalum (Ta) surface and a hydrogen DC plasma source as a part of an UHV cluster tool. The influence of atomic hydrogen on carbon and oxide removal is surveyed and the existing model for native oxide etching with an argon/hydrogen DC plasma is adapted.     

Chemical characterization of gallium droplets grown by LP-MOCVD

This study is concerned with the chemical characterization of metallic gallium droplets, obtained on silicon (1 0 0) substrates with a single growth step, by the LP-MOCVD technique with TMGa like precursor. These structures are characterized by SIMS, XPS and TEM. The analyses results lead to a structure proposition for the droplets. The core is composed of metastable metallic gallium with a non-negligible carbon quantity probably coming from incomplete precursor decomposition. The outer part, composed of gallium oxide maintains the structure stability. Covering of the substrate by a thin gallium layer of gallium compounds is observed.     

Characterization of Ohmic contacts on GaN/AlGaN heterostructures

The surface morphology and electrical resistance of the contacts on semiconductor devices are strongly influenced by metallization scheme and annealing conditions. In this work is presented an investigation of Ohmic contacts formed by metal-semiconductor alloying on epitaxial GaN/AlGaN heterostructures. After the deposition of metallic multi-layers (Ti, Al, Au and Pt), the process of rapid thermal annealing was carried out in nitrogen, argon and forming gas atmosphere.A series of the samples with different sequences of metallic layers and diverse thicknesses was prepared by employing electron beam evaporation and lift-off deposition techniques. The chemical composition of the samples before and after annealing was studied by means of X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) techniques combined with low energy Ar⁺ ion sputtering. The sputtering has been carried out in two different modes: by using constant (square) or gradually narrowed sputtered area. The changes in the chemical state of constituent elements and compositional profiles of the contacts after thermal annealing were revealed from the obtained results. Among the technological problems, influencing on the quality of the contact, were found to be the oxidation and nitridation of the contact surface during thermal annealing, as well as the intermediate sub-layers of Al and Ti oxides, formed during the deposition of metallic multi-layered structure.     

Organisation of carbon and boron nitride layers in mixed nanoparticles and nanotubes synthesised by arc discharge

2 bonds attests for the presence of ordered BN domains and of carbon domains; (ii) the elemental profiles show that BN layers and carbon layers are immiscible with a radial organisation into two to five domains; and (iii) the sets of layers at free surfaces – including the inner surfaces of tubes – are always made of carbon. The origin of this chemical organisation, which is most likely obtained during the growth, is discussed. For the hafnium-boride metallic particles coated by C/BN envelopes, a model based on the solidification from the outside to the inside of isolated liquid-like droplets is proposed: the carbon phase solidifies first according to theoretical phase diagrams, and forms the outer shells. For the tubes, a directional eutectic solidification process is shown to account for the observed C/BN/C sequence, in a vapour–liquid–solid scheme, with an hafnium-rich liquid-like particle at the tip of the tube. Received: 26 November 1998 / Accepted: 14 January 1999     

Surface roughening in Si1−xGex alloy films by 100 MeV Au: Composition dependency

Using a 100 MeV Au beam, the surface roughening kinetics of relaxed Si_1−xGe_x alloy films for x=0.5 and 0.7 are studied by means of ex-situ atomic force microscopy (AFM). Swift heavy ion (SHI) irradiation induced surface roughening behavior is demonstrated using the trend in variation of β as a function of fluence when the data are analyzed in terms of the Edwards-Wilkinson (EW) model. By employing the EW model, the observed surface roughening is explained on the basis of the competition between SHI induced sputtering and smoothening through redeposition of the sputtered atoms. The composition dependent variation of surface morphology with increasing fluence is discussed in the light of the strain distribution along the sample surface.