The influence of oxygen vacancies on the chemical bonding in titanium oxide

A self-consistent LAPW band structure calculation for TiO_0.75 has been performed, assuming long-range order of vacancies on the oxygen sublattice. The calculation is based on a hypothetical model structure which can be described as Ti ₃ ^[4] Ti^[6]O_3o, where _o denotes an oxygen vacancy. In the model structure two types of titanium atoms occur: Ti^[4] atoms which have two vacancies as neighbours and are quadratically surrounded by four oxygen atoms, and Ti^[6] atoms which are octahedrally surrounded by six oxygen atoms. The calculated density of states (DOS) and the local partial densities of states are compared with the respective values for stoichiometric TiO containing no vacancies. A characteristic difference is the appearance of two sharp peaks in the DOS curve below the Fermi energy which are caused by the vacancies. These vacancy states exhibit a considerable amount of charge in the vacancy muffin-tin sphere and are found to be derived from Ti 3d states extending into the vacancy sphere. The introduction of vacancies also leads to a lowering of the Fermi energy indicating a stabilizing effect. The bonding situation in TiO_0.75 as compared to TiO as well as the changes in chemical bonding in the series TiC_0.75–TiN_0.75–TiO_0.75 are discussed on the basis of electron density plots. The loss of Ti^[4]–O bonds (as compared to TiO) is compensated by the formation of Ti^[4]–_o–Ti^[4] bonds across the vacancy and by an increase of the bond strength of the Ti^[4]–O bonds. On the other hand, the Ti^[4]–Ti^[4] and particularly the Ti^[4]–Ti^[6] bonds are weakened by the introduction of vacancies.Dedicated to Professor F. Kohler on the occasion of his 65^th birthday     

Investigation of titanium and titanium hydride by AES and EELS

Effects of hydriding on the Auger spectrum of titanium are investigated and can clearly be distinguished from the changes induced by oxygen contamination of the surface. New transitions occur about 5 eV below all transitions involving metal valence band electrons. Beam induced decomposition of the hydride could be avoided by proper experimental procedure. The composition of the investigated hydride was inferred from the measured bulk plasmon energy shift.     

Depth dependence of photoluminescence and chemical bonding in porous silicon

Porous silicon (PS) is studied by stepwise peeling of the surface layer to clarify the non-uniformity in the photoluminescence (PL) and correlate it with the in-depth chemical bonding and structure of the 30 μm thick layer. The PL intensity grows by an order of magnitude after the peeling off of the first 10 μm and decreases five times in the next 5 μm while the peak maximum position shifts from 730 to 800 nm. X-ray photoelectron spectroscopy (XPS) measurements show that Si–Si and Si–O bonds are present both on the surface and below, and the preferential oxidation state of silicon changes from 3+ and 4+ on the surface to 1+ and 2+ below 10 μm. Using Raman spectroscopy silicon nanocrystals are shown to exist. Their mean size can be estimated at about 3 nm. These results show that the strongest PL comes from a region in the PS layer where silicon nanocrystallites are surrounded by oxides with a low level of oxidation and not from the strongly oxidized surface layer.     

Study by AES of the titanium nitruration in the growing of TiN thin films by PLD technique

A series of different TiN_x thin films were grown by PLD. The purpose for this work was to study through the AES interpretation, how the different conditions of the partial pressure of N inside the chamber during the growing of these thin films, affects the stoichiometry of the TiN_x deposited. The results obtained were that the different thin films change each one through TiN_x (x = 0.88-1.33). The results were supported with XPS and EELS spectroscopy doing also an analysis of elemental ratio to show the stoichiometry and sub-stoichiometry obtained. This work concludes the adequate conditions for this experiment to obtain TiN as thin film by PLD at room temperature, supported with the results in the present work and the interpretation of the AES spectra even when Ti and N peaks overlap.     

Avoiding silicon/glass bonding damage with fusion bonding method

A novel fusion bonding method between silicon and glass with Nd:YAG laser is described.This method overcomes the movable mechanical parts damage caused by the electrostatics force in micro-electronic machine-system(MEMS)device during the anodic bonding. The diameter of laser spot is 300 μm,the power of laser is 100 W,the laser velocity for bonding is 0.05 m/s,the average bonding tension is 6.3 MPa.It could distinctly reduce and eliminate the defects and damage,especially in movable sensitive mechanical parts of MEMS device.     

A sensitive technique for detecting chemical changes by AES

The measurement of Auger currents and their associated peak to peak heights from the first derivative spectra has provided the basis for an analysis of the various stages of nitric oxide absorption onto a W(110) surface at room temperature. This chemisorption system is a test case for the method since the nitrogen and oxygen KLL Auger spectra in first derivative form look similar at all stages of adsorption. The results indicate that the method is sensitive to chemical changes in the adsorbate to an extent comparable with XPS.     

Integration of GaN thin films with silicon substrates by fusion bonding and laser lift-off

GaN thin films grown on sapphire substrates by metalorganic chemical vapor deposition (MOCVD) are successfully bonded and transferred onto Si receptor substrates using fusion bonding and laser lift-off (LLO) technique. GaN/Al2O3 structures are joined to Si substrates by pressure bonding Ti/Au coated GaN surface onto Ti/Au coated Si receptor substrates at the temperature of 400 ℃. KrF excimer laser with 400-m J/cm2 energy density, 248-nm wavelength, and 30-ns pulse width is used to irradiate the wafer through the transparent sapphire substrates and separate GaN films from sapphire. Cross-section scanning electron microscopy (SEM) combined with energy dispersive X-ray spectrometer (EDS) measurements show that Au/Si solid solution is formed during bonding process. Atomic force microscopy (AFM) and photoluminescence (PL) measurements show that the qualities of GaN films on Si substrates degrade little after substrates transfer.     

Relative sensitivity factors of aluminum,silicon and phosphorus against iron,and those of titanium,vanadium, chromium,iron and nickel against silicon for AES

Relative Sensitivity Factors (RFs) for Fe, P, A1, Ti, V, Cr, Ni and Si Auger peaks are reported. Care must be taken when using RFs values for compounds owing to matrix effects.     

AES and ELS study of titanium oxidation in high vacuum

In the present work, results of the interaction of O₂ with polycrystalline titanium using AES, and ELS techniques, are presented. Changes in the shapes of Ti(LMV) and Ti(LMM) transitions and in the Ti(LM)O(V)/Ti(LMV) and Ti(LMV) Ti(LMM) amplitude ratios as well as a shift of the 34 eV loss peak [Ti(3p level], are studied as function of the oxygen exposure.At O₂ pressures equal or less than 10^–6 Pa and exposure up to 2000 L(O₂) (weak oxidation), the Ti(LM)O(V)/Ti(LMV) and Ti(LMV)/Ti(LMM) ratios show three clearly distinct regions: (i) up to 20L there is a chemisorbed phase with the Ti(LMV)/Ti(LMM) ratio remaining constant and a fast linear increase in the Ti(LM)O(V)/Ti(LMM) ratio. (ii) At exposures higher than 20L the oxidation begins being characterized by a linear variation of the Ti(LM)O(V)/Ti(LMV) and Ti(LMV)/Ti(LMV) ratios, with positive and negative slopes, respectively. (iii) At 125L there is a change in both slopes but no stable value is achieved, despite the O(KLL)/Ti(LMM) ratio remains constant. Hence, it can be concluded that TiO is the final oxide obtained after that treatment, from features like the shape of the transitions and a maximum shift of 3eV of the Ti(3p) level, complemented with ESD experiments.On the other hand, experiments at pressures higher than 10^–4Pa with or without the surfaces at 900K (strong oxidation) indicate that the most likely final oxide is TiO₂.Work presented to the IXIVC-VICSS. Madrid (1983)     

Study of silicon implanted with zinc and oxygen ions via Rutherford backscattering spectroscopy

The structural features and dopant profiles of a Si surface layer implanted with Zn⁺ and O⁺ ions are studied via Rutherford backscattering spectroscopy based on the analysis of He²⁺-ion spectra with the use of the channeling technique. The doping-impurity redistribution is analyzed upon the formation of zinc-oxide nanoparticles. The sample surface morphology is examined by means of atomic-force microscopy and scanning electron microscopy under secondary-electron emission conditions. X-ray phase analysis of the implanted layers is carried out.     

Directionality of the metallic bonding in titanium carbide

The ionic-covalent bonding in TiC is studied within a CNDO parameterized cluster model. Distribution of charge density reveals a directionality of the Ti-Ti metal bond as observed in the Ti dimer. This directionality is particularly significant at the Fermi level because of hybridisation involving d_xy ,d_xy and d_yz types of states. However, in the presence of a carbon vacancy the directionality of the metal bond is not as clear with charge spilling over into the vacant lattice site. The directional nature of the Ti-Ti bond at the Fermi level remains fairly unchanged.     

Study of the electrical and optical properties of silicon containing oxygen precipitates

The properties of n-type silicon with oxygen precipitates introduced by three-stage annealing were studied by the electron beam induced current (EBIC) method, deep-level transient spectroscopy (DLTS), and photoluminescence (PL). The presence of extended defects with concentration of ≤10⁹ cm^?3 is revealed by the EBIC method. The concentration of electrically active defects formed in silicon due to oxygen precipitation is estimated from the EBIC contrast and is compared to that obtained from the DLTS data. Comparing the spectra of samples with oxygen precipitates with those of plastically deformed crystals, we can assume that the DLTS and PL spectra of silicon with oxygen precipitates are mainly determined by dislocations.     

Direct bonding of silicon wafers with the concurrent formation of diffusion layers

An original technique for Si-Si direct bonding combined with impurity diffusion in a single process is suggested. A dopant (aluminum) source is located at the interface. The high-temperature treatment of the polished wafers in an oxidizing atmosphere results in the diffusion of Al atoms and the formation of a p-n junction in n-silicon. The presence of aluminum is shown to improve the continuity of the interface. Results obtained are explained within a model whereby the initial contact between the hydrophilic silicon surfaces in a water solution of aluminum nitrate Al(NO₃)₃ serves to increase the bonding area of the wafers at room temperature due to the interaction of Al-OH groups with water molecules adsorbed on the surfaces of the wafers.     

Interaction of oxygen and hydrogen with Pd-Au alloys: An AES and XPS study

Pd-Au alloys of three different concentrations have been studied with Auger Electron Spectroscopy and Photoelectron Spectroscopy. A quantitative method shows that the decontaminated surfaces possess the same composition as the bulk. Interaction of oxygen up to 600°C with gold rich alloys (>85%) is very weak. It starts around 300°C on the other two alloys and results in a significant palladium surface enrichment. On the 60 at% Pd-Au alloy, at 500–580°C, the surface may be completely covered with PdO. A hydrogen treatment at 350°C leads to a complete reduction of the oxide without reequilibration of the surface.     

Fabrication of silicon wafer with ultra low reflectance by chemical etching method

A pyramid and nanowire binary structure of monocrystalline silicon wafer was fabricated by chemical etching. Much lower reflectance of silicon wafer with this structure was obtained compared with that of single pyramid or nanowaire arrays. The morphology, reflectivity and etching thickness of this structure were studied, as well as the influence on them caused by etching time and thickness of silver film. An average reflectance of 0.9% was obtained under optimized condition. The formation mechanism of silicon nanowires was explained by experimental evidence.