Thin Native Oxide Research Articles

The Use of Dopants for Defect Monitoring for Silicon-Germanium Ultra-High Vaccuum Chemical Vapor Deposition

Si and SiGe epitaxy via UHVCVD requires an extremely clean and oxide free substrate but has the advantage of allowing low temperature epitaxy (LTE). In-situ bake-off of thin native oxides is possible at high temperatures, but is not an option for low temperature epitaxy. As a result, LTE processes are sensitive to surface preparation and the duration between oxide removal and epitaxy growth. Traditional techniques for observing interfacial contamination, such as secondary ion mass spectroscopy, are not easily integrated into a fabrication line. In addition, the off-line measurements of monitor wafers cannot detect contamination soon enough before the product wafers have gone through extensive further processing. A new monitor has been developed and demonstrated for observing the contamination of the substrate and process that occurs after the pre-epitaxy cleaning steps. This novel monitor used an ion implanted substrate along with defect etches. The sensitivity of this monitor can be controlled by adjusting the implant dose allowing tailoring to specific process targets and needs. A dilute Secco wet etch and HCl chemical vapor etch were both demonstrated for decorating the dislocation defects caused by interfacial contaminants. Using TEM, these defects were confirmed as originating from the substrate-epitaxy interface. In-line and off-line defect counting systems were then used to quantify the defect density of the novel monitor. These monitors were shown to have sensitivity to defects caused by range of interfacial contaminants. The result of this newly integrated method is a fully line integrated defect monitor using already commonplace equipment and chemicals, that has a rapid turnaround, and that is broadly sensitive to substrate surface contaminants.

Fabrication and characterization of oxygen – Diffused titanium using spectroscopy method

A thin native oxide film that forms on the titanium surface makes contact with the bone tissue has been considered to be of great importance to successful osseointegration. The study investigated oxygen-diffused grade 2 titanium obtained by introducing oxygen into the titanium crystal lattice using thermal treatment in fluidized bed performed at 610°C and 640°C in 6, 8, 12h. The thermal treatment at different temperatures and different times led to the formation of a TiO2 rutile film on the titanium surface and a concentration gradient of oxygen into titanium (XRD/GID analyses and GDOS results). Moreover Raman spectroscopy results showed that the TiO2 film on the surface titanium was composed of two oxides (TiO2), i.e. anatase and rutile, for the analyzed variants of heat treatment.The aim of the present study was to establish the optimum conditions for obtaining oxygen-diffused TiO2 film. The results obtained in the study demonstrated that the use of a fluidized bed for titanium oxidation processes allows for obtaining uniform oxide layers with good adhesion to the substrate, thus improving the titanium surface to suit biomedical applications.

Functionalization of Aluminum Nanoparticles Using a Combination of Aryl Diazonium Salt Chemistry and Iniferter Method

In this work, we propose an original strategy for the functionalization of aluminum nanoparticles (Al NPs), based on a combination of aryl diazonium salt chemistry and the photopolymerization iniferter method. It consists in grafting coupling agents, derived from diazonium salts, at the surface of Al NPs and in initiating the photopolymerization of methacrylic acid (MAA) directly from the surface. The hybrid NPs were fully characterized using XRD, TEM, TGA, and XPS. The results show that the obtained hybrids exhibit a core-double shell structure, the metallic core being preserved while a thin natural oxide layer and a strongly anchored organic shell surround it. The controlled and living character of the photopolymerization process allowed for the control of the polymer shell thickness with the polymerization time. Interestingly, the formation of compact aryl layers derived from the diazonium salts at the surface of Al NPs appears to provide an efficient protection against oxidation.

Effect of light illumination and temperature on P3HT films, n-type Si, and ITO

The secondary electron (SE) cutoff energy region spectra are recorded before (dark), during (light) and after laser exposure (dark) for P3HT, Si, and ITO. An SE cutoff energy shift is observed when the bare n-type doped Si substrate is exposed to 532nm light. This is attributed to the presence of a thin native oxide layer (∼1.5nm) on Si. No energy shift is detected on the Ar sputtered clean Si. Also, no shift was observed for ITO. When exposed to light, a net SE energy cutoff shift was measured for P3HT deposited on both Si and ITO substrates at room temperature. However, no significant valence band maximum (VBM) energy shifts were measured for P3HT that was spun cast on both substrates under dark and light illumination. Furthermore, light effect was investigated at three different temperatures; 25, 70, and 160̊C and it is found that for P3HT, the magnitude of the SE cutoff energy change is not only substrate dependent but also depends on temperature.

The Effect of Trapped Charge on Silicon Nanowire Pseudo-MOSFETs

The effects of organic molecules grafted on top of silicon nanowires are modeled as the oxide trap charges (Qot) and interface trap charges (Qit). The device investigated here is a pseudo-MOSFET with a thick bottom oxide (200 nm) and only a thin native oxide (5 nm) on top. With Qot = -5.0 x 10(11) cm(-2) and the U-shaped distribution of interface trap density (Dit) as a function of trap energy (Et), the structures are reproduced through the conventional technology computer aided design (TCAD) simulation tool, and the channel is imaginarily divided into several sections (5 x 5 regions) to apply the localized traps. The electrical parameters are extracted from the each part to quantitatively compare their effectiveness. The local position of the grafted molecules, modeled by these charges, is shown to result in strong variations in the relative change in the threshold voltage and subthreshold swing. These variations are explained by the surface depletion and scattering near the edges of the etched device and the series resistance effect.

Mosaic-like Monolayer of Graphene Oxide Sheets Decorated with Tetrabutylammonium Ions

We report the fabrication of mosaic-like monolayers of graphene oxide (G-O) coated with tetrabutylammonium ions (TBA) using a simple spin-coating method. The TBA-coated G-O (TG-O) sheets were prepared by "spontaneous exfoliation" of graphite oxide intercalated with tetrabutylammonium hydroxide (TBAOH) in the wet state, without the need for sonication. Mosaic-like monolayers could be formed on a variety of substrates such as Si wafer (coated with the thin native oxide), SiO2/Si wafer, graphene grown by chemical vapor deposition and then transferred on SiO2/Si wafer, Au film on Si wafer, and Cu foil. The mosaic-like monolayer of TG-O was compared with monolayers of G-O and TG-O prepared using a Langmuir-Blodgett (LB) trough. The formation of the mosaic-like TG-O monolayer films was attributed to (1) weakening of the electrostatic repulsion between G-O sheets by TBA, and (2) prevention of the overlap and stacking of TG-O sheets by disruption of the hydrogen bonding between the basal plane of one sheet and the basal plane or edge of another, by adsorbed TBA. External reflection FTIR spectroscopy showed that spectral features of the mosaic-like monolayer of TG-O made by simple spin-coating were the same as those for the monolayer fabricated using the LB assembly, indicating the same spatial orientations of functional groups. This study provides a very simple route to a complete monolayer of G-O without the need for an LB trough.

Doppler Broadening Spectroscopy of Positron Annihilation near Ge and Si (001) Single Crystal Surfaces

carrier mobility compared with Si. 1 Although closely related to Si, in some aspects Ge shows a quite different behavior. This should be taken into account when processing steps are developed for the production of electronic devices with active Ge layers, in which the Ge layer surfaces and interfaces will play an important role. 2 In this letter, we investigated the effect of the free (001) surface on positron annihilation spectroscopy (PAS) results, comparing Si and Ge substrates. PAS is a powerful tool for the study of vacancy-type defects in semiconductors, 3,4 e.g. in irradiated Si and Ge. Positron trapping at vacancies can be observed by the narrowing of the Doppler-broadened 511 keV annihilation γ-ray peak. By varying the incident positron energy, one can probe different sample depths in the submicron range. This method is called Doppler Broadening Spectroscopy (DBS). The so called S-parameter, extracted from DBS, corresponds to positron annihilation by the valence electrons and is sensitive to open volume defects. An increase of the S-parameter can be simply interpreted as an increase of the number of vacancy-type defects. The S-parameter obtained for an incident positron energy lower than 2 keV, however, in general differs from the one obtained for positron energies above 15 keV. Incident positrons with lower energy will indeed mainly interact with the near surface area of the sample, and will be sensitive for thin native oxide layers, surface contamination, surface roughness, surface defects, etc. The S-parameter decreases in general toward the surface for most materials due to positron diffusion toward and annihilation at the surface. 5 The present letter reports on the different behavior of Si and Ge with this respect. While in case of Si, the S-parameter decreases considerably near the Si (001) surface as expected and as is the case for other semiconductor materials, in the case of a Ge (001) surface, the S-parameter shows no remarkable dependence on depth although both are group IV elements and have the same diamond structure. For the PAS measurements, moderately doped p-type Si and n-type Ge (001) wafers were used with a resistivity at room temperature in the range of 10–100 ohm corresponding with a carrier concentration at room temperature in the range of 10 13 ∼10 15 cm −3 . As a reference for the Si bulk and at the same time the near surface of Ge, a Geon-Insulator (GOI) wafer with a un-doped Ge top-layer produced by the Ge condensation technique, was also included in the study. The carrier concentration in the n-type Ge film of the GOI wafer that

Formation of epitaxial Co1−xNixSi2 nanowires on thin-oxide-capped (001)Si

Epitaxial Co1−xNixSi2 alloy nanowires have been grown on (001)Si substrates by a combination of reactive deposition epitaxy and oxide-mediated epitaxy. The thin native oxide layer can serve as a diffusion barrier to diminish the flux of metal atoms from the top of oxide layer to Si surface and promote the growth of nanowires. The elemental distributions of Ni and Co in nanowires were determined by energy dispersive spectroscopy in a transmission electron microscope. The factors that cause the distributions of Ni and Co in nanowires were discussed.

Semiconducted symphony: ultrafast field emitter array

Semiconducted symphony: ultrafast field emitter array

Comparing Biocompatibility of Nanocrystalline Titanium and Titanium-Oxide with Microcrystalline Titanium

ABSTRACTTitanium (Ti) is the material of choice for orthopaedic applications because it is biocompatible and encourages osteoblast ingrowth. It was shown that the biocompatibility of Ti metal is due to the presence of a thin native sub-stoichiometric titanium oxide layer which enhances the adsorption of mediating proteins on the surface [1]. The present studies were devised to evaluate the adhesion, survival, and growth of cells on the surface of new engineered nano-crystal films of titanium and titanium oxides and compare them with orthopaedic-grade titanium with microcrystals. The engineered nano-crystal films with hydrophilic properties are produced by employing an ion beam assisted deposition (IBAD) technique. IBAD combines physical vapor deposition with concurrent ion beam bombardment in a high vacuum environment to produce films (with 3 to 70 nm grain size) with superior properties. These films are “stitched” to the artificial orthopaedic implant materials with characteristics that affect the wettability and mechanical properties of the coatings.To characterize the biocompatibility of these nano-engineered surfaces, we have studied osteoblast function including cell adhesion, growth, and differentiation on different nanostructured samples. Cell responses to surfaces were examined using SAOS-2 osteoblast-like cells. We also studied a correlation between the surface nanostructures and the cell growth by characterizing the SAOS-2 cells with immunofluorescence and measuring the amount alizarin red concentration produced after 7 and 14 days. The number of adherent cells was determined by means of nuclei quantification on the nanocrystalline Ti, TiO2, and microcrystalline Ti and analysis was performed with Image J. Our experimental results indicated that nanocrystalline TiO2 is superior to both nano and microcrystalline Ti in supporting growth, adhesion, and proliferation. Improving the quality of surface oxide, i.e. fabricating stoichiometric oxides as well as nanoengineering the surface topology, is crucial for increasing the biocompatibility of Ti implant materials.

Nanostructurally Designed Ultra-hydrophilic Hard Ceramic Oxide Coatings for Orthopaedic Application

ABSTRACTThis paper addresses the application of engineered nanocrystalline ultrahydrophilic titanium oxide films to artificial orthopaedic implants. Titanium (Ti) is the material of choice for orthopaedic applications and has been used for over fifty years because of its known bio-compatibility. Recently it was shown that biocompatibility of Ti metal is due to the presence of a thin native sub-stoichiometric titanium oxide layer [1] which enhances the adsorption of mediating proteins on the surface thus enhancing cell adhesion and growth [2,3,4]. Improving the quality of surface oxide, i.e. fabricating stoichiometric oxides as well as nanoengineering the surface topology that matches the dimensions of adhesive proteins, is crucial for the increase of protein adsorption [2] and, as a result, the biocompatibility of Ti implant materials. We have fabricated ultrahydrophilic nano-crystalline transparent films of anatase phase of titania (TiO2) by ion beam assisted deposition (IBAD) processes in an ultrahigh vacuum system. Source material was 99.9% pure rutile TiO2. Various ion beam conditions were used to produce these coatings with different grain sizes (4 to 70 nm) that affect the wettability, roughness, and the mechanical and optical properties of the coating [5]. Our biological experiments have shown that biocompatibility of these ultrahydrophilic nanoengineered TiO2 coatings are superior to commonly used orthopaedic titanium and even hydroxyapatite.

Selective streptavidin bioconjugation on silicon and silicon carbide nanowires for biosensor applications

Abstract

Metal nanoantenna plasmon resonance lineshape modification by semiconductor surface native oxide

We present reflectivity spectra of gold nanoantenna arrays fabricated directly onto GaAs substrates, which exhibit highly asymmetric line-shapes close to the localised surface plasmon resonance wavelength. Using detailed scattering matrix simulations, we show that the asymmetry is caused by an interference effect that is enhanced by the presence of a thin (few nm) native oxide layer on the GaAs surface. Our results have important implications for the correct design of nanoplasmonic systems for enhanced incoupling of light in semiconductor-based photovoltaic systems.

Investigation of proximity effects in electron microscopy and lithography

A fundamental challenge in lithographic and microscopic techniques employing focused electron beams are so-called proximity effects due to unintended electron emission and scattering in the sample. Herein, we apply a method that allows for visualizing electron induced surface modifications on a SiN substrate covered with a thin native oxide layer by means of iron deposits. Conventional wisdom holds that by using thin membranes proximity effects can be effectively reduced. We demonstrate that, contrary to the expectation, these can be indeed larger on a 200 nm SiN-membrane than on the respective bulk substrate due to charging effects.

Plastic response of the native oxide on Cr and Al thin films from in situ conductive nanoindentation

Abstract

Thermal and optical characterization of resonant coupling between surface plasmon polariton and semiconductor waveguides

Resonant coupling between an Au-InP surface plasmon polariton (SPP) and an InP/InGaAsP ridge waveguide is investigated. The general design requirements for evanescent coupling between a low-loss waveguide and a highly absorptive SPP are described, and experimental results are presented for fabricated devices. Coupling from the ridge to the SPP is confirmed using fiber-to-fiber optical power measurements, and thermoreflectance imaging is used to directly measure power coupled to the SPP along the length of the metal waveguide. The role of the thin native oxide at the Au-InP interface is also explored and found to have a significant impact on coupling.

Dynamic Adsorption and Structure of Interfacial Bilayers Adsorbed from Lipopeptide Surfactants at the Hydrophilic Silicon/Water Interface: Effect of the Headgroup Length

Lipopeptides are an important group of biosurfactants expressed by microorganisms. Because they are well-known for being biocompatible, biodegradable, and highly surface active, they are attractive for a wide range of applications. Natural lipopeptide surfactants are however impure; it is hence difficult to use them for exploring the structure-function relation. In this work, a series of cationic lipopeptide surfactants, C(14)K(n) (n = 1-4), where C denotes the myristic acyl chain and K denotes lysine (Lys), have been synthesized, and their interfacial behavior has been characterized by studying their adsorption at the silicon/water interface (bearing a thin native oxide layer) using spectroscopic ellipsometry and neutron reflection (NR). The dynamic adsorption was marked by an initial fast step within the first 2-3 min followed by a slow molecular relaxation process over the subsequent 20-30 min. The initial rate of time-dependent adsorption and the equilibrated adsorbed amount showed a steady decrease with increasing n, indicating the impact of the molecular size, structure, and charge. NR revealed the formation of sandwiched bilayers from C(14)K(n), similar to conventional surfactants such as nonionic C(12)E(6) and cationic C(16)TAB. However, the electrostatic attraction between K and the silica surface caused confinement of the K groups, forcing the head segments into a predominantly flat-on conformation. This characteristic structural feature was confirmed by the almost constant thickness of the headgroup regions ranging from 8 to 11 Å as determined from NR combined with partial deuterium labeling to the acyl tail. An increase in area per molecular pair with n resulted directly from increasing the footprint. As a result, the hydrophobic back-to-back tail mixing and acyl chain tilting rose with n. The extent of chain-head intermixing became so intensified that the C(14)K(4) bilayer could be approximated to a uniform layer distribution.

Effect of the chemistry and structure of the native oxide surface film on the corrosion properties of commercial AZ31 and AZ61 alloys

The purpose of this study has been to advance in knowledge of the chemical composition, structure and thickness of the thin native oxide film formed spontaneously in contact with the laboratory atmosphere on the surface of freshly polished commercial AZ31 and AZ61 alloys with a view to furthering the understanding of protection mechanisms. For comparative purposes, and to more fully describe the behaviour of the native oxide film, the external oxide films formed as a result of the manufacturing process (as-received condition) have been characterised. The technique applied in this research to study the thin oxide films (thickness of just a few nanometres) present on the surface of the alloys has basically been XPS (X-ray photoelectron spectroscopy) in combination with ion sputtering. Corrosion properties of the alloys were studied in 0.6 M NaCl by measuring charge transfer resistance values, which are deduced from EIS (electrochemical impedance spectroscopy) measurements after 1 h of exposure. Alloy AZ61 generally showed better corrosion resistance than AZ31, and the freshly polished alloys showed better corrosion resistance than the alloys in as-received condition. This is attributed to a combination of (1) higher thickness of the native oxide film on the AZ61 alloy and (2) greater uniformity of the oxide film in the polished condition. The formation of an additional oxide layer composed by a mixture of spinel (MgAl 2O 4) and MgO seems to diminish the protective properties of the passive layer on the surface of the alloys in as-received condition.

Structural Phase Control in Self-Catalyzed Growth of GaAs Nanowires on Silicon (111)

Au free GaAs nanowires with zinc blende structure, free of twin planes and with remarkable aspect ratios, have been grown on (111) Si substrates by molecular beam epitaxy. Nanowires with diameters down to 20 nm are obtained using a thin native oxide layer on the Si substrates. We discuss how the structural phase distribution along the wire length is controlled by the effective V/III ratio and temperature at the growth interface and explain how to obtain a pure twin plane free zinc blende structure.

Role of near-field enhancement in plasmonic laser nanoablation using gold nanorods on a silicon substrate

We present experimental results for the plasmonic laser ablation of silicon with nanoscale features as small as 22 x 66 nm using single near-infrared, femtosecond laser pulses incident on gold nanorods. Near the ablation threshold, these features are photo-imprints of gold nanorod particles positioned on the surface of the silicon and have feature sizes similar to the nanorods. The single rod-shaped ablation pattern matches the enhancement patterns of the Poynting vector magnitude on the surface of silicon, implying that the ablation is a result of the plasmonic enhancement of the incident electromagnetic waves in the near-field of the particles. Interestingly, the ablation pattern is different from the two separated holes at the ends of the nanorod, as would be expected from the electric field--|E|(2) enhancement pattern. We measured the plasmonic ablation threshold fluence to be almost two orders of magnitude less than the femtosecond laser ablation threshold of silica, present in the thin native oxide layer on the surface of silicon. This value also agrees with the enhancement of the Poynting vector of a nanorod on silicon as calculated with electromagnetic simulations. We thus conclude that plasmonic ablation with plasmonic nanoparticles depends directly on the polarization and the value of the near-field enhancement of the Poynting vector and not the square of the electric field as previously suggested.