Photoemission study of the reactivity of barium towards SiOx thermal films

Barium was deposited at room temperature on a thermal silicon oxide layer and the interfacial reaction was monitored by synchrotron induced photoemission (both core level and valence band). The first step of the growth consists of an interfacial reaction which leads to the formation of an interfacial silicate layer. The next step consists in formation of barium oxide while metallic barium occurs subsequently. The deposit can be also homogenized by annealing above 575 K. This results in the formation of several layers of silicate by consumption of silicon oxide. In the case of fractional coverage, subsequent annealing at 975 K induces the decomposition of barium silicate. However, such a decomposition process is strongly dependent on the initial film thickness. It can be avoided for deposits thicker than 3 eqML.     

An all-ZnO microbolometer for infrared imaging

Microbolometers are extensively used for uncooled infrared imaging applications. These imaging units generally employ vanadium oxide or amorphous silicon as the active layer and silicon nitride as the absorber layer. However, using different materials for active and absorber layers increases the fabrication and integration complexity of the pixel structure. In order to reduce fabrication steps and therefore increase the yield and reduce the cost of the imaging arrays, a single layer can be employed both as the absorber and the active material. In this paper, we propose an all-ZnO microbolometer, where atomic layer deposition grown zinc oxide is employed both as the absorber and the active material. Optical constants of ZnO are measured and fed into finite-difference-time-domain simulations where absorption performances of microbolometers with different gap size and ZnO film thicknesses are extracted. Using the results of these optical simulations, thermal simulations are conducted using finite-element-method in order to extract the noise equivalent temperature difference (NETD) and thermal time constant values of several bolometer structures with different gap sizes, arm and film thicknesses. It is shown that the maximum performance of 171 mK can be achieved with a body thickness of 1.1 μm and arm thickness of 50 nm, while the fastest response with a time constant of 0.32 ms can be achieved with a ZnO thickness of 150 nm both in arms and body.     

Marine environment compatible antireflection coating with nanotop layer on silicon optics

Antireflection coating on silicon optics have crucial importance in thermal device working in 3.6–4.9 μm wavelength region. When the thermal device is used in marine environment, the optics face harsh saline weather condition compared to normal field environment. This deteriorates coated optics and to improve mechanical strength of the coating, a nanotop layer on the antireflection coating has been developed. In this paper a study has been carried out to improve marine environment compatibility by employing a nanolayer on the top of antireflection coating on silicon optics. Optimac synthesis method was used to design the multilayer stack on the substrate with germanium and IR-F625 as high/low refractive index respectively and the layer number was restricted to four layers. The top nanolayer was 60 ± 2 nm thick hafnium dioxide layer developed with ion assisted deposition (End–Hall) on the optics during coating process. The deposition of multilayer coating was carried out inside the coating plant fitted with cryo pump and residual gas analyzer. The evaporation was carried out at high vacuum (2–6 × 10⁻⁶ mbar) using electron beam gun and layer thicknesses were measured with crystal monitor. The average transmission achieved was 97% in the spectral band of 3.6–4.9 μm with a hardness of 9.7 GPa on the coated optics.     

Fast hydrogen sorption kinetics for ball-milled Mg2Ni alloys☆

The sorption kinetics of Mg₂Ni alloys are strongly improved using two different surface treatments. One consists of the preparation of tailor-made Mg₂Ni/C composites by ball-milling with previously ground carbons. The strong reducing character of carbon, allowing for the reduction of NiO initially present at the alloy surface, leads to the partial removal of the oxide layer that strongly hinders the hydrogen migration throughout the alloy surface on desorption, whereas resulting Ni particles act as catalysts during the absorption process. The second surface treatment deals with the deposition of Pd particles on the alloy surface using the polyol process. The catalytic effect of Pd is responsible for an important enhancement of the absorption kinetic, whereas Pd particles probably act as hydrogen pumps, during the desorption process, leading to a faster hydrogen release. By combining both techniques, desorption rates as high as 2.7 wt% in 60 min and 2.9 wt% in 30 min are obtained at 150 and 200 °C, respectively.     

Low energy alkali ion scattering investigation of Au nanoclusters grown on silicon oxide surfaces

The atomic and electronic structures of Au nanostructures grown by deposition onto various silicon oxide surfaces were probed with low energy alkali ion scattering. Charge state-resolved time-of-flight spectra of scattered 2 keV ³⁹K⁺ ions were collected from Au deposited onto an untreated Si wafer with a native oxide, a thermally grown oxide surface, and atomically-clean Si(111). It is shown that nanoclusters form on both oxides, but not on the clean Si. A quantitative analysis of the ion scattering spectra indicates that the nanoclusters are initially flat, two-dimensional structures that start to develop a second layer at about 0.5 Å of deposited Au and then form three-dimensional islands. The neutral fraction of scattered 2 keV ³⁹K⁺ ions decreases with deposition indicating changes in the quantum state occupancy with cluster size. The shapes of the clusters differ on the native and thermal oxides, leading to shape-dependent neutralization.     

Electro-optic metal–insulator–semiconductor–insulator–metal Mach-Zehnder plasmonic modulator

The performance of a CMOS-compatible electro-optic Mach-Zehnder plasmonic modulator is investigated using electromagnetic and carrier transport simulations. Each arm of the Mach-Zehnder device comprises a metal–insulator–semiconductor–insulator–metal (MISIM) structure on a buried oxide substrate. Quantum mechanical effects at the oxide/semiconductor interfaces were considered in the calculation of electron density profiles across the structure, in order to determine the refractive index distribution and its dependence on applied bias. This information was used in finite element simulations of the electromagnetic modes within the MISIM structure in order to determine the Mach-Zehnder arm lengths required to achieve destructive interference and the corresponding propagation loss incurred by the device. Both inversion and accumulation mode devices were investigated, and the layer thicknesses and height were adjusted to optimise the device performance. A device loss of <8 dB is predicted for a MISIM structure with a 25 nm thick silicon layer, for which the device length is <3 μm, and <5 dB loss is predicted for the limiting case of a 5 nm thick silicon layer in a 1.2 μm long device: in both cases, the maximum operating voltage is 7.5 V.     

Surface reactions of TiCl4 and Al(CH3)3 on GaAs(100) during the first half-cycle of atomic layer deposition

GaAs(100) was exposed to pulses of trimethylaluminum (TMA, Al(CH₃)₃) and titanium tetrachloride (TiCl₄) to mimic the first half-cycle of atomic layer deposition (ALD). Both precursors removed the 9.0 ± 1.6 Å-thick mixed oxide consisting primarily of As₂O₃ with a small Ga₂O component that was left on the surface after aqueous HF treatment and vacuum annealing. In its place, TMA deposited an Al₂O₃ layer, but TiCl₄ exposure left Cl atoms adsorbed to an elemental As layer. This suggests that oxygen was removed by the formation of a volatile oxychloride species. A small TiO₂ coverage of approximately 0.04 monolayer remained on the surface for deposition temperatures of 89 °C to 135 °C, but no TiO₂ was present from 170 °C to 230 °C. The adsorbed Cl layer chemically passivated the surface at these temperatures and blocked TiO₂ deposition even after 50 full ALD cycles of TiCl₄ and water vapor. The Cl and As layers desorbed simultaneously at higher temperature producing peaks in the temperature programmed desorption spectrum in the range 237–297 °C. This allowed TiO₂ deposition at 300 °C in single TiCl₄ pulse experiments. On the native oxide-covered surface where there was a higher proportional Ga oxide composition, TiCl₄ exposure deposited TiO₂.     

The oxidation of Fe(111)

The oxidation of Fe(111) was studied using Auger electron spectroscopy (AES), low energy electron diffraction (LEED), X-ray photoelectron spectroscopy (XPS), ion scattering spectroscopy (ISS) and scanning tunnelling microscopy (STM). Oxidation of the crystal was found to be a very fast process, even at 200 K, and the Auger O signal saturation level is reached within ~ 50 × 10^? 6 mbar s. Annealing the oxidised surface at 773 K causes a significant decline in apparent surface oxygen concentration and produces a clear (6 × 6) LEED pattern, whereas after oxidation at ambient temperature no pattern was observed. STM results indicate that the oxygen signal was reduced due to the nucleation of large, but sparsely distributed oxide islands, leaving mainly the smooth (6 × 6) structure between the islands. The reactivity of the (6 × 6) layer towards methanol was investigated using temperature programmed desorption (TPD), which showed mainly decomposition to CO and CO₂, due to the production of formate intermediates on the surface. Interestingly, this removes the (6 × 6) structure by reduction, but it can be reformed from the sink of oxygen present in the large oxide islands simply by annealing at 773 K for a few minutes. The (6 × 6) appears to be a relatively stable, pseudo-oxide phase, that may be useful as a model oxide surface.     

Growth and electrical characterization of type II InAs/GaSb superlattices for midwave infrared detection

Herein, we report a type II InAs/GaSb superlattice structure (SLS) grown on GaSb(1 0 0) substrates by molecular beam epitaxy (MBE) and its electrical characterization for mid-wavelength infrared detection. A GaSb buffer layer was grown under optimized SLS growth conditions, which can decrease the occurrence of defects for similar pyramidal structures. The complications associated with these conditions include oxide desorption of the substrate, growth temperature of the SLS, the V/III ratio during superlattice growth and the shutter sequence. High-resolution X-ray diffraction (HRXRD) shows the sixth satellite peak, and the period of the SLS was 52.9 Å. The atomic force microscopy (AFM) images indicated that the roughness was less than 2.8 nm. High-resolution transmission electron microscopy (HRTEM) images indicated that the SLS contains few structural defects related to interface dislocations or strain relaxation during the growth of the superlattice layer. The photoresponse spectra indicated that the cutoff wavelength was 4.8 μm at 300 K. The SLS photodiode surface was passivated by a zinc sulfide (ZnS) coating after anodic sulfide.     

Metallization of the β-SiC(100) 3 × 2 surface: A DFT investigation

Using density functional theory (DFT) we report results for the electronic structure and vibrational dynamics of hydrogenated silicon carbide (001) (3 × 2) surfaces with various levels of hydrogenation. These results were obtained using density functional theory with a generalized gradient exchange correlation function. The calculations reveal that metallization can be achieved via hydrogen atoms occupying the second silicon layer. Further increase of hydrogen occupation on the second silicon layer sites results in a loss of this metallization. For the former scenario, where metallization occurs, we found a new vibrational mode at 1870 cm^? 1, which is distinct from the mode associated with hydrogen atoms on the first layer. Furthermore, we found the diffusion barrier for a hydrogen atom to move from the second to the third silicon layer to be 258 meV.     

Oxygen plasma activation of Cr(CO)6 on α-Fe2O3(0001)

The chemistry of Cr(CO)₆ on the Fe₃O₄(111) surface termination of α-Fe₂O₃(0001) was explored using temperature programmed desorption (TPD), Auger electron spectroscopy (AES), static secondary ion mass spectrometry (SSIMS) and low energy electron diffraction (LEED) both with and without activation from an oxygen plasma source. No thermal decomposition of Cr(CO)₆ was detected on the surface in the absence of O₂ plasma treatment, with first layer molecules desorbing in TPD at 215 K from a close-packed overlayer. The interaction of first layer Cr(CO)₆ with the Fe₃O₄(111)-termination was weak, desorbing only ～ 30 K above the leading edge of the multilayer state. Activation of multilayer coverages of Cr(CO)₆ with the O₂ plasma source at 100 K resulted in complete conversion of the outer Cr(CO)₆ layers, presumably to a disordered Cr oxide film, with Cr(CO)₆ molecules near the surface left unaffected. Absence of CO or CO₂ desorption states suggests that all carbonyl ligands are liberated for each Cr(CO)₆ molecule activated by the plasma. AES and SSIMS both show that O₂ plasma activation of Cr(CO)₆ results in a carbon-free surface (after desorption of unreacted Cr(CO)₆). LEED, however, shows that the Cr oxide film was disordered at 600 K and likely O-terminated based on subsequent water TPD. Attempts to order the film at temperatures above 650 K resulted in dissolution of Cr into the α-Fe₂O₃(0001) crystal based on SSIMS, an observation linked to the Fe₃O₄(111) termination of the surface and not to the properties of α-Cr₂O₃/α-Fe₂O₃ corundum interface. Nevertheless, this study shows that O₂ plasma activation of Cr(CO)₆ is an effective means of depositing Cr oxide films on surfaces without accompanying carbon contamination.     

The interaction of O2 with the surface of polycrystalline gadolinium at the temperature range 300–670 K

Auger-Electron-Spectroscopy (AES) and Direct-Recoils-Spectrometry (DRS) were applied to study the interaction of O₂ with a polycrystalline gadolinium surface, in the temperature range 300–670 K and oxygen pressure up to 2 × 10^? 6 Torr. It has been found that initial uptake of oxygen, at coverage measurable by the techniques used here, results in rapid oxide island formation. The subsurface is believed to be a mixture of oxide particles and oxygen dissolved in the Gd metal, the latter being the mobile species, even at relatively low temperatures.Enhanced inward diffusion of oxygen starts as early as 420 K and dictates the surface oxygen concentration and effective thickness of the forming oxide. The oxygen accumulation rate at the near-surface region, as measured by the O(KLL) AES signal intensity, goes through a maximum as a function of temperature at 420 K. This is a result of the combination of still efficient oxygen chemisorption that increases surface occupation and slow inward diffusion. The thickest oxide, ~ 1.7 nm, is formed at 300 K and its effective thickness was found to decrease with increasing temperature (due to oxygen dissolution into the metal bulk).Diffusion coefficients of the oxygen dissolution into the bulk were evaluated for various temperatures utilizing models for infinitely thin oxide layer and thick oxide layer, respectively. The best fit under our experimental procedure was obtained by the thick layer model, and the coefficients that were calculated are D₀ = 2.2 × 10^? 16m²s^? 1 and E_a = 46kJ/mol.     

The influence of oxygen on the growth of silver on Cu(110)

The influence of the (2 × 1)O reconstruction on the growth of Ag on a Cu(110) surface was studied by scanning tunneling microscopy (STM) and Auger electron spectroscopy (AES). On the bare Cu(110) surface, Stranski–Krastanov growth of silver is observed at sample temperatures between 277 K and 500 K: The formation of a Ag wetting layer is followed by the growth of three-dimensional Ag wires. In contrast, on the oxygen-precovered Cu(110) surface, the growth of silver depends heavily on the substrate temperature. Upon Ag deposition at room temperature, a homogeneous, polycrystalline Ag layer is observed, whereas at 500 K, three-dimensional wires separated by (2 × 1)O reconstructed areas are formed. The behavior of a deposited Ag layer upon annealing is also influenced greatly by the presence of oxygen. On the bare surface, annealing does not change the Ag wetting layer and gives rise to Ostwald ripening of the Ag wires. On the oxygen-precovered surface, however, the initial polycrystalline Aglayer first transforms into Ag wires at around 500 K. Above this temperature, the depletion of the (2 × 1)O reconstructed areas due to Ag-induced O desorption is balanced by the formation of a Ag wetting layer. On both, the bare and the oxygen-precovered Cu(110) surface, the deposited silver diffuses into the Cu bulk at temperatures above 700 K.     

Interaction of atomic H and CO with Cu(1 1 0) and bimetallic Ni/Cu(1 1 0)

Co-adsorption of hydrogen and CO on Cu(1 1 0) and on a bimetallic Ni/Cu(1 1 0) surface was studied by thermal desorption spectroscopy. Hydrogen was exposed in atomic form as generated in a hot tungsten tube. The Ni/Cu surface alloy was prepared by physical vapor deposition of nickel. It turned out that extended exposure of atomic hydrogen leads not only to adsorption at surface and sub-surface sites, but also to a roughening of the Cu(1 1 0) surface, which results in a decrease of the desorption temperature for surface hydrogen. Exposure of a CO saturated Cu(1 1 0) surface to atomic H leads to a removal of the more strongly bonded on-top CO (α₁ peak) only, whereas the more weakly adsorbed CO molecules in the pseudo threefold hollow sites (α₂ peak) are hardly influenced. No reaction between CO and H could be observed. The modification of the Cu(1 1 0) surface with Ni has a strong influence on CO adsorption, leading to three new, distinct desorption peaks, but has little influence on hydrogen desorption. Co-adsorption of H and CO on the Ni/Cu(1 1 0) bimetallic surface leads to desorption of CO and H₂ in the same temperature regime, but again no reaction between the two species is observed.     

Adsorption of O2 and CO2 on the Si(111)-7 × 7 surfaces

The interaction of O₂ and CO₂ with the Si(111)-7 × 7 surface has been studied with X-ray photoelectron spectroscopy (XPS). It was found that both O₂ and CO₂ molecules can readily oxidize the Si(111)-7 × 7 surface to form thin oxide films. Two oxygen species were identified in the oxide film: oxygen atoms binding to on-top sites of adatom/rest atoms with an O 1s binding energy of ~ 533 eV as well as to bridge sites of adatom/rest atom backbonds at ~ 532 eV. These two oxygen species can be interconverted thermally during the annealing process. Due to the low oxidation capability, the silicon oxide film formed by CO₂ has a lower O/Si ratio than that of O₂.     

Device-level vacuum packaged uncooled microbolometer on a polyimide substrate

Uncooled infrared detectors (IR) on a polyimide substrate have been demonstrated where amorphous silicon (a-Si) was used as the thermometer material. New concepts in uncooled microbolometers were implemented during the design and fabrication, such as the integration of a germanium long-pass optical filter with the device-level vacuum package and a double layer absorber structure. Polyimide was used for this preliminary work towards vacuum-packaged flexible microbolometers. The detectors were fabricated utilizing a carrier wafer and low adhesion strength release layer to hold the flexible polyimide substrate during fabrication in order to increase the release yield. The IR detectors showed a maximum detectivity of 4.54 × 10⁶ cm Hz^1/2/W at a 4 Hz chopper frequency and a minimum noise equivalent power (NEP) of 7.72 × 10⁻¹⁰ W/Hz^1/2 at a biasing power of 5.71 pW measured over the infrared wavelength range of 8–14 μm for a 35 μm × 35 μm detector. These values are comparable to other flexible microbolometers with device-level vacuum packaging which are found in literature.     

Reflectivity modeling of Si-based amorphous superlattices

The structural properties of superlattices composed by hydrogenated amorphous silicon/silicon carbide (a-Si:H/a- Si_1 − xC_x:H) and silicon/germanium (a-Si:H/a-Ge:H), deposited by the plasma-enhanced chemical vapor deposition (PECVD) technique, were analyzed by means of small-angle X-ray diffraction. The relevant structural parameters, such as the multilayer period, the individual layer thickness, the width of the interface and the optical constants, were determined by modeling the experimental reflectivity. The model was based on the dynamical diffraction theory, including material mixing at the interface, interface roughness and random variation of component thickness. In addition, the effect of the direct beam and background on the measured intensities were considered.     

Boron-doped nanocrystalline silicon germanium thin films for uncooled infrared bolometer applications

In this paper, boron-doped nanocrystalline Si_0.78Ge_0.22:H thin film is assessed for use as resistive sensing layer in uncooled infrared bolometer applications. The silicon germanium thin films were deposited by PECVD (plasma enhanced chemical vapor deposition) through decomposition of silane, germane and diborane diluted with argon at substrate temperature of 230 °C. Under optimum deposition parameters, the sensing films with modulate electrical resistivity (<10⁴ Ω cm) and high temperature coefficient of resistance (TCR) (>−3%/K) were obtained at room temperature. 1/f noise character in the form of the normalized Hooge parameter was measured in the frequency range of 1–64 Hz, resulting in a lower 1/f noise compared to other materials currently used for device application.     

Dynamical LEED analyses of the clean and the NO-adsorbed Ir(111) surface

The adsorption structure of nitric oxide (NO) on Ir(111) was studied by thermal desorption spectroscopy (TDS) and dynamical analyses of low-energy electron diffraction (LEED). At the saturation coverage at about 100 K, a 2 × 2 pattern was observed by LEED and two peaks appeared at 365 and 415 K in TDS. No change in the LEED I–V curves was observed by annealing at 280 K, which means that the NO-saturated surface was retained at this temperature. On the contrary, partial desorption and changes of the LEED I–V curves were observed by annealing at 360 K. Combined with previous vibrational studies, it is suggested that one adsorption species is not affected, while another species is partially desorbed and the rest of them are dissociated by annealing at 360 K. Dynamical analyses of LEED were performed for the 280 K-annealed and the 360 K-annealed surfaces, which correspond to the NO-saturated and the NO-dissociated Ir(111) surfaces, respectively. These revealed that NO occupies the atop, fcc-hollow and hcp-hollow sites (atop-NO + fcc-NO + hcp-NO) for the NO-saturated Ir(111) surface with the saturation coverage of 0.75 ML. For the 360 K-annealed surface, the atop-NO is not affected but the fcc-NO and the hcp-NO are partially desorbed as NO and partially dissociated to N and O, both of which occupy the fcc-hollow site on the surface.     

Surface structural evolution during the thermal decomposition of a PdO(101) thin film

We used scanning tunneling microscopy (STM) to characterize PdO(101) thin films grown on Pd(111), and the structural changes that occur during isothermal decomposition. We find that the PdO(101) thin films have high-quality surface structures that are characterized by large, crystalline terraces with low concentrations of point defects. Small domains of single-layer oxide are also present on the top layer of relatively thick PdO(101) films grown at 500 K. The thinner PdO(101) films exhibit negligible quantities of such domains, apparently because new domains agglomerate rapidly as the film thickness decreases. We find that the isothermal decomposition rate of a PdO(101) film at 720 K exhibits an autocatalytic regime in which the rate of oxygen desorption increases as the oxide decomposes. Our STM results demonstrate that reduced sites created during oxide decomposition catalyze further PdO decomposition, and reveal strong kinetic anisotropies in the decomposition. The kinetic anisotropies produce one-dimensional reaction fronts that propagate preferentially along the atomic rows of the PdO(101) surface, resulting in the formation of long chains of reduced sites. We also find that reduced sites promote oxygen recombination in neighboring rows of the Pd(101) structure, causing loops and larger aggregates of reduced sites to form. The promotion of decomposition across the atomic rows can qualitatively explain the autocatalytic desorption kinetics. Finally, the STM images provide evidence that underlying PdO(101) layers transfer oxygen to reduced surface domains, thus producing large domains of PdO(101) islands that coexist with reduced domains as well as the larger PdO(101) terraces of the initial surface. Re-oxidation of the surface acts to sustain the autocatalytic decomposition kinetics, and provides a mechanism for oxygen atoms to ultimately evolve from the subsurface of the PdO(101) film.