Water contamination in thermal oxide on silicon
Water contaminating effects on thin thermal oxide passivated silicon planar devices
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Water contaminating effects on thin thermal oxide passivated silicon planar devices
Mullite bond coats filled with silicon particles have recently been proposed for the next generation of environmental barrier coatings (EBCs). The sacrificial oxidation of the silicon particles eliminates some of the environmental durability issues associated with traditional EBC designs. To investigate this novel design approach, a mathematical formulation and resulting numerical method have been developed for simulating the oxidation of silicon particles embedded in a mullite matrix. The focus is on the oxidation of the silicon in a dry oxygen environment where the oxidant is presumably oxygen. Oxygen transport from the exterior environment through the mullite is assumed to occur via two lattice defect diffusion mechanisms. As a result, the rate of oxygen transport is dictated by the self-diffusivity of the lattice defects. The numerical method is implemented using the COMSOL Multiphysics® program (COMSOL, Inc.). The method is applied to simulate the oxidation of silicon particles in a mullite pellet in recent oxidation experiments. Numerical results compare favorably with the oxidation behavior observed in the oxidation experiments. The numerical method is also used to investigate the effects of various features of the mullite-silicon particle system on the oxidation behavior.
Heterojunction diodes of indium tin oxide films sputtered on to p-silicon using ion-beam techniques display significant photovoltaic effects when exposed to sunlight. Galvanomagnetic and optical measurements confirm that the oxide films are highly degenerate transparent semiconductors. At a tin oxide concentration of 10%, an open-circuit voltage of 0.51 V was observed along with a short-circuit current of 32 mA/sq cm, a fill factor of 0.70, and a conversion efficiency of 12%. As the concentration was raised to 70%, the voltage remained steady, the current fell to 27 mA/sq cm, and the fill factor fell to 0.60
Photoelectrochemical generation of a potent organic hydride donor at silicon is demonstrated. Two different oxide-coated p-type silicon photoelectrodes reduced 1,2,3,5,6-pentamethyl-1H-benzo[d]imidazol-3-ium hexafluorophosphate, [PMBI][PF 6 ], to its corresponding imidazole hydride, PMBIH, in the presence of a proton source. Under 1 sun illumination, in acetonitrile with 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) buffer, the p-Si photoelectrodes convert PMBI + to PMBIH with good Faradaic efficiencies (FEs): 78% FE at −2.3 V vs Fc +/0 for Si|TiO 2 and 83% FE at −2.6 V vs Fc +/0 for Si|SiO 2 (where Si|SiO 2 represents silicon coated with an oxide layer). Generally, the Si|TiO 2 catalyzed the reaction at milder potentials than Si|SiO 2 , but the Si|SiO 2 had better selectivity for PMBIH generation over H 2 evolution than Si|TiO 2 . In light of prior studies of these photoelectrodes, the differences in selectivity and onset potential suggest a difference in mechanism, likely an outer-sphere electron transfer (ET) mechanism at the SiO 2 surface and potentially a proton-coupled ET process at the TiO 2 surface. To help understand reaction efficiency and identify areas of improvement, a thermochemical model for understanding net hydride transfer from the semiconductor to an acceptor in solution was developed. We find that the reactions in the present system are quite downhill. The high overpotentials (even while maintaining selectivity over H 2 evolution) emphasize the need for improved catalysts. Furthermore, this approach to evaluate the thermodynamics of net hydride transfer should be broadly valuable for electrochemical and photoelectrochemical processes.
Ellipsometric studies on mechanism and kinetics of thin oxide films on silicon in air
The formulation of Deal and Grove for the oxidation of silicon and the growth of a silica layer is revisited to include the effects of a protective coating layer. The linear-parabolic equation of the form x_o^2+Ax_o=Bt is still applicable, but the expressions for the constants A and B must be modified to account for the coating. The modified expression for A is a linear function of the coating thickness. The expression for B is modified by the relative solubility of the outer coating layer. The modified expressions are applied to assess recently published experimental results for the oxidation of a silicon bond coat in an environmental barrier coating (EBC). Conclusions are drawn regarding the diffusivity and solubility of oxidants in the EBC top coating.
A complementary metal oxide/semiconductor (CMOS) image detector now undergoing development is designed to exhibit less cross-talk and greater full-well capacity than do prior CMOS image detectors of the same type. Imagers of the type in question are designed to operate from low-voltage power supplies and are fabricated by processes that yield device features having dimensions in the deep submicron range. Because of the use of low supply potentials, maximum internal electric fields and depletion widths are correspondingly limited. In turn, these limitations are responsible for increases in cross-talk and decreases in charge-handling capacities. Moreover, for small pixels, lateral depletion cannot be extended. These adverse effects are even more accentuated in a back-illuminated CMOS imager, in which photogenerated charge carriers must travel across the entire thickness of the device. The figure shows a partial cross section of the structure in the device layer of the present developmental CMOS imager. (In a practical imager, the device layer would sit atop either a heavily doped silicon substrate or a thin silicon oxide layer on a silicon substrate, not shown here.) The imager chip is divided into two areas: area C, which contains readout circuits and other electronic circuits; and area I, which contains the imaging (photodetector and photogenerated-charge-collecting) pixel structures. Areas C and I are electrically isolated from each other by means of a trench filled with silicon oxide. The electrical isolation between areas C and I makes it possible to apply different supply potentials to these areas, thereby enabling optimization of the supply potential and associated design features for each area. More specifically, metal oxide semiconductor field-effect transistors (MOSFETs) that are typically included in CMOS imagers now reside in area C and can remain unchanged from established designs and operated at supply potentials prescribed for those designs, while the dopings and the lower supply potentials in area I can be tailored to optimize imager performance. In area I, the device layer includes an n+ -doped silicon layer on which is grown an n-doped silicon layer. A p-doped silicon layer is grown on top of the n -doped layer. The total imaging device thickness is the sum of the thickness of the n+, n, and p layers. A pixel photodiode is formed between a surface n+ implant, a p implant underneath it, the aforementioned p layer, and the n and n+ layers. Adjacent to the diode is a gate for transferring photogenerated charges out of the photodiode and into a floating diffusion formed by an implanted p+ layer on an implanted n-doped region. Metal contact pads are added to the back-side for providing back-side bias.
Electrical properties and failure modes of integrated multilevel microcircuits with silicon oxide-silicon interfaces
X-ray photoelectron spectroscopy analysis, transmission electron microscopy, diffraction studies, and sliding friction experiments were conducted with ferrous-base metallic glasses in sliding contact with aluminum oxide at temperatures from room to 750 C in a vacuum of 30 nPa. The results indicate that there is a significant temperature influence on the friction properties, surface chemistry, and microstructure of metallic glasses. The relative concentrations of the various constituents at the surface of the sputtered specimens were very different from the normal bulk compositions. Contaminants can come from the bulk of the material to the surface upon heating and impart boric oxide and silicon oxide at 350 C and boron nitride above 500 C. The coefficient of friction increased with increasing temperature to 350 C. Above 500 C the coefficient of friction decreased rapidly. The segregation of contaminants may be responsible for the friction behavior.
Fabrication and characterization of high-efficiency metal insulator, n-p (MINP) cells is described. Particular attention was paid to development of measurement methods for surface recombination and density of surface states. A modified Rosier test structure was used successfully for density of surface states. Silicon oxide and silicon nitride passivants were studied. Heat treatment after plasma enhanced chemical vapor deposition (CVD) of silicon nitride was shown to be beneficial. A more optimum emitter concentration profile was modeled.
Results of experiments designed to demonstrate spectrally selective absorption in dielectric waveguides on semiconductor substrates are reported. These experiments were conducted with three waveguides formed by sputtering films of PSK2 glass onto silicon-oxide layers grown on silicon substrates. The three waveguide samples were studied at 633 and 532 nm. The samples differed only in the thickness of the silicon-oxide layer, specifically 256 nm, 506 nm, and 740 nm. Agreement between theoretical predictions and measurements of propagation constants (mode angles) of the six or seven modes supported by these samples was excellent. However, the loss measurements were inconclusive because of high scattering losses in the structures fabricated (in excess of 10 dB/cm). Theoretical calculations indicated that the power distribution among all the modes supported by these structures will reach its steady state value after a propagation length of only 1 mm. Accordingly, the measured loss rates were found to be almost independent of which mode was initially excited. The excellent agreement between theory and experiment leads to the conclusion that low loss waveguides confirm the predicted loss rates.
A knowledge of the dielectric properties of microwave substrates at low temperatures is useful in the design of superconducting microwave circuits. Results are reported for a study of the complex permittivity of sapphire (Al2O3), magnesium oxide (MgO), silicon oxide (SiO2), lanthanum aluminate (LaAlO3), and zirconium oxide (ZrO2), in the 20 to 300 Kelvin temperature range, at frequencies from 26.5 to 40.0 GHz. The values of the real and imaginary parts of the complex permittivity were obtained from the scattering parameters, which were measured using a HP-8510 automatic network analyzer. For these measurements, the samples were mounted on the cold head of a helium gas closed cycle refrigerator, in a specially designed vacuum chamber. An arrangement of wave guides, with mica windows, was used to connect the cooling system to the network analyzer. A decrease in the value of the real part of the complex permittivity of these substrates, with decreasing temperature, was observed. For MgO and Al2O3, the decrease from room temperature to 20 K was of 7 and 15 percent, respectively. For LaAlO3, it decreased by 14 percent, for ZrO2 by 15 percent, and for SiO2 by 2 percent, in the above mentioned temperature range.
A knowledge of the dielectric properties of microwve substrates at low temperatures is useful in the design of superconducting microwave circuits. Results are reported for a study of the complex permittivity of sapphire (Al2O3), magnesium oxide (MgO), silicon oxide (SiO2), lanthanum aluminate (LaAlO3), and zirconium oxide (ZrO2), in the 20 to 300 Kelvin temperature range, at frequencies from 26.5 to 40.0 GHz. The values of the real and imaginary parts of the complex permittivity were obtained from the scattering parameters, which were measured using an HP-8510 automatic network analyzer. For these measurements, the samples were mounted on the cold head of a helium gas closed cycle refrigerator, in a specially designated vacuum chamber. An arrangement of wave guides, with mica windows, was used to connect the cooling system to the network analyzer. A decrease in the value of the real part of the complex permittivity of these substrates, with decreasing temperature, was observed. For MgO and Al2O3, the decrease from room temperature to 20 K was of 7 and 15 percent, respectively. For LaAlO3, it decreased by 14 percent, for ZrO2 by 15 percent, and for SiO2 by 2 percent, in the above mentioned temperature range.
Ion implantation for reducing space charge buildup in thermal oxides on silicon exposed to ionizing radiation
A back-illuminated silicon photodetector has a layer of Al2O3 deposited on a silicon oxide surface that receives electromagnetic radiation to be detected. The Al2O3 layer has an antireflection coating deposited thereon. The Al2O3 layer provides a chemically resistant separation layer between the silicon oxide surface and the antireflection coating. The Al2O3 layer is thin enough that it is optically innocuous. Under deep ultraviolet radiation, the silicon oxide layer and the antireflection coating do not interact chemically. In one embodiment, the silicon photodetector has a delta-doped layer near (within a few nanometers of) the silicon oxide surface. The Al2O3 layer is expected to provide similar protection for doped layers fabricated using other methods, such as MBE, ion implantation and CVD deposition.
An analysis is made of the waveguiding properties of the oxygen-implanted, buried-oxide, silicon-on-insulator structures currently being developed for use in microelectronics. It is found that in spite of the fact that the buried-oxide layer is only a few tenths of a micrometer thick, the single-crystal overlayer can support TEo guided-wave propagation, at subbandgap wavelengths, with losses due to substrate radiation leakage at or below the benchmark level of 1 dB/cm.
Ellipsometer studies of oxide thin film growth on silicon in air
Hybrid photoelectrodes, comprised of a light-absorbing semiconductor and a surface-integrated molecular catalyst, are attractive for applications in artificial photosynthesis, since they combine the advantages of broadband semiconductor light absorption with the selectivity of molecular catalysis. A widely used class of hybrid photoelectrodes is based on Si substrates passivated by a thin (<3 nm) layer of silicon oxide, which is commonly prepared by controlled chemical or thermal oxidation, resulting in chemical oxide (ChO) or thermal oxide (ThO) layers, respectively. However, the electrochemical stability of these oxide layers, and the chemical stability of the semiconductor-molecule assembly in hybrid photoelectrodes, are not well understood, with evidence that covalently-bound molecules detach from the oxide surface upon application of cathodic bias. We have examined the intrinsic electrochemical reactivity of silicon oxide layers and how it affects the attachment of molecular monolayers. We determined that the surface of Si|ThO is primarily terminated with hydrophobic siloxane moieties, whereas that of Si|ChO contains a higher concentration of hydrophilic silanol groups. Initial high current densities for Si|ChO under applied bias up to -2 V vs. Ag/AgCl, decrease during repeated cyclic voltammetry scans, due to the consumption of surface-bound water. This is manifested by a reversible wave around -0.5 V in CH 3 CN solution, and a similar pH-dependent wave in water, revealing the pK a of the silanol groups to be ~4. Here, our combined observations support the electrochemically-induced dehydration of the SiO 2 surface, which converts silanol groups to siloxanes and proceeds through an H-atom intermediate that is most likely stabilized by pentavalent Si. We propose that similar reactivity is responsible for the electrochemical loss of alkylsiloxane-attached molecules under cathodic bias, which has important implications for the choice of catalyst attachment strategy in hybrid photoelectrodes.