Impact of MOVPE Environment on Silicon Substrates for III-V-on-Si Multijunction Solar Cells

With the final goal of integrating III-V materials to silicon for tandem solar cells, the influence of the metal-organic vapor phase epitaxy (MOVPE) environment on the minority carrier properties of silicon wafers has been evaluated. These properties will essentially determine the photovoltaic performance of the bottom cell in a III-V-on-Si tandem solar cell device. A comparison of the base minority carrier lifetimes obtained for different thermal processes carried out in a MOVPE reactor on Czochralski silicon wafers has been carried out. The effect of the formation of the emitter by phosphorus diffusion has also been evaluated.

Influence of PH3 exposure on silicon substrate morphology in the MOVPE growth of III-V on silicon multijunction solar cells

Dual-junction solar cells formed by a GaAsP or GaInP top cell and a silicon bottom cell seem to be attractive candidates to materialize the long sought-for integration of III-V materials on silicon for photovoltaic applications. One of the first issues to be considered in the development of this structure will be the strategy to create the silicon emitter of the bottom subcell. In this study, we explore the possibility of forming the silicon emitter by phosphorus diffusion (i.e. exposing the wafer to PH3 in a MOVPE reactor) and still obtain good surface morphologies to achieve a successful III-V heteroepitaxy as occurs in conventional III-V on germanium solar cell technology. Consequently, we explore the parameter space (PH3 partial pressure, time and temperature) that is needed to create optimized emitter designs and assess the impact of such treatments on surface morphology using atomic force microscopy. Although a strong degradation of surface morphology caused by prolonged exposure of silicon to PH3 is corroborated, it is also shown that subsequent anneals under H-2 can recover silicon surface morphology and minimize its RMS roughness and the presence of pits and spikes.

Si(100) versus Ge(100): Watching the interface formation for the growth of III-V-based solar cells on abundant substrates

We investigated the atomic surface properties of differently prepared silicon and germanium (100) surfaces during metal-organic vapour phase epitaxy/chemical vapour deposition (MOVPE/MOCVD), in particular the impact of the MOVPE ambient, and applied reflectance anisotropy/difference spectroscopy (RAS/RDS) in our MOVPE reactor to in-situ watch and control the preparation on the atomic length scale for subsequent III-V-nucleation. The technological interest in the predominant opto-electronic properties of III-V-compounds drives the research for their heteroepitaxial integration on more abundant and cheaper standard substrates such as Si(100) or Ge(100). In these cases, a general task must be accomplished successfully, i.e. the growth of polar materials on non-polar substrates and, beyond that, very specific variations such as the individual interface formation and the atomic step structure, have to be controlled. Above all, the method of choice to grow industrial relevant high-performance device structures is MOVPE, not normally compatible with surface and interface sensitive characterization tools, which are commonly based on ultrahigh vacuum (UHV) ambients. A dedicated sample transfer system from MOVPE environment to UHV enabled us to benchmark the optical in-situ spectra with results from various surfaces science instruments without considering disruptive contaminants. X-ray photoelectron spectroscopy (XPS) provided direct observation of different terminations such as arsenic and phosphorous and verified oxide removal under various specific process parameters. Absorption lines in Fourier-transform infrared (FTIR) spectra were used to identify specific stretch modes of coupled hydrides and the polarization dependence of the anti-symmetric stretch modes distinguished different dimer orientations. Scanning tunnelling microscopy (STM) studied the atomic arrangement of dimers and steps and tip-induced H-desorption proved the saturation of dangling bonds after preparati- n. In-situ RAS was employed to display details transiently such as the presence of H on the surface at lower temperatures (T <; 800°C) and the absence of Si-H bonds at elevated annealing temperature and also surface terminations. Ge buffer growth by the use of GeH4 enables the preparation of smooth surfaces and leads to a more pronounced amplitude of the features in the spectra which indicates improvements of the surface quality.

Optimization of the silicon subcell for III-V on silicon multijunction solar cells: key differences with conventional silicon technology

Dual-junction solar cells formed by a GaAsP or GaInP top cell and a silicon (Si) bottom cell seem to be attractive candidates to materialize the long sought-for integration of III-V materials on Si for photovoltaic (PV) applications. Such integration would offer a cost breakthrough for PV technology, unifying the low cost of Si and the efficiency potential of III-V multijunction solar cells. The optimization of the Si solar cells properties in flat-plate PV technology is well-known; nevertheless, it has been proven that the behavior of Si substrates is different when processed in an MOVPE reactor In this study, we analyze several factors influencing the bottom subcell performance, namely, 1) the emitter formation as a result of phosphorus diffusion; 2) the passivation quality provided by the GaP nucleation layer; and 3) the process impact on the bottom subcell PV properties.

Impact of metal-organic vapor phase epitaxy environment on silicon bulk lifetime for III–V-on-Si multijunction solar cells

With the final goal of integrating III-V materials on silicon substrates for tandem solar cells, the influence of the Metal-Organic Vapor Phase Epitaxy (MOVPE) environment on the minority carrier properties of silicon wafers has been evaluated. These properties will essentially determine the photovoltaic performance of the bottom cell in a III-V-on-Si tandem solar cell. A comparison of the base minority carrier lifetimes obtained for different thermal processes carried out in a MOVPE reactor on Czochralski silicon wafers has been carried out. An important degradation of minority carrier lifetime during the surface preparation (i.e. H2 anneal) has been observed. Three different mechanisms have been proposed for explaining this behavior: 1) the introduction of extrinsic impurities coming from the reactor; 2) the activation of intrinsic lifetime killing impurities coming from the wafer itself; and finally, 3) the formation of crystal defects, which eventually become recombination centers. The effect of the emitter formation by phosphorus diffusion has also been evaluated. In this sense, it has been reported that lifetime can be recovered during the emitter formation either by the effect of the P on extracting impurities, or by the role of the atomic hydrogen on passivating the defects.

Reflectance anisotropy spectroscopy assessment of the MOVPE nucleation of GaInP on Germanium (100)

This work summarizes the observations made on the variation and time evolution of the reflectanceanisotropy signal during the MOVPE growth of GaInPnucleation layers on Germanium substrates. This in situ monitoring tool is used to assess the impact of different nucleation routines and reactor conditions on the quality of the layers grown. This comparison is carried out by establishing a correlation between reflectanceanisotropy signature at 2.1 eV and the morphology of the epilayers evaluated by atomic force microscopy (AFM). This paper outlines the potential of reflectanceanisotropy to predict, explore, and therefore optimize, the best growth conditions that lead to a high quality III–V epilayer on a Ge substrate

Growth and Characterization of III-V Semiconductor Materials for MOCVD Reactor Qualification and Process Control

Metalorganic chemical vapor deposition is examined as a technique for growing compound semiconductor structures. Material analysis techniques for characterizing the quality and properties of compound semiconductor material are explained and data from recent commissioning work on a newly installed reactor at the University of Illinois is presented.

Electrochemical Oxidation Of Landfill Leachate In A Flow Reactor: Optimization Using Response Surface Methodology.

Response surface methodology based on Box-Behnken (BBD) design was successfully applied to the optimization in the operating conditions of the electrochemical oxidation of sanitary landfill leachate aimed for making this method feasible for scale up. Landfill leachate was treated in continuous batch-recirculation system, where a dimensional stable anode (DSA(©)) coated with Ti/TiO2 and RuO2 film oxide were used. The effects of three variables, current density (milliampere per square centimeter), time of treatment (minutes), and supporting electrolyte dosage (moles per liter) upon the total organic carbon removal were evaluated. Optimized conditions were obtained for the highest desirability at 244.11 mA/cm(2), 41.78 min, and 0.07 mol/L of NaCl and 242.84 mA/cm(2), 37.07 min, and 0.07 mol/L of Na2SO4. Under the optimal conditions, 54.99 % of chemical oxygen demand (COD) and 71.07 ammonia nitrogen (NH3-N) removal was achieved with NaCl and 45.50 of COD and 62.13 NH3-N with Na2SO4. A new kinetic model predicted obtained from the relation between BBD and the kinetic model was suggested.

The Influence Of The Buffering Capacity On The Production Of Organic Acids And Alcohols From Wastewater In Anaerobic Reactor.

Some bacteria common in anaerobic digestion process can ferment a broad variety of organic compounds to organic acids, alcohols, and hydrogen, which can be used as biofuels. Researches are necessary to control the microbial interactions in favor of the alcohol production, as intermediary products of the anaerobic digestion of organic compounds. This paper reports on the effect of buffering capacity on the production of organic acids and alcohols from wastewater by a natural mixed bacterial culture. The hypothesis tested was that the increase of the buffering capacity by supplementation of sodium bicarbonate in the influent results in benefits for alcohol production by anaerobic fermentation of wastewater. When the influent was not supplemented with sodium bicarbonate, the chemical oxygen demand (COD)-ethanol and COD-methanol detected in the effluent corresponded to 22.5 and 12.7 % of the COD-sucrose consumed. Otherwise, when the reactor was fed with influent containing 0.5 g/L of sodium bicarbonate, the COD-ethanol and COD-methanol were effluents that corresponded to 39.2 and 29.6 % of the COD-sucrose consumed. Therefore, the alcohol production by supplementation of the influent with sodium bicarbonate was 33.6 % higher than the fermentation of the influent without sodium bicarbonate.

TiO2-Photocatalyzed degradation of phenol in saline media in an annular reactor: hydrodynamics, lumped kinetics, intermediates, and acute toxicity

The photocatalytic degradation of phenol in aqueous suspensions of TiO2 under different salt concentrations in an annular reactor has been investigated. In all cases, complete removal of phenol and mineralization degrees above 90% were achieved. The reactor operational parameters were optimized and its hydrodynamics characterized in order to couple mass balance equations with kinetic ones. The photodegradation of the organics followed a Langmuir-Hinshelwood-Hougen-Watson lumped kinetics. From GC/MS analyses, several intermediates formed during oxidation have been identified. The main ones were catechol, hydroquinone, and 3-phenyl-2-propenal, in this order. The formation of negligible concentrations of 4-chlorophenol was observed only in high salinity medium. Acute toxicity was determined by using Artemia sp. as the test organism, which indicated that intermediate products were all less toxic than phenol and a significant abatement of the overall toxicity was accomplished, regardless of the salt concentration.

Development of a flow through photo-reactor to study degradation of organic compounds by Sequential Injection Analysis (SIA)

This work describes a photo-reactor to perform in line degradation of organic compounds by photo-Fenton reaction using Sequential Injection Analysis (SIA) system. A copper phthalocyanine-3,4',4²,4²¢-tetrasulfonic acid tetrasodium salt dye solution was used as a model compound for the phthalocyanine family, whose pigments have a large use in automotive coatings industry. Based on preliminary tests, 97% of color removal was obtained from a solution containing 20 µmol L-1 of this dye.

The development of an immobilized enzyme reactor containing glyceraldehyde-3-phosphate dehydrogenase from Trypanosoma cruzi: the effect of species' specific differences on the immobilization

Glyceraldehyde-3-phosphate dehydrogenase (GAPDH) plays an important role in the life cycle of the Trypanosoma cruzi, and an immobilized enzyme reactor (IMER) has been developed for use in the on-line screening for GAPDH inhibitors. An IMER containing human GAPDH has been previously reported; however, these conditions produced a T. cruzi GAPDH-IMER with poor activity and stability. The factors affecting the stability of the human and T. cruzi GAPDHs in the immobilization process and the influence of pH and buffer type on the stability and activity of the IMERs have been investigated. The resulting T. cruzi GAPDH-IMER was coupled to an analytical octyl column, which was used to achieve chromatographic separation of NAD+ from NADH. The production of NADH stimulated by D-glyceraldehyde-3-phosphate was used to investigate the activity and kinetic parameters of the immobilized T. cruzi GAPDH. The Michaelis-Menten constant (K-m) values determined for D-glyceraldehyde-3-phosphate and NAD(+) were K-m = 0.5 +/- 0.05 mM and 0.648 +/- 0.08 mM, respectively, which were consistent with the values obtained using the non-immobilized enzyme.

Simplified Mathematical Model for an Anaerobic Sequencing Batch Biofilm Reactor Treating Lipid-Rich Wastewater Subject to Rising Organic Loading Rates

This study proposes a simplified mathematical model to describe the processes occurring in an anaerobic sequencing batch biofilm reactor (ASBBR) treating lipid-rich wastewater. The reactor, subjected to rising organic loading rates, contained biomass immobilized cubic polyurethane foam matrices, and was operated at 32 degrees C +/- 2 degrees C, using 24-h batch cycles. In the adaptation period, the reactor was fed with synthetic substrate for 46 days and was operated without agitation. Whereas agitation was raised to 500 rpm, the organic loading rate (OLR) rose from 0.3 g chemical oxygen demand (COD) . L(-1) . day(-1) to 1.2 g COD . L(-1) . day(-1). The ASBBR was fed fat-rich wastewater (dairy wastewater), in an operation period lasting for 116 days, during which four operational conditions (OCs) were tested: 1.1 +/- 0.2 g COD . L(-1) . day(-1) (OC1), 4.5 +/- 0.4 g COD . L(-1) . day(-1) (OC2), 8.0 +/- 0.8 g COD . L(-1) . day(-1) (OC3), and 12.1 +/- 2.4 g COD . L(-1) . day(-1) (OC4). The bicarbonate alkalinity (BA)/COD supplementation ratio was 1:1 at OC1, 1:2 at OC2, and 1:3 at OC3 and OC4. Total COD removal efficiencies were higher than 90%, with a constant production of bicarbonate alkalinity, in all OCs tested. After the process reached stability, temporal profiles of substrate consumption were obtained. Based on these experimental data a simplified first-order model was fit, making possible the inference of kinetic parameters. A simplified mathematical model correlating soluble COD with volatile fatty acids (VFA) was also proposed, and through it the consumption rates of intermediate products as propionic and acetic acid were inferred. Results showed that the microbial consortium worked properly and high efficiencies were obtained, even with high initial substrate concentrations, which led to the accumulation of intermediate metabolites and caused low specific consumption rates.

Interesterification of milkfat with soybean oil catalysed by Rhizopus oryzae lipase immobilised on SiO(2)-PVA on packed bed reactor

The potential of the lipase from Rhizopus oryzae immobilised on SiO(2)-PVA to catalyse the interesterification of the milkfat with soybean oil in a packed bed reactor running on continuous mode was evaluated. The reactor operated continuously for 35 days at 45 degrees C, and during 12 days, no significant decrease in the initial lipase activity was verified. Interesterification yields were in the range from 35 to 38% wt, which gave an interesterified product having 59% lower consistency in relation to non-interesterified blend. Results showed the potential of the lipase from Rhizopus oryzae to mediate the interesterification of milkfat with soybean oil in packed bed reactor, attaining a more spreadable product under a cool temperature. The biocatalyst operational stability was assessed and an inactivation profile was found to follow the Arrhenius model, revealing values of 34 days and 0.034 day(-1), for half-life and a deactivation coefficient, respectively.

Evaluation of hydrodynamic parameters of a fluidized-bed reactor with immobilized yeast

The fluidized bed reactor has successfully been used to perform biotechnological processes addressed to the production of high added value. The present work evaluates hydrodynamic parameters of a bench-scale fluidized bed reactor with cells of the yeast Candida guilliermondii immobilized either in calcium alginate beads or in polyvinyl alcohol (PVA). The effects of the following variables on cell immobilization were evaluated at 30 degrees C and feeding a synthetic medium containing 50 g L-1 xylose: total particle density (cells plus support), terminal velocity, particle drag force, minimum fluidization velocity and bed porosity. According to the results obtained, the reactor was shown to operate like a fixed-bed bioreactor at xi < 0.5 and a fluidized bed bioreactor at xi > 0.5. The maximum flow rate needed to obtain maximum bed fluidization in the reactor was equal to the terminal velocity of the immobilized cell particles. Particles of cells immobilized within these supports showed values of drag coefficient lower than those reported for other high-density supports. The evaluation of these hydrodynamic characteristics lead to an adequate bed fluidization inside the reactor, thus improving oxygen transference and availability in the fermentation medium, making the process more viable for future scale-up. (c) 2008 Society of Chemical Industry.