Reactive wave propagation in energetic porous silicon composites

A parametric study of reactive wave propagations in porous silicon (PS) – oxidizer composites is presented. This study investigates the effects of the composite equivalence ratio and the oxidizer, and also the nanoscale and microscale structure, and the effect of dopant atoms, which are specific to this nanostructured composite material. The reactive wave speed and structure for energetic PS composites formed by depositing sodium, magnesium, or calcium perchlorates within the nanoscale pores were analyzed with high speed video recordings and spectroscopic temperature measurements. The findings indicate that heavily doped samples that do not yield a microscale structure result in slow propagation speeds, and low doped substrates with randomly formed micro-crack patterns during the electrochemical dissolution result in high speed propagations. A systematic study of the mixture composition revealed very wide flammability limits and flame speed and temperature measurements independent of the equivalence ratio, consistent with thermochemical equilibrium calculations. Also, while all the composites considered in this study are fuel rich with equivalence ratios greater than 1.60, the composites with equivalence ratios closer to unity exhibited lower temperatures and propagation speeds than more fuel rich composites. This unusual behavior of the composites is attributed to the inhomogeneity of the system even though the reactants are mixed at the nanometer scale. This was illustrated by developing a phenomenological model describing the interaction of silicon and the oxidizer within a single nanometer scale pore, which revealed that the reactive wave propagation is more strongly controlled by the specific surface area than the global equivalence ratio, due to the diffusion length scales involved.     

Enhancement of photovoltaic properties of multicrystalline silicon solar cells by combination of buried metallic contacts and thin porous silicon

Photovoltaic properties of buried metallic contacts (BMCs) with and without application of a front porous silicon (PS) layer on multicrystalline silicon (mc-Si) solar cells were investigated. A Chemical Vapor Etching (CVE) method was used to perform front PS layer and BMCs of mc-Si solar cells. Good electrical performance for the mc-Si solar cells was observed after combination of BMCs and thin PS films. As a result the current-voltage (I-V) characteristics and the internal quantum efficiency (IQE) were improved, and the effective minority carrier diffusion length (Ln) increases from 75 to 110 μm after BMCs achievement. The reflectivity was reduced to 8% in the 450-950 nm wavelength range. This simple and low cost technology induces a 12% conversion efficiency (surface area = 3.2 cm²). The obtained results indicate that the BMCs improve charge carrier collection while the PS layer passivates the front surface.     

Multicrystalline silicon solar cells with porous silicon emitter

A review of the application of porous silicon (PS) in multicrystalline silicon solar cell processes is given. The different PS formation processes, structural and optical properties of PS are discussed from the viewpoint of photovoltaics. Special attention is given to the use of PS as an antireflection coating in simplified processing schemes and for simple selective emitter processes as well as to its light trapping and surface passivating capabilities. The optimization of a PS selective emitter formation results in a 14.1% efficiency mc-Si cell processed without texturization, surface passivation or additional ARC deposition. The implementation of a PS selective emitter into an industrially compatible screenprinted solar cell process is made by both the chemical and electrochemical method of PS formation. Different kinds of multicrystalline silicon materials and solar cell processes are used. An efficiency of 13.2% is achieved on a 25 cm² mc-Si solar cell using the electrochemical technique while the efficiencies in between 12% and 13% are reached for very large (100–164 cm²) commercial mc-Si cells with a PS emitter formed by chemical method.     

The influence of porous silicon on junction formation in silicon solar cells

In this work the results of a structural investigation by SEM of porous silicon (PS) before and after diffusion processes are reported. The formation of PS n⁺/p structures were carried out on PS p/p silicon wafers with two methods: from POCl₃ in a conventional furnace and from a phosphorous doped paste in an infrared furnace. Sheet resistance was found to be a strong function of PS structure. Further details on sheet resistance distribution are reported. The electrical contacts in prepared solar cells were obtained by screen printing process, with a Du Ponte photovoltaic silver paste for front contacts and home-prepared silver with 3% aluminium paste for the back ones. Metallization was done in the infrared furnace. Solar cell current–voltage characteristics were measured under an AM 1.5 global spectrum sun simulator. The average results for multi-crystalline silicon solar cells without antireflection coating are: I_sc=720 (mA), V_oc=560 (mV), FF=69%, Eff=10.6% (area 25 cm²).     

Formation of porous silicon for large-area silicon solar cells: A new method

Luminescent porous silicon (PS) was prepared for the first time using a spraying set-up, which can diffuse in a homogeneous manner HF solutions, on textured or untextured (1 0 0) oriented monocrystalline silicon substrate. This new method allows us to apply PS onto the front-side surface of silicon solar cells, by supplying very fine HF drops. The front side of N⁺/P monocrystalline silicon solar cells may be treated for long periods without altering the front grid metallic contact. The monocrystalline silicon solar cells (N⁺/P, 78.5 cm²) which has undergone the HF-spraying were made with a very simple and low-cost method, allowing front-side Al contamination. A poor but expected 7.5% conversion efficiency was obtained under AM1 illumination. It was shown that under optimised HF concentration, HF-spraying time and flow HF-spraying rate, Al contamination favours the formation of a thin and homogeneous hydrogen-rich PS layer. It was found that under optimised HF-spraying conditions, the hydrogen-rich PS layer decreases the surface reflectivity up to 3% (i.e., increase light absorption), improves the short circuit current (I_sc), and the fill factor (FF) (i.e., decreases the series resistance), allowing to reach a 12.5% conversion efficiency. The dramatic improvement of the latter is discussed throughout the influence of HF concentration and spraying time on the I–V characteristics and on solar cells parameters. Despite the fact that the thin surfae PS layer acts as a good anti-reflection coating (ARC), it improves the spectral response of the cells, especially in the blue-side of the solar spectrum, where absorption becomes greater, owing to surface band gap widening and conversion of a part of UV and blue light into longer wavelengths (that are more suitable for conversion in a Si cell) throughout quantum confinement into the PS layer.     

Optimization of porous silicon reflectance for silicon photovoltaic cells

The antireflection properties of electrochemically formed porous silicon (PS) layers in the 0.3 μm thick n⁺ emitter of Si p–n⁺ junctions, have been optimized for application to commercial silicon photovoltaic cells. The porosity and thickness of the PS layers are easily adjusted by controlling the electrochemical formation conditions (current density and anodization time). The appropriate PS formation conditions were determined by carrying out a two steps experiment. A first set of samples allowed to determine the optimal porosity and a second one to adjust the thickness of the PS layers, by evaluating the interference features of the reflectance produced by the layers. A PS layer with optimal antireflection coating (ARC) characteristics was obtained in 30% HF in only 3.5 s. The effective reflectance is reduced to 7.3% between 400 and 1150 nm which leads to a gain of up to 33% in the theoretical short circuit current of a p–n⁺ shallow junction compared to a reference junction without a PS layer. The effective reflectance with optimized PS layers is significantly less than that obtained with a classical TiO₂ ARC on a NaOH pretextured multicrystalline surface (11%).     

Efficiency improvement by porous silicon coating of multicrystalline solar cells

Shallow junction multicrystalline Si solar cells have been processed by an anodical etching technique. More than 25% improvement in short-circuit current and photovoltaic energy conversion efficiency was demonstrated. It was shown that improved performance was caused by antireflection action of the porous silicon layer as well as by the cell surface and grain boundary passivation.     

Fabrication of buried contact silicon solar cells using porous silicon

We report the fabrication of buried contact solar cells using porous silicon as sacrificial layer to create well-defined channels (for buried contacts) in silicon. In this paper, the salient features of the technology have been presented. No detrimental effect was found in the performance of buried contact solar cell with partially filled contact area compared to the solar cells having conventional planar contacts. However, a marked difference in the short circuit current density was seen when channel was fully filled with metal by screen printing, without degradation in the open-circuit voltage. It is expected that improved processing in combination with optimized buried metallic contact parameters may yield higher efficiencies that may result in substantial decrease in solar cell cost.     

Photoluminescence from photochemically etched silicon

The photoluminescence (PL) of photochemically etched silicon is studied. In the photochemical etching process, an n-type silicon wafer is immersed in an etchant solution of hydrofluoric acid (HF) and H₂O₂. A low-power visible laser (typically He–Ne) is used to illuminate the samples. The etching process occurs through the photogeneration of carriers. Although no electrodes are used in this etching method, the final samples show PL similar to electrochemically etched porous silicon. The samples were prepared using (1 0 0) n-type silicon with a resistivity of 1.0–5.5 Ω cm. An He–Ne laser with 20 mW of maximum power output was used and the spot radius (on the samples) was varied from 1 to 4 mm. A strong emission in the red-yellow optical region can be present in the final samples depending on the HF:H₂O₂ concentration ratio, etching time and laser intensity of the etching process. The PL spectra excited with the monochromated output of an Xe light source as excitation is studied. The peak wavelength of the PL intensity shifts to the blue region of the spectrum when increasing the laser intensity. Quantum confinement can explain this blue shifting if smaller silicon nanocrystallites are formed with higher laser intensity. The peak PL intensity also decreases when increasing the laser intensity, although a “threshold” condition must be reached to have measurable PL. Each sample also exhibits a shifting in peak PL wavelength when varying the PL excitation wavelength. The corresponding dependence and the variations of the PL intensity are studied. Other experimental conditions are discussed.     

Correlation between reflectivity and photoluminescent properties of porous silicon films

Porous silicon (PS) layers were formed on p-type, 〈1 0 0〉 oriented, 1-5 Ω cm resistivity Cz silicon wafers by electrochemical etching in an HF:C₂H₅OH (1:2 by volume) electrolyte at room temperature at a constant current density 20 mA/cm². The etching duration was varied to achieve PS layers of different morphologies and thicknesses. Both the photoluminescence (PL) and the total diffused reflectivity spectra of the PS layers were measured. It was found that for the PS layers grown for etching durations of less than 90 s the PL emission is insignificant and reflectivity is quite low. Such PS layers can be used as antireflection coatings (ARC) on solar cells. The PS layers formed for etching durations greater than 90 s show a significant PL emission in 500-800 nm range with peak lying in 630-660 nm wavelength range. When etching duration increases from 90 s to 8 min the PL intensity increases and the PL peak shows a blue shift. With further increase in etching duration the PL intensity decreases and PL peak shows a red shift. The reflectivity of the photoluminescent layers increases with etching duration showing a highest value for a sample grown for 8 min. Further increase in etching duration up to 20 min the reflectivity decreases and then increases. Striking observation is that both the PL emission intensity and reflectivity in the wavelength range of 550-800 nm are maximum for the PS layer grown for the etching duration of 8 min.     

Analysis of the interband transitions in porous silicon

Porous silicon (PS) presents interesting phenomena such as efficient luminescence and a peculiar transport of carriers. Due to its possible optoelectronic applications, it is important to calculate the dielectric function from interband optical transitions in PS to include quantum effects. In this work, we apply a supercell model for PS within an sp³s^* tight-binding technique, to analyze the effects of pores on the above-mentioned transitions. The polarized light absorption is studied by observing the oscillator strength behavior within two different schemes, which are applied and compared. We have found a significant enlargement of the optically active zone in the k-space, due to the localization of the wave function. The calculated dielectric functions for crystalline silicon and PS are compared with experimental results, giving the correct energy range and shape.     

Formation and characterization of porous silicon layers for application in multicrystalline silicon solar cells

The electrochemical formation of porous silicon (PS) layers in the n⁺ emitter of silicon p–n⁺ homojunctions for solar energy conversion has been investigated. During the electrochemical process under constant polarization, a variation of the current density occurs. This effect is explained by considering the doping impurity gradient in the emitter and by TEM characterization of the PS layer structure. Optical transmission measurements indicate that modifications of the refractive index and absorption coefficient of PS are mainly related to the porosity value. Reflectivity measurements, spectral response and I–V characteristics show that PS acts as an efficient antireflection coating layer. However, beyond a critical layer thickness, i.e. when PS reaches the p–n⁺ interface, the junction properties are degraded.     

Modeling of combustion and ignition of solid-propellant ingredients

Techniques for modeling energetic-material combustion and ignition have evolved tremendously in the last two decades and have been successfully applied to various solid-propellant ingredients. There has been a paradigm shift in the predictive capability of solid-propellant combustion models as the field has advanced from a simple and global-kinetics approach to a detailed approach that employs elementary reaction mechanisms in the gas phase, and accommodates thermal decomposition and subsequent reactions in the condensed phase. The detailed models not only allow calculation of propellant burning-rate characteristics, such as pressure and temperature sensitivities, but also of the surface conditions and entire combustion-wave structure, including the spatial variations in temperature and species concentrations.

This paper provides a comprehensive review of recent advances in the modeling and simulation of various solid-propellant ingredients over a wide range of ambient conditions. The specific materials of concern include nitramines (RDX, HMX), azides (GAP), nitrate esters (NG, BTTN, TMETN), ADN, and AP monopropellants, as well as homogeneous mixtures representing binary (RDX/GAP, HMX/GAP, and AP/HTPB) and ternary (RDX/GAP/BTTN) pseudo-propellants. Emphasis is placed on the steady-state combustion and laser-induced ignition of nitramines. The capabilities and deficiencies of existing approaches are addressed. In general, the detailed gas-phase reaction mechanisms developed so far represent the chemistry of monopropellants and associated mixtures consistently well, and help understand the intricate processes of solid-propellant combustion. The reaction mechanisms in the condensed phase, however, still pose an important challenge. Furthermore, the current knowledge of the initial decomposition of molecules emerging from the propellant surface is insufficient to render the models fully predictive. Modeling is thus not yet a predictive tool, but it is a useful guide. In the near future, it is likely that detailed combustion models can assist in the formulation of advanced solid propellants meeting various performance and emission requirements.     

Gettering impurities from crystalline silicon by phosphorus diffusion using a porous silicon layer

The possible benefits of phosphorus-based gettering applied to crystalline silicon wafers have been evaluated. The gettering process is achieved by forming porous silicon (PS) layers on both sides of the Si wafers. The PS layers were formed by the stain-etching technique, and phosphorus diffusion using liquid POCl₃-based source was done on both sides of the Si wafer. The realized phosphorus/PS/Si/PS/phosphorus structure undergoes a heat treatment in an infrared furnace under an O₂/N₂ controlled atmosphere. This heat treatment allows phosphorus to diffuse throughout the PS layer and to getter eventual metal impurities towards the phosphorus doped PS layer. The gettering effect was evaluated using four probe points, Hall effect measurements and the light beam induced current (LBIC) technique. These techniques enable to measure the density and the mobility of the majority carrier and the minority carrier diffusion length (L_d) of the Si substrate. We noticed that the best gettering is achieved at 900 °C for 90 min of heat treatment. After gettering impurities, we found an apparent enhancement of the mobility and the minority carrier diffusion length as compared to the reference substrate.     

Surface contributions to the effective optical properties of porous silicon

Porous silicon (PS) presents efficient photoluminescence and electroluminescence with potential applications in the optoelectronic industry, in particular in photovoltaic devices. It is now generally accepted that the interesting optical properties of PS are due to two combined aspects: on the one hand, the quantum confinement and on the other, the surface states. Although there has been a great effort to study PS, its transport properties are still not well understood. Due to the complex structure of PS an averaging theory to describe its effective properties is justified. In this work the effective dielectric function, effective absorption coefficient and effective refractive index are calculated using the volume averaging method for a model of periodic columns with different surface coatings simulating porous silicon. This approach allows analytical results within certain approximations and the analysis of surface contributions. The method uses parameters to characterize the bulk and the surface. We choose for the bulk c-Si, and cover it with three different possible surfaces: siloxane, a-Si : H and SiO₂. The results are compared with experimental data and other theoretical approaches for silicon wires. We obtain good agreement with some experimental results showing the important role of the surface in the effective response of porous silicon.     

Performance improvements of crystalline silicon by iterative gettering process for short duration and with the use of porous silicon as sacrificial layer

In this work, we demonstrate that an efficient purification method of silicon wafers where iterative sequences were used. Each sequence consists of forming porous silicon (PS) on both sides of the samples, followed by thermal annealing in an infrared furnace under N₂/SiCl₄ ambient. Improvements of the electronic parameters were obtained by optimizing the heat treatments temperatures and the number and duration of the iteration sequences. Best results were obtained for temperatures below 980 °C and for three sequences of 20 min each one. After three sequences the mobility of the majority carrier improved from 94 cm² V⁻¹ s⁻¹ (for untreated wafer) to about 374 cm² V⁻¹ s⁻¹. The observed results were explained taking into account the transport properties of the impurities in the porous media and their concentration at the walls at each iteration. It was found that short iterative sequences give almost the same results than one long sequence duration. Silicon solar cells based on iterative gettered silicon wafers exhibit an increase in the short-circuit current and the open-circuit voltage. This fact seems to be important to ameliorate solar grade silicon (SGS) based solar cells performances.     

Characterization of porous silicon photovoltaic devices through rapid thermal oxidation, rapid thermal annealing and HF-dipping processes

The characteristics of a porous silicon Schottky barrier are improved through rapid thermal oxidation and rapid thermal annealing processes. However, the photovoltaic photocurrent at zero bias is degraded seriously by the thin oxide formed under the metal contact after the rapid thermal oxidation and the rapid thermal annealing processes. An HF-dipping process is used to remove the oxide of the metal contact area and to improve the short-circuit current and the open-circuit voltage. Under the optimum preparation conditions, a short-circuit current of about 4 mA and an open-circuit voltage of about 0.52 V are obtained under a tungsten lamp illumination of 22.4 mW/cm². The main problem is the series resistance of the high-resistivity substrate, the photovoltaic characteristics can be further improved if a low-resistivity substrate is used.     

Photocatalytic H2 evolution of porous silicon derived from magnesiothermic reduction of mesoporous SiO2

In this work, porous silicon (PSi) was synthesized by magnesiothermic reduction of mesoporous SiO₂ (MCM-41) and its photocatalytic hydrogen evolution performance was investigated. The unique mesoporous structure of PSi expands the band gap of silicon and shifts its conduction band to a more negative position. As a result, excellent photocatalytic water splitting efficiency of 604.7 μmol h⁻¹ g⁻¹ under visible-light radiation is recorded for the synthesized PSi photocatalysts without loading noble metal cocatalysts. This study presented a promising visible light response photocatalysts for the generation green renewable hydrogen energy basing on PSi material deriving from simple magnesiothermic reduction of mesoporous SiO₂.     

Double porous silicon layer on multi-crystalline Si for photovoltaic application

Double porous silicon (d-PS) layers formed by acid chemical etching on a top surface of n⁺/p multi-crystalline silicon solar cells were investigated with the aim to improve the performance of standard screen-printed silicon solar cells. First a macro-porous layer is formed on mc-Si. The role of this layer is texturization of surface. Next, the cells have been manufactured using standard technology based on screen-printing metallization. Finally, a second mezo-porous layer in n⁺ emitter of cell has been produced. The role of this PS layer is to serve as an antireflection coating. In this way, we have obtained d-PS layers on these solar cells. The paper present observation of d-PS microstructure with SEM as well as measurements of its effective reflectance at the level of 2.5% in the 400–1000 nm length wave range. The efficiency of the solar cells with this structure is about 12%.     

Porous silicon layer transfer processes for solar cells

A promising cost-effective way of converting sun light into electricity could be a solar cell realized in a thin monocrystalline silicon film, due to its potential to achieve cell efficiencies of more than 20% in a 20 μm thick film. A porous silicon layer transfer technique provides an opportunity to get monocrystalline films on low-cost substrates such as glass. This paper reviews various processes, which are being developed for the layer transfer using porous silicon as a sacrificial layer while reusing of starting silicon substrate. The four basic steps—porous silicon formation, active layer deposition, layer separation and transfer, and device fabrication—have been identified in layer transfer process. The processes have been categorized and compared on the basis of the sequence of steps used in individual processes.