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Controlled temperature profiles essential to production of solar cells. Studies of inverted meniscus process for depositing silicon coatings on ceramic substrates described in new report. When fully developed, processed used to manufacture low-cost solar photovoltaic cells.
Experimetnal fabrication process makes submicron-sized structures of single-crystal metallic CoSi2 on silicon substrates. Amorphous Co:Si(1:2) crystallized by electron beam becoming single-crystal CoSi2. Remaining amorphous Co:Si then preferentially etched away. When fully developed, process used to make fine wires or dots exhibiting quantum confinement of charge carriers.
The development of a vacuum die-casting process for producing silicon sheet suitable for photovoltaic cells with a terrestrial efficiency greater than 12 percent and having the potential to be scaled for large quantity production is considered. The initial approach includes: (1) obtaining mechanical design parameters by using boron nitride, which has been shown to non-wetting to silicon; (2) optimizing silicon nitride material composition and coatings by sessile drop experiments; (3) testing effectiveness of fluoride salt interfacial media with a graphite mold; and (4) testing the effect of surface finish using both boron nitride and graphite. When the material and mechanical boundary conditions are established, a finalized version of the prototype assembly will be constructed and the casting variables determined.
Semiempirical mathematical model proposed for control of growth of single crystals of silicon by Czochralski process. Expresses dependence of pulling rate and shape of liquid/solid interface upon important process variables; radius of growing crystal, temperature of crucible, level of melt, and height of exposed portion of crucible wall. Necessary to control shape of interface in manner consistent with other variables, to maintain radially uniform concentration of dopant, and reduce thermally induced stresses in vicinity of interface. Used to simulate complete growth cycles without requiring excessive computer time consumed by rigorous finite-element modeling.
Lithium-ion battery cathode materials suffer from bulk and interfacial degradation issues, which negatively affect their electrochemical performance. Oxide coatings can mitigate some of these problems and improve electrochemical performance. However, current coating strategies have low throughput, are expensive, and have limited applicability. In this article, we describe a low-cost and scalable strategy for applying oxide coatings on cathode materials. Here, we report synergistic effects of these oxide coatings on the performance of aqueously processed cathodes in cells. The SiO 2 coating strategy developed herein improved mechanical, chemical, and electrochemical performance of aqueously processed Ni-, Mn- and Co-based cathodes. This strategy can be used on a variety of cathodes to improve the performance of aqueously processed Li-ion cells.
A process for n-type (electron-donor) delta doping has shown promise as a means of modifying back-illuminated image detectors made from n-doped high-purity silicon to enable them to detect high-energy photons (ultraviolet and x-rays) and low-energy charged particles (electrons and ions). This process is applicable to imaging detectors of several types, including charge-coupled devices, hybrid devices, and complementary metal oxide/semiconductor detector arrays. Delta doping is so named because its density-vs.-depth characteristic is reminiscent of the Dirac delta function (impulse function): the dopant is highly concentrated in a very thin layer. Preferably, the dopant is concentrated in one or at most two atomic layers in a crystal plane and, therefore, delta doping is also known as atomic-plane doping. The use of doping to enable detection of high-energy photons and low-energy particles was reported in several prior NASA Tech Briefs articles. As described in more detail in those articles, the main benefit afforded by delta doping of a back-illuminated silicon detector is to eliminate a "dead" layer at the back surface of the silicon wherein high-energy photons and low-energy particles are absorbed without detection. An additional benefit is that the delta-doped layer can serve as a back-side electrical contact. Delta doping of p-type silicon detectors is well established. The development of the present process addresses concerns specific to the delta doping of high-purity silicon detectors, which are typically n-type. The present process involves relatively low temperatures, is fully compatible with other processes used to fabricate the detectors, and does not entail interruption of those processes. Indeed, this process can be the last stage in the fabrication of an imaging detector that has, in all other respects, already been fully processed, including metallized. This process includes molecular-beam epitaxy (MBE) for deposition of three layers, including metallization. The success of the process depends on accurate temperature control, surface treatment, growth of high-quality crystalline silicon, and precise control of thicknesses of layers. MBE affords the necessary nanometer- scale control of the placement of atoms for delta doping. More specifically, the process consists of MBE deposition of a thin silicon buffer layer, the n-type delta doping layer, and a thin silicon cap layer. The n dopant selected for initial experiments was antimony, but other n dopants as (phosphorus or arsenic) could be used. All n-type dopants in silicon tend to surface-segregate during growth, leading to a broadened dopant-concentration- versus-depth profile. In order to keep the profile as narrow as possible, the substrate temperature is held below 300 C during deposition of the silicon cap layer onto the antimony delta layer. The deposition of silicon includes a silicon- surface-preparation step, involving H-termination, that enables the growth of high-quality crystalline silicon at the relatively low temperature with close to full electrical activation of donors in the surface layer.
The program is designed to investigate the fabrication of solar cells on N-type base material by a simultaneous diffusion of N-type and P-type dopants to form an P(+)NN(+) structure. The results of simultaneous diffusion experiments are being compared to cells fabricated using sequential diffusion of dopants into N-base material in the same resistivity range. The process used for the fabrication of the simultaneously diffused P(+)NN(+) cells follows the standard Westinghouse baseline sequence for P-base material except that the two diffusion processes (boron and phosphorus) are replaced by a single diffusion step. All experiments are carried out on N-type dendritic web grown in the Westinghouse pre-pilot facility. The resistivities vary from 0.5 (UC OMEGA)cm to 5 (UC OMEGA)cm. The dopant sources used for both the simultaneous and sequential diffusion experiments are commercial metallorganic solutions with phosphorus or boron components. After these liquids are applied to the web surface, they are baked to form a hard glass which acts as a diffusion source at elevated temperatures. In experiments performed thus far, cells produced in sequential diffusion tests have properties essentially equal to the baseline N(+)PP(+) cells. However, the simultaneous diffusions have produced cells with much lower IV characteristics mainly due to cross-doping of the sources at the diffusion temperature. This cross-doping is due to the high vapor pressure phosphorus (applied as a metallorganic to the back surface) diffusion through the SiO2 mask and then acting as a diffusant source for the front surface.
The advantages of manufacturing solar cells for use in space on the moon rather than on Earth are discussed. It is shown how solar cells manufactured on the moon could significantly reduce the cost of transportation of power systems to space destinations, including the moon, Mars, earth orbit, and transfer orbits. Silicon is abundant on the moon, and refining processes are demonstrated which do not depend on extensive use of reactants imported from Earth. Because of the lower requirements for refined silicon, the amorphous silicon process is preferred, despite lower efficiencies. Calculations show that the specific power of amorphous silicon cells can be adequate for most uses.
Neutralization of poly(acrylic acid) (PAA)-based binders using lithium hydroxide is a common strategy for fabricating silicon anode laminates, which improves rheological properties of slurries toward high-quality electrode laminates. However, the significantly increased basicity causes degradation of Si particles while the irreversible conversion of carboxylic acid groups to lithium carboxylates undermines the binding strength, collectively leading to adverse cycling performance of the fabricated Si anodes. Herein, a novel neutralization process for PAA binders is developed. A weak base, ammonia (NH 3 ), was discovered as a neutralizing agent that still promotes rheological response of binder solutions but results in a reduced pH increase. Interestingly, the resulting ammonium carboxylate groups may cleave during the drying process to restore the neutralized PAA (PAA-NH 3 ) binders to their pristine states. The best-performing composition of 50% neutralization (PAA-50%NH 3 ) provides comparable rheological response as a PAA-Li binder as well as much improved cycling performance. Additionally, the half-cells using the PAA-50%NH 3 binder can deliver 60% capacity retention over 100 cycles at C/3 rate, affording a 23.8% increase compared to PAA-Li half-cells. This restorable neutralization process of PAA binders represents an innovative strategy of mitigating issues from slurry processing of Si particles to achieve concurrent improvements in high-quality lamination and cycling performance.
Silicon carbide (SiC) is a promising material for harsh environment sensors and electronics because it can enable such devices to withstand high temperatures and corrosive environments. Microfabrication techniques have been studied extensively in an effort to obtain the same flexibility of machining SiC that is possible for the fabrication of silicon devices. Bulk micromachining using deep reactive ion etching (DRIE) is attractive because it allows the fabrication of microstructures with high aspect ratios (etch depth divided by lateral feature size) in single-crystal or polycrystalline wafers. Previously, the Sensors and Electronics Branch of the NASA Glenn Research Center developed a DRIE process for SiC using the etchant gases sulfur hexafluoride (SF6) and argon (Ar). This process provides an adequate etch rate of 0.2 m/min and yields a smooth surface at the etch bottom. However, the etch sidewalls are rougher than desired, as shown in the preceding photomicrograph. Furthermore, the resulting structures have sides that slope inwards, rather than being precisely vertical. A new DRIE process for SiC was developed at Glenn that produces smooth, vertical sidewalls, while maintaining an adequately high etch rate.
Chemical processes relevant to the stability and processing of SiC-reinforced Si3N4 composites have been examined from thermochemical considerations. The thermodynamic stabilities of various interfaces, such as SiC-Si3N4, SiC-Si3N4-Si2ON2, and SiC-Si3N4-SiO2, have been examined as a function of temperature, and the temperatures above which these interfaces become unstable have been calculated. The degradation of SiC during the processing of the composite has been examined. The processing routes considered in this study include the reaction bonded silicon nitride (RBSN) process and the pressure-assisted sintering processes with suitable sintering additives.
Markets, applications, and production techniques for Siemens process-produced polycrystalline silicon are surveyed. It is noted that as of 1982 a total of six Si materials suppliers were servicing a worldwide total of over 1000 manufacturers of Si-based devices. Besides solar cells, the Si wafers are employed for thyristors, rectifiers, bipolar power transistors, and discrete components for control systems. An estimated 3890 metric tons of semiconductor-grade polycrystalline Si will be used in 1982, and 6200 metric tons by 1985. Although the amount is expected to nearly triple between 1982-89, research is being carried out on the formation of thin films and ribbons for solar cells, thereby eliminating the waste produced in slicing Czolchralski-grown crystals. The free-world Si production in 1982 is estimated to be 3050 metric tons. Various new technologies for the formation of polycrystalline Si at lower costs and with less waste are considered. New entries into the industrial Si formation field are projected to produce a 2000 metric ton excess by 1988.
Techniques are being developed to provide lower cost polysilicon material for solar cells. Existing technology which normally provides semiconductor industry polysilicon material is undergoing changes and also being used to provide polysilicon material for solar cells. Economics of new and existing technologies are presented for producing polysilicon. The economics are primarily based on the preliminary process design of a plant producing 1,000 metric tons/year of silicon. The polysilicon processes include: Siemen's process (hydrogen reduction of trichlorosilane); Union Carbide process (silane decomposition); and Hemlock Semiconductor process (hydrogen reduction of dichlorosilane). The economics include cost estimates of capital investment and product cost to produce polysilicon via the technology. Sensitivity analysis results are also presented to disclose the effect of major paramentes such as utilities, labor, raw materials and capital investment.
In situ mid-infrared spectroscopy is a powerful technique for understanding the mechanism of CO 2 reduction (CO 2 R) catalysts because it enables the direct detection of catalytic intermediates and products. Moreover, spectroelectrochemistry (SEC), the coupling of spectroscopy with electrochemistry, allows spectroscopic changes to be correlated with applied potentials to reveal potential-dependent intermediates that are often relevant to photoelectrochemical reactions. Hybrid photoelectrodes, comprised of a narrow bandgap semiconductor, like silicon (Si), with a covalently-linked molecular catalyst, are a promising platform for sunlight-driven catalysis, but characterization of the catalytic mechanism(s) is challenging under photoelectrochemical conditions, particularly when the catalyst is present in monolayer or less concentrations. Here, we have developed a new strategy to use multiple-reflection attenuated total reflectance IR spectroscopy (ATR-IR) coupled with electrochemistry to characterize catalysts directly integrated with a semiconductor surface under applied potential. We show that by surface-proximal n-type or p-type doping of the top ~100-200 nm of the crystal surface, Si ATR crystals can be used simultaneously as the internal reflection element and semiconductor working electrode for ATR-IR-SEC measurements. The surface-proximal doping strategy yields a quasi-equipotential surface with excellent infrared transparency that would have been compromised by free carrier absorption if the crystal was uniformly doped. This approach permits the catalytically-active functionalized surface to be directly probed without modification and overcomes signal-to-noise limitations of other strategies that use separately deposited working electrodes on Si ATR crystals. Proof-of-concept ATR-IR-SEC spectra were collected during the reduction and oxidation of monolayers of Re- and Ru-based transition metal carbonyl complexes, respectively, verifying the viability of the technique to probe redox processes associated with CO 2 R catalysts on Si electrode surfaces with high sensitivity.
The paper presents an experimentally developed surface macro-structuring process suitable for high volume production of silicon solar cells. The process lends itself easily to automation for high throughput to meet low-cost solar array goals. The tetrahedron structure observed is 0.5 - 12 micron high. The surface has minimal pitting with virtually no or very few undeveloped areas across the surface. This process has been developed for (100) oriented as cut silicon. Chemi-etched, hydrophobic and lapped surfaces were successfully texturized. A cost analysis as per Samics is presented.
We report on the bulk properties of of n- and p- type Czochralski silicon (Cz-Si) after a high-temperature annealing process known as Tabula Rasa (TR), which is primarily used to annihilate oxygen precipitates. We find significant differences in n- and p-type substrates as well as a strong dependence on the ambient in the resulting process induced degradation. We attribute this ambient dependence to either injection of interstitials or vacancies into the bulk during TR. Finally, we show that subsequent gettering is enhanced due to the annihilation of oxygen precipitates.
Improved plasma-spraying process deposits mullite on silicon carbide substrates. Prevents formation of amorphous mullite by maintaining high temperature of sprayed deposite to allow crystallization to occur. Deposited mullite adheres to substrate and exhibits little or no cracking during thermal cycling. Provides substantially greater resistance to oxidation in dry air and corrosion by molten salt. Process expected useful in depositing mullite on substrates made of other silicon-based ceramics and other ceramic substrates having coefficients of thermal expansion similar to those of mullite.
Processing experiments using wire-saw techniques to slice thin silicon wafers are described. Substrates were sliced directly to 17 mil, 8 mil, and 5 mil thicknesses. Some of the 8 mil substrates and all of the 5 mil substrates were chemically etched to 7 and 4 mils, respectively, to guarantee removal of any saw damage. The wafers wire sawed to 17 mil thicknesses were processed as reference cells. A baseline process which results in an n(+)-p cell structure, and two advanced processes which provide n(+)-p-p(+) structures were utilized. By using a p(+) enhancement layer on the solar cell back surface, the performance of the 7 mil wafers was increased to exceed that of the 17 mil solar cells with simple n(+)-p structures. Cells fabricated by an ion implantation sequence utilizing elemental boron and phosphorus implants were shown to be capable of equalling or exceeding the performance of cells fabricated by an equivalent all-diffusion process.