Engineering topics
Publications and source records attributed to Mccormick, J. R..
Solar cells made with lower capital and operating costs. Process based on chemical-vapor deposition (CVD) of dichlorosilane produces high-grade polycrystalline silicon for solar cells. Process has potential as cost-effective replacement for CVD of trichlorosilane.
Major process steps of a dichlorosilane based chemical vapor deposition (CVD) process for the production of polycrystalline silicon have been evaluated. While an economic analysis of the process indicates that it is not capable of meeting JPL/DOE price objectives ($14.00/kg in 1980 dollars), product price in the $19.00/kg to $25.00/kg range may be achieved. Product quality has been evaluated and ascertained to be comparable to semiconductor-grade polycrystalline silicon. Solar cells fabricated from the material are also equivalent to those fabricated from semiconductor-grade polycrystalline silicon.
The paper investigates the effects of metallic impurities on the performance of silicon solar cells. Czochralski and polycrystalline ingots were employed with boron and phosphorus as primary dopants and with controlled additions of secondary impurities. The data obtained from over 200 crystals indicate that impurity-induced performance loss is primarily due to a reduction of the base diffusion length. Based on this observation, a model is developed which predicts cell performance as a function of secondary impurity concentrations. The model calculations are in good agreement with experimental values except for Cu, Ni, Fe, and to a lesser degree, carbon, which at higher concentrations degrade the cell by junction defect mechanisms.
Two major topics are treated: methods to measure and evaluate impurity effects in silicon and comprehensive tabulations of data derived during the study. Discussions of deep level spectroscopy, detailed dark I-V measurements, recombination lifetime determination, scanned laser photo-response, conventional solar cell I-V techniques, and descriptions of silicon chemical analysis are presented and discussed. The tabulated data include lists of impurity segregation coefficients, ingot impurity analyses and estimated concentrations, typical deep level impurity spectra, photoconductive and open circuit decay lifetimes for individual metal-doped ingots, and a complete tabulation of the cell I-V characteristics of nearly 200 ingots.
The effects of impurities, various thermochemical processes, and any impurity process interactions on the performance of terrestrial silicon solar cells are defined. Determinations of the segregation coefficients of tungsten, tantalum, and cobalt for the Czochralski pulling of silicon single crystals are reported. Sensitive neutron activation analysis was used to determine the metal impurity content of the silicon while atomic absorption was used to measure the metal content of the residual liquid from which the doped crystals were grown. Gettering of Ti doped silicon wafers improved cell performance by one to two percent for the highest temperatures and longest times. The HCl is more effective than POCl3 treatments for deactivating Ti but POCl3 and HCl produced essentially identical results for Mo or Fe.
Results of the 14th quarterly report are presented for a program designed to assess the effects of impurities, thermochemical processes and any impurity process interactions on the performance of terrestrial silicon solar cells. The Phase 3 effort encompasses: (1) potential interactions between impurities and thermochemical processing of silicon; (2) impurity-cell performance relationships in n-base silicon; (3) effect of contaminants introduced during silicon production, refining or crystal growth on cell performance; (4) effects of nonuniform impurity distributions in large area silicon wafers; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells.
The 13th quarterly report of a study entitled an Investigation of the Effects of Impurities and Processing on Silicon Solar Cells is given. The objective of the program is to define the effects of impurities, various thermochemical processes and any impurity-process interactions on the performance of terrestrial silicon solar cells. The Phase 3 program effort falls in five areas: (1) cell processing studies; (2) completion of the data base and impurity-performance modeling for n-base cells; (3) extension of p-base studies to include contaminants likely to be introduced during silicon production, refining or crystal growth; (4) anisotropy effects; and (5) a preliminary study of the permanence of impurity effects in silicon solar cells. The quarterly activities for this report focus on tasks (1), (3) and (4).
Carbon, as a reductant for quartz, must be made available so as to have suitable reactivity in conjunction with high purity, especially with respect to boron and phosphorus. A detailed experimental plan was developed to do this. Different sources of carbon were selected to be subjected to various purification methods and reactivity-enhancement processes. A developmental scale arc furnace was installed to perform quartz-carbon reactivity testing.
The Dow Corning process consists of the carbothermic reduction of silica to produce silicon that is then purified by unidirectional solidification. The process has produced silicon of semiconductor quality with respect to all elements except boron and phosphorus at about 10 ppma and aluminum at 0.1 ppma. Solar cells produced from this silicon gave AM0 conversion efficiencies of 11%. A process cost analysis is presented.
The effects of controlled concentrations of secondary impurities (Al, C, Ca, Cr, Cu, Fe, Mg, Mn, Mo, Ta, Ti, V, Zn, and Zr), incorporated alone or in combinations into Czochralski and float zone crystals, on the performance of silicon solar cells were investigated. Impurity concentrations ranged from 10 to the 11th to 10 to the 17th/cu cm. Solar cells were fabricated by a conventional diffusion process and characterized by computer reduction of current-voltage data. The data suggest that performance loss primarily results from reduction of the base diffusion length. On the basis of this assumption, a first order analytic model which predicts cell performance as a function of impurity concentrations is developed. Calculated performance parameters are in good agreement with observation, except for some impurities, such as Fe, Cu and Ni, which degrade cells via recombination and defects in the junction space-charge region. N-base devices are less affected by impurities, although degradation mechanisms appear to be the same as in p-devices. There seems to be very limited interaction between impurities in multiply-doped cells.
The object of phase 2 of this program is to investigate and define the effects of various processes, contaminants and process-contaminant interactions in the performance of terrestrial solar cells. The major effort this quarter was in the areas of crystal growth and thermal processing, comparison of impurity effects in low and high resistivity silicon, modeling the behavior of p-type ingots containing Mo, and C and, quantitative analysis of bulk lifetime and junction degradation effects in contaminated solar cells. The performance of solar cells fabricated on silicon web crystals grown from melts containing about 10 to the 18th power/cu cm of Cr, Mn, Fe, Ni, Ti, and V, respectively were measured. Deep level spectroscopy of metal-contaminated ingots was employed to determine the level and density of recombination centers due to Ti, V, Ni, and Cr.
A completed preliminary survey of silica sources indicates that sufficient quantities of high-purity quartz are available in the U.S. and Canada to meet goals. Supply can easily meet demand for this little-sought commodity. Charcoal, as a reductant for silica, can be purified to a sufficient level by high-temperature fluorocarbon treatment and vacuum processing. High-temperature treatment causes partial graphitization which can lead to difficulty in smelting. Smelting of Arkansas quartz and purified charcoal produced kilogram quantities of silicon having impurity levels generally much lower than in MG-Si. Half of the goal was met of increasing the boron resistivity from 0.03 ohm-cm in metallurgical silicon to 0.3 ohm-cm in solar silicon. A cost analysis of the solidification process indicate $3.50-7.25/kg Si for the Czochralski-type process and $1.50-4.25/kg Si for the Bridgman-type technique.
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Purity requirements for solar cell grade silicon material was developed and defined by evaluating the effects of specific impurities and impurity levels on the performance of silicon solar cells. Also, data was generated forming the basis for cost-tradeoff analyses of silicon solar cell material. Growth, evaluation, solar cell fabrication and testing was completed for the baseline boron-doped Czochralski material. Measurements indicate Cn and Mn seriously degrade cell performance, while neither Ni nor Cu produce any serious reduction in cell efficiency.
The influence of metallic impurities on solar cell characteristics has been examined to establish the cost sensitive purity versus performance trade-offs. Solar cells were fabricated on 2 to 4 ohm-cm p-type substrates obtained by Czochralski and dendritic web growth processes. Controlled amounts of metallic impurities were introduced into the melt during growth and included Fe, Cr, Mn, Ni, Cu, Ti, V, Zr, Mg, Zn, and Al. Impurity concentrations in the crystals were determined using emission and mass spectrographic techniques and in some cases by neutron activation analysis. The solar cells were characterized by means of a computer program to curve-fit measured voltage-current data. The principal effect of the added impurities is a degradation of lifetime and diffusion length.
The long-term goal of this work is to produce silicon of solar-grade quality at 3 x 10 to the 6th kg/y for less than $10/kg by, or before 1986. The approach is to improve and expand upon the technology used today to commercially produce metallurgical-grade silicon (MG-Si). This is currently being accomplished by using purer raw materials in the arc furnace process for producing MG-Si, by upgrading the furnace itself, and by unidirectionally solidifying the molten silicon exiting the furnace. Solar cells fabricated from partially purified MG-Si have shown average AM0 efficiencies in the range of 9-11%. Since further MG-Si purification yet remains possible, fabrication of cells of considerably higher conversion efficiency is deemed feasible.