Methods of trichlorosilane synthesis for polycrystalline silicon production. Part 1: Direct synthesis

Novel technical solutions and ideas for increasing the yield of solar and semiconductor grade polycrystalline silicon processes have been analyzed. The predominant polycrystalline silicon technology is currently still the Siemens process including the conversion of technical grade silicon (synthesized by carbon-thermal reduction of quartzites) to trichlorosilane followed by rectification and hydrogen reduction. The cost of product silicon can be cut down by reducing the trichlorosilane synthesis costs through process and equipment improvement. Advantages, drawbacks and production cost reduction methods have been considered with respect to four common trichlorosilane synthesis processes: hydrogen chloride exposure of technical grade silicon (direct chlorination, DC), homogeneous hydration of tetrachlorosilane (conversion), tetrachlorosilane and hydrogen exposure of silicon (hydro chlorination silicon, HC), and catalyzed tetrachlorosilane and dichlorosilane reaction (redistribution of anti-disproportioning reaction). These processes remain in use and are permanently improved. Catalytic processes play an important role on silicon surface, and understanding their mechanisms can help find novel applications and obtain new results. It has been noted that indispensable components of various equipment and process designs are recycling steps and combined processes including active distillation. They provide for the most complete utilization of raw trichlorosilane, increase the process yield and cut down silicon cost

Potential of using inert gas flows for controlling the quality of as-grown silicon single crystal

We have improved the well-known Czochralski single crystal silicon growth method by using two argon gas flows. One flow is the main one (15–20 nl/min) and is directed from top to bottom along the growing single crystal. This flow entrains reaction products of melt and quartz crucible (mainly SiO), removes them from the growth chamber through a port in the bottom of the chamber and provides for the growth of dislocation-free single crystals from large weight charge. Similar processes are well known and have been generally used since the 1970s world over. The second additional gas flow (1.5–2 nl/min) is directed at a 45 arc deg angle to the melt surface in the form of jets emitted from circularly arranged nozzles. This second gas flow initiates the formation of a turbulent melt flow region which separates the crystallization front from oxygen-rich convective flows and accelerates carbon evaporation from the melt. It has been confirmed that oxygen evaporated from the melt (in the form of SiO) acts as transport agent for nonvolatile carbon. Commercial process implementation has shown that carbon content in as-grown single crystals can be reduced to below the carbon content in the charge. Single crystals grown with two argon gas flows have also proven to have highly macro- and micro-homogeneous oxygen distributions, with much greater lengths of single crystal portions in which the oxygen concentration is constant and below the preset limit. Carbon contents of 5–10 times lower than carbon content in the charge can be achieved with low argon gas consumption per one growth process (15–20 nl/min vs 50–80 nl/min for conventional processes). The use of an additional argon gas flow with a 10 times lower flowrate than that of the main flow does not distort the pattern of main (axial) flow circumvention around single crystal surface, does not hamper the “dislocation-free growth” of crystals and does not increase the density of microdefects. This suggests that the new method does not change temperature gradients and does not produce thermal shocks that may generate thermal stresses in single crystals

Methods of trichlorosilane synthesis for polycrystalline silicon production. Part 2: Hydrochlorination and redistribution

Novel technical solutions and ideas for increasing the yield of solar and semiconductor grade polycrystalline silicon processes have been analyzed. The predominant polycrystalline silicon technology is currently still the Siemens process including the conversion of technical grade silicon (synthesized by carbon-thermal reduction of quartzites) to trichlorosilane followed by rectification and hydrogen reduction. The cost of product silicon can be cut down by reducing the trichlorosilane synthesis costs through process and equipment improvement. Advantages, drawbacks and production cost reduction methods have been considered with respect to four common trichlorosilane synthesis processes: hydrogen chloride exposure of technical grade silicon (direct chlorination, DC), homogeneous hydration of tetrachlorosilane (conversion), tetrachlorosilane and hydrogen exposure of silicon (hydro chlorination silicon, HC), and catalyzed tetrachlorosilane and dichlorosilane reaction (redistribution of anti-disproportioning reaction). These processes remain in use and are permanently improved. Catalytic processes play an important role on silicon surface, and understanding their mechanisms can help find novel applications and obtain new results. It has been noted that indispensable components of various equipment and process designs are recycling steps and combined processes including active distillation. They provide for the most complete utilization of raw trichlorosilane, increase the process yield and cut down silicon cost

Possible causes of electrical resistivity distribution inhomogeneity in Czochralski grown single crystal silicon

Electrical resistivity distribution maps have been constructed for single crystal silicon wafers cut out of different parts of Czochralski grown ingots. The general inhomogeneity of the wafers has proven to be relatively high, the resistivity scatter reaching 1–3 %. Two electrical resistivity distribution inhomogeneity types have been revealed: azimuthal and radial. Experiments have been carried out for crystal growth from transparent simulating fluids with hydrodynamic and thermophysical parameters close to those for Czochralski growth of silicon single crystals. We show that a possible cause of azimuthal electrical resistivity distribution inhomogeneity is the swirl-like structure of the melt under the crystallization front (CF), while a possible cause of radial electrical resistivity distribution inhomogeneity is the CF curvature. In a specific range of the Grashof, Marangoni and Reynolds numbers which depend on the ratio of melt height and growing crystal radius, a system of well-developed radially oriented swirls may emerge under the rotating CF. In the absence of such swirls the melt is displaced from under the crystallization front in a homogeneous manner to form thermal and concentration boundary layers which are homogeneous in azimuthal direction but have clear radial inhomogeneity. Once swirls emerge the melt is displaced from the center to the periphery, and simultaneous fluid motion in azimuthal direction occurs. The overall melt motion becomes helical as a result. The number of swirls (two to ten) agrees with the number of azimuthally directed electrical resistivity distribution inhomogeneities observed in the experiments. Comparison of numerical simulation results in a wide range of Prandtl numbers with the experimental data suggests that the phenomena observed in transparent fluids are universal and can be used for theoretical interpretation of imperfections in silicon single crystals