WO2022071014A1 - シリコン単結晶の製造方法 - Google Patents

シリコン単結晶の製造方法 Download PDF

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Publication number
WO2022071014A1
WO2022071014A1 PCT/JP2021/034487 JP2021034487W WO2022071014A1 WO 2022071014 A1 WO2022071014 A1 WO 2022071014A1 JP 2021034487 W JP2021034487 W JP 2021034487W WO 2022071014 A1 WO2022071014 A1 WO 2022071014A1
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Prior art keywords
single crystal
dopant
flow rate
silicon single
furnace
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Ceased
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PCT/JP2021/034487
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English (en)
French (fr)
Japanese (ja)
Inventor
省吾 小林
宣人 深津
崇浩 金原
瞳 山本
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Sumco Corp
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Sumco Corp
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Priority to JP2022553849A priority Critical patent/JP7567929B2/ja
Priority to DE112021005126.1T priority patent/DE112021005126B4/de
Priority to CN202180066679.2A priority patent/CN116406433A/zh
Priority to US18/026,975 priority patent/US12351937B2/en
Publication of WO2022071014A1 publication Critical patent/WO2022071014A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/06—Silicon
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/02—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
    • C30B15/04—Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/14—Heating of the melt or the crystallised materials

Definitions

  • the present invention relates to a method for producing a silicon single crystal by the Czochralski method (CZ method), and more particularly to a method for additionally supplying a dopant during the crystal pulling process.
  • CZ method Czochralski method
  • the silicon single crystals used as substrate materials for semiconductor devices are manufactured by the CZ method.
  • a seed crystal is immersed in a silicon melt contained in a quartz turret, and the seed crystal and the quartet are gradually pulled up while rotating to form a single crystal having a large diameter below the seed crystal. Grow.
  • the CZ method it is possible to produce a high quality silicon single crystal with a high yield.
  • dopants In the growth of a silicon single crystal, various doping agents (dopants) are used to adjust the electrical resistivity of the single crystal (hereinafter, simply referred to as resistivity). Typical dopants are boron (B), phosphorus (P), arsenic (As), antimony (Sb) and the like. Usually, these dopants are put into a quartz crucible together with a polycrystalline silicon raw material and melted together with the polycrystalline silicon by heating with a heater. As a result, a silicon melt containing a predetermined amount of dopant is produced.
  • a method of supplying a dopant during the pulling of the silicon single crystal is effective. For example, by adding a p-type topant to the silicon melt during the pulling up of the n-type silicon single crystal, it is possible to suppress a decrease in the resistance of the silicon single crystal due to the influence of segregation of the n-type dopant.
  • Such a method of additionally supplying a conductive type sub-dopant opposite to the main dopant is called counter-doping.
  • Patent Document 1 a dopant is added so that the input rate of a dopant of a type (for example, p-type) opposite to that of the initially input type (for example, n-type) satisfies a predetermined relational expression.
  • Patent Document 2 describes a method of controlling the resistivity in the axial direction of a grown silicon single crystal by inserting a rod-shaped silicon crystal containing an auxiliary dopant into a raw material melt.
  • an object of the present invention is to provide a method for producing a silicon single crystal capable of preventing dislocation of a single crystal in a counter-doping method in which a sub-dopant is dropped during crystal pulling.
  • the method for producing a silicon single crystal comprises a melting step of producing a silicon melt containing a main dopant and a crystal pulling step of pulling the silicon single crystal from the silicon melt.
  • the crystal pulling step includes at least one additional doping step of dropping the sub-dopant into the silicon melt, and the flow rate of Ar gas supplied into the pulling furnace during the first period in which the sub-dopant is not dropped is the first. It is set to one flow rate, and the flow rate of the Ar gas supplied into the pulling furnace during the second period including the period in which the sub-dopant is dropped is set to a second flow rate larger than the first flow rate. It is a feature.
  • the present invention it is possible to prevent dislocation of a silicon single crystal due to the sub-dopant dropped into the silicon melt reaching the solid-liquid interface in an unmelted state and being incorporated into the silicon single crystal.
  • the amount of increase of the second flow rate with respect to the first flow rate is preferably 40 L / min or more and 300 L / min or less in terms of the converted flow rate at room temperature and atmospheric pressure. If it is less than 40 L / min, the effect is small, and if it exceeds 300 L / min, the liquid level temperature may decrease and the single crystal may be dislocated.
  • the amount of increase in the second flow rate with respect to the first flow rate is preferably 80 L / min or more and 160 L / min or less.
  • the second flow rate is preferably 120 L / min or more, preferably 1.5 times or more and 5 times or less, particularly twice the first flow rate in terms of converted flow rate at room temperature and atmospheric pressure. It is preferably 3 times or more and 3 times or less. This makes it possible to prevent dislocations of the silicon single crystal due to the unmelted sub-dopant being incorporated into the solid-liquid interface.
  • the flow rate of the Ar gas is increased to the second flow rate before the addition of the sub-dopant is started, and the flow rate of the Ar gas is increased after the addition of the sub-dopant is completed. It is preferable to return to the first flow rate. This makes it possible to further reduce the probability that the dopant dropped on the silicon melt is incorporated into the solid-liquid interface in an unmelted state.
  • the pressure in the hoisting furnace is set to the pressure in the first furnace during the first period, and the pressure in the hoisting furnace is set to be lower than the pressure in the first furnace during the second period. It is preferable to set the internal pressure. By changing the furnace pressure at the same time as the Ar gas flow rate, the probability of dislocation can be further reduced.
  • the amount of decrease in the pressure in the second furnace with respect to the pressure in the first furnace is preferably 1 Torr or more and 10 Torr or less.
  • the pressure inside the first furnace is often several tens of Torr, and if the amount of decrease in the pressure inside the second furnace is more than 10 Torr, the pressure inside the second furnace becomes too low and causes dislocation of the single crystal that is being pulled up. There is a risk.
  • the amount of decrease in the pressure inside the second furnace is less than 1 Torr, the pressure inside the second furnace is almost the same as the pressure inside the first furnace, so that it is difficult to obtain the effect of reducing the probability of dislocation.
  • the amount of decrease in the pressure in the second furnace with respect to the pressure in the first furnace is 1 Torr or more and 10 Torr or less, the probability of dislocation of the single crystal can be further reduced.
  • a substantially cylindrical heat-shielding member is arranged above the silicon melt so as to surround the silicon single crystal pulled up from the silicon melt, and the heat-shielding member It is preferable to pull up the silicon single crystal while controlling the flow velocity of the Ar gas passing through the gap between the lower end and the melt surface.
  • the present invention by increasing the flow rate of Ar gas during counter-doping, it is possible to increase the flow rate of Ar gas flowing from the center side of the silicon single crystal to the outside in the vicinity of the liquid surface of the silicon melt. It is possible to prevent the molten dopant from approaching the solid-liquid interface.
  • the Ar gas that passes through the gap between the lower end of the heat shield member and the melt surface and goes outward from the central axis side of the silicon single crystal.
  • the flow velocity can be increased, which is effective in preventing the unmelted dopant from approaching the solid-liquid interface.
  • the oxygen concentration in the silicon single crystal is preferably 6 ⁇ 10 17 atoms / cm 3 (ASTM F-121, 1979) or less, and 4 ⁇ 10 17 atoms / cm 3 (ASTM F-121, 1979). 1979) The following is particularly preferable.
  • the electrical resistivity of the silicon single crystal is preferably 10 ⁇ cm or more and 1000 ⁇ cm or less, and particularly preferably 20 ⁇ cm or more and 100 ⁇ cm or less. In this way, when pulling up a silicon single crystal with a low oxygen concentration and a narrow resistivity range, it is necessary to reduce the Ar gas flow rate in the furnace during the crystal pulling process, and the counter is under the condition that the Ar gas flow rate is low. When doping is performed, the probability of dislocation of the silicon single crystal is high. However, when the Ar gas flow rate is increased only during the counterdoping step as in the present invention, the probability of dislocation of the silicon single crystal can be reduced.
  • the method for producing a silicon single crystal includes a melting step of producing a silicon melt containing a main dopant and a crystal pulling step of pulling a silicon single crystal from the silicon melt, and the crystal pulling step includes a crystal pulling step.
  • the pressure in the furnace is set to the pressure in the first furnace, which comprises at least one additional doping step of dropping the sub-dopant into the silicon melt, and the sub-dopant is dropped. It is characterized in that the pressure in the pulling furnace is set to the pressure in the second furnace lower than the pressure in the first furnace during the second period including the period in which the
  • the present invention it is possible to prevent dislocation of a silicon single crystal due to the sub-dopant dropped into the silicon melt reaching the solid-liquid interface in an unmelted state and being incorporated into the silicon single crystal.
  • the amount of decrease in the pressure in the second furnace with respect to the pressure in the first furnace is preferably 1 Torr or more and 10 Torr or less.
  • the pressure inside the first furnace is often several tens of Torr, and if the amount of decrease in the pressure inside the second furnace is more than 10 Torr, the pressure inside the second furnace becomes too low and causes dislocation of the single crystal that is being pulled up. There is a risk.
  • the amount of decrease in the pressure inside the second furnace is less than 1 Torr, the pressure inside the second furnace is almost the same as the pressure inside the first furnace, so that it is difficult to obtain the effect of reducing the probability of dislocation.
  • the amount of decrease in the pressure in the second furnace with respect to the pressure in the first furnace is 1 Torr or more and 10 Torr or less, the probability of dislocation of the single crystal can be further reduced.
  • the present invention it is possible to provide a method for producing a silicon single crystal that can prevent dislocation of a single crystal in a counter-doping method in which a sub-dopant is dropped during crystal pulling.
  • FIG. 1 is a schematic cross-sectional view showing the configuration of a single crystal manufacturing apparatus according to an embodiment of the present invention.
  • FIG. 2 is a flowchart for explaining a method for producing a silicon single crystal according to an embodiment of the present invention.
  • FIG. 3 is a flowchart for explaining the straight body portion growing step S16 including the counter-doping step.
  • FIG. 4 is a graph showing the relationship between the dopant dropping period, the Ar gas flow rate, and the intracranial pressure.
  • FIG. 5 is a graph showing the change in resistivity in a silicon single crystal when two counter-dopings are performed.
  • FIG. 6 is a graph showing the results of measuring the resistivity of a silicon single crystal according to the examples by the four-probe method.
  • FIG. 1 is a schematic cross-sectional view showing the configuration of a single crystal manufacturing apparatus according to an embodiment of the present invention.
  • the single crystal manufacturing apparatus 1 includes a chamber 10 constituting a pulling furnace for a silicon single crystal 2, a quartz rut 12 installed in the chamber 10, and a graphite susceptor supporting the quartz rut 12. 13, a shaft 14 that supports the susceptor 13 so as to be able to move up and down and rotatably, a heater 15 arranged around the susceptor 13, a heat shielding member 16 arranged above the quartz rut 12, and above the quartz rut 12.
  • a single crystal pulling wire 17 arranged coaxially with the shaft 14, a wire winding mechanism 18 arranged above the chamber 10, and a dopant supply device 20 for supplying the dopant raw material 5 into the quartz acupoint 12. It includes a control unit 30 that controls each unit.
  • the chamber 10 is composed of a main chamber 10a, a top chamber 10b that covers the upper opening of the main chamber 10a, and an elongated cylindrical pull chamber 10c connected to the upper opening of the top chamber 10b.
  • the susceptor 13, the heater 15, and the heat shielding member 16 are provided in the main chamber 10a.
  • the susceptor 13 is fixed to the upper end of a shaft 14 provided in the vertical direction through the center of the bottom of the chamber 10, and the shaft 14 is moved up and down and rotationally driven by the shaft drive mechanism 19.
  • the heater 15 is used to melt the polycrystalline silicon raw material filled in the quartz crucible 12 to generate the silicon melt 3.
  • the heater 15 is a carbon resistance heating type heater, and is provided so as to surround the quartz crucible 12 in the susceptor 13.
  • a heat insulating material 11 is provided on the outside of the heater 15. The heat insulating material 11 is arranged along the inner wall surface of the main chamber 10a, whereby the heat retaining property in the main chamber 10a is enhanced.
  • the heat shielding member 16 is provided to prevent the silicon single crystal 2 from being heated by the radiant heat from the heater 15 and the quartz crucible 12 and to suppress the temperature fluctuation of the silicon melt 3.
  • the heat shielding member 16 is a substantially cylindrical member whose diameter decreases from the upper side to the lower side, and is provided so as to cover the upper part of the silicon melt 3 and surround the growing silicon single crystal 2. It is preferable to use graphite as the material of the heat shielding member 16.
  • An opening larger than the diameter of the silicon single crystal 2 is provided in the center of the heat shielding member 16 to secure a pulling path for the silicon single crystal 2. As shown, the silicon single crystal 2 is pulled upward through the opening.
  • the diameter of the opening of the heat shielding member 16 is smaller than the diameter of the quartz crucible 12 and the lower end portion of the heat shielding member 16 is located inside the quartz crucible 12, the upper end of the rim of the quartz crucible 12 is from the lower end of the heat shielding member 16.
  • the heat shielding member 16 does not interfere with the quartz crucible 12 even if it is raised upward.
  • the rise of the quartz rut 12 is controlled so that the distance (gap) between the melt surface and the heat shielding member 16 becomes constant.
  • the temperature fluctuation of the silicon melt 3 can be suppressed, and the flow rate of Ar gas flowing in the vicinity of the melt surface (purge gas guide path) can be kept constant to control the evaporation amount of the dopant from the silicon melt 3. Therefore, it is possible to improve the stability of the crystal defect distribution, the oxygen concentration distribution, the resistivity distribution, etc. in the pulling axis direction of the single crystal.
  • FIG. 1 shows a state in which the silicon single crystal 2 being grown is suspended from the wire 17.
  • a gas intake port 10d for introducing Ar gas (purge gas) into the chamber 10 is provided in the upper part of the pull chamber 10c, and a gas for exhausting the Ar gas in the chamber 10 is provided at the bottom of the main chamber 10a.
  • An exhaust port 10e is provided.
  • the Ar gas means that the main component of the gas (more than 50 vol.%) Is argon, and may contain a gas such as hydrogen or nitrogen.
  • the Ar gas supply source 31 is connected to the gas intake port 10d via the mass flow controller 32, Ar gas from the Ar gas supply source 31 is introduced into the chamber 10 from the gas intake port 10d, and the introduced amount is the mass flow controller. It is controlled by 32. Further, since the Ar gas in the sealed chamber 10 is exhausted to the outside of the chamber 10 from the gas exhaust port 10e, it is possible to recover the SiO gas and CO gas in the chamber 10 and keep the inside of the chamber 10 clean. Become.
  • the Ar gas heading from the gas intake port 10d to the gas exhaust port 10e passes through the opening of the heat shield member 16, pulls up along the melt surface from the center of the furnace to the outside, and further descends to the gas exhaust port 10e. To reach.
  • a vacuum pump 33 is connected to the gas exhaust port 10e via a pipe, and the vacuum pump 33 sucks Ar gas in the chamber 10 and controls the flow rate by the valve 34 to reduce the pressure in the chamber 10 to a constant level. It is kept in a state.
  • the air pressure in the chamber 10 is measured by a pressure gauge, and the amount of Ar gas exhausted from the gas exhaust port 10e is controlled so that the air pressure in the chamber 10 is constant.
  • the dopant supply device 20 includes a dopant supply tube 21 drawn from the outside of the chamber 10 into the inside thereof, a dopant hopper 22 installed outside the chamber 10 and connected to the upper end of the dopant supply tube 21, and a dopant supply tube 21. It is provided with a seal cap 23 for sealing the opening 10f of the top chamber 10b through which the top chamber 10b penetrates.
  • the dopant supply pipe 21 is a pipe that reaches directly above the silicon melt 3 in the quartz crucible 12 from the installation position of the dopant hopper 22 through the opening 10f of the top chamber 10b.
  • the dopant raw material 5 is additionally supplied from the dopant supply device 20 to the silicon melt 3 in the quartz crucible 12.
  • the dopant raw material 5 discharged from the dopant hopper 22 is supplied to the silicon melt 3 through the dopant supply pipe 21.
  • the dopant raw material 5 supplied from the dopant supply device 20 is granular silicon containing a sub-dopant.
  • a dopant raw material 5 is produced by growing a silicon crystal containing a high concentration of a secondary dopant by, for example, a CZ method, and then finely crushing the silicon crystal.
  • the dopant raw material 5 used for counter-doping is not limited to silicon containing a secondary dopant, and may be a simple substance of the dopant or a compound containing a dopant atom.
  • the shape of the dopant raw material 5 is not limited to the granular shape, and may be a plate shape or a rod shape.
  • FIG. 2 is a flowchart for explaining a method for producing a silicon single crystal according to an embodiment of the present invention.
  • the quartz crucible 12 is first filled with the polycrystalline silicon raw material together with the main dopant (raw material filling step S11).
  • the main dopant for pulling up an n-type silicon single crystal is, for example, phosphorus (P), arsenic (As) or antimony (Sb), and the main dopant for pulling up a p-type silicon single crystal is, for example, boron (B), aluminum ( Al), gallium (Ga) or indium (In).
  • the polysilicon in the quartz crucible 12 is heated by the heater 15 and melted to generate the silicon melt 3 containing the main dopant (melting step S12).
  • step S13 the seed crystal attached to the tip of the wire 17 is lowered and landed on the silicon melt 3 (step S13).
  • a crystal pulling step (steps S14 to S17) is carried out in which the seed crystal is gradually pulled up while maintaining the contact state with the silicon melt 3 to grow a single crystal.
  • the straight body part growing step S16 for forming a straight body part maintained at a specified diameter (for example, about 300 mm) and the tail part growing step S17 for forming a tail part having a gradually reduced crystal diameter are carried out in order.
  • the single crystal is separated from the melt surface. From the above, the silicon single crystal ingot is completed.
  • the straight body portion growing step S16 has at least one counter-doping step (additional doping step) in which a sub-dopant having a conductive type opposite to that of the main dopant contained in the silicon single crystal 2 is put into the silicon melt 3. Is preferable. As a result, it is possible to suppress a change in resistivity in the crystal longitudinal direction of the straight body portion of the silicon single crystal 2.
  • the oxygen concentration in the silicon single crystal for IGBT is preferably 6 ⁇ 10 17 atoms / cm 3 (ASTM F-121, 1979) or less, and preferably 4 ⁇ 10 17 atoms / cm 3 (ASTM F-121, 1979) or less. Is particularly preferable.
  • the resistivity of the silicon single crystal for IGBT is preferably 10 ⁇ cm or more and 1000 ⁇ cm or less, and particularly preferably 20 ⁇ cm or more and 100 ⁇ cm or less.
  • FIG. 3 is a flowchart for explaining the straight body portion growing step S16 including the counter-doping step.
  • the Ar gas flow rate and the furnace internal pressure are set to values suitable for growing a silicon single crystal (step S21).
  • a silicon single crystal for IGBT it is required that the resistivity is low and the interstitial oxygen concentration is low.
  • the Ar gas flow rate required for the normal straight body portion growing step S16 is defined as the first flow rate F1
  • the furnace internal pressure is defined as the first furnace internal pressure P1.
  • the dopant raw material 5 containing the sub-dopant is dropped into the silicon melt 3 (step S24).
  • the sub-dopant for pulling up an n-type silicon single crystal is, for example, boron (B), aluminum (Al), gallium (Ga) or indium (In), and the sub-dopant for pulling up a p-type silicon single crystal is, for example, phosphorus ( P), arsenic (As) or antimony (Sb).
  • the Ar gas flow rate and the intracranial pressure are changed to values suitable for counter-doping.
  • the Ar gas flow rate F 2 (second flow rate) during the dopant dropping period (second period) is larger than the Ar gas flow rate F 1 (first flow rate) during the normal crystal pulling period (first period) (F). 2 > F 1 ) is set.
  • the furnace pressure P 2 (second furnace pressure) during the counterdope period is set to a value (P 2 ⁇ P 1 ) lower than the furnace pressure P 1 (first furnace pressure) during the normal crystal pulling period. ..
  • the dopant dropping period is, in a narrow sense, the period during which the dopant raw material 5 is actually dropped, but in a broad sense, until the dopant dropped in the silicon melt is completely melted and the problem of dislocation does not occur. Refers to the period required for.
  • the amount of increase in the Ar gas flow rate F 2 with respect to the Ar gas flow rate F 1 is preferably 40 L / min or more and 300 L / min or less in terms of the converted flow rate at room temperature and atmospheric pressure. Further, the Ar gas flow rate F 2 is preferably 120 L / min or more in terms of a converted flow rate at room temperature and atmospheric pressure, and is preferably 1.5 times or more and 5 times or less the Ar gas flow rate F 1 . This makes it possible to prevent dislocations of the silicon single crystal due to the unmelted sub-dopant being incorporated into the solid-liquid interface.
  • the amount of decrease in the furnace pressure P 2 with respect to the furnace pressure P 1 is preferably 1 Torr or more and 10 Torr or less.
  • the gas flow rate is returned to the Ar gas flow rate F1 and the furnace pressure P1 during the normal crystal pulling period (first period), and the straight body portion is continued to grow (steps S25 and S26).
  • the counterdope step is repeated according to the required crystal length (steps S27Y, S22Y, S23 to S25). Even after the counterdope is completed, the straight body is continued to grow, and when the counterdope is needed again, the counterdope is started.
  • the number of times the counter-doping is repeated is predetermined, and the counter-doping is repeated until the specified number of times of counter-doping is completed.
  • the Ar gas flow rate and the furnace pressure are changed to values (F 2 , P 2 ) suitable for counter-doping. In this way, by pulling up the silicon single crystal of a desired length while performing counter-doping a predetermined number of times, it is possible to increase the yield of the silicon single crystal in which the change in the resistivity increasing axial direction is small.
  • FIG. 4 is a graph showing the relationship between the dopant dropping period, the Ar gas flow rate, and the intracranial pressure.
  • the Ar gas flow rate is increased and the furnace pressure is decreased during the dopant dropping period.
  • the Ar gas flow rate during the dopant dropping period (second period) is set to twice the Ar gas flow rate during the normal pulling period (first period) in which the dopant is not dropped.
  • the intracranial pressure in the dopant dropping period (second period) is set to 80% of the intracranial pressure in the normal raising period (first period).
  • FIG. 5 is a graph showing the change in resistivity in a silicon single crystal when two counter-dopings are performed, and the horizontal axis is the crystal length (relative value when the total length of the straight body is 1). , The vertical axis shows the resistivity (relative value), respectively.
  • the resistivity of the silicon single crystal is the highest at the start of pulling, and only gradually decreases as the pulling progresses. When the length exceeds about 0.44, the resistivity deviates from the standard.
  • the resistivity of the single crystal is within the standard.
  • the length can be as long as possible.
  • the method for producing a silicon single crystal includes a step of dropping a main dopant of the silicon single crystal and a reverse conductive type sub-dopant into the silicon melt during the step of pulling up the silicon single crystal. Since the Ar gas flow rate during the sub-dopant dropping period is made larger than that during the sub-dopant non-dropping period and the internal pressure in the furnace is lowered, it is possible to prevent the single crystal from undergoing rearrangement.
  • a sample is obtained by vertically dividing the crystal block near the dopant dropping position and grinding so that the sample thickness is 1.0 mm. It was processed and further subjected to donor killer treatment (heat treatment at 650 ° C. for 40 minutes) for resistivity measurement.
  • the resistivity of the sample was measured by the four-probe method.
  • the resistivity measurement pitch was 1 mm pitch in the vicinity of the sub-dopant dropping position and 5 mm pitch in other cases.
  • the result of the resistivity continuous measurement is shown in FIG. As shown in the figure, the resistivity increased immediately after the dopant was dropped, and then the resistivity was obtained according to segregation. The resistivity after the second drop of the sub-dopant was slightly lower than the target resistivity, but generally good results were obtained.
  • the silicon single crystal with the counter-doping as described above was pulled up four times, but no dislocation occurred in any of the silicon single crystals, and good results were obtained.

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  • Crystallography & Structural Chemistry (AREA)
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PCT/JP2021/034487 2020-09-29 2021-09-21 シリコン単結晶の製造方法 Ceased WO2022071014A1 (ja)

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JP2022553849A JP7567929B2 (ja) 2020-09-29 2021-09-21 シリコン単結晶の製造方法
DE112021005126.1T DE112021005126B4 (de) 2020-09-29 2021-09-21 Herstellungsverfahren für Silicium-Einkristall
CN202180066679.2A CN116406433A (zh) 2020-09-29 2021-09-21 单晶硅的制造方法
US18/026,975 US12351937B2 (en) 2020-09-29 2021-09-21 Production method for silicon monocrystal

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US19/257,911 Division US20250389045A1 (en) 2020-09-29 2025-07-02 Production method for silicon monocrystal

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024024134A1 (ja) * 2022-07-29 2024-02-01 グローバルウェーハズ・ジャパン株式会社 シリコン単結晶インゴットの評価方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116949554B (zh) * 2023-09-05 2023-11-21 鄂尔多斯市中成榆能源有限公司 直拉单晶硅的生产方法及生产系统

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009025336A1 (ja) * 2007-08-21 2009-02-26 Sumco Corporation Ｉｇｂｔ用のシリコン単結晶ウェーハ及びｉｇｂｔ用のシリコン単結晶ウェーハの製造方法
JP2012206874A (ja) * 2011-03-29 2012-10-25 Covalent Materials Corp 単結晶引上装置及び単結晶引き上げ方法
JP2014511146A (ja) * 2011-04-14 2014-05-12 ジーティー アドヴァンスト シーズィー， エルエルシー 均一な複数のドーパントを有するシリコンインゴット並びにそれを生成するための方法及び装置
JP2014125402A (ja) * 2012-12-27 2014-07-07 Globalwafers Japan Co Ltd シリコン単結晶の引き上げ方法
JP2015101498A (ja) * 2013-11-22 2015-06-04 信越半導体株式会社 シリコン単結晶の製造方法
JP2016060667A (ja) * 2014-09-18 2016-04-25 信越半導体株式会社 抵抗率制御方法、追加ドーパント投入装置、並びに、ｎ型シリコン単結晶
JP2018525308A (ja) * 2015-08-12 2018-09-06 エスケー シルトロン カンパニー リミテッド 単結晶成長方法
JP2018140915A (ja) * 2017-02-28 2018-09-13 株式会社Sumco シリコン単結晶インゴットの製造方法およびシリコン単結晶育成装置

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0777995B2 (ja) * 1989-11-16 1995-08-23 信越半導体株式会社 単結晶の比抵抗コントロール方法
JP2550739B2 (ja) 1990-02-23 1996-11-06 住友金属工業株式会社 結晶成長方法
JP4380204B2 (ja) 2003-04-10 2009-12-09 株式会社Ｓｕｍｃｏ シリコン単結晶及び単結晶育成方法
JP4631717B2 (ja) * 2006-01-19 2011-02-16 株式会社Sumco Ｉｇｂｔ用シリコン単結晶ウェーハ及びｉｇｂｔ用シリコン単結晶ウェーハの製造方法
JP6222013B2 (ja) * 2014-08-29 2017-11-01 信越半導体株式会社 抵抗率制御方法
JP6304125B2 (ja) 2015-05-21 2018-04-04 信越半導体株式会社 シリコン単結晶の軸方向の抵抗率制御方法
CN105970284B (zh) * 2016-05-30 2019-08-16 上海超硅半导体有限公司 一种p型单晶硅片及其制造方法
US20180087179A1 (en) * 2016-09-28 2018-03-29 Corner Star Limited Single crystal silicon ingots having doped axial regions with different resistivity and methods for producing such ingots
US11702760B2 (en) * 2017-04-25 2023-07-18 Sumco Corporation N-type silicon single crystal production method, n-type silicon single crystal ingot, silicon wafer, and epitaxial silicon wafer

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009025336A1 (ja) * 2007-08-21 2009-02-26 Sumco Corporation Ｉｇｂｔ用のシリコン単結晶ウェーハ及びｉｇｂｔ用のシリコン単結晶ウェーハの製造方法
JP2012206874A (ja) * 2011-03-29 2012-10-25 Covalent Materials Corp 単結晶引上装置及び単結晶引き上げ方法
JP2014511146A (ja) * 2011-04-14 2014-05-12 ジーティー アドヴァンスト シーズィー， エルエルシー 均一な複数のドーパントを有するシリコンインゴット並びにそれを生成するための方法及び装置
JP2014125402A (ja) * 2012-12-27 2014-07-07 Globalwafers Japan Co Ltd シリコン単結晶の引き上げ方法
JP2015101498A (ja) * 2013-11-22 2015-06-04 信越半導体株式会社 シリコン単結晶の製造方法
JP2016060667A (ja) * 2014-09-18 2016-04-25 信越半導体株式会社 抵抗率制御方法、追加ドーパント投入装置、並びに、ｎ型シリコン単結晶
JP2018525308A (ja) * 2015-08-12 2018-09-06 エスケー シルトロン カンパニー リミテッド 単結晶成長方法
JP2018140915A (ja) * 2017-02-28 2018-09-13 株式会社Sumco シリコン単結晶インゴットの製造方法およびシリコン単結晶育成装置

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024024134A1 (ja) * 2022-07-29 2024-02-01 グローバルウェーハズ・ジャパン株式会社 シリコン単結晶インゴットの評価方法
JP2024018608A (ja) * 2022-07-29 2024-02-08 グローバルウェーハズ・ジャパン株式会社 シリコン単結晶インゴットの評価方法
JP7692880B2 (ja) 2022-07-29 2025-06-16 グローバルウェーハズ・ジャパン株式会社 シリコン単結晶インゴットの評価方法

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