WO2017038347A1 - Procédé de fabrication de barreaux de silicium polycristallin, et procédé de fabrication de silicium monocristallin par fusion à zone flottante - Google Patents

Procédé de fabrication de barreaux de silicium polycristallin, et procédé de fabrication de silicium monocristallin par fusion à zone flottante Download PDF

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WO2017038347A1
WO2017038347A1 PCT/JP2016/072592 JP2016072592W WO2017038347A1 WO 2017038347 A1 WO2017038347 A1 WO 2017038347A1 JP 2016072592 W JP2016072592 W JP 2016072592W WO 2017038347 A1 WO2017038347 A1 WO 2017038347A1
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polycrystalline silicon
rod
region
silicon
core wire
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PCT/JP2016/072592
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English (en)
Japanese (ja)
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秀一 宮尾
哲郎 岡田
茂義 祢津
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信越化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/035—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition or reduction of gaseous or vaporised silicon compounds in the presence of heated filaments of silicon, carbon or a refractory metal, e.g. tantalum or tungsten, or in the presence of heated silicon rods on which the formed silicon is deposited, a silicon rod being obtained, e.g. Siemens process
    • 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

Definitions

  • the present invention relates to a technique for manufacturing a polycrystalline silicon rod, and more specifically, controls the stress remaining in a polycrystalline silicon rod synthesized by the Siemens method, and is suitable for manufacturing FZ single crystal silicon.
  • the present invention relates to a technique for manufacturing a rod.
  • Single crystal silicon substrates indispensable for the manufacture of semiconductor devices and the like are cut out from ingots grown by the CZ method or the FZ method.
  • Polycrystalline silicon rods and polycrystalline silicon blocks are used as raw materials for producing these ingots.
  • Siemens method is a method of vapor deposition (deposition) of polycrystalline silicon on the surface of silicon core wire by CVD (Chemical Vapor Deposition) method by contacting silane source gas such as trichlorosilane and monosilane with heated silicon core wire. It is a method to make it.
  • the heating of the silicon core wire is based on resistance heating by passing an electric current
  • the diameter of the polycrystalline silicon rod increases with the deposition of polycrystalline silicon
  • the current gradually becomes difficult to flow on the outer surface of the silicon rod.
  • the outer surface becomes relatively lower than the temperature of the central region, which causes a difference in thermal expansion coefficient and generates residual stress.
  • the occurrence of such residual stress is more conspicuous as the polycrystalline silicon rod has a larger diameter.
  • residual stress includes tensile stress and compressive stress
  • the former tends to cause a decrease in strength because cracks occur in polycrystalline silicon, and the latter tends to improve the strength of polycrystalline silicon.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-277874 discloses a stable single crystal in which a rod-like polycrystalline silicon serving as a raw material is melted without breaking and a raw material melt is supplied.
  • An invention is disclosed in which the maximum residual stress of rod-shaped polycrystalline silicon is less than 3.5 kgf / mm 2 under standard conditions for the purpose of providing a silicon single crystal pulling method that can be grown.
  • Patent Document 1 if the maximum residual stress is less than 3.5 kgf / mm 2 (measured value under a standard state), it is possible to prevent fracture while ensuring the optimum melting condition of rod-shaped polycrystalline silicon. Although there is a disclosure of knowledge that it will become, the only way to realize this is to apply heat treatment for stress removal such as annealing, and the possibility of residual stress control in the synthesis process of polycrystalline silicon rod No consideration has been given to.
  • the present invention has been made in view of such a situation, and the object of the present invention is to perform residual stress control during the synthesis process of the polycrystalline silicon rod, not after the synthesis process of the polycrystalline silicon rod, It is an object of the present invention to provide a technique that eliminates the need for heat treatment of the polycrystalline silicon rod.
  • a polycrystalline silicon rod manufacturing method is a method for producing a polycrystalline silicon rod having a radius R obtained by depositing polycrystalline silicon on a silicon core wire by a Siemens method.
  • T1> T2> T3 is set when the deposition temperatures of polycrystalline silicon in the vicinity region, R / 2 region, and outermost surface region of the silicon core wire are T1, T2, and T3, respectively.
  • the method for producing a polycrystalline silicon rod according to the second aspect of the present invention is a method for producing a polycrystalline silicon rod having a radius R obtained by depositing polycrystalline silicon on a silicon core wire by a Siemens method,
  • T1> T2 and T2 ⁇ T3 are characterized in that T1> T3 + ⁇ T is set, where ⁇ T is a temperature difference between the temperature T1 ′ in the vicinity of the silicon core wire during the deposition of polycrystalline silicon and T3.
  • the method for producing FZ single crystal silicon according to the present invention is a method for producing a single crystal by inductively heating the polycrystalline silicon rod obtained by the above-described method without performing a heat treatment after the precipitation step of the polycrystalline silicon rod. It is characterized by doing.
  • the present invention controls the residual stress by appropriately controlling the temperature during the process of obtaining polycrystalline silicon rods having a radius R by depositing polycrystalline silicon on a silicon core wire by the Siemens method.
  • a polycrystalline silicon rod suitable for producing crystalline silicon is provided.
  • Non-Patent Document 1 S. Timoshenko and JN Goodier, “Theory of Elasticity”, McGraw-Hill, New York (1970)
  • a method of thermal stress calculation based on this idea has also been proposed
  • Non-patent document 2 “Method of calculating thermal stress of cylinders and disks”, Journal of the Ceramic Society of Japan 101 [8] 932-935 (1993)
  • This calculation method is a method of calculating based on the temperature distribution inside a cylinder with a constant thickness.
  • the diameter gradually increases as in the case of precipitation of a polycrystalline silicon rod by the Siemens method the stress is calculated. I can't.
  • the stress generated due to the structure unique to the polycrystal is not taken into consideration.
  • the present inventors examined a method for obtaining the residual stress value by precisely measuring the interplanar spacing value d value by an X-ray diffraction measurement method (hereinafter referred to as XRD method). As a result of this study, it has been found that the tensile stress and the compressive stress are independently present in the crystal and cannot be determined only by a simple temperature distribution inside the cylinder.
  • XRD method X-ray diffraction measurement method
  • the inventors have conducted detailed analysis on the relationship between the CVD temperature at the time of polycrystalline silicon precipitation and the residual stress in the crystal, and found that the following regularity exists.
  • the final radius of the polycrystalline silicon rod obtained by depositing polycrystalline silicon on the silicon core wire by the Siemens method is R
  • the deposition temperature of polycrystalline silicon in the vicinity region, R / 2 region, and outermost surface region of the silicon core wire Are T1, T2, and T3, respectively, and when the temperature difference between the temperatures T1 ′ and T3 in the vicinity of the silicon core wire when the polycrystalline silicon is deposited in the outermost surface region is ⁇ T, the relationship summarized in Table 1 is recognized. It is done.
  • the residual stress means a residual stress component in the central axis direction (vertical direction: zz direction) of the polycrystalline silicon rod.
  • a radial direction growth direction: rr direction
  • a ⁇ direction that forms an angle of 90 ° in a plane perpendicular to the rr direction and the central axis. It does not participate in fracture when manufacturing FZ single crystal silicon using a polycrystalline silicon rod as a raw material.
  • the interplanar spacing d of the crystal lattice changes in proportion to the magnitude. Specifically, the lattice spacing increases when tensile stress is generated, and the lattice spacing decreases when compressive stress is generated.
  • the residual stress ⁇ in the crystal can be calculated from the slope of the least square approximation line ( ⁇ (2 ⁇ ) / ⁇ (sin 2 ⁇ )) of the points plotted in the 2 ⁇ -sin 2 ⁇ diagram obtained by X-ray diffraction as follows: Is given by equation (1).
  • ⁇ is an angle (deg.) Between the sample surface normal and the lattice surface normal.
  • K is a stress constant (MPa / deg.) And is given by the following equation (2).
  • Equation (2) E is the Young's modulus (MPa), ⁇ is the Poisson's ratio, and ⁇ 0 is the Bragg angle (deg.) Without any distortion.
  • the internal stress can be obtained from the expansion / contraction amount of the lattice plane interval by observing the behavior of a specific diffraction peak while changing the lattice plane normal.
  • the diffraction peak when there is no internal stress, of course, the diffraction peak does not shift, but when there is compressive stress, the diffraction peak shifts to the high angle side, and when there is tensile stress, the diffraction peak shifts to the low angle side. To do.
  • the residual stress of polycrystalline silicon synthesized under various CVD conditions is evaluated.
  • FIG. 1A and FIG. 1B show an example of collecting a plate-like sample 20 for measuring residual stress by X-ray diffraction measurement from a polycrystalline silicon rod 10 grown by chemical vapor deposition such as Siemens (No. 1). It is a figure for demonstrating 1), and is the sample collection example for measuring the residual stress component of rr direction and (theta) theta direction.
  • FIGS. 2A and 2B are diagrams for explaining an example (second) of collecting the plate-like sample 20 for measuring residual stress by the X-ray diffraction measurement method, and these are also residuals in the rr direction and the ⁇ direction. It is a sample collection example for measuring a stress component. is there.
  • 3A and 3B are diagrams for explaining an example (third) of collecting the plate-like sample 20 for residual stress measurement by the X-ray diffraction measurement method, for measuring the residual stress component in the zz direction. This is an example of sampling.
  • reference numeral 1 denotes a silicon core wire for depositing polycrystalline silicon on the surface to form a silicon rod.
  • the diameter of the polycrystalline silicon rod 10 illustrated in these drawings is approximately 140 to 160 mm, and a plate-like sample 20 for measuring residual stress is taken.
  • part of the plate-shaped sample 20 is not limited to these.
  • FIG. 1A when viewed in a plane perpendicular to the long axis direction, a portion close to the silicon core wire 1 (11 CTR ), a portion close to the side surface of the polycrystalline silicon rod 10 (11 EDG ), CTR A rod 11 having a diameter of approximately 20 mm is cut out from three portions (11 R / 2 ) in the middle of EGD and EGD. Then, as shown in FIG. 1B, a disk-shaped sample 20 having a thickness of approximately 2 mm is collected from the rod 11. The disc-shaped sample 20 taken from the rod 11 CTR 20 CTR, the rod 11 R / 2 the disc-shaped samples 20 taken from 20 R / 2, disc-shaped samples 20 taken from the rod 11 EDG 20 Indicated as EDG .
  • a disk 12 centered on the silicon core wire 1 is sampled by slicing perpendicularly to the long axis direction. Then, as shown in FIG. 2B, the diameter of the circular plate 12 is approximately 20 mm from three parts, a part close to the silicon core wire 1, a part close to the side surface of the polycrystalline silicon rod 10, and an intermediate part between CTR and EGD.
  • a disk-shaped sample (20 CTR , 20 R / 2 , 20 EDG ) is cut out.
  • a disk-shaped sample taken from a cross section perpendicular to the major axis direction of the polycrystalline silicon rod 10 can be obtained.
  • the X-ray irradiation region on the main surface of the disk-shaped sample with a slit By appropriately selecting the X-ray irradiation region on the main surface of the disk-shaped sample with a slit, the residual stress in the growth direction (rr) and the 90 degree direction ( ⁇ ) with respect to this direction is measured. be able to.
  • a rod 11 having a diameter of approximately 20 mm is cut out perpendicularly to the long axis direction.
  • the diameter of the rod 11 is approximately 20 mm from three parts, a part close to the silicon core wire 1, a part close to the side surface of the polycrystalline silicon rod 10, and an intermediate part between CTR and EGD.
  • a disk-shaped sample (20 CTR , 20 R / 2 , 20 EDG ) is collected.
  • a disk-shaped sample collected from a cross section parallel to the major axis direction of the polycrystalline silicon rod 10 is obtained.
  • the residual stress in the major axis direction (zz) can be measured by appropriately selecting the X-ray irradiation region on the main surface of the disk-shaped sample with a slit.
  • the disk-shaped sample 20 may also be collected from any part of the hollowed rod 11, but is preferably at a position where the properties of the entire silicon rod 10 can be reasonably estimated.
  • the diameter of the disk-shaped sample 20 is set to approximately 20 mm for illustration only, and the diameter may be appropriately determined within a range that does not hinder the residual stress measurement.
  • the residual stress ( ⁇ ) is the slope of the least square approximation line ( ⁇ (2 ⁇ ) / ⁇ (sin 2 ⁇ )) of the points plotted in the 2 ⁇ -sin 2 ⁇ diagram obtained by X-ray diffraction. Can be evaluated.
  • the Young's modulus E the value of Young's modulus of polycrystalline silicon, which is an actual measurement sample, should be adopted.
  • the literature value of 171.8 GPa for the Young's modulus of the ⁇ 111> orientation of single crystal silicon is adopted. did.
  • the cause of residual stress is the temperature difference that has been established so far, but from the viewpoint of crystal growth, the following reasons for the generation are the main reasons.
  • a polycrystalline silicon rod was grown under various CVD conditions summarized in Table 2, and the residual stress was examined.
  • the temperature was measured by attaching a peephole to the CVD reactor and installing a radiation thermometer there.
  • a radiation thermometer a radiation thermometer manufactured by Chino Corporation, model number IR-CAQ was used.
  • the measurement wavelength is 0.9 ⁇ m
  • the detection element material is silicon.
  • the measurement position is the center position of the height of the polycrystalline silicon rod, and the focus position gradually changes as it grows. Therefore, the measurement value was obtained after fine adjustment of the focus each time measurement was performed.
  • ⁇ T the average temperature of the rod was calculated according to the method described in Patent Document 2 (Japanese Patent Laid-Open No. 2001-146499), and then the center temperature was calculated from the above surface temperature.
  • T1> T2 and T2 ⁇ T3 when the deposition temperatures of polycrystalline silicon in the vicinity region, R / 2 region, and outermost surface region of the silicon core wire are T1, T2, and T3, respectively. Furthermore, when the temperature difference between the temperatures T1 ′ and T3 in the region near the silicon core wire at the time of deposition of polycrystalline silicon in the outermost surface region is ⁇ T, the polycrystal obtained by setting T1> T3 + ⁇ T. It is a crystalline silicon rod.
  • the present invention controls the residual stress by appropriately controlling the temperature during the process of obtaining polycrystalline silicon rods having a radius R by depositing polycrystalline silicon on a silicon core wire by the Siemens method.
  • a polycrystalline silicon rod suitable for producing crystalline silicon is provided. According to the method of the present invention, it is not necessary to perform heat treatment or the like conventionally performed after growing a polycrystalline silicon rod.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

Lors de la synthèse de barreaux de silicium polycristallin, lorsque les températures de dépôt d'un silicium polycristallin dans une région voisine d'un fil central de silicium, dans une région R/2 et dans une région de surface la plus externe, sont respectivement représentées par T1, T2 et T3, il est établi queＴ１＞Ｔ２＞Ｔ３, et le silicium polycristallin est ainsi déposé. En outre, lorsque les températures de dépôt d'un silicium polycristallin dans une région voisine d'un fil central de silicium, dans une région R/2 et dans une région de surface la plus externe, sont respectivement représentées par T1, T2 et T3, Ｔ１＞Ｔ２ et Ｔ２＜Ｔ３, et lorsque la différence de température entre une température Ｔ１´dans la région voisine du fil central de silicium lors du dépôt du silicium polycristallin dans la région de surface la plus externe, et Ｔ３, est représentée par ΔＴ, il est établi que Ｔ１＞Ｔ３＋ΔＴ, et le silicium polycristallin est ainsi déposé.
PCT/JP2016/072592 2015-09-04 2016-08-02 Procédé de fabrication de barreaux de silicium polycristallin, et procédé de fabrication de silicium monocristallin par fusion à zone flottante WO2017038347A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110133023A (zh) * 2019-05-17 2019-08-16 西安奕斯伟硅片技术有限公司 多晶硅选择方法、多晶硅及其在直拉法中的应用

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JP7128124B2 (ja) * 2019-01-18 2022-08-30 信越化学工業株式会社 多結晶シリコン棒、多結晶シリコンロッドおよびその製造方法
JP2023159508A (ja) 2022-04-20 2023-11-01 信越化学工業株式会社 多結晶シリコンロッド及び多結晶シリコンロッドの製造方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000511154A (ja) * 1997-03-13 2000-08-29 コリア リサーチ インスティチュート オブ ケミカル テクノロジー 発熱反応を利用したポリシリコンの調製方法
JP2008285403A (ja) * 2007-05-16 2008-11-27 Wacker Chemie Ag 帯域引き上げ用の多結晶シリコンロッド及びその製造方法
WO2013080556A1 (fr) * 2011-11-29 2013-06-06 信越化学工業株式会社 Procédé de production de silicium polycristallin et réacteur destiné à la production de silicium polycristallin
JP2015105917A (ja) * 2013-12-02 2015-06-08 信越化学工業株式会社 多結晶シリコン棒の表面温度測定方法および多結晶シリコンの製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000511154A (ja) * 1997-03-13 2000-08-29 コリア リサーチ インスティチュート オブ ケミカル テクノロジー 発熱反応を利用したポリシリコンの調製方法
JP2008285403A (ja) * 2007-05-16 2008-11-27 Wacker Chemie Ag 帯域引き上げ用の多結晶シリコンロッド及びその製造方法
WO2013080556A1 (fr) * 2011-11-29 2013-06-06 信越化学工業株式会社 Procédé de production de silicium polycristallin et réacteur destiné à la production de silicium polycristallin
JP2015105917A (ja) * 2013-12-02 2015-06-08 信越化学工業株式会社 多結晶シリコン棒の表面温度測定方法および多結晶シリコンの製造方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110133023A (zh) * 2019-05-17 2019-08-16 西安奕斯伟硅片技术有限公司 多晶硅选择方法、多晶硅及其在直拉法中的应用
CN110133023B (zh) * 2019-05-17 2022-04-26 西安奕斯伟材料科技有限公司 多晶硅选择方法、多晶硅及其在直拉法中的应用

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