US20170058427A1 - Polycrystalline silicon rod, method for producing polycrystalline silicon rod, and single-crystalline silicon - Google Patents

Polycrystalline silicon rod, method for producing polycrystalline silicon rod, and single-crystalline silicon Download PDF

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US20170058427A1
US20170058427A1 US15/308,438 US201515308438A US2017058427A1 US 20170058427 A1 US20170058427 A1 US 20170058427A1 US 201515308438 A US201515308438 A US 201515308438A US 2017058427 A1 US2017058427 A1 US 2017058427A1
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polycrystalline silicon
silicon rod
heat treatment
residual stress
mpa
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Shuichi Miyao
Shigeyoshi Netsu
Tetsuro Okada
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Assigned to SHIN-ETSU CHEMICAL CO., LTD. reassignment SHIN-ETSU CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: NETSU, SHIGEYOSHI, MIYAO, SHUICHI, OKADA, TETSURO
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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
    • C30B13/00—Single-crystal growth by zone-melting; Refining by zone-melting
    • C30B13/08—Single-crystal growth by zone-melting; Refining by zone-melting adding crystallising materials or reactants forming it in situ to the molten zone
    • 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
    • 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
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data

Definitions

  • the present invention relates to a technique for growing a silicon crystal, and more particularly, relates to a technique for producing a polycrystalline silicon rod suitable for a raw material for producing single-crystalline silicon.
  • Single-crystalline silicon is necessary to produce, for example, semiconductor devices and in many cases, is grown by the FZ or CZ method using a polycrystalline silicon rod or polycrystalline silicon lump produced by the Siemens process as a raw material.
  • the Siemens process is a process in which a source silane gas such as trichlorosilane or monosilane is brought into contact with a heated silicon core wire to conduct the vapor phase growth (deposition) of a polycrystalline silicon on the surface of the silicon core wire by CVD (Chemical Vapor Deposition) method.
  • the polycrystalline silicon As the diameter of the polycrystalline silicon increases during the deposition process by CVD, it gradually becomes difficult for an electric current, which flows through the core wire for heating-up, to flow through the outer surface of the polycrystalline silicon undergoing the deposition. As a result, the polycrystalline silicon has a lower temperature in and near the outer surface than in the central area. In such a situation, the progress of the deposition leads to the difference between the crystal properties in the outer area of the obtained polycrystalline silicon rod and the crystal properties in the central area. For example, the thermal expansion coefficients in the outer area and the central area of the crystal differ from each other, and thus, residual stress occurs in the crystal. As the diameter of the polycrystalline silicon rod increases, the above-described phenomenon occurs more significantly.
  • the polycrystalline silicon rod fractures in a furnace.
  • the polycrystalline silicon rod may also fracture in a furnace during the crystal growth.
  • Patent Literature 1 Japanese Patent No. 3357675 states that a polycrystalline silicon rod made from trichlorosilane as a source material involves large residual stress, and therefore, has been believed to be unsuitable for the silicon rod used for the FZ method or recharging silicon. Furthermore, among other descriptions, Patent Literature 1 includes the description that, when the polycrystalline silicon rod is subjected to heat treatment such as annealing in order to relieve the residual stress of this polycrystalline silicon rod and subsequently is melted, the purity of the polycrystalline silicon rod is significantly reduced due to contamination, and the polycrystalline silicon rod is no longer able to be used for producing a single crystal.
  • Patent Literature 1 proposes a method of heating a polycrystalline silicon rod until at least a portion of the surface of the polycrystalline silicon rod reaches to a temperature of not less than 1030° C. in order to obtain a highly-pure polycrystalline silicon rod, wherein the highly-pure polycrystalline silicon rod has residual strain reduced to such an extent that no problems due to cracking can occur after the highly-pure polycrystalline silicon rod is supplied directly into a furnace for melting process when single-crystalline silicon for producing, e.g., a certain electronic device is manufactured such as by silicon-recharging process, and wherein the highly-pure polycrystalline silicon rod also has stable melting-properties.
  • Patent Literature 2 Japanese Patent Laid-Open No. 7-277874 discloses an invention in which a rod-shaped polycrystalline silicon before melting process is subjected to heat treatment such as annealing to relieve residual stress of the rod-shaped polycrystalline silicon, so that the fracture of the rod-shaped polycrystalline silicon in melting process can be prevented in accordance with a finding that maximum residual stress of less than 3.5 kgf/mm 2 (a value determined under normal conditions) cannot result in the above-described fracture.
  • Patent Literature 3 Japanese Patent Laid-Open No. 2004-2772273 discloses an invention in order to provide a high-strength silicon rod having a good cracking resistance that is expected to allow the prevention of cracking in a silicon-recharging process without heat treatment, wherein a polycrystalline silicon rod is produced by the Siemens process by controlling the surface temperature of the polycrystalline silicon rod from 950° C. to 1010° C., so that a high-strength polycrystalline silicon rod can be obtained and can have the tensile strength of not less than 90 MPa at normal temperature in the longitudinal direction.
  • Patent Literature 1 Japanese Patent No. 3357675
  • Patent Literature 2 Japanese Patent Laid-Open No. 7-277874
  • Patent Literature 3 Japanese Patent Laid-Open No. 2004-277223
  • Patent Literature 4 Japanese Patent Laid-Open No. 2013-217653
  • Patent Literature 5 Japanese Patent Laid-Open No. 2014-31297
  • Patent Literature 6 Japanese Patent Laid-Open No. 2014-34506
  • Patent Literature 1 Japanese Patent No. 3357675
  • at least a portion of the surface of the polycrystalline silicon rod has to be heated at a relatively high temperature of not less than 1030° C., and heat treatment at such a high temperature may change the physical properties (such as crystal grain size distribution and thermal diffusivity) of the polycrystalline silicon rod after the heat treatment relative to the physical properties of the polycrystalline silicon rod before the heat treatment.
  • Patent Literature 2 Japanese Patent Laid-Open No. 7-277874 proposes to relieve the residual stress by heat treatment such as annealing before melting process; however, the detail of specific conditions for the residual-stress relief is not disclosed.
  • Patent Literature 3 Japanese Patent Laid-Open No. 2004-277223
  • the polycrystalline silicon rod is heat-treated at a temperature (from 950° C. to 1010° C.) lower than the temperature for the heat-treatment described in Patent Literature 1.
  • the physical properties of the polycrystalline silicon rod may be changed relative to the physical properties of the polycrystalline silicon rod before the heat treatment.
  • an object of the present invention is to provide a method for releasing and relieving residual stress in a polycrystalline silicon rod without changing the physical properties of the polycrystalline silicon rod after a growing process, so that the polycrystalline silicon rod has residual strain reduced to such an extent that no problems due to cracking can occur when single-crystalline silicon used for producing, e.g., a certain device is manufactured such as by silicon-recharging process.
  • a polycrystalline silicon rod according to the present invention is a polycrystalline silicon rod grown by the Siemens process having a residual stress ( ⁇ ) of not more than +20 MPa, wherein the residual stress is given by the formulae shown below and evaluated by the slope ( ⁇ (2 ⁇ )/ ⁇ (sin 2 ⁇ )) of a straight line by least fitted to data points square approximation which are obtained by X-ray diffraction and plotted onto a 2 ⁇ -sin 2 ⁇ diagram.
  • the polycrystalline silicon rod is heat-treated within a temperature range from 750° C. to 900° C. for stress relief.
  • the polycrystalline silicon rod after the heat treatment preferably retains a crystal grain size distribution and a thermal diffusivity before the heat treatment.
  • a method of producing a polycrystalline silicon rod according to the present invention comprises a step of growing a polycrystalline silicon rod by the Siemens process, followed by heat-treating the polycrystalline silicon rod at a temperature ranging from 750° C. to 900° C. for stress relief.
  • the heat treatment is conducted inside a furnace used to grow the polycrystalline silicon rod.
  • the heat treatment is conducted outside a furnace used to grow the polycrystalline silicon rod.
  • a single-crystalline silicon according to the present invention is grown using polycrystalline silicon as a raw material obtained from the above polycrystalline silicon rod.
  • a polycrystalline silicon rod with residual stress ( ⁇ ) of not more than +20 MPa evaluated by X-ray diffraction is provided.
  • FIG. 1A is a diagram for illustrating a first example of sampling a plate-shaped sample for determining residual stress by X-ray diffraction from a polycrystalline silicon rod.
  • FIG. 1B is a diagram for illustrating a first example of sampling a plate-shaped sample for determining residual stress by X-ray diffraction from a polycrystalline silicon rod.
  • FIG. 2A is a diagram for illustrating a second example of sampling a plate-shaped sample for determining residual stress by X-ray diffraction from a polycrystalline silicon rod.
  • FIG. 2B is a diagram for illustrating a second example of sampling a plate-shaped sample for determining residual stress by X-ray diffraction from a polycrystalline silicon rod.
  • FIG. 3A is a diagram for illustrating a third example of sampling a plate-shaped sample for determining residual stress by X-ray diffraction from a polycrystalline silicon rod.
  • FIG. 3B is a diagram for illustrating a third example of sampling a plate-shaped sample for determining residual stress by X-ray diffraction from a polycrystalline silicon rod.
  • One of methods of determining residual stress in a crystal is X-ray diffraction.
  • the distance between crystal lattice planes d varies in proportion to the degree of the stress.
  • the presence of tensile stress leads to a larger distance between lattice planes
  • the presence of compressive stress leads to a smaller distance between lattice planes.
  • Residual stress a in a crystal is given by the formula shown below from the slope ( ⁇ (2 ⁇ )/ ⁇ (sin 2 ⁇ )) of a straight line fitted to data points by least square approximation which are obtained by X-ray diffraction and plotted onto a 2 ⁇ -sin 2 ⁇ diagram.
  • ⁇ is an angle (deg.) between a sample-surface normal and a lattice-plane normal.
  • K is a stress constant (MPa/deg.), and is given by the following formula (2).
  • E in the above formula (2) is Young's modulus (MPa), ⁇ is Poisson's ratio, and ⁇ 0 is a Bragg angle (deg.) in a strain-free state.
  • heat treatment at a relatively high temperature for example a temperature above 950° C. may cause metal contamination, and in addition, the physical properties (such as crystal grain size distribution and thermal diffusivity) of a polycrystalline silicon rod may be changed after the heat treatment.
  • the intensity of X-ray diffraction from Miller index plane such as ⁇ 111> and ⁇ 220> is changed after the heat treatment, and also, the crystal grain size distribution is changed due to larger average grain size resulted from heat treatment, and also, thermal conductivity and thermal diffusivity are changed after the heat treatment.
  • the above-described change is an irreversible change and the value before the heat treatment cannot be recovered, and thus, a polycrystal with desired physical properties is less likely to be obtained even after residual stress relief.
  • the present inventors have studied a method of relieving the residual stress of a polycrystalline silicon rod with retaining the physical properties of the polycrystalline silicon rod, and thus, the present invention has been made.
  • this polycrystalline silicon rod is heat-treated at a temperature range from 750° C. to 900° C. to relieve residual stress inside the crystal.
  • Heat treatment is conducted at a relatively lower temperature in comparison to heat treatment for residual stress relief which is a known method in itself, and heat treatment at not less than 1030° C. disclosed in Patent Literature 1 and heat treatment from 950° C. to 1010° C. disclosed in Patent Literature 3.
  • residual stress can be relieved satisfactorily by heat treatment at the above-described low temperature, and in addition, metal contamination cannot be induced and the physical properties of the polycrystalline silicon rod cannot be changed.
  • the polycrystalline silicon rod after the heat treatment retains crystal grain size distribution and thermal diffusivity before the heat treatment.
  • the above heat treatment can be conducted inside a furnace used to grow the polycrystalline silicon rod, and can also be conducted outside a furnace used to grow the polycrystalline silicon rod.
  • a polycrystalline silicon rod with residual stress ( ⁇ ) of not more than +20 MPa evaluated by the above 2 ⁇ -sin 2 ⁇ diagram can be obtained.
  • this polycrystalline silicon rod is used as a raw material to grow single-crystalline silicon, the polycrystalline silicon rod cannot fracture inside a furnace for growing single-crystalline silicon by the CZ or FZ method, and thus, high-quality single-crystalline silicon can be obtained.
  • FIG. 1A and FIG. 1B are diagrams for illustrating an (first) example of sampling a plate-shaped sample 20 for determining residual stress by X-ray diffraction, from a polycrystalline silicon rod 10 grown through deposition by chemical vapor deposition such as the Siemens process.
  • FIG. 2A and FIG. 2B are diagrams for illustrating an (second) example of sampling a plate-shaped sample 20 for determining residual stress by X-ray diffraction.
  • FIG. 3A and FIG. 3B are diagrams for illustrating an (third) example of sampling a plate-shaped sample 20 for determining residual stress by X-ray diffraction.
  • a reference sign 1 shown in the drawings means a silicon core wire to be formed into a silicon rod by depositing polycrystalline silicon onto the surface of the silicon core wire.
  • the diameter of a polycrystalline silicon rod 10 illustrated in the above-described figures is approximately from 140 mm to 160 mm, and a plate-shaped sample 20 is sampled from the polycrystalline silicon rod 10 to determine residual stress. It is noted that a location for sampling a plate-shaped sample 20 is not limited to those shown in the drawings.
  • rods 11 with a diameter of approximately 20 mm are hollowed out from three domains, that is, a domain ( 11 CTR ) close to a silicon core wire 1 from a viewpoint in a plane perpendicular to the longitudinal direction of a polycrystalline silicon rod 10 , as well as a domain ( 11 EDG ) close to a side surface of the polycrystalline silicon rod 10 , and a domain ( 11 R/2 ) in the middle point between CTR and EDG.
  • disk-shaped samples 20 with the thickness of approximately 2 mm are sampled from the above rod 11 .
  • the disk-shaped sample 20 sampled from the rod 11 CTR is denoted as 20 CTR
  • the disk-shaped sample 20 sampled from the rod 11 R/2 is denoted as 20 R/2
  • the disk-shaped sample 20 sampled from the rod 11 DG is denoted as 20 EDG .
  • Residual stress in the growth direction (rr) and residual stress in the direction ( ⁇ ) with an angle of 90° to this growth direction can be determined by suitably selecting an area to be irradiated with X-ray on a principal surface of this disk-shaped sample through a slit.
  • a polycrystalline silicon rod 10 is sliced in the direction perpendicular to the longitudinal direction in order to sample a disk 12 having a silicon core wire 1 as a central part.
  • disk-shaped samples 20 CTR , 20 R/2 , and 20 EDG ) with a diameter of approximately 20 mm are hollowed out from three domains of the above disk 12 , that is, a domain close to the silicon core wire 1 , a domain close to a side surface of the polycrystalline silicon rod 10 , and a domain in the middle point between CTR and EGD.
  • disk-shaped samples are also sampled from a cross-sectional domain perpendicular to the longitudinal direction of the polycrystalline silicon rod 10 .
  • Residual stress in the growth direction (rr) and residual stress in the direction ( ⁇ ) with an angle of 90° to this growth direction can be determined by suitably selecting an area to be irradiated with X-ray on a principal surface of this disk-shaped sample through a slit.
  • a rod 11 with a diameter of approximately 20 mm is hollowed out from a polycrystalline silicon rod 10 in the direction perpendicular to the longitudinal direction.
  • a disk-shaped samples ( 20 CTR , 20 R/2 , and 20 EDG ) with a diameter of approximately 20 mm are sampled from three domains of the above rod 11 , that is, a domain close to a silicon core wire 1 , a domain close to a side surface of a polycrystalline silicon rod 10 , and a domain in the middle point between CTR and EGD.
  • Residual stress in the longitudinal direction can be determined by suitably selecting an area to be irradiated with X-ray on a principal surface of this disk-shaped sample through a slit.
  • a domain for sampling a rod 11 as well as the length and number of this rod can be appropriately specified according to the diameter of a silicon rod 10 and the diameter of the hollowed out rod 11 .
  • a disk-shaped sample 20 can be sampled from any domain of the hollowed out rod 11
  • the disk-shaped sample 20 is preferably sampled from a domain that allows reasonable estimation of the nature regarding to the entire silicon rod 10 .
  • the diameter of the disk-shaped sample 20 is indicated to be approximately 20 mm only for the purpose of illustration, and this diameter can be appropriately specified as long as no problems occur in the determination of residual stress.
  • the residual stress ( ⁇ ) can be evaluated by the slope ( ⁇ (2 ⁇ )/ ⁇ (sin 2 ⁇ )) of a straight line fitted to data points by least square approximation which are obtained by X-ray diffraction and plotted onto a 2 ⁇ -sin 2 ⁇ diagram.
  • Young's modulus E the value of Young's modulus regarding to polycrystalline silicon that is a sample actually used for determination should be employed as Young's modulus E.
  • a literature value of Young's modulus regarding to ⁇ 111> orientation of the single-crystalline silicon, that is, 171.8 GPa was employed due to a certain reason, for example, the fact that Young's modulus cannot be calculated with taking the abundance of all types of crystal orientation into account.
  • the polycrystalline silicon rods were heat-treated inside a furnace.
  • the above heat treatment was conducted only by heating using radiant heat for one to two hours while the surface temperatures of the above polycrystalline silicon rods were controlled to 750° C., without supplying electric power to the silicon core wire. It is noted that heat treatment was conducted under hydrogen atmosphere, and the surface temperatures of the polycrystalline silicon rods were monitored by a radiation thermometer (at wave length of 0.9 ⁇ m).
  • the above disk-shaped samples were sampled from the polycrystalline silicon rods after the above-described heat treatment to determine residual stress and as a result of this, the residual stress was found to be not more than +20 MPa in all of the three directions described above.
  • Residual stress in the polycrystalline silicon rods that have not been heat-treated was determined, and samples for evaluation of the physical properties were sampled in the above-described three directions with respect to each of the polycrystalline silicon rods. It is noted that the sample has a diameter of 19 mm and the thickness of 2 mm.
  • The-above-described samples were heat-treated at four conditions, that is, at 750° C. for 2 hours, at 800° C. for 2 hours, at 850° C. for 2 hours, and at 900° C. for 2 hours, and subsequently, changes in the residual stress, crystal structure, crystal grain size distribution, and thermal diffusivity after the heat treatment were studied.
  • the sample is fixed at a position with an angle that gives 20 peak at ⁇ 111>, ⁇ 220>, ⁇ 331>, and ⁇ 400> regarding to each sample surface, and subsequently, change in the crystal structure was judged by checking if change in the amount of the detected diffraction peaks and change in the peak shapes was observed with checking all orientations within the rotating direction of sample surface from 0° to 180° or from 0° to 360°.
  • Patent Literature 4 Japanese Patent Laid-Open No. 2013-217653.
  • the amount of the detected diffraction peaks is expressed by baseline value of the background and the number of peaks; however, when the value of the amount of the detected peaks themselves does not significantly differ from the background value, the physical properties of the crystal depend on the background. It is noted that, if the amount of the detected peaks is not negligible relative to a background value, the absolute amount of the detected peak has to be additionally evaluated.
  • the sample E1 was heat-treated at 750° C. inside a deposition furnace
  • the sample E2 was heat-treated at 750° C. outside a deposition furnace
  • the sample E3 was heat-treated at 900° C. outside a deposition furnace
  • the sample E4 was heat-treated at 850° C. inside a deposition furnace.
  • Any one of the samples C1, C2, and C3 has not been heat-treated after the deposition process.
  • the sample C4 was heat-treated at 720° C. outside the deposition furnace after the deposition process.
  • Table 1 and Table 2 The relevant conditions and the like are summarized in Table 1 and Table 2. It is noted that “BG” in the Tables is an abbreviation for the amount of the detected peaks of the background. Furthermore, “Peak/180°” means the number of peaks that are detected during the rotation by 180° at a diffraction angle of Miller index of interest.
  • any one of the samples (E1, E2, E3, and E4) heat-treated within a temperature range from 750° C. to 900° C. has residual stress ( ⁇ ) of not more than +20 MPa
  • the samples (C1, C2, and C3) without any heat treatment have residual stress ( ⁇ ) of greater than +20 MPa.
  • the sample C4 heat-treated at a temperature below 750° C. after the deposition process can be seen to tend to have lower residual stress than the residual stress of the samples without heat treatment; however, the residual stress ( ⁇ ) of sample C4 is still greater than +20 MPa.
  • “Fracture” at the bottom of Table 1 and Table 2 means (the presence and absence of) the fracture of the polycrystalline silicon rod inside a furnace when a single crystal is grown by FZ method using a polycrystalline silicon rod as a raw material.
  • Polycrystalline silicon rods (E1, E2, E3, and E4) with residual stress ( ⁇ ) of not more than +20 MPa caused no “fracture”; however, polycrystalline silicon rods (C1, C2, C3, and C4) with residual stress ( ⁇ ) of greater than +20 MPa caused “fracture”.
  • the present invention is based on a new finding of the present inventors that residual stress in a polycrystalline silicon rod grown by the Siemens process can be relieved by heat treatment at a relatively low temperature within a temperature range from 750° C. to 900° C. As a result, a polycrystalline silicon rod with residual stress ( ⁇ ) of not more than +20 MPa evaluated by X-ray diffraction is provided.
  • the present invention allows to release and relieve residual stress in a polycrystalline silicon rod without changing the physical properties of the polycrystalline silicon rod after a growing process, so that the polycrystalline silicon rod has residual strain reduced to such an extent that no problems due to cracking can occur when single-crystalline silicon used for producing, e.g., a certain device is manufactured such as by silicon-recharging process.

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  • Crystallography & Structural Chemistry (AREA)
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JP2014096188A JP6418778B2 (ja) 2014-05-07 2014-05-07 多結晶シリコン棒、多結晶シリコン棒の製造方法、および、単結晶シリコン
PCT/JP2015/002237 WO2015170459A1 (ja) 2014-05-07 2015-04-24 多結晶シリコン棒、多結晶シリコン棒の製造方法、および、単結晶シリコン

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US10066320B2 (en) 2016-04-04 2018-09-04 Shin-Etsu Chemical Co., Ltd. Polycrystalline silicon, FZ single crystal silicon, and method for producing the same
US11345603B2 (en) 2019-01-18 2022-05-31 Shin-Etsu Chemical Co., Ltd. Polycrystalline silicon bar, polycrystalline silicon rod, and manufacturing method thereof

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CN107881560A (zh) * 2017-11-24 2018-04-06 苏州阿特斯阳光电力科技有限公司 一种晶体硅棒的预处理方法
WO2022113460A1 (ja) * 2020-11-27 2022-06-02 株式会社トクヤマ 多結晶シリコンロッド、多結晶シリコンロッドの製造方法および多結晶シリコンの熱処理方法
JP7022874B1 (ja) * 2020-11-27 2022-02-18 株式会社トクヤマ 多結晶シリコンロッド、多結晶シリコンロッドの製造方法および多結晶シリコンの熱処理方法
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