WO2011120598A1 - Procédé pour la production de lingots de silicium de qualité convenant pour la fabrication de semi-conducteurs, creusets réutilisables et leur procédé de fabrication - Google Patents

Procédé pour la production de lingots de silicium de qualité convenant pour la fabrication de semi-conducteurs, creusets réutilisables et leur procédé de fabrication Download PDF

Info

Publication number
WO2011120598A1
WO2011120598A1 PCT/EP2010/065465 EP2010065465W WO2011120598A1 WO 2011120598 A1 WO2011120598 A1 WO 2011120598A1 EP 2010065465 W EP2010065465 W EP 2010065465W WO 2011120598 A1 WO2011120598 A1 WO 2011120598A1
Authority
WO
WIPO (PCT)
Prior art keywords
crucible
silicon
semiconductor
sic
temperatures
Prior art date
Application number
PCT/EP2010/065465
Other languages
English (en)
Other versions
WO2011120598A8 (fr
Inventor
Kai Johansen
Stein Julsrud
Tyke Laurence Naas
Gero Wolfgang Neuroth
Original Assignee
Rec Wafer Norway As
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GB1005399A external-priority patent/GB2479165A/en
Application filed by Rec Wafer Norway As filed Critical Rec Wafer Norway As
Priority to CN201080066044.4A priority Critical patent/CN102859049B/zh
Publication of WO2011120598A1 publication Critical patent/WO2011120598A1/fr
Publication of WO2011120598A8 publication Critical patent/WO2011120598A8/fr

Links

Classifications

    • 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
    • C30B11/00—Single-crystal growth by normal freezing or freezing under temperature gradient, e.g. Bridgman-Stockbarger method
    • C30B11/002—Crucibles or containers for supporting 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
    • C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/10—Crucibles or containers for supporting 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
    • 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
    • C30B35/00—Apparatus not otherwise provided for, specially adapted for the growth, production or after-treatment of single crystals or of a homogeneous polycrystalline material with defined structure
    • C30B35/002—Crucibles or containers

Definitions

  • This invention relates to a method for production of ingots of semiconductor grade silicon, including solar grade silicon, to reusable crucibles employed in the method and a method for manufacturing the reusable crucibles.
  • One such energy source is solar light, which irradiates the earth with vastly more energy than the present day consumption, including any foreseeable increase in human energy consumption.
  • One way of harvesting this source is by employing photovoltaic solar cells.
  • solar cell electricity has to this date been too expensive to be competitive. This needs to change if the huge potential of the solar cell electricity is to be realised.
  • the cost of electricity from a solar panel is a function of the energy conversion efficiency and the production costs of the solar panel. Both the production cost of solar cells and the energy efficiency should be improved.
  • the dominating process route for silicon based solar panels of multi-crystalline wafers is presently by sawing multi- crystalline ingots into blocks and then further to wafers.
  • the multi- crystalline ingots are formed by directional solidification using the Bridgman method or related techniques.
  • a main challenge in the ingot fabrication is to maintain the purity of the silicon raw material and to obtain a sufficient control of the temperature gradients during the directional solidification of the ingots in order to obtain satisfactory crystal quality.
  • the problem with contamination is strongly connected to the crucible material since the crucible is in direct contact (or indirect contact through a release coating) with the molten silicon.
  • Build-up of carbon in the silicon may lead to formation of SiC crystals, especially in the uppermost region of the ingot. These SiC crystals are known to short-cut pn-junctions of the semiconductor cell, leading to drastically reduced cell efficiencies.
  • Build up of interstitial oxygen may lead to oxygen precipitates and/or recombination active oxygen complexes after annealing of the formed silicon.
  • the material of the crucibles should therefore be chemically inert towards molten silicon and withstand the high temperatures up to about 1500 °C for relatively long periods.
  • the crucible material is also important for achieving an optimal control of the temperature since the heat extraction during solidification of the ingot in these production methods is obtained by maintaining a lower temperature in the area below the crucible support, creating a heat sink for the heat of crystallization and transported heat from the upper part of the furnace through the silicon melt, silicon crystals, crucible bottom and support plate.
  • the upper part of the furnace consists of the volume above the support plate, including the crucible or crucibles with contents.
  • the heat transport through the crucible bottom and further through the support plate is dominated by thermal conduction according to Fourier's law of heat conduction.
  • the crucibles In present day industrial production based on the Bridgman method, the crucibles usually stand on a graphite platform of dimensions sufficient to carry the load of the filled crucibles.
  • the necessary thickness for mechanical stability will be in the range 3-10 cm.
  • the thermal conductivity of isotropic graphite is in the range 50 - 100 W/mK.
  • the heat flux from the heat of crystallization of the silicon, the heat transported from the top heater to the bottom heater through the ingot and crucible and the heat stored in the materials in the hot zone should ideally be vertically oriented, i.e., have no lateral component.
  • the various known furnace designs are all characterized by lateral transport of heat. This gives rise to thermal stresses and generates dislocations in the crystallized silicon.
  • Silicon dioxide (fused silica), Si0 2 , is presently the preferred material for crucible and mould applications due to availability in high purity form.
  • the silica When employed for directional solidification methods, the silica is wetted by the molten silicon, leading to a strong adherence between the ingot and the crucible.
  • the strong adherence leads to cracking of the ingot due to build-up of mechanical tension resulting from the higher coefficient of thermal expansion of the silicon as compared to silica.
  • the silica material in the crucible is transformed from a glassy to a partly crystalline phase.
  • the crystalline Si0 2 undergoes a phase transition that causes cracking. For this reason, the silica crucibles may only be used once. This gives a significant contribution to the production cost of the ingots.
  • the thermal conductivity of the fused silica material from which the crucible is made is around 1-2 W/mK.
  • the crucible walls and bottom will typically have a thickness in the range of 1-3 cm.
  • the crucible bottom is the dominating thermal resistance.
  • 90 - 98% of the total temperature difference is localised across the crucible bottom.
  • the attainable rate of heat removal is limited by the great thermal resistance of the silica crucible.
  • any attempt to vary the heat flux locally, e.g. in the lateral direction will be hampered by the very limited possibility to control the heat flux.
  • silicon oxide crucibles also entails a problem of contamination of the silicon ingot, since the reaction products of Si and Si0 2 is gaseous SiO, which may subsequently escape the molten phase and react with graphite in the hot zone forming CO gas.
  • the CO gas readily enters the silicon melt and thus introduces carbon and oxygen into the silicon. That is, the use of a crucible of oxide-containing materials may cause a sequence of reactions leading to introduction of both carbon and oxygen in the solid silicon.
  • Typical values associated with the Bridgman method is interstitial oxygen levels of 1 ⁇ 10 17 - 6 ⁇ 10 17 /cm 3 and 1 ⁇ 10 17 - 6 ⁇ 10 17 /cm 3 of substitutional carbon. Frequently, carbon is present above the saturation level as precipitates of SiC.
  • Such a crucible needs to be made of a material that is sufficiently pure and chemically inert towards the molten silicon to allow high-purity ingots being formed, and which has a thermal expansion that does not lead to the strong mechanical tensions between ingot and crucible during cooling.
  • Another candidate has been crucibles made from essentially silicon carbide.
  • a problem with these has been that the linear thermal expansion is higher than the linear thermal expansion of silicon, thus leading to the ingot being stuck in the crucible after cooling or the crucible cracking, preventing reuse.
  • RBSN Reaction Bonded Silicon Nitride
  • NBSN Niride Bonded Silicon Nitride
  • the crucible is mounted by sealing wall elements and a bottom element together by use of silicon particle containing paste which is nitrided to form solid silicon nitride by heating in a nitrogen atmosphere.
  • the RBSN- or NBSN-crucible may be formed in one piece. But neither of these has so far found industrial application, most likely due to problems with mechanical stability during the furnace process.
  • silicon carbide is an important structural ceramic, because of its many excellent properties, such as oxidation resistance, strength retention at high temperature, wear resistance and thermal shock resistance.
  • it is generally notch-sensitive and has a low toughness, resulting in relatively low reliability as structural components and thus limited applications. Therefore, a number of investigations have focused on the improvement in the reliability, and continuous fibre reinforced SiC composites have been demonstrated to be the most effective approach to improving toughness.
  • a material known to have extreme resistance towards thermal shock and mechanical wear is ceramic composites comprising carbon fibre-reinforced silicon carbide ceramics (C-C/SiC or C/SiC composites). These materials have presently found use as friction linings in braking systems of automotive applications, in aero-space applications, as combustor chamber linings, in turbine blades, in jet engine nozzles, etc.
  • C-C/SiC or C/SiC composites may be produced by forming an intermediate body of carbon fibre-reinforced polymer (CRFP), heating the CRFP until the polymer is pyrolysed to form a porous green body of carbon fibre-reinforced carbon (C/C-body), contacting the green C/C-body with molten silicon and allow the silicon to infiltrate the green C/C-body (often termed Liquid Silicon Infiltration, LSI in the literature) such that at least some of the silicon reacts with the carbon phase of the C/C-body and forms silicon carbide, and thus providing a carbon fibre-reinforced composite ceramic having a matrix comprising SiC, Si, and C. Similar techniques and materials are known from
  • EP 1 547 992 disclose a method for manufacturing C-C/SiC composites from a mixture of resin and carbon fibres which is pyrolysed to a green body directly without first hardening the resin. Then the green body is infiltrated with silicon to form the C-C/SiC composite.
  • the relative amounts of the ingredients it is possible to produce composites with tailored amounts of C/C and C/SiC, and thus make composites with different thermal conductivities.
  • the main objective of the invention is to provide a method for manufacturing high- purity ingots of semiconductor/solar grade silicon employing reusable crucibles.
  • a further objective is to provide reusable crucibles for production of high-purity ingots of semiconductor/solar grade silicon.
  • a further objective of the invention is to provide a method for manufacturing the reusable crucibles.
  • the invention is based on the realisation that C-C/SiC composites may be employed to form reusable crucibles for manufacturing semiconductor/solar grade silicon ingots.
  • C-C/SiC composites have no oxygen-containing components such that the problem with formation of gaseous SiO in the hot zone of the furnace and subsequent migration of CO into the silicon melt is significantly alleviated.
  • the avoidance of SiO-formation in the hot zone alleviates the problem of oxygen induced LID affecting charge-carrier lifetimes. It is also relatively easy to control the level of other detrimental impurities in C-C/SiC composites to acceptable levels for use as crucibles for the manufacture of semiconductor/solar grade silicon ingots.
  • the effect of employing a crucible with no oxygen-containing components may be enhanced by employing a hot zone of the
  • melting/solidification furnace made of materials without oxygen-containing compounds.
  • materials are carbon and/or graphite materials carbon and/or graphite materials as insulating and structural load carrying elements and electric insulating elements made of silicon nitride, S1 3 N 4 .
  • C-C/SiC composites may be manufactured with a tailored coefficient of thermal expansion such that the crucibles may be given a lower thermal expansion than the silicon ingot, and thus avoid the problem of a higher shrinkage of the crucible than the solid ingot during cooling, resulting in breakage of the crucible or the ingot.
  • the coefficient of thermal expansion of crystalline silicon is as shown in Table 1 , and the melting point of crystalline silicon is 1414 °C.
  • the coefficient of thermal expansion of the C-C/SiC composite to be used in crucibles for production of crystalline silicon ingots should be less than 4- 10 "6 K 1 at temperatures above 400 °C and less than 3 - 10 "6 K "1 at temperatures below 400 °C.
  • C-C/SiC composites also may be given tailored anisotropic thermal conductivities providing C-C/SiC composites with thermal conductivities typically in the range from 10 W/mK up to about 35 W/mK at room temperature, and from about 10 W/mK up to about 25 W/mK at 1600 °C
  • the thermal resistance across the graphite support carrying the crucible is typically in the order from 0.002 to 0.0003 m 2 K/W (thickness typically from about 3 to about Table 1
  • the thermal conductivity of the crucible material should be at least about 5 W/mK or higher.
  • the C-C/SiC composite crucible may obtain thermal conductivities from 10 up to 35 W/mK.
  • C-C/SiC composites will thus have a thermal conductivity of a factor of 5 to 30 higher than the presently employed Si02-crucibles, and thus significantly alleviate the problem with the bottom of the crucible dominating the thermal resistance during the directional solidification of the ingot.
  • due to the more advantageous mechanical properties of the C-C/SiC composites it is possible to manufacture a mechanically stable crucible with a thinner bottom than the presently used Si02-crucibles.
  • C-C/SiC composites may form reusable crucibles which in the case of CZ-process for growth of mo no -crystal line silicon crystals allows semi-continuous pulling by multiple usage of the crucible.
  • the method according to the first aspect of the invention may be employed for any known process including for crystallising semiconductor grade silicon ingots, including solar grade silicon ingots, such as the Bridgman process or related direct solidification methods, the block-casting process, and the CZ-process for growth of mo no -crystal line silicon crystals.
  • semiconductor grade silicon ingots including solar grade silicon ingots, such as the Bridgman process or related direct solidification methods, the block-casting process, and the CZ-process for growth of mo no -crystal line silicon crystals.
  • inert atmosphere means an atmosphere which is essentially chemically inert towards the materials of the melting and solidification furnace, crucible, and the silicon phase, both in the solid and liquid state.
  • the term as used herein includes any gas pressure of the inert atmosphere, including vacuum.
  • Argon is an example of suitable inert gases, other examples includes the other noble gases.
  • any gas known to be chemically inert towards silicon and carbon at temperatures from room temperature up to about 1700 °C may be employed as inert atmosphere.
  • the C-C/SiC composite crucible may be coated with a release coating before use to alleviate the release of the silicon ingot after melting and solidification. This may be obtained by spraying the surface of the crucible which is to be coated by a slurry containing silicon particles and silicon nitride particles, followed by heating the crucible including coating in a nitrogen atmosphere up to a temperature of about 1200 °C or higher.
  • silicon particles of the paste in close proximity to carbon phases of the C-C/SiC composite crucible will react to form SiC and thus form a tight bonding to the crucible, while silicon particles of the paste which comes in contact with nitrogen gas is nitrided to form S1 3 N 4 and thus bind the paste into a solid and wear resistant SiC-Si- S1 3 N 4 release coating. If the coating is thin, all Si in the paste may be reacted such that a SiC- S1 3 N 4 coating is formed. The coating is able to withstand several rounds of melting and
  • the release coat may advantageously be combined with a layer of conventional S1 3 N 4 slip coating onto the SiC-Si- Si 3 N 4 or SiC-Si 3 N 4 coating.
  • the invention relates to a method for production of semiconductor grade silicon ingots, wherein the method comprises
  • Both the first and second aspect of the invention may advantageously be combined with applying a layer of conventional S1 3 N 4 slip coating, either directly onto the inner walls of the crucible or onto the SiC-Si- S1 3 N 4 or SiC-Si 3 N4 coating.
  • C-C/SiC composites with a relatively high thermal conductivity at the bottom of the crucible and apply C-C/SiC composites with a low thermal conductivity compared to the bottom at the walls of the crucible.
  • This will provide the possibility of employing an increased rate of crystallization combined with a more vertically oriented and linear heat flux in the crucible and silicon.
  • the situation where heat is extracted in such a way that the temperature gradients are linear within one material layer with respect to vertical position can be termed a quasi steady state cooling (or heating). It is possible to maintain this situation over a much wider range of cooling (heating) rates using the present invention than in conventional methods employing silica crucibles.
  • the thermal insulation effect of the walls may be enhanced by employing a layer of graphite or carbon felt outside the crucible walls.
  • the invention in a third aspect, relates to crucibles for production of semiconductor or solar grade silicon ingots, wherein the crucibles are made of carbon fibre- reinforced silicon carbide composite which has a coefficient of thermal expansion of less than 4- 10 "6 K "1 at temperatures above 400 °C and less than 3 - 10 "6 K “1 at temperatures below 400 °C, and a thermal conductivity of at least 5 W/mK at temperatures from 25 °C to 1500 °C.
  • the crucible may advantageously be given a relatively high thermal conductivity across the bottom and a comparably lower thermal conductivity across the walls in order to alleviate problems with heat fluxes in lateral direction and with too high thermal resistance across the crucible.
  • the crucible according to the invention may thus advantageously employ carbon fibre-reinforced silicon carbide composite with thermal conductivity in the range from 25 to 35 W/mK as the bottom of the crucible, and employ carbon fibre-reinforced silicon carbide composite with thermal conductivity in the range from about 10 to 15 W/mK as the wall elements of the crucible.
  • This may be obtained by forming plate elements of the low thermal conductivity C-C/SiC composite for the wall and high thermal conductivity C-C/SiC composite for the bottom of the crucible, and mount the elements to form a crucible by employing the coating slurry containing silicon particles and silicon nitride particles to both coat the inner walls with a release coating and to bind the bottom and wall elements together.
  • the bonding is obtained by the reaction of the silicon particles with nitrogen and with carbon phases of the C-C/SiC composite when heated to at least 1200 °C to form silicon nitride and silicon carbide, respectively.
  • the release coating and assembly of the crucible may be combined to one operation.
  • the present invention relates to a method for manufacturing reusable crucibles for production of semiconductor or solar grade silicon ingots, wherein the method comprises:
  • the dimensions and shape of the C-C/SiC composite bottom and wall elements may be any conceivable for present and future production of semiconductor or solar grade silicon ingots.
  • the crucible may advantageously be given a square shape where the bottom element is formed as a square shape and wall elements are formed as plates with square or rectangular shape. In this case one may use four plate elements and one bottom element, as shown in WO 2007/148986.
  • the crucible may advantageously be cylindrical, which may be obtained by employing a circular bottom plate element and one tubular wall element?
  • the thickness of the bottom and wall elements will usually be in the range from 1 to 3 cm.
  • the bottom is typically 2 cm thick, while the wall elements are 1 - 2 cm thick.
  • Example embodiment 1 The invention will be described in further detail by way of example embodiments of the first and second aspect of the invention. These examples should not be considered as a limitation of the general inventive idea of employing reusable C- C ⁇ SiC-crucibles with tailored properties for production of solar grade silicon feedstock.
  • Example embodiment 1
  • This example embodiment is related to production of multi-crystalline material for solar cells.
  • a square C-C ⁇ SiC crucible of internal dimensions 690x690x420 mm, with 8 mm wall thickness, was manufactured by liquid silicon infiltration of a crucible made of a carbon/graphite fibre composite material, in accordance with a standard procedure (See e.g. Heidenreich 2007, [3]).
  • the average coefficient of thermal expansion of the material after fabrication in the temperature range 30 - 1500 °C was 3 - 10 "6 K _1 .
  • the crucible was coated with slurry of 33 wt% S1 3 N 4 in de-ionized water, and afterwards cured following a temperature program ramping from room temperature to 1000 °C in 4 hours followed by 2 hours at top temperature of about 1200 °C.
  • the process was conducted in a vacuum furnace under argon atmosphere. Without undue exposure to ambient and in a controlled atmosphere room, the crucible was charged with 275 kg of PV grade silicon. Without undue delay the crucible was placed in the chamber of a crystallization furnace for the production of multi- crystalline material for solar cells. The crystallization furnace had before the test been baked out at 1500 °C for one hour to minimize the amount of adsorbed humidity and condensed oxides from previous runs. The run was conducted under standard conditions only modified to take into account the thermal properties of the crucible.
  • the CO content in the atmosphere was monitored during the run, and it was observed that the CO content was significantly lower that under runs with standard crucibles.
  • the maximum content observed was less than 500 ppm while a typical run showed between 200 and 3000 ppm.
  • the ingot could be slid out of the crucible using a turning device. No sticking to the crucible was observable. After demolding the ingot was cut with higher than normal yield. Some of the material was analyzed for carbon and oxygen, and showed very low values ( ⁇ 1 ppma of C and O). Several wafers from the ingot were processed further into solar cells. The average solar efficiency of the cells was higher than the average solar efficiency of cells made from standard production material.
  • the crucible was vacuum cleaned, recoated and reused according to the same procedure presented above and used for a second production round of producing multi-crystalline material for solar cells.
  • the obtained results were similar to the results obtained in the first round described above.
  • This example embodiment is related to production of mono-crystalline material for solar cells by the Czochralski-method.
  • the crucible was charged in a controlled clean room with 120 kg of PV grade silicon. Without undue delay the crucible was placed in the chamber of an industrial CZ puller for the production of mo no -crystal line ingot material for solar cells.
  • the CZ puller had before the test been baked out at 1500 °C for one hour to minimize the amount of adsorbed humidity and condensed oxides from previous runs.
  • the run was conducted under standard conditions only modified to take into account the thermal properties of the crucible.
  • the CO content in the atmosphere was monitored during the run, and it was observed that the CO content was significantly lower that under runs with standard crucibles.
  • the maximum content observed was less than 500 ppm while a typical run showed between 200 and 3000 ppm.
  • the pot scrap (remaining silicon melt) in the crucible was removed using a graphite felt sponge.
  • the ingot was demounted from the puller and test slugs have been taken in regular distances. Some of the material was analyzed for carbon and oxygen, and showed very low values ( ⁇ 1 ppma of C and O). Several wafers from the ingot were processed further into solar cells. The average solar efficiency of the cells was higher than the average solar efficiency of cells made from standard production material.
  • the crucible was reused according to the same procedure.
  • the results were similar to the results obtained in the first round described above.
  • the solar grade material obtained has comparable properties as FZ Silicon material when it comes to very low oxygen values which is used in semiconductor industry mainly for power device fabrication. Therefore the usage of C-C ⁇ SiC as crucible material for CZ crystal pulling is applicable as well for mo no -crystal line Silicon ingots for semiconductor purpose when it comes to low oxygen values as e.g. for electronic power devices.

Landscapes

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

Abstract

Cette invention porte sur un procédé pour la production de lingots de silicium de qualité convenant pour la fabrication de semi-conducteurs, dont le silicium de qualité solaire, sur des creusets réutilisables employés dans le procédé et sur un procédé pour la fabrication des creusets réutilisables, le procédé étant caractérisé en ce que les lingots de silicium sont produits dans des creusets réutilisables constitués de composite de carbure de silicium renforcé par des fibres de carbone qui a un coefficient de dilatation thermique inférieur à 4 x 10-6 K-1 à des températures au-dessus de 400°C et inférieur à 3 x 10-6 K-1 à des températures au-dessous de 400°C et une conductivité thermique d'au moins 5 W/mK à des températures de 25°C à 1 500°C.
PCT/EP2010/065465 2010-03-30 2010-10-14 Procédé pour la production de lingots de silicium de qualité convenant pour la fabrication de semi-conducteurs, creusets réutilisables et leur procédé de fabrication WO2011120598A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201080066044.4A CN102859049B (zh) 2010-03-30 2010-10-14 制造半导体级硅晶锭的方法、可再使用的坩埚及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB1005399.9 2010-03-30
GB1005399A GB2479165A (en) 2009-10-14 2010-03-30 Reusable crucible

Publications (2)

Publication Number Publication Date
WO2011120598A1 true WO2011120598A1 (fr) 2011-10-06
WO2011120598A8 WO2011120598A8 (fr) 2011-12-22

Family

ID=44720368

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2010/065465 WO2011120598A1 (fr) 2010-03-30 2010-10-14 Procédé pour la production de lingots de silicium de qualité convenant pour la fabrication de semi-conducteurs, creusets réutilisables et leur procédé de fabrication

Country Status (2)

Country Link
CN (1) CN102859049B (fr)
WO (1) WO2011120598A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103628126A (zh) * 2012-08-21 2014-03-12 浙江昱辉阳光能源有限公司 一种类单晶晶体硅锭的制作方法和多晶硅铸锭炉
CN103628125A (zh) * 2012-08-21 2014-03-12 浙江昱辉阳光能源有限公司 一种多晶硅铸锭炉和多晶硅铸锭方法
WO2014056157A1 (fr) * 2012-10-10 2014-04-17 浙江昱辉阳光能源有限公司 Lingot de silicium polycristallin, procédé pour le produire, et creuset
WO2015132399A1 (fr) * 2014-03-06 2015-09-11 Ald Vacuum Technologies Gmbh Creuset hybride pour la cristallisation des matériaux

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102017204257A1 (de) 2017-03-14 2018-09-20 Schunk Kohlenstofftechnik Gmbh Beschichtetes Produkt und Verfahren zur Herstellung

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132145A (en) * 1987-04-27 1992-07-21 Societe Anonyme Method of making composite material crucible for use in a device for making single crystals
JPH10273369A (ja) * 1997-03-28 1998-10-13 Nissan Motor Co Ltd 耐Ｓｉアタック性に優れたＣ／Ｃ複合材の製造方法およびＣ／Ｃ製るつぼ
EP0915070A2 (fr) 1997-11-10 1999-05-12 Deutsches Zentrum für Luft- und Raumfahrt e.V. Procédé de fabrication d'un corps moulé céramifié et renforcé par fibres de carbone et l'utilisation d'un tel corps moulé
US6030913A (en) 1997-03-12 2000-02-29 Sgl Technik Gmbh Silicon carbide articles reinforced with short graphite fibers
EP1547992A1 (fr) 2003-12-18 2005-06-29 Deutsches Zentrum für Luft- und Raumfahrt e.V. Procédé pour fabriquer un matériau composite renforcé par des fibres et le matériau composite renforcé par des fibres
US7238308B2 (en) 2002-03-19 2007-07-03 Audi Ag Process for the infiltration of porous carbon composites
WO2007148986A1 (fr) 2006-06-23 2007-12-27 Rec Scanwafer As Creusets réutilisables et procédé de fabrication de ceux-ci
WO2007148987A1 (fr) * 2006-06-23 2007-12-27 Rec Scanwafer As Procédé et creuset pour la solidification directe de lingots de silicium multicristallin de qualité semi-conducteur

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6837952B1 (en) * 1999-11-24 2005-01-04 Snecma Moteurs Method for making a bowl in thermostructural composite material
JP2006131451A (ja) * 2004-11-05 2006-05-25 Tokai Carbon Co Ltd 単結晶引き上げ用ルツボとその製造方法
EP2035604A1 (fr) * 2006-06-23 2009-03-18 Rec Scanwafer AS Dispositif et procede pour la fabrication de silicium de qualite semi-conducteur
CN101643933B (zh) * 2009-08-19 2012-05-02 湖南南方搏云新材料有限责任公司 Cz法硅单晶生长炉石英坩埚碳素护埚及其制造工艺

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5132145A (en) * 1987-04-27 1992-07-21 Societe Anonyme Method of making composite material crucible for use in a device for making single crystals
US6030913A (en) 1997-03-12 2000-02-29 Sgl Technik Gmbh Silicon carbide articles reinforced with short graphite fibers
JPH10273369A (ja) * 1997-03-28 1998-10-13 Nissan Motor Co Ltd 耐Ｓｉアタック性に優れたＣ／Ｃ複合材の製造方法およびＣ／Ｃ製るつぼ
EP0915070A2 (fr) 1997-11-10 1999-05-12 Deutsches Zentrum für Luft- und Raumfahrt e.V. Procédé de fabrication d'un corps moulé céramifié et renforcé par fibres de carbone et l'utilisation d'un tel corps moulé
US7238308B2 (en) 2002-03-19 2007-07-03 Audi Ag Process for the infiltration of porous carbon composites
EP1547992A1 (fr) 2003-12-18 2005-06-29 Deutsches Zentrum für Luft- und Raumfahrt e.V. Procédé pour fabriquer un matériau composite renforcé par des fibres et le matériau composite renforcé par des fibres
WO2007148986A1 (fr) 2006-06-23 2007-12-27 Rec Scanwafer As Creusets réutilisables et procédé de fabrication de ceux-ci
WO2007148987A1 (fr) * 2006-06-23 2007-12-27 Rec Scanwafer As Procédé et creuset pour la solidification directe de lingots de silicium multicristallin de qualité semi-conducteur

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Properties of crystalline silicon", 1999, INSPEC
HEIDENREICH; BERNHARD: "Carbon Fibre Reinforced SiC Materials Based on Melt Infiltration", 6TH INTERNATIONAL CONFERENCE ON HIGH TEMPERATURE CERAMIC MATRIX COMPOSITES, 2007
KVANDE R ET AL: "Influence of crucible and coating quality on the properties of multicrystalline silicon for solar cells", JOURNAL OF CRYSTAL GROWTH, vol. 311, no. 3, 2 October 2008 (2008-10-02), ELSEVIER SCIENCE B.V. [NL], pages 765 - 768, XP025947286, ISSN: 0022-0248, DOI: 10.1016/j.jcrysgro.2008.09.152 *
XIN-BO ET AL.: "Carbon-fiber-reinforced silicon carbide composites", JOURNAL OF MATERIALS SCIENCE LETTERS, vol. 19, 2000, pages 417 - 419

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103628126A (zh) * 2012-08-21 2014-03-12 浙江昱辉阳光能源有限公司 一种类单晶晶体硅锭的制作方法和多晶硅铸锭炉
CN103628125A (zh) * 2012-08-21 2014-03-12 浙江昱辉阳光能源有限公司 一种多晶硅铸锭炉和多晶硅铸锭方法
WO2014056157A1 (fr) * 2012-10-10 2014-04-17 浙江昱辉阳光能源有限公司 Lingot de silicium polycristallin, procédé pour le produire, et creuset
CN104703914A (zh) * 2012-10-10 2015-06-10 浙江昱辉阳光能源有限公司 多晶硅锭及其制造方法、坩埚
WO2015132399A1 (fr) * 2014-03-06 2015-09-11 Ald Vacuum Technologies Gmbh Creuset hybride pour la cristallisation des matériaux
US10100427B2 (en) 2014-03-06 2018-10-16 Ald Vacuum Technologies Gmbh Hybrid crucible for crystallizing materials

Also Published As

Publication number Publication date
CN102859049B (zh) 2016-01-20
WO2011120598A8 (fr) 2011-12-22
CN102859049A (zh) 2013-01-02

Similar Documents

Publication Publication Date Title
US20090314198A1 (en) Device and method for production of semiconductor grade silicon
US20090249999A1 (en) Reusable crucibles and method of manufacturing them
US10294584B2 (en) SiC single crystal sublimation growth method and apparatus
US20090208400A1 (en) Method and crucible for direct solidification of semiconductor grade multi-crystalline silicon ingots
JP5304600B2 (ja) ＳｉＣ単結晶の製造装置及び製造方法
CN101545135B (zh) 太阳能级硅晶体的制备及提纯方法
EP2471979B1 (fr) Creuset composite et son procédé de fabrication
WO2011120598A1 (fr) Procédé pour la production de lingots de silicium de qualité convenant pour la fabrication de semi-conducteurs, creusets réutilisables et leur procédé de fabrication
JP4815003B2 (ja) シリコン結晶成長用ルツボ、シリコン結晶成長用ルツボ製造方法、及びシリコン結晶成長方法
US20130247334A1 (en) Crucible for Solidifying a Silicon Ingot
JPH11116229A (ja) シリコンの精製方法
GB2479165A (en) Reusable crucible
US20100178195A1 (en) Method of solidifying metallic silicon
US20090297425A1 (en) Metallic silicon and method for manufacturing the same
JP2013522160A (ja) シリコンの純化方法
EP2655705A1 (fr) Creusets
TW201019480A (en) High temperature support apparatus and method of use for casting materials
CN102211936A (zh) 一种高纯铝硅碳块体的合成方法
EP2738141B1 (fr) Récipient de silicium polycristallin
JP4693932B1 (ja) 筒状シリコン結晶体製造方法及びその製造方法で製造される筒状シリコン結晶体
KR20180117760A (ko) 실리카 도가니 내벽에 질화규소를 코팅하는 방법
Prakash et al. Use of silicon oxynitride as a graphite mold releasing coating for the growth of shaped multicrystalline silicon crystals
JP2007184496A (ja) 結晶半導体粒子の製造方法および光電変換装置
JP2013144624A (ja) シリコン製造装置

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080066044.4

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10766274

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10766274

Country of ref document: EP

Kind code of ref document: A1