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WO2006005416A1 - Method for producing a nonstick ingot mold - Google Patents

Method for producing a nonstick ingot mold Download PDF

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Publication number
WO2006005416A1
WO2006005416A1 PCT/EP2005/006675 EP2005006675W WO2006005416A1 WO 2006005416 A1 WO2006005416 A1 WO 2006005416A1 EP 2005006675 W EP2005006675 W EP 2005006675W WO 2006005416 A1 WO2006005416 A1 WO 2006005416A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon
container
indicates
wall
layer
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2005/006675
Other languages
German (de)
French (fr)
Inventor
Peter Woditsch
Armin Müller
Bert Geyer
Bernhard Freudenberg
Carsten Wobst
Gerd Schwichtenberg
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SolarWorld Industries Sachsen GmbH
Original Assignee
Deutsche Solar GmbH
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
Application filed by Deutsche Solar GmbH filed Critical Deutsche Solar GmbH
Publication of WO2006005416A1 publication Critical patent/WO2006005416A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/003—General methods for coating; Devices therefor for hollow ware, e.g. containers
    • C03C17/004—Coating the inside
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/225—Nitrides
    • 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
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/20—Materials for coating a single layer on glass
    • C03C2217/28—Other inorganic materials
    • C03C2217/281—Nitrides

Definitions

  • the invention relates to a method for producing a container for melting and / or crystallizing non-ferrous metals, in particular of silicon.
  • the invention further relates to a container produced by the erfindungsge ⁇ MAESSEN container.
  • the invention relates to Weite ⁇ Ren the use of a container according to the invention for receiving silicon melt.
  • silicon nitride as non-stick coating is known from EP 0 963 464 A.
  • the effectiveness of the coating as a reliable release and release layer depends on various factors.
  • organic binders are added thereto. Due to the high temperature of the liquid silicon, the added organic adhesion promoters but decomposes, so that it always comes back to a caking of the silicon on the mold wall.
  • the invention has for its object to provide a method for producing a container for melting and / or crystallizing Tinei ⁇ senmetallen and a corresponding container, in which there is no adhesion of the non-ferrous metal to the container inner wall.
  • the core of the invention consists of applying a silicon nitride powder-containing layer to the inner wall of the container blank.
  • the silicon nitride powder-containing layer is then burned ein ⁇ by a baking process in the inner wall of the container blank.
  • the baked-on layer acts as a non-stick coating for a silicon melt, which is not decomposed even at the high temperatures of the silicon melt.
  • the coating produced in this way offers a considerably higher resistance to caking and sticking between the solidified silicon and the container inner wall and has a substantially lower contamination of the crystallized block surface of the silicon with the coating.
  • molds designed as containers are used, which essentially have the shape of an upwardly open cuboid and a cuboidal interior limit five pages, that is not upwards.
  • round molds are used.
  • such containers are referred to as molds and container blanks as mold blanks.
  • the ingot blank is a green compact which is produced either by compression of silicon dioxide powder or by shaping and subsequent drying of sludge containing silicon dioxide powder.
  • a layer containing silicon nitride powder is subsequently applied to the inner wall of the green body.
  • the silicon nitride powder is preferably dispersed in a solvent with or without an organic or inorganic dispersant and / or an adhesion promoter.
  • the silicon nitride powder can be applied to the inner wall of the green body in dispersed or powdered state, for example by brushing, spraying, spraying, dipping or by electrostatic application as suspension, slip or powder. If required, several layers can be applied one after the other.
  • the layers of silicon nitride powder have a silicon dioxide content of ⁇ 70 wt .-%, in particular ⁇ 60 wt .-%, in particular ⁇ 45 wt .-%, an alkali and alkaline earth metal content of ⁇ 3000 ppm, in particular ⁇ 1000 ppm, a fluoride content of ⁇ 3000 ppm, in particular ⁇ 2000 ppm, a chloride content of ⁇ 3000 ppm, in particular
  • the layers of silicon nitride powder have an oxygen content of from 0.1% by weight to 10% by weight, in particular from 0.3% by weight to 5% by weight, in particular from 1% by weight to 3% by weight .-% on.
  • the ratio of length to diameter of the particles of the silicon nitride powder is less than 10.
  • the mean particle size of the silicon nitride powder is ⁇ 100 .mu.m, in particular ⁇ 50 .mu.m, in particular ⁇ 30 .mu.m.
  • the silicon nitride powder contains, in addition to other phases of the silicon nitride, 1% to 100%, in particular 1% to 5%, in the beta phase.
  • the silicon nitride powder may be amorphous.
  • the green compact is heat-treated, in particular sintered, with the layers burning into the inner wall of the green compact.
  • the baking of the layers into the inner wall and the burning of the green body preferably takes place simultaneously. Alternatively, separate method steps may be provided.
  • the baking is preferably carried out by means of a heating of the green body by an incoherent radiation and / or by convection.
  • the firing takes place in a furnace provided for this purpose, in particular in a tunnel kiln customary in the ceramics industry. Such burn-in is inexpensive compared to burn-in with laser radiation.
  • a stable silicon nitride layer is present as a non-stick coating on the inner wall of the finished mold.
  • the sintering process is preferably carried out at 1100 0 C and leads to a compaction and curing of the green compact.
  • the particles of the silicon dioxide powder of the green compact and of the silicon nitride powder applied thereto form fusions, so that the resulting non-stick coating is firmly bonded to the inner wall of the mold.
  • the particles of the silicon dioxide powder also form enamel with one another, as a result of which the sintered green body acquires its strength.
  • the non-stick-coated mold resulting from the firing process is particularly suitable for receiving liquid silicon and for crystallizing liquid silicon into silicon blocks, rods, billets or granules.
  • the non-stick coating according to the invention offers better resistance to caking and sticking than known methods.
  • the generated silicon can be used to produce silicon wafers.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Ceramic Products (AREA)

Abstract

The invention relates to a method for producing a receptacle for melting and/or crystallizing nonferrous metals, which comprises the following steps: providing a container blank having an inner wall and an outer wall, applying at least one silicon-nitride powder-containing layer to at least the inner wall of the container blank and burning in the at least one layer into the container blank. The nonstick coat produced by burning provides an improved resistance to adhesions or material sticking to the mold during the reception of liquid silicon or during the crystallization of liquid silicon.

Description

Herstellungsverfahren für Kokille mit AntihaftbeschichtungProduction process for mold with non-stick coating

Die Erfindung betrifft ein Verfahren zur Herstellung eines Behälters zum Schmelzen und/oder Kristallisieren von Nichteisenmetallen, insbesondere von Silizium. Die Erfindung betrifft ferner einen nach dem erfindungsge¬ mäßen Verfahren hergestellten Behälter. Die Erfindung betrifft des Weite¬ ren die Verwendung eines erfindungsgemäßen Behälters zur Aufnähme von Siliziumschmelzen.The invention relates to a method for producing a container for melting and / or crystallizing non-ferrous metals, in particular of silicon. The invention further relates to a container produced by the erfindungsge¬ MAESSEN container. The invention relates to Weite¬ Ren the use of a container according to the invention for receiving silicon melt.

Es ist seit langem bekannt, Silizium in Quarzkokillen einzuschmelzen und kristallisieren zu lassen, um multikristalline Siliziumblöcke herzustellen. Trifft dabei während des Schmelz- und Kristallisationsvorganges flüssiges Silizium auf die Quarz-Kokilleninnenwand, so bildet sich infolge einer chemischen Reaktion ein fester Verbund zwischen Silizium und Quarz. Aufgrund des unterschiedlichen Wärmeausdehnungsverhaltens beider Werkstoffe entstehen Spannungen, so dass es zu Rissen in dem Silizium¬ block kommen kann. Um dies zu vermeiden, wird eine Schicht aus Silizi¬ umnitrid als hochtemperaturstabile Antihaftschicht eingesetzt, die das schmelzflüssige Silizium von der Kokillenoberfläche trennt. Bisher wurde dazu die Quarz-Kokillenoberfläche vor dem Einbringen des flüssigen Sili¬ ziums mit einer dünnen Siliziumnitridschicht versehen, um den direkten Kontakt des geschmolzenen Siliziums mit der Quarzkokille zu vermeiden. Die Verwendung von Siliziumnitrid als Antihaftbeschichtung ist aus der EP 0 963 464 A bekannt. Jedoch hängt die Wirksamkeit der Beschichtung als zuverlässige Trenn- und Antihaftschicht von verschiedenen Faktoren ab. Zur Verbesserung des Anhaftens des Siliziumnitrids werden diesem organische Bindehilfsmittel zugesetzt. Aufgrund der hohen Temperatur des flüssigen Siliziums werden die zugegebenen organischen Haftvermittler jedoch zersetzt, so dass es immer wieder zu einem Anbacken des Siliziums an der Kokillenwand kommt.It has long been known to melt silicon in quartz molds and crystallize to produce multicrystalline silicon ingots. If liquid silicon hits the quartz inner mold wall during the melting and crystallization process, a solid bond between silicon and quartz is formed as a result of a chemical reaction. Due to the different thermal expansion behavior of both materials, stresses occur so that cracks can occur in the silicon block. In order to avoid this, a layer of silicon nitride is used as a high-temperature stable non-stick layer, which separates the molten silicon from the mold surface. To date, the quartz mold surface has been provided with a thin silicon nitride layer prior to introduction of the liquid silicon in order to avoid direct contact of the molten silicon with the quartz mold. The use of silicon nitride as non-stick coating is known from EP 0 963 464 A. However, the effectiveness of the coating as a reliable release and release layer depends on various factors. To improve the adhesion of the silicon nitride, organic binders are added thereto. Due to the high temperature of the liquid silicon, the added organic adhesion promoters but decomposes, so that it always comes back to a caking of the silicon on the mold wall.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren zur Herstellung eines Behältnisses zum Schmelzen und/oder Kristallisieren von Nichtei¬ senmetallen sowie ein entsprechendes Behältnis zu schaffen, bei dem es zu keinem Anhaften des Nichteisenmetalls an der Behälterinnenwand kommt.The invention has for its object to provide a method for producing a container for melting and / or crystallizing Nichtei¬ senmetallen and a corresponding container, in which there is no adhesion of the non-ferrous metal to the container inner wall.

Die Aufgabe wird durch die Merkmale der unabhängigen Ansprüche 1, 11 und 12 gelöst. Der Kern der Erfindung besteht darin, auf die Innenwand des Behälter-Rohlings eine Siliziumnitridpulver enthaltende Schicht aufzu¬ tragen. Die Siliziumnitridpulver enthaltende Schicht wird anschließend durch einen Einbrennvorgang in die Innenwand des Behälter-Rohlings ein¬ gebrannt. Die eingebrannte Schicht wirkt als Antihaftbeschichtung für eine Siliziumschmelze, die auch bei den hohen Temperaturen der Silizium¬ schmelze nicht zersetzt wird. Die auf diese Weise hergestellte Beschich- tung bietet einen wesentlich höheren Widerstand gegenüber Anbackungen und Verklebungen zwischen dem erstarrten Silizium und der Behälterin¬ nenwand und weist eine wesentlich niedrigere Kontamination der kristalli- sierten Blockoberfläche des Siliziums mit der Beschichtimg auf.The object is solved by the features of independent claims 1, 11 and 12. The core of the invention consists of applying a silicon nitride powder-containing layer to the inner wall of the container blank. The silicon nitride powder-containing layer is then burned ein¬ by a baking process in the inner wall of the container blank. The baked-on layer acts as a non-stick coating for a silicon melt, which is not decomposed even at the high temperatures of the silicon melt. The coating produced in this way offers a considerably higher resistance to caking and sticking between the solidified silicon and the container inner wall and has a substantially lower contamination of the crystallized block surface of the silicon with the coating.

Weitere vorteilhafte Ausgestaltungen ergeben sich aus den Unteransprü¬ chen.Further advantageous embodiments will become apparent from the Unteransprü¬ surfaces.

Zusätzliche Merkmale und Einzelheiten der Erfindung ergeben sich aus der Beschreibung eines Ausfuhrungsbeispiels. Zum Schmelzen und Kristalli¬ sieren von Nichteisenmetallen, insbesondere Silizium, werden als Behälter ausgebildete Kokillen verwendet, die im Wesentlichen die Form eines nach oben offenen Quaders besitzen und einen quaderförmigen Innenraum nach fünf Seiten, das heißt nicht nach oben, begrenzen. Ebenso werden runde Kokillen verwendet. Für die vorliegende Erfindung werden derartige Be¬ hälter als Kokillen und Behälter-Rohlinge als Kokillen-Rohlinge bezeich¬ net.Additional features and details of the invention will become apparent from the description of an exemplary embodiment. For melting and crystallizing non-ferrous metals, in particular silicon, molds designed as containers are used, which essentially have the shape of an upwardly open cuboid and a cuboidal interior limit five pages, that is not upwards. Likewise round molds are used. For the present invention, such containers are referred to as molds and container blanks as mold blanks.

Zur Herstellung der für die Aufnahme des flüssigen Siliziums fertigen Ko¬ kille muss zunächst ein Kokillen-Rohling bereitgestellt werden. Bei dem Kokillen-Rohling handelt es sich um einen Grünling, der entweder durch Verpressen von Siliziumdioxidpulver oder durch Formung und anschlie- ßendes Trocknen von Siliziumdioxidpulver enthaltendem Schlicker herge¬ stellt wird. Auf die Innenwand des Grünlings wird anschließend eine Sili¬ ziumnitridpulver enthaltende Schicht aufgetragen. Das Siliziumnitridpulver ist zu diesem Zweck vorzugsweise in einem Lösungsmittel mit oder ohne organischem oder anorganischem Dispergator und/oder einem Haftvermitt- ler dispergiert.In order to produce the mold which is used to take up the liquid silicon, it is first necessary to provide a mold blank. The ingot blank is a green compact which is produced either by compression of silicon dioxide powder or by shaping and subsequent drying of sludge containing silicon dioxide powder. A layer containing silicon nitride powder is subsequently applied to the inner wall of the green body. For this purpose, the silicon nitride powder is preferably dispersed in a solvent with or without an organic or inorganic dispersant and / or an adhesion promoter.

Das Siliziumnitridpulver kann in dispergiertem oder pulverförmigem Zu¬ stand beispielsweise durch Streichen, Sprühen, Spritzen, Tauchen oder durch elektrostatischen Auftrag als Suspension, Schlicker oder Pulver auf die Innenwand des Grünlings aufgetragen werden. Bei Bedarf können auch mehrere Schichten nacheinander aufgetragen werden.The silicon nitride powder can be applied to the inner wall of the green body in dispersed or powdered state, for example by brushing, spraying, spraying, dipping or by electrostatic application as suspension, slip or powder. If required, several layers can be applied one after the other.

Die Schichten aus Siliziumnitridpulver weisen einen Siliziumdioxidgehalt von <70 Gew.-%, insbesondere <60 Gew.-%, insbesondere <45 Gew.-%, einen Alkali- und Erdalkali-Metallgehalt von <3000 ppm, insbesondere < 1000 ppm, einen Fluoridgehalt von ≤3000 ppm, insbesondere <2000 ppm, einen Chloridgehalt von <3000 ppm, insbesondereThe layers of silicon nitride powder have a silicon dioxide content of <70 wt .-%, in particular <60 wt .-%, in particular <45 wt .-%, an alkali and alkaline earth metal content of <3000 ppm, in particular <1000 ppm, a fluoride content of ≤3000 ppm, in particular <2000 ppm, a chloride content of <3000 ppm, in particular

BESTATIGUNGSKOPIE <2000 ppm, einen Gesamtkohlenstoffgehalt von <3000 ppm, insbesonde¬ re <2000 ppm, und einen Eisen-, Chrom-, Kobalt-, Nickel-, Wolfram- und/oder Titan-Gehalt von jeweils <1000 ppm, insbesondere <500 ppm, auf. Des Weiteren weisen die Schichten aus Siliziumnitridpul- ver einen Sauerstoffgehalt von 0,1 Gew.-% bis 10 Gew.-%, insbesondere 0,3 Gew.-% bis 5 Gew.-%, insbesondere 1 Gew.-% bis 3 Gew.-% auf. Das Verhältnis Länge zu Durchmesser der Teilchen des Siliziumnitridpulvers ist kleiner als 10. Die mittlere Partikelgröße des Siliziumnitridpulvers ist <100 μm, insbesondere <50 μm, insbesondere <30 μm. Das Siliziumnit- ridpulver enthält neben anderen Phasen des Siliziumnitrids 1 % bis 100 %, insbesondere 1 % bis 5 % in der Beta-Phase. Das Siliziumnitridpulver kann amorph sein.BESTATIGUNGSKOPIE <2000 ppm, a total carbon content of <3000 ppm, insbesonde¬ re <2000 ppm, and an iron, chromium, cobalt, nickel, tungsten and / or titanium content of <1000 ppm, in particular <500 ppm , on. Furthermore, the layers of silicon nitride powder have an oxygen content of from 0.1% by weight to 10% by weight, in particular from 0.3% by weight to 5% by weight, in particular from 1% by weight to 3% by weight .-% on. The ratio of length to diameter of the particles of the silicon nitride powder is less than 10. The mean particle size of the silicon nitride powder is <100 .mu.m, in particular <50 .mu.m, in particular <30 .mu.m. The silicon nitride powder contains, in addition to other phases of the silicon nitride, 1% to 100%, in particular 1% to 5%, in the beta phase. The silicon nitride powder may be amorphous.

Nach dem Aufbringen der Siliziumnitridpulver enthaltenden Schichten auf die Innenwand des Grünlings wird der Grünling wärmebehandelt, insbe¬ sondere gesintert, wobei sich die Schichten in die Innenwand des Grünlings einbrennen. Das Einbrennen der Schichten in die Innenwand und das Bren¬ nen des Grünlings erfolgt vorzugsweise gleichzeitig. Alternativ können auch separate Verfahrensschritte vorgesehen sein. Das Einbrennen erfolgt vorzugsweise mittels einer Erwärmung des Grünlings durch eine inkohä¬ rente Strahlung und/oder durch Konvektion. Das Einbrennen erfolgt in ei¬ nem dafür vorgesehenen Ofen, insbesondere in einem in der Keramikin- dustrie üblichen Tunnelofen. Ein derartiges Einbrennen ist im Vergleich zu einem Einbrennen mit einer Laserstrahlung kostengünstig. Insbesondere sind hohe Investitionskosten und hohe Betriebskosten in Folge von zu tref¬ fenden Sicherheitsmaßnahmen, wie dies bei einem Einbrennen mit Laser¬ strahlung der Fall ist, nicht erforderlich. Nach dem Brennvorgang liegt eine stabile Siliziumnitrid-Schicht als Antihaftbeschichtung auf der Innenwand der fertiggestellten Kokille vor. Der Sintervorgang erfolgt vorzugsweise bei 1100 0C und fuhrt zu einer Verdichtung und Aushärtung des Grünlings. Während des Sintervorgangs bilden die Teilchen des Siliziumdioxidpulvers des Grünlings und des darauf aufgetragenen Siliziumnitridpulvers An¬ schmelzungen, so dass die dadurch entstehende Antihaftbeschichtung fest mit der Innenwand der Kokille verbunden wird. Die Teilchen des Silizium¬ dioxidpulvers bilden untereinander ebenfalls Anschmelzungen, wodurch der gesinterte Grünlings seine Festigkeit erhält.After applying the silicon nitride powder-containing layers to the inner wall of the green compact, the green compact is heat-treated, in particular sintered, with the layers burning into the inner wall of the green compact. The baking of the layers into the inner wall and the burning of the green body preferably takes place simultaneously. Alternatively, separate method steps may be provided. The baking is preferably carried out by means of a heating of the green body by an incoherent radiation and / or by convection. The firing takes place in a furnace provided for this purpose, in particular in a tunnel kiln customary in the ceramics industry. Such burn-in is inexpensive compared to burn-in with laser radiation. In particular, high investment costs and high operating costs are not required as a consequence of safety measures to be taken, as is the case when burning in with laser radiation. After firing, a stable silicon nitride layer is present as a non-stick coating on the inner wall of the finished mold. The sintering process is preferably carried out at 1100 0 C and leads to a compaction and curing of the green compact. During the sintering process, the particles of the silicon dioxide powder of the green compact and of the silicon nitride powder applied thereto form fusions, so that the resulting non-stick coating is firmly bonded to the inner wall of the mold. The particles of the silicon dioxide powder also form enamel with one another, as a result of which the sintered green body acquires its strength.

Die durch den Brennvorgang entstandene antihaftbeschichtete Kokille eig- net sich besonders zur Aufnahme von flüssigem Silizium und zur Kristalli¬ sation von flüssigem Silizium zu Siliziumblöcken, -Stäben, -knüppeln oder -granulaten. Die erfindungsgemäße Antihaftbeschichtung bietet einen bes¬ seren Widerstand gegenüber Anbackungen und Verklebungen als bekannte Verfahren. Das erzeugte Silizium kann zur Herstellung von Siliziumwafern verwendet werden. The non-stick-coated mold resulting from the firing process is particularly suitable for receiving liquid silicon and for crystallizing liquid silicon into silicon blocks, rods, billets or granules. The non-stick coating according to the invention offers better resistance to caking and sticking than known methods. The generated silicon can be used to produce silicon wafers.

Claims

Patentansprüche claims 1. Verfahren zur Herstellung eines Behälters zum Schmelzen und/oder Kristallisieren von Nichteisenmetallen umfassend die folgenden Schrit- te: a. Bereitstellen eines Behälter-Rohlings mit einer Innenwand und ei¬ ner Außenwand, b. Aufbringen mindestens einer Siliziumnitridpulver enthaltenden Schicht zumindest auf die Innenwand des Behälter-Rohlings, und c. Einbrennen der mindestens einen Schicht in den Behälter-Rohling.1. A method for producing a container for melting and / or crystallizing non-ferrous metals, comprising the following steps: a. Providing a container blank having an inner wall and an outer wall, b. Applying at least one silicon nitride powder-containing layer at least to the inner wall of the container blank, and c. Baking the at least one layer in the container blank. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Sili¬ ziumnitridpulver dispergiert ist.2. The method according to claim 1, characterized in that the Sili¬ ziumnitridpulver is dispersed. 3. Verfahren nach Ansprach 1 oder 2, dadurch gekennzeichnet, dass der Behälter-Rohling ein Grünling ist.3. The method according to spoke 1 or 2, characterized in that the container blank is a green body. 4. Verfahren nach einem der vorangegangenen Ansprüche, dadurch ge¬ kennzeichnet, dass das Einbrennen ein Sintervorgang ist.4. The method according to any one of the preceding claims, characterized ge indicates that the baking is a sintering process. 5. Verfahren nach einem der vorangegangenen Ansprüche, dadurch ge¬ kennzeichnet, dass die mindestens eine Schicht aus Siliziumnitridpul¬ ver Siliziumdioxid enthält.5. The method according to any one of the preceding claims, characterized ge indicates that the at least one layer of Siliziumnitridpul¬ ver contains silicon dioxide. 6. Verfahren nach einem der vorangegangenen Ansprüche, dadurch ge¬ kennzeichnet, dass die mindestens eine Schicht aus Siliziumnitridpul¬ ver <70 Gew.-%, insbesondere <60 Gew.-%, insbesondere <45 Gew.-% Siliziumdioxid aufweist. 6. The method according to any one of the preceding claims, characterized ge indicates that the at least one layer of Siliziumnitridpul¬ ver <70 wt .-%, in particular <60 wt .-%, in particular <45 wt .-% silicon dioxide. 7. Verfahren nach einem der vorangegangenen Ansprüche, dadurch ge¬ kennzeichnet, dass die mittlere Partikelgröße des Siliziumnitridpul¬ vers <100 μm, insbesondere <50 μm, insbesondere <30 μm beträgt.7. The method according to any one of the preceding claims, characterized ge indicates that the average particle size of the Siliziumnitridpul¬ verse <100 .mu.m, in particular <50 .mu.m, in particular <30 microns. 8. Verfahren nach einem der vorangegangenen Ansprüche, dadurch ge¬ kennzeichnet, dass Siliziumnitridpulver neben anderen Phasen des Si¬ liziumnitrids 1 % bis 100 %, insbesondere 1 % bis 5 % in der Beta- Phase enthält.8. The method according to any one of the preceding claims, characterized ge indicates that silicon nitride powder in addition to other phases of Si liziumnitrids 1% to 100%, in particular 1% to 5% in the beta phase. 9. Verfahren nach einem der vorangegangenen Ansprüche, dadurch ge¬ kennzeichnet, dass das Einbrennen im Wesentlichen mittels einer in¬ kohärenten Strahlung und/oder Konvektion erfolgt.9. The method according to any one of the preceding claims, characterized ge indicates that the burning takes place substantially by means of an in¬ coherent radiation and / or convection. 10. Verfahren nach einem der vorangegangenen Ansprüche, dadurch ge- kennzeichnet, dass das Einbrennen in einem Ofen, insbesondere in ei¬ nem Tunnelofen, erfolgt.10. The method according to any one of the preceding claims, character- ized in that the burning in an oven, in particular in ei¬ nem tunnel oven takes place. 11. Behälter zum Schmelzen und/oder Kristallisieren von Nichteisenmetal¬ len hergestellt nach dem Verfahren gemäß einem der Ansprüche 1 bis 10.11. Container for melting and / or crystallizing non-ferrous metals produced by the process according to any one of claims 1 to 10. 12. Verwendung des nach dem Verfahren gemäß einem der Ansprüche 1 bis 10 hergestellten Behälters zur Aufnahme von flüssigem Silizium und/oder zur Kristallisation von flüssigem Silizium zu Siliziumblö- cken, Siliziumstäben, Siliziumknüppeln, Siliziumgranulat und/oder Si- liziumwafern. 12. Use of the container produced by the process according to one of claims 1 to 10 for receiving liquid silicon and / or for crystallizing liquid silicon to silicon blocks, silicon rods, silicon billets, silicon granules and / or silicon wafers.
PCT/EP2005/006675 2004-07-08 2005-06-21 Method for producing a nonstick ingot mold Ceased WO2006005416A1 (en)

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