EP4168373A1 - Procédé de fabrication additive de structures contenant du sic - Google Patents

Procédé de fabrication additive de structures contenant du sic

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Publication number
EP4168373A1
EP4168373A1 EP20764360.2A EP20764360A EP4168373A1 EP 4168373 A1 EP4168373 A1 EP 4168373A1 EP 20764360 A EP20764360 A EP 20764360A EP 4168373 A1 EP4168373 A1 EP 4168373A1
Authority
EP
European Patent Office
Prior art keywords
precursor
sic
precursor material
laser
context
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.)
Withdrawn
Application number
EP20764360.2A
Other languages
German (de)
English (en)
Inventor
Siegmund Greulich-Weber
Rüdiger SCHLEICHER-TAPPESER
Erik THIEL
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.)
PSC Technologies GmbH
Original Assignee
PSC Technologies 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 PSC Technologies GmbH filed Critical PSC Technologies GmbH
Publication of EP4168373A1 publication Critical patent/EP4168373A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
    • C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
    • C04B35/573—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained by reaction sintering or recrystallisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
    • B23K26/144—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor the fluid stream containing particles, e.g. powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/14—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor
    • B23K26/146—Working by laser beam, e.g. welding, cutting or boring using a fluid stream, e.g. a jet of gas, in conjunction with the laser beam; Nozzles therefor the fluid stream containing a liquid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00—Working by laser beam, e.g. welding, cutting or boring
    • B23K26/34—Laser welding for purposes other than joining
    • B23K26/342—Build-up welding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/90—Carbides
    • C01B32/914—Carbides of single elements
    • C01B32/956—Silicon carbide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K2103/00—Materials to be soldered, welded or cut
    • B23K2103/50—Inorganic material, e.g. metals, not provided for in B23K2103/02 – B23K2103/26
    • B23K2103/52—Ceramics
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
    • C04B2235/428—Silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
    • C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/66—Specific sintering techniques, e.g. centrifugal sintering
    • C04B2235/665—Local sintering, e.g. laser sintering

Definitions

  • the present invention relates to the technical field of the production of SiC-containing materials, in particular by means of additive manufacturing processes.
  • the present invention relates to a method for producing SiC-containing structures which are obtained by a repeated and / or continuous input of energy into a precursor material by at least one radiation source.
  • the present invention further relates to a use of a radiation source, in particular a laser, preferably a laser array, for the production of SiC-containing structures.
  • a radiation source in particular a laser, preferably a laser array
  • the present invention relates to SiC-containing structures obtainable by the method according to the invention.
  • Generative manufacturing processes also known as additive manufacturing or additive manufacturing (AM) denote processes for the rapid manufacture of models, samples, tools and products from shapeless materials, such as liquids, gels, pastes or powders.
  • AM additive manufacturing
  • generative manufacturing processes are used both for the production of spatial structures and objects from inorganic materials, in particular metals and ceramics, as well as from organic materials.
  • High-energy processes such as selective laser melting (SLM), electron beam melting or build-up welding, are preferably used especially for the production of structures from inorganic materials, since the starting materials or precursors used only react or melt when higher energy input is used.
  • SLM selective laser melting
  • electron beam melting or build-up welding
  • generative manufacturing processes enable time-efficient and flexible production of, among other things, highly complex spatial structures that would be difficult to access using subtractive manufacturing processes.
  • the economic viability of these, in particular high-energy, processes is not yet fully developed for industrial applications, with the manufacture of larger components and structures or the production of larger series in particular still Causes problems and sometimes takes a relatively long time.
  • Silicon carbide also known as carborundum, is an extremely interesting and versatile material for mechanically heavily loaded structures or components as well as for semiconductor applications. Silicon carbide, with the chemical formula SiC, is extremely hard and has a high sublimation point. It is therefore often used, for example, as an abrasive or as an insulator in high-temperature reactors.
  • silicon carbide forms alloys or alloy-like compounds with a large number of elements and compounds, which have a large number of advantageous material properties, such as high hardness, high resistance, low weight and low sensitivity to oxidation, even at high temperatures.
  • SiC-containing materials are usually accessible by sintering processes from educts or educt mixtures which contain SiC particles.
  • educts or educt mixtures which contain SiC particles.
  • SiC particles are obtained relatively porous bodies, which are accordingly only suitable for a limited number of fields of application.
  • the properties of the porous SiC material produced using conventional sintering processes do not correspond to those of compact crystalline silicon carbide, so that the generally advantageous properties of silicon carbide cannot be fully exploited.
  • silicon carbide does not melt, but sublimes, at high temperatures - depending on the respective crystal type - in the range between 2,300 and 2,700 ° C. This means that silicon carbide changes directly from the solid to the gaseous state of aggregation. Silicon carbide is therefore not suitable or only suitable to a very limited extent as a starting material in high-energy processes for the efficient production of corresponding inorganically based structures or bodies.
  • silicon carbide-containing materials or bodies An efficient possibility of producing silicon carbide-containing materials or bodies consists in the use of suitable precursor compounds or materials which, under the action of energy, react to form silicon carbide or SiC-containing materials.
  • DE 10 2015 100 062 A1 describes a method for producing SiC-containing materials, in particular SiC crystals or fibers, which are obtained by deposition from the gas phase.
  • a precursor granulate is used as the starting material, which is obtained by a sol-gel process and then subjected to a thermal treatment at over 1,000 ° C.
  • DE 10 2015 105 085 A1 describes, for example, a method for producing bodies from SiC crystals, the silicon carbide being obtained in particular by laser irradiation of precursor materials formed from suitable carbon and silicon sources. Under the action of the laser beam, the precursor materials decompose selectively and silicon carbide is formed without sublimation processes occurring.
  • the reproducible representation of the precursor material according to DE 10 2015 105 085 A1 which is obtained via a sol-gel process, is lengthy and complex.
  • the aging of the compounds used from a sol to a gel is initially very time-consuming.
  • the product obtained from the sol-gel process by simple drying has varying compositions, since, inter alia, solvents and acids that are necessarily used partly remain in the dried product. These residues tend to side reactions, especially at higher drying temperatures and in the course of the thermal aftertreatment.
  • a reductive thermal treatment of the precursor material is therefore preferably carried out at high temperatures in order to bring about the conversion into a stable and reproducible precursor material form.
  • DE 102019 121 062.3 describes an optimized process that allows a defined, uniformly composed SiC precursor granulate to be obtained reproducibly by first homogenizing or dissolving the individual components or starting materials of the granulate composition in a preferably colloidal solution or dispersion. This is followed by the rapid removal of the solvent or dispersant, since it has been shown that aging of the colloidal solution to form a gel, as described in DE 102015 105085 A1, is not necessary.
  • the complex thermal treatment at temperatures of over 1,000 ° C. can be dispensed with, and in this way significant time and energy savings can be achieved. This also implies, as it were, a significant reduction in the costs for the production of an SiC precursor granulate.
  • DE 10 2017 110 362 A1 or WO 2018/206645 A1 relates to the production of objects containing SiC, in particular from silicon carbide alloys, based on powdery precursor materials by means of the so-called selective synthetic crystallization.
  • the selective synthetic crystallization relates in detail to high-energy processes for the production of silicon carbide and silicon carbide alloys, preferably by means of additive manufacturing.
  • Selective synthetic crystallization includes processes that are based on laser deposition welding, as described, for example, in DE 10 2018 128 434.9, selective laser melting, as described, for example, in DE 10 2017 110 362 A1 or WO 2018/206645 A1, or inkjet -Printing method, as known for example from DE 10 2017 110 361 A1 or WO 2018/206643 A1, are based and in which by a targeted energy input, in particular a location-selective energy input, a SiC precursor material successively containing object is generated.
  • the energy input into the material provided, in particular the SiC precursor material is carried out by a high-energy radiation source.
  • Lasers such as CO2 lasers, Nd: YAG lasers or fiber lasers are often used for this purpose. These radiation sources achieve the necessary power to induce a sufficiently high energy input into the precursor material so that the formation of silicon carbide can take place.
  • the laser variants mentioned are only radiation sources that can only be used individually. This is due to the fact that CO2 lasers, Nd: YAG lasers or fiber lasers cannot or only poorly be arranged in groups, since, for example, efficient heat dissipation during ongoing, combined and concerted operation of the lasers is hardly possible.
  • the prior art therefore still lacks efficient generative manufacturing processes, in particular for spatial structures that contain and / or consist of silicon carbide.
  • the present invention is therefore based on the object of eliminating the aforementioned disadvantages associated with the prior art, or at least reducing them.
  • one object of the present invention is to provide a method for producing SiC-containing structures which represents an improvement and increase in efficiency compared to the previous methods known from the prior art.
  • Another object of the present invention in this regard is to provide a manufacturing method for SiC-containing structures that allows shorter manufacturing times and can also be classified as energy-saving compared to known methods of the prior art and is therefore suitable for use in industrial productions, especially series productions.
  • the present invention according to a first aspect of the present invention is therefore a method for producing SiC-containing structures according to claim 1; further advantageous refinements of this aspect of the invention are the subject matter of the relevant subclaims.
  • a further subject matter of the present invention according to a second aspect of the present invention is a use of a radiation source, in particular a laser, for the production of SiC-containing structures according to claim 17.
  • the present invention again further provides an SiC-containing structure according to claim 18.
  • the present invention - according to a first aspect of the present invention - is a process for the production of SiC-containing structures, whereby a precursor material containing at least one silicon source and at least one carbon source is produced by a repeated and / or continuous input of energy by at least one radiation source. Source, is converted to a SiC-containing material.
  • the method according to the invention allows a significant increase in the method efficiency and, in particular, the production speed with which a structure containing SiC can be obtained.
  • radiation sources are used in the context of the present invention that can be grouped or combined so that a concerted time-specific and site-selective irradiation and conversion of a precursor material, preferably provided in the form of a material bed, to SiC-containing structures becomes possible.
  • a radiation source is understood to mean, in particular, an irradiation device which emits electromagnetic radiation, in particular laser radiation.
  • the radiation source or irradiation device can have, in addition to the means for generating the radiation, in particular the actual radiators, preferably lasers, further means and devices, such as deflection means for deflecting the electromagnetic radiation, in particular mirror arrangements, optical waveguides, lenses, etc., which have a focusing and allow local limitation of the effective range of the electromagnetic radiation.
  • the radiation source used preferably has a plurality or a plurality of individual radiators, which accordingly can individually irradiate a predefined area of a material bed over a predetermined period of time in coordination with one another, so that the entirety of all individual radiators in comparison to a single radiator in a significantly shorter time can cover all areas of the material bed to be irradiated.
  • the individual emitters, in particular laser diodes, which can be used to generate SiC-containing structures individually have much lower powers and are, as it were, arranged and grouped overall in such a way that in the course of the irradiation of the SiC precursor material, energy inputs and temperatures are generated in it, as they are prerequisites for the formation of silicon carbide.
  • the radiation sources used according to the invention are characterized in that they have a small focus, so that the energy input is locally limited, that is to say particularly selective. In this way, a particularly high printing precision can be achieved and, in particular, filigree spatial structures are still well resolved. The method according to the invention thus allows improved access even to small-part SiC-containing molded structures, and this within a shorter time than could be achieved with comparable methods of the prior art.
  • the method according to the invention is characterized by a high degree of flexibility with regard to usable precursor materials.
  • the manufacturing process for SiC-containing structures according to the present invention can be carried out both with solid and liquid precursor material mixtures, i.e. both SiC precursor powder and SiC precursor dispersions can be used without problems and efficiently converted and built up to form SiC-containing structures.
  • this aspect also impressively illustrates the pronounced user-friendliness of the method according to the invention.
  • Another advantage of the method according to the invention for manufacturing SiC-containing structures is the possibility of performing the method on devices, in particular print bed-based generative manufacturing devices, which are usually provided for processing plastics into spatial structures. This is possible because, in the context of the method according to the invention, it is also possible in particular to use such low-energy radiation sources as have hitherto only been used in the field of additive manufacturing of plastics.
  • the temperature in the precursor material can be increased to such an extent that decomposition can occur through repeated and / or continuous input of energy, in particular by irradiating the precursor material, preferably with a laser array of in particular low-energy individual radiators such as diode lasers of the precursor material as well as the recombination of the generated precursor material fragments to form crystalline SiC-containing material can be achieved reliably and efficiently despite an intrinsically low energy input.
  • diode lasers such as VCSEL diode lasers
  • VCSEL diode lasers are characterized, among other things, by their compact design, long service life and low power degradation.
  • the crystallinity and compactness of the SiC-containing material can be increased in a special way if the temperature at the irradiated areas also exceeds the decomposition of the precursor material, ie during the recombination and deposition of the SiC-containing material , remains increased, in particular by direct irradiation with low-energy radiation or by irradiating directly adjacent regions.
  • silicon carbide or an SiC-containing compound in particular an SiC-containing material
  • SiC-containing material is understood to mean a binary, ternary or quaternary inorganic compound whose empirical formula contains silicon and carbon.
  • an SiC-containing compound does not contain any molecularly bound carbon, such as in the case of carbon monoxide or carbon dioxide, for example, but rather the carbon in the SiC-containing compound is in the form of a solid structure.
  • an SiC-containing structure is understood to be a two- or three-dimensional structure.
  • the two-dimensional structures are characterized in that they extend almost exclusively in only two spatial directions, ie in one plane, while the extent in the third spatial direction is negligible compared to the extent in the other two spatial directions.
  • Such two-dimensional structures are particularly suitable for use in semiconductor technology and are often formed by doped silicon carbides.
  • three-dimensional semiconductor components made from solid silicon carbide, which are also accessible with the method according to the invention.
  • the three-dimensional structures are, in particular, three-dimensional objects or bodies which generally consist of SiC-containing material, in particular high-performance ceramics or silicon carbide alloys.
  • a precursor material is understood to mean a chemical compound or a mixture of chemical compounds which can react to one or more target compounds by chemical reaction and / or under the action of energy.
  • a silicon source and carbon source contained in a precursor material are understood to mean one or more chemical compounds that contain carbon and silicon, it being possible for the individual compounds to contain carbon and / or silicon.
  • Compounds which contain carbon and silicon are preferably suitable as corresponding silicon or carbon sources in precursor materials according to the invention for the target compound containing SiC to be produced.
  • the energy input is limited in terms of location and / or time, in particular is limited in terms of location and time. Especially Good results can be obtained within the scope of the present invention if the energy input takes place selectively in a time-specific manner.
  • a location-selective, time-specific energy input is understood to mean that energy is input into the precursor material at a specifically selected location, which is in particular spatially narrowly limited, at a specific, previously determined point in time over a specific, predetermined period of time .
  • the energy input into the material can take place parallel to one another by a plurality or plurality of radiation sources, so that a plurality or plurality of, in particular spatially narrowly limited, locations, for example in the form of pixels, are individually variable can be irradiated.
  • the energy input has an effective range of less than 750 pm, in particular of less than 500 pm, preferably of less than 300 pm, preferably of less than 150 pm.
  • the effective area which the energy input has is understood to mean the smallest area of the simultaneous action of radiation in the irradiated material. In the case of laser beams, this corresponds in particular to the cross-section or diameter of the laser beam when it strikes the material or to the smallest extent of the radiation on the material point that occurs when masks are used. The larger the area which is at least covered by the energy input, the lower the resolution of the energy input.
  • the energy input has an effective range of 0.1 to 750 pm, in particular 0.2 to 500 pm, preferably 0.5 to 300 pm, preferably 1 to 150 pm.
  • the energy input results in a temperature increase, in particular a locally and / or temporally limited temperature increase, preferably a local one and time-limited temperature rise.
  • a temperature increase in particular a locally and / or temporally limited temperature increase, preferably a local one and time-limited temperature rise.
  • Very particularly good results are observed within the scope of the present invention when the energy input causes a temperature increase that is limited in a location-selective manner and in a time-specific manner.
  • the energy input causes a temperature rise to temperatures in the range of more than 1,000 ° C, in particular more than 1,400 ° C, preferably more than 1,600 ° C.
  • the energy input causes a temperature rise to temperatures in the range from 1,300 to 2,200 ° C, in particular 1,700 to 2,000 ° C, preferably 1,700 to 1,900 ° C.
  • the radiation source used according to the invention can have a structure known per se to the person skilled in the art.
  • the radiation source is formed by a single radiation source, in particular a single-beam laser.
  • the single-beam laser can preferably be designed as a pulse laser, in particular as a short pulse laser, preferably as an ultra-short pulse laser.
  • the radiation source has a plurality of, in particular more than 20, preferably more than 50, preferably more than 100, individual radiators, in particular individual emitters, in particular is formed from them.
  • the radiation source is a laser, in particular a diode laser, preferably a grouping of several diode lasers, preferably a laser array, more preferably a VCSEL laser array.
  • a grouping of several diode lasers in the context of the present invention is such an arrangement of diode lasers understood, in which a plurality or plurality of individual diode lasers or laser diodes are electrically and / or optically, in particular electrically and optically, combined or connected.
  • Such groupings are often also referred to as bars or laser bars or laser bars and are provided on a strip-shaped chip having the diode laser.
  • the grouped diode lasers are usually operated electrically in parallel and mounted on a heat sink.
  • the radiation source is designed as a laser bar or laser bar.
  • the radiation source has a combination of at least one individual radiator with at least one optical waveguide, in particular fiber optic cable, and / or at least one lens.
  • the radiation source has a combination of a plurality of individual radiators with a plurality, in particular a bundle, of optical waveguides, in particular glass fiber cables, and / or a plurality of lenses. It is further preferred here if the radiation source has both optical waveguides, in particular glass fiber cables, and at least one lens.
  • the radiation source namely the means for generating the electromagnetic radiation, in particular the radiators
  • the means for generating the electromagnetic radiation ie in particular the single beam laser or also the grouping of individual emitters or in particular individual emitters, preferably diode lasers
  • the at least one optical waveguide, in particular glass fiber cable, or the plurality of optical waveguides, in particular glass fiber cables then makes it possible for laser beams to be guided to a movable exposure means that preferably has the at least one lens, or in particular a plurality of lenses.
  • the lens or lenses in turn allow the deflection or focusing of laser beams, so that the result is also according to this Embodiment of the present invention, the energy input takes place locally and / or temporally limited, in particular spatially and temporally limited, preferably limited in a location-selective manner in a time-specific manner.
  • An advantage of this alternative embodiment of the present invention is that it is possible to focus the laser beams, in particular pixel-by-pixel, without the radiation source, in particular the grouping of the individual emitters or, in particular, individual emitters, preferably diode lasers, having to be arranged in the form of these pixels , ie the distance between the individual radiators can be greater than the area of a pixel.
  • an optimized weight distribution of the radiation source can in particular also be achieved through this arrangement.
  • the radiation source in particular the individual radiators, have powers of less than 7 W, in particular less than 5 W, preferably less than 4 W, preferably less than 3 W.
  • the radiation source in particular the individual radiators, have powers of less than 7 W, in particular less than 5 W, preferably less than 4 W, preferably less than 3 W.
  • the radiation source in particular the individual radiators, emit radiation with an effective range of less than 500 ⁇ m, in particular less than 300 ⁇ m, preferably less than 200 ⁇ m, preferably less than 150 ⁇ m . It has also proven to be advantageous if the radiation source, in particular the individual radiators, radiation with an effective range of 0.1 to 500 ⁇ m, in particular 0.2 to 300 ⁇ m, preferably 0.3 to 200 ⁇ m, preferably 0.5 to 150 pm, emit.
  • the present invention ideally combines the preferred use of low-energy and, at the same time, particularly sharply focussing radiation sources, in particular in the form of groups of corresponding individual emitters, such as in laser arrays, for example.
  • a particularly high resolution can be achieved in the manufacture of a structure containing SiC.
  • a precursor material containing at least one silicon source and at least one carbon source is provided in the form of a layer, in particular a layer, and
  • (b) is converted into a SiC-containing material by repeated and / or continuous energy input by at least one radiation source, at least in some areas, with process steps (a) and (b) being repeated so often that a SiC-containing structure is obtained.
  • a distribution of this material in a certain thickness on a plane, in particular a cutting plane through the structure to be produced , Roger that.
  • the plane can be completely covered with the precursor material.
  • the plane is not completely covered with the material, but rather only certain areas of the plane.
  • the application of the precursor material as a layer, in particular a layer, in the form of the described planes, in particular sectional planes through the structure to be produced also ultimately defines the structure in such a way that the overall result is a layered structure of the SiC-containing structure.
  • an at least regional conversion of the precursor material into a SiC-containing material is understood within the scope of the invention to mean that the energy input required for this is limited in terms of location and / or time, in particular limited in terms of location and time, preferably time-specifically limited in terms of location, through which at least one radiation source occurs can.
  • a spatially and time-resolved energy input through the at least one radiation source is possible, so that only special, predetermined areas of the plane, in particular the cutting plane through the structure to be produced, in which the precursor material is provided as a layer, in particular a layer, are converted to the silicon carbide-containing structure.
  • the precursor material is provided as a layer, in particular a layer
  • the method according to the invention can in particular also be designed as a multi-material printing method, preferably in the form of an inkjet method.
  • a layer or layer of the precursor material can preferably also be provided in such a way that several different precursor materials are provided simultaneously in the form of a layer or layer, in particular by means of printing processes, preferably by means of inkjet processes.
  • the precursor material is selected from the group of solid-in-solid precursor material mixtures, solid-in-liquid precursor material mixtures, and liquid-in-liquid precursor material mixtures .
  • the precursor material is selected from the group of precursor powders, precursor dispersions, preferably from precursor granules or precursor sols.
  • Solid-in-solid precursor material mixtures, in particular a precursor powder, preferably a precursor granulate, in the context of the present invention is understood to mean a particulate mixture of precursor substances, in particular starting compounds, preferably precursors, which react to form the desired target compounds.
  • Solid-in-liquid precursor material mixtures or liquid-in-liquid precursor material mixtures is to be understood in the context of the present invention as a solution or dispersion of precursor substances, in particular starting compounds, preferably precursors, which react to the desired target compounds.
  • precursor material mixtures in particular precursor dispersions, preferably precursor sols
  • the chemical compounds or mixtures of chemical compounds are no longer necessarily in the form of the originally used chemical compounds, but for example as flydrolysates, condensates or other reaction or intermediate products.
  • sol inorganic materials are usually converted into reactive intermediates or agglomerates and particles, the so-called sol, by hydrolysis or solvolysis, which then age to form a gel, in particular through a condensation reaction, with larger particles and agglomerates in the Solution or dispersion arise.
  • sol By choosing a suitable concentration or adding or dispensing with reactor accelerators and catalysts, the physical properties of the sol or gel, in particular also particle sizes, can be adjusted in such a way that it can be processed in conventional printing processes.
  • a precursor sol can therefore also be understood to mean gels in the context of the present invention.
  • a solution is to be understood as meaning a usually liquid single-phase system in which at least one substance, in particular a compound or its building blocks, such as ions, is homogeneously distributed in a further substance, the so-called solvent.
  • a dispersion is to be understood as an at least two-phase system, a first phase, namely the dispersed phase, being present in a distributed manner in a second phase, the continuous phase.
  • the continuous phase is also referred to as the dispersion medium or dispersant.
  • the continuous phase is usually in the form of a liquid, so that dispersions in the context of the present invention are therefore generally solid-in-liquid or liquid-in-liquid dispersions.
  • SiC-containing materials or different silicon carbide namely stoichiometric, non-stoichiometric, doped or alloyed silicon carbide or SiC-containing material.
  • a stoichiometric silicon carbide or SiC-containing material is to be understood as a material which contains carbon and silicon at least essentially in the molar silicon-to-carbon ratio in a range around 1: 1.
  • a non-stoichiometric silicon carbide is to be understood as meaning a silicon carbide which does not contain carbon and silicon in a molar ratio of 1: 1.
  • a non-stoichiometric silicon carbide usually has a molar excess of silicon.
  • doped silicon carbide is generally to be understood as meaning a silicon carbide which, in addition to silicon and carbon, has further, in particular intercalating, doping elements.
  • Alloyed silicon carbide in the context of the present invention is generally to be understood as meaning a silicon carbide which, in addition to silicon and carbon, has one or more alloying elements.
  • the composition of the precursor material can therefore vary within wide ranges.
  • the precursor material has an at least essentially stoichiometric silicon-to-carbon ratio, in particular a silicon-to-carbon quantity ratio in the range of 35:65 wt % to 65:35% by weight, preferably 40:60% by weight to 60:40% by weight, preferably 45:55% by weight to 55:45% by weight, particularly preferably 50:50 % By weight, based on the precursor material.
  • the non-stoichiometric silicon carbide is usually a silicon carbide of the general formula (I)
  • SiC-i- x (I) with x 0.05 to 0.8, in particular 0.07 to 0.5, preferably 0.09 to 0.4, preferred
  • the correspondingly obtainable silicon-rich silicon carbides have a particularly high mechanical strength and are suitable for a large number of applications as ceramics.
  • the precursor material usually contains it
  • the carbon source in amounts of 10 to 40% by weight, in particular 15 to 35% by weight, preferably 20 to 30% by weight, in each case based on the precursor material.
  • precursor materials which are intended to be used to produce non-stoichiometric silicon carbide or SiC-containing material thus generally have a comparatively higher proportion of the silicon source than the carbon source.
  • the precursor material has a silicon-to-carbon ratio in the range from 65:35% by weight to 85:15% by weight, preferably 70:30% by weight to 80:20% by weight %, preferably 72:28% by weight to 78:22% by weight, based on the precursor material.
  • the silicon carbide alloy is usually selected from MAX phases, alloys of silicon carbide with elements, in particular metals, and alloys of silicon carbide with metal carbides and / or metal nitrides.
  • Such silicon carbide alloys contain silicon carbide in varying and strongly fluctuating proportions.
  • silicon carbide is the main component of the alloys.
  • the silicon carbide alloy contains silicon carbide only in small amounts.
  • the silicon carbide alloy usually contains the silicon carbide, in particular the elements silicon and carbon, in amounts of 10 to 95% by weight, in particular 15 to 90% by weight, preferably 20 to 80% by weight, based on the silicon carbide alloy.
  • M stands for an early transition metal from the third to sixth group of the Periodic Table of the Elements, while A stands for an element of the 13th to the 16th group of the Periodic Table of the Elements.
  • X is either carbon or nitrogen.
  • MAX phases are of interest whose empirical formula contains silicon carbide (SiC), ie silicon and carbon.
  • MAX phases have unusual combinations of chemical, physical, electrical and mechanical properties, as they show both metallic and ceramic behavior depending on the conditions. This includes, for example, high electrical and thermal conductivity, high resistance to thermal shock, very high levels of hardness and low coefficients of thermal expansion.
  • the silicon carbide alloy is a MAX phase
  • the MAX phase is selected from TUSiC3 and T SiC.
  • the SiC-containing compound is an alloy of silicon carbide
  • the alloy is an alloy of silicon carbide with metals
  • the alloy is selected from alloys of silicon carbide with metals from the group of Al, Ti, V, Cr, Mn, Co, Ni, Zn, Zr and their mixtures.
  • the alloy of silicon carbide is selected from alloys of silicon carbide with metal carbides and / or nitrides, it has proven useful if the alloys of silicon carbide with metal carbides and / or nitrides is selected from the group of boron carbides, in particular B4C, chromium carbides, in particular Cr2C3 , Titanium carbides, in particular TiC, molybdenum carbides, in particular M02C, niobium carbides, in particular NbC, tantalum carbides, in particular TaC, vanadium carbides, in particular VC, zirconium carbides, in particular ZrC, tungsten carbides, in particular WC, boron nitride, in particular BN, and mixtures thereof.
  • boron carbides in particular B4C
  • chromium carbides in particular Cr2C3
  • Titanium carbides in particular TiC
  • molybdenum carbides in particular M02C
  • niobium carbides in particular Nb
  • the precursor material is to be used to produce a silicon carbide alloy, then the precursor material usually contains
  • the precursor material is to be used to produce doped silicon carbide, provision can be made for a doping reagent to be added to the precursor material.
  • the doping reagent is used in amounts of 0.000001 to 15% by weight, in particular 0.000001 to 10% by weight, preferably 0.000005 to 5% by weight. -%, preferably 0.00001 to 1% by weight, based on the mixture, is added.
  • the doping reagent can be selected from common suitable doping elements.
  • the doping reagent or the doping element is preferably selected from elements of the third and fifth main groups of the periodic table.
  • the doping reagent is suitable for n- or p-doping, in particular is selected from the group of the elements nitrogen, phosphorus, boron, aluminum and indium, and mixtures thereof.
  • the solution can contain nitric acid, ammonium chloride or melanin. If doping with phosphorus is provided, for example phosphoric acid or phosphates or phosphonic acids can be used. In addition, nitrogen doping is also possible by performing the method according to the invention in a nitrogen atmosphere.
  • doping with boron for example boric acids, borates or boron salts, such as boron trichloride, are used.
  • indium is doped
  • water-soluble indium salts such as indium chloride, are usually used as the doping reagent.
  • the silicon carbide produced with the method according to the invention in particular the SiC-containing material, can therefore, as stated, be selected within the scope of the present invention from stoichiometric silicon carbide, doped stoichiometric silicon carbide, non-stoichiometric silicon carbide, doped non-stoichiometric silicon carbide and silicon carbide alloys.
  • SiC-containing materials in particular different silicon carbide compounds, is thus accessible to the method according to the invention.
  • DE 102017 110362 A1 or WO 2018/206645 A1 discloses a solid precursor material, in particular a precursor granulate, which is preferably obtained by a sol-gel process with subsequent reductive thermal treatment and which is excellent for producing a wide variety of SiC-containing materials in Powder bed process is suitable.
  • DE 10 2018 127 877.2 describes an optimized manufacturing process for a solid precursor material which allows a defined, uniformly composed SiC precursor granulate to be obtained in a reproducible manner.
  • the granules can be used both in processes that are carried out as solid processes, in particular powder bed processes, and in the form of solid-in-liquid dispersions.
  • DE 102017 110 361 A1 and WO 2018/206643 A1 describe the production of precursor materials in the form of solutions or dispersions, in particular precursor sols, which are suitable for use in printing processes, in particular inkjet printing processes.
  • the precursor material for producing the SiC-containing materials is present as a precursor powder, in particular as a granular precursor powder, or as a precursor dispersion, in particular as a solid-in-liquid precursor dispersion.
  • the precursor powder or the precursor dispersion consists of homogeneous particles, in particular microparticles, preferably nanoparticles, or contains them, preferably consists of them.
  • the precursor powder or the precursor dispersion is composed of composite particles, in particular homogeneous composite particles, preferably composite particles with a core-shell structure (core-shell structure), consists or contains this, preferably consists thereof.
  • composite particles with a core-shell structure are generally understood to mean particles which have an inner core and an outer shell.
  • the inner core can be formed, for example, by the silicon sources, in particular elemental silicon, so that the outer shell is formed by the carbon source, in particular, for example, at least one organic carbon compound.
  • the precursor material is a solid-in-solid precursor material mixture, in particular a precursor powder, preferably a precursor granulate.
  • a precursor powder preferably a precursor granulate.
  • precursors or precursor mixtures are particularly suitable for use in powder bed processes.
  • the precursor material is a precursor material mixture having a crystalline component, in particular a precursor powder having a crystalline component.
  • a particularly suitable precursor powder of this type is disclosed in DE 10 2019 121 062.3.
  • the precursor material having a crystalline constituent is present as, in particular granular, precursor powder
  • the precursor material is composed of homogeneous particles, in particular microparticles, preferably nanoparticles, and these particles are preferably granules.
  • precursor materials composed in this way are distinguished by an overall high degree of homogeneity.
  • this circumstance allows particularly good conversions as well as the formation of silicon carbide of particularly uniform composition in relation to the quantitative ratio between carbon and silicon.
  • the precursor material has particle sizes in the range from 0.1 ⁇ m to 1,500 ⁇ m, in particular 0.1 ⁇ m to 1,000 ⁇ m, preferably 0.5 ⁇ m to 800 ⁇ m, preferably 1 ⁇ m to 600 pm.
  • the solid-in-solid precursor material mixtures in particular the precursor powder, have particle sizes in the range from 0.1 to 1,000 ⁇ m, in particular 0.5 to 500 ⁇ m, preferably 1 to 200 ⁇ m, preferably 10 to 100 pm, particularly preferably 40 to 80 pm, in particular if the process according to the invention is carried out as a solid process, in particular a powder bed process.
  • the position of the precursor material for solid-in-solid precursor material mixtures, in particular precursor powder preferably has a layer thickness in the range from 1 to 1,000 ⁇ m, in particular 2 to 500 ⁇ m, preferably 5 to 250 ⁇ m 10 to 180 ⁇ m, particularly preferably 20 to 150 ⁇ m, very particularly preferably 20 to 100 ⁇ m when the process according to the invention is carried out as a solid process.
  • a solid-in-liquid precursor material mixture or liquid-in-liquid precursor material mixture in particular a precursor dispersion, preferably a precursor sol, is used.
  • the solvent or dispersant in the precursor material mixture according to the invention in particular precursor dispersion or precursor sol, as far as is concerned, this can be selected from any suitable solvent or dispersant.
  • the solvent or dispersant is selected from water and organic solvents and mixtures thereof.
  • the starting compounds which are usually hydrolyzable or solvolyzable are converted to inorganic hydroxides, in particular metal hydroxides and silicas, which then condense, so that solid-in-liquid or liquid-in Liquid precursor material mixtures, in particular precursor dispersions or precursor sols, from which SiC-containing compounds can be produced, are present.
  • elemental silicon can also be used in a dispersant or composite particles containing a carbon source, in particular sucrose or invert sugar syrup, which have a carbon and a silicon source and are present in a suitable solvent or dispersant.
  • the starting compounds used should also have sufficiently high solubilities in the solvents used, in particular in ethanol and / or water, in order to be able to form finely divided dispersions or solutions, in particular sols, and must not be mixed with other components of the solution or the during the production process Dispersion, especially the sol, react to form insoluble compounds.
  • the reaction speed of the individual reactions taking place must be coordinated with one another, since the hydrolysis, condensation and in particular the gelation should take place undisturbed if possible in order to obtain the most homogeneous possible distribution of the individual components in the sol or gel.
  • the reaction products formed must not be sensitive to oxidation and, moreover, should not be volatile.
  • the organic solvent is selected from alcohols, in particular methanol, ethanol, 2-propanol, acetone, ethyl acetate and mixtures thereof. It is particularly preferred in this context if the organic solvent is selected from methanol, ethanol, 2-propanol and mixtures thereof, with ethanol being particularly preferred.
  • the above-mentioned organic solvents are miscible with water over a wide range and in particular are also suitable for dispersing or dissolving polar inorganic substances, such as, for example, metal salts.
  • mixtures of water and at least one organic solvent are preferably used as solvents or dispersants in the context of the present invention.
  • the solvent or dispersant has a weight ratio of water to organic solvent of 1:10 to 20: 1, in particular 1: 5 to 15: 1, preferably 1: 2 to 10: 1, preferably 1 : 1 to 5: 1, particularly preferably 1: 3.
  • the rate of hydrolysis and, on the other hand, the solubility and reaction rate of both the silicon source and the carbon source can be adjusted.
  • the amount in which the precursor mixture contains the solvent or dispersant can vary within a wide range depending on the particular application conditions and the type of SiC-containing compound to be produced - as already stated above.
  • the solid-in-liquid or liquid-in-liquid precursor material mixture, in particular the precursor dispersion, the solvent or dispersant in amounts of 10 to 80% by weight, in particular 15 to 75% by weight, preferably 20 to 70% by weight, preferably 20 to 65% by weight, based on the composition.
  • precursor material mixtures in particular precursor dispersions or precursor sols
  • precursor dispersions or precursor sols can also be used.
  • different precursor materials can be used in areas in a layer or layer of the precursor material.
  • SiC-containing structures can be obtained, the mechanical and electrical properties of which can be set in a targeted manner in certain areas or locally.
  • mechanically particularly stressed zones of ceramic components can thus be specifically reinforced or, for example, conductor tracks can be produced in a component.
  • Suitable printing processes are based, for example, on the simultaneous print application of different precursor materials, in particular by different nozzles of a print head in the inkjet process, or on the immediately successive printing of different precursor materials by means of one or more print heads, the simultaneous print job being preferred.
  • Such printing methods are familiar to the person skilled in the art and are described in particular in DE 10 2017 110 361 A1 and WO 2018/206643 A1.
  • the process according to the invention is carried out as a liquid printing process, it has proven to be advantageous in the context of this preferred embodiment of the present invention if the solid-in-liquid precursor material mixture or the liquid-in-liquid precursor material mixture, in particular the precursor dispersion , has a dynamic Brookfield viscosity at 25 ° C. in the range from 3 to 500 mPas, in particular from 4 to 200 mPas, preferably from 5 to 100 mPas.
  • highly viscous precursor material mixtures, in particular precursor dispersions which are, however, also suitable for spray or print application, are used, since in this way even protruding structures are accessible to a certain extent without support structures.
  • the layer of the precursor material for solid-in-liquid precursor material mixtures or liquid-in-liquid precursor material mixtures, in particular precursor dispersions has a layer thickness in the range from 0.1 to 250 ⁇ m, in particular 0.2 to 100 ⁇ m, preferably 0.5 to 50 ⁇ m, preferably 1 to 25 ⁇ m, when the method according to the invention is carried out as a liquid printing method.
  • the type of silicon source can generally be selected from a large number of materials or chemical compounds.
  • the silicon source is selected from the group of silanes, silane hydrolysates, silicates, silica sols, orthosilicic acids, water glasses, elemental silicon, and their mixtures, in particular silanes, silane hydrolysates, elemental silicon , and their mixtures.
  • Orthosilicic acid and its condensation products can be obtained, for example, from alkali metal silicates, the alkali metal ions of which have been exchanged for protons by ion exchange.
  • alkali metal compounds are not included in the precursor material used because they are also embedded in the SiC-containing compound. Accordingly, alkali metal doping is generally not desired in the context of the present invention. However, if this should be desired, suitable alkali metal salts, for example those of the silicon source or else alkali metal phosphates, can be used.
  • silane is used as the silicon source, it has proven useful if the silane is selected from silanes of the general formula II
  • R alkyl, in particular Cr to Cs-alkyl, preferably Cr to C 3 -alkyl, preferably Cr and / or C 2 -alkyl;
  • Aryl in particular Ce to C 2 o aryl, preferably Ce to C is aryl, preferably C 6 to Cio aryl;
  • Olefin in particular terminal olefin, preferably C 2 to Cio olefin, preferably C 2 to Cs olefin, particularly preferably C 2 to Cs olefin, very particularly preferably C 2 and / or C 3 olefin, particularly preferred Vinyl;
  • Amine in particular C 2 - to Cio-amine, preferably C 2 - to Cs-amine, preferably C 2 - to Cs-amine, particularly preferably C 2 - and / or C 3 -amine;
  • Carboxylic acid in particular C 2 to Cio carboxylic acid, preferably C 2 to C 8 carboxylic acid, preferably C 2 to C 5 carboxylic acid, particularly preferably C 2 and / or C 3 carboxylic acid;
  • Alcohol in particular C 2 to Cio alcohol, preferably C 2 to Cs alcohol, preferably C 2 to Cs alcohol, particularly preferably C 2 and / or C 3 alcohol;
  • X flalogenide, in particular chloride and / or bromide
  • silane is selected from silanes of the general formula Ila
  • R 4 -nSlXn (lla) with R Cr to C3-alkyl, in particular Cr and / or C2-alkyl;
  • condensed orthosilicic acids or siloxanes can also be obtained in a simple manner, which have only very small particle sizes, and further elements, in particular metal hydroxides, can also be incorporated into the basic structure.
  • the silicon source is selected from tetraalkoxysilanes, trialkoxysilanes and mixtures thereof, preferably tetraethoxysilane, tetramethoxysilane or triethoxymethylsilane and mixtures thereof.
  • elemental silicon is used as the silicon source, it has proven useful in this case if the elemental silicon is used in the form of a powder, in particular in the form of a microscale powder, preferably in the form of a nanoscale powder.
  • the elemental silicon is used in the form of particles, in particular in the form of microparticles, preferably in the form of nanoparticles.
  • the elemental silicon is used in the form of monocrystalline particles, in particular in the form of monocrystalline microparticles, preferably in the form of monocrystalline nanoparticles.
  • the elemental silicon is obtained from reusable raw material sources and / or comes from excess material residues from silicon processing.
  • elemental silicon with a degree of purity of at least 95%, in particular at least 98%, preferably at least 99%, preferably at least 99.5%, is used. This makes it possible on the one hand to obtain highly pure and defined silicon carbide ceramics, on the other hand it is also possible to produce silicon carbides with specific and preselected electrical properties.
  • the silicon source it is also generally possible with regard to the carbon source that it can be selected from a large number of materials or compounds, in particular depending on the precursor material and the desired silicon carbide or SiC-containing material.
  • the carbon source is selected from the group of carbohydrates, in particular glucose, fructose, invert sugar, sucrose, maltose, lactose, amylose, amylopectin, starch, starch derivatives, or from the group of organic polymers, in particular phenol-formaldehyde resin and resorcinol-formaldehyde resin, and mixtures thereof.
  • the carbon source is selected from the group of sugars, in particular sucrose, glucose, fructose, invert sugar, maltose, starch, starch derivatives, organic polymers, in particular phenol-formaldehyde resin and resorcinol-formaldehyde resin , and their mixtures.
  • the carbon source is selected from the group of sugars, starch, starch derivatives and mixtures thereof, preferably sugars, since the use of sugars and starch or starch derivatives in particular increases the viscosity of the Composition on the one hand, as well as the stickiness of the On the other hand, the composition can be adjusted in a targeted manner, which is particularly advantageous when using precursor sols and liquid precursor dispersions.
  • the carbon source in particular selected from sugars or starch, is dissolved or predispersed in a small amount of solvent or dispersant, whereupon this solution or dispersion is processed further into the actual precursor material.
  • the carbon source is used in a solution or dispersion which contains the carbon source in amounts of 10 to 90% by weight, in particular 30 to 85% by weight, preferably 50 to 80% % By weight, in particular 60 to 70% by weight, based on the solution or dispersion of the carbon source.
  • this dissolving and dispersing process after the carbon and silicon sources have been combined, can be followed by a drying step to form the actual precursor material, in which the solvent or dispersant is again removed.
  • the silicon source is elemental silicon
  • the carbon source is an organic carbon compound of the type described below.
  • an organic carbon compound is understood to mean a compound which is composed predominantly of the elements carbon, hydrogen and oxygen.
  • other heteroatoms such as nitrogen, sulfur or phosphorus can also be contained in the organic carbon compound, these heteroatoms only being desirable if doping of the silicon carbide is to be achieved.
  • the carbon compound in the context of this embodiment of the present invention it is preferably provided that the carbon compound is used in liquid form.
  • the organic carbon compound if it is present as a solid, is first brought into solution and only then is used for the production of the corresponding precursor material.
  • the organic carbon compound is already in the form of a liquid or at least essentially in liquid form, it is used as such directly for the manufacturing process.
  • the organic carbon compound can in particular be present in a liquid or in the form of a liquid solution or dispersion which contain the organic carbon compound, as explained below.
  • the organic carbon compound in liquid form is preferably suitable for forming a homogeneous dispersion with the elemental silicon, in particular in the form of a nano- or microscale powder.
  • the organic carbon compound is a polymer or an oligomer or monomer.
  • a monomer is generally understood to mean a low molecular weight, reactive molecular unit which can be converted in polyreactions to form higher molecular weight compounds such as oligomers or polymers.
  • structurally identical or structurally similar, at least similarly reactive, monomers are linked to one another via reactive groups such as multiple bonds or functional groups and thus form the basic units of an oligomer or polymer.
  • Exemplary polyreactions can be polycondensations, polyadditions and radical or coordinative polymerizations, without wishing to limit the type of possible polyreactions by this list.
  • an oligomer is understood to mean a molecule that results from monomers reacted with one another in a polyreaction.
  • an oligomer is composed of at least two monomer units. These monomer units can be the same or different, so that homooligomers or heterooligomers are obtained.
  • oligomers have a definable number of repeating units, in particular between two and 50 repeating units.
  • polymers are understood to mean macromolecular compounds which are built up in a polyreaction from one or more different monomers.
  • polymer therefore includes both homopolymers and heteropolymers; Homopolymers are obtained by reacting the same monomers and heteropolymers are obtained by reacting different monomers. Furthermore, polymers can have a relatively broad distribution of the monomeric repeat units. Overall, for the purposes of the invention, polymers are characterized by a number of monomer units that is difficult to define and have high average molecular weights.
  • the organic carbon compound in this alternative, preferred embodiment is a polymer or oligomer
  • the organic carbon compound is preferably characterized in that the polymer or oligomer is selected from the group of polyethers, polyethylene glycols, polysaccharides, polyketones, polyether ketones , Polyesters, polycarbonates, polyhydroxyalkanoates and mixtures thereof, in particular polyethers, polysaccharides, polyesters, polycarbonates and mixtures thereof, is preferably a polysaccharide.
  • the organic carbon compound is a monomer
  • the monomer is a monomer for producing the aforementioned polymers or oligomers, in particular selected from the group of ethers, saccharides, esters, carbonates, carboxylic acids and mixtures thereof, preferably a saccharide is.
  • the organic carbon compound in particular the polymer or oligomer, has ether, carbonyl, acetal, ester and / or carbonate repeat units.
  • Organic carbon compounds of the aforementioned nature and composition show in the context of this embodiment of the present invention an advantageous mixing behavior with the elemental silicon in the course of the production of the precursor material as well as excellent properties in the production of silicon carbide from the precursor material, since they contain in particular carbon, hydrogen and oxygen and thus possibly forming by-products which are preferably highly volatile and do not reduce the quality of the silicon carbide produced.
  • the organic carbon compound in particular the polymer or oligomer or monomer, is linear and / or branched and / or cyclic. Branched or cyclic monomers can occur in particular when using sugars or other substances that can react to form oligomers or polymers.
  • the organic carbon compound in particular the polymer or oligomer or monomer, has functional groups, in particular hydroxyl groups, in addition to the repeating units.
  • the organic carbon compound is present as a heterogeneous mixture, in particular as a heterogeneous mixture of monomers and monomer condensate, preferably as a heterogeneous mixture of monomer and dimeric, oligomeric or polymeric monomer condensate.
  • the organic carbon compound in particular the polymer or oligomer or monomer, is a polyalcohol.
  • the polyalcohol is a saccharide.
  • the saccharide is selected from the group of hexoses or pentoses or mixtures thereof.
  • saccharides as a special form of the organic carbon compound according to this particular embodiment of the present invention is particularly advantageous in that saccharides have a particularly balanced ratio between carbon, hydrogen and oxygen and thus in the context of this embodiment of the production process according to the invention of silicon carbide show ideal reaction behavior. Above all, it should be emphasized here that saccharides are particularly pure in the formation Silicon carbides make it possible since, apart from carbon, only volatile by-products are released, in particular water.
  • the saccharide is selected from the group of glucose and its stereoisomers, fructose and its stereoisomers, xylose and its stereoisomers, the disaccharides of the aforementioned compounds, in particular glucose and / or fructose, preferably glucose and fructose, the oligosaccharides of the aforementioned compounds, in particular glucose and / or fructose, the polysaccharides of the aforementioned compounds, in particular glucose, or mixtures thereof.
  • the saccharide is in the form of a liquid, in particular in the form of a syrup, preferably in the form of a highly concentrated syrup.
  • a highly concentrated syrup is understood to mean an aqueous solution of the saccharide with a water content of less than 25% by weight, based on the total amount of the syrup.
  • Aqueous saccharide solutions with a water content equal to or greater than 25% by weight are regarded as syrup.
  • saccharide is invert sugar syrup.
  • Invert sugar syrup in the context of the invention means an aqueous solution of sucrose or starch which has been partially inverted by flydrolysis.
  • the invert sugar syrup can usually contain varying proportions of the glucose and fructose obtained by partial flydrolysis. These proportions are preferably between 5 to 95% for glucose and accordingly between 95 to 5% for fructose, based on the total amount of monosaccharides in the invert sugar syrup.
  • elemental silicon can be mixed so well with invert sugar syrup that a particularly homogeneous distribution of elemental silicon in powder or particle form can be achieved. This creates the ideal conditions for deployment a uniformly composed and reproducible and controllable high-quality precursor material, from which silicon carbide can subsequently be produced efficiently and reliably by the method according to the invention.
  • elemental silicon is mixed with at least one organic carbon compound, in particular the mixture of elemental silicon and organic carbon compound being in the form of a, preferably homogeneously distributed, dispersion.
  • the dispersion of elemental silicon and organic carbon compound is converted into a powder, in particular a precursor powder, by drying, in particular afterwards.
  • the dispersion is converted into a powder, in particular a precursor powder, with the supply of heat and / or reduction in pressure, in particular with supply of heat and reduction in pressure and stirring.
  • the precursor material in the course of the production of the precursor material, it has proven to be advantageous that it is converted into a powder, in particular a microscale powder, preferably a nanoscale powder, by comminuting, in particular crushing, preferably grinding, preferably grinding.
  • the reaction of the precursor material is carried out under a protective gas atmosphere, in particular a nitrogen and / or argon atmosphere, preferably an argon atmosphere, as already indicated above.
  • a protective gas atmosphere in particular a nitrogen and / or argon atmosphere, preferably an argon atmosphere, as already indicated above.
  • a protective gas is understood to mean a gas which effectively prevents the oxidation of the constituents of the carbon and silicon source by, in particular, atmospheric oxygen.
  • the manufacturing method is a generative manufacturing method, in particular a printing bed-based generative manufacturing method.
  • powdered SiC precursor materials can be converted to silicon carbide-containing materials, in particular non-stoichiometric silicon-rich silicon carbides and silicon carbide alloys, including a device based on selective laser sintering (SLS) or selective laser melting (selective laser melting, SLM) is used.
  • SLS selective laser sintering
  • SLM selective laser melting
  • the method according to the invention based on selective synthetic crystallization can also be based on 3D printing techniques, in particular in inkjet processes, in combination with the targeted input of energy into the material in analogy to DE 10 2017 110 361 A1 or WO 2018/206643 A1.
  • the process is an inkjet printing process, i.e. H. the precursor material mixture, in particular the precursor solution or dispersion, is applied to the substrate by means of inkjet printing.
  • inkjet printing processes allows, in particular, a high-resolution and locally sharply delimited application of the precursor material while at the same time using little material, so that even filigree structures are accessible for semiconductor applications.
  • drop-on-demand processes or printers are used, only the drops of liquid being generated which are actually actually applied to the substrate.
  • FIG. 1 schematically shows a perspective illustration of a device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-on-solid precursor material mixture, preferably a precursor powder, in the initial state;
  • FIG. 2 schematically shows a cross-sectional representation of a device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, in the initial state;
  • FIG. 3 schematically shows a cross-sectional representation of a device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, in the working state;
  • FIG. 4 schematically shows a further cross-sectional representation of a device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-on-solid precursor material mixture, preferably a precursor powder, in the working state;
  • Fig. 5 schematically yet another cross-sectional representation of a device for performing the method according to the invention for Production of a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, in the working state;
  • FIG. 6 shows a schematic representation of a device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, in plan view;
  • FIG. 7 schematically shows a perspective illustration of an alternative device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion, in the initial state;
  • FIG. 8 schematically shows a cross-sectional illustration of an alternative device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably one
  • FIG. 9 schematically shows a cross-sectional illustration of an alternative device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably one
  • FIG. 10 schematically shows a further cross-sectional illustration of an alternative device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion, in the working state ;
  • FIG. 11 schematically shows yet another cross-sectional illustration of an alternative device for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion, in the working state;
  • FIG. 12 schematically shows an illustration of an alternative device for carrying out the method according to the invention for producing a SiC containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion, in plan view.
  • Another object of the present invention - according to a second aspect of the present invention - is a use of a radiation source, in particular a laser, preferably a diode laser, preferably a grouping of several diode lasers, more preferably a laser array, very particularly preferably a VCSEL laser array, for setting up SiC-containing structures, in particular by the method described above.
  • a radiation source in particular a laser, preferably a diode laser, preferably a grouping of several diode lasers, more preferably a laser array, very particularly preferably a VCSEL laser array, for setting up SiC-containing structures, in particular by the method described above.
  • a radiation source in particular a laser, which is preferably formed from a grouping or combination of individual radiation sources, in particular individual emitters
  • the speed at which an SiC-containing structure can be manufactured can be significantly increased . It is a central advantage of the radiation source used according to the invention that the individual radiation sources can be controlled individually and at the same time coordinated with one another in concert.
  • the present method overcomes a significant disadvantage of common laser-based methods, in which high-energy individual lasers are usually used that can only scan a predetermined area linearly over time.
  • the production speed for these processes is therefore severely limited, so that the production processes are altogether too lengthy to be of interest for industrial application.
  • a radiation source which is preferably designed as a grouping of several diode lasers, ie preferably as a laser array, very particularly preferably as a VCSEL laser array, allows those individual areas which are to define the SiC-containing structure in their entirety, simultaneously can be selectively irradiated side by side at specifically defined times for a specific duration.
  • the SiC precursor material can be converted into SiC-containing material in a much shorter time overall within the previously defined areas.
  • an SiC precursor material layer or layer which - computationally, ie already during CAD modeling - is divided into a large number of pixel-like individual areas is broken down, can now be converted to the SiC-containing material in a location-selective manner and in accordance with a specific time setting in several of these pixel-like individual areas simultaneously. This is not possible with the previously known methods for generative SiC production.
  • Another object of the present invention - according to a third aspect of the present invention - is an SiC-containing structure obtainable by the process described above.
  • the silicon carbide-containing structure can be a two-dimensional structure, for example a conductor track, or also a three-dimensional structure, ie. H. a three-dimensional object or body.
  • FIG. 1 shows a perspective representation of a generative manufacturing device 1 for carrying out the method according to the invention for producing SiC-containing structures, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, in the initial state, ie before the start of the inventive method Manufacturing process.
  • a solid-in-solid precursor material mixture preferably a precursor powder
  • the generative manufacturing device 1 for performing the method according to the invention is therefore preferably based on devices for performing it of powder bed processes, in particular on devices for performing selective laser sintering (SLS).
  • SLS selective laser sintering
  • the generative manufacturing device 1 for carrying out the method according to the invention preferably has a printing bed 2 for providing the precursor material, a solid-in-solid precursor material mixture, in particular a precursor powder, preferably a precursor granulate, preferably being used for the particular embodiment of the present invention in this regard.
  • the printing bed 2 is preferably designed, in particular, to be at least essentially flat and / or planar and preferably has a construction platform 3 and a printing area 4.
  • the printing area 4 serves in particular as an area in which the method according to the invention for the production of SiC-containing structures can be carried out and preferably comprises a smaller area than the building platform 3 and is also preferably arranged centered on the building platform 3.
  • the building platform 3 is preferably movable, in particular lowerable, in the vertical direction and, according to a further preferred embodiment of the generative manufacturing device 1, has a boundary 5 on its surface edges, in particular the boundary 5 framing the building platform 3.
  • the delimitation 5 is preferably designed in such a way that in the initial state it is flush with the surface of the building platform 3, in particular flush.
  • the manufacturing device 1 preferably has an application device 6 for the, in particular powdery, precursor material 7 onto the printing bed 2.
  • the application device 6 for equalizing the precursor material 7 is at least essentially cylindrical, in particular at least essentially cylindrical, preferably in the form of an applicator roller 6a.
  • the application device 6 is designed in the form of a doctor blade, in particular having a rubber lip.
  • the application device 6 can be moved in the horizontal direction over the printing bed 2.
  • the application device 6 is arranged in such a way that it can apply the precursor material 7 in layers 7a, in particular layers, of the precursor material.
  • the layers 7a, in particular layers have a layer thickness in the range from 1 to 1,000 pm, in particular 2 to 500 pm, preferably 5 to 250 pm, preferably 10 to 180 pm, particularly preferably 20 to 150 pm, very particularly preferably 20 to 100 pm.
  • the application device 6 is preferably arranged directly above, in particular above and at least essentially flush with the delimitation 5 of the print bed 2.
  • the construction platform 3 can be lowered, preferably - in correlation with the method according to the invention - by an amount that corresponds to the thicknesses of the layers 7a, in particular layers of the precursor material 7, in particular the precursor powder, preferably the precursor granulate , corresponds.
  • the delimitation 5 of the generative manufacturing device 1 then protrudes beyond the construction platform 3 by the amount of the thickness of the layer 7a, in particular the layer.
  • the generative manufacturing device 1 according to the present preferred embodiment furthermore has a radiation source 8 - also called irradiation device 8 - which is arranged above the printing bed 2.
  • the radiation source 8 can be designed in such a way that it has a plurality of individual radiators 10.
  • the radiation source 8 can have more than 20, preferably more than 50, preferably more than 100 individual radiators 10, in particular individual emitters.
  • the radiation source 8 is a laser, in particular a diode laser, preferably a grouping of several diode lasers, preferably a laser array, more preferably a VCSEL laser array.
  • the radiation source 8 is thus arranged in the form of a grouping of several individual radiators 10, in particular diode lasers, the individual radiators 10, in particular the individual diode lasers or laser diodes, being combined or - electrically and / or optically, in particular electrically and optically. are switched.
  • This advantageously allows in particular coordinated or concerted control of the individual radiators 10, so that both an isolated individual radiator 10 and a plurality of, in particular isolated or adjacent, individual radiators 10 are controlled at a given, predetermined time over a specific period of time, ie a - and can be switched off.
  • the grouping of several individual radiators 10, in particular diode lasers, can in particular also be designed as (laser) bars or laser bars on a strip-shaped chip, having the individual radiators 10, in particular the diode lasers.
  • the individual radiators 10, in particular the diode lasers, of a laser bar are generally operated electrically in parallel and are mounted on a heat sink.
  • the laser bars preferably have the individual radiators 10 both in the x and in the y direction within a plane z.
  • the z-plane in which the individual radiators 10 are arranged in a laser bar is preferably oriented parallel to the surface of the print bed 2, so that an in particular at least substantially uniform distance between the individual radiators 10 and the print bed 2 or one applied to it Layer 7a of the precursor material 7 consists. This advantageously ensures a uniformly intensive input of energy in all areas of the printing bed 2 and also allows a reliable, locally specific focusing of the irradiation. In this way, temperatures such as are necessary for the formation of silicon carbide or SiC-containing material can be generated and maintained precisely in a narrowly limited range.
  • the individual radiators 10 in the radiation source 8, in particular the laser bar are each arranged in rows in x and y correct, so that a particularly regular arrangement of the individual radiators 10 results, which is preferably in a space-saving manner the the maximum possible arrangement of individual radiators 10 on the irradiation device 8, in particular the laser bar, which can be implemented in practical terms in terms of numbers.
  • the radiation source 8 according to a particularly preferred embodiment of the generative manufacturing device 1 is designed as a laser array 8a.
  • the radiation source 8 is arranged over the entire width of the printing area 4 in which the freezing method according to the invention can be carried out. That is to say that the radiation source 8, in particular the laser bar, preferably the laser array 8a, corresponds in particular in one dimension at least substantially to the extent of the print bed 2, for example in the x or y direction. Furthermore, it has proven to be advantageous if the radiation source 8 is designed in such a way that it can be moved in the horizontal direction over the print bed 2.
  • one layer of the SiC-containing structure can be placed in each case with a single scan, ie by moving the radiation source 8 over or moving over the print bed 2, in particular the laser bar or preferably the laser array 8a be generated.
  • the radiation source 8 is arranged in such a way above the print bed that the irradiation of the precursor material 7, in particular the layers 7a of the precursor material, is essentially limited in terms of location and / or time, in particular is limited in terms of location and time, preferably can take place in a location-selective, time-specific manner, so that the energy input takes place in particular essentially precisely and avoiding a local deflection of the laser radiation 9.
  • the above-described preferably arrangement of the individual radiators 10 in the radiation source 8, in particular the laser bar, preferably the laser array 8a, which lies in a plane z which is oriented parallel to the surface of the print bed 2, contributes to this.
  • the radiation source 8 in particular the laser array 8a, is designed in such a way that it has a compact, area-optimized shape and a reduced shape Number of individual radiators 10, which can be particularly suitable for an application of the method according to the invention on an extrusion basis.
  • the radiation source 8 is a combination of at least one means for generating electromagnetic radiation, in particular at least one radiator, with at least one optical waveguide, in particular fiber optic cable and / or at least one lens.
  • the radiation source 8 particularly preferably has a combination of a plurality of means for generating electromagnetic radiation, in particular radiators, with a plurality of optical waveguides, in particular glass fiber cables, and a plurality of lenses.
  • the radiation source 8 namely the means for generating electromagnetic radiation, in particular the radiators, separately, ie locally independent of the printing bed 2 or printing area 4, and in particular also stationary are arranged.
  • the combination of the means for generating electromagnetic radiation, ie in particular the single beam laser or also the grouping of individual lasers, in particular diode lasers, with optical waveguides enables the laser beams 9 to be guided to a movable exposure means that has the plurality of lenses .
  • the lens or lenses in turn allow the deflection or focusing of the laser beams 9, so that, as a result, also according to this embodiment, the energy input is limited in terms of location and / or time, in particular limited in terms of location and time, preferably limited in terms of location and time.
  • One advantage of this alternative embodiment of the manufacturing device 1 is that it is possible to focus the laser beams 9, in particular pixel-by-pixel, without the radiation source 8, in particular the grouping of individual lasers, in particular diode lasers, having to be arranged in the form of these pixels, ie the distance between the individual lasers can be greater than the area of a pixel.
  • an optimized weight distribution of the radiation source 8 can in particular also be achieved through this arrangement.
  • the radiation source 8 in particular the individual radiators 10, powers of less than 7 W, in particular less than 5 W, preferably less than 4 W, preferably less than 3 W, have or emit with an effective range of significantly less than 500 pm, in particular of less than 300 pm, preferably of less than 200 pm, preferably of less than 150 pm.
  • the application device 6 for the precursor powder and the irradiation device or radiation source 8 are preferably positioned orthogonally to one another and each on an edge of the print bed 2, which is in particular formed by the delimitation 5.
  • FIG. 2 schematically shows a cross-sectional representation of the generative manufacturing device 1 for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, in the initial state.
  • the manufacturing device 1 - according to a further preferred embodiment of the manufacturing device 1 - has a storage device 12 for the, in particular powdery, precursor material 7, which is arranged laterally next to the printing bed 2.
  • the storage device 12 for the precursor material 7 is designed in such a way that, analogously to the printing bed 2, it has in particular an essentially flat and / or planar and preferably vertically movable, in particular liftable, base surface 12a.
  • the storage device 12 also has a delimitation 5 on its surface edges, in particular a delimitation 5 that frames the storage device 12.
  • the storage device 12 contains the precursor material 7 at the beginning of the production process.
  • the application device 6, in particular in the form of the application roller 6a or in the form of the doctor blade, also via the storage device 12 is movable in the horizontal direction, so in particular is movable over the print bed 2 and the storage device 12 in the horizontal direction.
  • FIG. 3 schematically shows a cross-sectional representation of the production device 1 when the method according to the invention is carried out for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, according to the previously described method step (a). , in the course of which the precursor material 7, containing at least one silicon source and at least one carbon source, is provided in the form of a layer 7a, in particular a layer.
  • the construction platform 3 is preferably first lowered by the amount of the thickness of the layer 7a, in particular the layer, and the base area 12a of the storage device 12 for the precursor powder is raised by an amount that provides sufficient material of the precursor material 7, see above that the application device 6, in particular the application roller 6a or the doctor blade, can apply a layer 7a, in particular a layer, to the building platform 3 with a thickness in the aforementioned range.
  • the application device 6, in particular the application roller 6a or the doctor blade is moved over the printing bed 2 starting from the storage device 12, so that the precursor material 7 is distributed in the course of this.
  • FIG. 4 shows a schematic cross-sectional representation of the generative manufacturing device 1 when the method according to the invention is carried out for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, according to step (b), in
  • the precursor material 7 is converted into a SiC-containing material, in particular successively a SiC-containing structure 13, through a repeated and / or continuous input of energy by at least one radiation source.
  • the radiation source 8 is moved horizontally over the print bed 2.
  • the energy is introduced, in particular by electromagnetic radiation or preferably by laser radiation 9, into the precursor material 7 by the corresponding individual radiators 10, in particular the individual emitters.
  • the individual radiators 10 are set in such a way that they can be individually controlled so that the energy input is limited in terms of location and / or time, particularly in terms of location and time limited, preferably location-selective time-specifically limited, can take place.
  • the energy input causes a temperature increase, in particular a locally and / or temporally limited temperature increase, preferably a spatially and temporally limited temperature increase, preferably a locally time-specifically limited temperature increase, in the precursor material 7. It can thus be achieved that the conversion of the precursor material 7 to the SiC-containing structure 13 takes place in a predefinable and in particular spatially and time-resolved manner.
  • FIG. 5 shows a schematic cross-sectional representation of the generative manufacturing device 1 when the method according to the invention is carried out for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, according to the repetition of method steps (a). and (b), which takes place so often that the predefined SiC-containing structure 13 is obtained.
  • FIG. 6 shows a schematic representation of the production device 1 for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-solid precursor material mixture, preferably a precursor powder, in plan view.
  • the manufacturing device 1 is arranged analogously to the initial state.
  • the finished three-dimensional SiC-containing structure 13 is located within the printing area 4, in which the production method according to the invention for producing the SiC-containing structure 13, but is still surrounded by unreacted precursor material 7 within the printing bed 2.
  • a final process step (c) can therefore follow in a further preferred embodiment of the present invention, in the course of which the SiC-containing structure 13 obtained is cleaned and / or reworked.
  • FIG. 7 schematically shows a perspective illustration of the generative manufacturing device 1 according to an alternative preferred embodiment of the method according to the invention for producing a structure containing SiC, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion 16, in the context of a liquid printing process, in particular an inkjet process, in the initial state.
  • a solid-in-liquid or liquid-in-liquid precursor material mixture preferably a precursor dispersion 16
  • a liquid printing process in particular an inkjet process
  • the production device 1 is designed essentially analogously to the production device according to FIG. 1, with the difference that the production process is carried out as a liquid printing process, so that instead of the application device 6 for the precursor powder, it has an alternative application device 14 for the precursor dispersion 16, in particular a plurality of, application nozzles 15, is provided in connection with a storage device 12 for the precursor dispersion.
  • the application device 14 is designed in combination with the radiation source 8.
  • the explanations regarding the radiation source 8 according to the preceding FIGS. 1 to 6 can be applied, as it were, to the present particular configuration of the manufacturing device 1, in particular also to the combination of application device 14 and radiation source 8.
  • the application device 14 is preferably designed such that it has several, preferably a plurality of, application nozzles 15, for example at least 10, preferably at least 20, for applying the, in particular liquid, precursor material 7 to the printing bed 2, in particular the printing area 4 .
  • the application nozzles 15 are preferably individually controllable and at the same time enable the, in particular liquid, precursor material 7 to be applied, preferably by uniform, fine droplets, in particular sprinkling, spraying, drizzling and / or wetting.
  • the application device 14 is preferably arranged in such a manner above the printing bed 2 that the application of the precursor material 7 can take place essentially precisely and avoiding local deflection.
  • the application device 14 for the Precursor dispersion 16 is designed in such a way that different precursor materials can be selectively applied, in particular in different areas or planes of the printing bed 2. This allows in particular the production of conductor tracks or generally of semiconductor electronics from and in SiC-containing materials.
  • the application nozzles 15 are designed so that different precursor dispersions 16, in particular different precursor sols or components for the production of precursor sols, separately and specifically, in particular in different areas or levels of the printing bed 2 or already thereon generated layers, in particular layers, of SiC-containing material can be applied.
  • the application nozzles 15 have separate lines, in particular to the, preferably several, storage devices 12 of the different precursor dispersions 16, and can be controlled individually. It is very particularly preferred in this context if the metering and the location-selective or time-specific application of the different precursor dispersions are coordinated and controlled via a control device. In this way, in the context of this preferred embodiment of the method according to the invention, it is particularly possible to carry out the method according to the invention as a multi-material printing method, in particular based on the inkjet method.
  • FIG. 8 schematically shows a cross-sectional representation of the alternative preferred embodiment of the generative manufacturing device 1 for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion, in the initial state.
  • FIG. 9 schematically shows a cross-sectional representation of the alternative preferred embodiment of the manufacturing device 1 for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion , in the working state, in particular when carrying out the method according to the invention in accordance with method step (a) described above, in the course of which the precursor material 7, in particular the liquid-in-liquid or solid-in-liquid precursor material mixture containing at least one silicon source and at least one carbon source is provided in the form of a layer 7a, in particular a layer.
  • the layer 7a has a layer thickness in the range from 0.1 to 250 gm, in particular 0.2 to 100 gm, preferably 0.5 to 50 gm, preferably 1 to 25 gm, is applied.
  • the building platform 3 is lowered by a corresponding amount of the layer thickness of the layer 7a, in particular the layer.
  • FIG. 10 schematically shows a cross-sectional illustration of the alternative preferred embodiment of the manufacturing device 1 for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion
  • a precursor material mixture preferably a precursor dispersion
  • the precursor material 7 at least regionally to a SiC-containing material, in particular successively to a SiC-containing structure 13, is implemented.
  • Analogous reference can be made here to the explanations relating to method step (b) under FIG. 4.
  • FIG. 11 again shows a schematic cross-sectional representation of the alternative embodiment of the manufacturing device 1 for carrying out the method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion , in the working state, during which process steps (a) and (b) are repeated so often that a SiC-containing structure 13 is obtained.
  • a solid-in-liquid or liquid-in-liquid precursor material mixture preferably a precursor dispersion
  • FIG. 12 shows a schematic representation of the alternative embodiment of the manufacturing device 1 for carrying out the Method according to the invention for producing a SiC-containing structure, in particular from a solid-in-liquid or liquid-in-liquid precursor material mixture, preferably a precursor dispersion, as a top view.
  • the manufacturing device 1 is arranged analogously to its initial state. Analogous reference can be made here to the relevant further explanations according to FIG. 6.

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Abstract

L'invention concerne en particulier un procédé additif pour la fabrication de structures contenant du SiC qui sont obtenues par apport d'énergie répété et/ou continu dans un matériau précurseur à partir d'au moins une source de rayonnement.
EP20764360.2A 2019-08-28 2020-08-27 Procédé de fabrication additive de structures contenant du sic Withdrawn EP4168373A1 (fr)

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DE102019123100.0A DE102019123100A1 (de) 2019-08-28 2019-08-28 Verfahren zur generativen Herstellung von SiC-haltigen Strukturen
PCT/EP2020/074017 WO2021038006A1 (fr) 2019-08-28 2020-08-27 Procédé de fabrication additive de structures contenant du sic

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US10300624B2 (en) * 2014-10-17 2019-05-28 United Technologies Corporation Functional inorganics and ceramic additive manufacturing
DE102015100062A1 (de) 2015-01-06 2016-07-07 Universität Paderborn Vorrichtung und Verfahren zum Herstellen von Siliziumcarbid
DE102015105085A1 (de) 2015-04-01 2016-10-06 Universität Paderborn Verfahren zum Herstellen eines Siliziumcarbid-haltigen Körpers
DE102017110361A1 (de) 2017-05-12 2018-11-15 Psc Technologies Gmbh Verfahren zur Herstellung von siliciumcarbidhaltigen Strukturen
DE102017110362A1 (de) 2017-05-12 2018-11-15 Psc Technologies Gmbh Verfahren zur Herstellung von siliciumcarbidhaltigen dreidimensionalen Objekten
DE102018127877A1 (de) 2018-11-08 2020-05-14 Psc Technologies Gmbh Präkursormaterial für die Herstellung siliciumcarbidhaltiger Materialien
DE102018128434A1 (de) 2018-11-13 2020-05-14 Psc Technologies Gmbh Verfahren zur Erzeugung von dreidimensionalen siliciumcarbidhaltigen Objekten

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