EP4587609A1 - VERFAHREN UND VORRICHTUNG ZUM ABSCHEIDEN n-DOTIERTEM SiC - Google Patents
VERFAHREN UND VORRICHTUNG ZUM ABSCHEIDEN n-DOTIERTEM SiCInfo
- Publication number
- EP4587609A1 EP4587609A1 EP24808954.2A EP24808954A EP4587609A1 EP 4587609 A1 EP4587609 A1 EP 4587609A1 EP 24808954 A EP24808954 A EP 24808954A EP 4587609 A1 EP4587609 A1 EP 4587609A1
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- EP
- European Patent Office
- Prior art keywords
- gas
- doping
- flows
- flow
- gas flow
- 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.)
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/32—Carbides
- C23C16/325—Silicon carbide
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
- C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4488—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by in situ generation of reactive gas by chemical or electrochemical reaction
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45502—Flow conditions in reaction chamber
- C23C16/45508—Radial flow
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
- C23C16/45512—Premixing before introduction in the reaction chamber
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
- C23C16/4582—Rigid and flat substrates, e.g. plates or discs
- C23C16/4583—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally
- C23C16/4584—Rigid and flat substrates, e.g. plates or discs the substrate being supported substantially horizontally the substrate being rotated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/52—Controlling or regulating the coating process
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/24—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials using chemical vapour deposition [CVD]
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/32—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials characterised by intermediate layers between substrates and deposited layers
- H10P14/3202—Materials thereof
- H10P14/3204—Materials thereof being Group IVA semiconducting materials
- H10P14/3208—Silicon carbide
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/34—Deposited materials, e.g. layers
- H10P14/3402—Deposited materials, e.g. layers characterised by the chemical composition
- H10P14/3404—Deposited materials, e.g. layers characterised by the chemical composition being Group IVA materials
- H10P14/3408—Silicon carbide
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
- H10P14/20—Formation of materials, e.g. in the shape of layers or pillars of semiconductor materials
- H10P14/34—Deposited materials, e.g. layers
- H10P14/3438—Doping during depositing
- H10P14/3441—Conductivity type
- H10P14/3442—N-type
Definitions
- the invention relates to a method for depositing a SiC layer on a substrate in a process chamber of a CVD reactor, wherein walls of the process chamber are heated to a process temperature using a heating device.
- a process gas flow is fed into the process chamber through a gas inlet element.
- the process gas flow flows through the process chamber and flows over the substrates arranged therein in a horizontal direction.
- the process gas flow contains growth gas flows which contain a silicon-containing and a carbon-containing reactive gas.
- the process gas flow also contains doping gas flows which contain gaseous dopant carriers.
- US 2020/0043725 A1 describes an apparatus and a method for depositing n-doped SiC, wherein NH 3 and N 2 are used as dopants.
- JP 2015-143168 A describes a process in which a process gas containing a silicon compound and a carbon compound as well as NH3 is fed into a process chamber heated on all sides. The surfaces of the walls of the process chamber are coated with SiC. N-doped SiC is deposited on a substrate rotating about an axis of rotation using NH3 as a dopant carrier. The partial pressure of the components of the process gas decreases continuously in the direction of flow.
- DE 112017006965 T5 describes a method for depositing N- doped SiC layers, wherein either ammonia or gaseous nitrogen is used as the dopant.
- Summary of the Invention [0009] The invention is based on the object of improving the dopant homogeneity during the deposition of n-doped SiC, and in particular in a CVD reactor in which a gas inlet element is surrounded by substrates to be coated, which are simultaneously coated with a SiC layer.
- the model calculations and experiments show that when using nitrogen compounds with a non-triple-bonded nitrogen atom, for example ammonia, as the dopant carrier, the incorporation of nitrogen into the SiC layer depends on the Si/C ratio.
- a particularly important criterion is the Si availability in the gas phase directly above the substrate. It has been shown that the Si availability or the Si/C ratio increases in a region of the process chamber downstream of the pre-flow zone, i.e., particularly at the beginning of the deposition zone where the substrate is located. The Si availability or the Si/C ratio then reaches a maximum above the substrate.
- On the side of the substrate facing the gas inlet element there is therefore a reduced dopant incorporation into the deposited layer.
- the substrate is rotated about its center during layer deposition, resulting in a rotationally symmetric doping profile.
- the doping profile is characterized by a flat central profile and decreases towards the edge of the substrate, so that the doping profile can be described as bell-shaped.
- the conditioning layer consists of Si-C compounds, whereby these compounds can have polycrystalline structures in which the Si atoms are located on the surface.
- the unsaturated bonds that form during the deposition of the conditioning layer are saturated by the hydrogen used as a carrier gas during the deposition.
- One hydrogen atom of a hydrogen molecule remains on the Si surface, and the other hydrogen atom enters the gas phase as a radical. Radical formation is therefore not catalytic, as a reaction product, namely the hydrogen atom, remains on the surface.
- the H radical can then react with NH3 in the gas phase, forming an NH2 radical and H2. In an analogous manner, it can also react with the NH2 radical there, forming NH and H2 .
- the prerequisite for ammonia decomposition in the gas phase is therefore the continuous creation of unsaturated bonds on the surface.
- This means that the conditioning layer must grow continuously, since each incorporation of a SiC pair creates an unsaturated bond on the surface.
- the growth of the SiC layer is preferably carried out by means of a carbon-containing first growth gas flow and a silicon-containing second growth gas flow, wherein the first growth gas flow contains a carbon compound.
- Ethene can hydrogenate to ethane (C2H6) at the process temperatures.
- Ethane can decompose into two CH3 radicals in a homolytic bond cleavage in the gas phase or in a heterolytic bond cleavage on the surface.
- CH3 can react with a silicon-containing molecule, for example silicon trichloride ( SIHCl3 ), on the surface with hydrogen bound to the surface, whereby a SiC pair is incorporated into the surface of the conditioning layer and one bond of the silicon atom is not saturated.
- SIHCl3 silicon trichloride
- the decomposition of N2 or the formation of the H radicals for the decomposition of ammonia depends on the size of the surface over which N2 or ammonia flows before reaching the substrate.
- the flow path, which is directed from the gas inlet element directly towards the center of the substrate, is the shortest path along which
- N2 and NH3 as dopant carriers thus creates the possibility of compensating for the reduced dopant incorporation observed at the edge when using NH3 as a dopant with the increased dopant incorporation observed at the edge when using N2 as a dopant.
- the conditioning layer should therefore be as porous or fissured as possible.
- the conditioning layer is preferably deposited on a surface that is not monocrystalline, so that the conditioning layer consists of a large number of small columnar structures or dendrites.
- the process parameters are preferably set so that the effective surface area of the conditioning layer increases in the direction of flow.
- the height or diameter of the columnar structures or dendrites thus increases in the direction of flow of the process gas through the process chamber.
- the effective area of the conditioning layer i.e. the free SiC surface of the conditioning layer, is significantly larger than its surface area on the susceptor, particularly in the region of the deposition zone . It can be at least 1.5 times or twice as large.
- the conditioning layer is preferably deposited on a polycrystalline or quasi-amorphous SiC coating or on a TaC coating on the surface of the susceptor facing the process chamber.
- the coating can also consist of solid solutions SiTaC.
- the conditioning layer is deposited in a conditioning step before the actual deposition of an N-doped SiC layer on a SiC substrate in the process chamber. This takes place before the process chamber is loaded with the substrate to be coated and in particular using a dummy substrate which is located in a storage location, for example a substrate holder, in the process chamber instead of the substrate to be coated. After the conditioning layer has been deposited, the dummy substrate is removed from the process chamber and replaced with a SiC substrate to be coated.
- the process chamber is purged with hydrogen and heated.
- the substrate temperature is increased to such an extent that the native oxides on the SiC surface of the substrate are removed and the surface is terminated with H.
- a process gas flow is then fed into the process chamber.
- This contains a first growth gas flow containing carbon, wherein the first growth gas flow preferably consists of ethene (C 2 H 4 ).
- the process gas flow contains a second growth gas flow containing silicon, wherein the second growth gas flow preferably consists of silicon tetrachloride (SiHCl 3).
- the process gas flow also contains a first doping gas flow containing ammonia and a second doping gas flow containing molecular nitrogen.
- the process gas flow is fed into the process chamber together with a carrier gas flow of H 2. This occurs in such a way that hydrogen radicals and HCN are continuously generated at the conditioning layer, whereby this requires that the conditioning layer
- 31222N1PCT – 11/8/2024 Ai 2023-13 through continuous growth has surface areas that have unsaturated bonds (dangling bonds) that are required for the generation of hydrogen radicals and HCN.
- the lateral doping profile created by the first doping gas flow has a dopant concentration that decreases towards the edge of the substrate and the second lateral doping profile has a dopant concentration that increases towards the edge of the substrate.
- one of the doping gas flows can generate a dopant profile measured along a diametrical line through the substrate, which is A-, U-, V-, or W-shaped.
- the other of the doping gas flows can generate a dopant profile opposite to this dopant profile, which, for example, corresponds to the shape of an upside-down A, U, V, or W.
- the different dopant carriers are fed into the process chamber, in particular, through different gas inlet zones, wherein the gas inlet zones are located at different vertical levels.
- the dopant carrier of a first doping gas flow can, for example, be a
- 31222N1PCT – 11/8/2024 Ai 2023-13 Create a doping profile that is curved upwards in the center.
- the dopant carrier of a second doping gas flow can, for example, create a doping profile that is curved downwards in the center .
- An effective doping profile can be set by suitably mixing the two doping gas flows.
- the two doping profiles can also be flat in the center and only decrease or increase in the edge region, so that edge inhomogeneities can be compensated for.
- a doping gas flow containing NH3 does not flow through the same gas inlet zone through which a growth gas flow containing chlorine, for example trichlorosilane, flows.
- Another growth gas flow can contain carbon, for example methane, ethane or ethene.
- the growth gas flow can also contain dichlorosilane.
- HCl can also be fed into the process chamber.
- the growth gas flow can contain silane or disilane.
- the following nitrogen compounds are particularly suitable as dopant carriers : N 2 , NH 3 HCN, pyridine (C 5 H 5 N), hydrazine (N 2 H 4 ), dimethylhydrazine (C 2 H 8 N 2 ) or asymmetrical dimethylhydrazine.
- the reaction and decomposition mechanism of ammonia described above applies there, for example, to the aforementioned nitrogen compounds, in which the nitrogen is bound with lower bonding forces than in N 2 . It is particularly preferred that the nitrogen atoms in the molecules of the dopant carriers are bonded to the other atoms of the molecules with bonding forces of different strengths. Thus, it can be provided that in one dopant carrier the nitrogen is bonded to the other molecules with a single bond and in another dopant carrier the nitrogen is bonded to the other molecules in a double or triple bond.
- the device according to the invention has a CVD reactor and a gas mixing device, as well as a control device.
- the gas mixing device has storage containers for the reactive gases containing silicon and carbon. It also has storage containers for the at least one dopant carrier, but preferably storage containers for at least two dopant carriers.
- the gas mixing device also has mass flow controllers and valves to appropriately distribute the reactive gases and the dopant carriers as growth gas flows and doping gas flows to the vertically stacked gas inlet zones of the gas inlet element.
- FIG. 7 is a diagram showing two dopant profiles through a SiC layer at the top and two dopant profiles each at the bottom, which are generated by different dopant carriers.
- Fig. 8 is a schematic representation of a second exemplary embodiment with regard to the composition and distribution of the process gas flow.
- Fig. 9 is a representation according to Figure 8 of a third exemplary embodiment .
- Fig. 10 a representation according to Figure 8 of a fourth embodiment , 31222N1PCT – 8.11.2024 Ai 2023-13
- Fig. 11 is a representation according to Fig. 8 of a fifth exemplary embodiment
- Fig. 12 is a representation according to Fig. 8 of a sixth exemplary embodiment , Fig .
- FIG. 13 is a schematic representation of the temperature profile of the susceptor in the radial direction
- Fig. 14 is a schematic representation of the temperature profile of the process chamber ceiling in the radial direction.
- Figures 1 and 2 schematically show the structure of a CVD reactor 1.
- a housing of the CVD reactor 1 which can be made of stainless steel
- a susceptor 10 which can be made of graphite and whose surface can be coated with SiC, TaC, or SiTaC.
- the susceptor can be driven to rotate about a central axis.
- the susceptor has the circular disk shape shown in Figure 2.
- Above the susceptor 10 is a process chamber 2, which is bounded at the top by a process chamber ceiling.
- the process chamber ceiling is formed by a ceiling plate 19, which can be supported on a holding element 18.
- the ceiling plate 19 can also be supported on a gas outlet element 9 arranged around the susceptor 10.
- the ceiling plate 19 can be made of graphite coated with SiC, TaC, or SiTaC.
- the gas outlet element 9 can also be made of this material. However, it can also be made of a ceramic material. 31222N1PCT – 8.11.2024 Ai 2023-13 [0028]
- the susceptor 10 is covered with cover plates 15, 16, which can also be made of graphite coated in this way. However, they can also be made of SiC, TaC, or SiTaC. Pockets 17 are formed, which have a pocket bottom into which a gas supply line 13 opens.
- the purge gas flowing from the gas supply line 13, for example hydrogen, can generate a rotating gas cushion that suspends a substrate holder 11, which can also be made of SiC, TaC, or SiTaC-coated or uncoated graphite, and rotates the substrate holder 11 about a rotational axis.
- a heating device 14 is provided below the susceptor 10, which can be an RF heater, with which the susceptor 10 is heated.
- a further heating device (not shown) can be provided to heat the process chamber ceiling, i.e., the ceiling plate 19, so that the process chamber 2 is heated from all sides.
- the ceiling plate 19 is preferably not actively heated.
- the ceiling plate 19 is passively heated via thermal radiation from the susceptor 10 or from the cover plates 15, 16, so that the surface temperature of the ceiling plate 19 is significantly lower than the surface temperature of the cover plates 15, 16. This has the consequence that different surface reactions take place on the ceiling plate 19 than on the cover plates 15, 16 or on the susceptor 10.
- the intermediate products mentioned above, which arise during the decomposition of NH3 or N2, can thus arise to a reduced extent in the upper region of the process chamber 2. This can also influence the doping profile.
- a gas inlet element 3 which is made of a ceramic material, stainless steel, quartz or a 31222N1PCT – 8.11.2024 Ai 2023-13 SiC, TaC or SiTaC-coated graphite.
- the gas inlet element 3 forms three (see Figure 3) superimposed gas inlet zones 4, 5, 6, each of which is connected to a feed line 24, 25, 26 through which portions of a process gas flow can be fed into the respective gas inlet zone 4, 5, 6.
- the process gas flow is provided in a gas mixing system having a gas source 27 for nitrogen, a gas source 28 for ammonia, a gas source 29 for trichlorosilane and a gas source 30 for ethene (C2H4) .
- a gas source for HCl can also be provided.
- the gas inlet element 3 has, for example, four or five or more superimposed gas inlet zones.
- Each of the gas sources 27 to 30 is connected to at least one of the supply lines 24, 25, 26 via valves 22 and mass flow controllers 21.
- the mass flow controllers 21 and the valves 20 are controlled according to a program of the control device 20.
- the gas mixing system provides at least two doping gas flows D1, D2, each containing a dopant carrier, for example N2 or NH3 or one of the above-mentioned nitrogen compounds that can also be used.
- the gas mixing system also provides at least two growth gas flows Q1, Q2, but preferably several growth gas flows Q1, Q2, Q3, Q4, Q5.
- the growth gas flows contain carbon and silicon.
- One of these gases can also contain chlorine, for example trichlorosilicon, dichlorosilicon or HCl.
- the growth gas flows can also contain other carbon-containing or silicon-containing gases.
- all hydrocarbons, especially alkenes, alkanes, or alkynes are considered carbon-containing gases.
- 31222N1PCT – 8.11.2024 Ai 2023-13 Silane, disilane, or silicon chlorides, in particular silicon tetrachloride can also be considered as silicon-containing gases.
- the components of the doping gas flows and the growth gas flows can also react on the surfaces of the cover plates 15 or the ceiling plate 19.
- intermediate products and in particular decomposition products are formed.
- the intermediate or decomposition products and possibly undecomposed dopant carriers migrate from the gas phase above the substrate holder 11 in a deposition zone 8 towards the surface of a rotating substrate 12 resting on the substrate holder 11. This occurs essentially by diffusion due to a depletion of the gas phase caused by the condensation or consumption of the intermediate or decomposition products on the substrate surface 12 .
- Figure 1 schematically shows two doping profiles a and b, which are measured over a diameter of the substrate 2.
- the linear doping profiles a and b shown as curved lines, are rotationally symmetrical and represent a section through the lateral doping profile in the layer deposited on the substrate 12.
- the doping profile a is generated in a SiC layer deposited on the substrate 11 when the substrate 11 is rotated during deposition and only the first doping gas flow D1 is fed into the process chamber 2 through the gas inlet zone 6 or another gas inlet zone.
- the dopant profile b is generated in a SiC layer deposited on the substrate 11 when the substrate 11 is rotated during deposition and only the second doping gas flow D2 is fed into the process chamber 2 through the gas inlet zone 5 or another gas inlet zone.
- the dopant profiles a, b in Figure 1 are essentially symbolic in nature. The actual dopant profiles may deviate from this and may be flat, particularly in the central region.
- the dopant carrier of the first doping gas flow D1 is NH3 and the dopant carrier of the second doping gas flow D2 is N2 . It can be seen that the two doping profiles are not straight, but curved.
- the selection of the dopant carriers or the selection of the gas inlet zones 4, 5, 6, through which the respective doping gas flow D1, D2 flows, is carried out in such a way that two doping profiles a, b are formed , which are curved in opposite directions.
- the doping profile a is curved upwards and the doping profile b is curved downwards.
- a doping profile can be set that is almost straight.
- a straight doping profile has the consequence that an almost homogeneous dopant distribution is formed in the SiC layer deposited on the substrate 12.
- the choice of the dopant carriers and the choice of the gas inlet zones 4, 5, 6 through which the dopant carriers are fed into the process chamber can be made such that the inhomogeneous rotationally symmetric doping profile generated by one dopant carrier is compensated by the likewise inhomogeneous rotationally symmetric doping profile generated by another dopant carrier, in the direction of a homogeneous rotationally symmetric sum profile.
- One doping profile can, for example, be U-shaped or trough-shaped.
- the other doping profile can be in the shape of an inverted U or bell-shaped.
- hydrogen and a fourth growth gas flow Q4, which is C2H4 are fed into the lowest gas inlet zone 4.
- the mass flow of the fourth growth gas flow Q4 corresponds to approximately 10% of the sum of all carbon- containing growth gas flows Q1 + Q3 + Q4.
- a third growth gas flow Q3 is fed, which contains C2H4, and a second growth gas flow Q2, which contains HCl3SI.
- the third growth gas flow Q3 contains approximately 80% of the sum of all carbon-containing growth gas flows.
- a second doping gas flow D2 which is nitrogen, is fed through the middle gas inlet zone 5.
- the mass flow of this growth gas flow Q1 corresponds to approximately 10% of the sum of all carbon-containing growth gas flows.
- a first doping gas flow D1, which contains NH3, is fed in through the uppermost gas inlet zone 6.
- a dummy substrate is located on the substrate storage area, which is removed again after the conditioning layer K has been deposited. It is essential that the conditioning layer K extends at least as far as a line bordering the center Z of the substrate 12 or a storage location for the substrate 12, which is shown in dashed lines in Figure 3.
- the process parameters for depositing the conditioning layer K are set such that a surface element of the conditioning layer K has an effective free surface that is larger (at least 1.5 times or at least 2 times) than the area of the susceptor covered by the surface element .
- the effective free surface of the conditioning layer should be as large as possible , i.e. the ratio of the free surface to the covered surface of the susceptor 10 should be >1.5 or greater than 2 if possible.
- the process parameters are set such that the conditioning layer K consists of a SiC compound and in particular of polycrystalline SiC.
- the conditioning layer K should be as porous as possible and in particular fissured.
- the process parameters are preferably adjusted such that columnar structures or dendrites 33 are deposited on the susceptor surface in the area of the pre-run zone 7 and the secondary zone 7'.
- the layer thickness or the ratio of the effective surface to the covered surface of the conditioning layer should be, as shown in Figure 5 31222N1PCT – 8.11.2024 Ai 2023-13 shown, increase in the flow direction S, so that this ratio is greatest in the area of the secondary zone 7', which separates two adjacent substrates 12 from one another.
- the dendrites 33 are, as shown in Figure 3, irregularly distributed over the surface.
- the distance between adjacent dendrites 33 can approximately correspond to the diameter of the dendrites 33.
- the height of the dendrites 33 can be greater than the diameter of the dendrites 33.
- the height of the dendrites can, as shown in Figure 5, increase in the flow direction.
- the diameters of the dendrites 33 increase in the flow direction or that the distance between adjacent dendrites 33 becomes smaller in the flow direction.
- the peripheral surfaces of the dendrites 33 form reaction surfaces at which chemical reactions can take place .
- suitable silicon compounds and carbon compounds are fed into the process chamber, with the susceptor temperature being an essential process parameter.
- the dummy substrate or all dummy substrates are removed from the process chamber.
- Monocrystalline Si substrates with a smooth surface are placed on the storage locations.
- One or more layers are deposited onto these substrates, with at least one of these multiple layers being an n-doped SiC layer, with nitrogen being used as the dopant.
- the deposition process is carried out as previously described.
- the surfaces of the substrates are cleaned of any oxides adhering thereto. This takes place in a hydrogen atmosphere at elevated temperatures, so that the silicon atoms lying on top according to the model underlying the invention are each 31222N1PCT – 8.11.2024 Ai 2023-13 are bonded to a hydrogen atom.
- ⁇ H(s)-Si(b) ⁇ denotes a hydrogen-terminated silicon compound
- SiHCl ⁇ ( ⁇ ) adsorbed silicon trichloride CH ⁇ ( ⁇ ) adsorbed CH3 on the surface
- ⁇ Si( ⁇ ) ⁇ C( ⁇ ) ⁇ a SiC pair deposited on the layer surface where Si has a non-saturated bond.
- SiHCl3 adsorbs directly on the surface.
- C2H4 hydrogenates beforehand according to the following reaction to ethane and subsequently decomposes according to the reaction CH ⁇ g ⁇ ⁇ C ⁇ 2 ⁇ H ⁇ ( ⁇ ) to a radical CH ⁇ ⁇ ( ⁇ ) . 31222N1PCT – 8.11.2024 Ai 2023-13 [0047]
- unsaturated bonds are constantly forming on the free surface of the conditioning layer K.
- the unsaturated bonds are saturated by taking up an H atom from an H 2 atom that is adsorbed on the surface or forms a strong bond with Si.
- NH* ⁇ is formed in a first step.
- NH is formed in a second step. Both NH ⁇ ⁇ and NH are transported to the substrate. This occurs on the one hand with the carrier gas in the flow direction and on the other hand perpendicular to it by diffusion. A surface reaction then occurs on the substrate, in which hydrogen is released and N is incorporated into the layer.
- Gaseous nitrogen can be adsorbed on the surface of the conditioning layer K. This occurs at an unsaturated bond of the silicon according to the following reaction 31222N1PCT – 11/8/2024 Ai 2023-13 where ⁇ CH ⁇ ( ⁇ ) ⁇ Si( ⁇ ) ⁇ is a cation adsorbed on a neighboring silicon atom Si(s) represents a nitrogen atom incorporated into the surface and bonded to a silicon atom.
- the gaseous HCN produced is transported to the substrate and can then be deposited on the surface of the substrate according to react, whereby nitrogen is incorporated into the layer.
- FIG. 7 describes the effect that the feeding of different doping gas flows D1, D2 through gas inlet zones 5, 6 arranged at different levels has on the dopant distribution within the deposited layer.
- the upper curve represented as open and closed triangles, shows a section through the center of a layer deposited on the substrate 12 and the dopant distribution in the layer, which is almost uniform. A slight reduction in the dopant concentration can only be observed in the region near the edge of the layer of the circular disk-shaped substrate 12.
- the two lower curves show the dopant incorporation that would be generated by only one of the two different dopant carriers.
- the open and closed squares represent the dopant incorporation, 31222N1PCT – 8.11.2024 Ai 2023-13 which only N2 would cause.
- N2 as the dopant carrier
- the open and closed circles represent the dopant incorporation that only NH3 would cause.
- a strong center enhancement of the dopant incorporation is observed.
- a doping profile can be generated that leads to a compensation of the center enhancement or edge enhancement.
- a third doping gas flow D3 which is NH3, is additionally fed through the lowest gas inlet zone 4.
- no doping gas flow is fed into the process chamber 2 through the topmost gas inlet zone 6.
- the susceptor 10 can have a diameter in the range between 400 and 420 mm .
- six substrates, each having a diameter of 200 mm, can be arranged on a circular line around the center of the susceptor 10, wherein the centers of the circular substrates 31222N1PCT – 8.11.2024 Ai 2023-13 approximately 240 to 260 mm from the center.
- the gas inlet element 6 can have an outer diameter of between 50 and 60 mm, so that the advance zone 7 extends between a circular line with a radius in the range between 25 and 30 mm and a circular line with a radius between 140 and 150 mm .
- the secondary zone 7' then extends to a radial distance of 240 to 260 mm.
- the height of the process chamber can be 20 to 30 mm.
- the pressure in the process chamber can be in a range between 50 and 100 mbar (preferably 80 mbar).
- the minimum distance between two adjacent substrates can be in a range between 50 and 7 mm.
- the susceptor 10 can have the same diameter.
- the average flow velocity of the gas flow in the area of the beginning of the advance zone 7 can be in the range of 15 to 25 m/s, but it can also be in a range between 18 and 20 m/s. This is a parabolic flow profile . As the gas flow heats up, its volume increases, so that the flow velocity increases.
- the susceptor 10 can have a diameter in the range between 350 and 370 mm .
- Eight substrates with a diameter of 150 mm can be arranged on a circular arc with a radius of 210 to 230 mm around the center of the susceptor 10.
- the outer diameter of the gas inlet element 6 can be 31222N1PCT – 8.11.2024 Ai 2023-13 range between 60 and 70 mm.
- the minimum distance between two substrates lying directly next to one another can be 20 to 30 mm.
- the average flow velocity of the gas flow in the region of the beginning of the pre-run zone 7 can be in the range between 10 and 20 m/s.
- two doping gas flows D1, D2 are fed simultaneously through the uppermost gas inlet zone 6 into the process chamber 2.
- N2 and NH3 are fed through the same gas inlet zone 6 into the process chamber 2.
- the doping gas flows D1, D2 are fed into the process chamber exclusively through the uppermost gas inlet zone 6 and that no doping gas flows are fed through the remaining gas inlet zones 5, 4, but at most a carrier gas or growth gas flows.
- a gas mixture comprising two different dopant carriers flows through a gas inlet zone 6, the gas mixture consisting of NH3 and N2 .
- two different doping gas flows D1, D2, D3, D4 are fed into the process chamber 2 through two different gas inlet zones 5, 6, which are preferably upper gas inlet zones.
- a gas mixture comprising two different dopant carriers flows through a gas inlet zone 5, 6.
- the gas mixture can consist of NH3 and N2 in each case.
- the NH3 flow through the gas inlet zone 5 can be different 31222N1PCT – 8.11.2024 Ai 2023-13 be from the NH3 flow through the gas inlet zone 6.
- the two N2 flows can also differ.
- a chlorine-containing growth gas flow is fed into the process chamber exclusively through a central gas inlet zone 5.
- a gas flow of a carbon-containing growth gas flows through all gas inlet zones 4, 5, 6 .
- the dopant carriers have different nitrogen bonds (in- 31222N1PCT – 8.11.2024 Ai 2023-13 (multiple, double, or triple bonds), or if the dopants of the dopant carriers are bound with chemical bonds of varying strengths in the molecule of the dopant carrier.
- NH 3 is fed in through the uppermost and lowermost gas inlet zones 4, 6, and N 2 is fed in through the middle gas inlet zone 5.
- the carbon-containing reaction gas for example C2H4, is preferably fed into the process chamber 2 in the following mass distribution: 10% each through the lowest and the uppermost gas inlet zones 4, 6 and 80% through the middle gas inlet zone 5.
- the silicon-containing reactive gas in particular trichlorosilane or dichlorosilane, is preferably fed into the process chamber 2 exclusively through the middle gas inlet zone 5.
- Figure 13 shows, by way of example, the temperature profile on the surface of the susceptor in a susceptor according to the first or second exemplary embodiment. It can be seen that the temperature in the advance zone 7 is lower than in the region of the deposition zone or the secondary zone 7'.
- the surface temperature of the susceptor (where technically the surface temperature of a cover plate 15 is meant here) can be between 1650 and 1800°C.
- Figure 14 shows, by way of example, the temperature profile on the underside of the process chamber ceiling 19. It can be seen that this temperature is at least 100°C lower than the temperature of the susceptor.
- the temperature 31222N1PCT – 8.11.2024 Ai 2023-13 The temperature of the process chamber ceiling (where technically the surface temperature of the underside of the ceiling panels 19 is meant here) can be between 1401 and 1600°C .
- these statements also include a coating of a cover plate 15, 16, which covers a base body previously described as susceptor 15.
- the statements refer to a surface that delimits the process chamber 2 at the bottom.
- a method for depositing a SiC layer on a substrate with the following steps: - Providing a CVD reactor 1 with a process chamber 2, a susceptor 10 arranged therein, which can be heated to a process temperature TS by a heating device 14, and with a gas inlet element 3 for feeding a process gas flow into the process chamber 2 - Providing a first growth gas which has carbon-containing molecules, a second growth gas which has silicon-containing molecules, a first doping gas which contains a non-triply bonded nitrogen compound, a second doping gas which contains molecular nitrogen, and a carrier gas containing hydrogen; 31222N1PCT – 8.11.2024 Ai 2023-13 - Arranging a substrate 12 in a deposition zone 8 on the susceptor 10, wherein
- a method for depositing a SiC layer on a substrate 12, comprising the following steps: wherein a susceptor 10 is heated to a susceptor temperature TS using a heating device 14, 31222N1PCT - 8.11.2024 Ai 2023-13 wherein a process gas flow is fed into a process chamber 2 delimited downwards by the susceptor 10 by means of a gas inlet element 3 together with a carrier gas flow, wherein a process chamber ceiling 19' delimiting the process chamber 2 upwards has a process chamber ceiling temperature TD, wherein the process gas flow contains a carbon-containing first growth gas flow Q1, a silicon-containing second growth gas flow Q2, a first doping gas flow D1 containing ammonia or another, in particular non-triply bonded nitrogen compound, and a second doping gas flow D2 containing molecular nitrogen, wherein the carrier gas flow contains hydrogen, wherein the substrate 12 is arranged in a deposition zone 8 which, with respect to the process gas flow , is arranged downstream of a pre-
- process parameters namely in particular the susceptor temperature TS and the process chamber ceiling temperature TD as well as the mass flows of the first and second doping gas flows D
- 31222N1PCT – 8.11.2024 Ai 2023-13 A method characterized in that the method parameters are selected such that the conditioning layer has a top side facing the process chamber 2, which top side has a maximized free surface and in particular dendrites.
- a method characterized in that the susceptor temperature TS is higher than the process chamber ceiling temperature TD, wherein the process chamber ceiling temperature TD is selected in particular such that no reactions of the ammonia take place at the process chamber ceiling 19'.
- a method characterized in that the first and second dopant carriers and the mass flows of the doping gas flows D1, D2 carrying them are selected such that a sum of the two profiles a, b weighted by the ratio of the mass flows approximates a plane.
- a device which is characterized in that the control device 20 is configured to carry out a method according to one of the preceding claims and/or in that the surface of the susceptor 10 or cover plates 15, 16 resting on the susceptor 10 are coated with a conditioning layer K which consists of SiC, wherein the conditioning layer K is ratio of a free surface of the conditioning layer K to the claimed area increases in a direction away from the gas inlet element 3.
- All disclosed features are essential to the invention (individually, but also in combination with one another).
- the disclosure content of the associated/attached priority documents (copy of the prior application) is hereby fully incorporated into the disclosure of the application, also for the purpose of incorporating features of these documents into claims of the present application.
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Abstract
Description
Claims
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102023132598 | 2023-11-22 | ||
| PCT/EP2023/084516 WO2024121228A1 (de) | 2022-12-09 | 2023-12-06 | VERFAHREN UND VORRICHTUNG ZUM ABSCHEIDEN VON SiC-SCHICHTEN AUF EINEM SUBSTRAT |
| PCT/EP2023/084519 WO2024121230A1 (de) | 2022-12-09 | 2023-12-06 | VORRICHTUNG ZUM ABSCHEIDEN VON SiC-SCHICHTEN AUF EINEM SUBSTRAT MIT EINEM VERSTELLBAREN GASAUSTRITTSELEMENT |
| DE102023136517.7A DE102023136517A1 (de) | 2023-11-22 | 2023-12-22 | Verfahren und Vorrichtung zum Abscheiden n-dotiertem SiC |
| PCT/EP2024/082806 WO2025108923A1 (de) | 2023-11-22 | 2024-11-19 | VERFAHREN UND VORRICHTUNG ZUM ABSCHEIDEN n-DOTIERTEM SiC |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4587609A1 true EP4587609A1 (de) | 2025-07-23 |
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ID=96173111
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP24808954.2A Pending EP4587609A1 (de) | 2023-11-22 | 2024-11-19 | VERFAHREN UND VORRICHTUNG ZUM ABSCHEIDEN n-DOTIERTEM SiC |
Country Status (2)
| Country | Link |
|---|---|
| EP (1) | EP4587609A1 (de) |
| TW (1) | TW202532673A (de) |
-
2024
- 2024-11-19 EP EP24808954.2A patent/EP4587609A1/de active Pending
- 2024-11-21 TW TW113144794A patent/TW202532673A/zh unknown
Also Published As
| Publication number | Publication date |
|---|---|
| TW202532673A (zh) | 2025-08-16 |
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