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WO2025136086A1 - Cleaning method for removing parasitic grown silicon carbides and an interior part of an epitaxy process chamber and an epitaxy process system - Google Patents

Cleaning method for removing parasitic grown silicon carbides and an interior part of an epitaxy process chamber and an epitaxy process system Download PDF

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Publication number
WO2025136086A1
WO2025136086A1 PCT/NL2023/050682 NL2023050682W WO2025136086A1 WO 2025136086 A1 WO2025136086 A1 WO 2025136086A1 NL 2023050682 W NL2023050682 W NL 2023050682W WO 2025136086 A1 WO2025136086 A1 WO 2025136086A1
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Prior art keywords
interior part
cleaning method
epitaxy process
parasitic
process chamber
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Application number
PCT/NL2023/050682
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French (fr)
Inventor
Guiming SONG
Bernd KOFER
Marc VAN MUNSTER
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Schunk Kohlenstofftechnik GmbH
Schunk Xycarb Technology BV
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Schunk Kohlenstofftechnik GmbH
Schunk Xycarb Technology BV
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Priority to PCT/NL2023/050682 priority Critical patent/WO2025136086A1/en
Priority to PCT/NL2024/050698 priority patent/WO2025136109A1/en
Publication of WO2025136086A1 publication Critical patent/WO2025136086A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/4401Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4405Cleaning of reactor or parts inside the reactor by using reactive gases
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22Chemical 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
    • C23C16/30Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/32Carbides
    • C23C16/325Silicon carbide
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/4401Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C16/00Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44Chemical 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
    • C23C16/4401Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4407Cleaning of reactor or reactor parts by using wet or mechanical methods

Definitions

  • the present invention relates to a cleaning method for removing parasitic grown silicon carbides from an interior part of an epitaxy process chamber for epitaxial growth of silicon carbide, to an interior part of an epitaxy process chamber, and to a and epitaxy process system.
  • the silicon carbide epitaxy equipment market is experiencing rapid growth, primarily driven by the increasing electrification of the automotive industry.
  • CVD chemical vapor deposition
  • the epitaxy layer tends to deposit on both the surfaces of the wafer carrier or susceptor and the interior parts inside the chamber, even though this simultaneous deposition is unnecessary.
  • parasitic grown silicon carbides leads to the emission of particles and disruption of the gas flow, significantly impacting the quality of the epitaxial layer.
  • parasitic grown silicon carbides may lead to dimensional issues as the layers of the parasitic grown silicon carbides can grow very thick thereby hindering movement and/or placement of parts. Consequently, it becomes imperative to periodically remove these parasitic silicon carbide layers from the surfaces of the parts. This removal process cannot be achieved easily through chemical methods, mechanical methods, or a combination of both, ensuring the repeatability and continued usability of the parts.
  • uncoated graphite is porous and tends to trap and release impurities, thereby impacting the silicon carbide epitaxy's quality.
  • silicon atoms within the silicon carbide- coated graphite parts may escape from the silicon carbide coating surface and deposit onto the silicon carbide wafer surface, disrupting the silicon carbide epitaxy process.
  • metallic carbide coatings such as niobium carbide (NbC) and tantalum carbide (TaC) are utilized as a protective coating material.
  • NbC niobium carbide
  • TaC tantalum carbide
  • both NbC and TaC-coated graphite parts can be extremely expensive options.
  • these materials offer a better protection of the graphite as these do not sublime and leave TaC or NbC on the SiC wafer backside as SiC does when heated above 1600 °C.
  • the thickness and distribution of the parasitic silicon carbide layer or particle-like layer on the graphite parts are often highly non-uniform.
  • incomplete removal of parasitic silicon carbide in one area may lead to the exposure of the graphite substrate to etching gases in another area.
  • Both CIF3 and F2 gases can etch and degrade the graphite substrate.
  • pyrolytic carbon (PyC) can be used as a coating on the substrate. Nevertheless, CIF3 and F2 gases still have the potential to etch the pyrolytic carbon layer. While it is possible to tune the etch process and introduce additional steps, the overall cleaning process becomes complex, and a precise temperature control is crucial.
  • silicon carbide coating and tantalum carbide coating are deposited on the surfaces of the graphite parts, but the current cleaning work of the parasitic silicon carbide layer or particles on the protective coating surface with CIF3, NF3 or CI2, HCI etc. and even mechanical machining always damage both protective layers (silicon carbide and tantalum carbide layers), and therefore the lifetime of both silicon carbide coated graphite parts and tantalum carbide coated parts are short.
  • a cleaning method for removing parasitic grown silicon carbides from an interior part of an epitaxy process chamber for epitaxial growth of silicon carbide, said interior part comprising a pyrolytic carbon coating said method comprising the steps of: la) subjecting said interior part to a halogen-containing gas at a temperature of from 150 to 1700 °C to convert said parasitic grown silicon carbides present on said interior part into carbide-derived carbon (CDC) material, wherein said halogencontaining gas does not consist of or contain chlorine trifluoride or fluorine gas, or l b) subjecting said interior part to an inert gas at a temperature of from 1200 to 2400 °C and at a pressure of from 1x1 O' 10 to 500 mbar to convert said parasitic grown silicon carbides present on said interior part into said CDC material;
  • a pyrolytic carbon (PyC) layer is used as a protective layer on the interior part.
  • the PyC layer seals the porous surface of the interior part and reduces the likelihood of impurities becoming trapped and later released from the pores. Furthermore, the PyC layer shields the interior part from chemical attack during etching processes, thereby minimizing damage during the etch process of the silicon carbide wafer in which hydrogen gas is used.
  • the cleaning method according to the present invention removes the parasitic grown silicon carbides from the interior part’s surface without damaging the pyrolytic carbon coating on the interior part. Therefore, the pyrolytic carbon coated interior part can be reused multiple times for the silicon carbide epitaxy process.
  • a less complex method uses a halogen-containing gas, such as chlorine gas, to convert the parasitic silicon grown carbides deposited on the surface of the pyrolytic carbon coated interior parts to carbon.
  • a halogen-containing gas such as chlorine gas
  • CDC carbide-derived carbon
  • the claimed method provides the possibility to apply a high temperature in the first step of the cleaning method. This has the benefit that the overall time needed for the cleaning process to complete can be strongly reduced compared to known cleaning processes, because a higher temperature in the first step results in faster conversion of the SiC to the CDC material and reduces the cooldown time between the SiC deposition in the CVD process and the first step of the claimed cleaning method.
  • any of step 1a) and step 1 b) not only enables mechanically/manually removing the CDC material, but it also enables removing the CDC chemically not damaging the coating by using a pyrolytic carbon coating instead of a conventional metal carbide coating, such as silicon carbide or tantalum carbide.
  • step 1a) A benefit of step 1a) is that the resulting CDC material retains the original shape and crystalline surface morphology of silicon carbide (SiC), but with silicon atoms removed from the crystal structure, resulting in atomic vacancies. This unique crystalline structure of the CDC material exhibits different oxidation behaviour compared to the pyrolytic carbon coating on the interior part.
  • step 1b) A benefit of step 1b) is that there is no need for the epitaxy process system or parts thereof to be adapted for a halogen-containing gas, like CI2. Possibly, the system or parts thereof merely needs limited redesign for it to be withstand temperatures above 1600 °C.
  • the oxidation onset temperature of the CDC material obtained in both step 1a) and step 1 b) is significantly lower than that of graphite and pyrolytic carbon. Consequently, the CDC material can be effectively removed from the pyrolytic carbon coating surface, for example by oxidizing it using an oxygen-containing gas, while minimizing oxidation of the pyrolytic carbon and graphite. This not only enables the repeated use of a pyrolytic carbon-coated graphite part without significant surface damage to the interior part, but also enables in situ cleaning of the interior part.
  • the cleaning method allows the use of an interior part comprising a coating of pyrolytic carbon instead of a coating of, for example, silicon carbide or tantalum carbide.
  • Depositing a protective pyrolytic carbon layer on the interior part strongly reduces the costs for producing interior parts, compared to the production of an interior part that includes depositing a silicon carbide or tantalum carbide layer on the interior part.
  • a second aspect of the present invention relates to an interior part of an epitaxy process chamber for epitaxial growth of silicon carbide suitable to be cleaned by a cleaning method according to the first aspect of the present invention, said interior part comprising a pyrolytic carbon coating, wherein said interior part is arranged to be subjected to said cleaning method, and/or wherein said interior part is cleaned according to said cleaning method, and/or an interior part contaminated with parasitic grown silicon carbides arranged to be subjected to said cleaning method.
  • Said interior part may also comprise a diamond-like carbon layer or a glass carbon layer instead of said pyrolytic carbon layer, or a combination of the foregoing types of carbon layers.
  • a third aspect of the present invention relates to an epitaxy process system, comprising a controller and a epitaxy process chamber, wherein said epitaxy process chamber comprises at least one interior part according to the second aspect of the present invention, and wherein said controller is arranged for running said epitaxy process chamber in a cleaning mode, wherein parasitic grown silicon carbides on said at least one interior part in said epitaxy process chamber are removed in accordance with a cleaning method according to the first aspect of the present invention.
  • inter is meant the inner surfaces of the epitaxy process chamber for epitaxial growth of silicon carbide and the surfaces of the interior parts of said epitaxy process chamber that are inside said epitaxy process chamber.
  • the present cleaning method is elucidated below with a detailed description.
  • inter part a part, such as a carbon-based part or more in general, a carbon-based consumable part, inside an epitaxy process chamber that is exposed to a process of epitaxial silicon carbide deposition and as such susceptible to parasitic growth of silicon carbides.
  • pyrolytic carbon is meant a form of carbon that is produced through the process of pyrolysis, which involves heating a hydrocarbon to nearly its decomposition temperature and permitting the graphite to crystalize. This results in the formation of a material with a high degree of graphitic structure.
  • CDC carbide-derived carbon
  • metal carbide silicon carbide (SiC) or titanium carbide (TiC) serve as precursors. The selective removal of metal leaves behind a carbon structure with a porous and high surface area.
  • the CDC material may be present as a layer or film.
  • the formed CDC may even look like a crystal structure.
  • gaseous metal chlorides or fluorides may be formed as well. These are directly removed during the step 1a) of subjecting the interior part to the halogen-containing gas, e.g., the etching step.
  • said step 2) is done by subjecting said CDC material to an oxygencontaining gas at a temperature of from 390 to 670 °C, preferably 450 to 600 °C.
  • Step 2) may be conducted for 0.5 to 24 hours, preferably 3 to 12 hours, more preferably 5 to 10 hours.
  • said step 2) may be conducted once every 1 or 2 weeks or as soon as the parasitic grown silicon carbide layer thickness exceeds a certain predefined thickness, such as 300 pm.
  • silicon carbide SiC
  • SiC silicon carbide
  • said oxygen-containing gas may comprise an oxygen content up to 100 vol.%, such as from 15 to 50 vol.% or from 18 to 25 vol.%.
  • oxygencontaining gas examples include air, oxygen-enriched air, (pure) oxygen, oxygen mixed with one or more inert gases like argon, and nitrogen oxides, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), and dinitrogen tetroxide (N2O4).
  • nitrogen oxides such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), and dinitrogen tetroxide (N2O4).
  • the CDC material in step 2), may be removed by oxidizing the CDC material into carbon monoxide and carbon dioxide.
  • said step 2) may be done by subjecting said CDC material to a gas containing hydrogen and/or ammonia at a temperature of from 500 to 2300 °C, preferably 1000 to 1500 °C.
  • said step 2) may be done by mechanically removing, such as by mechanical polishing or grinding with metal or silicon carbide brushes, gas blowing/blasting, shock wave impulse cleaning, laser ablation, or plasma-assisted cleaning, said CDC material from said outer surface of said interior part.
  • said interior part further comprises a graphite core and said pyrolytic carbon coating is deposited on said graphite core.
  • said interior part is a wafer carrier, also known as a substrate carrier, susceptor, susceptor plate, teller, cover segment, half-moon, ring, upper or lower electrode, shower head, liner, wafer lift pin, pre-heat ring, planetary disc, spindle, spider, ceiling part, or cover segment.
  • a wafer carrier also known as a substrate carrier, susceptor, susceptor plate, teller, cover segment, half-moon, ring, upper or lower electrode, shower head, liner, wafer lift pin, pre-heat ring, planetary disc, spindle, spider, ceiling part, or cover segment.
  • said step 1 a) is conducted at a temperature of from 500 to 1450 °C, preferably 850 to 1200 °C.
  • Step 1a) or step 1b) may be conducted for 0.25 to 6 hours, preferably 1 to 4 hours. Furthermore, step 1a) or step 1b) may be conducted once or twice per week or as soon as the parasitic grown silicon carbide layer thickness exceeds a certain predefined thickness, such as 300 pm.
  • step 1 b) argon is used as inert gas.
  • said step 1 b) is conducted at a temperature of from 1500 to 2200 °C, preferably 1800 to 2000 °C and/or at a pressure of from 0.0001 to 250 mbar, preferably 0.1 to 100 mbar.
  • said step 1a) and/or step 2) is/are conducted at a pressure of from 100 to 1200 mbar, preferably 500 to 1100 mbar, more preferably 800 to 1050 mbar.
  • said halogen-containing gas is chlorine, bromine, or a combination of two or more thereof, which may be mixed with nitrogen, argon, helium, or a combination thereof, preferably chlorine or chlorine mixed with nitrogen or argon.
  • said step 1a), said step 1 b), and/or said step 2) is done in situ or ex situ.
  • the CDC material can be removed via multiple ways in step 2). Subjecting the CDC material to the oxygen-containing gas or to the gas containing hydrogen and/or ammonia to remove said CDC material can be done both in situ and ex situ.
  • the removing in step 2) may be done ex situ by mechanically removing, such as by mechanical polishing or grinding with metal or silicon carbide brushes, gas blowing/blasting, shock wave impulse cleaning, laser ablation, or plasma-assisted cleaning, said CDC material from said outer surface of said interior part.
  • the CDC material may be removed from the outer surface of the interior part by milling, turning, grinding, and polishing with loose or bonded grit.
  • Particle blasting e.g., sand blasting
  • said step 2) may be done ex situ by dry chemically cleaning or wet cleaning, such as by cleaning with steam or chemicals, water jet, liquid blasting, or ultrasonic cleaning, or by laser pulsing, plasma cleaning, compressive gas blowing, and plasma enhanced oxidation, using an oxygen plasma.
  • step 2) can be done in situ, for example by dry chemically removing the CDC material.
  • the density of the CDC layer is lower compared to the original SiC layer. This results in a relatively soft layer and therefore, making it relatively easy to remove the CDC layer manually, mechanically, or by blasting.
  • Said method may further comprise the step of:
  • washing and optionally drying of said interior part that is free or substantially free of said CDC material to obtain an interior part with reduced impurities and dust particles can be done with a liquid, such as demineralised or deionised water. Drying can be done in air under ambient conditions.
  • the interior part of the epitaxy process chamber for epitaxial growth of silicon carbide is specifically suitable for growing silicon carbide epitaxial layers on silicon carbide wafers, or silicon substrates, or graphite substrates.
  • AI2O3 may also be a possible substrate material, but is a less suitable material to be used as a substrate, because chloride can etch the AI2O3 in the presence of carbon:
  • said interior part comprises a graphite core that is selected from the group consisting of porous graphite, a graphite matrix, a carbon matrix containing other phases such as carbon fibres or particles.
  • said pyrolytic carbon coating is deposited on said interior part using chemical vapor deposition (CVD) or physical vapor deposition (PVD).
  • said pyrolytic carbon coating is deposited on said interior part using CVD and wherein a precursor gas containing a carbon source, such as methane or propane, is used, and/or a deposition temperature of from 900 to 2200 °C, preferably 1100 to 2000 °C, more preferably 1400 to 1900 °C.
  • a precursor gas containing a carbon source such as methane or propane
  • said pyrolytic carbon coating has a thickness of from 3 to 70 pm, preferably 5 to 50 pm, more preferably 5 to 25 pm, even more preferably 10 to 20 pm.
  • Fig. 1 shows a cleaning method for removing parasitic grown silicon carbides from an interior part
  • Fig. 2 shows an interior part comprising a pyrolytic carbon coating
  • Fig. 3 shows a cross-sectional view of an interior part comprising a pyrolytic carbon coating
  • Fig. 4 shows an interior part comprising a pyrolytic carbon coating on which a layer of silicon carbide is deposited
  • Fig. 5 shows an interior part comprising a pyrolytic carbon coating that has undergone two cycles of repeated silicon carbide deposition, etching, and oxidation.
  • Fig. 1 shows a flow chart of the cleaning method 1 for removing parasitic grown silicon carbides 101 from an interior part 103 of an epitaxy process chamber for epitaxial growth of silicon carbide.
  • the cleaning method 1 may comprise a first step 1a) of subjecting 3a the interior part 103 to a halogen-containing gas, such as chlorine gas, at a temperature of from 150 to 1700 °C to convert the parasitic grown silicon carbides 101 present on the interior part into carbide-derived carbon (CDC) material 107.
  • a halogen-containing gas such as chlorine gas
  • the cleaning method 1 may comprise a first step 1b) of subjecting 3b the interior part 103 to an inert gas, such as argon, at a temperature of from 1200 to 2400 °C and at a pressure of from 1x10 -10 to 500 mbar to convert the parasitic grown silicon carbides 101 present on the interior part into the CDC material 107.
  • an inert gas such as argon
  • a second step is removing 5 the CDC material 107, formed in the step of subjecting 3a, 3b, from the interior part 103 to obtain an outer surface 109 of the interior part 103 that is free of substantially free of the CDC material 107.
  • Fig. 2 shows an interior part 103 of an epitaxy process chamber for epitaxial growth of silicon carbide.
  • the interior part 103 comprises a graphite plate 101 coated with a layer of pyrolytic carbon (PyC) 105.
  • the PyC 105 is deposited onto the graphite substrate 101 through a high-temperature vapor deposition process.
  • the interior part 103 is arranged to be subjected to silicon carbide (SiC) deposition.
  • Fig. 3 shows a cross-sectional view of an interior part 103 that comprises a graphite plate 111 and is coated with a layer of PyC 105.
  • the PyC layer 105 on top of the graphite plate 111 , or graphite core, is clearly shown in the scanning electron microscopy (SEM) image and has an average thickness of approximately 7 to 8 pm.
  • the outer surface 109 of the interior part 103 is free of CDC material 107.
  • Fig. 4 shows an interior part 103 that comprises a graphite core 111 and a PyC coating 105.
  • Parasitic grown silicon carbides 101 is present on the surface of the interior part 103 as a silicon carbide coating having a thickness of approximately 100 pm.
  • the parasitic grown silicon carbide coating 101 is deposited onto the pyrolytic carbon- coated 105 graphite plate 111 using high-temperature chemical vapor deposition.
  • Fig. 5 shows an interior part 103, comprising a graphite plate 111 and a PyC coating 105.
  • the interior part 103 has undergone two cycles of repeated SiC deposition, subjecting 3a the interior part 103 coated with deposited SiC 101 , being parasitic grown SiC, to a halogen-containing gas to convert the parasitic grown SiC 101 into CDC material 107, and removing 5 the CDC material 107 from the interior part 103 to obtain an interior part 103, being a PyC 105 coated graphite plate 111 , having an outer surface 109 that is substantially free of the CDC material 107.

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Abstract

A cleaning method for removing parasitic grown silicon carbides from an interior part of an epitaxy process chamber for epitaxial growth of silicon carbide, said interior part comprising a pyrolytic carbon coating, said method comprising the steps of: 1a) subjecting said interior part to a halogen-containing gas at a temperature of from 150 to 1700 °C to convert said parasitic grown silicon carbides present on said interior part into carbide-derived carbon (CDC) material, wherein said halogen-containing gas does not consist of or contain chlorine trifluoride or fluorine gas, or 1b) subjecting said interior part to an inert gas at a temperature of from 1200 to 2400 °C and at a pressure of from 1x10-10 to 500 mbar to convert said parasitic grown silicon carbides present on said interior part into said CDC material; 2) removing said CDC material from said interior part to obtain an outer surface of said interior part that is free or substantially free of said CDC material. An interior part of an epitaxy process chamber for epitaxial growth of silicon carbide suitable to be cleaned by the cleaning method and an epitaxy process system, comprising a controller and an epitaxy process chamber, wherein said epitaxy process chamber comprises at least one interior part, and wherein said controller is arranged for running said epitaxy process chamber in a cleaning mode, wherein parasitic grown silicon carbides on said at least one interior part in said epitaxy process chamber are removed in accordance with the cleaning method.

Description

TITLE Cleaning method for removing parasitic grown silicon carbides and an interior part of an epitaxy process chamber and an epitaxy process system
TECHNICAL FIELD
The present invention relates to a cleaning method for removing parasitic grown silicon carbides from an interior part of an epitaxy process chamber for epitaxial growth of silicon carbide, to an interior part of an epitaxy process chamber, and to a and epitaxy process system.
BACKGROUND
The silicon carbide epitaxy equipment market is experiencing rapid growth, primarily driven by the increasing electrification of the automotive industry. However, a challenge arises during the chemical vapor deposition (CVD) process of the silicon carbide epitaxy layer on silicon carbide wafers. The epitaxy layer tends to deposit on both the surfaces of the wafer carrier or susceptor and the interior parts inside the chamber, even though this simultaneous deposition is unnecessary.
The accumulation of these parasitic or unnecessary silicon carbide layers, also known as parasitic grown silicon carbides, leads to the emission of particles and disruption of the gas flow, significantly impacting the quality of the epitaxial layer. Furthermore, the parasitic grown silicon carbides may lead to dimensional issues as the layers of the parasitic grown silicon carbides can grow very thick thereby hindering movement and/or placement of parts. Consequently, it becomes imperative to periodically remove these parasitic silicon carbide layers from the surfaces of the parts. This removal process cannot be achieved easily through chemical methods, mechanical methods, or a combination of both, ensuring the repeatability and continued usability of the parts.
Unlike the epitaxy of silicon, where frequent etching of parasitic silicon deposits can be removed using HCI, with a minimal impact on the surfaces that are polycrystalline silicon carbide (SiC) coated graphite that in turn are used to protect the process chamber from otherwise exposed graphite. The deterioration issue arises primarily due to the vulnerability of wafer susceptor or interior parts in the epitaxy chamber, such as graphite or silicon carbide-coated graphite, to etching and degradation in the high-temperature epitaxy environment containing hydrogen. During the epitaxy process, hydrogen gas is used in the etching or baking step prior to the silicon carbide deposition. This hydrogen gas attack can cause problems for uncoated porous graphite parts used in the epitaxy process chamber, resulting in carbon particle contamination within the chamber.
Moreover, uncoated graphite is porous and tends to trap and release impurities, thereby impacting the silicon carbide epitaxy's quality. In addition, when the temperature exceeds approximately 1450 °C, silicon atoms within the silicon carbide- coated graphite parts may escape from the silicon carbide coating surface and deposit onto the silicon carbide wafer surface, disrupting the silicon carbide epitaxy process.
To address these challenges, metallic carbide coatings, such as niobium carbide (NbC) and tantalum carbide (TaC), are utilized as a protective coating material. However, both NbC and TaC-coated graphite parts can be extremely expensive options. Moreover, these materials offer a better protection of the graphite as these do not sublime and leave TaC or NbC on the SiC wafer backside as SiC does when heated above 1600 °C.
To address the issue of cleaning parasitic grown silicon carbide layers or films from carbide-coated graphite parts or susceptors, a combination of chemical etch methods and mechanical methods is employed. In the US 11028474 B2 patent, a method is disclosed using a mixed gas containing fluorine gas and inert gas at temperatures ranging from 200 to 500 °C.
The thickness and distribution of the parasitic silicon carbide layer or particle-like layer on the graphite parts are often highly non-uniform. During the chemical cleaning process, incomplete removal of parasitic silicon carbide in one area may lead to the exposure of the graphite substrate to etching gases in another area. Both CIF3 and F2 gases can etch and degrade the graphite substrate. To protect the graphite, pyrolytic carbon (PyC) can be used as a coating on the substrate. Nevertheless, CIF3 and F2 gases still have the potential to etch the pyrolytic carbon layer. While it is possible to tune the etch process and introduce additional steps, the overall cleaning process becomes complex, and a precise temperature control is crucial.
Mechanical polishing or grinding of the parasitic grown silicon carbides from coated graphite parts is an extremely challenging task, inevitably having a risk of causing extensive surface damage to the coated parts, including silicon carbide-coated graphite, tantalum carbide-coated graphite, niobium carbide-coated graphite, and pyrolytic carbon-coated graphite parts. The existing methods, whether chemical or mechanical, for removing parasitic silicon carbide, result in damage to the tantalum carbide coating, original silicon carbide coating, pyrolytic carbon coating, and graphite part, thus reducing the lifetime of these coatings. Especially, the mechanical grinding method used to remove parasitic silicon carbide layer from tantalum carbide coated graphite parts is being unacceptable now.
To protect the graphite parts used inside the chamber of silicon carbide epitaxy process, silicon carbide coating and tantalum carbide coating are deposited on the surfaces of the graphite parts, but the current cleaning work of the parasitic silicon carbide layer or particles on the protective coating surface with CIF3, NF3 or CI2, HCI etc. and even mechanical machining always damage both protective layers (silicon carbide and tantalum carbide layers), and therefore the lifetime of both silicon carbide coated graphite parts and tantalum carbide coated parts are short.
Therefore, there exists a need for a solution to remove parasitic grown silicon carbides from the surfaces of interior parts and/or the inside of the epitaxy process chamber that is used for epitaxial growth of silicon carbide that solves one or more of the above- mentioned problems. OBJECTIVE
It is therefore an object of the invention to provide for an improved cleaning method for removing parasitic grown silicon carbides from an interior part of an epitaxy process chamber.
SUMMARY
The foregoing object is achieved according to a first aspect of the present invention that relates to a cleaning method for removing parasitic grown silicon carbides from an interior part of an epitaxy process chamber for epitaxial growth of silicon carbide, said interior part comprising a pyrolytic carbon coating, said method comprising the steps of: la) subjecting said interior part to a halogen-containing gas at a temperature of from 150 to 1700 °C to convert said parasitic grown silicon carbides present on said interior part into carbide-derived carbon (CDC) material, wherein said halogencontaining gas does not consist of or contain chlorine trifluoride or fluorine gas, or l b) subjecting said interior part to an inert gas at a temperature of from 1200 to 2400 °C and at a pressure of from 1x1 O'10 to 500 mbar to convert said parasitic grown silicon carbides present on said interior part into said CDC material;
2) removing said CDC material from said interior part to obtain an outer surface of said interior part that is free or substantially free of said CDC material.
A pyrolytic carbon (PyC) layer is used as a protective layer on the interior part. The PyC layer seals the porous surface of the interior part and reduces the likelihood of impurities becoming trapped and later released from the pores. Furthermore, the PyC layer shields the interior part from chemical attack during etching processes, thereby minimizing damage during the etch process of the silicon carbide wafer in which hydrogen gas is used.
Compared to depositing silicon carbide, niobium carbide, or tantalum carbide as a coating on graphite, it is less complex and more economical to deposit the PyC layer on the interior part. The cleaning method according to the present invention removes the parasitic grown silicon carbides from the interior part’s surface without damaging the pyrolytic carbon coating on the interior part. Therefore, the pyrolytic carbon coated interior part can be reused multiple times for the silicon carbide epitaxy process.
With the cleaning method according to the invention, a less complex method is provided that uses a halogen-containing gas, such as chlorine gas, to convert the parasitic silicon grown carbides deposited on the surface of the pyrolytic carbon coated interior parts to carbon. These so-called carbide-derived carbon (CDC) layers can be removed from the PyC-coated interior part’s surface at relatively easy and at relatively mild conditions without damaging the PyC coating.
Furthermore, the claimed method provides the possibility to apply a high temperature in the first step of the cleaning method. This has the benefit that the overall time needed for the cleaning process to complete can be strongly reduced compared to known cleaning processes, because a higher temperature in the first step results in faster conversion of the SiC to the CDC material and reduces the cooldown time between the SiC deposition in the CVD process and the first step of the claimed cleaning method.
As said, mechanical polishing or grinding of parasitic grown silicon carbides from coated graphite parts is an extremely challenging task, having the risk of causing extensive surface damage to the coated parts. However, the CDC material is a much softer material compared to the parasitic grown silicon carbides and this results in that mechanically - and also manually - removing the CDC material from the interior part strongly reduces the risk of damaging the interior parts. In other words, due to the cleaning method according to the invention, mechanical removing of the CDC material becomes a more attractive option.
There exist other methods to convert the parasitic grown SiC to the CDC material, like hydrothermal decomposition, but such methods might damage the PyC coating during the process due to the formation of SiC>2. It would be very complex to prevent this. The first step of the cleaning method, thus any of step 1a) and step 1 b), not only enables mechanically/manually removing the CDC material, but it also enables removing the CDC chemically not damaging the coating by using a pyrolytic carbon coating instead of a conventional metal carbide coating, such as silicon carbide or tantalum carbide.
A benefit of step 1a) is that the resulting CDC material retains the original shape and crystalline surface morphology of silicon carbide (SiC), but with silicon atoms removed from the crystal structure, resulting in atomic vacancies. This unique crystalline structure of the CDC material exhibits different oxidation behaviour compared to the pyrolytic carbon coating on the interior part.
A benefit of step 1b) is that there is no need for the epitaxy process system or parts thereof to be adapted for a halogen-containing gas, like CI2. Possibly, the system or parts thereof merely needs limited redesign for it to be withstand temperatures above 1600 °C.
The oxidation onset temperature of the CDC material obtained in both step 1a) and step 1 b) is significantly lower than that of graphite and pyrolytic carbon. Consequently, the CDC material can be effectively removed from the pyrolytic carbon coating surface, for example by oxidizing it using an oxygen-containing gas, while minimizing oxidation of the pyrolytic carbon and graphite. This not only enables the repeated use of a pyrolytic carbon-coated graphite part without significant surface damage to the interior part, but also enables in situ cleaning of the interior part.
The cleaning method allows the use of an interior part comprising a coating of pyrolytic carbon instead of a coating of, for example, silicon carbide or tantalum carbide. Depositing a protective pyrolytic carbon layer on the interior part strongly reduces the costs for producing interior parts, compared to the production of an interior part that includes depositing a silicon carbide or tantalum carbide layer on the interior part.
Furthermore, the PyC coated interior parts can be reused multiple times for silicon carbide epitaxy, enabling long lifetime. A second aspect of the present invention relates to an interior part of an epitaxy process chamber for epitaxial growth of silicon carbide suitable to be cleaned by a cleaning method according to the first aspect of the present invention, said interior part comprising a pyrolytic carbon coating, wherein said interior part is arranged to be subjected to said cleaning method, and/or wherein said interior part is cleaned according to said cleaning method, and/or an interior part contaminated with parasitic grown silicon carbides arranged to be subjected to said cleaning method. Said interior part may also comprise a diamond-like carbon layer or a glass carbon layer instead of said pyrolytic carbon layer, or a combination of the foregoing types of carbon layers.
A third aspect of the present invention relates to an epitaxy process system, comprising a controller and a epitaxy process chamber, wherein said epitaxy process chamber comprises at least one interior part according to the second aspect of the present invention, and wherein said controller is arranged for running said epitaxy process chamber in a cleaning mode, wherein parasitic grown silicon carbides on said at least one interior part in said epitaxy process chamber are removed in accordance with a cleaning method according to the first aspect of the present invention.
In the present disclosure, with “interior” is meant the inner surfaces of the epitaxy process chamber for epitaxial growth of silicon carbide and the surfaces of the interior parts of said epitaxy process chamber that are inside said epitaxy process chamber.
Corresponding embodiments disclosed below for the first aspect are also applicable for the interior part of an epitaxy process chamber (second aspect) and the device for cleaning of an interior of an epitaxy process chamber (third aspect) according to the present invention, unless stated otherwise.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The present cleaning method is elucidated below with a detailed description.
In the present description, with “interior part” is meant a part, such as a carbon-based part or more in general, a carbon-based consumable part, inside an epitaxy process chamber that is exposed to a process of epitaxial silicon carbide deposition and as such susceptible to parasitic growth of silicon carbides.
In the present description, with “pyrolytic carbon” is meant a form of carbon that is produced through the process of pyrolysis, which involves heating a hydrocarbon to nearly its decomposition temperature and permitting the graphite to crystalize. This results in the formation of a material with a high degree of graphitic structure.
In the present description, with “carbide-derived carbon” (CDC) is meant any form of carbon material that is produced by selectively removing metal atoms, like Si or Ti, from a metal carbide, for example through a process called etching or extraction. Typically, metal carbides like silicon carbide (SiC) or titanium carbide (TiC) serve as precursors. The selective removal of metal leaves behind a carbon structure with a porous and high surface area.
In an embodiment, the CDC material, or residuals or species, may be present as a layer or film. The formed CDC may even look like a crystal structure. In step 1a), besides the formation of CDC material, gaseous metal chlorides or fluorides may be formed as well. These are directly removed during the step 1a) of subjecting the interior part to the halogen-containing gas, e.g., the etching step.
In an embodiment, said step 2) is done by subjecting said CDC material to an oxygencontaining gas at a temperature of from 390 to 670 °C, preferably 450 to 600 °C. Step 2) may be conducted for 0.5 to 24 hours, preferably 3 to 12 hours, more preferably 5 to 10 hours. Furthermore, said step 2) may be conducted once every 1 or 2 weeks or as soon as the parasitic grown silicon carbide layer thickness exceeds a certain predefined thickness, such as 300 pm.
In the present disclosure, with "parasitic grown silicon carbide" is meant silicon carbide (SiC) deposited on surfaces in the reactor area not being the SiC wafer, thus on surfaces of the epitaxy process chamber or on surfaces of the interior parts. It may be present as a layer or (poly crystalline) film and once said layer or film becomes thicker - 1 few mm in thickness - it may have a shape like broccoli flower. In an embodiment, said oxygen-containing gas may comprise an oxygen content up to 100 vol.%, such as from 15 to 50 vol.% or from 18 to 25 vol.%. Examples of the oxygencontaining gas are air, oxygen-enriched air, (pure) oxygen, oxygen mixed with one or more inert gases like argon, and nitrogen oxides, such as nitrous oxide (N2O), nitric oxide (NO), nitrogen dioxide (NO2), and dinitrogen tetroxide (N2O4).
In an embodiment, in step 2), the CDC material may be removed by oxidizing the CDC material into carbon monoxide and carbon dioxide.
In an alternative embodiment, said step 2) may be done by subjecting said CDC material to a gas containing hydrogen and/or ammonia at a temperature of from 500 to 2300 °C, preferably 1000 to 1500 °C.
In another alternative embodiment, said step 2) may be done by mechanically removing, such as by mechanical polishing or grinding with metal or silicon carbide brushes, gas blowing/blasting, shock wave impulse cleaning, laser ablation, or plasma-assisted cleaning, said CDC material from said outer surface of said interior part.
In an embodiment, said interior part further comprises a graphite core and said pyrolytic carbon coating is deposited on said graphite core.
In an embodiment, said interior part is a wafer carrier, also known as a substrate carrier, susceptor, susceptor plate, teller, cover segment, half-moon, ring, upper or lower electrode, shower head, liner, wafer lift pin, pre-heat ring, planetary disc, spindle, spider, ceiling part, or cover segment.
In an embodiment, said step 1 a) is conducted at a temperature of from 500 to 1450 °C, preferably 850 to 1200 °C.
Step 1a) or step 1b) may be conducted for 0.25 to 6 hours, preferably 1 to 4 hours. Furthermore, step 1a) or step 1b) may be conducted once or twice per week or as soon as the parasitic grown silicon carbide layer thickness exceeds a certain predefined thickness, such as 300 pm.
In an embodiment, in step 1 b) argon is used as inert gas.
In an embodiment, said step 1 b) is conducted at a temperature of from 1500 to 2200 °C, preferably 1800 to 2000 °C and/or at a pressure of from 0.0001 to 250 mbar, preferably 0.1 to 100 mbar.
In an embodiment, said step 1a) and/or step 2) is/are conducted at a pressure of from 100 to 1200 mbar, preferably 500 to 1100 mbar, more preferably 800 to 1050 mbar.
In an embodiment, said halogen-containing gas is chlorine, bromine, or a combination of two or more thereof, which may be mixed with nitrogen, argon, helium, or a combination thereof, preferably chlorine or chlorine mixed with nitrogen or argon.
In an embodiment, said step 1a), said step 1 b), and/or said step 2) is done in situ or ex situ.
The CDC material can be removed via multiple ways in step 2). Subjecting the CDC material to the oxygen-containing gas or to the gas containing hydrogen and/or ammonia to remove said CDC material can be done both in situ and ex situ. The removing in step 2) may be done ex situ by mechanically removing, such as by mechanical polishing or grinding with metal or silicon carbide brushes, gas blowing/blasting, shock wave impulse cleaning, laser ablation, or plasma-assisted cleaning, said CDC material from said outer surface of said interior part.
The CDC material may be removed from the outer surface of the interior part by milling, turning, grinding, and polishing with loose or bonded grit. Particle blasting, e.g., sand blasting, whereas instead of sand any material with a hardness in between graphite and CDC can be used, can also be used to remove the CDC material. Alternatively, said step 2) may be done ex situ by dry chemically cleaning or wet cleaning, such as by cleaning with steam or chemicals, water jet, liquid blasting, or ultrasonic cleaning, or by laser pulsing, plasma cleaning, compressive gas blowing, and plasma enhanced oxidation, using an oxygen plasma.
As another alternative, step 2) can be done in situ, for example by dry chemically removing the CDC material.
As the remaining CDC layer mainly keeps the same volume and topography as the original SiC, the density of the CDC layer is lower compared to the original SiC layer. This results in a relatively soft layer and therefore, making it relatively easy to remove the CDC layer manually, mechanically, or by blasting.
Said method may further comprise the step of:
3) washing and optionally drying of said interior part that is free or substantially free of said CDC material to obtain an interior part with reduced impurities and dust particles. Washing can be done with a liquid, such as demineralised or deionised water. Drying can be done in air under ambient conditions.
The interior part of the epitaxy process chamber for epitaxial growth of silicon carbide is specifically suitable for growing silicon carbide epitaxial layers on silicon carbide wafers, or silicon substrates, or graphite substrates.
Alumina (AI2O3) may also be a possible substrate material, but is a less suitable material to be used as a substrate, because chloride can etch the AI2O3 in the presence of carbon:
Figure imgf000013_0001
In an embodiment, said interior part comprises a graphite core that is selected from the group consisting of porous graphite, a graphite matrix, a carbon matrix containing other phases such as carbon fibres or particles. In an embodiment, said pyrolytic carbon coating is deposited on said interior part using chemical vapor deposition (CVD) or physical vapor deposition (PVD).
In an embodiment, said pyrolytic carbon coating is deposited on said interior part using CVD and wherein a precursor gas containing a carbon source, such as methane or propane, is used, and/or a deposition temperature of from 900 to 2200 °C, preferably 1100 to 2000 °C, more preferably 1400 to 1900 °C.
In an embodiment, said pyrolytic carbon coating has a thickness of from 3 to 70 pm, preferably 5 to 50 pm, more preferably 5 to 25 pm, even more preferably 10 to 20 pm.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is described hereinafter with reference to the accompanying drawings in which embodiments are shown and in which like reference numbers indicate the same or similar elements. The invention is in no manner whatsoever limited to the embodiments disclosed therein.
Fig. 1 shows a cleaning method for removing parasitic grown silicon carbides from an interior part;
Fig. 2 shows an interior part comprising a pyrolytic carbon coating;
Fig. 3 shows a cross-sectional view of an interior part comprising a pyrolytic carbon coating;
Fig. 4 shows an interior part comprising a pyrolytic carbon coating on which a layer of silicon carbide is deposited;
Fig. 5 shows an interior part comprising a pyrolytic carbon coating that has undergone two cycles of repeated silicon carbide deposition, etching, and oxidation.
DETAILED DESCRIPTION OF THE DRAWINGS
Fig. 1 shows a flow chart of the cleaning method 1 for removing parasitic grown silicon carbides 101 from an interior part 103 of an epitaxy process chamber for epitaxial growth of silicon carbide. The cleaning method 1 may comprise a first step 1a) of subjecting 3a the interior part 103 to a halogen-containing gas, such as chlorine gas, at a temperature of from 150 to 1700 °C to convert the parasitic grown silicon carbides 101 present on the interior part into carbide-derived carbon (CDC) material 107.
As an alternative to said step 1a), the cleaning method 1 may comprise a first step 1b) of subjecting 3b the interior part 103 to an inert gas, such as argon, at a temperature of from 1200 to 2400 °C and at a pressure of from 1x10-10 to 500 mbar to convert the parasitic grown silicon carbides 101 present on the interior part into the CDC material 107.
A second step is removing 5 the CDC material 107, formed in the step of subjecting 3a, 3b, from the interior part 103 to obtain an outer surface 109 of the interior part 103 that is free of substantially free of the CDC material 107.
Fig. 2 shows an interior part 103 of an epitaxy process chamber for epitaxial growth of silicon carbide. The interior part 103 comprises a graphite plate 101 coated with a layer of pyrolytic carbon (PyC) 105. The PyC 105 is deposited onto the graphite substrate 101 through a high-temperature vapor deposition process. The interior part 103 is arranged to be subjected to silicon carbide (SiC) deposition.
Fig. 3 shows a cross-sectional view of an interior part 103 that comprises a graphite plate 111 and is coated with a layer of PyC 105. The PyC layer 105 on top of the graphite plate 111 , or graphite core, is clearly shown in the scanning electron microscopy (SEM) image and has an average thickness of approximately 7 to 8 pm. The outer surface 109 of the interior part 103 is free of CDC material 107.
Fig. 4 shows an interior part 103 that comprises a graphite core 111 and a PyC coating 105. Parasitic grown silicon carbides 101 is present on the surface of the interior part 103 as a silicon carbide coating having a thickness of approximately 100 pm. The parasitic grown silicon carbide coating 101 is deposited onto the pyrolytic carbon- coated 105 graphite plate 111 using high-temperature chemical vapor deposition.
Fig. 5 shows an interior part 103, comprising a graphite plate 111 and a PyC coating 105. The interior part 103 has undergone two cycles of repeated SiC deposition, subjecting 3a the interior part 103 coated with deposited SiC 101 , being parasitic grown SiC, to a halogen-containing gas to convert the parasitic grown SiC 101 into CDC material 107, and removing 5 the CDC material 107 from the interior part 103 to obtain an interior part 103, being a PyC 105 coated graphite plate 111 , having an outer surface 109 that is substantially free of the CDC material 107.
Modifications and additions to the embodiments disclosed above are obvious to those skilled in the art and covered by the scope of the appended claims. Embodiments and examples of the first aspect of the present invention are also applicable to the second and third aspects of the present invention.
Other variations to the disclosed embodiments can be understood and effected by those skilled in the art in practicing the claimed invention, from a study of the drawings, the disclosure, and the appended claims. In the claims, the word “comprising” does not exclude other elements or steps, and the indefinite article “a” or “an” does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. Any reference signs in the claims should not be construed as limiting the scope thereof. One or more of the objects of the invention are achieved by the appended claims.

Claims

1. A cleaning method (1) for removing parasitic grown silicon carbides (101) from an interior part (103) of an epitaxy process chamber for epitaxial growth of silicon carbide, said interior part comprising a pyrolytic carbon coating (105), said method (1) comprising the steps of: la) subjecting (3a) said interior part to a halogen-containing gas at a temperature of from 150 to 1700 °C to convert said parasitic grown silicon carbides (101) present on said interior part (103) into carbide-derived carbon (CDC) material (107), wherein said halogen-containing gas does not consist of or contain chlorine trifluoride or fluorine gas, or l b) subjecting (3b) said interior part (103) to an inert gas at a temperature of from 1200 to 2400 °C and at a pressure of from 1x1O'10 to 500 mbar to convert said parasitic grown silicon carbides (101) present on said interior part (103) into said CDC material (107);
2) removing (5) said CDC material (107) from said interior part (103) to obtain an outer surface (109) of said interior part (103) that is free or substantially free of said CDC material (107).
2. Cleaning method (1) according to claim 1 , wherein said step 2) is done by subjecting said CDC material (107) to an oxygen-containing gas at a temperature of from 390 to 670 °C, preferably 450 to 600 °C.
3. Cleaning method (1) according to claim 1 , wherein said step 2) is done by subjecting said CDC material (107) to a gas containing hydrogen and/or ammonia at a temperature of from 500 to 2300 °C, preferably 1000 to 1500 °C.
4. Cleaning method (l)according to claim 1 , wherein said step 2) is done by mechanically removing, such as by mechanical polishing or grinding with metal or silicon carbide brushes, gas blowing/blasting, shock wave impulse cleaning, laser ablation, or plasma-assisted cleaning, said CDC material (107) from said outer surface
Figure imgf000017_0001
5. Cleaning method (1) according to any of the preceding claims, wherein said interior part (103) further comprises a graphite core (111) and said pyrolytic carbon coating (105) is deposited on said graphite core (111).
6. Cleaning method (1) according to any of the preceding claims, wherein said interior part (103) is a wafer carrier, also known as a substrate carrier, susceptor, susceptor plate, teller, cover segment, half-moon, ring, upper or lower electrode, shower head, liner, wafer lift pin, pre-heat ring, planetary disc, spindle, spider, ceiling part, or cover segment.
7. Cleaning method (1) according to any of the preceding claims, wherein said step 1a) is conducted at a temperature of from 500 to 1450 °C, preferably 850 to 1200 °C.
8. Cleaning method (1) according to any of the preceding claims, wherein said step 1 b) is conducted at a temperature of from 1500 to 2200 °C, preferably 1800 to 2000 °C, and/or at a pressure of from 0,001 to 250 mbar, preferably 0,1 to 100 mbar.
9. Cleaning method (1) according to any of the preceding claims, wherein said step 1a) and/or step 2) is/are conducted at a pressure of from 100 to 1200 mbar, preferably 500 to 1100 mbar, more preferably 800 to 1050 mbar.
10. Cleaning method (1) according to any of the preceding claims, wherein said halogen-containing gas is chlorine, bromine, or a combination of two or more thereof, which may be mixed with nitrogen, argon, helium, or a combination thereof, preferably chlorine or chlorine mixed with nitrogen or argon.
11. Cleaning method (1) according to any of the preceding claims, wherein said step 1a), said step 1 b), and/or said step 2) is done in situ or ex situ.
12. An interior part (103) of an epitaxy process chamber for epitaxial growth of silicon carbide (101) suitable to be cleaned by a cleaning method (1) according to any of the preceding claims, said interior part (103) comprising a pyrolytic carbon coating (105), wherein said interior part (103) is arranged to be subjected to said cleaning method (1), and/or wherein said interior part (103) is cleaned according to said cleaning method (1), and/or an interior part (103) contaminated with parasitic grown silicon carbides (101) arranged to be subjected to said cleaning method (1).
13. Interior part (103) according to claim 12, wherein said interior part (103) comprises a graphite core (111) that is selected from the group consisting of porous graphite, a graphite matrix, a carbon matrix containing other phases such as carbon fibres or particles.
14. Interior part (103) according to claim 12 or 13, wherein said pyrolytic carbon coating (105) is deposited on said interior part (103) using chemical vapor deposition (CVD) or physical vapor deposition (PVD).
15. Interior part (103) according to any of the claims 12 to 14, wherein said pyrolytic carbon coating (105) is deposited using CVD on said interior part (103) and wherein a precursor gas containing a carbon source, such as methane or propane, is used, and/or a deposition temperature of from 900 to 2200 °C, preferably 1100 to 2000 °C, more preferably 1400 to 1900 °C.
16. Interior part (103) according to any of the claims 12 to 15, wherein said pyrolytic carbon coating (105) has a thickness of from 3 to 70 pm, preferably 5 to 50 pm, more preferably 8 to 25 pm, more preferably 10 to 20 pm.
17. An epitaxy process system, comprising a controller and a epitaxy process chamber, wherein said epitaxy process chamber comprises at least one interior part (103) according to any of the claims 12 to 16, and wherein said controller is arranged for running said epitaxy process chamber in a cleaning mode, wherein parasitic grown silicon carbides (101) on said at least one interior part (103) in said epitaxy process chamber are removed in accordance with a cleaning method (1) according to any of the claims 1 to 11.
PCT/NL2023/050682 2023-12-22 2023-12-22 Cleaning method for removing parasitic grown silicon carbides and an interior part of an epitaxy process chamber and an epitaxy process system Pending WO2025136086A1 (en)

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US20160002574A1 (en) * 2013-02-14 2016-01-07 Central Glass Company, Limited Cleaning Gas and Cleaning Method
US20160172215A1 (en) * 2014-12-12 2016-06-16 Tokai Carbon Korea Co., Ltd Method for repairing semiconductor processing components
US11028474B2 (en) 2015-12-28 2021-06-08 Showa Denko K.K. Method for cleaning SiC monocrystal growth furnace
US20210285100A1 (en) * 2016-08-31 2021-09-16 National University Corporation Yokohama National University Method for cleaning semiconductor production chamber
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