EP4182490A1 - Procédé et dispositif pour le revêtement de parois externes et/ou de parois internes de corps creux - Google Patents

Procédé et dispositif pour le revêtement de parois externes et/ou de parois internes de corps creux

Info

Publication number
EP4182490A1
EP4182490A1 EP21749105.9A EP21749105A EP4182490A1 EP 4182490 A1 EP4182490 A1 EP 4182490A1 EP 21749105 A EP21749105 A EP 21749105A EP 4182490 A1 EP4182490 A1 EP 4182490A1
Authority
EP
European Patent Office
Prior art keywords
magnetic field
plasma
hollow body
coils
process chamber
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.)
Pending
Application number
EP21749105.9A
Other languages
German (de)
English (en)
Inventor
Montgomery Jaritz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rheinisch Westlische Technische Hochschuke RWTH
Original Assignee
Rheinisch Westlische Technische Hochschuke RWTH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rheinisch Westlische Technische Hochschuke RWTH filed Critical Rheinisch Westlische Technische Hochschuke RWTH
Publication of EP4182490A1 publication Critical patent/EP4182490A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C23C16/04—Coating on selected surface areas, e.g. using masks
    • C23C16/045—Coating cavities or hollow spaces, e.g. interior of tubes; Infiltration of porous substrates
    • 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
    • C23C16/40—Oxides
    • C23C16/401—Oxides containing silicon
    • 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
    • C23C16/50—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 using electric discharges
    • 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
    • C23C16/50—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 using electric discharges
    • C23C16/511—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 using electric discharges using microwave discharges
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32192—Microwave generated discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32009—Arrangements for generation of plasma specially adapted for examination or treatment of objects, e.g. plasma sources
    • H01J37/32403—Treating multiple sides of workpieces, e.g. 3D workpieces
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32458—Vessel
    • H01J37/32513—Sealing means, e.g. sealing between different parts of the vessel
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3266—Magnetic control means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/3266—Magnetic control means
    • H01J37/32669—Particular magnets or magnet arrangements for controlling the discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32816—Pressure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32917—Plasma diagnostics
    • H01J37/32935—Monitoring and controlling tubes by information coming from the object and/or discharge
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/18—Vacuum control means
    • H01J2237/182—Obtaining or maintaining desired pressure
    • H01J2237/1825—Evacuating means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
    • H01J2237/245—Detection characterised by the variable being measured
    • H01J2237/24571—Measurements of non-electric or non-magnetic variables
    • H01J2237/24578—Spatial variables, e.g. position, distance

Definitions

  • the invention relates to a method for coating the outer and/or inner walls of hollow bodies made of an electrically non-conductive material, in particular plastic bottles or canisters, preferably made of PE (HD-PE, LD-PE), PET, PP, PC or PLA , in which the hollow body is inserted into a process chamber which is divided by the hollow body into an inner and an outer reaction chamber, with at least one process gas being introduced into one of the two reaction chambers at a process pressure, while the other of the two reaction chambers is pressurized to a pressure which is less than or equal to is kept greater than the process pressure and wherein a plasma is generated in the reaction space kept under process pressure and fragments and/or reaction products formed in the plasma are separated from the at least one process gas to form a layer on the side of the wall of the hollow body that faces the plasma.
  • PE high-PE, LD-PE
  • PET polyethylene
  • PP polyethylene
  • PC PC or PLA
  • the invention also relates to a device for coating the outer and/or inner walls of hollow bodies made of an electrically non-conductive material, in particular plastic bottles or canisters, comprising a process chamber into which the hollow body can be inserted and which from the hollow body inserted into an inner and an outer reaction chamber, at least one vacuum pump with which the reaction chambers can be evacuated, in particular optionally, at least one process gas feed line, by means of which at least one process gas can be introduced, in particular optionally, into one of the reaction chambers, in particular by means of the in connection with the at least one vacuum pump a process pressure with the at least one process gas in one of at least one energy generating unit, in particular at least one microwave generator, with which energy can be radiated, in particular selectively, into one of the two reaction chambers to generate a plasma.
  • the energy for igniting the plasma is preferably radiated from a reaction space in which no plasma ignites, through the hollow body into the reaction space in which the plasma is to be ignited.
  • the irradiated reaction space is kept at a pressure that is lower than the process pressure.
  • Such a device can be used to alternatively provide the inner wall or the outer wall or both sequentially with a layer, in particular to use the layer to deposit a diffusion barrier or other functional layer on the respective wall from at least one process gas comprising precursors on a respective wall.
  • a gas containing gaseous monomers can be used as a process gas.
  • a process gas for example, it is known to deposit SiOx as a diffusion barrier on a hollow body, e.g. bottles, from a process gas mixture containing hexamethyldisiloxane (HMDSO) and oxygen as precursors.
  • HMDSO hexamethyldisiloxane
  • the invention preferably makes use of this application as well, but is not limited to it.
  • Other process gases are e.g. hexamethyldisilazane (HMDSN), silane (S1H4), ethyne (C2H2), methane (CH4), difluoroethylene (C2H2F2) or similar.
  • a process pressure that is lower than the surrounding atmospheric pressure is generated in the reaction space, which contains the process gas or into which the process gas is supplied, in order to create conditions for a plasma.
  • this process pressure is in the range from 10 Pa to 30 Pa.
  • a plasma is generated by irradiating energy, for example microwave radiation, which is generated by the energy generating unit.
  • the plasma fragments the at least one process gas.
  • the fragments and/or reaction products formed from the fragments are deposited as a layer on the wall of the hollow body that faces the plasma.
  • this is evacuated, for example, to a pressure that is lower than the process pressure.
  • this pressure is less than 10 Pa, preferably less than or equal to 5 Pa.
  • the energy is supplied by irradiating microwaves into the reaction space containing the process gas, preferably through the other reaction space.
  • the procedure of the invention is the same, but not limited to this.
  • any electromagnetic radiation can be generated by at least one signal generator of the energy generating unit, which generates radiation with a frequency that is suitable for igniting the plasma with the selected process gas.
  • the radiation can preferably be matched to the absorption bands of the process gas used. More preferably, the radiation can be irradiated in a pulsed manner.
  • a signal generator used in particular one each for inner and outer coating, can be designed as a module in which the components for generating and irradiating the electromagnetic radiation are combined, with each module being arranged exclusively in the reaction space in which no plasma ignites.
  • a respective signal generator can generate electromagnetic waves in the microwave band and/or the HF band.
  • the plasma Due to the large extent of the plasma, there is still a large energy requirement in order to generate a sufficient energy density throughout the plasma. This is relevant on the one hand for large hollow bodies and on the other hand for external coatings, since here the plasma is not limited by the inner volume of the hollow body, but rather by the process chamber surrounding the hollow body, which is always larger than the hollow body.
  • This object is also achieved in the above-mentioned method, inter alia, in that the plasma is influenced with regard to at least one operating parameter by means of a magnetic field penetrating the process chamber, in particular both reaction chambers.
  • the object is achieved in the device in that it comprises at least one element with which a magnetic field penetrating the process chamber can be generated, in particular for influencing the plasma that can be generated with regard to at least one parameter of the plasma.
  • the at least one element with which a magnetic field penetrating the process chamber can be generated is preferably at least one element that is provided in addition to the power generation unit and/or in addition to devices that interact with the power generation unit during plasma generation and with which the plasma is generated .
  • it can be provided, especially when microwaves are preferably used for plasma generation, that electromagnetic radiation is generated with the microwaves, with which a time-varying, in particular with the frequency of the microwaves, time-varying radiation magnetic field is generated.
  • the invention therefore provides that the magnetic field penetrating the process chamber for influencing the plasma is different, or is generated with different devices, than the possibly existing magnetic field with which the plasma is generated.
  • the magnetic field, which influences the plasma in the process chamber can thus be adjusted and/or changed separately from the plasma generation, in order in this way to enable the plasma generated to be influenced.
  • the magnetic field with which the plasma is influenced can preferably be static over time, preferably at least during the existence of a plasma or if it changes over time, have a lower frequency of change over time compared to the plasma-generating magnetic field.
  • the invention makes use here of the fact that the ions of the fragments and/or reactive products of the one or more process gases that are present in the plasma can be deflected by a magnetic field, and in particular can therefore be influenced. There is thus the possibility of exerting an influence on the plasma with regard to one or more parameters by means of a magnetic field which penetrates the process chamber during the implementation of the method and thus also penetrates the two reaction chambers, in particular the one in which the plasma is present.
  • the magnetic field causes the ions to accelerate along the magnetic field lines due to the Lorentz force.
  • This leads to spatial flomogenization of the plasma in particular by which is meant that greater homogeneity is achieved under the effect of the magnetic field compared to a plasma without an active magnetic field.
  • the homogeneity can be observed at a constant distance along the wall of the hollow body to be coated. This effect is particularly advantageous in the case of comparatively large hollow bodies.
  • the magnetic field can be chosen such that in a given longitudinal direction of the hollow body, in which it has its greatest extent, the field lines run predominantly in this longitudinal direction. This can be achieved, for example, if the poles of the generated magnetic field are spaced apart in this longitudinal direction. Accordingly, the magnetic field generating elements can be positioned on the device to effect this.
  • the invention can also provide for the energy density of the plasma to be increased by the magnetic field, in particular with a greater energy density being achieved under the effect of the magnetic field in comparison to a plasma without an active magnetic field. In this way, the energy requirement can be reduced, particularly in the case of comparatively large hollow bodies.
  • the local position of the plasma can be influenced with the magnetic field. This is preferably done in such a way that the effect of the magnetic field keeps the plasma at a greater distance from the process chamber wall and/or elements in the process chamber compared to the distance that would exist without an active magnetic field. It is precisely this that leads to the plasma being restricted to an area directly around the hollow body to be coated. The plasma is therefore closer to the hollow body in comparison to the plasma without a magnetic field. Due to the effect of the magnetic field, a co-coating of the process chamber or of elements in the process chamber can be reduced or advantageously completely prevented, particularly in the case of layer deposits on the outer wall of the hollow body. As a result, the exterior wall coating can be carried out much more economically than was previously possible.
  • At least one sensor preferably an optical sensor, in particular a camera
  • the local position of the plasma generated is detected in particular during the influence of the magnetic field
  • the at least one element generating the magnetic field is controlled, in particular in order to influence or change the magnetic field depending on this data.
  • a regulation can be implemented in this way that keeps the plasma at a predetermined minimum distance or within a predetermined distance range from the wall of the hollow body to be coated and/or from the process chamber wall.
  • the invention can offer a high degree of flexibility for the coating system with regard to the container sizes and geometries to be coated.
  • the plasma can be flexibly adapted to the geometry of the container, both for the inner and outer coating.
  • a further possible embodiment of the invention can therefore provide that the expansion and intensity of the plasma influenced by the magnetic field lines is detected by the aforementioned at least one optical sensor, preferably an imaging sensor, such as a CCD or infrared camera system, and feedback of this Data is made with the coil system.
  • an imaging sensor such as a CCD or infrared camera system
  • the magnetic field and thus the plasma can be flexibly adapted to any container geometry and size during the process and be calibrated.
  • a coil can preferably be used as an element generating a magnetic field. This has the advantage of being able to have a direct influence on the magnetic field strength through the current strength. Plasma parameters can thus be changed by changing the current supply.
  • the current supply can preferably be selected depending on the shape and/or size of the flotation body to be coated. In this way, the device and the method can be individually adapted to the flea body.
  • the invention can provide that the effective magnetic field is generated by superimposing the magnetic fields of a plurality of magnetic field-generating elements, in particular a plurality of coils.
  • the magnetic field lines of the effective magnetic field can thereby be controlled, in particular by controlling the magnetic field as a function of the shape of the flea body Generating elements, in particular by depending on the shape of the hollow body energization of the coils, are at least partially adapted in their course to the course of the wall of the hollow body to be coated.
  • the invention can provide that it comprises a plurality of elements with which a magnetic field penetrating the process chamber can be brought about by superimposition of the magnetic fields generated by the respective elements.
  • the at least one element can advantageously be designed as a coil that can be energized.
  • a variation of the magnetic field e.g. to change plasma parameters, can be generated by changing the coil energization, in particular with a base magnetic field strength being able to be generated by the permanent magnets, around which the variation is possible.
  • the invention can provide that at least one of the coils is arranged on an axial end of the process chamber, in particular opposite an axial end face of a hollow body, and has a smaller winding diameter than the other coils, in particular which are arranged on the outside around the process chamber , or, in the case of an arrangement in the process chamber, surround at least one hollow body which can be inserted therein on the outside.
  • the coils arranged at the axial end can produce the effect of a magnetic mirror, as a result of which the plasma can be limited to the axial length of the hollow body, and in particular can be kept at a distance from the axial process chamber walls.
  • At least one of a plurality of coils or the sole coil for radial confinement of the plasma is preferably external to the Process chamber wall arranged.
  • the process chamber wall is non-metallic, for example made of glass, preferably borosilicate glass or quartz glass.
  • Coils at the axial end, opposite the axial end face of a hollow body, can be arranged in the process chamber or outside. In particular depending on the choice of material for the axial process chamber wall.
  • An embodiment of the invention can also provide that at least one energy transmission element, in particular at least one waveguide, through which energy can be radiated into the process chamber, is arranged in an axial spaced area between axially adjacent different coils or between axially adjacent winding sections of the same coil. In this way, the energy can be radiated through the coil arrangement.
  • at least one energy transmission element in particular at least one waveguide, through which energy can be radiated into the process chamber
  • the invention can also provide that several elements generating the influencing magnetic field are designed such that they comprise or form at least two groups of energizable coils, with which a magnetic field influencing the plasma can be generated or generated in the process becomes, in particular, independent for each group and/or also dependent on another group. Provision can be made for the at least two groups to generate the plasma-influencing magnetic field, in particular the same plasma-influencing magnetic field in each case in chronological succession, in particular for successive coating cycles of different hollow bodies or for a coating cycle of the same hollow body, in particular with a temporary overlap in the energization of two groups.
  • the device can comprise a control unit, which is set up for the corresponding energization.
  • Each group preferably has at least one coil that can be energized, preferably several coils that can be energized, in particular which can have one of the aforementioned arrangements, i.e. in particular can include coils which limit the magnetic field radially with respect to the longitudinal axis of the container and/or limit it axially, preferably in the manner of aforementioned magnetic mirror.
  • each group of coils can have at least essentially the same magnetic field configuration or magnetic field geometry generate, in particular form a respective so-called magnetic bottle.
  • the magnetic bottles of all groups are preferably identical, in particular in a respective at least temporarily static case during plasma generation.
  • the same magnetic field configuration/geometry is understood to mean that the magnetic fields generated by the groups each have the same local field strength in the process chamber, in particular with at least substantially identical course of field lines.
  • Coils and permanent magnets can also be combined in one group in order to generate the magnetic field, in particular as described above.
  • the invention preferably includes the coating of flea bodies on the inside and/or outside with a volume of 0.2-500 liters, preferably 1-100 liters and more preferably 5-30 liters.
  • the electrical power introduced into the coils can be higher than the thermal energy loss via convection and radiation, so that the coils can heat up considerably during continuous operation.
  • the invention can provide for the coils to be assigned at least one cooling system.
  • the invention can also provide, in particular to avoid a cooling system, to reduce the heating of coils by sequential switching and energizing of groups of the aforementioned type or by an energizing strategy, in particular which makes it possible to dispense with additional cooling of the coils .
  • One aim of the invention is preferably to keep an average temperature of the coils in the fatigue strength range of the coil material by assigning sufficiently long cooling times to these coils or groups. This can be done by allowing at least one other group to cool down when current is supplied to one group to generate the influencing magnetic field. In order to be able to ensure the fatigue strength of the coils, they should preferably not get hotter than 90° C. or the current through them should not exceed a value of approx. 2.5 A/mm 2 , in particular not on average over time.
  • the device according to the invention shown in FIG. 1 makes it possible to apply a sequential and respectively exclusive inner and/or outer coating to a flotation device 4 made of plastic, e.g. to large-volume containers 4 made of plastic.
  • a process gas is introduced into the respective reaction space 4a or 4b via one of the respective flea antennas 3 and excited to form a plasma, as a result of which plasma polymerisation is produced.
  • the reaction space 4a is given here by the interior of the float body 4 .
  • the reaction space 4b through the space between the outer wall of the float body 4 and the process chamber 12.
  • the coating process takes place overall under low pressure, i.e. a pressure lower than the surrounding atmospheric pressure.
  • the necessary pressure can be generated for each of the two reaction chambers 4a/4b by means of a vacuum pump 15.
  • the plasma is ignited with pulsed microwave excitation, which is generated by the signal generators 1 and emitted by flea antennas 3 and/or waveguides 5 .
  • the plasma is influenced here by a magnetic field that is generated by energized coils 13, 16 and 17.
  • the flea body 4 is fixed gas-tight in the process chamber 12 .
  • process gases are first introduced into the outer reaction space 4b through a gas lance 3 in the reactor cover 2, which is also a microwave antenna for the inner coating, for example for the outer coating, and a process pressure of 10 to 30 Pa, for example, is regulated.
  • the inner reaction space 4a of the container 4 preferably remains under atmospheric pressure or close to atmospheric pressure.
  • Microwave radiation is transmitted via an antenna 3, which is adapted in particular to the container geometry, in particular, which in turn is also a gas lance for the internal coating, is introduced into the process chamber 12 .
  • the radiation traverses the inner reaction space 4a of the hollow body 4 with almost no loss.
  • the significantly higher pressure in the inner reaction space 4a prevents the ignition of a plasma here.
  • the microwave radiation reaches the outer reaction space 4b of the hollow body 4 and meets suitable conditions there for a plasma state, as a result of which the deposition process on the outer wall of the hollow body 4 is initiated.
  • a magnetic field is generated via a coil arrangement of coils 16 and 17, which homogenizes the plasma along the field lines by the generated acceleration of the charged particles and at the same time keeps it away from the chamber walls of the process chamber 12 by magnetic confinement.
  • a coil 17 is provided at the axial end and opposite the upper axial end wall of the hollow body 4 and has a smaller diameter than the coil 16, which constricts the field lines at the axial end and thus has the effect of a magnetic Mirror generated for the plasma.
  • a coil 17 is only arranged at one axial end, here the upper end of the hollow body 4 .
  • the invention can also provide for such a coil 17 to be provided at the other end, here the lower end of the hollow body, in particular as shown in FIG.
  • Figure 2 visualizes the course of the field lines for a schematically illustrated embodiment with coils 17 arranged at both axial ends.
  • the course of the field lines of the effectively acting magnetic field is shown and illustrates the magnetic pole spacing in the axial direction A.
  • the constriction of the field lines can be clearly seen at the axial end, the is effected by the coils 17 with a smaller winding diameter than the coils 16, which are arranged radially with respect to the axis A around the hollow body 4.
  • the field lines of the magnetic field are forced into a bottleneck-shaped course, in particular so that the field lines are largely bent back into themselves inside the confinement volume.
  • the plasma can be limited to the immediate vicinity of the surface of the hollow body to be coated and kept away from the process chamber walls.
  • the plasma homogenized and preferably compressed, which increases the energy density and thus the layer deposition rate.
  • the magnetic influence on the plasma is based on the Lorentz force, which keeps the charged plasma particles, electrons and ions, in the magnetic field on helical paths, in particular thereby limiting the possible local areas, homogenizing the plasma and preferably also increasing the local energy density.
  • This magnetic confinement can preferably be achieved here in this example, but also with general validity for the invention, with cylindrical coils, since the magnetic field of such a coil is directed parallel to the coil axis, which prevents the loss of the particles in the radial direction.
  • the gas supply to the outer reaction chamber 4b can be terminated after the outer coating process for the following inner coating and this can be evacuated to a pressure level below the process pressure, preferably to about 5 Pa.
  • Process gas is introduced into the inner reaction space 4a of the hollow body 4 via the gas lance 3 and regulated to a process pressure, e.g. a pressure of approximately 10 to 30 Pa.
  • a process pressure e.g. a pressure of approximately 10 to 30 Pa.
  • Microwave radiation which is now introduced into the process chamber 12 through the antenna 3 lying opposite and the laterally slotted waveguide 5, traverses the exterior space without losses due to the significantly lower pressure, which corresponds to an increased free path length.
  • the radiation now meets suitable conditions for a plasma state in the interior 4a of the hollow body 4, as a result of which the layer deposition process on the inner wall of the hollow body 4 is initiated.
  • the magnetic field is switched on again, this time preferably solely for the purpose of homogenizing the plasma, which is particularly advantageous for the internal coating of large hollow bodies.
  • the total cycle time for the inner and outer coating is, for example, 10 to 120 seconds, in particular 1-30 seconds are required for the coating in each case. The remaining seconds are needed for evacuation and changing samples.
  • FIG. 3 shows a further exemplary embodiment of the invention.
  • the cylindrical coils 13 and 22 can be designed with a smaller diameter than the coils 16 to 21 and preferably with a core made of a ferromagnetic material, so that high magnetic flux densities are possible with low current intensities. These coils 13 and 22 are therefore less critical with regard to the temperature load.
  • the antenna/gas lance 3 can preferably be made of a ferromagnetic material in order to achieve an increase in the magnetic flux density of the outer coils 16 to 21.
  • This embodiment is particularly interesting for the magnetic confinement of the plasma igniting around the outside of the container wall, ie in the reaction space 4b, since the field lines will then run through and to the antenna 3.
  • the kinetic energy of the ions Ekin in a microwave plasma can typically reach values of up to 30 eV or 4.8E-18 J and depends on the coating process and the type of system.
  • a magnetic flux density of up to 0.01 T to 1 T is required, depending on Ekin.
  • the inside diameter of the process chamber 12 must be approximately 350 mm for a 10 L container, for example.
  • a magnetic flux density of approximately 0.05 T can be achieved, for example, with a cylinder coil with this inner diameter, preferably without a core, with, for example, 5000 turns and an energization of 3 A.
  • the strength of this magnetic field can be further increased by the coils 13 and 22 depending on the power required.
  • the coil reaches a critical fatigue strength temperature of e.g. B. 90 C°. After the coil has been switched off, it may take a few minutes for it to reset itself has cooled sufficiently.
  • a critical fatigue strength temperature e.g. B. 90 C°.
  • Loading and unloading processes, vacuum generation and gas introduction are preferably included in the overall cycle time, so that this is determined depending on the container size and can be 10 s to 120 s, for example.
  • the coils of a specific group of coils are switched on in order to generate the plasma-influencing magnetic field, so that the coils of at least one other group of coils, in particular the coils used previously, can cool down.
  • the coils 16, 18 and 20 of a first group could be used in the first coating process and then the coils 17, 19 and 21 of another group could be used in the subsequent process. In this way, a uniform magnetic field can be generated in each case, in particular an at least essentially identical magnetic field in each case, and the coils of the groups experience sufficient cooling for renewed use in the following process.
  • the groups of coils are alternately switched on and off within a coating cycle
  • the charging and discharging processes of the coils must be observed.
  • a current that is accentuated by induction always counteracts the cause of its creation (change in the magnetic field).
  • the flow of current is inhibited by the self-induced voltage of the coil.
  • the discharging and charging processes of the coils can last from a few milliseconds to a few tens of seconds. Taking these charging and discharging processes into account, groups of coils are alternately energized during the coating process, in particular so that a sufficiently high mean magnetic flux density is achieved at a sufficiently low maximum operating temperature.
  • the inductances can be taken into account by means of a current increase in one group that is adapted to one another over time, while the current in another group is reduced until the Generation of the magnetic field which one group has replaced the other group.
  • it is preferably ensured that the superimposed magnetic fields of both groups at the times when two groups are energized at the same time correspond to the magnetic field that each group also generates alone after the other group has been switched off.
  • the same magnetic field is generated both during the sole operation of a group and during the time interval of the operational changeover from one group to another.
  • FIG. 3 additionally shows reference number 23 for an optical sensor for detecting the plasma during operation in order to regulate it using the sensor measured values, in particular with regard to the plasma position or the distance between plasma and process chamber wall or plasma and hollow body wall.
  • Gas lance / antenna (optionally made of ferromagnetic material)
  • Guide rod e.g. made of PEEK or similar materials that have a high permeability to microwaves and magnetic fields
  • Process chamber e.g. with radial walls made of borosilicate glass or similar materials that are highly permeable to microwaves and magnetic fields

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plasma & Fusion (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)
  • Plasma Technology (AREA)

Abstract

L'invention concerne un dispositif et un procédé pour le revêtement de parois externes et/ou de parois internes de corps creux (4) réalisés en un matériau électriquement non conducteur, en particulier des bouteilles ou des boîtes en matière plastique, dans lesquels le corps creux (4) est placé dans une chambre de traitement (12), qui est divisée par le corps creux (4) en un espace de réaction interne et un espace de réaction externe (4a, 4b), au moins un gaz de traitement étant introduit dans l'un des deux espaces de réaction (4a, 4b) sous une pression de traitement, en particulier tandis que l'autre des deux espaces de réaction (4b, 4a) est maintenu à une pression inférieure ou égale à la pression de traitement, un plasma étant généré dans l'espace de réaction (4a, 4b) qui est maintenu à la pression de traitement, et des produits et/ou des fragments de réaction formés dans le plasma sont précipités hors du ou des gaz de traitement de façon à former une couche sur le côté de la paroi du corps creux (4) qui fait face au plasma, et lesquels sont caractérisés en ce que le plasma est influencé vis-à-vis d'au moins un paramètre de fonctionnement à l'aide d'un champ magnétique traversant les deux espaces de réaction (4a, 4b).
EP21749105.9A 2020-07-15 2021-07-09 Procédé et dispositif pour le revêtement de parois externes et/ou de parois internes de corps creux Pending EP4182490A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102020118718.1A DE102020118718A1 (de) 2020-07-15 2020-07-15 Verfahren und Vorrichtung zur Außenwand- und/oder Innenwandbeschichtung von Hohlkörpern
PCT/EP2021/069135 WO2022013087A1 (fr) 2020-07-15 2021-07-09 Procédé et dispositif pour le revêtement de parois externes et/ou de parois internes de corps creux

Publications (1)

Publication Number Publication Date
EP4182490A1 true EP4182490A1 (fr) 2023-05-24

Family

ID=77168211

Family Applications (1)

Application Number Title Priority Date Filing Date
EP21749105.9A Pending EP4182490A1 (fr) 2020-07-15 2021-07-09 Procédé et dispositif pour le revêtement de parois externes et/ou de parois internes de corps creux

Country Status (6)

Country Link
US (1) US20230323529A1 (fr)
EP (1) EP4182490A1 (fr)
JP (1) JP2023533569A (fr)
CN (1) CN115605631A (fr)
DE (1) DE102020118718A1 (fr)
WO (1) WO2022013087A1 (fr)

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3697250B2 (ja) * 2000-02-24 2005-09-21 三菱重工業株式会社 プラズマ処理装置及び炭素被覆形成プラスチック容器の製造方法
DE10010831A1 (de) * 2000-03-10 2001-09-13 Pierre Flecher Niederdruck-Mikrowellenplasmabehandlung von Kunststoffflaschen
KR20040106292A (ko) * 2002-04-11 2004-12-17 미쯔비시 쇼지 플라스틱 가부시키가이샤 플라즈마 ｃｖｄ 막 형성 장치 및 ｃｖｄ 막 코팅플라스틱용기의 제조 방법
US8062470B2 (en) 2008-05-12 2011-11-22 Yuri Glukhoy Method and apparatus for application of thin coatings from plasma onto inner surfaces of hollow containers
ES2513866T3 (es) 2009-05-13 2014-10-27 Sio2 Medical Products, Inc. Revestimiento e inspección de recipientes
AU2013352436B2 (en) 2012-11-30 2018-10-25 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition on medical syringes, cartridges, and the like
US9764093B2 (en) * 2012-11-30 2017-09-19 Sio2 Medical Products, Inc. Controlling the uniformity of PECVD deposition
FR3035881B1 (fr) * 2015-05-04 2019-09-27 Sidel Participations Installation pour le traitement de recipients par plasma micro-ondes, comprenant un generateur a etat solide
JP6788680B2 (ja) * 2016-09-28 2020-11-25 株式会社日立ハイテク プラズマ処理装置およびプラズマ処理方法

Also Published As

Publication number Publication date
CN115605631A (zh) 2023-01-13
DE102020118718A1 (de) 2022-01-20
JP2023533569A (ja) 2023-08-03
WO2022013087A1 (fr) 2022-01-20
US20230323529A1 (en) 2023-10-12

Similar Documents

Publication Publication Date Title
DE10202311B4 (de) Vorrichtung und Verfahren zur Plasmabehandlung von dielektrischen Körpern
EP0326824B1 (fr) Source de particules pour un dispositif réactif d'érosion à faisceau ionique ou de déposition à plasma
DE60033312T2 (de) Plasmabehandlungsvorrichtung und -verfahren
DE4340224C2 (de) Einrichtung zum Erzeugen von Plasma mittels Mikrowellenstrahlung
DE3913463C2 (fr)
DE4437050A1 (de) Vorrichtung zum Behandeln von Oberflächen von Hohlkörpern, insbesondere von Innenflächen von Kraftstofftanks
DE19722205A1 (de) Verfahren und Vorrichtung zur Beschichtung von Kunststoff- oder Glasbehältern mittels eines PCVD-Beschichtungsverfahrens
EP2208597B2 (fr) Unité de résonateur, procédé d'expansion et dispositif de chauffage de récipients
WO2003015122A1 (fr) Dispositif pour munir des objets d'un revetement
DE60003690T2 (de) Vorrichtung zum behandeln eines behälters mit einem mikrowellen-plasma
DE19925493C1 (de) Linear ausgedehnte Anordnung zur großflächigen Mikrowellenbehandlung und zur großflächigen Plasmaerzeugung
DE4214401C1 (en) Plasma-aided CVD of coating inside hollow body - by introducing atmos. contg. cpd. vapour into cavity at below atmos. pressure and passing microwaves into cavity
EP4182490A1 (fr) Procédé et dispositif pour le revêtement de parois externes et/ou de parois internes de corps creux
DE19652454C2 (de) Verfahren und Vorrichtung zur Außenbeschichtung von Lampen
DE102008027363B4 (de) Vorrichtung zur Behandlung großvolumiger Substrate im Plasma und Verfahren zur Anwendung
DE102010055188B4 (de) Resonatoreinheit für eine Vorrichtung zum Erwärmen von Behältnissen und Verfahren zum Erwärmen von Kunststoffbehältnissen
EP3671805A1 (fr) Dispositif et procédé de revêtement et en particulier de revêtement plasma des récipients
DE102009044496B4 (de) Vorrichtung zur Erzeugung von Plasma mittels Mikrowellen
WO2019233750A1 (fr) Source de plasma à micro-ondes linéaire comportant des espaces à plasma séparés
EP0568049B1 (fr) Dispositif et méthode pour la formation d'un revêtement sur la paroi interne d'un objet creux par CVD assisté par plasma à micro-ondes
EP1900493B1 (fr) Procédé destiné à la modification de surfaces intérieures des corps creux tubulaires au moyen d'un plasma, et système mettant en oeuvre ledit procédé
DE4403125A1 (de) Vorrichtung zur Plasmaerzeugung
DE3638942C2 (fr)
WO2005069703A2 (fr) Traitement du plasma de composants a grand volume
WO1992006224A1 (fr) Procede et dispositif pour l'enduction de pieces

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20221116

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)