WO2017153356A1 - Dispositif de dépôt de couches minces - Google Patents

Dispositif de dépôt de couches minces Download PDF

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Publication number
WO2017153356A1
WO2017153356A1 PCT/EP2017/055224 EP2017055224W WO2017153356A1 WO 2017153356 A1 WO2017153356 A1 WO 2017153356A1 EP 2017055224 W EP2017055224 W EP 2017055224W WO 2017153356 A1 WO2017153356 A1 WO 2017153356A1
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WO
WIPO (PCT)
Prior art keywords
film web
plate
gas
plates
coating
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Application number
PCT/EP2017/055224
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German (de)
English (en)
Inventor
Jules Fischer
Andreas Bernhard
Original Assignee
Fofitec Ag
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Publication date
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Publication of WO2017153356A1 publication Critical patent/WO2017153356A1/fr

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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
    • C23C16/44—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
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated 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
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45523—Pulsed gas flow or change of composition over time
    • C23C16/45525—Atomic layer deposition [ALD]
    • C23C16/45544—Atomic layer deposition [ALD] characterized by the apparatus
    • C23C16/45548—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction
    • C23C16/45551—Atomic layer deposition [ALD] characterized by the apparatus having arrangements for gas injection at different locations of the reactor for each ALD half-reaction for relative movement of the substrate and the gas injectors or half-reaction reactor compartments
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45563—Gas nozzles
    • C23C16/45568—Porous nozzles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/458—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber
    • C23C16/4581—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for supporting substrates in the reaction chamber characterised by material of construction or surface finish of the means for supporting the substrate

Definitions

  • the invention relates to an apparatus for depositing thin films through at least two self-limiting surface reactions on a substrate, the apparatus having a coating plate and a counter-plate oppositely disposed therebetween, means being provided for moving the substrate between the two plates
  • Coating plate comprises a plurality of, run over by the substrate supply areas and discharge areas for reaction and purge gas and the counter plate at least one supply area for purge gas or air, and wherein the supplied gases form gas cushion, which supported the substrate in the passage between the two plates against this and at a distance hold by them.
  • Self-limiting surface reactions of the type considered are in particular the so-called “Atomic Layer Deposition” (ALD) or the so-called “Molecular Layer Deposition” (MLD).
  • ALD Atomic Layer Deposition
  • MLD Molecular Layer Deposition
  • the surface to be coated is brought into contact successively with different, but not self-reactive, so-called precursors or reaction gases containing precursors. In between is rinsed with an inert gas in each case. Since each individual reaction gas does not react with itself, the partial reactions are self-limiting. The layer growth is thereby limited to only one monolayer at any partial reaction, even at arbitrarily long time.
  • the reaction gases may be trimethylaluminum (TMA) on the one hand and steam (H 2 O) on the other hand.
  • TMA trimethylaluminum
  • H 2 O steam
  • the purge gas is nitrogen (N 2 ) in question.
  • the hereby achievable AlO x layer is at suffi ⁇ cient quality and thickness as a transparent barrier layer for so-called Organic Light Emitting Diodes (OLEDs) suitable to protect them against water vapor and air oxygen.
  • OLEDs Organic Light Emitting Diodes
  • a so-called Water Vapor Transmission Rate (WVTR) is less than 1 0 ⁇ 6 g nr 2 day "1 and
  • WVTR Water Vapor Transmission Rate
  • oxygen oxygen transmission rate
  • OTR oxygen transmission rate of less than 1 CT 5 cm 3 rrr 2 day “1 bar 1 at at least 20 ° C. and 50% relative humidity is required 25 nm, preferably combined with other inorganic and / or organic layers, to achieve a thickness of 25 nm
  • AIO x approximately 50-400 coating cycles are required, for which use the substrate should also be transparent.
  • the device mentioned above is based on the principle of the so-called “Spatial ALD", wherein the substrate is moved relative to a coating head from which simultaneously but spatially separated, the reaction and purge gases flow continuously against the substrate.
  • the article "Poodt, P. et al. Provides a good overview of this technology, its mode of operation, its development and its possible applications.” (201 2).
  • Spatial atomic layer deposition a route towards further industrialization of atomic layer deposition. Journal of Vacuum Science and Technology. A: Vacuum, Surfaces, and Films, 30 (1), 01 0802- 1/1 1. [01 0802]. DOI: 1 0.1 1 1 6/1 .3670745.
  • wafers were first used as substrates, which required special devices for their transport relative to the coating head. Since it is important here to maintain only a small distance between the coating head and the substrates, previously known solutions from similar coating technologies have been used, as described, for example, in US Pat. No. 4,587,002 B2. In this case, the substrates are kept at a distance from the coating head (or, conversely, from the substrates) on gas pads which are formed by the pressure of the gases flowing out of the coating head. The substrates are sometimes even transported through the gas cushion.
  • WO 201 2/005577 A1 discloses an apparatus for depositing AlG layers by means of ALD technology on substrates in the form of wafers, which are moved individually between a coating plate and a counter plate arranged opposite thereto.
  • the coating plate points along The direction of movement of the wafer on a plurality of these run over supply areas for reaction and purge gas. These are arranged in groups according to the above-mentioned coating cycles.
  • the counter plate is provided with several supply areas for purge gas. Together with side walls, the two plates form a tunnel, wherein discharge areas for reaction and purge gas are provided in the side walls. The gases supplied via the two plates thereby flow in the tunnel transversely to the direction of travel of the substrates.
  • the supplied gases form gas bags, which support the substrates during the passage between the two plates against these and keep them at a distance from them.
  • pressure differences in the direction of movement of the substrates on successive zones serve.
  • suction openings are provided alternately transversely to the running direction of the substrates with feed openings, by means of which the substrates can additionally be set in rotation. Both plates are designed as coating plates.
  • a device of the aforementioned type in which likewise substrates in the form of wafers are moved individually between a coating plate and one of these oppositely disposed counterplates.
  • the coating plate has, along the direction of movement of the wafers, a plurality of reaction and purge gas supply and discharge regions, which are traversed by them.
  • the back plate is provided with multiple supply and discharge areas for purge gas.
  • the gases supplied via the two plates flow both in and against the direction of movement of the wafers.
  • the supplied gases form gas bags, which support the substrates during the passage between the two plates against these and keep them at a distance from them.
  • As a means to move the wafers between the two plates serve outer, not further described transport elements.
  • the device known from WO 201/1 51 430 A1 differs from that known from WO 201/193234 A1 in that the counter-plate is designed like the coating plate. Since the reaction gases used in the ALD Technology must not come into contact with each other, they are allowed to flow out of spatially spaced, mostly slot-shaped channels against the substrate. For the formation of sufficiently stable gas cushion, it is considered indispensable in US Pat. No. 7,789,961 B2 that there are sufficiently wide zones with a closed surface between the individual gas supply and drainage channels, these zones contributing more than 75% and even up to 95%.
  • the use of a diffuser is also proposed in US Pat. No. 7,789,961 B2.
  • the back pressure should be beneficial to the formation of the aforementioned gas cushion.
  • porous material is contemplated which, however, does not contribute to gas distribution if it is embedded in narrow channels of the diffuser, or preferably does not permit crossflow, or at least does not contribute much, if it also uses as such a thin layer is that no significant cross-flow can take place in it.
  • the horizontal distribution occurs between a plurality of stacked plates with surfaces substantially parallel to each other. The flow is within the plates perpendicular to their surface and between the plates parallel to it. If porous material e.g. The "nozzle plate 1 42" replaced, the flow within the porous material is therefore also perpendicular to the surface.
  • WO 201 1/056521 A1 a later application of the same Applicant, porous material is no longer mentioned in connection with the diffuser.
  • support measures are proposed for web-shaped, flexible substrates with which it is intended to prevent the flexible substrates from being bent by pressure differences in the gas cushion between still slot-shaped supply and discharge channels. Also, zones with a closed surface are still present between the individual gas supply and discharge channels.
  • WO 201 4/1 2341 5 A1 discloses a device with a rotating coating drum circumscribed by a film web on a partial circumference.
  • the coating drum has a plurality of supply and discharge regions for reaction and purge gas, which are traversed by the film web.
  • the gases supplied via the feed regions thereby flow predominantly in or against the direction of travel of the film web to the discharge regions.
  • the films web In the feed areas, the films web, as is basically already described in the earlier DE 1 0339262 A1, held on a gas cushion at a distance from the surface of the coating drum.
  • an outer cover is present.
  • the distance of the film web from the coating drum results from the strength of said gas cushion on the one hand and the web tension in conjunction with the curvature of the film web on the other.
  • the supply and discharge areas are again arranged in groups according to the above-mentioned coating cycles. When the coating drum rotates, the individual feed and discharge areas or the groups formed with these are used several times per revolution of the film web. To supply and discharge of the reaction and purge gases in or out of the rotating drum complex connections between mutually moving parts are required.
  • a discharge device of a Schlauchfolienextrusions- plant with a turning bar which comprises a support tube with a lateral surface which is formed as an air-permeable, microporous layer.
  • Possible layer thicknesses are 0.5-2 mm and the possible average pore sizes are 5 to 100 micrometers.
  • One of the objects of the invention is to improve a device of the type mentioned in terms of scope and performance. In particular, it should enable high production rates and, with a structurally simple design, be economical to purchase and operate.
  • This object is achieved by a device having the features of claim 1, which is accordingly characterized in that the means are designed to move as a substrate and two film webs in abutment with each other in a straight alignment between the two plates.
  • the coating plate and the counterplate are designed to be porous in at least one feed region for a gas outlet which is distributed over this region in a planar manner.
  • the counterplate is also formed as a coating plate and has along the direction of the at least one film web on several supply and discharge areas for reaction and purge gas.
  • the two plates are mounted in a variable, by the pressure of the gas cushion against a certain distance determined against each other movable.
  • the device according to the invention can be used for double-sided coating of a film web or else for one-sided coating of two film webs in abutment with one another.
  • the device according to the invention can be used for double-sided coating of a film web or else for one-sided coating of two film webs in abutment with one another.
  • two film webs or, as will be explained below, two webs of a film web can thus also be meant.
  • the device according to the invention is thus designed to coat a film web in one pass and is not limited to individual wafers or the like.
  • the advantages achieved by the device known from WO 201 4/1 2341 5 A1 are at least achieved by the device according to the invention.
  • by moving the film web in a straight orientation through the device according to the invention its positioning relative to the two plates is independent of their web tension. This makes the web guide more stable and less susceptible to interference than the web guide to a coating drum.
  • the claimed movement of the film web between the two plates is also much easier to implement than the drive of the wafers in the device known from WO 201 2/005577 A1, in particular by pressure differences in the direction of successive zones.
  • the two plates of the device according to the invention can be mounted stationary (apart from their mobility with regard to their mutual distance), which eliminates the considerable design effort required for the rotation of the coating drum in the device known from WO 201/1 2341 5 A1. Above all, however, no complicated connections between mutually moved parts are required for the supply and discharge of the reaction and purge gases.
  • the reciprocal mobility of the plates can be accommodated by flexible gas inlets and outlets on one of the plates.
  • the robust gas cushion also makes it possible to choose the distance between the film web and the coating and / or the counterplate very small, in particular less than 1 00 ⁇ , preferably even less than 50 ⁇ .
  • a high flow rate is beneficial to the effectiveness of flushing with the purge gas.
  • the feed regions in the direction of travel of the film web, in particular for purge gas can be made short. This in turn allows to accommodate a large number of groups along the length of the coating plate.
  • a further advantage of the porous surface is that a uniform gas outlet can be realized even with feed regions that are transverse to the direction of travel of the film web.
  • the two plates in a variable by the pressure of the gas cushion against a counterforce determined distance are mounted movable against each other, this distance and thus their distances from the film web with the aforementioned advantages can be set extremely low. Thickness variations of the film web are compensated automatically and without delay, hereinafter referred to as a robust gas cushion.
  • the mutual distance of the two plates should adjust as uniformly as possible over their area, therefore, should be possible certain angles of the plates against each other and thus a mobility in three axes to automatically compensate for variations in thickness of the continuous film web.
  • the reaction gases may be trimethylaluminum (TMA) on the one hand and water vapor (H 2 O) on the other hand to produce an AlO x layer.
  • TMA trimethylaluminum
  • H 2 O water vapor
  • the purge gas is nitrogen (N 2 ) in question.
  • TiCl 4 can be used as Ti0 2 -Preavesor.
  • the coating plate and the counterplate are preferably made porous in all feed regions.
  • individual feed areas could also be designed with slots and / or holes. This can be especially true for the supply of reaction gases with low vapor pressure, such as those for MLD loading. Stratifications be advantageous.
  • the slots and / or holes can be cleaned more easily than the porous material, whereby any deposits, for example due to thermal decomposition of a reaction gas, are more tolerable.
  • the film web can also be kept in the discharge areas on a gas cushion at a distance from the surface of the coating plate ⁇ , by generating a small, defined back pressure in the gas discharge.
  • the drainage regions are preferably designed as slots, because slits over, for example, holes due to the continuous discharge give a more effective separation of feed and rinse areas.
  • the inventive device is preferably suitable for coating film webs up to a width of 200 cm and thus by inline or subsequent parts of the web for standard widths, for example, 30 to 50 cm.
  • the entire apparatus is further preferably designed for a web speed of the film web up to 1 20 m / min. For an ALD process of the type mentioned, web speeds in the range of 20 m / min to 80 m / min are suitable.
  • the extent of the feed regions in the direction of travel of the film web need only be 5 mm to 30 mm, in particular 10 mm to 20 mm, even at such web speeds.
  • the extent of the discharge areas in the direction of the film web even needs to be only 0.3 mm to 1 .5 mm, in particular 0.5 mm to 1 mm. This is especially true if the distance between the film web and the coating plate is kept smaller than 100 microns.
  • the front feed region of the pair of feed regions is preferably a feed region for purge gas and the rear, preferably a feed region for reaction gas, results in improved utilization of the feed regions for purge gas.
  • the movement of the film web also supports the purge gas partial flow in the direction of the feed region for reaction gas which subsequently adjoins in the film running direction.
  • the separation of the various reaction gases can be ensured in spite of the respective adjacent only to a pair of feed areas Ab effets Kunststoffe that the supply ranges for purge gas in the direction of the film web are measured longer than the respective adjacent supply areas for reaction gas and / or in that the purge gas a higher pressure than the reaction gases is supplied.
  • the porous material preferably forms a layer directly adjacent to the gap between the two plates. This can and should extend over virtually the entire area of the respective feed area and thus at least close to adjacent discharge areas or an adjacent feed area. Compared with their areal expansion (typically in the range of 1 to 2 cm in the direction of travel of the film web), the thickness of this porous layer can be substantially lower (typically about 1 mm). It thus forms only a comparatively thin surface layer of the overall much thicker, supporting them and preferably dimensionally stable plate.
  • the gas is supplied to the porous layer from the interior of the plate through channels, for example in the form of bores, and these grooves adjoining, extending along the feed regions.
  • a plurality of grooves can be provided parallel to each other per supply region.
  • the spacing of the grooves from one another and / or from the edges of the porous layer can be dimensioned approximately five times greater than the width of the grooves.
  • the pore size of the porous material of Layer could be 1 0 - 20 microns.
  • the flow resistance of such a porous material is so high that the pressure drop of the gas supplied in the porous layer is substantially greater than the pressure drop in the gas cushion. This in turn has the consequence that the gas flow exiting the porous layer is comparatively stable and only changes due to changes or disturbances in the flow conditions in the gap between the plates (for example when a splice passes where two foil webs are joined together with an adhesive strip) is little influenced.
  • the gas cushion is thus robust and this with particular advantage over the entire surface of the porous layer. Although narrow pockets for the gas supply according to the prior art with adjacent closed surfaces up to the next discharge areas, gas cushion can also form, but their robustness, if any, is essentially limited to the immediate slot area.
  • the robustness of the gas cushion and the mounting of the two plates in a variable distance allow this distance to be kept very low by suitably adjusting the pressure for the gas supply.
  • this increases the danger that, for example, in the case of thickness variations of the film web, undesired contact with the sheets occurs with the sheets. Thickness variations are often caused by foreign matter such as film snippets, thickening of pre-coatings, roll-edge markers, wrapped and roll-wrapped film edges, improper roll feeders from suppliers by overlapped rather than blunt foils, as well as two instead of one glue web or thick adhesive web. This is particularly critical for stepped thickening as in the mentioned splices.
  • the distributed gas outlet from the porous layer over the gas outlet from a narrow slit of considerable advantage results directly from the contact of the thickening with the areal effective, robust gas cushion pressure increase therein, by which immediately an increase in distance between the plates is initiated, which in the best case undesirable contact with the thickening Prevents plates.
  • this effect occurs only when the thickening has reached the narrow slot, which may have come in the area of the upstream closed surface to a collapse of the non-robust gas cushion and a touch.
  • the inlet area may additionally be designed in the manner of a mouth opening.
  • the two plates are slightly bevelled there, so that a thickening critical, caused by an upstream, thinner film web section, lower plate spacing is achieved only after a certain distance. An incoming thickening can thus bring about an increase in this distance even before the plate spacing in the inlet region, which may be too small for it, is reached.
  • a mouth opening can also be provided in the outlet region.
  • this mouth opening in the outlet area causes the plate spacing to be retarded to the normal value when a thickening of the pair of plates expires.
  • partition walls may be provided for gas separation between such areas and / or opposite discharge areas.
  • the partitions can taper outwards and, for example, have a trapezoidal or pointed cross section.
  • the porous material is embedded in ladle-like recesses.
  • corresponding partitions do not necessarily have to extend to the outside, but could already end below the respective porous surfaces. The porous one Material from adjoining feed areas would in this case be partially in mutual contact and would accordingly extend continuously across the two feed areas.
  • the space between the two plates is preferably laterally open in the device according to the invention. Therefore, and in view of the fact that reaction gas such as TMA should preferably not escape into the environment, it is advantageous to provide in each case a discharge region for the reaction gas in the coating plate transverse to the running direction of the film web on both sides adjacent to at least one feed region for a reaction gas.
  • the coating plate has on both sides of at least one supply region for a reaction gas transversely to the direction of the film web still one, overrun by the film web supply area for purge gas.
  • the film web of an invented The device according to the invention are fed several times in succession.
  • several devices according to the invention could be operated in series with pairs of coating and counter plates.
  • the plurality of pairs of coating and counterplates are arranged in series and preferably in a stack, and web deflecting means are present in order to feed the film web to the individual pairs in succession. In an arrangement in the stack results in an extremely compact design.
  • the coating plate and the counterplate which is likewise designed as a coating plate, are preferably designed congruently with respect to their feed and discharge regions.
  • the inventive device is except for double-sided coating of a film web or for one-sided coating of two film webs in contact with each other with particular advantage for double coating only one side of a film web usable if the film web after a first pass between the two plates with suitable web turning means turned and the two plates are fed back to back with a part of the film web located in the first pass for a second pass between the two plates again.
  • formed as a coating plates plates do not have the same ⁇ chen reaction gases are supplied.
  • AlOx could be coated over one of the two plates and Ti0 2 over the other. Especially in such a case, the supply and discharge areas of both plates could be different and not congruent.
  • At least one feed region in the coating plate of the device according to the invention is assigned a UV lamp.
  • Ozone radicals O ('D) can be generated from the ozone (0 3 ) as a reaction gas in the ozone-containing gas supplied there according to the reaction equation:
  • the UV lamp is preferably an amalgam lamp (low-pressure mercury vapor lamp) which emits UVC radiation and / or VUV radiation with wavelengths of 254 nm and / or 1 85 nm.
  • the ozone-containing gas must be externally generated, for example, from oxygen-containing gas with an ozone generator.
  • the mentioned 1 85 nm radiation is less suitable for ozone photolysis than the 254 nm radiation, but can support the process by the cleavage of adsorbed and optionally partially oxidized precursor molecules.
  • oxygen radicals O can also be generated as a reaction gas locally from supplied, oxygen-containing gas by using a VUV lamp:
  • the VUV lamp is a 1 72nm Xe 2 * excimer lamp.
  • the 1 72 nm radiation can also support the process by the cleavage of adsorbed and possibly partially oxidized Pre Kunststofformolekülen.
  • this embodiment eliminates the mentioned ozone generator.
  • Another possibility for the local production of oxygen radicals from supplied, oxygen-containing gas is the use of a plasma source. Such could also generate other radicals, for example H radicals from H 2 for the deposition of metallic layers or N radicals from N 2 or NH 3 for the deposition of nitride layers.
  • a higher process temperature than ambient temperature is generally favorable.
  • suitable means for heating may be arranged upstream of the two plates in their running direction. These means preferably comprise a heating section equipped with hot air feeds and / or IR radiators.
  • the film web can be heated on the heating to a higher temperature than the process temperature, for example, to dry the carrier film and / or the planarization or to compensate for a possible cooling of the film web between the heating and the inlet between the first two plates. If a plurality of plate pairs are arranged in series or in a stack, each plate pair may be preceded by means for heating the film web in its direction of travel.
  • the device according to the invention can furthermore be provided with a measuring device through which the film web passes, which is arranged downstream of only one coating and counterplate or only one precoat and precoat counterplate for the inline determination of oxygen or nitrogen transmission rates (OTR or NTR ) of the thin layers deposited during the passage between these plates.
  • the measuring device is preferably connected in terms of data technology to a device arranged later in the direction of travel of the film web for inscribing and / or coding the film web (FB) with the determined OTR or NTR values.
  • These data could alternatively or additionally also be stored electronically together with a running meter identification (inter alia being stored on mobile storages and, for example, in the film sleeve), so that they can be retrieved during the further processing of the coated film web or for other requirements.
  • the device according to the invention is preferably part of a system in which the film web is unrolled from a first roll and rolled up again after being coated on a second roll. Since ALD or MLD coatings with thicknesses in the nanometer range are very sensitive to mechanical loads, it is known per se to roll up the coated film web together with a protective intermediate layer (so-called interleave), that of another Unwinding is supplied. However, the intermediate layer is usually saturated with the gases present in their environment as well as with water. According to a development of the invention, means are provided for producing the intermediate layer inline from a shapeless mass in the same pass as the coating of the film web.
  • the intermediate layer can be prepared virtually anhydrous and be equipped by incorporating getters for water molecules in the material of the intermediate layer even with the functionality to keep dry by receiving water molecules, the coated film web on the roll to their further processing or even dry.
  • the material of the interlayer must be permeable to water molecules.
  • a protective coat can also be applied inline in the same pass with the ALD or MLD coating on an ALD or MLD coating , which remains in the wide processing of the coated film web on this.
  • the protective layer may also contain getter for water molecules. If the ALD or MLD coating is to serve as a transparent barrier layer for OLEDs, these must also be transparent. According to a further development of the invention, therefore, means are provided to generate the protective layer inline from a shapeless mass in the same run with the ALD or MLD coating.
  • the protective layer becomes part of an end product such as an OLED, it is advantageous if the protective layer contains, in addition to a getter for water, also a getter for oxygen molecules.
  • the getters must be present in sufficient quantity, and the getter-containing film web must be sufficiently protected against ingress of atmospheric moisture and atmospheric oxygen.
  • the getters are largely protected, since air can only be admitted at the end of the roll, which can be prevented by suitably designed protective packaging of the roll or blanks. The scope of the role is determined by the also protected on the film web, produced by ALD / MLD thin layers.
  • the protective layer may be electrically conductive to later form a transparent anode, for example, an OLED. If the protective layer is to contain getters and should be electrically conductive, two separate layers are preferably applied, wherein the layer applied first contains getters and the subsequently applied layer is electrically conductive.
  • FIG. 1 shows an embodiment of a device according to the invention with a coating plate and a counter plate arranged opposite thereto, with rolling-up and unrolling means and various auxiliary aggregates;
  • FIG. 3 is a) a top view of a group of reaction and purge gas supply and discharge regions of a coating plate for performing an ALD coating cycle and b) a cross section of this group;
  • Fig. 4 at a) is a plan view of a different set of supply and discharge areas for reaction and purge gas of a coating plate for performing an ALD coating cycle and b) a cross section of this group; a cross section of a group of reaction and purge gas supply and discharge regions of a coating plate for performing an ALD coating cycle with a UV lamp associated with a reaction gas supply region; a cross section of a group of reaction and purge gas supply and discharge regions of a coating plate for performing an ALD coating cycle with a plasma source associated with a reaction gas supply region; a cross section of a group of reaction and purge gas supply and discharge regions of a coating plate for performing an ALD coating cycle with another plasma source associated with a reaction gas supply region; under a) a plurality of pairs of coating and counter-plates, to
  • Fig. 1 3 a stacking arrangement with three pairs of plates through the two film webs or two parts of a film web in series, wherein in each case separate guide rollers are provided for the two webs between the plate pairs;
  • FIG. 1 shows an embodiment of an inventive device having four plate pairs of coating plates arranged in a stack for a double pass of the film web, wherein a measuring device is arranged between the first and the second plate pair.
  • Fig. 1 5 an embodiment of an inventive device with four
  • Pairing stacked coating sheets for a double pass of the film web wherein a measuring device is disposed between a pair for a one-sided precoating and the stack;
  • Fig. 1 6 an embodiment of an inventive device with seven pairs of individually horizontally arranged coating plates for a double pass of the film web, wherein a measuring device between the third and the fourth plate pair is arranged;
  • Fig. 1 7 shows an embodiment of the measuring device with a measuring plate and a counter-plate under a) in a plan view of the inside of the measuring plate and b) in a cross section.
  • the apparatus of Figure 1 comprises a roll R 1 for unwinding and a roll R 2 for unwinding a film web FB in a roll-to-roll process.
  • the core of the device is a plate pair 1 0 with a coating plate. 1 and a backing plate 2 for an ALD or MLD coating of the film web.
  • the film web runs between two guide rollers U 1, U 2 stretched straight through a gap between the two plates 1, 2 by without touching them by being held on gas cushion at a distance from the surface thereof.
  • a particulate cleaning aggregate 31 for example in the form of a soft adhesive rubber roller or air blade
  • a surface treatment aggregate 32 for adhesion enhancement such as corona discharge, plasma treatment or ultraviolet irradiation
  • a coating application aggregate 33 This may include a so-called slot die.
  • the aggregate 33 for coating is followed by a drying section 34 for its drying and / or thermal or radiation-related crosslinking.
  • the coating can be a so-called pre-planarizer and primer.
  • a heating channel 35 is present, which is equipped for example with hot air feeds and / or with IR lamps to heat the film web to a favorable process temperature for their coating. Subordinate to the plate pair 1, 2 in FIG.
  • FIG. 1 is a measuring device 40 which, in terms of data technology, is connected to a device 50 arranged further in the direction of travel of the film web for inscribing and / or coding the film web. These two devices will be described in more detail below.
  • the device of FIG. 1 is preferably set up and operated in a clean room, which is indicated by the frame drawn in FIG. 1.
  • At least the deflecting rollers provided with a dot pattern are so-called air rollers with a porous surface layer from which purified air or nitrogen flows out to form a gas cushion, which keeps the film web at a distance from its web tension and so deflects it without contact.
  • FIG. 2a and 2b each show in section two short, opposite sections of two, in the running direction of the film web FB per se substantially longer plates 1, 2.
  • Fig. 2a below a coating plate 1 and above a counter-plate 2 is shown. The at the of the film web FB traversed gap 1 1 between see the two plates 1, 2 adjacent surfaces of these plates are flat.
  • the coating plate 1 has a plurality of feed and purge gas supply regions, which are formed by ladle-like depressions filled with an open-pored, porous sintered material.
  • One of these pan-like depressions is denoted by 1 2.
  • the connection between the channels 1 3 and the pan-like recesses 1 2 is made by narrow grooves 1 4 in the bottom of the pan-like recesses 1 2.
  • the gas is supplied with a certain overpressure. Below and in the porous material distributes the gas supplied and occurs evenly distributed from this into the gap 1 1. Compared to the film web forms this supporting gas cushion.
  • gases Ab effets Kunststoffe are present, which are designed as grooves, one of which is denoted by 1 5.
  • the grooves 15 open into further channels, one of which is denoted by 1 6. In order for the supplied gas to flow to the discharge areas, it requires a certain pressure drop in the direction of this. Derivative regions are present in Fig.
  • the 2a has at least one gas supply region extending over a plurality of supply and discharge regions of the coating plate 1, this supply region also being formed using porous material in a socket-like depression 17. Also from this porous material, the supplied gas exits evenly distributed and forms a gas cushion against the film web.
  • the two-sided gas cushion keep the film web at a distance from the surfaces of the two plates 1, 2, so that the film web passes without contact between them.
  • One of the feed channels for the supply of the at least one feed region with gas in the counter plate 2 is denoted by 1 8.
  • the counterplate is formed in the case of only one plate pair, or at least one counterplate in the case of several plate pairs, likewise as a coating plate.
  • a design results from Fig. 2a by forming the counter-plate 2 as a coating plate corresponding to the coating plate.
  • the first four feed regions of FIG. 2a in the direction of travel of the film web, together with the two derivation regions shown, are suitable as a group, in particular for an ALD coating cycle using TMA and H 2 O as reaction gases and of N 2 as purge gas.
  • the coating plate 1 is provided with a plurality of such groups, wherein in the partial view of Fig. 2a of the following group only two feed areas are shown.
  • the extent of the feed and discharge regions in the direction of travel of the film web can be dimensioned as already indicated above. With these dimensions, 1 0 - 1 00 groups for a corresponding number of ALD coating cycles can be accommodated over a length of 1-3 m in the direction of the film web.
  • the preferred length of the two plates 1, 2 is 1 m with 20 groups.
  • FIG. 2 b shows a pair of plates with two plates 1, 2 designed as coating plates, which, moreover, are congruent or mirror-image-shaped, as is preferred for most applications.
  • This embodiment is suitable for a double-sided coating of a film web, or as shown, for only one-sided coating of two film webs, which run through one another in planar contact between the two coating plates.
  • the illustrated section of the plates 1, 2 here comprises the inlet region, in which an enlarged mouth opening is formed and is supplied in the purge gas.
  • the feeding regions following in the film running direction are arranged in pairs again as in FIG. 2a, whereby tapered partitions between them, however, are lower than in FIG. not reaching to the surface of the porous material, are formed.
  • the inlet area is measured in the film running direction longer than the subsequent feed areas, on the other hand in the example of Fig. 2b but only as this fed by a channel 1 3 and grooves 1 4.
  • the number of channels 1 3 and / or grooves 1 4 in the inlet region could of course be increased. Possibly.
  • Other channels 1 3 and especially grooves 1 4 could be provided because of the greater length of the inlet region but also perpendicular to the illustrated, as indicated in each case by a dashed line below the porous layers in the two plates 1, 2.
  • two mutually parallel grooves 1 4 are provided in each case in FIG. 2 a and FIG. 2 b, which are in communication with the channels 1 3.
  • the grooves are relatively narrow in relation to the channels 1 3, wherein their mutual distance in the representations of Fig. 2a and Fig. 2b corresponds approximately to the diameter of the channels 1 3. If a greater spacing of the grooves 1 4 would be advantageous from one another, this could be achieved without increasing the diameter of the channels 1 3 at the same time by arranging the grooves 14 at an angle to one another and towards the porous layer.
  • the supply and discharge channels are not led out individually from the coating plate 1, but are connected to one another within them, so that the number of gas connections to the coating plate 1 is substantially smaller.
  • only one gas connection is present per gas type on the coating plate.
  • these would be five ports, namely three for the supply of these gases and one port for the separate dissipation of TMA / N in the derivation regions 2 or H2O / N2 exhaust gases.
  • the connections between supply and discharge channels with the respective associated connections are preferably realized within a solid coating plate by means of different, arranged at different levels holes.
  • the distances of the film web to both plates 1, 2 should be as low as stated above. This is achieved inter alia by the fact that the distance of the coating plate 1 of the counter-plate 2 is variable and determined by the pressure of the gas cushion against a counter force.
  • a suitable counterforce can be applied mechanically, for example by compression springs, or pneumatically or hydraulically, wherein a plate is preferably arranged stationary. In a horizontal arrangement, the weight of the upper plate at least contribute to the counterforce.
  • Fig. 3a) shows a plan view of the area of a group of supply and discharge areas for reaction and purge gas of a coating plate 1 for performing an ALD coating cycle, and Fig. 3b) a cross section of this group.
  • the coating plate 1 may or should be provided with a plurality of such groups adjacent to one another.
  • a feed region for TMA as a reaction gas is cross-hatched transversely to the direction of the film web and H 2 0 as a reaction gas in the direction of the film web.
  • the areas are provided, through which N 2 is supplied as purge gas.
  • the derivation areas are not hatched. Except for the discharge areas, all surfaces are porous and designed for an evenly distributed gas outlet.
  • N2 or simply cleaned ambient air is supplied.
  • the first supply area for purge gas N 2 in the direction of travel of the film web is wider than the three subsequent ones.
  • the first feed zone for purge gas N 2 follows a feed zone for H 2 0.
  • the widening of the first feed zone for purge gas N 2 takes into account the fact that the desorption of H 2 0 is a slower process than that of TMA.
  • the feed range for purge gas N 2 for H 2 0 desorption for example by a factor of 2 but also the feed range for H 2 0 could be extended, because depending on the temperature and H 2 0 concentration can instead of the H 2 0 desorption the Reaction with H 2 0 be rate-limiting.
  • the H 2 0 concentration should be at a high in order to ensure a high reactivity, on the other hand prevents a limitation of the H 2 0 concentration to about 1 0% -relative humidity, that an H is sorbed 2 0 multilayer adsorption, which in turn would slow H 2 O desorption.
  • the feed ranges for H 2 O are extended by, for example, a factor of 1 .5, the relative humidity of, for example, 1 5% to 1 0% can be reduced while maintaining the amount of H 2 0 supplied and the gas volume flow per area.
  • the extension factor can be, for example, 1 .5 both for the feed region for purge gas N 2 for H 2 O desorption and for the feed region for H 2 O.
  • discharge regions in the direction of travel of the film web are respectively provided adjacent to each of the two supply regions for reaction gas TMA and H 2 O, wherein the flows illustrated by the arrows in FIG. 3 b are established. All gases flow in and against the direction of the film web to the nearest discharge area.
  • discharge regions are provided transversely to the running direction of the film web only adjacent to the feed region for the reaction gas TMA. As a result, its outflow from the gap between the two plates 1, 2 can be prevented transversely to the direction of travel of the film web.
  • Corresponding derivation portions are not provided at the feed section for the reaction gas H 2 0, since the leakage of water into the environment is generally not critical.
  • the feed region for the purge gas extends transversely to the direction of travel of the film web on both sides beyond it, so that the film web is supported over its entire area on a gas cushion.
  • the counter-plate 2 which preferably terminates at the edge with the coating plate 1.
  • Fig. 4a shows a plan view of a different set of supply and discharge areas for reaction and purge gas of a coating plate 1 for performing an ALD coating cycle
  • Fig. 4b a cross section of this group.
  • the purge gas flows in majority against the direction of the film web, whereas the reaction gases flow in the direction of the film web.
  • the feed areas for purge gas can be utilized virtually throughout its entire length, instead of only half the length for desorption of the reaction gases. Halving the number of exhaust slots allows reducing gas consumption for the gas bags. Furthermore, the reaction gases are thereby better utilized: In the embodiment according to FIG. 3, TMA, for example, which flows out in the vicinity of an exhaust region adjoining to the left, can get into it without ever having come into contact with the film web.
  • the separation of the various reaction gases can be ensured by setting the purge gas pressure slightly higher than the reaction gas pressure. A small part of the purge gas will thereby flow over the adjacent feed region for reaction gas into a more remote discharge region, which is also indicated in FIG. 4b) by a short arrow.
  • a reduction in the thickness of the porous material in the purge gas supply region or some extension of the purge gas supply regions for example, by 20% relative to the reaction gas supply regions.
  • the purge gas supply region adjacent to the TMA supply region is made longer than the purge gas supply region for H 2 O adjacent to the feed region for purge gas.
  • FIG. 5 shows a cross section of a group of reaction and purge gas supply and discharge regions of a coating plate 1 with opposing backplate 2 for performing an ALD coating cycle.
  • discharge regions in the direction of travel of the film web FB are present only adjacent to a pair of feed regions.
  • a UV lamp 22 is assigned to a supply region 21 for a reaction gas. This is arranged in a groove between the feed region 21 and a discharge region 23 and extends transversely to the direction of travel of the film web over the width thereof.
  • an ozone-containing gas is supplied which flows in the running direction of the film web completely over the UV lamp to the discharge region 23.
  • the ozone (0 3 ) in the ozone-containing gas is preferably generated centrally for all supply areas to be supplied thereto in an external ozone generator (not shown) of oxygen-containing gas.
  • the UV lamp 22 preferably generates UVC radiation and / or VUV radiation having a wavelength of 254 nm and / or 1 85 nm. With this radiation, oxygen radicals O ('D) are produced from the ozone in the ozone-containing gas supplied via the UV lamp 22 by photolysis. These react with a metal-containing reaction gas to form a metal oxide, which in the subsequent coating cycle in the second feed region is fed to the following group of feed and discharge regions (corresponding to the second feed region 24 of the illustrated group).
  • the UV lamp Since the oxygen radicals O ⁇ D) are very short-lived, the UV lamp with only a small distance of, for example, 2 mm from the film web is arranged. Thus, a sufficiently large part of the generated radicals can come into contact with the film web.
  • the UV lamp 22 may be provided on the back with a reflector in order to exploit the light emitted backwards against the coating plate 1. By touching contact with the coating plate 1, the UV lamp could also be cooled.
  • ozone-containing gas oxygen radicals 0 ( 1 D) as a reaction gas from supplied in Zu Replacement Scheme 1 7
  • oxygen-containing gas locally by using a VUV lamp such as a Xe 2 * -Excimer- lamp instead of the UV lamp 22 be generated.
  • FIG. 6 shows a cross section of a group of supply and discharge areas for reaction and purge gas according to Fig. 5, but instead of the UV or VUV lamp 22 for generating oxygen radicals, a plasma source 25 is provided.
  • a plasma is generated here by surface discharge (Surface Dielectric Barrier Discharge Plasma (SDBD)) directly in the gap between the plasma source 25 and the film web FB, which in turn is low in terms of short-lived oxygen radicals due to short distances.
  • SDBD Surface Dielectric Barrier Discharge Plasma
  • 25.1 and 25.2 designate high-voltage electrodes which are embedded in a dielectric 25.3.
  • 25.5 designates a channel for a cooling liquid also in the dielectric 25.3.
  • Fig. 7 shows a cross section of a group of supply and discharge areas for reaction and purge gas according to Fig.
  • a plasma source 26 is provided.
  • the plasma is generated in a discharge zone in a gap between two adjacent dielectrics 26.3 and 26.4.
  • the high-voltage electrodes 26.1 and 26.2 are embedded with cooling channels 26.5 and 26.6 in the two dielectrics.
  • the oxygen-containing gas is not supplied via an adjoining supply region as in FIG. 6, but flows directly through the gap between the two dielectrics 26.3 and 26.4.
  • the supply area 21 of FIG. 6 is thereby eliminated, with its space being used for the slightly wider plasma source 26.
  • ion bombardment of the film web is avoided.
  • a high flow rate can be adjusted. Because of the resulting high amount of gas can be used as the oxygen-containing gas air. If the gas flow through the discharge zone is sufficiently high, the cooling of the electrode can be dispensed with.
  • the coating is carried out only slightly above the ambient temperature, so that heating means such as the heating channel 35 can be dispensed with at the same time moderate expense for the cooling of the plasma sources.
  • a plurality of pairs of coating and counterplates 1, 2 can be provided, to which the film web is fed successively to achieve greater layer thicknesses.
  • FIG. 8a shows an arrangement with three pairs for ALD coating a film side, wherein the coating plates are each marked with ALD and the counter-plates each with N 2 .
  • the film web FB is deflected suitably by means of deflection rollers 61, 62.
  • the freshly coated side of the film web is directed against the 61 designated deflection rollers.
  • At least these are designed as so-called air rollers with porous surface layers. Gas bubbles, which carry the film web and redirect it without contact, form from this outflowing gas in relation to the film web.
  • the guide rollers 61, 62 preferably each move together with the plates 1, 2, as shown in FIG. 8b) also shows.
  • FIG. 9a shows an arrangement again with three pairs of plates 1, 2, but these are particularly space-saving arranged in a compact stack.
  • one of the plates is mounted in a stationary manner and the other plates are movably mounted relative thereto.
  • a gap 1 1 after the other is extended.
  • FIG. 9 shows the stack with an extended gap 11.
  • the width of the column 11 is variable during the passage of the film web FB and is determined by the pressure of the gas cushion against a counterforce.
  • N 2 in FIG. 8 and / or FIG. 9, simply cleaned air can also be supplied via the counterplates 2 to form the gas cushion.
  • the counter-plate 2 is also designed according to the invention as a coating plate 1, the film web FB is coated on both sides. This may be convenient or necessary for certain applications. If two film webs are brought into contact with one another simultaneously by the device of FIG. 10, only their outsides are coated in each case. In view of the fact that a multiple pass through a pair of plates 1, 2 to achieve a desired layer thickness may be required anyway, the device of Fig. 10 may be provided with web inverting means to double pass the same web in only one pass. Further according to the invention, it can also be provided here that the width of the gap between the two plates is variable during the passage of the film web FB and is determined by the pressure of the gas cushion against a counterforce. Fig.
  • FIG. 1 1 shows web turning means to perform the same film web in only one pass twice through a device according to Fig. 1 0.
  • the film web FB coming from the left for the first time passes the horizontally arranged coating plate pair 1, 1 and then with a first guide roller 71 at right angles to the side (in Fig. 1 upwards) deflected.
  • a second guide roller 72 brings it in the opposite direction to its original direction so that it runs back past the coating plate pair 1, 1 over.
  • With a third guide roller 73 is a rectangular deflection of the film web to the side against its incoming part (in Fig. 1 down) until it comes after a fourth, right-angle deflection with a guide roller 74 back in flight with its incoming part, but still moving in the opposite direction.
  • a fifth deflection roller 75 With a fifth deflection roller 75, it is finally deflected by 1 80 ° without lateral deflection, whereafter, together with its incoming part, it passes through the coating plate pair 1, 1 a second time. Thereafter, it runs double-sided coated in Fig. 1 1 straight ahead to the right.
  • the deflection rollers 71-74 are each diagonally aligned with respect to the respective running direction of the film web. directed and preferably have the same diameter. In the first deflection, the film web is offset by this diameter upwards and at the second deflection by the same amount back down to its original height. In the case of the third and the fourth deflection, in each case an offset is made downwards by this amount so that the film web passes under its incoming part.
  • the double offset downwards is compensated by the fifth guide roller 75 by being twice as thick as the guide rollers 71-74.
  • the film web is raised to its original height and that of its incoming part.
  • Through the described deflections also takes a turn of the film web, so it comes to lie back-to-back with its incoming part on the second pass.
  • All deflecting rollers 71-75 are designed as porous air rollers for contactless deflection of the film web.
  • a double pass of the film web is also possible in series by several pairs of plates or a stack of plates. An example with four plate pairs is shown in FIG.
  • the film web FB passes in Fig. 1 2 from the left horizontally first, the lowest pair of plates and occurs after passing through the two middle pairs of plates from the top plate pair horizontally to the left running from. Thereafter, it is first deflected at right angles to the side with a diagonal deflection roller 71 '.
  • a second guide roller 72 ' deflects it at a right angle downward without lateral deflection, after which it passes through the plate stack and its incoming part.
  • a third deflecting roller 73 ' a further right-angled deflection takes place without lateral deflection of the film web back in the direction of its incoming part.
  • Fig. 1 3 shows in cross-section a stack arrangement with three pairs of plates, wherein in contrast to Fig. 9 here all plates are formed as coating plates through which two film webs or two parts of a film web in series.
  • separate guide rollers 63, 64 are provided for the two webs or partial webs between the plate pairs. This takes into account the fact that the respective outer track at the deflections must cover a longer path than the respective inner track.
  • the deflecting rollers 63, against which the freshly coated side of the film web is directed, are designed as air rollers for contactless deflection.
  • FIG. 1 shows an embodiment of an inventive device with four pairs of coating plates 1-8 arranged in a stack for a double pass of the film web FB as described above.
  • the measuring device 40 is here arranged between the first 1, 2 and the second plate pair 3, 4, wherein the film web, however, passes through the measuring device 40 only after its first passage through this plate pair 1, 2.
  • a placeholder 9 is arranged between the first 1, 2 and the second plate pair 3, 4.
  • the example according to FIG. 1 2 executed return and turn the film web for a second pass is not shown in detail in Fig. 14. Only a portion of the recycled portion of the film web is designated by FB ' .
  • the film web in the exemplary embodiment of FIG. 14 passes through further aggregates 80 for inline production of a layer or further coating of the film web, whereby these could in principle also be provided in FIG.
  • the layer produced with the aggregates 80 may be an intermediate layer (interleave), which is rolled up together with the film web on the roll R2, but in the case of its further processing at the latest after production of the end product (eg OLED) is removed again. It must be detachable from the film web for this purpose.
  • Such an intermediate layer serves primarily to cushion the thin and sensitive ALD or MLD layers on the roll R2 and to protect against damage.
  • the film web can namely be exposed to a considerable winding pressure.
  • the intermediate layer can be produced from a formless, in particular liquid, crosslinkable resin composition which is cast or extruded, for example, from a sheet die onto a rotating coating roll. Even on the coating roller, the mass can be crosslinked with UV light, so that a self-supporting web is formed. This can then be merged with another roll with the film web.
  • the material for the intermediate layer can also be an extruded, thermoformable, so-called hotmelt mixture, which requires no crosslinking after application. In this case, the UV irradiation can be omitted, but the coating roller would have to be designed as a cooling roller.
  • the intermediate layer as well as the mentioned for their preparation inline suitable units are not shown in Fig. 1 4.
  • the material used to produce the intermediate layer can be provided with particular advantage also with getters for water molecules in order to keep the coated film web on the roll R2 dry until it is further processed, or even to dry it additionally.
  • the getter can also be applied to an additionally separately supplied film web (not shown) or enclosed between two additional separately supplied film webs.
  • the intermediate layer is provided with adhesive effects, as is known, for example, in WO 201/1/3241 0 A1.
  • the layer produced with the aggregates 80 may be a protective layer permanently bonded to the film web for the ALD or MLD layers, which remains in the processing of the film web on this.
  • the layer produced by the aggregates 80 can be permanently connected to the film web and must also be applied to the coated side of the film web, as shown in FIG. In FIG.
  • the units 80 correspondingly comprise an aggregate 81 for applying the coating to the moving film web, for example, again in the form of a slot die followed by a drying section 82 for its drying and / or thermal or radiation-related crosslinking.
  • a protective layer permanently attached to the ALD or MLD layer may contain getters suitable for water and oxygen.
  • FIG. 15 shows a further embodiment of a device according to the invention, again with four pairs of coating plates 1-8 arranged in a stack for a double pass of the film web FB as in FIG. 1.
  • the measuring device 40 is here however, disposed between a precoat plate 91 and a precoat counter plate 92 and the complete stack of the eight coating plates 1-8.
  • the counter plate is located directly on the back of the coating plate 1.
  • the localized in Fig. 1 4 heating channel 35 is moved accordingly against film travel direction.
  • the precoat plate 91 may be configured like a counter plate 2 according to any one of the above-described coating plates 1 and the precoat counter plate 92. In the latter, air is preferably used to form the gas cushion.
  • FIG. 16 shows yet another embodiment of a device according to the invention with a total of seven pairs of individual pairs in side by side and in four levels, for example, in a frame one above the other arranged coating plates 1-1 4 for a double pass of the film web FB.
  • the individual pairs of coating plates are aligned horizontally here, wherein the lower plates each mounted stationary and the upper plates are opposite to the lower plates in height respectively movable.
  • the upper plates Under the pressure of the above and above the film web FB forming gas cushion, the upper plates are dynamically raised until the film web FB without contact between them can go through.
  • the counterforce to the dynamic adjustment of the plate spacing is preferably applied exclusively by the weight of the upper plates.
  • the measuring device 40 is arranged here between the third and fourth plate pair, but could also be positioned differently, even after which thickness is desired or favorable for the already formed coating.
  • the film web FB passes through the measuring device 40 only after its first pass and is guided around it in a wide pass.
  • the turn, for example, according to FIG. 1 2 executed return and turn the film web for its second pass is not shown in detail in Fig. 1 6. Only a portion of the recycled portion of the film web is designated by FB ' .
  • a corresponding encapsulation could also be provided in FIG. 1.
  • FIG. 17 shows an embodiment of a measuring device 40, as is preferably used in FIGS. 1, 14, 15 and 16. It serves to determine an OTR value of the ALD or MLD coating previously produced during the passage through the plate pair 1, 2 or 91, 92.
  • the measuring device 40 has, similar to the pairs of coating and counter plates 1, 2, two opposing flat plates, wherein one of these plates is referred to below as a measuring plate 41 and the other as a counter-measuring plate 42.
  • the film web FB runs between the two plates 41, 42 in a straight line supported on gas cushion contactless, as can be seen in Fig. 1 6b). Their previously coated during the passage through the pair of plates 1, 2 and 91, 92 coated side is directed against the measuring plate 41.
  • Both plates 41, 42 are identical and arranged congruent. Their insides, as shown in FIG. 16a) in plan view of the inside of the measuring plate 41, have a central measuring zone 43 in which a collecting groove 44 with a central removal opening 45 is formed.
  • the measuring zone 43 is encircled on all sides by a porous region 46 for the areally distributed supply of gas to form the gas cushion.
  • In the area 46 are In the direction of the film web in front of and behind the measuring zone 43 there are in each case two discharge regions extending transversely to this running direction, one of which is denoted by 47.
  • the resulting gas flows are indicated in Fig. 1 6b) by arrows.
  • the measuring plate 41 is used as gas for the gas cushion highly pure nitrogen N 2, respectively.
  • the gas cushion of the measuring plate 41 In the counter plate 42, however, ambient air or pure oxygen is supplied to the gas cushion. In each case, a much smaller amount of gas is taken from the measuring zones, so that a certain back pressure is formed there.
  • the gas taken from the measuring zone 43 of the measuring plate 41 is supplied as a measuring gas to an oxygen sensor (not shown) and subsequently discharged into the environment.
  • a corresponding quantity of the high-purity nitrogen N 2 supplied to the gas cushion of the measuring plate 41 in the region 46 is branched off for background measurement and supplied to a further oxygen sensor (not shown) and subsequently likewise discharged into the environment.
  • the difference erstoffsensoren of two sow determined in terms of the oxygen content in the two measuring gases is based on the diffusion of oxygen from the supplied via the counter measuring plate 42 ambient air through the coated sheet in the oxygen-free nitrogen gas, the measuring plate 41 and is thus a measure of the gewünsch ⁇ th OTR-value ,
  • the determination of the OTR value after only one pass of the film web through the plate pair 1, 2 or the plate pair 91, 92 is advantageous over the determination of the OTR value after an optionally even double pass through all plate pairs 1-8, because the generated here Barrier layer is not very thick and the OTR value is still relatively large. Accordingly, this value can be measured directly inline in a relatively short measuring time in the passage of the film web by the measuring device 40.
  • the arrangement of the measuring device in FIG. 15 has the advantage over that of FIG. 14 that the use of oxygen-containing air in the counter-precoating plate 92 makes the film web preconditioned with respect to O 2 .
  • the OTR value that probably results after an optionally double pass through all disk pairs 1 - 8 can be determined by extrapolation based on offline comparative measurements.
  • a favorable effect here is that probable leaks of the complete barrier, in particular due to foreign particles present on the film web, are already recognizable on the still incomplete barrier.
  • an NTR value can also be determined.
  • high-purity argon may be supplied as the gas for the gas cushion in the measuring plate 41, and instead of oxygen sensors, N 2 sensors must be used.
  • the counter-plate would in this case pure nitrogen N 2 or air supply.
  • the film web can be labeled and / or coded with the measured value determined by the measuring device 40 or a data derived therefrom in the same pass.
  • This can be done by printing, embossing technology, punching technology, or by a change of material properties, for example with a laser.
  • inkjet printing technology the required information can be accommodated in a few square millimeters, for example in the form of a 2D matrix code. So that the imprint does not bother or is not easily recognizable, it can be made with transparent or fluorescent ink.
  • the coated film web Since in the further processing of the coated film web, for example OLED structures only relatively short sections of 40 - 50 cm of the film web are required and these are even further subdivided, it is preferable to each such section or even part with at least one reading provided even if a reliable measurement can be determined only on a longer portion of the film web.
  • the measured values can be distributed, for example, in a grid of 1 00 mm ⁇ 1 00 mm, or in a subsequent pattern, in a peripheral zone which is not critical for subsequent further processing, but also on the uncoated rear side of the film web over its coated area.
  • the coding can also be carried out so that it is later automatically readable, for example by contactless coding of in an edge zone to existing magnetic stripe or transponders.
  • the corresponding data could alternatively or additionally also be stored electronically together with a running meter identifier (inter alia stored on mobile storage devices and, for example, in the film sleeve), so that they can be retrieved during the further processing of the coated film web or for other requirements ,

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'objet de l'invention concerne un dispositif pour le dépôt de couches minces par au moins deux réactions de surface auto-restrictives (ALD/MLD) sur un substrat (FB), le dispositif présentant une plaque de revêtement (1) et une contre-plaque (2) disposée en face de celle-ci, également conçue comme plaque de revêtement, la plaque de revêtement présentant plusieurs zones d'introduction et d'évacuation pour le gaz de réaction et le gaz le rinçage et la contre-plaque présentant au moins une zone d'introduction pour le gaz de rinçage ou de l'air, des moyens (R1, R2 ; U1, U2) étant présents, également deux qui déplacent des bandes de feuille entre les deux plaques et les gaz introduits formant des coussins gazeux qui supportent ladite au moins une bande de feuille lors du passage entre les deux plaques et qui la maintiennent à une certaine distance de celles-ci. Les deux plaques sont montées de manière mobile l'une par rapport à l'autre à une distance variable déterminée par la pression du coussin gazeux par rapport à une contre-force et sont conçues de manière poreuse dans au moins une zone d'introduction pour une sortie du gaz répartie de manière plane sur cette zone.
PCT/EP2017/055224 2016-03-07 2017-03-06 Dispositif de dépôt de couches minces WO2017153356A1 (fr)

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CH294/16 2016-03-07
CH00294/16A CH712199A1 (de) 2016-03-07 2016-03-07 Vorrichtung zur Abscheidung dünner Schichten auf einem Substrat und Rollenmaterial mit einem Substrat mit solchen Schichten.

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WO2014123415A1 (fr) 2013-02-07 2014-08-14 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procédé et appareil permettant de déposer des couches atomiques sur un substrat
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WO2015132410A1 (fr) 2014-03-07 2015-09-11 Fofitec Ag Matériau en rouleau pour une couche submicrométrique ou pourvu d'une couche submicrométrique sur un support flexible et utilisation dudit matériau
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US4587002A (en) 1982-08-24 1986-05-06 Edward Bok Apparatus for floating transport and processing of substrate or tape
DE19902936A1 (de) 1998-12-23 2000-06-29 Bachofen & Meier Ag Buelach Vorrichtung zum berührungslosen Führen oder Behandeln einer laufenden Materialbahn, insbesondere einer Papier- oder Kartonbahn, Metall- oder Kunststoffolie
DE20309429U1 (de) 2003-06-17 2003-09-18 Reifenhäuser GmbH & Co. Maschinenfabrik, 53844 Troisdorf Abzugsvorrichtung einer Schlauchfolienextrusionsanlage
DE10339262A1 (de) 2003-08-26 2005-03-17 Voith Paper Patent Gmbh Bahnführungseinrichtung
US20080166884A1 (en) * 2007-01-08 2008-07-10 Nelson Shelby F Delivery device comprising gas diffuser for thin film deposition
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US20110049285A1 (en) * 2009-08-31 2011-03-03 E.I. Du Pont De Nemours And Company Apparatus and method for loading a film cassette for gaseous vapor deposition
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WO2011056521A1 (fr) 2009-10-27 2011-05-12 Eastman Kodak Company Collecteur de distribution de fluide comprenant des plaques reliées
WO2012005577A1 (fr) 2010-07-07 2012-01-12 Levitech B.V. Procédé et appareil servant à faire avancer sans contact des substrats
WO2013151430A1 (fr) 2012-04-03 2013-10-10 Solaytec B.V. Procédé de fabrication d'un substrat à multiples couches de dépôt
US20150275373A1 (en) * 2012-09-28 2015-10-01 Osram Gmbh Device and method for coating substrates
WO2014123415A1 (fr) 2013-02-07 2014-08-14 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Procédé et appareil permettant de déposer des couches atomiques sur un substrat
WO2014193234A1 (fr) 2013-05-30 2014-12-04 Solaytec B.V. Tête d'injecteur pour dépôt de couche atomique
WO2015132410A1 (fr) 2014-03-07 2015-09-11 Fofitec Ag Matériau en rouleau pour une couche submicrométrique ou pourvu d'une couche submicrométrique sur un support flexible et utilisation dudit matériau
WO2016072850A2 (fr) 2014-11-04 2016-05-12 Asm International N.V. Appareil de dépôt de couche atomique et procédé de traitement de substrats au moyen d'un appareil

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