Apparatus and method for depositing carbon-containing structures

Abstract

The present invention relates to an apparatus for depositing carbon-containing structures on a substrate (2) transported through the interior space of a housing (1). The interior space of the housing comprises a central region (5) arranged between a first peripheral region (3) and a second peripheral region (4). The substrate (2) enters the housing (1) through a first opening (6) assigned to the first peripheral region (3), passes through the central region (5) in a transport direction (F), and exits the housing (1) through a second opening (7) assigned to the second peripheral region (4). The apparatus comprises a gas inlet (8) intended to supply a carbon-containing process gas to the housing (1), a heating device (9) intended to thermally activate the process gas, and a gas outlet (16) connected to a pump (10) intended to direct the gas supplied to the interior space of the housing (1) outward. In the present invention, a means for controlled introduction of a reactive gas into the peripheral regions (3, 4) is provided. Gas outlet holes (20) are also provided, through which a gas that reacts with oxygen can be supplied to the apparatus. The gas that reacts with oxygen is intended to be preheated by a heating device (9), which is partially arranged in the central region (5).

Description

[Technical Field]

[0001] The present invention relates to an apparatus for depositing carbon-containing structures on endless substrates transported through a housing having a gas inlet for supplying the housing with a carbon-containing process gas, a heating device for thermal activation of the process gas, a gas outlet connectable to a gas removal system, e.g., a pump, for directing the gas supplied into the housing outward, and a central region arranged between a first peripheral region and a second peripheral region, the substrates entering through a first opening assigned to the first peripheral region, passing through the central region in the transport direction, and leaving the housing through a second opening assigned to the second peripheral region.

[0002] The present invention further relates to a method for depositing carbon-containing structures on an endless substrate transported through a housing, the substrate entering the housing through a first opening allocated to a first peripheral region, passing through a central region of the housing in a transport direction, and exiting the housing through a second opening allocated to a second peripheral region of the housing. A carbon-containing process gas is supplied through the gas inlet, the process gas being thermally activated by a heating device. The gas supplied into the housing is removed from the housing through the gas outlet by a gas removal system, e.g., a pump.

[0003] Apparatus for depositing carbon-containing structures, such as nanotubes, graphene or the like, are known from US Pat. No. 5,623,299, US Pat. No. 5,623,299 and US Pat. No. 5,623,299.

[0004] US Pat. No. 5,629,999 and US Pat. No. 5,629,999 describe an apparatus and method for depositing carbon nanostructures.

[0005] A CVD reactor with multiple growth zones for coating endless substrates is described in US Pat. No. 6,213,999.

[0006] The apparatus comprises a housing having openings on two opposite sides thereof. Through the first opening, the endless substrate to be coated with carbon structures enters a cavity in which a process chamber is located. The endless substrate exits the housing on the opposite side; it is unwound from a first roll and wound onto a second roll. Within the housing, a carbon-containing process gas is brought up to a process temperature such that a chemical reaction in the process gas forms carbon-containing structures on the endless substrate passing through the process chamber in a transport direction.

[0007] The area where the substrate enters the housing and where the substrate exits the housing includes a diffusion barrier. The diffusion barrier comprises a cleaning chamber into which an inert gas is supplied. For this purpose, a plurality of gas outlet and inlet holes are provided, located on both sides of the substrate, through which the cleaning gas can enter and exit the cleaning chamber. In this way, the intrusion of ambient air into the interior of the housing is suppressed.

[0008] The substrate to be coated with the carbon structure in the central region of the housing must have a clean surface. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] European Patent Application No. 3 015 425 [Patent Document 2] European Patent Application No. 2 450 310 [Patent Document 3] International Publication No. 2013 / 043247 [Patent Document 4] DE 10 2018 110 348 A1 [Patent Document 5] Korean Patent No. 101760653 [Patent Document 6] US Patent No. 2013 / 0 071 565 Summary of the Invention [Problem to be solved by the invention]

[0010] The underlying object of the invention is to describe a means for refining the type of apparatus concerned or the type of method concerned in such a way as to improve the coating results.

[0011] This object is solved by the invention as defined in the claims, which, like those set out in the independent claims, represent not only advantageous further inventive developments but also independent solutions.

[0012] The present invention relates to an apparatus and method for depositing carbon-containing structures, particularly but not exclusively graphene layers or carbon nanotubes, the apparatus having a housing or chamber with adjustable gas pressure, for example in the range between 950 mbar and 1500 mbar.

[0013] First, it is proposed that a means be provided in one of the two peripheral regions where the substrate enters and exits, by which gas is supplied to the peripheral region. The reactive gas may be an oxidizing gas and preferably enters the housing through the first opening. An inflow of the reactive gas then occurs in the transport direction, and the uncoated substrate comes into contact with the reactive gas in the first peripheral region. Inside the process chamber formed by the central region, the temperature of the substrate and / or the reactive gas is controlled in such a way that a chemical reaction occurs. In the substrate inlet region formed by the peripheral region on the substrate inlet side, the temperature of the reactive gas and / or the substrate is increased to a point where the reactive gas can perform a cleaning action. Means may be provided for establishing a concentration gradient in the flow direction of the reactive gas by extracting gas from the housing or by supplying an inert gas into the housing. As the substrate passes through the housing, the reactive gas may have a high partial pressure in the gas phase in the housing. This partial pressure decreases as the distance from the inlet opening where the substrate enters the housing increases.

[0014] The reactive gas may chemically react with the substrate surface or with substances adhering to the substrate surface. The chemical reaction may produce volatile reaction products that are removed from the housing interior by a gas removal system, e.g., a pump and a gas outlet. A supply line may be provided through which the reactive gas, which may be oxygen or dry air, is supplied to the housing interior. The inlet or outlet opening may be an openable or lockable opening. In particular, the substrate may be provided as an endless substrate.

[0015] The first and second openings may each be or form a diffusion barrier that is cleaned by an inert gas, for example nitrogen. Such a diffusion barrier may comprise a number of gas outlet holes uniformly distributed over the gas outlet array, through which the inert gas exits towards each of the two broad faces opposite the substrate. The gas outlet holes may be located adjacent to the gas inlet holes, through which the inert gas introduced into the cleaning chamber in such a way as to pass over the substrate is sucked out.

[0016] However, it is also possible for the gas outlet holes alone to function as a diffusion barrier, in which case the housing interior is preferably set to an underpressure, so that the inert gas supplied to the gap between the substrate surface and the gas outlet holes flows entirely or almost entirely into the housing interior, where it can carry ambient air, together with the oxygen contained therein, into the housing interior.

[0017] The resulting gas flow can be directed in the direction of substrate transport or against the direction of transport. In a preferred variant of the invention, the first opening can be positioned vertically above the second opening, allowing the substrate to move through the process chamber from the top to the bottom. Reactive gases are preferably supplied only through the top or inlet opening. The process gas can be hydrogen, methane, acetylene, ethylene, or other carbon-containing gases, or combinations of the aforementioned gases, either in pure form or mixed with an inert gas.

[0018] The process gas may be a mixture of these gases, preferably containing hydrogen in addition. The ratio of carbon-containing gas to hydrogen or inert gas, e.g., nitrogen, in the process gas may range between 0.25 and 2, or between 0.5 and 2, or equal to 1. In the latter case, no nitrogen or inert gas is supplied to the interior of the housing.

[0019] The inert gas may be nitrogen, argon, or another non-reactive gas. The reactive gas capable of performing a cleaning action on the substrate is preferably oxygen. In a preferred variant of the invention, the diffusion barrier is designed so that atmospheric oxygen passes through it. In a preferred variant, the diffusion barrier assigned to the first opening is controlled by the control device in such a way that a controlled small amount of oxygen passes through it and enters the peripheral area. In contrast, the diffusion barrier assigned to the second opening is controlled by the control device in such a way that little or no oxygen passes through the diffusion barrier and enters the peripheral area assigned to the second opening.

[0020] On the one hand, the diffusion barrier can be controlled by varying the mass flow rate of the inert gas. On the other hand, however, it may also be controlled through varying the height of the gap between the gas outlet holes or, if provided, between the gas inlet holes. In that case, the gas inlet or outlet holes are arranged in an inlet array or gas outlet array extending parallel to the substrate surface. Control can be affected by varying the distance from the gas inlet or outlet array to the substrate surface.

[0021] In particular, both diffusion barriers are controlled in such a way that the partial pressure of oxygen directly on the first edge of the peripheral region adjacent to the first opening has a value of at least 0.1% (1000 ppm), and the partial pressure of oxygen directly on the second edge of the peripheral region adjacent to the second opening has a value of 0.01% (100 ppm). In that case, the initial partial pressure in the central region is preferably no greater than 0.005% (50 ppm) or 0.001% (10 ppm). The two partial pressures directly on the edges of each peripheral region may be set to differ from each other by at least 5, 10, or at least 100 times. By means of means arranged inside the housing for influencing the partial pressure of the reactive gas, a concentration gradient is preferably provided that decreases from the periphery to the center of the process chamber by at least 10, 20, 50, 100, 200, 500, or 1000 times.

[0022] The diffusion barriers assigned to the first opening and the second opening are not completely airtight. As a result, a gas flow from the surrounding atmosphere can pass through both diffusion barriers and enter the housing interior. The two diffusion barriers are designed differently to ensure that the partial pressure of the reactive gas is lower in the second peripheral region than in the first peripheral region. For example, the gap through which the substrate passes into the cleaning chamber of the diffusion barriers can have different gap widths, heights, or cross-sectional areas. Alternatively, or interactively therewith, the mass flow rates of the cleaning gas may be controlled differently by the controller in such a way that a greater mass flow rate of the reactive gas enters the housing interior through the first opening than through the second opening. However, alternatively or in combination therewith, a gas may be provided in the vicinity of the second opening, in particular in the second peripheral region, to chemically react with the reactive gas and to obtain an inert gas as a reaction product. In particular, gas outlet holes are provided, preferably arranged in the second peripheral region for a process gas that chemically reacts with the reactive gas, and one or more gas outlet holes are provided therein in order to create a concentration gradient of the reactive gas that decreases in the transport direction in the region of the first opening or the first peripheral region, by means of which the gas can be exhausted out of the housing interior.

[0023] The reactive gas reacts with the process gas as well as with contaminants on the substrate surface. The process gas may be supplied to the process chamber formed by the housing interior at a supply point remote from the reactive gas supply point. The process gas supply point is preferably located in the second peripheral region. Preferably, the distance from the gas inlet for supplying the process gas to the gas outlet hole is about 5-10% of the total length of the process chamber from the second opening. In this case, the total length corresponds to the distance between the first and second openings. The length of the first peripheral region measured in the transport direction may be between 20% and 30%, preferably equal to 25% of the total length. The length of the second peripheral region may be between 15% and 25% of the total length, preferably equal to 20% of the total length. The process gas flows through the process chamber in a direction opposite to the substrate transport direction and chemically reacts with the reactive gas preferably only in the region of the first peripheral region. This leads to a decrease in both the partial pressure of the reactive gas and the partial pressure of the process gas in the first peripheral region, but prevents the reactive gas from entering the central region. The first peripheral region is therefore a clean region, in which a chemical reaction occurs between the reactive gas and the carbon-containing gas of the process gas. The central region is the growth region, in which the carbon structures are deposited without being combusted by the reactive gas. During the deposition of the graphene multilayer structures, the temperature in the growth region is preferably between 500°C and 1200°C, preferably between 600°C and 900°C. On the other hand, if a graphene monolayer is to be deposited, the temperature can be in the range between 500°C and 1200°C, in particular between 850°C and 1100°C. Otherwise, if carbon nanotubes (CNTs) are to be deposited, the temperature may be in the range between 500°C and 1000°C, preferably between 600°C and 700°C. In this case, the temperature is preferably in the range between 600°C and 660°C, or between 615°C and 625°C, respectively. The temperature of the substrate in the first peripheral region may be in the range between 500°C and the substrate temperature in the central region.

[0024] A cooling device may be provided, by which the substrate can be cooled before it leaves the housing interior. The cooling device is preferably formed by a diffusion barrier allocated to the second opening. The diffusion barrier allows heat to be dissipated from the substrate exiting the housing interior. This occurs preferably due to an inert gas being supplied to the diffusion barrier. The temperature of the inert gas is controlled to be below a given temperature, for example 50°C. By supplying the inert gas to the gap between the gas outlet hole and the substrate, the substrate is cooled to a temperature below 150°C or below 100°C. This prevents the carbon structures deposited on the substrate from being burned in the ambient air. Furthermore, the second diffusion barrier is arranged to function in such a way that as little ambient air as possible enters the housing interior. [Brief explanation of the drawings]

[0025] In the following, the invention will be explained in more detail with reference to exemplary embodiments. [Figure 1] FIG. 1 shows a schematic cross section of a first embodiment of an apparatus according to the present invention. [Figure 2] FIG. 2 shows the evolution of the partial pressure of the reactive gas in the transport direction of the substrate. [Figure 3] FIG. 3 shows a second embodiment in a similar manner to FIG. [Figure 4] FIG. 4 shows a second embodiment in a similar manner to FIG. DETAILED DESCRIPTION OF THE INVENTION

[0026] The device shown in the figure has an elongated housing 1 with a housing case, which is closed at the bottom and opposite top by end caps. Each of the two end caps has an opening 6, 7, which has an elongated shape, through which a substrate 2 can pass into the housing 1 and out of the housing 1. The substrate 2 is an endless substrate that is unwound from a first roll 18 and wound onto a second roll 19.

[0027] The upper first opening 6 forms an inlet opening for the substrate 2, and the lower opening 7 forms an outlet opening for the substrate 2. The substrate 2 passes through the device oriented linearly, vertically downwards, in a transport direction F. Within the device there is a gas inlet hole 8, through which a process gas, for example methane, acetylene or ethylene, is fed into the process chamber. A heating device 9 is provided, by means of which the process gas is heated. A further heating device 21 may also be provided, by means of which the substrate 2 is heated.

[0028] The interior of the housing 1 forms three regions arranged one after the other in the transport direction F. A first peripheral region 3 is directly adjacent to the first opening 6. A second peripheral region 4 is directly adjacent to the second opening 7. Between them there is a central region 5, in which a coating process is carried out, in which carbon structures are deposited on one of the two large faces of the substrate through a chemical reaction of process gases. The carbon structures may be carbon nanotubes or graphene.

[0029] A gas outlet 16 is provided to allow gas to exit the volume of the housing 1. The gas outlet 16 is connected to a pump 10.

[0030] A diffusion barrier is provided before the first opening 6 in the transport direction and after the second opening 7 in the transport direction, which prevents or controls the ingress of ambient air. By means of a control device 15, the diffusion barrier on the substrate inlet side is controlled in such a way that a constant flow of ambient air, i.e. a flow of oxygen-containing gas, passes through the first opening 6 into the first peripheral region 3. On the other hand, the diffusion barrier on the substrate outlet side is controlled by the control device in such a way that no or only a small amount of ambient air, i.e., oxygen contained in the ambient air, can enter the second peripheral region 4 through the diffusion barrier.

[0031] Each diffusion barrier, which is designed substantially identically, forms a cleaning chamber 17 through which the substrate 2 is transported. The cleaning chamber 17 therefore has two parts, each assigned to one of the two broad faces of the substrate 2. A gas inlet structure with a gas inlet volume 11 and a gas outlet structure with a gas outlet volume 12 are assigned to each of the two parts of the cleaning chamber 17. An inert gas, for example nitrogen, enters through gas outlet holes 13 in the respective part of the cleaning chamber 17 and is supplied to the gas inlet volume 11. The inert gas is deflected at the broad face of the substrate 2, in the transport direction or against the transport direction, into a gas outlet connected to the gas outlet volume 12. entranceIt flows towards the holes 14 and the gas outlet volume is evacuated so that a gas flow is formed in the cleaning chamber 17. This gas flow forms a diffusion barrier where ambient air entering the cleaning chamber is bled through the gas outlet holes 14.

[0032] The barrier function of the cleaning chamber 17 can be varied via its width. The greater the distance between two oppositely positioned gas outlet or inlet arrays, the weaker the barrier function. The barrier function can be influenced not only by the width, height, and cross-sectional area of ​​the cleaning chamber 17, but also by the volumetric flow rate of the inert gas. The control device 15 is set so that the barrier functions of the two diffusion barriers differ from each other. The barrier function of the diffusion barrier on the substrate inlet side is adjusted so that oxygen-containing air passes through the cleaning chamber 17 at a volumetric flow rate that results in an oxygen partial pressure not exceeding 1%, preferably not exceeding 0.2%, immediately adjacent to the opening 6 in the peripheral region 3.

[0033] On the other hand, the barrier function of the diffusion barrier on the substrate outlet side is adjusted so that oxygen-containing air passes through the cleaning chamber 17 at a volumetric flow rate that results in a low partial pressure, particularly less than 0.1% or less than 0.02%, immediately adjacent to the opening 7 in the peripheral region 4.

[0034] The gas outlet 16 is designed so that a concentration gradient of the reactive gas is created in the transport direction F. The oxygen partial pressure in the process chamber decreases continuously in the transport direction F as shown in FIG.

[0035] For this purpose, the gas outlet 16 may comprise a plurality of gas outlet holes arranged in the conveying direction, which form bleed holes.

[0036] The gas inlet 8 may have gas outlet holes arranged on the substrate outlet side of the peripheral region 4. The process gas flows through it in the direction opposite to the transport direction F, leaving the peripheral region 4 and heading towards the central region 5. The heating device 9 causes an increase in the temperature of the process gas. In this connection, the process gas may be thermally decomposed while in the gas supply line. The gas inlet pipeline may thus form a loop extending through the heated central region 5. A heating device 21 is provided for heating the central region 5.

[0037] The process gas may include hydrogen or other reducing gases in addition to the carbon-containing gas.

[0038] The process gas reacts with oxygen. In particular, preheating provides that the process gas and / or the substrate 2 are raised to a temperature at which they chemically react with oxygen. In this regard, it is advantageous for the process gas, or a portion of the process gas, to be supplied to the second peripheral region 4 immediately adjacent to the second opening 7 in order to react with the oxygen diffusing through the diffusion barrier. This results in a significant additional reduction in the oxygen partial pressure in this region.

[0039] Thus, the device of the present invention has two openings 6 and 7. The second opening 7 is a passive opening through which as little oxygen as possible enters the housing interior. The first opening, on the other hand, is an active opening through which controlled oxygen can enter the housing interior. The substrate passes through the active opening into the housing interior and through the passive opening out of the housing interior. Immediately after opening 6, the oxygen partial pressure entering the housing interior ranges between 0% and 1% of the total pressure. The total pressure can be atmospheric pressure. The oxygen flow rate through opening 6 can be controlled by adjusting the flow rate of the inert gas in the diffusion barrier. In this way, the substrate 2 formed with the film is cleaned as it enters the housing interior. A separate oxygen source, e.g., an oxygen supply line, is provided, by which oxygen is supplied to the first peripheral region in a targeted manner. For this purpose, a separate gas inlet, e.g., a showerhead, can be provided there.

[0040] The gas outlet hole 20 through which the reducing gas is supplied to the second peripheral region 4 may be a second gas outlet hole of the gas inlet device, whereby the process gas is supplied to the central region 5. A further gas inlet, not shown in Figure 1, may be so provided, whereby the process gas is supplied directly to the central region.

[0041] The temperature in the region of the central region will be higher than in the regions in the peripheral regions 3, 4. It is therefore advantageous if the pipeline of the gas inlet 8 passes through the central region 5 and the preheated process gas leaves through the gas outlet holes 20. In the region of the second peripheral region 4, the preheated process gas can react with atmospheric oxygen entering through the diffusion barrier to produce, for example, CO2.

[0042] The two diffusion barriers in front of the openings 6, 7 that become the housing caps create, to some extent, a gas curtain seal, which is controlled in such a way that a controlled flow rate of oxygen enters the process chamber through the seal on the substrate inlet side, reducing the concentration gradient in the process chamber to a preset value approximately equal to the center of the process chamber, while as little oxygen as possible enters the process chamber through the seal on the substrate outlet side, where chemical reactions occur involving the oxygen that enters the process chamber.

[0043] The carbon-containing process gas may be supplied through an inlet element in the form of a showerhead located in the central region 5 .

[0044] In one variant, the gas outlet through which gas phase reaction products of reactive gases and process gases are removed from the interior of the housing, i.e., the process chamber and adjacent peripheral regions, can be designed in such a way that a concentration gradient of reactive gas is established, with a high concentration, e.g., up to 20 ppm, approximately near the inlet opening 6, a low value, e.g., up to 5 ppm or 1 ppm, at the border of the central region 5, and approaching 0 at the center M of the process chamber. The total pressure inside the housing can be 15 mbar to 50 mbar below the external pressure.

[0045] The invention relates in particular to an apparatus or method in which oxygen is supplied in a targeted manner to an inlet region and a gas that reacts with oxygen is introduced in a targeted manner in an outlet region, wherein a concentration gradient of the reactive gas that decreases in the transport direction is generated inside the housing by a gas outlet device arranged close to the inlet region.

[0046] The embodiment shown in FIG. 3 is substantially the same as the embodiment shown in FIGS. 1 and 2, and reference is made to the relevant descriptions therein.

[0047] A diffusion barrier arranged on the outside of the housing 1 is adjacent to the first opening 6. Apart from two distribution volumes 11, each located opposite one of the two wide faces of the substrate 2, the inert gas passes through the gas outlet holes 13 into the gap between the two gas outlet arrays carrying the gas outlet holes 13. The substrate 2 is transported through this gap, which forms a cleaning chamber 17, and then through the opening 6 into the housing 1, which forms the process chamber. Ambient air flows through the gap, which forms the cleaning chamber 17, into the process chamber. In one variant, the diffusion barrier is designed and controlled in such a way that the partial pressure of oxygen contained in the ambient air has a value not exceeding 1000 ppm in the region of the first opening 6.

[0048] The bleed holes 24 through which gas is sucked out of the process chamber by the pump 10 are preferably located beside both broad faces of the substrate 2 in the region of the boundary between the first peripheral region 3 and the central region 5 .

[0049] A diffusion barrier is also positioned adjacent the second opening 7. It is constructed in the same manner as the diffusion barrier of the first opening 6 described above, but is designed and functions in such a way that as little ambient air as possible is allowed to pass through the diffusion barrier into the process chamber.

[0050] Atmospheric oxygen through the first opening 6 and atmospheric oxygen through the second opening 7 enter the process chamber and reacts with the process gas supplied into the process chamber through the gas outlet holes 20, and in particular with the carbon-containing gas and / or hydrogen-containing gas contained therein. The chamber in which the chemical reaction occurs adjacent to the second opening 7 is limited to the immediate vicinity of the second opening 7. In this regard, measures are taken that are designed to prevent the carbon structures disposed on the substrate from being burned by atmospheric oxygen.

[0051] 4 shows that the partial pressure of the oxygen supplied through the first openings 6 continuously decreases. This occurs on the one hand due to the reaction of atmospheric oxygen with contaminants on the substrate 2, and on the other hand due to the bleeding of gas through the gas outlets 16 and also due to chemical reactions between atmospheric oxygen and the process gas in the region of the first peripheral region 3. In this connection, measures are taken designed to prevent atmospheric oxygen from reaching the central region 5. The partial pressure of the process gas, and in particular of the carbon-containing gas contained in the process gas, is substantially constant over the entire length of the central region and drops off in the region at the end of the central region 5 adjacent to the first peripheral region 3.

[0052] In the present invention, the diffusion barrier adjacent to the second opening 7 functions as a cooling device to cool the substrate exiting the process chamber to a temperature below 150° C. For this purpose, heat is extracted from the substrate 2 by an inert gas supplied to the cleaning chamber 17.

[0053] The foregoing is intended to serve to describe inventions within the full scope of this application, which also advance the relevant art independently through at least the combinations of features described below, and which may also combine two, more, or all of said combinations of features.

[0054] 10. An apparatus characterized in that means are provided for the controlled introduction of reactive gas into the first peripheral region (3).

[0055] A method comprising: a reactive gas entering a first peripheral region (3) in a controlled manner, the gas chemically reacting with contaminants on the substrate in the first peripheral region.

[0056] An apparatus characterized in that means are provided for supplying the mass flow rate of reactive gas to both the first peripheral region (3) and the second peripheral region (4) in a controlled manner, in which the mass flow rate entering the first peripheral region (3) is greater than the mass flow rate entering the second peripheral region (4).

[0057] An apparatus or method characterized in that each of the first opening 6 and the second opening 7 is formed by a diffusion barrier 11, 12, 13, 14 that is washed with an inert gas, and through which the substrate 2 is transported, the diffusion barriers 11, 12, 13 are configured in such a way that the mass flow rate of ambient air containing oxygen that enters through the first opening 6 as a reactive gas is adjustable or regulated, or controllable or controlled by a control device, or the mass flow rate of the inert gas that washes them is controlled in such a way.

[0058] 10. An apparatus or method characterized in that the diffusion barriers (11, 12, 13, 14) are controllable or controlled by varying the flow rate of the inert gas and / or by their spacing from the gas outlet hole (13) or the gas inlet hole (14).

[0059] 10. An apparatus or method characterized in that reactive gas is supplied into the can or at least into the first peripheral region 3 through reactive gas inlet holes 23.

[0060] An apparatus or method characterized in that, inside the housing, the gas outlet holes (20) and the bleed holes (24) are arranged or function in such a way that the partial pressure of the reactive gas is continuously reduced from the first opening (6) in the transport direction (F), so that chemical reaction of the reactive gas with contaminants on the substrate (2) and with the process gas occurs only in the first peripheral region (3) to a rate of 90% or at least to a rate of 90%.

[0061] 1. An apparatus or method characterized in that the diffusion barriers (11, 12, 13, 14) have inlet holes (13) for generating a gas flow directed transversely to the transport direction F into the cleaning chamber (17), which flow exits or is bled from the cleaning chamber (17) through gas outlet holes (14) or flows into the interior of the housing.

[0062] 10. An apparatus or method, characterized in that the gas outlet holes (20) in the second peripheral region (3) are arranged or function in such a way that the partial pressure of the process gas drops in the direction opposite to the transport direction (F).

[0063] 10. An apparatus or method, characterized in that the gas inlet (8) or the pipeline of the gas inlet (8) is preheatable or preheated by a second heating device (9).

[0064] 10. An apparatus or method, characterized in that the second heating device (9) is at least partially arranged in the central region (5).

[0065] an apparatus or method, characterized in that an air bleed hole (24) is positioned or functions at the boundary between the first peripheral region (3) and the central region (5) inside the housing in such a way that a reactive gas in the first peripheral region (3) chemically reacts with contaminants on the surface of the substrate (2) to clean the substrate (2), and carbon-containing structures are deposited in the central region (5).

[0066] An apparatus or method characterized in that a cooling device is provided, by which the substrate 2 emerging from the second opening 7 can be or is cooled.

[0067] An apparatus or method characterized in that the diffusion barrier (11, 12, 13, 14) is designed or functions as a cooling device, by means of which the substrate (2) is cooled.

[0068] An apparatus or method characterized in that the diffusion barrier (11, 13) has a gas outlet hole (13) directed towards the surface of the substrate (2), through which an inert gas is supplied into the gap between the gas outlet hole (13) and the substrate (2), and in that case the total pressure inside the housing is adjusted in such a way that the inert gas supplied into the gap flows into the gas interior.

[0069] An apparatus or method characterized in that the substrate 2 is an endless substrate that is or can be unwound from a first roll 18, and that after cleaning the surface of the substrate inside the housing and coating the surface of the substrate 2 inside the housing, it is or can be wound onto a second roll 19.

[0070] 1. An apparatus characterized in that the length of the first peripheral region 3 is equal to 20-30% or 25% of the total length defined by the distance between the first opening 6 and the second opening 7 measured in the conveying direction F, and / or the length of the second peripheral region 4 is equal to 15-25% or 20% of the total length.

[0071] The device is characterized in that the gas outlet hole (20) is located away from the second opening (7) in the direction opposite to the conveying direction (F), or the distance measured in the conveying direction (F) between the gas outlet hole (20) and the second opening (7) corresponds to 5 to 10% of the total length.

[0072] The method is characterized in that the total pressure inside the housing is at least 50 mbar lower than the ambient pressure.

[0073] 1. A method according to claim 1, wherein in the central region 5 the substrate 2 is raised to a temperature in the range between 500°C and 1200°C or between 600°C and 900°C for depositing graphene multilayer structures, or to a temperature in the range between 500°C and 1200°C or between 850°C and 1100°C for depositing graphene monolayers, or to a temperature in the range between 500°C and 1000°C or between 600°C and 700°C for depositing carbon nanotubes (CNTs).

[0074] A method characterized in that the partial pressure of the reactive gas in the region of the first opening 6 is not greater than 0.1% (1000 ppm) of the total pressure inside the housing and / or the partial pressure of the reactive gas at the boundary between the first peripheral region 3 and the central region 5 is less than 0.005% (50 ppm) or 0.001% (10 ppm) of the total pressure.

[0075] A method characterized in that the substrate temperature in the first peripheral region (3) is raised to a temperature above 500°C.

[0076] 10. A method according to claim 9, wherein the process gas comprises at least one of CH4, C2H2, C2H4, N2 and / or is a mixture of at least two of these gases.

[0077] A method characterized in that the mass ratio of carbon-containing gas to hydrogen or inert gas in the process gas is in the range between 0.25 and 2, or in the range between 0.5 and 2, or equal to 1.

[0078] A method characterized in that in the central region (5) neither a direct gas supply nor a direct gas extraction is carried out.

[0079] A method characterized in that, when leaving the housing interior through the second opening 7, the substrate 2 is cooled at the diffusion barriers 11, 12, 13, 14 to a temperature below 150°C or below 100°C by dissipation of heat in the inert gas.

[0080] All disclosed features are essential to the invention (both by themselves and in combination with one another). The disclosure of the present application includes in its entirety the disclosure content of the relevant / attached priority documents (copies and earlier applications), also for the purpose of incorporating the features of these documents into the claims of the present application. The dependent claims are characterized by an independent, inventive further development of the prior art, even without the features of the claims cited therein, in particular for the purpose of filing a divisional application based on these claims. The invention specified in each claim may additionally have one or more features specified in the preceding description, particularly those given reference signs and / or specified in the sign explanations. The present invention also relates in particular to embodiments in which individual features set forth in the preceding description are not implemented, insofar as they are clearly unnecessary for the respective intended use or can be replaced by other means having the same technical effect. [Explanation of symbols]

[0081] 1. Housing 2 Endless board 3. First Peripheral Area 4. Second Peripheral Area 5 Central area 6 First opening 7 Second opening 8 Gas inlet 9 Heating device 10 Pump 11 Gas distribution volume 12 Gas extraction volume 13 Gas outlet hole 14 Gas inlet hole 15 Control device 16 Gas outlet 17 Washing Chamber 18 Roll 1 19 Roll 2 20 Gas outlet hole 21 Heating device 22 reactive gas supply line 24 Bleed hole F Conveying direction

Claims

1. 1. A method for depositing carbon-containing structures onto a substrate (2) transported through a housing interior of a housing (1), the housing interior having a first peripheral region (3) adjacent to a first opening (6), a second peripheral region (4) adjacent to a second opening (7), and a central region (5) disposed between the peripheral regions (3, 4), The substrate (2) enters the housing (1) through the first opening (6), passes through the central area (5) in a conveying direction (F), and leaves the housing (1) through the second opening (7), a gas inlet (8) having a gas outlet hole (20) for supplying a carbon-containing process gas into the housing interior; The central region (5) is heated by a first heating device (21), Gas is drawn from the interior of the housing by a gas outlet (16) having a bleed hole (24) and connecting the bleed hole (24) to a pump (10); a reactive gas is introduced into the first peripheral region (3) in a controlled manner; The method, wherein a first chemical reaction occurs in the first peripheral region (3), and the reactive gas reacts with contaminants on the surface of the substrate (2), the first peripheral area (3) and the second peripheral area (4) are located within a common housing; and the gas outlet holes (20) and the bleed holes (24) are arranged and operated inside the housing such that the partial pressure of the reactive gas is continuously reduced from the first opening (6) in the transport direction (F), whereby the first chemical reaction of the reactive gas and the second chemical reaction of the reactive gas with the carbon-containing process gas occur at least 90% in the first peripheral region (3).

2. 2. The method of claim 1, wherein a controlled mass flow rate of reactive gas is supplied to both the first peripheral region (3) and the second peripheral region (4), the mass flow rate entering the first peripheral region (3) being greater than the mass flow rate entering the second peripheral region (4).

3. the first opening (6) is formed by a diffusion barrier (11, 12, 13, 14) flushed with an inert gas, through which the substrate (2) is transported; 3. The method according to claim 1, wherein the diffusion barrier (11, 12, 13) is configured such that oxygen is a reactive gas and the mass flow rate of the inert gas washing it is controlled so that the mass flow rate of the ambient air containing oxygen entering through the first opening (6) is adjusted or controlled by a control device.

4. 4. The method according to claim 3, characterized in that the diffusion barrier (11, 12, 13, 14) is controlled by changing the flow rate of the inert gas and / or by the gap between the inert gas outlet holes (13) or between the gas inlet holes (14).

5. 5. The method according to claim 1, further comprising providing a reactive gas inlet (22) through which the reactive gas is supplied to at least the first peripheral region (3).

6. 6. The method according to claim 1, wherein the length of the first peripheral region (3) represents 20-30% or 25% of the total length defined by the distance between the first opening (6) and the second opening (7) measured in the conveying direction (F), and / or the length of the second peripheral region (4) represents 15-25% or 20% of the total length, and / or the total pressure inside the housing is at least 50 mbar lower than the ambient pressure.

7. 7. The method according to any of claims 1 to 6, wherein in the central region (5), the substrate (2) is raised to a temperature in the range between 500°C and 1200°C or between 600°C and 900°C for depositing graphene multilayers, or to a temperature in the range between 500°C and 1200°C or between 850°C and 1100°C for depositing graphene monolayers, or to a temperature in the range between 500°C and 1000°C or between 600°C and 700°C for depositing carbon nanotubes (CNTs).

8. 8. A method according to any one of claims 1 to 7, characterized in that the partial pressure of the reactive gas in the region of the first opening (6) is not greater than 0.1% (1000 ppm) of the total pressure inside the housing, and / or the partial pressure of the reactive gas at the boundary between the first peripheral region (3) and the central region (5) is less than 0.005% (50 ppm) or 0.001% (10 ppm) of the total pressure.

9. a mass ratio of carbon-containing gas to hydrogen or an inert gas in the carbon-containing process gas is in the range between 0.25 and 2, or in the range between 0.5 and 2, or equal to 1, and the carbon-containing process gas is CH ４ , C ２ H ２ , C ２ H ４ , N ２ 9. The method according to claim 1, wherein the gas mixture comprises at least one of the following:

10. A device comprising a housing (1) having a housing interior, the housing interior having a first peripheral region (3) adjacent to a first opening (6), a second peripheral region (4) adjacent to a second opening (7), and a central region (5) disposed between the peripheral regions (3, 4), The substrate (2) enters the housing (1) through the first opening (6), passes through the central area (5) in a conveying direction (F), and leaves the housing (1) through the second opening (7), a gas inlet (8) having a gas outlet hole (20) for supplying a carbon-containing process gas into the housing interior; The central region (5) is heated by a first heating device (21), Gas is drawn from the interior of the housing by a gas outlet (16) having a bleed hole (24) and connecting the bleed hole (24) to a pump (10); The apparatus further comprises means for controlled entry of a reactive gas into the first peripheral region (3) and for a first chemical reaction to occur in the first peripheral region (3), the reactive gas reacting with contaminants on the surface of the substrate (2), Both said peripheral areas (3, 4) are located within a common housing, and the gas outlet holes (20) and the bleed holes (24) are arranged and operated inside the housing so that the partial pressure of the reactive gas is continuously reduced from the first opening (6) in the transport direction (F), whereby the first chemical reaction of the reactive gas and the second chemical reaction with the carbon-containing process gas occur at least 90% in the first peripheral region (3).

11. 11. The apparatus according to claim 10, further comprising means for controlling the mass flow rate of reactive gas also in the second peripheral region (4), the mass flow rate entering the first peripheral region (3) being greater than the mass flow rate entering the second peripheral region (4).

12. each of the first opening (6) and the second opening (7) is formed by a diffusion barrier (11, 12, 13, 14) flushed with an inert gas, through which the substrate (2) is transported; 12. The device according to claim 10 or 11, characterized in that the diffusion barriers (11, 12, 13, 14) are controllable by changing the flow rate of the inert gas and / or by the gap between the inert gas outlet holes (13) or between the gas inlet holes (14), so that oxygen is the reactive gas and the mass flow rate of the ambient air containing this oxygen through the first opening (6) is controlled by a control device (15).

13. 13. The apparatus according to claim 10, further comprising a reactive gas inlet (22) through which reactive gas is supplied to at least the first peripheral region (3).

14. 14. The device according to any one of claims 10 to 13, characterized in that the gas inlet (8) or the pipeline of the gas inlet (8) is preheated by a second heating device (9), the second heating device (9) being at least partially arranged in the central region (5).

15. 15. The apparatus of claim 10, wherein the bleed holes are located at the boundary between the first peripheral region and the central region such that the reactive gas in the first peripheral region chemically reacts with contaminants on the surface of the substrate to clean the substrate, and carbon-containing structures are deposited in the central region.

16. 16. Apparatus according to any of claims 12 to 15, characterized in that the diffusion barrier (11, 12, 13, 14) is configured or operated as a cooling device, by means of which the substrate (2) is cooled.

17. 17. Apparatus according to any one of claims 10 to 16, characterized in that the substrate (2) is an endless substrate that can be or has been unwound from a first roll (18), and after cleaning the surface of the substrate inside the housing and coating the surface of the substrate (2) inside the same housing, the substrate is wound onto a second roll (19).

Images