WO2018087420A1

WO2018087420A1 - A system and a method for producing continuous and monolithic graphene

Info

Publication number: WO2018087420A1
Application number: PCT/FI2017/050536
Authority: WO
Inventors: Alexander Christian PYYMAKI PERROS
Original assignee: Nanovate Oy
Priority date: 2016-11-08
Filing date: 2017-07-12
Publication date: 2018-05-17
Also published as: EP3551778A1

Abstract

This invention is about a system for chemical vapor deposition (CVD) production comprising a rotating belt system (1200, 2101) where at least one belt (1200) serves as a substrate for film (1300) growth, a CVD reactor (1000, 1101) through which the belt passes and film (1300) growth occurs, and a transfer apparatus (1400) which lies on the rotating belt line for transferring at least one film (1300) from the belt (1200), to a target substrate (1403, 9103), and that after the transfer apparatus (1400) is an apparatus for collecting the film (1300) and delivering the film (1300) for further processing as a continuous process. Invention also includes a method for producing continuous and monolithic graphene where a CVD is used to grow graphene on a rotating belt, a transfer apparatus is used to collect at least one film from the belt and from the transfer apparatus the film is fed for further processing, collection etc.

Description

A system and a method for producing continuous and monolithic graphene

This invention relates to a system and a method for producing continuous and monolithic graphene unconstrained by growth substrate size. More precisely the invention is about continuous chemical vapor deposition (CVD) graphene and oth- er materials.

The preferred growth technique for high quality 2D films such as graphene involves synthesizing the films atop a growth substrate, which is usually catalytic, via the CVD of appropriate precursor gas(es). In the case of graphene, CVD of hydrocarbons (HC) or other suitable precursors atop a catalytically-active growth sub- strate (Cu, Ru, Ge, Ni, Pt, etc.) is performed.

The preferred substrate material for graphene is copper (Cu) due to its low cost, high commercial availability, and low carbon solubility. Most often the copper substrate is in the form of a foil. Due to these favorable factors, the bulk of the research on monolayer graphene growth has been performed on copper substrates which therefore have led to a great body of knowledge concerning the growth of graphene on copper.

Prior art CVD graphene synthesis atop Cu foil typically results in the foil's exposed surface being fully covered with a graphene film that is polycrystalline, that is, consisting of a patchwork of crystals referred to as 'grains' (typically less than 25 pm) which are joined/stitched together at grain boundaries. Depending on the grain boundary, mechanical and electrical properties are potentially degraded by their presence. While chemically-exfoliated graphene is monocrystalline (i.e. a single crystal) its size is very small (micrometer/millimeter) and not generally utilizable for large-area application. Alternatively, monocrystalline (i.e. a single unbroken or perturbed crystal) CVD graphene film has been demonstrated on some materials, such as on hydrogen- terminated Ge. Prior art CVD synthesis on Ge substrates has produced single crystal graphene film that grows epitaxially atop a polished and hydrogen terminated Ge surface and fully covers the underlying substrate's surface without any of the defects associated with the grain boundaries of polycrystalline graphene films. As with copper, carbon does not easily form bonds with or diffuse into germanium which enables germanium to be repeatedly used for graphene growth. Monocrystalline graphene films produced on germanium and similar substrates generally possess superior electrical and mechanical properties to polycrystalline graphene and should thus achieve theoretically expected performance.

Optimization of CVD graphene synthesis typically involves the optimization of a host of parameters: temperature degree and profile; selection of hydrocarbon, or similar, precursor gas; pressure; flow; exposure/reaction time; annealing; pre- treatment steps; post-processing steps etc.

Prior art CVD graphene tools typically employ an enclosed chamber where the substrate sits atop a plate or susceptor during graphene synthesis. The chamber is usually made from quartz or graphite with the plate also usually made of quartz or graphite. These chambers are typically heated either resistively, in a hot-wall or cold-wall design, or photothermally. Although the quality with these CVD systems can be superb, the throughput is typically low and, depending on the size of the chamber, limited to dimensions in the centimeter range. Prior art scale-up efforts have revolved around using stacked trays inside the chamber, upon which the substrates sit, to increase the yield a few times.

Recent attempts to address the shortcomings of the low yield of prior arts involve incorporating various roll-to-roll tool configurations and production methods for graphene growth. Such tool configurations typically utilize either a tube, usually of quartz, or some other enclosed chamber for synthesizing graphene atop a sub- strate foil that is fed through the reactor/reactor heating zone. The substrate material which has two parallel length directions much greater (typically >10x) than two perpendicular length directions (i.e. a rectangular shape) is rolled up in a spiral along its longer direction into a roll or unwinder. For such systems, the substrate foil is rolled or folded over multiple times to provide a substrate foil possessing ex- tended length, usually in the feed direction, to enable large-area deposition. In such prior art tools the processed substrate foil-graphene is often also collected in a roll. Alternatively, in other prior art a thin adhesive polymer (epoxy, thermoplastic, etc.) is deposited atop the graphene layer and the substrate foil is etched away resulting in transfer of the graphene to the adhesive polymer film. Other prior art for mass production of graphene involve growing graphene on suspended large area (few square meters) copper sheets in a CVD setup employing photothermal growth with heater lamps. After graphene growth, the copper sheet is processed in a roll-to-roll system where the copper substrate is etch removed and the graphene is ultimately transferred to a target material usually after inter- mediary transfer to a polymer support. To date, prior art attempting to increase graphene throughput rely on methods where the size of the growth substrate defines the maximum size of monolithic graphene that can be produced. As an interruption in production is incurred when a substrate foil is consumed and needs replacing the prior art are not truly contin- uous. In addition, some of the prior art destroys the substrate foil and precludes its reuse. Scale-up efforts and efforts to increase production revolve around using larger substrates or multiple substrates simultaneously. The impractical ities and costs associated with larger substrates ultimately limit their adoption. For roll-to-roll systems, larger rolls or multiple rolls only push back when an interruption is in- curred to replace a substrate roll and do not remove the limitation that the growth substrate defines the maximum size of monolithic graphene that can be produced.

The present invention has the ability to continuously and very rapidly produce large area of mechanically and electronically high quality continuous graphene- monolayer or multilayer-using tooling and a production method that would cause a collapse in the production cost of graphene.

Also the present invention produces a CVD system serving as a platform capable of incorporating additional tooling for in-line and continuous processing with the graphene layer grown atop a rotating belt. Such an unbroken in-line production system can be used, for example, the continuous production or a variety of devic- es, components and functional materials of varying degrees of complexity.

From prior art documents are known many equipment and methods for producing graphene. Such documents are for example CN 204356403 U, CN 103435035 A and CN 104495824 A.

In CN 204356403 U is described an apparatus that produces large area, "few me- ters", of 2D material from a recyclable substrate. This is achieved by having the growth substrate in a form of a rotating belt that passes through particular processing modules. While the growth substrate is continuous, the processing atop the belt is not continuous (i.e. processed layer length < belt length), or segmented, and with very asynchronous processing. Rapid production and production of a continuous unbroken layer produced from >1 rotation of the belt is not enabled by the apparatus or mentioned in the description or claims. The very disparate processing times of the different processing modules makes it impractical to produce a layer greater than said 'few meters' in the description. The present invention is based on the apparatus being in continuous op- eration, with synchronicity between modules, with many rotations of the belt to rapidly produce a continuous and monolithic layer in length that exceeds the length of the belt.

In CN 103435035 A is described an apparatus where the rotating belt does not form the growth substrate but rather serves to transport metal plates which are the growth substrate. Therefore the apparatus is not producing a continuous layer of graphene film.

In CN 104495824 A is described a semi-continuous production of graphene film which is based on sheets of copper attached by an adhesive. The graphene is col- lected to a roll. Conveyor belt is used as a support/transport layer for growth substrate (Cu). The method is a -roll-to-roll method.

The first objective of this invention to enable manufacture of a truly continuous unbroken CVD graphene film with a continual manufacturing process which removes the consumption of the substrate film by its continual reuse. Continuous unbroken graphene production is achieved by removing the unwinder/winder substrate foil rolls that limit the graphene production to a finite length and replacing these with a rotating belt system where the substrate foil forms part of the belt, partially or totally, which is continually reused.

The second objective of this invention is to enable rapid high volume production of a continuous high quality CVD graphene film without interruption on a growth substrate in the form of a rotating belt that can make more than one revolution . This results in an unbroken graphene film of a length which, in theory, is unbounded. In practice, a film of a few to hundreds of kilometers is plausible with the invention described herein. The third objective of this invention is the removal and/or decrease of the duration of the anneal step before CVD graphene growth through the continual reuse of a substrate film that once initially annealed either does not require further annealing or alternatively requires annealing of shorter duration.

The fourth objective of this invention is to provide a CVD system design capable of consistently producing CVD graphene film that exhibits high mechanical and electrical quality without sacrificing the other objectives outlined herein.

The fifth objective of this invention is to provide a CVD system design capable of meeting the production requirements and mechanical/physical/electrical character- istics necessary to extend the applicability area of graphene towards macroscopic or large-scale applications. Such applications can broadly include, for example, mechanical applications that require rapid high volume production of mechanically strong graphene films. The sixth objective of this invention is the reduction of the production cost, resource consumption, and reliance on etch chemicals for the production of high quality continuous graphene.

The seventh objective of this invention is to provide a CVD system capable of integrating any number of stand-alone processing systems in addition to the CVD reactor through which the substrate film, as part of the belt of the belt conveyor system, passes. Such stand-alone integrable processing systems for example can include, but are not limited to, an additional CVD reactor system, a spatial atomic layer deposition system, an anneal station, polymer application station etc. either alone or in any combination and number. Such systems would allow devices, complex structures or useful material combinations to be produced on the same processing line.

The eighth objective of this invention is to provide CVD system design that uses a growth substrate (foil) that is flat and wrinkle-free.

The ninth objective of this invention is to provide CVD system design that enables large substrate material grains on the growth substrate when the initial anneal of the substrate film is performed.

The tenth objective of this invention is to provide a CVD system which, unlike roll- to-roll systems, the length/area of the substrate does not determine the length/area of the graphene film. The twelfth objective of this invention is to provide a CVD system design that allows modification of the original belt substrate/substrate foil. Such modification can include the adding and selective removal of materials. Such modifications are made by the addition of tooling on the rotating belt line (e.g. an annealing station, a deposition station etc.). The thirteenth objective of this invention is to make the choice of transfer apparatus technology arbitrary as long as it 1 ) does not significantly consume, damage or otherwise impair the growth substrate's suitability for continuous reuse and 2) reliably transfers continuously and monolithically without interruption the desired film(s) from the rotating belt.

The fourteenth objective of this invention is to extend all the previous objectives to the continuous deposition of other 2D materials (WS2, MoS2, BN etc.) and 2D ma- terial composites (e.g. graphene-MoS2) in addition to graphene on the rotating belt.

The fifteenth objective of this invention is to extend all the previous objectives to the continuous deposition of other CVD materials (AIN, GaN etc.) and CVD material composites (e.g. graphene-AIN) in addition to graphene on the rotating belt. These and additional objectives of the presented invention disclosed herein are accomplished with a CVD system which utilizes a reusable substrate in the form of a rotating belt that passes through a CVD reactor where film is deposited atop the belt and a transfer apparatus for collecting from the belt the deposited film, as well as by the corresponding method that utilizes the main tool design described here- in.

The term graphene includes both single layer and multilayer graphene which is formed by a CVD process on a catalytic-active substrate selected from various materials (e.g. copper, nickel, Ge, Ru, Pt etc.) using an appropriate carbon- containing (CH) precursor gas (e.g. CH4, C2H4, C2H2, etc.). The CH precursor gas is typically used together with Ar, H2, or an oxygen-based gas in one or more process steps.

The disclosed invention's presented CVD system design achieves graphene growth on a catalytic-active material (substrate foil) that forms the belt wholly or partially of the rotating belt system which passes through a CVD reactor. The CVD reactor is quasi-gas-tight and sufficiently isolated from the outside atmosphere and kept at a pressure (typically -1 -100 mbar but up to ~1 bar) and temperature (typically -700 - 1 100 °C) appropriate for graphene growth.

Isolation from the outside atmosphere is achieved by enclosing the said invention either wholly or partially in enclosed space(s) where the atmosphere and pressure is controlled. The catalytic-active substrate material which forms the belt is appropriately heated/cooled as it enters/leaves and passes through the CVD reactor and/or any preceding/successive zones/systems that form part of the CVD system in order to meet the required time dependent heat profile and graphene deposition reaction temperature. As the substrate passes through the CVD reactor, it is exposed to the required process gas flows and compositions for a duration necessary to complete substrate coverage with graphene with the desired number of layers. The graphene deposition reaction time (i.e. the duration or, alternatively, the residence time, the substrate material is at the appropriate temperature range while exposed to necessary reaction process gases) is determined both by the feed through rate of the belt through the CVD reactor reaction zone (i.e. zone where process gases and growth temperature are appropriate for graphene growth) and the path length in the CVD reactor reaction zone. The graphene pro- duction rate can be defined by the belt width multiplied by the speed (for example, 0.1 mm/s) the belt passes through the CVD reactor reaction zone. The production rate may further be limited by limits imposed by the method of graphene transfer (i.e. maximum transfer rate) from the rotating belt.

Optionally a number of antechambers at the entry/exit ports of the CVD reactor each with controlled pressure, gas composition and temperature can be utilized to further isolate the CVD reactor from outside atmosphere.

The presented invention herein disclosed includes all the required systems and components which are typical and/or necessary for a CVD reactor system and its auxiliary tooling and related functions (e.g. gas injectors, exhaust gas lines, ther- mocouple sleeves, supporting plates, vacuum pump, gauges, piping etc.).

The presented invention herein disclosed also includes all the required systems and components which are typical and/or necessary for a rotating belt system (e.g. rollers, belt guiding wheels, pulleys, tension roller, drive roller, belt bottom cover, driving motor(s), idlers etc.). The growth substrate forms the belt of the belt con- veyor system, either wholly or partially, and is of a catalytic-active material or combination of materials.

The presented invention herein disclosed includes all the required auxiliary systems and components which are typical and/or necessary for a quasi-gas-tight CVD reactor system. Furthermore, this invention includes the option of modifying/repairing/treating/conditioning the belt by adding material to/alloying/annealing/cleaning the belt using systems described herein in order to provide a belt surface conducive for repeated high quality growth. This option is envisioned to involve additional stand-alone systems/tooling on the belt line for inline modifying/repairing/treating/conditioning of the belt.

Graphite and other carbon-based materials along with quartz are the preferred tooling materials for surrounding the substrate for both the resistively heated and photothermally heated (e.g. via infrared lamp) embodiments of the CVD reactor that forms part of the herein disclosed invention. Other materials which do not or only minimally interact or interfere with the substrate, graphene or other growth material, process gases, and other components and materials of the presented invention at the chosen process temperatures may also be selected as tooling mate- rial. Other materials, passivated by coating with suitable material expand the tooling material options. In addition, for those auxiliary components of the belt system exposed to heat and/or located within the CVD reactor, the preferred tooling materials and material options are the same as that for the CVD reactor.

In the following the invention is described more precisely referring to figures where Fig. 1 is a perspective view of an illustrative simplified exemplary embodiment of the disclosed invention herein showing graphene continuously produced and continuously transferred from a rotating belt substrate onto a second flexible substrate with an exemplary transfer apparatus.

Fig. 2a is a cross-section view of an illustrative simplified exemplary embodiment of the disclosed invention herein showing graphene continuously produced and continuously transferred from a rotating belt substrate onto a second flexible substrate with an exemplary transfer apparatus.

Fig. 2b is perspective view of a magnified section illustrating the graphene growth zone of the exemplary embodiment shown in Fig. 2a in accordance to the dis- closed invention herein.

Fig. 3a is cross-section view of another exemplary embodiment of the disclosed invention herein showing a configuration that increases the belt path length in the CVD reactor by feeding the belt in a serpentine manner through the CVD reactor with graphene being continuously produced and continuously transferred from the rotating belt onto a second flexible substrate with an exemplary transfer apparatus.

Figs. 3b are cross-section views of magnified sections of the rotating belt substrate from the exemplary embodiment of the invention shown in Fig. 3a. Figs. 4a-h are cutaway exemplary drawings of a segment of various embodiments of the rotating belt, which is part of the herein disclosed invention, illustrating the growth substrate(s) and some of the various forms the supporting material, if present, can take. Fig. 5a is a cross-section view of another illustrative simplified exemplary embodiment of the invention herein disclosed showing a configuration incorporating a polymer spray station on the belt line for coating the continuously produced graphene as it exits the CVD reactor. In this exemplary embodiment, the graphene is collected from the belt with an exemplary transfer apparatus that both winds up and axially draws out the transferred graphene-polymer laminate to make a cord.

Fig. 5b is perspective view of a magnified section of the exemplary transfer apparatus of the exemplary embodiment of the disclosed invention embodiment shown in Fig. 5a. The exemplary transfer apparatus both winds up and axially draws out the transferred graphene-polymer laminate as a cord. Fig. 6 is a cross-section view of another illustrative simplified exemplary embodiment of the invention herein disclosed showing a configuration utilizing both surfaces of the rotating belt for continuous graphene film growth and transfer to a flexible film via two exemplary transfer apparatuses.

Fig. 7 is cross-section view of another simplified exemplary embodiment of inven- tion herein disclosed showing a configuration incorporating on the rotating belt line an arbitrary number of pre- and post-processing tools in addition to the CVD reactor and a transfer apparatus.

Fig. 8 is a cross-section view of another simplified exemplary embodiment of the invention herein disclosed showing a configuration using more than one rotating belt. One rotating belt is exclusively devoted to growing a CVD graphene film which is transferred to another rotating belt for additional processing with the transferred layer.

Fig. 1 shows an exemplary embodiment of the presented invention from a perspective view that illustrates this disclosed invention's main parts (those parts be- ing the CVD reactor 1000, rotating belt system 1200 and 2101 , and transfer apparatus 1400). The CVD reactor 1000, in this embodiment a quartz tube-based CVD reactor, has quasi-gas-tight ports 1 102 which act to create an enclosed space separating the atmosphere inside the CVD reactor 1 101 from that without to achieve a desired pressure and gas composition. A rotating belt 1200 fed through the CVD reactor 1000 forms part of the rotating belt system of the invention described herein. A graphene film 1300 is grown atop the belt 1200 as it transverses through the CVD reactor 1000. The gaps 1 103 at the ports 1 102 are kept at a min- imum to ensure further isolation of the CVD reactor's enclosed space 1 101 . In order to better isolate the CVD reactor from the outside atmosphere, an arbitrary number of antechambers (not show in the figure) may precede/follow the CVD reactor, each with ports (like 1 102) and gaps (like 1 103) , with controlled pressure, gas composition and/or temperature. In this exemplary embodiment a transfer ap- paratus 1400, composed of cylinders/rolling pins 1401 , is used to transfer the graphene 1300 from the moving belt 1200 and onto a flexible substrate film 1403 thus creating a graphene-flexible substrate layer 1404. As earlier described the type or design of the transfer apparatus itself is arbitrary and independent of the configuration of the rest of the invention as long as it meets the objectives outlined throughout this disclosure.

Fig. 2a presents an exemplary embodiment of the presented invention from a cross-section view. As shown in Fig. 2a, the CVD system is placed in a controlled atmosphere by placing it in an enclosed space 10 which has a controlled gas mixture, pressure, temperature etc. in order to, amongst other considerations (safety, contamination etc.), prevent spoilage of the belt substrate surface (e.g. from oxygen exposure). In this exemplary embodiment, the enclosed space 10 includes ports 1 1 as necessary for feeding in a flexible substrate film 1403 and feeding out the transferred films 1404 (transferred films being graphene 1300 and the flexible substrate film 1403) as needed for the exemplary transfer apparatus 1400 illus- trated in this exemplary embodiment. An arbitrary number of antechambers (not shown) may also precede/follow the enclosed space 10 for better isolation of the CVD system.

The graphene growth zone 1301 is illustrated in Fig. 2b and is a magnified perspective view of a portion of Fig 2a and illustrates graphene grains nucleating and coalescing into a monolithic graphene film 1300 atop the belt 1200 as it passes through the CVD reactor 1000. In the exemplary embodiment of the invention illustrated in Figs. 2a-b, as the belt 1200 transverses the CVD reactor 1000 it is photo- thermally heated by a lamp fixture 1 104 containing filaments 1 104a which are isolated from the gases in the enclosed space 1 101 of the CVD reactor 1000 by a transparent cover 1 104b. Another exemplary embodiment of the invention is shown in FIG. 3a. This embodiment of the invention disclosed herein utilizes a serpentine configuration for the rotating belt 1200 within the CVD reactor 2100 in order to increase its path length in the CVD reactor 2100. By increasing the path length in the CVD reactor 2100 the feed rate of the belt 1200 can be increased which in turn facilitates increasing the graphene production rate.

Fig. 3b illustrates magnified views of portions of the embodiment of the invention illustrated in Fig. 3a which captures basic stages the rotating belt undergoes during one complete rotation. The belt 1200 is fed towards the CVD reactor 2100, magni- fied in I of Fig. 3b, wherein a graphene layer 1300 is grown atop it as magnified in II of Fig. 3b. The belt 1200 exits the CVD reactor 2100 with a complete graphene layer 1300, magnified in III of Fig. 3b, and continuous its journey towards an exemplary transfer apparatus 1400 which is magnified in IV of Fig. 3b. In this exemplary embodiment the graphene layer 1300 is transferred from the belt 1200 and joined to a moving flexible substrate 1403 using cylinders/rolling pins 1401 , forming a graphene-flexible substrate layer 1404. After transfer the belt 1200 completes one rotation as it again is fed again toward the CVD reactor 2100.

The belt 1200 as part of the rotating belt system that forms part of the invention disclosed herein acts as the substrate for continuous graphene growth and is illus- trated in the various embodiments of this disclosed invention shown in Figs. 1 -3 and Figs. 5-8.

Figs. 4a-h show cutaway views of various non-exhaustive exemplary embodiments of the belt 1200. The belt 1200 contains a growth substrate 1201 usually being of catalytic material(s) and/or whose surface is otherwise conducive for the desired material growth (e.g. graphene). The catalytic material of choice for the growth substrate 1201 for graphene growth is copper but can also alternatively be of other materials such as platinum, germanium, ruthenium etc. The belt 1200 may also include mechanical supporting material 1202 in various forms, layout, materials, and arrangements. The supporting material consists 1202 of material(s) that either through compatible physical properties or configuration in the belt 1200, or combination thereof, can be used to ensure the belt 1200 can tolerate tension when heated, separate the growth substrate 1201 from contact with the rotating belt system components (rollers, pins, tension rollers etc.) and other environmental and physical stresses encountered during processing. Such may be especially beneficial when the belt 1200 is in a serpentine configuration in the CVD reactor as illustrated in Fig. 3a Controlling the tension of the heated segment of the belt 1200 is one strategy envisioned in the invention described herein to mitigate damage of the heated belt 1200 from excessive tension.

In another exemplary embodiment of the invention described herein and shown in Fig. 5a, a post-processing tool is located on the rotating belt line through which the belt 1200 passes after the CVD reactor 2100 and before a transfer apparatus 1400 and collection apparatus 1406. In this exemplary embodiment, a polymer application station 9100 represents a post-processing tool whose function is to apply a thin polymer layer 9103 atop the graphene layer 1300 that has been grown atop the belt 1200. This exemplary polymer application station 9100 may further include a bake station etc., not shown, through which the belt passes through. In this exemplary embodiment a transfer apparatus 1400 transfers the graphene-polymer layer 1405 as it passes from the cylinders/rolling pins 1401 from the belt 1200 and collects it in a collection apparatus 1406 which is a special winder. The special winder both winds up the collected layer using a rotating shaft and draws the wound up layer axially in a manner to draw a cord. FIG. 5b presents a perspective view of the transfer apparatus 1400 and collection apparatus 1406.

Another embodiment of the invention described herein can utilize both sides of the belt 1200 for film growth as it passes through the CVD reactor 2100. An exemplary embodiment of such a system in accordance to the invention described herein is shown in Fig. 6 where exemplary transfer apparatus 1400 on the belt line are illustrated showing graphene films 1300 being transferred to a flexible substrate 1403 both of which are subsequently collected in a winder 1407. An unwinder 1405 feeds the flexible substrate 1403 and the transfer occurs via the assistance of cyl- inders/rolling pins 1401 .

The invention described herein, in addition to including on the rotating belt line a CVD reactor 2100 to grow graphene film on the belt 1200 and a transfer apparatus 1400 for transferring/collecting the graphene from the belt 1200, can include any number of pre- and post-processing tooling on the belt line which, when part of the same system (i.e. are using the same rotating belt line), are considered as being part of the invention disclosed herein. Fig. 7 illustrates the invention described herein with an arbitrary number (yry_n) of preprocessing tools 8000 and an arbitrary number (xi-x_n) of post processing tools 9000 on the belt line 1200. Preprocessing tooling 8000 such as a belt cleaning station, anneal station, and a station for reconditioning of the belt 1200 by, for example, depositing additional catalyst material atop the belt, are a couple examples of preprocessing tooling. Post processing tooling 9000 can include any number and type of deposition tools for depositing/growing additional layers of material atop and/or stitched in-plane with the graphene layer 1300, any number and type of patterning tools and any number or type of etching tools or combination thereof etc. Together, the pre- and postprocessing tooling allow the fabrication of structures, components, devices etc. 1350 consisting of various patterned materials atop and/or stitched in-plane with the graphene layer 1300 which is grown atop the belt 1200 as it passes through the CVD reactor 2100. The disclosed invention described herein and shown in the exemplified embodiment in Fig. 7 can enable the continuous uninterrupted monolithic fabrication of layer(s) of structures, components, devices etc. 1350 atop the belt 1200 which can be with the aid of a transfer apparatus be collected. An exemplary transfer apparatus 1400 is illustrated in Fig. 7 showing the transfer of a graphene layer and layer(s) of structures, components, devices etc. 1350 to a flexible substrate 1403.

Another embodiment of the invention includes a rotating belt system consisting of multiple rotating belts 1200 serially connected via a transfer apparatus 1400a as exemplified in Fig. 8. In this exemplary embodiment one rotating belt 1200 is devoted to graphene 1300 production and passes through a CVD reactor 2100. A transfer apparatus 1400a transfers a graphene 1300 and flexible layer 1403 to another rotating belt 1200 for additional processing with post processing tooling 9000 and later transfers the processed layer 1351 via a transfer apparatus 1400b to another flexible layer 1403.

Yet another embodiment is to rotate the belt system and/or CVD reactor so that the surface of the belt is vertical (at least the main parts of the belt). This minimizes the stretching and wrinkling of the belt and enables to produce better quality product. This embodiment is presented for example in Fig. 3a if the figure is considered to be presented from a top view instead of the side view. Also the same effect can be achieved if the Fig. 3a is a side view and the figure is just rotated 90 degrees. Also any alignment of the belt and/or CVD reactor between horizontal or vertical position is possible.

The invention is described here referring to preferred embodiments of the invention. These embodiments are not limiting the scope of protection and the scope of protection is defined by the following set of claims.

Claims

1 . A system for chemical vapor deposition (CVD) production comprising a rotating belt system (1200, 2101 ) where at least one belt serves as a substrate for film (1300) growth, a CVD reactor (1000, 2100) through which the belt pass- es and film (1300) growth occurs, and a transfer apparatus (1400) which lies on the rotating belt line for transferring at least one grown film (1300) from the belt to a target substrate (1403), characterized in that after the transfer apparatus (1400) is an apparatus for collecting the film (1300) and delivering the film (1300) for further processing as a continuous process.

2. The system for chemical vapor deposition (CVD) production according to claim 1 , characterized in that apparatus(es) for further processing is e.g. another system for chemical vapor deposition (CVD), transfer apparatus (1400a) or winders for film collection apparatus (1406, 1407).

3. The system for chemical vapor deposition (CVD) production according to claim 1 or 2, characterized in that the rotating belt system (1200, 2101 ) comprises multiple rotating belts of the same or different materials/surfaces/finishes and are connected serially via a transfer apparatus (1400a).

4. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 3, characterized in that film deposition, other processing on or transferring/collecting from, is done either on one or both faces of the rotating belt (1200).

5. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 4, characterized in that the system is placed in a gas-tight or quasi-gas-tight enclosure (10), with controlled temperature, gas composition and pressure, to further isolate it from outside atmosphere.

6. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 5, characterized in that the system comprises integrated standalone processing systems (8000, 9000, 9100) for additional processing such as an additional CVD reactor system for processing atop the graphene film

(1300) (e.g. AIN, GaN, Ge etc.), an atomic layer deposition system, an anneal station, a polymer application station, a lithography station, a etch station etc. either alone or in any combination and number.

7. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 6, characterized in that the belt(s) comprises the moving growth substrate (1201 ) as part of the rotating belt(s) (1200), either wholly or partial- ly, is of a catalytic material, with said catalyst being, e.g., copper, platinum, ruthenium, nickel, germanium, etc. or any combination or alloy thereof.

8. The system for chemical vapor deposition (CVD) production according to claim 7, characterized in that the rotating belt further comprises fibers, fab- rics, meshes, carbon-based composite materials, alloys, metals, ceramics and/or some combination thereof to provide mechanical support (1202) to the growth substrate (1201 ).

9. The system for chemical vapor deposition (CVD) production according to claim 8, characterized in that mechanical support (1202) can be incorpo- rated in the belt(s) (1200) in a continuous layer that forms one face of the belt

(1200) with the other face being the growth substrate (1201 ), a continuous layer imbedded within the growth substrate (1201 ) such that the growth substrate (1201 ) forms both faces of the belt (1200), a semi-continuous layer occupying one face of the belt (1200) patterned in any number of ways (e.g. grid pattern, honeycomb pattern etc.), a semi-continuous layer imbedded within the belt (1200) patterned in any number of ways (e.g. grid pattern, honeycomb pattern etc.), at the edges of the belt (1200), either on one or both faces or imbedded within the growth substrate (1201 ), as wires, threads, fibers, cords, rods, meshes etc. or any combination of the above.

10. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 9, characterized in that the system is applicable and transferable to other CVD materials and material combinations (including in combination with graphene) where only the belt growth substrate (1201 ) material changes, if necessary.

1 1 . The system for chemical vapor deposition (CVD) production according to any of claims 1 - 10, characterized in that the belt (1200) and/or CVD reactor (1000, 2100) is aligned to any orientation e.g. horizontally, vertically or any position in between.

12. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 1 1 , characterized in that CVD reactor has 1 or 2 port(s) (1 103) for entrance and exit of the belt.

13. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 12, characterized in that one or more antechamber(s) are connected to the CVD reactor(s) entrance port(s) with each having controlled pressure, gas composition, and temperature in order to isolate the CVD reactor from the outside atmosphere.

14. The system for chemical vapor deposition (CVD) production according to any of claims 1 - 13, characterized in that additional processing tooling (8000, 9000, 9100) are included on the same or connected rotating belt lines for additional material processing, component processing, belt conditioning etc. on the belt(s).

15. A method for producing continuous and monolithic graphene where:

a chemical vapor deposition (CVD) is used to grow graphene film (1300) on a rotating belt (1200),

a transfer apparatus (1400) is used to collect at least one film (1300) from the belt (1200),

characterized in that

- from the transfer apparatus (1400) the film (1300) is collected and delivered for further processing as a continuous process.

16. The method for producing continuous and monolithic graphene according to claim 15, characterized in that the further processing is collection (e.g. in a roll), depositing/growing additional layers of material atop and/or stitched in- plane, patterning and/or transfer to another substrate.

17. The method for producing continuous and monolithic graphene according to claim 15 or 16, characterized in that rotating belt system (1200, 2101 ) uses multiple rotating belts (2100) of the same or different materials/surfaces/finishes (1201 ) and are connected serially via a transfer apparatus (1400a).

18. The method for producing continuous and monolithic graphene according to any of claims 15 - 17, characterized in that film deposition, other processing on or transferring/collecting from, is done either on one or both faces of the rotating belt (1200).

19. The method for producing continuous and monolithic graphene according to any of claims 15 - 18, characterized in that the system is placed in a gas- tight or quasi-gas-tight enclosure (10), with controlled temperature, gas com- position and pressure, to further isolate it from outside atmosphere.

20. The method for producing continuous and monolithic graphene according to any of claims 15 - 19, characterized in that the integrated stand-alone processing systems (8000, 9000, 9100) are used for additional processing such as an additional CVD reactor system for processing atop the graphene film (e.g. AIN, GaN, Ge etc.), an atomic layer deposition system, an anneal station, a polymer application station, a lithography station, a etch station etc. either alone or in any combination and number.

21 . The method for producing continuous and monolithic graphene according to any of claims 15 - 20, characterized in that fibers, fabrics, meshes, carbon- based composite materials, alloys, metals, ceramics and/or some combination thereof are used to provide mechanical support (1202) to the growth substrate (1201 ).

22. The method for producing continuous and monolithic graphene according to claim 21 , characterized in that mechanical support (1202) can be incorporated in the belt(s) (1200) in a continuous layer that forms one face of the belt with the other face being the growth substrate (1201 ), a continuous layer im- bedded within the growth substrate (1201 ) such that the growth substrate

(1201 ) forms both faces of the belt (1200), a semi-continuous layer occupying one face of the belt (1200) patterned in any number of ways (e.g. grid pattern, honeycomb pattern etc.), a semi-continuous layer imbedded within the belt (1200) patterned in any number of ways (e.g. grid pattern, honey- comb pattern etc.), at the edges of the belt (1200), either on one or both faces or imbedded within the growth substrate (1201 ), as wires, threads, fibers, cords, rods, meshes etc. or any combination of the above.

23. The method for producing continuous and monolithic graphene according to any of claims 15 - 22, characterized in that the method is applicable and transferrable to other CVD materials and material combinations (including in combination with graphene) where only the belt growth substrate (1201 ) material changes, if necessary.

24. The method for producing continuous and monolithic graphene according to any of claims 15 - 23, characterized in that the belt (1200) and/or CVD reac- tor (1000, 2100) is aligned to any orientation e.g. horizontally, vertically or any position in between.

25. The method for producing continuous and monolithic graphene according to any of claims 15 - 24, characterized in that CVD reactor uses 1 or 2 port(s) (1 103) for entrance and exit of the belt (1200).

26. The method for producing continuous and monolithic graphene according to any of claims 15 -25, characterized in that that one or more antechamber(s) are connected to the CVD reactor(s) (1000, 2100) entrance port(s) (1 103) with each having controlled pressure, gas composition, and temperature in order to isolate the CVD reactor (1000, 2100) from the outside atmosphere. 27. The method for producing continuous and monolithic graphene according to any of claims 15 - 26, characterized in that additional processing tooling (8000, 9000, 9100) are included on the same or connected rotating belt lines (1200, 2101 ) for additional material processing, component processing, belt conditioning etc. on the belt(s) (1200).