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    • 专利摘要:
    HETEROEPITAXIALLY DEVELOPED GRAPHEN SHUT DOWN AND TRANSFER TECHNIQUES AND PRODUCTS THAT INCLUDE THE SAMEThe present invention relates to the use of graphene as a transparent conductive coating (RCT). In some examples of embodiments, thin graphene films developed heteroepitaxially over large areas, for example, on a thin catalyst film, from a hydrocarbon gas (such as, for example, C2H2, CH4 or so on similarly). The thin graphene films of some examples of embodiments can be doped or non-doped. In some examples of modalities, thin graphene films, once formed, may be removed from their substrates that function as vehicles and transferred to receive substrates, for example, for inclusion in an intermediate or final product. Graphene developed, removed and transferred in this way may exhibit low blade resistances (for example, less than 150 ohms / square and less when doped) and high transmission values (for example, at least in the visible and infrared spectra).
    公开号:BR112012002705A2
    申请号:R112012002705-0
    申请日:2010-07-22
    公开日:2020-08-11
    发明作者:Vijayen S. Veerasamy
    申请人:Guardian Industries Corp.；
    IPC主号:
    专利说明:

    Invention Patent Descriptive Report for "TECHNIQUES 7 FOR SHUTDOWN AND TRANSFER OF HETEROEPTICALLY DEVELOPED GRAPHEN AND PRODUCTS THAT INCLUDE THE MONTH '.
    FIELD OF THE INVENTION The present invention relates to thin films comprising graphene. More particularly, some examples of embodiments of this invention relate to the use of graphene as a transparent conductive coating (RCT). In some examples of embodiments, thin graphene films developed heteroepitaxially over large areas, for example, on a thin catalyst film, from a hydrocarbon gas 7 (such as, for example, C2H2, CH, or so on). ). : The thin graphene films of some examples of modalities can be doped or not doped. In some examples of modalities, thin graphene films, once formed, may be removed from their substrates that function as vehicles and transferred to receive substrates, for example, for inclusion in an intermediate or final product. BACKGROUND AND SUMMARY OF EXAMPLES OF MODALITIES OF
    VENTION Indium tin oxide (OIE) and fluorine doped tin oxide coatings (OEF or SnO: F) are widely used as window electrodes in optoelectronic devices. These transparent conductive oxides (OCTs) have been immensely successful in a variety of applications. Unfortunately, however, the use of OIE and OEF is becoming increasingly problematic for several reasons. Such problems include, for example, the fact that there is a limited amount of the Indian element available on Earth, the instability of OCTs in the presence of an acid or base, their susceptibility to the diffusion of ions from ion-conducting layers, their limited transparency in near infrared region (for example, spectrum rich in power), high current leakage from OEF devices caused by defects in the OEF structure, etc. The fragile nature of the OIE and its high deposition temperature can also limit its applications. In addition, roughness on the surface of SnO2: F can cause problematic arc production. 2 Thus, it will be understood that there is a need in the state of the art for smooth and standardized flat materials for electrodes with good stability, high transparency and excellent conductivity.
    The search for new materials for electrodes with good stability, high transparency and excellent conductivity is underway. One aspect of this search involves identifying viable alternatives for such conventional OCTs. In this regard, the inventor of the present developed a viable transparent conductive coating (RCT) based on carbon, specifically graphene.
    'The term graphene generally refers to one or more atomic layers of graphite, for example, with a single layer of graphene, or UCG, which is extendable to n-layers of graphite (for example, where n can be as high as about 10). A recent discovery about graphene and insulation (through cleavage of crystalline graphite) at the University of Manchester comes at a time when the trend in electronics is to reduce the dimensions of circuit elements to the nanometer scale.
    In this sense, graphene has unexpectedly led to a new world of unique optoelectronic properties, not found in standard electronic materials. This fact stems from the linear dispersion relationship (E versus k), which gives rise to charge carriers in graphene that have a zero resting mass and behave like relativistic particles. The similarly relativistic behavior of electrons with no location that move around carbon atoms results from the interaction of these electrons with the periodic potential of the alveolar structure of graphene that gives rise to new quasi-particles that under low energies (E < 1.2 eV) are precisely described by the Dirac equation (2 + 1) -dimensional, with an effective speed of light vr = c / 300 = 10 ms. Therefore, well-established techniques of quantum electrodynamics (EDQ) (which deal with photons) can be used to support the study of graphene - with the additional advantageous aspect being that in which these effects are amplified in graphene by a factor of 300. For example, the universal coupling constant a is approximately 2 in graphene compared to 1/137 in vacuum.
    See K.S.
    Novoselov, Electrical Field Effect in Atomically Thin Carbon Films, Science, vol. 306, pp. 666-69 (2004), whose content is incorporated here
    Despite having the thickness of only one atom (at least), graphene is chemically and thermally stable (although graphene can be oxidized on the surface at 300 degrees C), thus allowing graphene-based devices manufactured in successfully withstand ambient conditions.
    High-quality graphene sheets were first produced by micromechanical cleavage of crude graphite.
    Is the same technique being made more accurate to currently provide high quality graphene crystallites up to 100 µm of size.
    This size is sufficient for most microelectronics research objectives.
    Consequently, most of the techniques developed to date, mainly in universities, have focused on the microscopic sample and the preparation and characterization of devices instead of their amplification.
    action.
    Contrary to most current research trends, in order to understand the full potential of graphene as a possible RCT, it is essential to deposit high quality material on large area substrates (for example, glass or plastic substrates). So far, large-scale graphene production processes are based on the exfoliation of crude graphite using chemicals on a wet basis, and start with highly ordered pyrolytic graphite (GPAO) and chemical exfoliation.
    As is known, GPAO is a form of highly ordered pyrolytic graphite with an angular opening of the c axes less than one degree, and is usually produced by annealing under tension at 3,300 K.
    GPAO behaves much like a pure metal because it is generally reflective and electrically conductive, although friable and scaly.
    Graphene produced in this way is filtered and then adhered to a surface.
    However, there are disadvantages to the exfoliation process.
    For example, exfoliated graphene tends to bend
    . and become wrinkled, exists as small tapes and depends on a bonding / sewing process for deposition, lacks inherent control over the number of graphene layers, etc. The material thus produced is often contaminated by interspersed and thus has a low degree of electronic properties An in-depth analysis of the carbon phase diagram shows suitable process window conditions to produce not only graphite and diamond, but also other allotropic forms such as, for example, nanotubes carbon (NTC) catalytic deposition of nanotubes is carried out from a gas phase at temperatures as high as 1,000 degrees C by means of several groups. 'In contrast to these conventional research areas and conventional techniques, some examples of modalities of this invention | refer to a scalable technique to develop heteroepitaxially | 15 monocrystalline graphite (n as large as about 15) and convert it to graph and high electronic grade (GAE) (n <about 3). Some examples of modalities also refer to the use of graphene GAE in films | transparent conductive ultrafine graphene (in terms of visible and infrared spectra), for example, as an alternative to the metal oxide window electrodes ubiquitously employed in a variety of applications (including, for example, solid state solar cells). The technique of developing some examples of modalities is based on a catalytically driven heteroepitaxial DVC process that occurs at a temperature that is low enough to be convenient to the glass. —For example, thermodynamic as well as kinetic principles allow GAE graphene films to be crystallized from the gas phase over a catalyst seed layer at a temperature below about 700 degrees C. Some examples of modalities also use atomic hydrogen , which has been proven to be a potent radical to hijack account. amorphous carbonaceous mining on substrates and be able to act at low process temperatures. He is also extremely good at re- | SA
    . removal of oxides and other overlays normally left by caustication procedures. : Some examples of embodiments of this invention refer to a method of insulating a thin graphene film. The graphene film is heteroepitaxially developed on a thin catalyst film. A polymer-based coating is placed on the thin graphene film on a surface opposite to the thin catalyst film. The polymer-based coating is cured. The thin graphene film and the polymer based coating are caused to be released from the thin catalyst film. | In some exemplary embodiments, the thin catalyst film is arranged on a back support substrate with that substrate. posterior support being formed in the thin catalyst film on a surface opposite to the thin graphene film. The release layer of | 15 thin film is arranged between the backing substrate and the foil | thin catalyst.
    In some examples of embodiments, the thin graphene film and the polymer based coating are released from the thin catalyst film by stripping the thin catalyst film.
    In some examples of embodiments, the thin graphene film and the polymer-based coating are arranged, directly or indirectly, on a target receiving substrate using contact pressure, with the thin graphene film being closer to the target receiving substrate than the polymer-based coating. The polymer-based layer can be removed by dissolving it using a solvent and / or by exposure to UV radiation.
    Some examples of embodiments of this invention relate to a method of disposing a thin graphene film on a target receptor substrate. The thin graphene film is heteroepitaxially developed on a thin catalyst film. A powder-based coating. The polymer is placed on the thin graphene film on a surface opposite to the thin catalyst film. The thin graphene film and the coating
    polymer-based materials are caused to be released from the thin catalyst film. The thin graphene film and the polymer based coating. they are placed, directly or indirectly, on the target receiving substrate using contact pressure, with the thin graphene film being closer to the target receiving substrate than the polymer based coating. The polymer-based layer is removed by exposing it to a solvent and / or UV radiation.
    Some examples of embodiments of this invention relate to a method of disposing a thin graphene film on a target sub-toreceptor. The thin graphene film is heteroepitaxially developed on a thin metallic catalyst film. The thin graphene film and the thin catalyst film are arranged, directly or indirectly,. on the target recipient substrate. The thin catalyst film below the graphene is electrochemically anodized to make the catalyst film a substantially transparent metal oxide.
    Some examples of embodiments of this invention relate to a method of disposing a thin graphene film on a target receptor substrate. The thin graphene film is heteroepitaxially developed on a thin catalyst film. An adhesive is applied to the thin graphene film on a surface opposite to the thin catalyst film. The thin graphene film is caused to be released from the thin catalyst film. The thin graphene film is adhered to the target recipient substrate.
    The characteristics, aspects, advantages and examples of modalities described here can be combined to further implement additional modalities.
    BRIEF DESCRIPTION OF THE DRAWINGS These and other characteristics and advantages can be better understood and more fully understood by reference to the following detailed description of exemplary illustrative modalities in conjunction with the drawings, in which: Figure 1 is a high level flowchart that illustrates the general techniques of some examples of modalities;
    7I34 figure 2 is a schematic example of the catalytic development techniques of some examples of modalities, illustrating the introduction of hydrocarbon gas, the dissolution of carbon and the possible results of extinguishing the reaction, according to some examples of modalities;
    figure 3 is a flow chart illustrating a first example technique for doping graphene according to some examples of modalities;
    figure 4 is a flow chart illustrating a second example technique for doping graphene according to some examples of modalities;
    figure 5 is a schematic example view illustrating a third example technique for doping graphene according to some examples of modalities;
    figure 6 is a graph showing temperature versus time involved in doping graphene according to some examples of modalities;
    Figure 7 is a stack of example layers useful in the techniques of releasing or shutting down graphene according to some examples of modalities;
    figure 8 is a schematic example view of a laminating apparatus that can be used to arrange graphene on the target glass substrate according to some examples of modalities;
    figure 9 is a schematic cross-sectional view of a reactor
    suitable for depositing high-grade electronic graphene (GAE) according to an example of modality;
    figure 10 is an example process flow that illustrates a little of the catalytic development by CVD, removal and transfer techniques of some examples of modalities;
    figure 11 is an image of a graphene sample produced according to some examples of modalities;
    figure 12 is a schematic cross-sectional view of a device
    . solar photovoltaic unit that incorporates layers based on graphene according | 'with some examples of modalities; figure 13 is a schematic cross-sectional view of a touch screen that incorporates layers based on graphene according to some examples of modalities; figure 14 is a flow chart illustrating an example technique for forming a data / bus line according to some examples of modalities; and figure 15 is a schematic view of a technique for forming a conductive data / bus line according to some examples 1 of modalities. | DETAILED DESCRIPTION OF EXAMPLES OF IN- MODALITIES: VENTION Some examples of modalities of this invention refer to a scalable technique for developing heteroepitaxially mono-crystalline graphite (not as large as about 15) and converting it to high-grade graphene (GAE) (n <about 3). Some examples of modalities also refer to the use of GAE graphene in transparent conductive ultrafine graphene films (in terms of visible and infrared spectra), for example, as an alternative to the metal oxide window electrodes used by ubiquitous in a variety of applications (including: including, for example, solid state solar cells). The technique of developing some examples of modalities is based on a catalytically driven heteroepitaxial DVC process that occurs at a temperature that is low enough to be convenient to the glass.
    For example, thermodynamic as well as kinetic principles allow GAE graphene films to be crystallized from the gas phase over a catalyst seed layer (for example, at a temperature below about 600 degrees C). “30 Figure 1 is a high-level flowchart that illustrates the techniques. general and some examples of modalities.
    As shown in figure 1, the general techniques and some examples of modalities can be classified | O .- .. ô.ô2 «0 BONE A
    %: as belonging to one of four basic steps: crystallization of graphene! 'on a suitable back support (step S101), release or shutdown' of graphene from the back support (step S103), transfer of graphene to the target substrate or surface (step S105) and incorporation of the target substrate or surface into a product (step S107). As explained in greater detail below, it will be understood that the product referred to in step S107 can be an intermediate product or a final product. Graphene Crystallization Example Techniques Graphene crystallization techniques of some examples of modalities may be conceived as involving "cracking" of a hydrocarbon gas and reassembling the carbon atoms in the familiar honeycomb structure over a large area (for example, example, an area of about: 1 (one) meter or more), for example, influencing the catalytic pathway in the su-; surface. Graphene crystallization techniques of some examples of | dalities occur under high temperature and moderate pressures. Details' illustrative of this example process will be described below. The catalytic development techniques of some examples of modalities are to some degree related to the techniques that have been used to develop graphite in a heteroepitaxial area. A catalyst for graphene crystallization is arranged on a suitable back support. The back support can be any suitable material capable of withstanding high temperatures (for example, temperatures up to about
    1,000 degrees C) such as, for example, certain ceramic or glass products, materials including zirconium, aluminum nitride materials, silicon disks, etc. A thin film is placed, directly or indirectly, on the back support, thereby ensuring that its surface is substantially uncontaminated before the crystallization process. O | inventor of the present invention discovered that crystallization of graphene is easy! when when the catalyst layer substantially has a crystalline structure with a single orientation. In that respect, it was determined. that small grains are less advantageous, since their mosaic structure will essentially be transferred to the graphene layer. In IT IS
    In any case, the particular orientation of the crystalline structure is found to be largely insignificant for crystallization of graphene, provided that the catalyst layer, at least in substantial part, has a crystalline structure of a single orientation.
    In fact, it appears that the comparative absence of grain limits (or low grain content) in the catalyst results in the same or a similar orientation for the developed graphene, and it is found to provide high-grade graphene. electric grade
    (GAE). The catalyst layer itself can be disposed on the back support using any suitable technique such as, for example, spraying, combustion vapor deposition (DVC), "flame pyrolysis, etc."
    The catalyst layer itself may comprise any suitable metal material or material with metal inclusion.
    For example, the catalyst layer may comprise, for example, metals such as nickel, cobalt, iron, permalinkle (eg nickel-iron alloys, generally comprising about 20% iron and 80% nickel), nickel and chromium alloys, copper and combinations thereof.
    Of course, other metals can be used in conjunction with some examples of modalities.
    The inventor has found that layers of nickel catalyst or that includes nickel are particularly advantageous for graphene crystallization, and that nickel and chromium alloys are even more advantageous.
    In addition, the inventor found that the amount of chromium in nickel-chromium layers (also sometimes called nichrome or NiCr layers) can be optimized to promote the formation of large crystals.
    In particular, 3-15% Cr in the NiCr layer is preferable, 5-12% Cr in the NiCr layer is more preferable and 7-10% Cr in the NiCr layer is even more preferable.
    It is also found that the presence of vanadium in the thin metal film is advantageous for promoting the development of large crystals.
    The catalyst layer can be relatively thin or thick.
    For example, the thin film may be 50-1,000 nm thick, more preferably 75-750 nm thick, and even more preferably 100-500 nm thick. A "large crystal development" may in certain cases of e -
    example include crystals that have a length along an axis
    7 of the order of tenths of microns, and occasionally even more. : Once the thin catalyst film is placed on the back support, a hydrocarbon gas (for example, CaH> gas, CH gas, etc.) is introduced into a chamber in which the back support with the film is located of thin catalyst arranged in it.
    The hydrocarbon gas can be introduced under a pressure ranging from about 5-150 mTorr, more preferably from 10-100 mTorr.
    In general, the higher the pressure, the faster the development of graphene.
    The back support and / or the camera as a whole is / are then heated (s) to dissolve or for "open cracking" of the hydrocarbon gas.
    For example, the back support can be raised to a temperature in the range of 600-1,200 degrees C, more. preferably 700-1,000 degrees C, and even more preferably 800-900 degrees C.
    Heating can be carried out by any suitable technique such as, for example, via a short-wave infrared (IR) heater.
    Heating can take place in an environment that comprises a gas such as argon, nitrogen, a mixture of nitrogen and hydrogen, or another suitable environment.
    In other words, the heating of the hydrocarbon gas may occur in an environment that comprises other gases without some examples of modalities.
    In some examples of modalities, it may be desirable to use a mixture of hydrocarbon gases,
    another inert gas or another gas (for example, CH, mixed with Ar). Graphene will develop in this environment or another suitable environment.
    To stop development and help ensure that graphene is grown on the surface of the charalizer (for example, as opposed to being embedded in the catalyst), some examples of modalities employ a reaction quenching process.
    The reaction can be extinguished using an inert gas such as, for example, argon, nitrogen, combinations of these, etc.
    To promote the development of graphene on the surface of the catalyst layer, the reaction must be extinguished reasonably quickly.
    More particularly, it has been found that extinction of the reaction too fast or too slow results in unsatisfactory development.
    or without graphene on the surface of the catalyst layer.
    Generally, 7 it appears that cooling in order to reduce the temperature of the substrate: and / or posterior substrate of about 900 degrees C to 700 degrees C (or less) during the course of several minutes promotes good graffiti development, for example, via chemosorption.
    Thus, figure 2 is a schematic example of the catalytic development techniques of some examples of modalities, illustrating the introduction of hydrocarbon gas, the dissolution of carbon and the possible results of extinction of the reaction, according to some examples of modalities.
    The graphene development process imposes the strict relation of film thickness t = n x SLG, where n involves a certain number: discrete stages.
    Identifying very quickly whether graphene was produced and BR determining the value of n in the film area is strictly equivalent to measuring film quality and uniformity in a single measurement.
    Although graphene slides can be observed using atomic force microscopy or scanning electron microscopy, these techniques are time consuming and can also lead to contamination of graphene.
    Therefore, some examples of modalities employ a phase contrast technique that increases the visibility of graphene on the desired catalyst surfaces.
    This can be done in order to map any variation in the value of n on the deposition surface on the metallic catalyst peel.
    The technique lies in the fact that the contrast of graphene can be enhanced substantially by rotating a material over it.
    For example, a widely used UV curable coating (for example, PMMA) can be coated by rotation, printed with canvas, coated by engraving or otherwise arranged on graphene / metal / back support, for example, in a thickness enough to make the film visible and continuous (for example, about 1 (one) micron thick). As explained in greater detail below, the inclusion of a polymer coating can also facilitate the process of removing graphene before transferring it to the final surface.
    That is, in addition to providing an indication of when graphene formation is complete, the polymer coating can also provide a support for highly elastic graphene when the metal layer is released or otherwise disconnected: from the back support as explained in detail below.
    In the event that a layer is developed too thick (intentionally or unintentionally), the layer can be reduced by caustication, for example, using hydrogen atoms (H *). This technique can be advantageous in several example situations. For example, where development occurs too quickly, unexpectedly, irregularly, etc., H * can be used to correct such problems. As another example, to ensure that sufficient graphene is developed, graphite can be created, graphene can be deposited and graphene can be selectively etched back to GAE graphene at an undesired level, for example, using H *. With the other . for example, H * can be used to selectively remove by causticising graphene, for example, to create conductive and non-conductive areas. This can be accomplished by applying an appropriate mask, performing etching and then removing the mask, for example.
    Theoretical studies of graphene have shown that carrier mobility can exceed 200,000 in / (V.s). Experimental measurements of graphene developed heteroepitaxially and treated in a gas phase show resistivity as low as 3 x 10º Q-cm, which is better than that of thin silver films. The resistance of the blades to these graphene layers is found to be around 150 ohms / square. One factor that can vary is the number of layers of graphene that is needed to provide the lowest resistivity and strength of the sheets, and it will be understood that the desired thickness of the graphene can vary depending on the target application. In general, suitable graphene for most applications may be n = 1-15 layers of graphene, more preferably n = 1-10 layers of graphene, even more preferably n = 1-5 layers of graphene and occasionally n = 2 -3 layers of graphene. A layer of graphene n = 1 is found to result in a drop in transmission of about 2.3-2.6%. It appears that this reduction in transmission is generally linear across substantially the entire spectrum, for example, ranging from ultraviolet (UV),
    passing through the visible and the IV.
    In addition, it appears that the loss of "transmission is substantially linear with each successive increment of n. Example Doping Techniques
    Although a blade resistance of 159 ohms / square may be suitable for certain example applications, it will be understood that a further reduction in blade resistance may be desirable for different example applications.
    For example, a 10-20 ohm / square blade resistance will be understood to be desirable for certain example applications.
    The inventor of the present invention determined that the resistance
    The strength of the blade can be lowered via graphene doping.
    In this respect, having an atomic thickness of only one layer, graphene exhibits ballistic transport on a submicron scale. it can be doped densely - either by gate stresses or adsorbates or molecular interleaved in the case where n 2 2 - without significant loss of mobility.
    It was determined by the inventor of the present invention that in graphene, with the exception of the donor / recipient distinction, there are generally two different classes of dopants, namely, paramagnetic and non-magnetic.
    Unlike common semiconductors, these latter types of impurities generally act as rather weak dopants, while para- “magnetic impurities produce strong doping.
    Due to linear polishing, the density of symmetrical states of electron holes (DOS in English) close to the Dirac point of graphene, impurity states located without spin polarization, are attached to the center of the pseudolacuna.
    Thus, states of impurities in graphene are strongly distinguished from their counterparts in usual semiconductors, in which the DOS in the valence and conductance ranges are very different and levels of impurities are generally removed from the center of the gap.
    Although a strong doping effect that requires well-defined donor (or recipient) levels several tenths of electron volts away from the Fermi level cannot be expected, if the impurity has a local magnetic moment, its energy levels they are more or less symmetrically divided by the Hund exchange, of the order of 1 eV, which provides a favorable situation for a strong doping impurity effect in the electronic structure of two-dimensional systems with a spectrum similar to "Dirac such as those present This line of reasoning can be used to guide the choice of molecules that form both systems of unique paramagnetic molecules and systems of dia-magnetic dimers to dopene graphene and increase its conductivity from 10º S / cm to 10º S / cm, and sometimes up to 10º S / cm.
    Sample dopants suitable for use in conjunction with some examples of modalities include nitrogen, boron, phosphorus, fluorides, lithium, potassium, ammonium, etc. Sulfur-based dopants (eg sulfur dioxide) can also be used in conjunction with some example modalities. For example, sulphides present in glass substrates can be caused to flow out of the glass and thus dope the graphene-based layer. Several example techniques for graphene doping are presented in greater detail below.
    Figure 3 is a flowchart that illustrates a first example technique for doping graphene according to some examples of modalities. The example technique in figure 3 essentially involves a beam of ions that implant the doping material into graphene. In this example technique, graphene grows on the metallic catalyst (step S301), for example, as described above. The catalyst with the graphene formed on it is exposed to a gas that comprises a material to be used as a dopant (also sometimes referred to as a dopant gas) (step S303). A plasma is then excited in a chamber that contains the catalyst with the graphene formed on it and the doping gas (S305). An ion beam is therefore used to implant the dopant in graphene (S307). Techniques for example of ion beam suitable for this kind of doping are described in, for example, United States Patent Nos. 6,602,371,
    6,808,606 and Re. 38,358, and United States Publication No. 2008/0199702, each of which is incorporated herein by reference. The ion beam power may be about 10-200 eV, more preferably 20-50 eV, even more preferably 20-40 eV.
    Figure 4 is a flow chart illustrating a second example technique for doping graphene according to some examples of modalities. The example technique of Figure 4 essentially involves pre-implanting 'solid-state dopants into the target receptor substrate, and then causing those solid-state dopants to migrate to graphene when it is applied to the receptor substrate. In this example technique, graphene grows on the metallic catalyst (step S401), for example, as described above. The receiving substrate is prefabricated to include solid state dopants (step S403). For example, solid-state dopants can be included via fusion in the glass formulation. About 1-10% atomic dopant, more preferably 1-5% atomic dopant, and even more preferably 2-3% atomic dopant, can be included in the molten glass. Graphene is applied to the receiving substrate, for example, using one of the example techniques described in detail below (step S405). Then, the solid-state dopants in the recipient substrate are driven to migrate paraografene. The heat used in the deposition of graphene will cause dopants to migrate to the layer of graphene that is formed. Similarly, additionally doped films can be included on the glass and the dopants in it can be made to migrate through these layers by thermal diffusion, for example, creating a layer of doped graphene (n> = 2).
    An ion beam can also be used to implant dopants directly into the glass in some examples of modalities. The power of the ion beam can be about 10-1,000 eV, more preferably 20-500 eV, even more preferably 20-100 eV. When an intermediate layer is doped and used to provide impurities in the graphene, the ion beam can operate at about 10-200 eV, more preferably 20-50 eV, even more preferably 20-40 eV.
    Figure 5 is a schematic example view that illustrates a third example technique for doping graphene according to some examples of modalities. The example techniques in Figure 5 essentially involve pre-implanting solid state dopants 507 into the metal catalyst layer 503 and then getting those solid state dopants 507 to migrate to the catalyst layer 503 as they graphene is formed, thereby creating doped graphene 509 on the surface of the catalyst layer 503. More particularly, in this example technique,. the catalyst layer 503 is arranged on the back support 505. The catalyst layer 503 includes solid-state dopants 507. In other words, the catalyst has solid-state doping atoms in its volume (for example, about 1-10% , more preferably about 1-5% and even more preferably about 1-3%). Hydrocarbon gas 501 is introduced, at high temperature, close to the formed catalyst layer 503. The dopants of solid state 507 in the catalyst layer 503 are caused to migrate to its outer surface, for example, by means of this high temperature, as the crystallization of graphene occurs. At the rate at which dopants reach the surface, it has been lifted to be a function of the thickness of the catalyst and the temperature. Crystallization is stopped via quenching and finally, a doped graphene 509 forms on the surface of catalyst layer 503 '. After the formation of doped graphene 509, the catalyst layer 503 'now has less (or none) solid state dopant 507 located therein. An advantage of this example technique is the potential to control the development of ultra-thin film by carefully varying the temperature of the metal surface, partial pressure and residence time of the deposition gas species, as well as the reactive radicals used in the rate process reaction extinction. It will be understood that these sample doping techniques can be used alone and / or in various combinations and subcombination with another technique and / or additional techniques. It will also be understood that some examples of modalities may include a single doping material or multiple doping materials, for example, using a particular example technique once, a particular technique repeatedly or through a combination of multiple techniques one or more more times each. For example, p-type and n-type dopants are possible in some examples of modalities.
    Figure 6 is a graph that plots temperature versus time involved in graphene doping according to some examples of modalities.
    activities.
    As indicated above, cooling can be carried out using, for example, "an inert gas.
    In general, and also as indicated above, the high. The temperature can be around 900 degrees C in some examples of modalities and the low temperature can be around 700 degrees C, and the cooling can take place over several minutes.
    The same heating / cooling profile shown in figure 6 can be used regardless of whether graphene is doped.
    Grapefruit Release / Shutdown and Transfer Techniques Once graphene has been heteroepitaxially developed, it can be released or disconnected from the metal catalyst and / or back support, "for example, before being placed on substrate to be incorporated into. intermediate or final product.
    Several procedures can be implemented to lift epitaxial films from their development substrates according to some examples of modalities.
    Figure 7 is a stack of example layers useful in techniques for releasing or shutting down graphene of some examples of modalities.
    Referring to Figure 7, in some exemplary embodiments, an optional release layer 701 can be provided between the backing support 505 and the catalyst layer 503. That release layer 701 can be of or include, for example, zinc oxide (for example, ZnO or other suitable stoichiometry). After graphene deposition, substrate 505 coated with graphene stack 509 / layer of metallic catalyst 503 / release layer 701 may receive a polymeric layer 703 with a special top coating (eg multi-micron thickness), for example , applied via a rotating coating, distributed by a meniscus flow, etc., which can be cured.
    As mentioned above, this polymer layer 703 can act as the main chain or support for graphene 509 during lifting and / or shutting down, keeping the extremely flexible graphene film continuous, while reducing the likelihood of the graphene film spiraling. become wrinkled or otherwise deformed.
    Also as mentioned above, PMMA can be used as a polymer that allows graphene to be visible by phase contrast and 7 for support before and / or during removal. However, a wide range of. polymers whose mechanical and chemical properties can be combined with those of graphene can be used during the support phase, as well as the transfer by release phase together with some examples of modalities. The survey work can be carried out in parallel with the main branch of epitaxial development, for example, through experimentation with graphene films that can be chemically exfoliated from graphite.
    The release layer can be chemically induced to disconnect the graphene / metal from the parent substrate, once the polymer layer is disposed on it. For example, in the case of a release layer of: zinc oxide, washing in vinegar can trigger the release of the graphene. The use of a zinc oxide release layer is also advantageous, since the inventor of the present invention has found that the metallic catalyst layer is also removed from the graphene with the release layer. This is believed to be the result of texturing caused by the zinc oxide release layer along with its interconnections formed with the grains in the catalyst layer. It will be understood that this reduces (and occasionally even eliminates) the need to remove the catalyst layer later.
    Certain lifting / shutdown and transfer techniques essentially take the original substrate into account as a reusable epitaxial development substrate. As such, selective etching to reduce and dissolve the thin metallic catalyst film of epitaxially developed graphene (with polymer on top) may be desirable in these example modalities. Thus, the catalyst layer can be removed by caustication, regardless of whether a release layer is used, in some examples of modalities. Suitable causticants include, for example, acids such as hydrochloric acid, phosphoric acid, etc.
    The surface of the final container glass substrate can be prepared to receive the graphene layer. For example, a Langmuir-Blodgett film (for example, a Langmuir-Blodgett acid) can be applied to the glass substrate.
    The final container substrate can change. native or additionally be coated with a smooth graphenophilic layer such as, for example, a silicone-based polymer, etc., making it highly responsive to graphene.
    This can help to ensure electrostatic bonding, thereby preferably allowing the transfer of graphene during transfer.
    The target substrate may additionally or alternatively be exposed to UV radiation, for example, to increase the surface energy of the target substrate and thus make it more receptive to graphene.
    Graphene can be applied to the substrate via blanket stamping and / or lamination in some examples of modalities.
    Such processes allow graphene to be previously grown and chemosorbed in the metallic vehicle. co is transferred to the container glass by pressure contact.
    As an example, graphene can be applied to the substrate via one or more lamination cylinders, for example, as shown in figure 8. In this sense, figure 8 shows upper and lower cylinders 803a and 803b, which will apply pressure and take 509 graphene and the polymeric layer 703 to be laminated on the target substrate 801. As noted above, the target substrate 801 has a layer with the inclusion of silicon or another graphenephilic layer disposed on it to facilitate lamination.
    It will be understood that polymer layer 703 will be applied as the outermost layer and that graphene 509 will be closer to (or even directly on) target substrate 801. In some examples of modalities, one or more layers may be provided on the substrate before the application of the graphene Once the graphene is disposed on the target substrate, the polymer layer can be removed.
    In some examples of modalities, the polymer can be dissolved using an appropriate solvent.
    When photosensitive material such as PMMA is used, the polymer can be removed via exposure to UV light.
    Of course, other removal techniques are also possible.
    It will be understood that the thin catalyst film can be removed
    caused by caustication after graphene has been applied to the target substrate in some examples of modalities, for example, using one of the causticants. examples described above.
    The choice of causticant may also be based on the presence or absence of any layers underlying the graphene.
    Some examples of modalities electrochemically anodize more directly the thin metallic catalyst film below graphene.
    In such examples of modalities, the graphene itself can act as a catalyst, in that the metal below is anodized in a transparent oxide while it still binds to the original substrate.
    These examples of modalities can be used to avoid the use of polymer overcoating when performing essentially e removal processes. one-step transfer.
    However, anodization by electrochemical means can affect the electronic properties of graphene and, therefore, may need to be compensated.
    In some examples of embodiments, the catalyst layer below graphene can be oxidized in other ways to make it transparent.
    For example, a conductive oxide can be used to "bond" the graphene-based layer to a substrate, semiconductor or other layer.
    In this regard, cobalt, chromium-cobalt, nickel-chromium-cobalt and / or the like can be oxidized.
    In some examples of modalities, this procedure may also reduce the need to remove graphene, making it easier to transfer, manipulate and other graphene handling.
    Graphene can also be extracted using an adhesive material similar to tape in some examples of modalities.
    The adhesive can be positioned on the target substrate.
    Graphene can be transferred to the target substrate, for example, after applying pressure, adhering more strongly to the substrate than the tape, etc.
    Sample Reactor Design Reactors with sprinklers typically employ a perforated or porous flat surface to distribute reagent gases more or less evenly over a second heated parallel flat surface.
    Such a configuration can be used to develop graphene using the example heteroepitaxial techniques described here.
    Reactors with sprinklers. they are also advantageous for processing large square ultra-smooth glass or ceramic substrates.
    A basic schematic view of a reactor with sprinklers is figure 9, with the plenum project being expanded.
    In other words, figure 9 is a schematic cross-sectional view of a reactor suitable for depositing high-grade electronic graphene (GAE) according to an example of modality.
    The reactor includes a 901 frame portion with several inlets and outlets.
    More particularly, a gas inlet 903 is provided at the top and in the approximate horizontal center of the reactor housing portion 901.
    The gas inlet 903 may receive gas from one or more sources and therefore can provide a number of gases, including, for example, hydrocarbon gas, the gas (s) used to form the environment during development heteroepitaxial, the extinguishing gas (s) of the reaction, etc.
    The gas flow will be described in greater detail below, for example, with reference to the plenum design of the 907 spray reactor. A variety of 905 exhaust ports can be provided at the bottom of the 901 housing portion of the reactor.
    In the fashion example in figure 9, two exhaust ports 905 are provided close to the ends of the reactor housing portion 901, for example, in order to extract gas supplied by the gas inlet 903 which will generally flow at - substantially through the entrance of the carcass portion 901. It will be understood that more or less 905 exhaust ports may be provided in some examples of embodiments (for example, additional 905 exhaust ports may be provided in the approximate horizontal center of the portion housing 901 of the reactor, on top or sides of the housing portion 901 of the reactor, etc.). The backing substrate 909 can be cleaned and presented with the thin catalyst film disposed on it (for example, by physical vapor deposition, or DFV, spraying, DVC, flame pyrolysis or so on similarly ) before entering the reactor by means of a load blocking mechanism in some examples of modalities.
    In terms of susceptor design, the surface of the postero support substrate 909 can be quickly heated (for example, using a heater. RTA, an IR shortwave heater or other suitable heater that is capable of inductively heating the substrate and / or layers on it without necessarily also heating the entrance chamber) to a controllable temperature level and uniformity that allows (i) the metal film to crystallize and activate, and (ii) preferential deposition of graphene of substantially uniform and controllable thickness of a gas phase pre-cursor on its surface.
    The heater may be controllable in order to account for the deposition rate ratio / (temperature * thickness) parameter of the catalyst.
    The rear support substrate 909 can move through the reactor in the R direction or it can remain. stationary under spray 907. Spray 907 may be cooled, for example, using a cooling fluid or gas introduced by one or more refrigerant inlets / outlets 913.
    In summary, and as shown in the enlargement of figure 9, the plenum project can include a multiplicity of openings in the bottom of the spray bottle 907, with each of these openings
    only a few millimeters wide.
    By changing the opening of the ceiling Hc, or the height between the bottom surface of the sprayer 907 and the top surface on which the back support substrate 909 moves, it can have different effects.
    For example, the chamber volume and thus the surface-to-volume ratio can be modified, thereby affecting the residence time of the gas, consumption time and radial velocities.
    It appears that changes in residence time strongly influence the degree of reactions in the gas phase.
    A sprayer configuration operated as shown in figure 9 (with a hot surface below a cooled surface) has the potential for Bernard's natural convection variant if operated at high pressures (for example, in hundreds of Torr), and such trend is strongly influenced by height by —the Rayleigh number (a dimensionless number associated with fluctuation-oriented flow, also known as free convection or natural convection; when it exceeds a critical value for a fluid, the transfer
    heat transfer occurs mainly in the form of convection). Consequently, the opening of the Hc roof can be varied by means of simple changes. in the equipment structure, providing adjustable mounting of the substrate electrode, etc., in order to affect the heteroepitaxialdialene development.
    The modality example in figure 9 is not necessarily intended to operate a plasma in the reactor. This stems from the fact that the mechanism of development of crystalline film occurs through heteroepithelium by superficial sorption (usually occurring only on the catalyst). It appears that the development of the plasma phase gives rise to mainly amorphous films and has also been found to allow the formation of "macroparticles or the formation of dust that can greatly reduce the quality of the film and result in small holes that would be harmful to a film with one to ten atomic layers. Instead, some examples of modalities may involve producing graphite (for example, monocrystalline tape), etching it into graphene (for example, of a certain value n) and making graphene in graphene (for example, in graphene GAE). Naturally, an endpoint technique in situ can be implemented as a feedback parameter.
    In some examples of modalities, an ion beam source may be located in line, but externally to the reactor in figure 9, for example, to perform doping according to the example techniques described above. However, in some examples of embodiments, an ion beam source may be located within the housing portion of a reactor.
    Example Process Flow Figure 10 is an example process flow that illustrates certain modalities of example catalytic DVC development, removal and transfer techniques for some example modalities. The sample process shown in figure 10 begins as the glass in the back support is inspected, for example, using a conventional glass inspection method (step S1002), and washed (step S1004). The back support glass can then be cleaned using ion beam cleaning, plasma incineration or the like (step S1006). The catali-. (eg, a metal catalyst) is placed on the back support, for example, using DFV (step S1008). It is noted that the cleaning process of step S1006 can be carried out within the graphene coating applicator / reactor in some examples of embodiments of this invention. In other words, the glass of the back support with or without the thin metallic catalyst film can be loaded into the graphene coating applicator / reactor before step S1006 in some examples of modalities, for example, depending on whether the layer of metal catalyst is deposited on or before the coating applicator / reactor. The catalytic deposition of a graphene with n layers can then happen (eta-. Pa S1010). Graphene can be reduced by caustication by introducing hydrogen atoms (H *) in some examples of modalities, and graphene can optionally be doped, for example, depending on the target application (step S1012). The end of graphene formation is detected, for example, by determining whether sufficient graphene has been deposited and / or whether the causticization of H * was sufficient (step S1014). To stop the formation of graphene, a quick reaction quenching process is used, and the glass of the backing as graphene formed comes out of the coating applicator / reactor (step S $ 1016). Visual inspection can optionally be performed at this point. After formation of graphene, a polymer useful in transferring graphene can be laid over graphene, for example, by means of rotation, sheet or other coating technique (step S1018). This product can optionally be inspected, for example, to determine whether the required color change occurs. If it has happened, the polymer can be cured (for example, using heat, UV radiation, etc.) (step S1020) and therefore inspected again. The metal catalyst can be partially etched or released in another way (step S1022), for example, to prepare graphene for removal (step S1024).
    Once removal has been achieved, the polymer and graphene can optionally be inspected and then washed, for example, to
    move any remaining caustic by-products and / or uncured polymer * (step S1012). Another optional inspection process can be: performed at that point. A surfactant can be applied (step S1028), pins are placed at least in the polymer (step S1030), and the membrane is inverted (step S1032), for example, with the help of these pins. The removal process is now complete, and the graphene is therefore ready to be transferred to the container substrate.
    The container substrate is prepared (step S1034), for example, in a clean room. The surface of the container substrate can be made functional, for example, by exposing it to UV light to increase its surface energy, to apply grapheneophilic coatings on it, etc. (step: S1036). The graphene / polymer membrane can then be transferred to the. host substrate (step S1038). Once the transfer is complete, the receiving substrate with the graphene and polymer attached to it can be fed into a module to remove the polymer (step S1040). This can be done by exposing the polymer to UV light, heat, chemicals, etc. The substrate with graphene and polymer at least partially dissolved can then be washed (step S1042), with any excess water or other evaporated and dried materials (cover S1044). Thus, the polymer removal process can be repeated as needed.
    After removing the polymer, the strength of the graphene sheet on the substrate can be measured (step S1046), for example, using a standard four-point probe. Optical transmission (eg, Tvis, etc.) can also be measured (step S1048). Assuming that the intermediate or final products meet quality standards, they can be packaged (step S1050). Using these techniques, film samples were prepared. The film samples showed high conductivity of 15,500 Clem and transparency above 80% under the wavelength of 500-
    3000 nm. In addition, the films showed good chemical and thermal stability. Figure 11 is an image of a sample of graphene produced according to some examples of modalities. The image in figure 11 highlights the removal of graphene developed epitaxially from a thin film of permaliga.
    Example of Applications with the inclusion of Graphene As mentioned above, graphene-based layers can be used in a wide variety of applications and / or electronic devices. In these examples of applications and / or electronic devices, ITO and / or other conductive layers can simply be replaced by graphene-based layers. Producing devices with graphene will normally involve producing contacts with metals, degenerate semiconductors such as ITO, semiconductors of solar cells such as a-Si and CdT among others, and / or so on similarly.
    . In spite of presenting a zero band interval and a state disappearance density (DOS) at the K points in the Glossulin zone, graphene that remains free presents a metallic behavior. However, adsorption on a metallic, semiconductor or insulating substrate can alter its electronic properties. To compensate for this, additionally or alternatively, in examples of applications and / or electronic devices, the graphene-based layer can be doped according to any semiconductor layers adjacent to it. That is, in some examples of embodiments, if a graphene-based layer is adjacent to an n-type semiconductor layer, the graphene-based layer may be doped with an n-type dopan. Likewise, in some examples of modalities, if a graphene-based layer is adjacent to a p-type conductor layer, the graphene-based layer can be doped with a p-type dopant. Naturally, the displacement at the Fermi level in graphene with respect to the conical points can be modeled, for example, using functional density theory (TFD). Bank range calculations show that metal / graphene interfaces can be classified into two broad classes, namely, chemosorption and physiosorption. In the latter case, an upward (downward) shift means that electrons (holes) are donated by the metal to graphene. In this way, it is possible to predict which metal or TCO to use as contacts with graphene depending on the application.
    "A first example of an electronic device that can make use of one or more graphene-based layers is a solar photovoltaic device. This example device can include front electrodes or rear electrodes. In these devices, the layers based on graphene can simply replace the ITO normally used in devices. Photovoltaic devices are described in, for example, United States Patent Nos. 6,784,361, 6,288,325, 6,613,603 and 6,123,824; United States publications Nos. 2008/0169021, 2009/00332098, 2008/0308147 and 2009/0020157; and Order Serial Nos 12 / 285,374, 12 / 285,890 and 12 / 457,006, the descriptions of which are incorporated herein by reference.
    Í Alternatively, or in addition, graphite-based layers. in doping they can be included in order to combine with adjacent semi-conductive layers. For example, figure 12 is a schematic cross-sectional view of a solar photovoltaic device that incorporates layers based on graphene according to some examples of modalities. In the example of modality in figure 12, a glass substrate is provided
    1202. For example and without limitation, the glass substrate 1202 can be any of the glasses described in any of United States Patent Applications Nos. 11 / 049.292 and / or 11 / 122.218, the descriptions of which are incorporated herein by reference. The glass substrate can optionally be nanotextured, for example, to increase the efficiency of the solar cell. An anti-reflective (AR) coating 1204 can be provided on the outer surface of the glass substrate 1202, for example, to increase transmission. The anti-reflective coating 1204 can be a single-layer anti-reflective coating (ARUC) (for example, a silicon oxide anti-reflective coating) or a multi-layer anti-reflective coating (ARCM). These AR coatings can be provided using any suitable technique.
    One or more adsorption layers 1206 can be provided on the glass substrate 1202 opposite the AR coating 1204, for example, in the case of a rear electrode device such as that
    PE shown in the modality example in figure 12. The adsorption layers. 1206 can be sandwiched between first and second semiconductors. In the modality example of figure 12, absorption layers 1206 are sandwiched between semiconductor layer type n 1208 (closest to the glass substrate 1202) and semiconductor layer type p 1210 (furthest from the glass substrate 1202). A further 1212 contact (for example, aluminum or other suitable material) can also be provided. Instead of providing ITO or other conductive material (s) between semiconductor 1208 and glass substrate 1202 and / or between semiconductor € 12 and subsequent contact 1212, first and second layers based on graphene 1214 and 1216 can be provided. The 1214 and 1216 grain-based layers can be doped to match the ca-. adjacent semiconductor layers 1208 and 1210, respectively. Thus, in the embodiment example of figure 12, the graphene-based layer 1214 can be doped with n-type dopants and the graphene-based layer 1216 can be doped with p-type dopants.
    Because graphene is difficult to directly texture, an optional layer 1218 can be provided between the glass substrate 1202 and the first layer based on graphene 1214. However, because graphene is very pliable, it will generally conform to the surface on which it is placed. . Consequently, it is possible to texturize the optional layer 1218 so that the texture of that layer can be "transferred" or differently reflected in the generally conformative graphene-based layer 1214. In this regard, the optional textured layer 1218 may comprise zinc doped tin oxide (OEZ). It is observed that one or both semiconductors 1208 and 1210 may be replaced by conductive polymeric materials in some examples of modalities. Because graphene is essentially transparent in the near and middle IR bands, it means that more penetrating long wavelength radiation can penetrate and generate carriers of depth in layer i of both single and tandem junction solar cells. This means that texturing subsequent contacts may not be necessary with graphene-based layers, as efficiency will already increase by around several percentage points.
    Screen printing, evaporation and sintering technologies and CdCk treatment at high temperatures are presently used in CdS / CdTe solar cell heterojunctions. These cells have high load factors (HR> 0.8). However, resistance in series Rs is an efficiency limiting artifact. In Rs, there is a distributed part of the resistance of the CdS layer on the slide and a distinct component associated with CdTe and graphite based on contact at the top of the slide. The use of one or more layers based on graphene can help to reduce both contributions to Rs, while preserving good heterojunction properties. "By including graphene in this solar structure for both front and rear contact arrangements, a substantial efficiency boost can be achieved.
    It will be understood that some examples of modalities may involve solar cells from a single junction, whereas some examples of modalities may involve tandem solar cells. Some examples of modalities can be CdS, CdTe, CIS / CIGS, aSi and / or other types of solar cells.
    Another example of a modality that may incorporate one or more layers of graphene is a touch panel display. For example, the touch panel display can be a capacitive or resistive touch panel display that includes ITO or other conductive layers. See, for example, United States Patents Nos. 7,436,393, 7,372,510, 7,215,331,
    6,204897,6,177,918 and 5,650,597, and Order No. Serial 12 / 292,406, the descriptions of which are incorporated herein by reference. The ITO and / or other conductive layers can be replaced and can be replaced in these touch panels with graphene-based layers. For example, figure 13 is a schematic cross-sectional view of a touch screen that incorporates layers based on graphene according to some examples of modalities. Figure 13 includes an underlying display 1302, which may, in some instances, be an LCD, plasma or other flat panel display.
    An optionally transparent adhesive 1304 couples the viewfinder 1302 to a * thin sheet of glass 1306. A deformable PET sheet 1308 is provided as the topmost layer in the embodiment example of figure 13. PET sheet 1308 is spaced from the upper surface of thin glass substrate 1306 by means of a multiplicity of column spacers 1310 and seals 1312. The first and second layers based on graphene 1314 and 1316 can be provided on the surface of the PET slide 1308 closest to the display 1302 and thin glass substrate 1306 on the surface facing the PET slide 1308, respectively. One or both of the layers based on graphene 1314 and 1316 can be standardized, for example, by means of ion beam and / or laser etching. It is observed that the 'graphene-based layer on the PET sheet can be transferred from its development site to the intermediate product that uses the PET film itself. In other words, the PET sheet can be used in place of a photoresist or other material when removing the graph and / or displacing it.
    A sheet resistance of less than about 500 ohms / square for graphene-based layers is acceptable in modalities similar to those shown in figure 13, and a sheet resistance of less than about 300 ohms / square is advantageous for layers based on graphene.
    It will be understood that the ITO normally found in display 1302 may be replaced by one or more graphene-based layers. For example, when viewfinder 1302 is an LCD viewfinder, graphite-based layers can be provided as a common electrode on the color filter substrate and / or as standard electrodes on the so-called TFT substrate. Of course, graphene-based layers, doped or undoped, can also be used in conjunction with the design and manufacture of individual TFTs. Similar arrangements can also be provided in conjunction with plasma displays and / or other flat panel displays.
    Graphene-based layers can also be used to create conductive data / bus coatings, bus bars, antennas and / or the like.
    Such structures can be formed on / applied to glass substrates, silicon disks, etc.
    Figure 14 is a flowchart that illustrates an example technique for forming a conductive coating of data / buses according to some examples of modalities.
    In step S1401, a graphene-based layer is formed on an appropriate substrate.
    In an optional step, step S1403, a protective layer can be provided over the graphene-based layer.
    In step S1405, the graphene-based layer is selectively removed or patterned.
    This removal or standardization can be carried out by laser etching.
    In such cases, the need for a protective layer can be reduced, as long as the laser resolution is. good enough.
    Alternatively or additionally, caustication can be performed via exposure to an ion beam / plasma treatment.
    Also, as explained above, H * can be used, for example, in conjunction with a hot filament.
    When an ion beam / plasma treatment is used to etch, a protective layer may be desirable.
    For example, a photoresist material can be used to protect the graphene areas of interest.
    This photoresist material can be applied, for example, by means of a rotating coating or similar in step S1403. In these cases, in another optional step, S1407, the optional protective layer is removed.
    Exposure to UV radiation can be used with appropriate photoresist materials, for example.
    In one or more steps not shown, the conductive graphene-based pattern can be transferred to an intermediate or final product if the pattern has not already been formed on it, for example, using any appropriate technique (such as, for example, those described -
    above). Although some examples of modalities have been described as causticable or removable graphene-based layers, some examples of modalities can simply change the conductivity of the graphene-based layer.
    In such cases, some or all of the graphene may not be removed.
    However, because conductivity has been adequately changed
    only the appropriately standardized areas can be used. ras.
    Figure 15 is a schematic view of a technique for forming a conductive coating of data / buses according to some examples of modalities. As shown in figure 15, the conductivity of graphene is selectively changed due to exposure to an ion beam. A photoresist material is applied in a suitable pattern, for example, in order to protect desired portions of the graphene-based layer, whereas the other portions of the graphene-based layer remain exposed to the ion / plasma beam. Mobility data are presented in the table below after 'several samples have been deposited and etched.
    . Samples Thickness Rô Conductivity Mobility [am [1 [957] & [en [EE] Es [rss | room 20,000 | [and 6 624605 | rotonoo | 143000 | [e and 6 s.662 | rs00000 [50,000 | Bs Ss reso2 [rstoco 60000 | It will be understood that standardizing graphene in this and / or other ways can be advantageous for several reasons. For example, the layer will be vastly transparent. Thus, it is possible to provide "seamless" antics where the pattern cannot be seen. A similar result can be provided in conjunction with bus bars that can be incorporated in vehicle windows (for example, for defrosting, use in antennas, electrical components, etc.), flat panel display devices (for example, example, LCD, plasma and / or others), skylights, doors / windows of refrigerators / freezers, etc. This can also advantageously reduce the need for black fries often found in these products. In addition, graphene-based layers can be used instead of ITO in electrochromic devices. Although certain examples of applications / devices have been described here, as shown above, it is possible to use conductive graphene-based layers instead of or in addition to other transparent conductive coatings (RCTs), such as ITO, zinc oxide , etc. As used in this report, the terms "about", "supported by" and so on similarly should not be interpreted to mean that two elements are directly adjacent to each other, unless explicitly stated. In other words, a first layer can be referred to as "over" or "supported by" a second layer, even though there are one or more layers between them.
    Although the invention has been described in conjunction with what is presently considered to be the most practical and preferred modality, it should be understood that the invention should not be limited to the modality described, but "on the contrary, it is intended to cover various modifications and provisions equivalents included in the spirit and scope of the appended claims.
    权利要求:
    Claims (11)
    [1]
    CLAIMS. 1. Method of isolating a thin graphene film, comprising this method: to develop heteroepitaxially the thin graphene film on a thin catalyst film; arranging a polymer based coating on the thin graphene film on a surface opposite the thin catalyst film; cure the polymer based coating; and causing the thin graphene film and the polymer based coating to be released from the thin catalyst film.
    [2]
    Method according to claim 1, wherein the 'thin catalyst film is arranged on a back support substrate, with that back support substrate being formed on the' thin catalyst film on a surface thereof opposite the thin graphene, and wherein the thin film release layer is disposed between the backing substrate and the thin catalyst film.
    [3]
    A method according to claim 2, wherein the release layer comprises zinc oxide.
    [4]
    Method according to claim 2, in which the thin graphene film and the polymer based coating are released from at least the substrate by chemical induction of the release layer.
    [5]
    Method according to claim 3, in which the thin graphene film and the polymer based coating are released from the substrate and the thin catalyst film by chemical induction of the deliberation layer using vinegar.
    [6]
    A method according to claim 1, wherein the thin graphene film and the polymer-based coating are released from the thin catalyst film by etching the thin catalyst film.
    [7]
    Method according to claim 4, in which the thin graphene film and the polymer based coating are released from the thin catalyst film by etching off at least a portion of the thin catalyst film. %
    [8]
    A method according to claim 1, which comprises preparing a target recipient substrate by coating the target recipient substrate with a grapheneophilic coating.
    [9]
    A method according to claim 8, wherein the graphenophilic coating is a coating with inclusion of silicon or a Langmuir-Blodgett film.
    [10]
    10. Method according to claim 1, which further comprises exposing a target receptor substrate to UV radiation to increase the surface energy of the target receptor substrate, thereby making the target receptor substrate more receptive to the film of thin graphene than it would otherwise be. .
    [11]
    11. Method according to claim 1, which further comprises placing the thin graphene film and the polymer-based coating, directly or indirectly, on a target receiving substrate using contact pressure, with the film of fine graphene being closer to the target receptor substrate than the polymer based coating.
    12. The method of claim 11, wherein the thin graphene film and polymer-based coating on the target receptor substrate is carried out using blanket stamping.
    13. The method of claim 11, wherein the thin graphene film and polymer based coating are arranged on the target recipient substrate using one or more cylinders.
    15. Method of disposing a thin graphene film on a target recipient substrate, comprising this method: heteroepitaxially developing the thin graphene film on a thin catalyst film; arranging a polymer based coating on the thin graphene film on a surface opposite the thin catalyst film; taking the thin graphene film and the polymer-based coating to be released from the thin catalyst film; dispose of the thin graphene film and the powder-based coating
    polymer directly or indirectly on a target recipient substrate using. contact pressure, with the thin graphene film being closer to the target receptor substrate than the polymer based coating; and Ú removing the polymer-based layer by exposing it to a solvent and / or UV radiation.
    16. The method of claim 15, wherein the polymer-based layer is PMMA.
    17. Method of disposing a thin graphene film on a target recipient substrate, comprising this method: heteroepitaxially developing the thin graphene film on a thin metallic catalyst film; 'lay the thin graphene film and the thin catalyst film: directly or indirectly, on the target recipient substrate; and electrochemically anodizing the thin catalyst film below graphene so as to make the thin catalyst film a substantially transparent metal oxide.
    18. The method of claim 18, wherein the electrochemical anodization of the thin graphene film is produced so as to act as a cathode as the thin metallic catalyst film is anodized.
    19. Method of disposing a thin graphene film on a target receptor substrate, comprising this method: heteroepitaxially developing the thin graphene film on a thin catalyst film; applying an adhesive to the thin graphene film on a surface opposite the thin catalyst film; causing the thin graphene film to be released from the thin catalyst film; and adhering the thin graphene film to the target recipient substrate.
    20. The method of claim 19, wherein the thin graphene film is released from the thin catalyst film by virtue of a stronger bond between the thin graphene film and the adhesive than between the graphene film thin and the thin catalyst film during des-. cascading of the adhesive.
    21. The method of claim 19, wherein the thin graphene film is released from the thin catalyst film by selectively causticizing the thin catalyst film.
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    同族专利:
    公开号 | 公开日
    IN2012DN00998A|2015-04-10|
    US8236118B2|2012-08-07|
    US8591680B2|2013-11-26|
    KR20120083303A|2012-07-25|
    CN102713025B|2016-08-03|
    CN102713025A|2012-10-03|
    JP2013502050A|2013-01-17|
    US20120312693A1|2012-12-13|
    PL2462263T3|2019-02-28|
    ES2686329T3|2018-10-17|
    TW201114940A|2011-05-01|
    RU2568718C2|2015-11-20|
    EP2462263B1|2018-06-27|
    WO2011016836A2|2011-02-10|
    WO2011016836A3|2011-04-21|
    DK2462263T3|2018-10-15|
    KR101724773B1|2017-04-07|
    US20110030879A1|2011-02-10|
    TWI509099B|2015-11-21|
    RU2012108624A|2013-09-27|
    JP5714012B2|2015-05-07|
    MX2012001604A|2012-04-11|
    EP2462263A2|2012-06-13|
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    法律状态:
    2020-08-25| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-11-10| B25A| Requested transfer of rights approved|Owner name: GUARDIAN GLASS, LLC (US) |
    2020-12-08| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US12/461,347|2009-08-07|
    US12/461,347|US8236118B2|2009-08-07|2009-08-07|Debonding and transfer techniques for hetero-epitaxially grown graphene, and products including the same|
    PCT/US2010/002056|WO2011016836A2|2009-08-07|2010-07-22|Debonding and transfer techniques for hetero-epitaxially grown graphene, and products including the same|
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