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      ELECTRONIC DEVICE INCLUDING LAYER (S) BASED ON GRAPHENE, AND / OR THE MANUFACTURING METHOD OF THE SAME.The present invention relates to the use of graphene as a transparent conductive coating (TCC). In certain example embodiments, thin films of graphene developed over large areas hetero-epitaxially, for example, in a thin film of catalyst, from a hydrocarbon gas (such as, for example, CoH2, CH4, or similar). Thin graphene films of certain example embodiments can be doped or non-doped. In certain exemplary embodiments, they can be doped or non-doped. In certain exemplary embodiments, thin films of graphene, once formed, can be detached from their carrier substrates and transferred to receive the substrates, for example, for inclusion in an intermediate or final product. Graphene developed, elevated, and transferred in this way can have 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:BR112012002653A2
    申请号:R112012002653-4
    申请日:2010-07-16
    公开日:2021-02-02
    发明作者:Vijayen S. Veerasamy
    申请人:Guardian Industries Corp；
    IPC主号:
    专利说明:

    Invention Patent Specification Report for "ELECTRONIC DEVICE" INCLUDING LAYER (S) BASED ON GRAPHENE, AND / OR METHOD OF MANUFACTURING THE SAME ". Mm FIELD OF THE INVENTION The present invention relates to thin films comprising graphene. More particularly , certain exemplary embodiments of this invention refer to the use of graphene as a transparent conductive coating (TCC) .In certain exemplary embodiments, thin films of graphene developed in large heteroepitaxially areas, for example, in a thin film of catalyst, from a hydrocarbon gas (such as, for example, CaH> 2, CHa, or the like). doped or non-doped. In certain example embodiments, NM thin films of graphene, once formed, can be detached from their carrier substrates and transferred to receive the substrates, for example, to inc in an intermediate or final product. BACKGROUND AND SUMMARY OF THE WAYS OF CARRYING OUT E-
    EXAMPLE OF THE INVENTION Indium tin oxide (ITO) and fluorine doped tin oxide (FTO or SnO: F) coatings are widely used as window electrodes in opto-electronic devices. These transparent conductive oxides (TCOs) have been immensely successful in a variety of applications. Unfortunately, however, the use of ITO and FTO 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 TCOs in the presence of an acid or base, their susceptibility to the diffusion of ions from the conducting layers of ions, their limited transparency in the near infrared region (for example, energy-rich spectrum), high leakage current from FTO devices caused by structural defects in the FTO, etc. The fragile nature of ITO and its high deposition temperature can also limit its applications. In addition, surface roughness in SnO2: F can
    cause the formation of a problematic arc. ms Thus, it will be noted that there is a need in the technique with 'relation to smooth and moldable electrode materials with good stability, high' transparency and excellent conductivity.
    Research on new electrode materials with good stability, high transparency and excellent conductivity is ongoing. One aspect of this research involves identifying viable alternatives for such conventional TCOs. In this regard, the inventor of the present invention has developed a viable transparent conductive coating (TCC) based on carbon, especially graphene. The term graphene generally refers to one or more "atomic layers of graphite, for example, with a single layer of graphene or SGL being extendable up to n-layers of graphite (for example, where n À can be as high as about 10) The recent discovery and isolation of graphene (by the cleavage of crystalline graphite) at the University of Manchester comes at a time when the trend in electronics is to reduce the dimensions of the circuit elements to the nanoscale. hay unexpectedly led to a new world of unique opto-electronic properties, not found in standard electronic materials. This arises from the linear dispersion ratio (E vs. k), which gives rise to the charge carriers in graphene having a zero resting mass and behave like relativistic particles. The displaced electrons of relativistic behavior that move around carbon atoms result from their interaction with the periodic potential of the grapevine's honeycomb lattice in what gives rise to new - quasi-particles that at low energies (E <1.2 eV) are accurately described by the Dirac (2 + I) -dimensional equation with an effective speed of light vr = c / 300 = 10 ms ”. Therefore, the well-established techniques of quantum electrodynamics (QED) (which deals with photons) can be exercised in the study of graphene - with the most advantageous aspect being that such effects are amplified in graphene by a factor of 300. For example, universal coupling constant a is almost 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 contents are incorporated in this document.
    , Although it is only worth the thickness of an atom (at least), Á graphene is chemically and thermally stable (although graphene can be oxidized on the surface at 300 degrees C), thus allowing graphene-based devices successfully manufactured resist environmental conditions. High quality graphene sheets were the first produced by the micro-mechanical cleavage of mass graphite. Is the same technique being adjusted to currently supply high quality graphene crystallites up to 100 µm of size. This size is sufficient for most micro-electronics research purposes. Consequently, most "of the techniques developed so far, mainly in universities, have focused more on the microscopic sample, and preparation and characterization of the 'device rather than the enlargement.
    Contrary to most current research trends, in order to realize the full potential of graphene as a possible CBT, the deposition of a large area of high quality material on substrates (for example, glass or plastic substrates) is essential. So far, most large-scale graphene production processes rely on mass graphite exfoliation using wet-based chemicals and start with highly ordered pyrolytic graphite (HOPG) and chemical exfoliation. As it is known, HOPG is a highly ordered form of pyrolytic graphite with an angular wingspan of less than 1 degree, and is generally produced by annealing under stress at 3300 K. HOPG behaves like a very pure in that it is generally reflective and electrically conductive, although fragile and flaky. The graphene produced in this way is filtered and then adheres to a surface. However, there are disadvantages with the exfoliation process. For example, exfoliated graphene tends to bend and become wrinkled, exists as small strips and depends on a gluing / stitching process for deposition, lacks inherent control over the number of layers of graphene, etc. The material thus produced is often contaminated by interleaving and, as such, has low degree of electronic properties.
    o An in-depth analysis of the carbon phase diagram shows the appropriate process window conditions to produce not only graphite and diamond, but also other allotropic forms such as, for example, carbon nanotubes (CNT) . The catalytic deposition of nanotubes is made from a gas phase at temperatures as high as 1000 degrees C by a variety of groups. Unlike these conventional research areas and conventional techniques, certain exemplary embodiments of this invention concern a gradable technique for hetero-epitaxially mono-crystalline graphite to develop (not as large as about 15) and convert " in high-grade electronic graphene (HEG) (n <about 3). Certain exemplary embodiments also refer to the use of HEG graphene in ultra-thin conductive transparent graphene cells (in terms of spectra both visible and infrared), for example, as an alternative to metal oxide window electrodes ubiquitously employed for a variety of applications (including, for example, solid state solar cells). example is based on a catalytically driven hetero-epitaxial CVD process that occurs at a temperature that is low enough to be principles of thermodynamics as well as kinetics allow HEG graphene films to be crystallized from the gas phase in a layer of seed catalyst at a temperature less than about 700 degrees C.
    Certain exemplary embodiments also use atomic hydrogen, which has been proven to be a potent radical for decontamination of amorphous carbonaceous contamination on substrates and which is capable of doing so at low process temperatures. It is also extremely effective in removing oxides and others on layers typically left by design procedures.
    Certain exemplary embodiments refer to a solar cell. The solar cell comprises a glass substrate. A first
    conductive layer based on graphene is located, directly or indirectly, on the glass substrate. A first semiconductor layer is in contact with the first graphene-based conductive layer. At least one absorption layer is located, directly or indirectly, on the first semiconductor layer. A second semiconductor layer is located, directly or indirectly, on at least one absorption layer. The second conductive layer based on graphene is in contact with the second semiconductor layer. A back contact is located, directly or indirectly, on the second conductive layer based on graphene. In certain example embodiments, the first "semiconductor layer is a n-type semiconductor layer and the first graphene-based layer is doped with n-type dopants, and the second semiconductor layer is a p-type semiconductor layer. - graphene-based layer is doped with p-type dopants. In certain example embodiments, a layer of zinc-doped tin oxide interposes between the glass substrate and the first graphene-based layer. / or second semiconductor layers may comprise polymeric material in certain exemplary embodiments.
    Certain exemplary embodiments refer to a photovoltaic device. The photovoltaic device comprises a substrate; at least one layer of photovoltaic thin film; first and second electrodes; and first and second layers based on transparent conductive graphene. The first and second layers based on graphene are doped with n and p dopants respectively.
    Certain exemplary embodiments refer to a sub-assembly of the touch panel. The subset of the touch panel comprises a glass substrate. A first layer based on transparent conductive graphene is provided, directly or indirectly, on the glass substrate. The deformable sheet is provided, with the deformable sheet being substantially parallel and spaced in relation to the glass substrate. The second layer based on transparent conductive graphene is provided directly or indirectly on the deformable sheet.
    ! In certain example embodiments, the first and / or the 'second layer based on graphene is standardized. A plurality of columns can be located between the deformable sheet and the glass substrate, and at least one edge seal can be provided on the periphery of the subassembly in certain example embodiments. Certain exemplary embodiments refer to a touch panel mechanism comprising a touch panel subassembly. A display can be connected to a substrate surface of the subassembly to the touch panel opposite the deformable sheet. The touch panel mechanism may be a resistive or capacitive touch panel mechanism in certain embodiments.
    Certain exemplary embodiments refer to a data / bus line, comprising a layer based on graphene supported by a substrate. A part of the graphene-based layer was exposed to an ion / plasma beam treatment and / or outlined with H *, thereby reducing the conductivity of the part. In certain certain example embodiments, the part is not electrically conductive. In certain example embodiments, the substrate is a glass substrate, thin slice of silicon, or another substrate. In certain example embodiments, the part can be at least partially removed by exposure to the ion beam / plasma treatment and / or the H * delineation.
    Certain exemplary embodiments refer to an ante. A graphene-based layer is supported by a substrate. A part of the graphene-based layer was exposed to an ion / plasma beam treatment and / or outlined with H * to fine-tune the part of the graphene-based layer compared to other parts of the graphene-based layer. The graphene-based layer as a whole has a visible transmission of at least 80%, more preferably at least 90%.
    Certain exemplary embodiments refer to a method of producing an electronic device. A substrate is provided. The graphene-based layer is formed on the substrate. The layer based on graphene is selectively patterned by one of: ion beam / plasma exposure and H * delineation.
    In certain example embodiments, the graphene-based layer is transferred to a second substrate before standardization. In certain exemplary embodiments, standardization is carried out to reduce conductivity and / or remove parts of the layer with base- graphene. The features, aspects, advantages and embodiments It is for example described here that they can be combined to further realize the embodiments. : BRIEF DESCRIPTION OF THE DRAWINGS These and other features and advantages can be better and more fully understood by reference to the following detailed description of the exemplary illustrative embodiments in conjunction with the drawings, of which: Figure 1 is a high level flowchart that illustrates the general techniques of certain example embodiments; Figure 2 is a schematic example view of the catalytic development techniques of certain example embodiments, which illustrates the introduction of hydrocarbon gas, the carbon that dissolves, and the possible extinction results, according to certain forms of realization of example; Figure 3 is a flow chart illustrating a first example technique for doping graphene according to certain forms of example implementation; Figure 4 is a flow chart illustrating a second example technique for doping graphene in accordance with certain example embodiments; Figure 5 is a schematic example view showing a third example technique for doping graphene in accordance with certain example embodiments; Ú Figure 6 is a graphical plot of the temperature vs time involved in doping graphene in accordance with certain forms of sample implementation;
    Figure 7 is a stack of example layers useful in releasing graphene or shutting down techniques for certain example embodiments;
    Figure 8 is a schematic example view of a mechanism
    laminating mechanism that can be used to arrange graphene on the target glass substrate according to certain exemplary embodiments: example; Figure 9 is a schematic cross-sectional view of a: suitable reactor for the deposition of high-grade electronic graphene (HEG) according to an example embodiment;
    Figure 10 is an example process flow that illustrates some of the techniques of catalytic CVD development, take-off and transfer of certain example embodiments;
    Figure 11 is an image of a sample of graphene produced
    according to certain example embodiments;
    Figure 12 is a schematic cross-sectional view of a solar photovoltaic device that incorporates layers based on graphene according to certain exemplary embodiments;
    Figure 13 is a schematic cross-sectional view of a touch screen incorporating layers based on graphene according to certain exemplary embodiments; and Figure 14 is a flow chart illustrating an exemplary technique for forming a conductive data / bus line according to certain example embodiments; and Figure 15 is a schematic view of a technique for forming a conductive data / bus line according to certain example embodiments.
    DETAILED DESCRIPTION OF THE EMBODIMENTS Flight of the Example of the Invention i Certain exemplary embodiments of this invention refer to a gradable technique for heteroepitaxially developing graphono-crystalline (not as large as about 15) and convert it to high-grade electronic graph (HEG) (n <about 3). Certain exemplary embodiments also relate to the use of HEG graphene in transparent conductive ultra-thin graphene films (in terms of both visible and infrared spectra), for example, as an alternative electrode metal oxide window frames most ubiquitously employed for a variety of applications (including, for example, solid state solar cells). The growth technique of certain example embodiments is based on a heterogeneous CVD process epitaxial catalytically conducted that occurs at a temperature that is low enough to be friendly glassy.
    For example, thermodynamics as well as kinetic principles allow HEG graphene films to be crystallized from the gas phase in a seed catalyst layer (for example, at a temperature less than about 600 degrees C). Fig. 1 is a high-level flowchart that illustrates the general techniques of certain example embodiments.
    As shown in Fig. 1, the general techniques of certain example embodiments can be classified as belonging to one of four basic steps: crystallization of graphene in a suitable reverse support (step S101), release of graphene or detachment of the reverse 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 more detail below, it will be noted that the product referred to in step S107 can be an intermediate product or a final product.
    Exemplary Graphene Crystallization Techniques The graphene crystallization techniques of certain examples of realization can be conceived of as involving the "cracking" of a hydrocarbon gas and reassembling the carbon atoms in the familiar alveolar structure in a large area (for example, an area E f of about 1 meter, or greater), for example, taking advantage of the superficial catalytic pathway. Graphene crystallization techniques for certain example embodiments occur at high temperatures and moderate pressures. Details illustrating this exemplary process will be described in detail below.
    The catalytic development techniques of certain example embodiments are somewhat related to the techniques that were used to develop graphite over a hetero-epitaxial area. A catalyst for the crystallization of graphene is arranged on a suitable reverse support. The reverse support can be any suitable material 'capable of withstanding high temperatures (for example, temperatures up to about 1000 degrees C) such as, for example, some ceramics or glass products, materials including zirconium, nitride materials aluminum, thin slices of silicon, etc. A thin film is placed, directly or indirectly, on the reverse support, thus ensuring that its surface is substantially uncontaminated before the crystallization process. The inventor of the present invention has found that crystallization of graphene is facilitated when the catalyst layer has a substantially isolated crystalline structure of orientation. In this regard, small grains have been determined to be less advantageous, since their mosaic structure will ultimately be transferred to the graphene layer. In any case, the specific orientation of the crystalline structure was observed to be of little significance for the crystallization of graphene, as long as the catalyst layer, at least in substantial part, has a single-oriented crystalline structure. In fact, the comparative absence of grain (or low) limits in the catalyst has been observed to result in the same orientation or similarity for the developed graphene, and it has been observed to provide high-grade graphene (HEG). The catalyst layer itself can be arranged on the reverse support by any suitable technique such as, for example, excitation, combustion vapor deposition (CVD), flame pyrolysis, etc. The catalyst layer itself can comprise any suitable metal flights or inclusive metal material.
    For example, the catalyst layer may comprise, for example, metals such as nickel, cobalt, iron, permaloyl (for example, nickel and iron alloys, generally comprising about 20% iron and 80% nickel), alloys nickel and chromium, copper, and combinations thereof.
    Of course, other metals can be used in connection with certain example embodiments.
    The inventor has found that the layers of nickel catalyst or including nickel are particularly advantageous for the crystallization of graphene, and that the nickel and chromium alloys are even more advantageous.
    In addition, the inventor found that the amount of chromium in the nickel-chromium layers (sometimes also called 'nichrome or NiCr layers) can be optimized in order to promote. formation of large crystals.
    In particular, from 3 to 15% Cr in the NIiCr layer is preferable, from 5 to 12% Cr in the NiCr layer is more preferable, and from 7 to 10% Cr in the NiCr layer is even more preferable.
    The presence of vanadium in the thin metallic film has also been found to be advantageous for promoting large crystal development.
    The catalyst layer can be relatively thin or thick.
    For example, the thin film can be 50 to 1000 nm thick, more preferably 75 to 750 nm thick, and even more preferably 100 to 500 nm thick.
    A "large crystal development" may in certain instances include crystals having a length along a major axis in the order of 10s of microns, and sometimes even greater.
    After the thin film of catalyst is placed on the reverse support, a hydrocarbon gas (for example, C2H> gas, CH gas, etc.) is introduced into a chamber in which the reverse support with the thin film of catalyst arranged on it is located.
    The hydrocarbon gas can be introduced at a pressure ranging from about 5 to 150 mTorr, more preferably from 10 to 100 mTorr.
    In general, the higher the pressure, the faster the development of graphene.
    The back support and / or the chamber as a whole are then heated to dissolve or "open" the hydrocarbon gas.
    For example, the reverse support can be raised to a temperature in the range of 600 to 1200 degrees C, more preferably from 700 to 1000 degrees C, and even more preferably from 800 to 900 j degrees C. Heating can be carried out by any suitable technique It is such as, for example, through 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, heating of the hydrocarbon gas can occur in an environment comprising other gases in certain example embodiments. In certain example embodiments, it may be desirable to use a pure hydrocarbon gas (for example, with C2H2), while it may be desirable to use a 'mixture of hydrocarbon gas or other inert gas, or another gas (for example ,. CH, mixed with Ar).
    Graphene will develop in this or another suitable environment. To stop development and to help ensure that the graphene is developed on the catalyst surface (for example, instead of being incorporated into the catalyst), certain embodiments of the example employ an extinguishing process. Extinction can be carried out using an inert gas such as, for example, argon, nitrogen, their combinations, etc. To promote the development of graphene on the surface of the catalyst layer, the extinction must be performed reasonably quickly. More particularly, it has been observed that very rapid or very slow extinction results in the development of little or no graphene on the surface of the catalyst layer. Generally, extinction in order to reduce the temperature of the reverse support and / or substrate from about 900 degrees C to 700 degrees (or lower) over the course of several minutes has been observed to promote good development of graphene, for example , through chemisorption. In this regard, Fig. 2 is an exemplary schematic view of the catalytic development techniques of certain example embodiments, which illustrates the introduction of hydrocarbon gas, the dissolution of carbon, and the possible extinction results, according to certain example embodiments.
    The graphene development process imposes the strict relation of film thickness t = n x SLG, where n involves a discrete number of steps.
    The very fast identification if graphene was produced and the determination of the value of n over the film area is approximately equivalent to the measurement of film quality and uniformity in a single measurement.
    Although graphene sheets can be seen by atomic force and scanning electron microscopy, these techniques are time consuming and can also lead to contamination of graphene.
    Therefore, certain example embodiments employ a phase contrast technique that increases the visibility of graphene on the planned catalyst surfaces.
    This can be done with a view to mapping any variation in value, from n on the deposition surface of the metallic catalyst film.
    THE . technique is based on the fact that the contrast of graphene can be improved substantially by the rotating coating of a material on it.
    For example, a widely used UV curable substance (eg PMMA) can be coated in a rotating motion, screen printing, coated engraving or otherwise arranged on the graphene / metal / reverse support, for example, in a thickness sufficient to make the film visible and continuous (for example, around 1 micron thick). As explained in more detail below, the inclusion of a polymeric substance can also facilitate the process of taking the graphene off before transferring it to the final surface.
    That is, in addition to providing an indication of when graphene formation is complete, the polymeric substance can also provide a support for highly elastic graphene when the metal layer is released or otherwise detached from the reverse support as explained in details below.
    In the event that a very thick layer is developed (intentionally or not), the layer can be etched, for example, using hydrogen atoms (H *). This technique can be advantageous in several exemplary situations.
    For example, where development occurs very quickly, unexpectedly, unevenly, etc., H * can be used to correct such problems.
    As another example, to ensure that graphene suffices
    Once it is developed, graphite can be created, graphene can be deposited, and graphene can be selectively etched back to the desired level W HEG graphene, for example, using H *. As yet another example, H * can be used to selectively cauterize graphene from a distance, for example, to create conductive and non-conductive areas.
    This can be done by applying an appropriate mask, which performs the cauterization, and then removing the mask, for example.
    Theoretical studies of graphene have shown that the mobility of carriers can be higher than 200000 cmº / (Vs). Experimental measurements of graphene developed hetero-epitaxial treated in the gas phase show resistivity as low as 3 x 106 O-cm, which is better than that of thin silver films.
    The blade resistance for such graphene layers was observed to be about 150 ohms / square.
    One factor that may vary is the number of layers of graphene that are required to provide the lowest resistivity and sheet strength, and it will be noted that the desired thickness of the graphene may vary depending on the target application.
    In general, the graphene suitable for most applications can be graphene n = 1a5, more preferably graphene n = 1 to 10, even more preferably graphene n = 1 to 5, and sometimes graphene n = 2 to 3. A layer of graphenon = 1 has been observed to result in a drop in transmission of about 2.3 to 2.6%. This reduction in transmission was observed to be generally linear across substantially all spectra, for example, ranging from ultraviolet (UV), through the visible, and even IR.
    In addition, the transmission loss was observed to be substantially linear with each successive increment of n.
    Exemplary Doping Techniques Although a blade resistance of 150 ohms / square may be suitable for certain exemplary applications, it will be noted that another reduction in blade resistance may be desirable for different exemplary applications.
    For example, it will be noted that a blade resistance of 10 to 20 ohms / square may be desirable for certain exemplary applications.
    The inventor of the present invention determined that the resistance
    blade strength can be reduced by doping graphene. e 'In this respect, being only an atomic layer thickness, graphene presents ballistic transport on a sub-micron scale and i can be heavily doped - by unlocking voltages or molecular adsorbents or interposed in the case where n> 2 - without significant loss of mobility. It was determined by the inventor of the present invention that in graphene, in addition to the donor / recipient distinction, there are generally two different classes of dopants, namely paramagnetic and non-magnetic. Unlike ordinary semiconductors, the latter type of impurities generally acts as a rather weak dopant, while paramagnetic impurities cause strong doping: Because of the disappearance of the 'linear' shape, the symmetric density of the electron holes of states ( DOS) close to the Dirac point of graphene, the impurity states located without the polarization in rotating motion, are fixed in the center of the pseudo-openings. Thus, the states of impurity in graphene are strongly distinguished from their counterparts in usual semiconductors, where DOS in valence and conduction ranges are very different and levels of impurity are generally far from the middle of the opening. Although a strong doping effect cannot be expected, which requires the existence of well-defined donor levels (or acceptors) of several tens of electron volts away from the Fermi level, if the impurity has a local magnetic moment, their energy levels are divided more or less symmetrically 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 in the graphene. This line of reasoning can be used to guide the choice of molecules that form systems of both isolated paramagnetic molecules and diamagnetic dimers to dopene graphene and improve its conductivity from 10º S / cm to 10º S / cm, and sometimes even to 10th S / cm.
    Exemplary dopants suitable for use in connection with certain exemplary embodiments include nitrogen, boron, phosphorus, fluorides, lithium, potassium, ammonium, etc. Sulfur-based dopants (eg sulfur dioxide) can also be used in connection with “ú” certain exemplary embodiments. For example, the sulfides present in E. glass substrates can be motivated to flow out of the glass and thus dope the layer based on graphene. Several exemplary degrafene doping techniques are presented in greater detail below.
    Fig. 3 is a flowchart that illustrates a first exemplary technique for doping graphene in accordance with certain forms of sample implementation. The exemplary technique of Fig. 3 essentially involves implanting the ion beam of the doping material into graphene. In this exemplary technique, graphene is developed in a metal 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 S $ 303). A plasma is then stimulated inside a chamber containing the catalyst with the graphene formed on it and the doping gas (S305). An ion beam is then used to implant the dopant into the graphene (S307). Exemplary ion beam techniques suitable for this kind of doping are disclosed, for example, in US Patents no.
    6,602,371; 6,808,606; and Re. 38,358, and U.S. Publication No. 2008/0199702, each of which is hereby incorporated by reference. The power of the ion beam can be from about 10 to 200 ev, more preferably from 20 to 50 ev, even more preferably from 20 to 40 ev. Fig. 4 is a flow chart illustrating a second exemplary technique for doping graphene in accordance with certain exemplary embodiments. The exemplary technique of Fig. 4 essentially involves the pre-implantation of solid-state dopants in the target recipient substrate, and then motivating these solid-state dopants to migrate into the graphene when the graphene is applied to the receiving substrate. In this exemplary technique, graphene is developed in a metal catalyst (step S401), for example, as described above. The receiving substrate is prefabricated to include dopants in solid state (step S403). For example, solid-state dopants can be included
    through the fusion in the formulation of the glass. About 1 to 10% atomic, plus Flight preferably from 1 to 5% atomic, and even more preferably from 2 to 3%: dopant atomic can be included in the glass fusion. Graphene is applied to the receiving substrate, for example, using one of the exemplary techniques described in detail below (step S405). Then, solid-state dopants on the receiving substrate are motivated to migrate into the graphene. The heat used in the deposition of graphene will motivate dopants to migrate to the graphene layer being formed. Similarly, additionally doped films can be included in the glass and the dopants in it can be motivated to migrate through these layers through thermal diffusion, for example, creating a doped graphene layer '(n> == 2).
    . An ion beam can also be used to implant dopants directly into the glass in certain example embodiments. The ion beam power can be from about 10 to 1000 ev, more preferably from 20 to 500 ev, even more preferably from 20 to 100 ev. When an intermediate layer is doped and used to supply impurities to the graphene, the ion beam can operate in about 10 to 200 ev, more preferably from 20 to 50 ev, even more preferably from 20 to 40 ev. Fig. 5 is an exemplary schematic view illustrating a third exemplary technique for doping graphene in accordance with certain exemplary embodiments. The exemplary techniques in Fig. 5 essentially involve the pre-implantation of solid state dopants 507 in the metal catalyst layer 503, and then the motivation of- those solid state dopants 507 to migrate through the layer of carbons. talisler 503 when graphene is being formed, thus creating a doped graphite 509 on the surface of the catalyst layer 503. More particularly, in this exemplary technique, the catalyst layer 503 is arranged on the reverse support 505. The layer of catalyst 503 includes in it disadvantaged solid state 507. In other words, the catalyst has solid-state doping atoms within its mass (for example, from about 1 to 10%, more preferably from about 1 to 5%, and most preferably about 1 to 3%). Hydrocarbon gas 501 is introduced near the catalyst layer 503 formed at a high temperature. The dopants in - solid state 507 in the catalyst layer 503 are motivated to migrate to their external surface, for example, by this high temperature, when the crystallization of graphene occurs. The rate at which dopants reach the surface was observed to be a function of the thickness and temperature of the catalyst. Crystallization is interrupted by extinction and, finally, a doped graphene 509 is formed on the surface of the catalyst layer 503 ". After the formation of doped graphene 509, the catalyst layer 503 'now has fewer (or not) dopants solid state 507. An advantage of this exemplary technique concerns the potential to control the development of ultrafine film by judiciously varying the temperature of the metal surface, partial pressure and dwell time of the gas species. deposition, as well as the reactive radicals used in the extinction rate process.
    It will be noted that these exemplary doping techniques can be used alone and / or in various combinations and sub-combinations with each other and / or other techniques. It will also be appreciated that certain exemplary embodiments may include a single doping material or several doping materials, for example, by using a particular exemplary technique once, a particular technique repeatedly, or through a combination of multiple techniques. one or more times each. For example, type p and type n dopants are possible in certain exemplary forms.
    Fig. 8 is a graphical plot of the temperature vs. time involved in doping graphene in accordance with certain example embodiments. As indicated above, cooling can be carried out using, for example, an inert gas. In general, and also as indicated above, the high temperature can be about 900 degrees C in certain example embodiments, and the low temperature can be about 700 degrees C, and cooling can occur over several minutes. The same heating / cooling profile as the one shown in the figure.
    6 can be used regardless of whether graphene is doped. "Exemplary Techniques for Releasing / Taking Off and Transferring Graphene i 'Once graphene has been hetero-epitaxially developed, it can be released or detached from the metal catalyst and / or the reverse support, for example, before being placed on the substrate to be incorporated in the intermediate or final product, several procedures can be implemented for the suspension of epitaxial films from their development substrates according to certain example embodiments. a stack of example layers useful in releasing graphene or detaching techniques from certain example embodiments. In Fig. '7, in certain example embodiments, an optional release layer 701 can be provided between the support reverse layer 505 and catalyst layer 503. This release layer 701 can be or include, for example, zinc oxide (for example, ZnO or other suitable stoichiometry). substrate 505 coated with graphene stack 509 / metal catalyst layer 503 / release layer 701 can receive a thick finish layer (for example, several micrometers thick) of polymer 703, for example, applied through the coating in a rotating motion, dispensed by a flow of meniscus, etc., which can be cured. As mentioned above, this polymer layer 703 can act as a main chain or support for graph 509 during take-off and / or detachment, keeping the graphene film extremely flexible continuously, while also reducing the probability of the film. graphene curl, wrinkle or warp.
    In the same way as mentioned above, PMMA can be used as the polymer that allows graphene to be made visible by phase contrast and to sustain before and / or during take-off. However, a wide range of polymers whose mechanical and chemical properties can be compared with those of graphene can be used during the support phase, as well as the release transfer phase in connection with certain example embodiments. Take-off work can be carried out in parallel with the main developmental branch of epitaxial flights, for example, through experimentation with. graphene that can be chemically exfoliated from graphite.
    ] The release layer can be chemically induced to - descolarographene / metal from the parent substrate as soon as the polymer layer is disposed on it. For example, in the case of a zinc oxide release layer, washing with vinegar can activate the release of graphene. The use of a zinc oxide release layer is also advantageous, since the inventor of the present invention has found that the metal catalyst layer is also removed from graphene with the release layer. This is believed to be a result of the texturing caused by the zinc oxide release layer together with its y-interconnections with the grains in the catalyst layer. It will be seen that this reduces (and sometimes even eliminates) the need to remove the catalyst layer later.
    Certain take-off / take-off and transfer techniques essentially consider the original substrate as a reusable epitaxial development substrate. As such, selective cauterization to destroy and dissolve out of the thin film of metallic catalyst away from the epitaxially developed graphene (with polymer on top) may be desirable in such exemplary embodiments. Thus, the catalyst layer can be etched, regardless of whether a release layer is used, in certain example embodiments. Suitable etching liquids include, for example, acids such as hydrochloric acid, phosphoric acid, etc.
    The glass substrate surface of the final receiver 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 receptor substrate, alternatively or additionally, can be coated with a smooth graphene -ophilic layer, such as a silicone-based polymer, etc., making the latter receptive to graphene. This can help ensure electrostatic bonding,
    preferably thus allowing the transfer of graphene during the 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 through covered printing and / or scrolling in certain exemplary embodiments. Such processes allow the graphene previously developed and chemisorbed in the metal carrier, to be transferred to the receiving glass by means of contact pressure. As an example, graphene can be applied to the substrate through one or more lamination rollers, for example, as shown in Fig. 8. In this regard, Fig. 8 shows the upper and lower rollers 803a and 803b, which will apply pressure and make the graphene. 509 and polymer layer 703 are laminated to target substrate 801. As noted above, target substrate 801 has an inclusive silicon layer or other graphenephilic layer disposed therein to facilitate lamination. It will be seen that the polymer layer 703 will be applied as the outermost layer and that the graphene 509 will be closer (or even directly over) the target substrate 801. In certain embodiments of the example, one or more layers can be supplied on the substrate prior to the application of graphene.
    As soon as the graphene is laid on the target substrate, the polymer layer can be removed. In certain exemplary embodiments, the polymer can be dissolved using an appropriate solvent. When a photosensitive material such as PMMA is used, it can be removed by exposure to UV light. Of course, other removal techniques are also possible.
    It will be appreciated that the thin film of catalyst can be made after graphene has been applied to the target substrate in certain example embodiments, for example, using one of the sample etching liquids described above. The choice of the etching liquid can also be based on the presence or absence of any layers underlying the graphene.
    Certain embodiments of the example more directly direct electrochemically anodize the thin film of metal catalyst below. graphene.
    In such example embodiments, graphene itself can act as the cathode when the metal below is anodized in a transparent oxide while it is still being bonded to the original substrate.
    Such exemplary embodiments can be used to divert the use of the polymeric finish by essentially executing the detachment and transfer processes in a single step.
    However, anodizing by electrochemical means can affect the electronic properties of graphene and thus may need to be compensated.
    In certain example embodiments, the catalyst layer below the 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 certain example embodiments, this can also reduce the need for take-off of graphene, making transferring, handling and other handling of graphene easier.
    Graphene can also be recovered using an adhesive or material as a tape in certain example embodiments.
    The adhesive can be positioned on the target substrate.
    Graphene can be transferred to the target substrate, for example, after applying pressure, by adhering more strongly to the substrate than to the tape, etc.
    Exemplary Reactor Design Shower screen reactors typically employ a perforated or porous planar surface to dispense the reactant gases more or less uniformly along a second parallel planar heated surface.
    Such a configuration can be used to develop graphene using the exemplary hetero-epitaxial techniques described in this document.
    Shower screen reactors are also advantageous for processing large square glass or ceramic substrates.
    A basic diagram of a shower screen reactor is Fig. 9, with the plenum project being expanded.
    In other words, Fig. 9 is a schematic cross-sectional view of a reactor suitable for the deposition of high-grade electronic graphene (HEG) according to an example embodiment.
    The reactor includes a body part 901 with several outlets. More particularly, a gas inlet 903 is provided at the top and in the approximate horizontal center of the body part 901 of the reactor.
    The gas inlet 903 can receive gas from one or more sources and thus can supply various gases including, for example, hydrocarbon gas, the gas used to form the environment during hetero-epitaxial development, extinguishing gas, etc.
    The flow and course of the gas will be described in greater detail below, for example, with reference to the 907 shower screen plenum design. A plurality of 905 exhaust ports may be provided. located at the bottom of the body part 901 of the reactor.
    In the example embodiment of Fig. 9, two exhaust holes 905 are provided close to the ends of the body part 901 of the reactor, for example, in order to extract the gas supplied by the gas inlet 903 which generally it will flow through substantially the entire body part 901. It will be appreciated that more or less exhaust holes 905 may be provided in certain exemplary embodiments (for example, other exhaust holes 905 may be provided in the approximate horizontal center of the reactor body part 901, at the top or on the sides of the reactor body part 901, etc.). The 909 reverse support substrate can be cleaned and have the thin film of catalyst disposed (for example, by physical deposition of vapor or PVD, excitation, CVD, flame pyrolysis, or the like) before entering the reactor by a locking loading mechanism in certain example embodiments.
    In terms of susceptor design, the surface of the 909 reverse support substrate can be quickly heated (for example, using an RTA heater, a shortwave IR heater, or another suitable heater that is capable of inductively heating the substrate and / or the layers on it without necessarily also heating the entire chamber) to a uniformly controllable temperature level
    that it allows (i) the metal film to crystallize and activate, and (ii) the preferred air deposition of graphene of substantially uniform thickness and to control it "from a gas phase precursor on its surface. The heater] can be controllable in order to consider the deposition rate of the parameter ((temperature * thickness) of the catalyst ratio.The reverse support substrate 909 can move through the reactor in the R direction or it can sit stationary under the shower screen 907. Shower screen 907 can be cooled, for example, using a cooling fluid or gas introduced by one or more cooling inlets / outlets 913. In summary, as shown in the enlargement of Fig. 9, the plenum design may include a plurality of openings at the bottom of the shower screen 907, with each such opening being only a few millimeters wide.
    . Changing the maximum opening Hc, or the height between the bottom surface of the shower screen 907 and the top surface after which the reverse support substrate 909 moves, can have several effects. For example, the volume of the chamber and thus the surface-to-volume ratio can be modified, thereby affecting the residence time of the gas, consumption time, and radial speeds. Changes in residence time have been observed to strongly influence the extent of gas phase reactions. A shower screen configuration operated as shown in Fig. 9 (with a hot surface below a cooled surface) has the potential for natural convection of the Beard variety if operated at high pressures (for example, in the hundreds of Torr ), and such a trend is strongly influenced by height through the Rayleigh number (a dimensionless number associated with flow driven by fluctuation, also known as free convection or natural convection; when a critical value for a fluid is exceeded, the transfer heat is mainly in the form of convection). Consequently, the maximum opening Hc can be varied through simple hardware changes, by providing adjustable substrate electrode mounting, etc., in order to affect the hetero-epitaxial development of graphene. The example embodiment of Fig. 9 is not necessarily
    intended to operate a plasma within the reactor. This is because the mechanism of development of crystalline film is through hetero-epitaxy and through superficial sorption (usually occurring only in the catalyst). Í The development of the plasma phase has been observed to give rise to mainly amorphous particles and has also been observed to leave the formation of macro-particles or the formation of dust which can greatly reduce the quality of the film and result in holes that would be harmful to an atomic layer film from one to ten. Instead, certain example embodiments may involve producing graphite (for example, mono-crystalline graphite), cauterizing it into graphane (for example, of a certain value n), and converting the graphane to graphene (for example , in HEG graphene). Naturally, an end-point in-situ technique can be implemented as a 'regeneration parameter'. In certain example embodiments, an ion beam source can be located in line, but external to the reactor of Fig. 9, for example, to perform doping according to the exemplary techniques described above. However, in certain example embodiments, an ion beam source may be located in the body part of a reactor.
    Exemplary Process Flow Fig. 10 is an exemplary process flow that illustrates some of the catalytic techniques of CVD development, take-off, and transfer of certain example embodiments. The exemplary process shown in Fig. 10 begins when the reverse support glass is inspected, for example, using a conventional glass inspection method (step S1002) and washed (step S 1004). The reverse support glass can be cleaned with ion beam cleaning, plasma cauterization, or the like (step S1006). The catalyst (for example, a metal catalyst) is arranged on the reverse support, for example, using PVD (step S1008). - It is noted that the cleaning process of step S1006 can be performed inside the graphene applicator / reactor in certain embodiments of the example of this invention. In other words, the reverse support glass with or without the thin film of metal catalyst formed on it can be NA loaded into the graphene applicator / reactor before step S1006 nm in certain example embodiments, for example, depending on whether the metal catalyst layer is deposited inside or before the applicator / cooler. Catalytic deposition of a n-layer graphene can then occur (step S1010). Graphene can be etched downwards by introducing hydrogen atoms (H *) in certain example embodiments, 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 enough graphene has been deposited and / or whether the cauterization of H * has been sufficient i (step S1014). To stop the formation of graphene, a process of. Rapid extinguishing is used, and the reverse support glass with the graphene formed in it exits the reactor / applicator (step S 1016) Visual inspection can optionally be performed at this time.
    After the formation of graphene, a polymer useful in transferring graphene can be disposed in graphene, for example, by rotating motion, foil, or another coating technique (step S1018). This product can optionally be inspected, for example, to determine if the “required color change occurs. If it has occurred, the polymer can be cured (for example, using heat, UV radiation, etc.) (step S1020), and then inspected again. The metal catalyst can be sub-cauterized or otherwise not released (step S1022), for example, to prepare graphene for take-off (step S1024).
    Once take-off has been achieved, the polymer and graphene can optionally be inspected and then washed, for example, to remove any remaining etching liquids and / or uncured polymer (step S 1026). Another optional inspection process can be performed at this time. A surfactant can be applied (step S1028), the pins are placed at least in the polymer (step S1030), and the membrane is shaken (step S1032), for example, with the help of these pins. The peeling process is now complete, and the graphene is now ready to be transferred to the receiving substrate. - f The receiving substrate is prepared (step S1034), for example, Se in a clean environment. The surface of the receiving substrate can be made functional, for example, by exposing it to UV light to increase its surface energy, to apply graphenophilic coatings, 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 the] graphene and the polymer at least partially dissolved can then be. washed (step S1042), with any excess water or other materials extracted by evaporation and drying (step S1044). This polymer removal process can be repeated, if necessary.
    After removing the polymer, the sheet strength of graphene 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 intermediate or final products meet quality standards, they can be packaged (step S1050).
    Using these techniques, sample films were prepared. The sample films showed high conductivity of 15500 S / cm and transparency of more than 80% over the wavelength of 500 to 3000 nm. In addition, the films showed good chemical and thermal stability. Fig. 11 is an image of a sample graphene produced according to certain example embodiments. The image in Fig. 11 highlights the detachment of graphene hetero-epitaxially developed from a thin film of permali.
    Exemplary Inclusive Graphene Applications As mentioned above, graphene-based layers can be used in a wide variety of applications and / or electronic devices. In such exemplary applications and / or electronic devices, ITO E 'and / or other conductive layers can simply be replaced with ne layers based on graphene. The manufacture of devices with graphene will typically involve the manufacture of contacts with metals, degenerate semiconductors such as ITO, solar cell semiconductors, such as a- Si and CdTe among others, and / or the like. In spite of having a zero-band opening and a density of missing states (DOS) at the K points in the Brillouin zone, graphene at rest has a metallic behavior. However, adsorption on the metallic, semiconductor or insulating substrate can alter its electronic properties. To compensate for this, additionally, or alternatively, in exemplary applications and / or electronic devices, the graphene-based layer can be doped according to any adjacent semiconductor layers. That is, in certain example embodiments, if a graphene-based layer is adjacent to an n-type semiconductor layer, the graphene-based layer can be doped with an n-type dopan. Likewise, in certain example embodiments, if a graphene-based layer is adjacent to a p-type semiconductor layer, the graphene-based layer can be doped with a p-type dopant. Naturally, the change in the Fermi level in graphene with respect to the conical points can be modeled, for example, using the theory of functional density (DFT). The range coverage calculations show that the metal / graphene interfaces can be classified into two major classes, namely, chemosorption and physiosorption. In the latter case, an upward (downward) shift means that the electrons (holes) are donated by the metal to graphene. Thus, it is possible to predict which metal or TCO is used for contacts with graphene, depending on the application.
    A first example electronic device that can make use of one or more layers based on graphene is a solar photovoltaic device. Such sample devices may include frontal electrodes or dorsal electrodes. In such devices, graphene-based layers can simply replace the ITO typically used. Photovoltaic devices are disclosed, for example, in US Patent No. 6,784,361, "to 6,288,325, 6,613,603 and 6,123,824; US Publication No. 2008/0169021; 2009/0032098; 2008/0308147 and 2009 / 0020157; and Order No. Serials 12 / 285,374,12 / 285,890 and 12 / 457,006, the disclosures of which are hereby incorporated by reference.
    Alternatively, or in addition, layers based on doped graphene can be included to coincide with the adjacent semiconducting layers. For example, Fig. 12 is a schematic cross-sectional view of a solar photovoltaic device that incorporates layers based on graphene according to certain exemplary embodiments. In the example embodiment of Fig. 12, a substrate of: glass 1202 is provided. For example, and without limitation, the glass substrate 1202 can be any of the glasses described in any of U.S. Patent Applications Nos. Series 11 / 049.292 and / or 11 / 122.218, whose disclosures of which are hereby incorporated by reference. The glass substrate can optionally be of nano-texture, for example, to increase the efficiency of the solar cell. An anti-reflective (AR) coating 1204 can be provided on an 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 (SLAR) (for example, a silicon oxide anti-reflective coating) or a multi-layer anti-reflective coating (MLAR). Such AR coatings can be supplied using any suitable technique.
    One or more absorption layers 1206 can be provided on the glass substrate 1202 opposite the AR coating 1204, for example, in the case of a reverse electrode device like the one shown in the example embodiment of Fig. 12. The absorbent layers 1206 can be sandwiched between the first and second semiconductors. In the example embodiment of Fig. 12, the absorbent layers 1206 are interspersed between the n-type semiconductor layer 1208 (closest to the glass substrate 1202) and the p-type semiconductor 1210 (furthest from the glass substrate 1202). A 1212 back contact (for example, aluminum or other suitable material) can also be provided. Instead of for- -. To provide ITO or other conductive material between semiconductor 1208 and / or glass substrate 1202 and / or between semiconductor 1210 and back contact 1212, the first and second layers based on graphene 1214 and 1216 can be provided. Graphene-based layers 1214 and 1216 can be doped to match adjacent semiconductor layers 1208 and 1210, respectively. Thus, in the example embodiment of Fig. 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, one. optional layer 1218 can be provided between the glass substrate 1202 and the first layer based on graphene 1214. However, because the graphene is very flexible, it will generally conform to the surface on which it is placed. Consequently, it is possible to texture the optional layer 1218 so that the texture of that layer can be "transferred" or in another way reflected in the generally shaped graphene-based layer.
    1214. In this regard, the optional textured layer 1218 may comprise zinc doped tin oxide (ZTO). It is noted that one or both semiconductors 1208 and 1210 can be replaced with polymeric conductive materials in certain exemplary embodiments. As graphene is essentially transparent in the near and medium ranges to the IR, it implies that the more penetrating long wavelength radiation can penetrate and generate intense carriers in layer i of both isolated and tandem junction solar cells. This implies that the need to texturize the back contacts may not be necessary with graphene-based layers, when efficiency will already be increased by as much as several percentage points. The technologies of screen printing, evaporation, and sintering and CdClI2 treatment at high temperatures are currently used in CdS / CdTe solar cell hetero junctions. These cells have highly fulfilling factors
    floor (FF> 0.8). However, the Rs series resistance is an artifact of limited efficiency and science. At Rs, there is a distributed part of blade resistance of n. CdS layer and a discrete component associated with the CdTe-based contact and graphite on top. The use of one or more layers based on graphene can help to reduce both contributions to Rs, while preserving the good heterojunction properties. By including graphene in such a solar structure for both forward and backward contact arrangements, a substantial increase in efficiency can be achieved.
    It will be appreciated that certain exemplary embodiments may involve single-junction solar cells, while certain exemplary embodiments may involve tandem solar cells. y Certain exemplary embodiments can be CdS, CdTe, CIS / CIGS, a-Si, and / or other types of solar cells.
    Another example embodiment that can incorporate one or more graphene-based layers in a touch panel display. For example, the touch panel display may be a capacitive or resistive touch panel display including ITO or other conductive layers. See, for example, US Patent No.
    7,436,393; 7,372,510; 7,215,331; 6,204,897; 6,177,918 and 5,650,597, and Order No. Serial 12 / 292,406, whose disclosures are hereby incorporated by reference. ITO and / or other conductive layers can be replaced on such touch sensitive panels, they can be replaced with graphene based layers. For example, Fig. 13 is a schematic cross-sectional view of a touchscreen that incorporates layers based on graphene according to certain example embodiments. Fig. 13 includes an underlying display 1302, which may, in certain exemplary embodiments, be an LCD, plasma or other plane display. An optically transparent adhesive 1304 joins the display 1302 to a thin sheet of glass 1306. A thin deformable PET sheet 1308 is provided as the topmost layer in the example embodiment of Fig. 13. The thin PET sheet 1308 is space-
    of the upper surface of the thin glass substrate 1306 by the virtual of a "Tan plurality of column spacers 1310 and edge seals 1312. The pri-". first and second layers based on graphene 1314 and 1316 can be supplied on the surface of the thin PET blade 1308 closest to the display 1302 and to the thin glass substrate 1306 on the front surface for the thin PET blade 1308, respectively .
    One or both layers based on graphene 1314 and 1316 can be standardized, for example, by ion beam and / or laser etching.
    Note that the graphene-based layer on the PET thin sheet can be transferred from its development site to the intermediate product using the PET thin sheet itself.
    In other words, the PET 'thin sheet can be used instead of a photosensitive material or another when: it detaches from graphene and / or moves it.
    The blade resistance of less than about 500 ohms / square for graphene-based layers is acceptable in embodiments similar to those shown in Fig. 13, and a blade resistance of less than about 300 ohms / square is advantageous for graphene-based layers.
    It will be appreciated that the ITO typically found on the display 1302 can be replaced with one or more graphene based layers.
    For example, when display 1302 is an LCD monitor, graphene-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 connection with the design and manufacture of individual TFTs.
    Similar provisions can also be provided in connection with the plasma panel displays and / or other plans.
    Graphene-based layers can also be used - conductor / bus data parallels, bus bars, antennas and / or the like.
    Such structures can be formed on / applied to glass substrates, thin slices of silicon, etc.
    Fig. 14 is a flow chart illustrating an exemplary technique for forming a conductor / bus data line according to certain example embodiments. oa 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 on top of the graphene-based layer. In step S1405, the graphene-based layer is selectively removed or patterned. This removal or standardization can be performed by laser caution. In such cases, the need for a protective layer can be reduced, as long as the laser resolution is fine enough. Alternatively or in addition, cauterization can be performed through exposure to an ion / plasma beam treatment. Likewise, as] explained above, H * can be used, for example, in connection with a hot wire. When an ion / plasma beam treatment is used for cauterization, a protective layer may be desirable. For example, a photosensitive material can be used to protect the graph areas of interest. Such a photosensitive material can be applied, for example, by coating in a rotating motion or the like in step S1403. In such cases, in another optional step, S1407, the optional protective layer is removed. Exposure to UV radiation can be used with the appropriate photosensitive material, for example. In one or more steps not shown, the pattern based on conductive graphene can be transferred to an intermediate or final product, if it was not already formed on it, for example, using any appropriate technique (such as, for example, those described above) ).
    Although certain example embodiments have been described as distant cauterization or removal of graphene-based layers, certain example embodiments can simply change the conductivity of the graphene-based layer. In such cases, some or all of the graphene cannot be removed. However, because the - conductivity has been changed accordingly, only the appropriately standardized areas can be conductive.
    Fig. 15 is a schematic view of a technique for the formation
    conducting a line of conductive data / bus according to certain "- example embodiments. As shown in figure. 15, the conductivity of graphene is selectively altered due to exposure to an ion beam The photosensitive material is applied in a suitable pattern, for example, in order to protect the desired parts of the graphene-based layer, while the other parts of the graphene-based layer remain exposed to the ion / plasma beam.
    The mobility data are shown in the table below after several samples have been deposited and etched. cauterized Dem) 1 / Qcm in "2 / Vs)! 1a js | 6 frei om | 1200 |, 8 dx | 6 [6266] io | 1500 | | e | | 6 [sound] time | 150000 | Lp ls | 6 146602] 150000 | 160000 | It will be noted that the standardization of graphene in this and / or other media can be advantageous for several reasons, for example, the layer will be basically transparent, so it is possible to provide seamless antennas where the pattern cannot be seen, a similar result can be provided in connection with the bus bars that can be embedded in vehicle windows (for example, for defrosting, antenna use, power components, etc.), flat panel display devices (eg, LCD, plasma, and / or others), skylights, refrigerator / freezer doors / windows, etc. This can also advantageously reduce the need for black fries frequently found in such products.
    - In addition, graphene-based layers can be used in place of ITO in electrochromic devices.
    Although certain exemplary applications / devices have been described here, as shown above, it is possible to use conductive layers based on graphene in place of or in addition to other transparent conductive coatings (TCCs), such as ITO, zinc oxide, etc. As used herein, the terms "about", "supported by", and others 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 said to be "on" or '"supported by" a second layer, even if there is one or more layers between them.
    Although the invention has been described in connection with what is currently considered to be the most practical and preferred embodiment, it should be understood that the invention should not be limited to the disclosed embodiment, but on the contrary, it is intended to cover the various modifications and equivalent provisions included within the spirit and scope of the appended claims.
    权利要求:
    Claims (30)
    [1]
    CLAIMS mo 1. Solar cell, comprising:: a glass substrate; a first conductive layer based on graphene located, directly or indirectly, on the glass substrate; a first semiconductor layer in contact with the first conductive layer based on graphene; at least one absorption layer located, directly or indirectly, on the first semiconductor layer; a second semiconductor layer located, directly or indirectly, on the at least one absorbent layer; 1 a second conductive layer based on graphene in contact with the second semiconductor layer; e There is a reverse contact located, directly or indirectly, on the second conductive layer based on graphene.
    [2]
    A solar cell according to claim 1, which further comprises an anti-reflective coating provided on a substrate surface opposite the first graphene-based conductive layer.
    [3]
    Solar cell according to claim 1, wherein the first semiconductor layer is a type n semiconductor layer and the first layer based on graphene is doped with type n dopants.
    [4]
    Solar cell according to claim 3, wherein the second semiconductor layer is a p-type semiconductor layer and the second graphene-based layer is doped with p-type dopants.
    [5]
    Solar cell according to claim 4, which further comprises a layer of zinc doped tin oxide interposed between the glass substrate and the first layer based on graphene.
    [6]
    Solar cell according to claim 1, wherein the first and / or second semiconductor layers comprise polymeric material (s).
    [7]
    7. Photovoltaic device, comprising: a substrate;
    at least one layer of photovoltaic thin film; To first and second electrodes; and ". first and second layers based on transparent conductive graphene; wherein the first and second layers based on graphene are doped respectively with ne-type dopants.
    [8]
    8. Subassembly of a touch panel, comprising: a glass substrate; a first layer based on transparent conductive graphene supplied, directly or indirectly, on the glass substrate; a deformable blade, the deformable blade being substantially parallel and spaced in relation to the glass substrate; and a second layer based on transparent conductive graphene supplied, directly or indirectly, on the deformable sheet.
    [9]
    A touch panel subassembly according to claim 8, wherein the first and / or the second layer (s) based on graphene is / are standardized (s).
    [10]
    10. Subassembly of the touch panel according to claim 9, which further comprises: a plurality of columns located between the deformable blade and the glass substrate, and at least one edge seal on the periphery of the subassembly.
    [11]
    11. Subassembly of touch panel according to claim 10, wherein the deformable sheet is a PET sheet.
    [12]
    A touch panel subassembly according to claim 8, wherein the first and / or the second graphene-based layer (s) have / have a blade resistance of less than 500 ohms / square.
    [13]
    A touch panel subassembly according to claim 8, wherein the first and / or the second graphene-based layer (s) has / have a blade resistance of less than 300 ohms / square.
    [14]
    14. Touch panel mechanism, comprising: To the touch panel subassembly as defined in "claim 8; and a display connected to a substrate surface of the touch panel sub-assembly opposite the deformable blade.
    [15]
    15. Touch panel mechanism according to claim 14, in which the display is an LCD screen.
    [16]
    16. Touch panel mechanism according to claim 15, wherein the touch panel mechanism is a capacitive touch panel mechanism.
    [17]
    17. Touch panel mechanism according to claim 15, wherein the touch panel mechanism is a resistive touch panel mechanism.
    [18]
    18. Data / bus line, comprising a graphene-based layer supported by a substrate, in which: a part of the graphene-based layer was exposed to an ion / plasma beam treatment and / or etched with H * , thereby reducing the conductivity of the part.
    [19]
    19. Data / bus line according to claim 18, in which part is not electrically conductive.
    [20]
    The data / bus line according to claim 18, wherein the substrate is a glass substrate.
    [21]
    21. Data / bus line according to claim 18, wherein the substrate is a thin slice of silicon.
    [22]
    22. Data / bus line according to claim 18, wherein the part is at least partially removed by exposure to ion beam / plasma treatment and / or cauterization with H *.
    [23]
    23. Antenna, comprising: a graphene-based layer supported by a substrate, in which: a part of the graphene-based layer has been exposed to an ion / plasma beam treatment and / or etched with H * to fine tune the part of the graphene-based layer compared to other parts r - of the graphene-based layer, "" where the graphene-based layer, as a whole, has a visible transmission of at least 80%.
    [24]
    24. The antenna of claim 23, wherein the graphene-based layer as a whole has a visible transmission of at least 90%.
    [25]
    25. Method of producing an electronic device, the method comprising: providing a substrate; forming a layer based on graphene on the substrate; e 'selectively standardize the layer based on graphene by, one of: ion beam / plasma exposure and cauterization with H *.
    [26]
    26. The method of claim 25, which further comprises transferring the graphene-based layer to a second substrate prior to standardization.
    [27]
    27. The method of claim 26, wherein the standardization is performed to reduce conductivity and / or remove parts of the layer based on graphene.
    [28]
    28. The method of claim 26, which further comprises providing a protective mask over the parts of the graphene-based layer prior to standardization.
    [29]
    29. The method of claim 28, wherein the protective mask comprises a photosensitive material.
    [30]
    30. The method of claim 28, which further comprises removing the protective mask.
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    同族专利:
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    RU2535235C2|2014-12-10|
    TWI669781B|2019-08-21|
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    法律状态:
    2021-02-17| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-02-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-18| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|Free format text: REFERENTE A 11A ANUIDADE. |
    2021-06-08| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|
    2021-12-14| 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
    US12/461,349|US10164135B2|2009-08-07|2009-08-07|Electronic device including graphene-based layer, and/or method or making the same|
    US12/461,349|2009-08-07|
    PCT/US2010/002016|WO2011016832A2|2009-08-07|2010-07-16|Electronic device including graphene-based layer,and/or method of making the same|
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