deposition of graphene in a large area on substrate, and products including the same.

专利摘要:
GRAPHEN DEPOSITION IN A LARGE AREA ON SUBSTRATES, AND PRODUCTS INCLUDING THE SAME. Certain exemplary embodiments of the present invention relate to the use of graphene as a transparent conductive coating (TCC). A substrate having a surface to be coated is provided. A self-assembled monolayer (SAM) model is placed on the surface to be coated. A precursor comprising a precursor molecule is provided, with the precursor molecule being a polycyclic aromatic hydrocarbon (PHA) and discotic molecule. The precursor is dissolved to form a solution. The solution is applied to the substrate with the SAM model arranged on it. The precursor molecule is photochemically linked to the SAM model. The substrate is heated to at least 450 ° C to form an included graphene film. Advantageously, the included graphene film can be supplied directly on the substrate, for example, without the need for a lift-off process.
公开号:BR112012015878A2
申请号:R112012015878-3
申请日:2010-11-24
公开日:2020-09-08
发明作者:Vijayen S. Veerasamy
申请人:Guardian Industries Corp.；
IPC主号:

专利说明:

| In the 1151 Invention Patent Descriptive Report for "DEPOSITION OF GRAPHENE IN A LARGE AREA ON SUBSTRATES, AND PRODUCTS INCLUDING THE SAME". This application incorporates by reference all the contents of each of the serial number applications the priority and benefit of the US provisional patent application US serial number 12 / 461,343, 12 / 461,346, 12 / 461,347 and 12 / 461,349; each was deposited on August 7, 2009. Field of the Invention Certain embodiments by way of example of the present CS 10 invention relate to thin films comprising graphene.
More particularly, certain embodiments as an example of this. The invention relates to the deposition of graphene on a large surface, directly or indirectly, on glass and / or other substrates, and / or products, including the same.
This can be achieved in certain embodiments by way of example through pyrolysis of aromatic polycyclic precursors.
Certain embodiments by way of example of the present invention advantageously do not require the take-off and transfer of a graphene sheet. Background and Summary of Example Modalities of the Invention Tin and indium oxide (ITO) and fluorine doped (FTO or SnO: F) coatings are widely used as window electrodes in opto-electronic devices.
These clear conductive oxides (TCOs) have been extremely successful in a variety of applications.
Unfortunately, however, the use of ITO and FTO is becoming increasingly problematic for a number of reasons.
These 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 acids or bases, their susceptibility to ion diffusion | from ion-conducting layers, their limited transparency in the near infrared region (for example, power-rich spectrum), the high current leakage from FTO devices caused by defects in the FTO structure, etc.
The fragile nature of ITO and its deposition temperature
SN 2/51 high can also limit your applications. In addition, surface roughness in SnO2: F can cause problematic sparks (in some applications).
Thus, it will be appreciated that there is a need in the art for smooth and standardized electrode materials with good stability, high transparency, and excellent conductivity.
The search for new electrode materials with good stability, high transparency, and excellent conductivity is ongoing. One aspect of this research involves the identification of viable alternatives for such conventional and 10 TCOs. In this regard, the inventor of the present invention developed a viable transparent conductive coating (TCC) based on carbon, - specifically graphene. The term graphene generally refers to one or more layers of 'graphite atoms, for example, with a single layer of graphene or SGL being extendable to n-layers of graphite (for example, where n can be as high as about 10). The recent discovery of graphene and insulation (by crystalline graphite cleavage) at the University of Manchester comes in time when the trend in electronics is to reduce the dimensions of circuit elements to the nanoscale. In this regard, graphene has unexpectedly led to a new world of unique and optoelectronic properties, not found in standard electronic materials. This emerges from the linear dispersion ratio (E vs. k), which gives rise to charging graphene carriers having a zero resting mass and behaving like relativistic particles. The relocated electrons of relativistic behavior that move around the results of carbon atoms from their interaction with the periodic potential of the alveolar graphene network give rise to new almost particles that at low energies (E <1.2 eV ) are accurately described by the Dirac (2 + 1) -dimensional equation with an effective light speed yr - c / 300 = 10º ms ”. Therefore, the well-established techniques - built in 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 , the a- | | | |
OA o SN 3/51 constant universal coupling a is close to 2 in graphene compared to 1/137 in vacuum. See K.S. Novoselov, "Effect of electric field on atomically thin carbon particles", Science, vol. 306, pp 666-69 (2004), the contents of which are incorporated here.
Despite being only an atom thick (at least), graphene is chemically and thermally stable (although graphene can be oxidized at 300ºC), thus allowing you to successfully manufacture devices based on graphene to withstand environmental conditions. High quality graphene sheets were first manufactured by micro- and mechanical cleavage of bulk graphite. Is the same technique being perfected to currently supply high quality graphene crystals up to 100 µm of size. This size is sufficient for most microelectronics research purposes. Consequently, most of the techniques developed so far, mainly at universities, have focused more on microscopic sampling, preparation and characterization of devices rather than scaling up.
Contrary to most current research trends, in order to realize the full potential of graphene as a possible CBT, large surface deposition of high quality material on substrates (eg glass or plastic substrates) is essential. To date, most of the major graphene production processes rely on mass graphite exfoliation using wet-based chemicals and start with highly ordered pyrolytic graphite (HOPG) and chemical exfoliation. As is known, HOPG is a highly ordered form of pyrolytic graphite with an angular opening of the C axes of less than 1 degree, and is normally produced by tensile with annealing at 3300 K. HOPG behaves like a pure metal as far as which is generally reflective and electrically conductive, although fragile and scaly. Graphene produced in this way is filtered and then adhered to a surface. However, there are disadvantages with the exfoliation process. For example, exfoliated graphene tends to bend and become crushed, comes out as small strips and depends on a gluing process / points for deposition, it lacks inherent control of the number of layers.
NR o DN o 4151 graphene layers, etc.
The material thus produced is often contaminated by interleaving and, as such, has low-grade electronic properties.
An in-depth analysis of the carbon phase diagram shows the conditions of the window process suitable to produce not only graphite, and diamond, but also other allotropic forms, such as, for example, carbon nano-tubes (CNT). Catalytic deposition of nano-tubes is made from a gas phase at temperatures as high as 1000ºC by a variety of groups. oe 10 In contrast to these areas of conventional research and conventional techniques, the applicant of the present patent application previously described a technique adaptable to the hetero-epitaxially growing (HEG) of monocrystalline graphite (not as large as about 15 ) and Ú converting it to a high quality electronic grade graphene (HEG) (n <about 3). See, for example, patent application serial no. 12 / 461,343; 12 / 461,346; 12 / 461,347, and 12 / 461,349, each of which is incorporated herein by reference in its entirety.
The applicant for this patent application also described the use of HEG graphene in transparent films (both in terms of visible and infrared spectra), ultra-thin conductive graphene films, for example, as an alternative to window electrodes of metal oxides ubiquitously employed for a variety of applications (including, for example, solid-state solar cells). The growth technique described above was based on a catalytically driven hetero-epitaxial CVD process that has a temperature that is low enough to be favorable for glass.
For example, thermodynamic as well as kinetic principles allow HEG graphene films to be crystallized from the gas phase | over a layer of seed catalyst at a temperature below about 700ºC.
Certain modalities in such earlier descriptions used atomic hydrogen, which has been proven to be a potent radical for cleaning amorphous carbonaceous contamination on substrates and being able to do so at
BR MM SN 5/51 low process temperatures. It is also extremely effective in eliminating | oxides and others on layers normally left by attack procedures. Certain modalities of examples of the present invention, on the contrary, can provide for the deposition of graphene over a large area, directly or indirectly on glass and / or other substrates. Such techniques can be performed through pyrolysis of aromatic polycyclic precursors. More particularly, certain exemplary embodiments of the present invention involve the hetero-epitaxial growth of graphene from a supramolecular species. Advantageously, graphene can be formed on substrates without the need for a peeling process in certain - example embodiments. In certain exemplary embodiments of the present invention, a method of making a coated article is provided. A substrate having a surface to be coated is provided. A self-assembled monolayer (SAM) model is placed on the surface to be coated. A precursor comprising a precursor molecule is provided, with the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) and discotic molecule. The precursor is dissolved to form a solution. The solution is applied to the substrate with the SAM model placed on it. The precursor molecule is photochemically linked to the SAM model. The substrate is: slowly heated to at least 450ºC (potentially as high as 900ºC) to form a film of graphene included in an atmosphere comprising or consisting of inert gas and / or hydrocarbons.
In certain exemplary embodiments of the present invention, a method of making a coated article is provided. A substrate having a surface to be coated is provided. An automatic monolayer model (SAM) is arranged on the surface to be coated. A solution is applied to the substrate having the SAM model arranged therein, with the solution comprising a precursor including a precursor molecule, and with the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) molecule. The precursor molecule is attached to the SAM model by the 6/51 irradiation by UV energy in it. The substrate is heated to at least 450ºC to form an included graphene film. The SAM and / or model | The precursor molecule comprises (m) one or more alkyl groups to help ensure that the c-axis of the precursor molecule is substantially perpendicular to the substrate before and / or after the photochemical bond. | In certain exemplary embodiments of the present invention, a | method of making an electronic device is provided. A substrate having a surface to be coated is provided. An au- monolayer model | tomontage (SAM) is placed on the surface to be coated. A pre- and 10 cursor comprising a precursor molecule is provided, with the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) and the discotic molecule. The precursor is dissolved to form a solution. The solution is applied to the substrate with the SAM model arranged on it. 'The precursor molecule is photochemically linked to the SAM model.
The substrate is heated to at least 450ºC to form an included graphene film. The substrate with the included graphene film is embedded | on the electronic device. | In certain exemplary embodiments of the present invention, a method of making an electronic device is provided. A substrate having | a surface to be coated is provided. A monolayer model of self-mount (SAM) is arranged on the surface to be coated. A solution is applied to the substrate with the SAM model arranged therein, with the solution comprising a precursor including a precursor molecule, and with the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) molecule. The precursor molecule is attached to the SAM model by irradiation by UV energy in it. The substrate is heated to at least 450ºC to form an included graphene film. The substrate | with the included graphene film is embedded in the electronic device. The SAM model and / or the precursor molecule comprises (m) one or more alkyl groups to help ensure that the precursor molecule c axis is substantially perpendicular to the substrate before and / or after the photochemical bond. |
: 7/51 In certain exemplary embodiments of the present invention, a method of making a coated article is provided. A substrate having a surface to be coated is provided. A monolayer model is arranged on the surface to be coated. A gaseous stream comprising a carrier gas and a precursor molecule is supplied close to the substrate having the monolayer model arranged therein, with the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) molecule. The precursor molecule is attached to the monolayer model by irradiation by UV energy in it. The substrate with the mono- and 10-layer model and the precursor molecule is heated to form an included graphene film. The monolayer model and / or the precursor molecule - comprises (m) one or more alkyl groups to help ensure that the precursor molecule c axis is substantially perpendicular to the substrate before and / or after the photochemical bond.
The characteristics, aspects, advantages and example modality described here can be combined to achieve even more modalities.
Brief Description of the Drawings These and other characteristics and advantages can be better and more fully understood by reference to the following detailed description of exemplary illustrative modalities together with the drawings, of which: Figure 1 is a high level flowchart illustrating the general techniques of certain example modalities; Figure 2 is a schematic example view of the catalytic growth techniques of certain example modalities, illustrating the introduction of hydrocarbon gas, the dissolving carbon, and the possible tempering results, according to certain example modalities; Figure 3 is a flow chart illustrating a technique of the first example for doping graphene according to certain example modalities;
o 8/51 Figure 4 is a flow chart that illustrates a technique of the second | example for doping graphene according to certain example modalities; Figure 5 is a schematic view illustrating a technique of the third example for doping graphene according to certain example modalities; Figure 6 is a graph plotting temperature as a function of the time involved in doping graphene according to certain example modalities; | e 10 Figure 7 is a stack of sample layers useful in release | graphene or take-off techniques of certain example modalities; Figure 8 is a schematic example of a laminating apparatus which can be used to arrange graphene on the target glass substrate according to certain example modalities; Figure 9 is a schematic cross-sectional view of a reactor suitable for the deposition of high-quality electronic graphene (HEG) according to an example modality; Figure 10 is an example of process flow that illustrates certain CVD catalytic growth of the example, detachment, and transfer techniques for certain example modalities; oe Figure 11 is an image of a sample of graphene produced according to certain example modalities; Figure 12 is a schematic cross-sectional view of a photovoltaic device incorporating layers based on graphene according to certain example modalities; Figure 13 is a schematic cross-sectional view of a touch screen incorporating layers based on graphene according to certain example modalities; and | Figure 14 is a flowchart illustrating an example technique for forming a data / bus line according to certain exemplary embodiments; Figure 15 is a schematic view of a technique for training
'9/51 formation of a conductive data / bus line according to certain example modalities; Figure 16 is an example precursor that is both a PAH and discotic; Figure 17 shows the example PAH molecules with varying numbers, N, of hexagonal carbons or sextets.
Represented in figure 17 are N = 10.17 and 18; Figure 18 illustrates the variation in the LUMO-HOMO energy difference for carbon molecules and PAH molecules with numbers and 10 variables, N, for hexagonal or sextet carbons; Figure 19 shows the Raman spectrum and the peak G 'of graphene films grown according to certain example modalities; Figures 20 (a) and 20 (b) show a possible route for HBC; and 'Figure 21 shows an HBC-PhC12 molecule. | Detailed Description of Example Modes of the Invention Certain example modalities of the present invention refer to a technique of adapting to the hetero-epitaxially mono-crystalline growth of graphite (not as large as about 15) and converting it to graffiti - high electronic grade (HEG) (n <about 3). Certain modalities of | 20 examples also concern the use of HEG graphene in o-transparent (in terms of visible and infrared spectra), conductive films | ultrafine graphene, for example, as an alternative to the metal oxide window electrodes most commonly used for a variety of applications (including, for example, solid state solar cells). The growth technique of certain example embodiments is based on a catalytically driven hetero-epitaxial CVD process that takes place at a temperature that is low enough to be easy on the glass.
For example, thermodynamics as well as kinetic principles allow HEG graphene films to be crystallized from the gas phase over a layer of seed catalyst (for example, at a temperature below about 600ºC). Figure 1 is a high-level flow chart illustrating the techniques
”: 10/51 general of certain example modalities. As shown in figure 1, the general techniques of certain example modalities can be classified as belonging to one of the four basic steps: crystallization of the graphite on a suitable back support (step S101), the release of graphene or taking off from from the back support (step S103), transferring graphene to the target substrate or surface (step S105), and incorporating the target substrate or surface into a product (step S107). As explained in more detail below, it will be appreciated that the product referred to in step S107 can be an intermediate product or a final product.
oe 10 Example of Graphene Crystallization Techniques Graphene crystallization techniques of certain modalities - for example, can be thought of as involving "cracking" of a hydrocarbon gas and reassembling the carbon atoms in the familiar alveolar structure over a large area ( for example, an area of about 1 meter, or greater), for example, using the catalytic surface path. The graphene crystallization techniques of certain example embodiments take place at an elevated temperature and moderate pressures. Illustrative details of this example process will be described in detail below. The catalytic growth techniques of certain example modalities are somewhat related to the techniques that have been used to grow graphite over a hetero-epitaxial area. A catalyst for the crystallization of graphene is arranged on a suitable back support. The back support can be any suitable material capable of withstanding high heat (for example, at temperatures up to about 1000ºC), such as, for example, certain ceramic or glass products, materials including zirconium, aluminum nitride materials , silicon wafers, etc. A thin film is disposed, directly or indirectly, on the back 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 crystal structure of substantially single orientation (for example, less creases are formed). In this regard,
o 11/51 that 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 particular orientation of the crystal structure has been found to be largely insignificant for the crystallization of graphene, provided that the catalyst layer, at least in substantial part, has a unique orientation crystal structure.
Indeed, the comparative absence of grain limits (or low) in the catalyst has been found to result in the same or a similar orientation for grown graphene, and it has been found to provide high quality electrical graphene (HEG). and 10 The catalyst layer itself can be arranged on the back support bracket by any suitable technique, such as,. for example, sputtering, vapor deposition combustion (CVD), flame pyrolysis, etc.
The catalyst layer itself may comprise any suitable metal or enclosed metal material.
For example, the catalyst layer may comprise, for example, metals, such as nickel, cobalt, iron, permalloy (for example, iron and nickel 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 connection with certain exemplary modalities.
The inventor found that the catalyst layers of or including nickel are especially 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 nickel-chromium layers (also sometimes called nichrome or NiCr layers) can be optimized in order 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.
The presence of vanadium in the thin metal film has also been found to be advantageous for promoting large crystal growth.
The catalyst layer can be relatively thin or thick.
For example, the thin film can be 50-1000 nm thick, more preferably 75- 750 nm thick, and even more preferably 100-500 nm of 12/51 thickness.
A "large crystal growth" can, in certain example cases, include crystals with a length along a major axis of the order of 10s of micros, and sometimes even greater.
Since the thin film of catalyst is arranged on the rear support, a hydrocarbon gas (for example, CaH7 gas, CH, gas, etc.) is introduced into a chamber in which the rear support with the thin film of catalyst arranged is located in it.
The hydrocarbon gas can be introduced at a pressure ranging from about 5-150 mTorr, more preferably 10-100 mTorr.
In general, the higher the pressure, the faster the growth of graphene.
The back support and / or the chamber as a whole is / are then heated (s) to dissolve or "open" the hydro gas | - carbide.
For example, the rear support can be raised to a temperature in the range of 600-1200ºC, more preferably 700-1000ºC, and even more: preferably 800-900ºC.
Heating can be carried out by any suitable technique, such as, for example, with a short-wave infrared (IR) heater. Heating can be carried out in an environment | entity comprising a gas such as argon, nitrogen, a mixture of nitrogen and hydrogen, or other suitable medium.
In other words, the heating of the hydrocarbon gas can take place in an environment that comprises other gases in certain exemplary embodiments.
In certain example modalities, 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 another inert gas or another gas (for example, example, CH, mixed with Ar). Graphene will grow in this or another suitable environment.
To stop growth and to help ensure that graphene is grown on the surface of the catalyst (for example, instead of being incorporated into the catalyst), certain example modalities employ a tempering process.
Tempering can be carried out using an inert gas such as, for example, argon, nitrogen, combinations thereof, etc.
In order to promote the growth of graphene on the surface of the catalyst layer, quenching must be carried out very quickly.
More particularly-
NS 13/51 | : | quently, it was found that quenching too fast or too slow re- | * grooves in poor growth or none of graphene on the surface of the | catalyst layer. Generally, quenching in order to reduce the temperature of the back support and / or substrate by about 900ºC at 700 degrees (or below) over several minutes, has been found to promote good growth of graphene, for example, through chemisorption . In this respect, figure 2: is a schematic example of the catalytic growth techniques of certain example modalities, illustrating the introduction of hydrocarbon gas, dissolution carbon, and possible tempering results, oe 10 de according to certain example modalities.
The graphene growth process imposes a strict relation - film thickness t = n x SLG, where n involves a discrete number of steps. Identifying very quickly whether graphene was produced and determining the value of n over the film area is roughly equivalent by measuring 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 exemplary modalities employ a phase contrast technique that improves 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 film. The technique is based on the fact that the contrast of graphene can be increased substantially by coating by centrifuging a material on it. For example, a widely used UV-curable resistance (eg PMMA) can be coated by rotation, printed canvas, coated engraving, or otherwise arranged on the graphene / metal / back support, for example, to a sufficient thickness to make the film visible and continuous (for example, about 1 micron thick). As explained in more detail below, —including a resist polymer can also facilitate the process of displacing graphene before transferring it to the final surface. That is, in addition to providing an indication of when the graphene formation is complete 14/51, the resist polymer can also provide a support for the highly elastic graphene when the metal layer is released or otherwise detached from the rear support, as explained in detail below.
In the event that a layer is grown too thick (intentionally or not), the layer can be stripped down, for example, using hydrogen atoms (H *). This technique can be advantageous in a number of example situations.
For example, where growth occurs very quickly, unexpectedly, uncontrollably | the gular 10, etc., H * can be used to correct these problems.
Like another | For example, to ensure that enough graphene is grown, graphite can be - created, graphene can be deposited, and graphene can be selectively pickled back to the desired level HEG graphene, for example,] using H *. As yet another example, H * can be used to selectively strip the graphene out, for example, to create conductive and non-conductive areas.
This can be achieved by applying an appropriate mask, stripping, and then removing the mask, for example.
Theoretical studies of graphene have shown that the mobility of carriers can be greater than 200,000 cm / (V.s). Experimental measurements of gas phase treated with grown hetero-epitaxial graphene show resistivity as low as 3 x 10º O-cm, which is better than that of. thin silver films.
The sheet strength for such layers of graphene was found to be about 150 ohms / square.
A factor that can vary the number of layers of graphene that are needed to give the lowest resistivity and sheet strength, and it will be appreciated that the desired thickness of the graphene may vary depending on the target application.
In general, suitable graphene for most applications can be n = 1-15 graphene, more preferably n = 1-10 graphene, even more preferably n = 1-5 graphene, and sometimes n = 2-3 graphene.
A layer of graphene n = 1 was found to result in a transmission variation of about 2.3-2.6%. This reduction in transmission was found to be generally linear over
| o 15/51 substantially across the spectrum, for example, ranging from ultraviolet (UV), 7 through the visible, and through IR.
In addition, the loss in transmission was found to be substantially linear with each successive increment of n.
Sample Doping Techniques Although a sheet resistance of 150 ohms / square may be suitable for certain sample applications, it will be appreciated that an additional reduction in sheet resistance may be desirable for different sample applications.
For example, it will be appreciated that a resistance of 10 and 10-20 ohms / square sheet may be desirable for certain example applications.
The inventor of the present invention has determined that the resistance of. sheet can be reduced by doping graphene.
In this respect, being only an atomic layer thickness, graphene exhibits ballistic transport on a submicron scale and can be doped strongly, either by gate stresses or molecular or intercalated adsorbates, in the case where n> 2 - without significant loss of mobility.
It was determined by the inventor of the present invention that it is in graphite, in addition to the donor / acceptor distinction, in general there are two different classes of dopants, that is, paramagnetic and non-magnetic.
In cons | 20 fret with common semiconductors, this last type of impurities generally acts as rather weak dopants, whereas paramagnetic impurities cause strong doping: due to the linear leakage form, the symmetrical electron-hole density of states (DOS) near the Dirac point of graphene, localized impurity states, without spin polarization are fixed to the center of the pseudo-opening.
Thus, the impurity states in graphene are strongly distinguished from their counterparts in usual semiconductors, in which the valence DOS and conduction bands are very different and impurity levels are generally far from the center of the cover.
Although a strong doping effect that requires well-defined donor (or acceptor) levels of several tenths of an electron volt away from the Fermi level could not be expected, if the impurity has a local magnetic moment, its energy levels are divided more or less the. | : 16/51 | symmetrically by Hund exchange, of the order of 1 eV, which provides a favorable situation for a strong doping effect of impurities on the electronic structure of two-dimensional systems with a Dirac spectrum such as those present in graphene. This line of reasoning can be used to guide the choice of molecules that form both individual paramagnetic molecules and diamagnetic dimer systems for graphene doping and increase their conductivity from 10º S / cm to 105º S / cm, and, sometimes even to 10º S / cm. Examples of dopants suitable for use in connection with 10 certain examples include nitrogen, boron, phosphorus, fluorine, lithium, potassium, ammonium, etc. Sulfur-based dopants (eg, sulfur dioxide, sulfuric acid, hydrogen peroxide, etc.) can also be used in connection with certain example modalities. For example, sulfites Ú present in glass substrates can be caused to flow out of the glass and therefore dope the layer based on graphene. Several examples of graphene doping techniques are defined in more detail below.
Figure 3 is a flowchart illustrating a first example technique for doping graphene according to certain example modalities. The technical example in figure 3 essentially involves an ion beam | 20 de-implantation of doping material in graphene. In this example technique, graphene is grown on a metal catalyst (step S301), for example, as described above. The catalyst with the graphene formed therein is exposed to a gas comprising a material to be used as the dopant (also sometimes referred to as a dopant gas) (step S303). A plasma is then excited inside a chamber that contains the catalyst with the graphene formed in it and the doping gas (S305). An ion beam is then used to implant the dopant in graphene (S307). Examples of ion beam techniques suitable for this type of doping are disclosed in, for example, US patent no. 6,602,371; 6,808,606; and Re. 38,358, and publication - US No. 2008 / 0.199.702, each of which is incorporated herein by reference. The ion beam power can be about 10-200 ev, more preferably 20-50 ev, even more preferably 20-40 ev.
DOS A o 17/51 | : - | Figure 4 is a flowchart illustrating a second - example technique for doping graphene according to certain example modalities.
The technical example in figure 4 essentially involves pre-implantation of solid dopants in the substrate receiving the target, and then causing these solid dopants to migrate to graphene when graphene is applied to the recipient substrate.
In this example technique, graphene is grown on a metal catalyst (step S401), for example, as described above.
The receiving substrate is prefabricated so as to include solid dopants in it (step S403). For example, solid state dopants can be included by melting the formulation into the glass.
About 1-10% atomic, more preferably 1-5% atomic, and even more preferably 2-3% atomic dopant can be included in the glass fusion.
Graphene is applied to the receiving substrate, for example, using one of the example techniques described in detail below (step S405). Then, the dopants in the solid state on the receiving substrate are migrated to graphene.
The heat used to deposit the graphene will cause the dopants to migrate to the graphene layer being formed.
In the same way, additionally doped films can be included in the glass and the dopants in it can be made to migrate through these layers by thermal diffusion, for example, creating a thick layer | doped hay (n> = 2). i An ion beam can also be used to implant dopants directly into the glass in certain example modalities.
The ion beam power can be about 10-1000 ev, more preferably 20-500 ev, even more preferably 20-100 ev.
When an intermediate layer is doped and used to supply impurities to 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 view illustrating a third technical example of doping graphene according to certain modalities. example activities.
Figure 5 of example techniques essentially involves the pre-implantation of dopants in the solid state 507 in the catalyst layer.
o 18/51 - metal sizer 503, and then causing these dopants in the solid state 507 to migrate through the catalyst layer 503 when graphene is being formed, thus creating a doped graphene 509 on the surface of the layer of catalyst 503. More particularly, in this example technique, layer of catalyst 503 is arranged on the back support 505. The catalyst layer 503 includes dopants in solid state 507 therein.
In other words, the catalyst has doping atoms in the solid state within its volume (e.g., about 1-10%, more preferably about 1-5%, and most preferably about 1-3%). Gas and hydrocarbon 10 501 are introduced near the formed catalyst layer 503, at a high temperature.
Doping agents in the solid state 507 in ca-. catalyst layer 503 are made to migrate towards the outer surface thereof, for example, by this elevated temperature, when crystallization of graphene occurs.
The rate at which dopants reach the surface has been found to be a function of catalyst thickness and temperature.
Crystallization is stopped by quenching and, ultimately, 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 none) solid state dopants 507 located therein. | 20 An advantage of this example technique refers to the potential to control the growth of ultrafine film by judiciously varying the surface temperature of the metal, the partial pressure, and residence time of the | species of gas deposition, as well as the reactive radicals used in the quenching process.
It will be appreciated that these doping sample techniques can be used alone and / or in various combinations and sub-combinations with one another and / or other techniques.
It will also be appreciated that certain example modalities may include a single doping material or several | doping materials, for example, using a particular sample technique | 30 once, a particular technique, repeatedly, or through a combination of several techniques one or more times each.
For example, dopants | p-type and n-type are possible in certain example modalities.
: 19/51: Figure 6 is a graph plotting temperature as a function of the time involved in graphene doping according to certain modalities of | example.
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 around 900ºC in certain exemplary modalities, and at low temperature it can be around 700ºC, and the cooling can occur over several minutes.
The same heating / cooling profile as shown in figure 6 can be used regardless of whether graphene is doped. and 10 Example Graphene Release / Take-off and Transfer Techniques Once graphene has been hetero-epitaxially grown, it can be released or detached from the metal catalyst and / or the back support, for example, before be placed on the substrate to be incorporated into the intermediate or final product.
Several procedures can be implemented to survey epitaxial films from | their growth substrates according to certain example modalities.
Figure 7 is a stack of example layers useful in the release of graphene or take-off techniques of certain example modalities.
Refer to figure 7, in certain example modalities, a layer of release | | 20 optional section 701 can be provided between the back support 505 and the catalyst layer 503. This release layer 701 can be of, or include, for example, zinc oxide (for example, ZnO or other suitable stoichiometry). Post-graphene deposition, graphene 509 / metal catalyst layer 503 / release layer 701 of the cell-coated substrate - 505 can receive a layer of overlay thickness (for example, several microns thick) of 703 polymer, for example, applied through | centrifuge coating ves dispensed by a meniscus flow, | etc., which can be cured.
As mentioned above, this polymer layer 703 can act as a backbone or support for 509 graphene during displacement and / or take-off, maintaining the graphene film | extremely flexible continuously, while reducing the likelihood of the graphene film rolling, folding, or otherwise warping. | :
| CC 20/51 In addition, as mentioned above, PMMA can be used as the polymer that allows graphene to be visible by phase contrast and to the support, before and / or during detachment. 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 release transfer phase, in connection with certain example modalities. The detachment work can be carried out in parallel with the main epitaxial growth branch, for example, by experimenting with graphene films and 10 which can be chemically exfoliated from graphite.
The release layer can be chemically induced to remove the graphene / metal from the mother substrate once the polymer layer is disposed thereon. For example, in the case of a release layer of zinc oxide, washing in vinegar can trigger the release of the graphite. The use of a zinc oxide release layer is also advantageous, as the inventor of the present invention has found that the metal catalyst layer is also removed from graphene with the release layer. It is believed that this is a result of the texturing caused by the release layer of zinc oxide, together with its interconnections formed with the grains in the catalyst layer. It will be appreciated that this reduces (and sometimes even eliminates) the need to remove the back layer of the catalyst. Certain take-off / take-off techniques and transfer techniques essentially regard the original substrate as a reusable epitaxial growth substrate. As such, selective pickling to mine and dissolve the thin film of metallic catalyst away from the epitaxially grown graphene (with polymer on top) may be desirable in such exemplary embodiments. Thus, the catalyst layer can be stripped off, regardless of whether a layer of deliberation is used, in certain example modalities. Suitable strippers include, for example, acids such as hydrochloric acid, phosphoric acid, etc.
sm O o | 21/51 The surface of the final substrate of the glass container can be pre-stopped to receive the graphene layer. For example, a Langmuir Blodgett film (for example, from a Langmuir-Blodgett acid) can be applied to the glass substrate. The final recipient substrate may alternatively or additionally be coated with a smooth graphenophilic layer such as, for example, a silicone-based polymer, etc., making the latter receptive to graphene. This can help to ensure electrostatic bonding, thus 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 using standard stamping and / or material in certain example modalities. Such processes allow the graphene previously cultivated and chemo-vivid on the metal carrier to be transferred to the beneficiary glass by pressure | contact. As an example, graphene can be applied to the substrate by | means of one or more laminating rollers, for example, as shown in figure 8. In this regard, figure 8 shows upper and lower rollers 803a and 803b, which will apply pressure and cause the 509 graphene and | Polymer 703 is laminated to target substrate 801. As noted above, target substrate 801 has a silicon layer included therein or another graphene layer arranged to facilitate lamination. It will be appreciated that polymer layer 703 will be applied as the outermost layer, and that graphene 509 will be closer (or even directly to) the target substrate
801. In certain exemplary embodiments, one or more layers may be provided on the substrate, prior to the application of graphene.
Once the graphene is disposed on the target substrate, the polymer layer can be removed. In certain exemplary embodiments, the polymer can be dissolved using an appropriate solvent. When photosensitive material such as PMMA is used, it can be removed by exposure to UV light. Of course, other removal techniques are also possible.
RPA | . 22/51 | It will be appreciated that the thin film of catalyst can be stripped off after graphene has been applied to the target substrate in certain example modalities, for example, using one of the example paint strippers described above.
The choice of the stripping product can also be based on the presence or absence of any layers underlying the graffiti.
Certain example modalities more directly electrochemically anodize the thin film of metal catalyst below graphene.
In certain exemplary embodiments, the graphene itself can act as the whole dog, when the metal below is anodized in a transparent oxide, while still being bonded to the original substrate.
Such exemplary modalities can be used to avoid the use of the overcoated polymer by essentially performing the detachment and transfer processes in one step.
However, anodization by electrochemical means can affect the electronic properties of graphene and, therefore, may need to be compensated.
In certain exemplary embodiments, the catalyst layer below the graphene can be oxidized to other forms to become transparent.
For example, a conductive oxide can be used to "bond" the graphene-based layer to a substrate, semiconductor, or- | 20 tracamada.
In this regard, cobalt, chromium cobalt, nickel chromium | o balto and / or the like can be oxidized.
In certain exemplary modalities | example, it can also reduce the need for graphene to take off, making the | graphene transfer, handling and other handling easier. | Graphene can also be taken up using an adhesive or material, in certain example modalities.
The adhesive can be positioned on the target substrate.
Graphene can be transferred to the target substrate, for example, following the application of pressure, even more strongly adhering to the substrate than the tape, etc.
Example of Reactor Design Shower-type reactors typically employ a perforated or porous planar surface to dispense reactant gases more or less uniformly on a second heated parallel planar surface
CC 23/51 acidic. Such a configuration can be used to grow graphene using the 7 example hetero-epitaxial techniques described here. Shower type reactors are also advantageous for processing ceramic substrate or large ultra-smooth, square glass. A basic diagram of a shower-type reactor is figure 9, with the full design being expanded. In other words, figure 9 is a schematic cross-sectional view of a reactor suitable for the deposition of high-quality electronic graphene (HEG) according to an example modality. The reactor includes a body portion 901 with several inlets and outlets. More particularly, a gas inlet 903 is provided at the top and in the approximate horizontal center of the body portion 901 of the reactor. The gas inlet 903 can receive gas from one or more sources and therefore can supply several gases, including, for example, hydrocarbon gas, the gas (s) used 'to form the environment during the hetero-epitaxial growth, quenching gas (s), etc. Gas flow and flow will be described in more detail below, for example, with reference to the full shower design
907. A plurality of exhaust ports 905 can be provided at the bottom of the body portion 901 of the reactor. In figure 9 example mode, two exhaust ports 905 are provided close to the ends of the body portion 901 of the reactor, for example, in order to extract o gas supplied by the gas inlet 903, which will generally flow through substantially of the entire body portion 901. It will be appreciated that the few exhaust ports, 905 can be provided in certain example modalities (for example, additional exhaust ports 905 can be provided in the approximate horizontal center of the body portion 901 of the reactor, on the top or sides of the body portion 901 of the reactor, etc.) The back support substrate 909 can be cleaned and have the thin layer of catalyst disposed on it (for example, by physical vapor deposition or PVD, sputtering, CVD, flame pyrolysis, or the like) before entering the reactor by a charge-lock mechanism in certain example embodiments. In terms of a sus- tained design, the surface of the rear support substrate 909 can be quickly!
24/51 heated (eg using an RTA heater, a short-wave IR heater, or another suitable heater that is capable of inductively heating the substrate and / or layers in it without necessarily also heating the chamber at all) at a controllable temperature and uniformity level that allows (i) the metal film to crystallize and activate, and (ii) preferential deposition of graphene of substantially uniform thickness and controllable from a gas phase precursor on its surface. The heater can be controllable to take account of the deposition rate of parameter / (temperature * thickness) of the catalyst ratio. e 10 The posterior support substrate 909 can move through the reactor in the | direction R or can remain stationary under shower 907. Shower '907 can 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 in figure 9, the full design may include a plurality of openings in the bottom of shower 907, with each opening only a few millimeters wide.
Changing the top opening Hc, or the height between the bottom surface of the shower 907 and the top surface on which the back support substrate 909 moves, can have various effects. For example, you | 20 chamber fire and thus the surface-to-volume ratio can be changed | o and modified, thus affecting the residence time of the gas, the consumption time, and radial speeds. Changes in residence time were observed to strongly influence the extent of reactions in the gas phase.
A shower configuration operated as shown in figure 9 (with a hot surface below a cooled surface) has the potential for convection of Benard's natural variety if operated at high pressures (for example, in the order of hundreds of Torr), and such a trend is | strongly influenced by height through the Rayleigh number (a dimensionless number associated with oriented buoyancy flow, also known as free convection or natural convection; when it exceeds a critical value for a fluid, heat transfer is mainly in the form of convection). Therefore, the difference in the upper aperture Hc
'25/51 can be varied through simple hardware changes, through the provision of adjustable mounting of the substrate electrode, etc., in order to affect the hetero-epitaxial growth of graphene.
The example mode in figure 9 is not necessarily intended to operate a plasma within the reactor. This is because the mechanism of growth of the crystalline film is by hetero-epitaxy by the surface sorption of (usually occurring only in the catalyst). Growth of the plasma phase has been found to give rise to mostly amorphous films and has also been found to allow the formation of macro particles or the formation of dust, which can significantly reduce the quality of the film and result in holes that would be harmful for an atomic layer film: one to ten. Instead, certain example modalities can manufacture graphite (eg, monocrystalline graphite), attack graphene (eg, by a certain value of n), and make graphene graphene (eg, HEG graphene) ). Of course, an intrinsic endpoint technique can be implemented as a feedback parameter.
In certain example embodiments, an ion beam source may be located in-line, but external to the reactor of figure 9, for example, to perform doping according to the example techniques described above. However, in certain example embodiments, an ion beam source may be located within the body portion of a reactor.
Example Process Flow Figure 10 is an example process flow that illustrates some of the example catalytic CVD growth, detachment, and example mode transfer techniques. The sample process shown in figure 10 begins when the back support glass is inspected, for example, using a conventional glass inspection method (step S1002) and washed (step S1004). The glass backing can then be cleaned using ion beam cleaning, plasma calcination, or similar (step S1006). The catalyst (for example, a metal catalyst) is arranged on the back support, for example, using PVD
GC 26/51 (step S1008). It is to be noted that the cleaning process of step S1006 can - be carried out within the graphene coating / reactor in certain exemplary embodiments of the present invention.
In other words, the back support glass with or without the thin film of metal catalyst formed on it can be loaded into the graphene coater / reactor before the S1006 step in certain example embodiments, for example, depending on whether the layer of metal catalyst is deposited inside or before the coater / reactor.
Catalytic deposition of a n-layer graphene can then occur (step S 1010). Graphene can be stripped down through 10 times the introduction of hydrogen atoms (H *) in certain example modalities, and, optionally, graphene can 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 Ú and / or whether H * pickling was sufficient (step S1014). To stop the degrafene formation, a quick tempering process is used, and that the backing glass with the graphene formed in it leaves the reactor / coater (step S1016). Visual inspection can optionally be performed at this point.
Following the formation of graphene, a polymer useful in transferring graphene can be disposed on graphene, for example, by rotation, o and foil, or another coating technique (step S 1018). This product can optionally be checked, for example, to determine whether the color change requirement takes place.
If so, the polymer can be cured (for example, using heat, UV radiation, etc.) (step S1020), and then inspected again.
The metal catalyst may be under-blasted or otherwise released (step S1022), for example, to prepare graphene for peeling (step S1024). Once detachment has been achieved, the polymer and graphene can optionally be inspected and then washed, for example, to remove any remaining under-strippers and / or uncured polymer (step S1026). Another optional inspection process can be performed at this point.
A surfactant can be applied (step | s CG 27/51 | S1028), pins are placed, at least on the polymer (step S1030) and the membrane is shaken (step S1032), for example, with the aid of these pins. The peeling process is now complete, and the graphene is now ready to be transferred to the receiving substrate.
The receiving substrate is prepared (step S1034), for example, in a clean room. The surface of the receiving substrate can be functionalized, for example, by exposure to UV light to increase its surface energy, to apply graphene-phyllic coatings to them, etc. (step S1036). The graphene / polymer membrane can then be transferred to the host substrate 10 (step S 1038). 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 subtotomograph and at least partially dissolved polymer can then be washed (step S1042), with any excess water or other materials evaporated and dried (step S1044). This polymer removal process can be repeated, if necessary. After removing the polymer, the strength of the graphene sheet on the substrate can be measured (step S1046), for example, using | o a standard four-point probe. Optical transmission (eg, Tvis, etc.) can also be measured (step S 1048). Assuming that the intermediate or final products are within the quality standards, they can be packaged (step S1050). Using these techniques, sample films were prepared. The sample films exhibited a high conductivity of 15500 S / cm and a transparency of more than 80% in relation to 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 certain example modalities. The image in figure 11 highlights the detachment of graphene hetero-epitaxially cultivated from a thin permalio film. CC
% 28/51 Graphene Example Deposition Directly or Indirectly on Glass, Without Detachment As explained in detail above, high quality graphene can be epitaxially grown using CVD catalytic techniques.
However, the techniques described above generally involved a process of peeling off the graphene sheet from the thin film metallic catalyst.
These techniques have problems that can sometimes affect the electrical conductivity of the resulting films, including, for example, damage to the graphene films during pickling of the metal, creasing of the graphene during transfer, etc.
One factor that can sometimes affect the creasing density and tension in the sheet is related to the potential incompatibility in thermal expansion between the metal catalyst and the grown graphene, especially during the rapid cooling often used when S forming. graphene.
The potential for creating defects for the graphene film can be a barrier to the development of a large-scale process to make a high quality optoelectronic grade of the material.
Therefore, it will be appreciated that there is a need in the art for growing graphene on any given suitable substrate, (such as, for example, metal, semiconductor, and / or glass substrates). Certain example modalities provide alternative techniques | which avoid the need for a detachment process.
More particularly, certain exemplary embodiments of the present invention involve the hetero-epitaxial growth of graphene from a supramolecular species (which inherently has several aromatic rings). In this regard, the graphene can be grown in certain exemplary modalities from supramolecules that self-organize on a substrate, and then the system can be heated very gradually in an appropriate atmosphere (for example, a inert atmosphere, in the presence of an inert gas, in an inert / hydrocarbon mixture, including, for example, acetylene, etc.) to produce high quality graphene grade products.
This technique may involve a slow temperature ramp up, for example, from room temperature, to just above 400ºC, and then more quickly |
| "29/51 as high as about 800ºC. This example process can advantageously reduce (and sometimes even completely eliminate) the need for quick thermal quenching and detachment and transfer. In certain example embodiments, the slow temperature can be achieved using, for example, a highly controllable long wave IR lamp and then activating a short IR lamp to then increase the temperature above 600 ° C. In any case, such example modalities depends on the examination of the inventor of some precursors that belong to a class of large molecules that are both hydrocarbon- polycyclic aromatic grandchildren (PAHs) and discotic 10. Such an example precursor that is both a PAH and discotic is shown in figure 16. It was it has been discovered that C96 and C34 HAP molecules (for example, C96-C12 and C34-C12), and derivatives thereof, can be used in connection with certain exemplary modalities of the present invention.
Polycyclic aromatic hydrocarbons (also sometimes called polynuclear hydrocarbons) have two or more simple or fused aromatic rings if a pair of carbon atoms is shared between the rings in their molecules. The term "PAH" generally refers to compounds comprising carbon and hydrogen atoms, while the broader term "polycyclic aromatic compounds" includes derivatives and substituted alkyls and their functional derivatives, such as nitro- and hydro- xi-PAH, as well as heterocyclic analogs, which contain one or more heteroatoms in the aromatic structure. PAHs exist in various combinations that manifest various functions, such as light sensitivity, heat resistance, conductivity, corrosion resistance and physiological action. The simplest examples are naphthalene with two benzene rings side by side, and biphenyl having two connected bonded benzene rings. PAH are not found in “synthetic products and are not essential for the growth of living cells. The general characteristics of PAH include high melting and boiling points (they are solid), low vapor pressure, and very low water solubility, decreasing with increasing molecular weight while increasing resistance to oxidation, reduction, and vaporization. Pressure |
. . '30/51 of steam tends to decrease with increasing molecular weight.
PAHs are highly lipophilic and easily soluble in organic solvents.
The low molecular weight of PAHs of 2 or 3 ring groups such as naphthalenes, fluorines, phenanthrenes, and anthracenes have toxicity that tends to decrease with increasing molecular weight.
PAHs are not chemically synthesized for industrial purposes, but are isolated from concentrated coal tar products (or from coal hydrocarbon pyrolysis), followed by subsequent purification by repeated distillation and crystallization.
As is known, the term "discotic" refers to the & 10 columnar stacking capacity of flat, disk-like molecules.
Example approaches that avoid the need for a detachment process are described in more detail below, and it will be appreciated that they are still bottom-up approaches.
However, such example approaches involve molecules that are more complex than —acetylene.
The nucleus of these molecules can, in a certain example, be considered as molecular subunits of graphene.
These molecules self-organize themselves into columnar 1-dimensional supramolecular structures (or substantially 1-dimensional, substantially columnar supramolecular structures) due to the large TI-Tr interactions between aromatic core regions.
The use of appropriate solvents to first dissolve and see PAHs, for example, simple Langmuir-Blodgett techniques can be used to deposit PAHs on glass.
As is known, Langmuir-Blodgett deposition generally involves depositing a material from the surface of a liquid onto a solid by immersing the solid in the liquid.
In general, a monolayer is adsorbed homogeneously with each immersion or immersion step.
In any case, the organization of these molecules in highly ordered layers similar to graphene is then facilitated.
After a gradual heating process in a vacuum and under inert gas (Ar, He, etc.) and / or other gases, graphene can be formed, directly or indirectly, on the glass substrate.
That is, it will be appreciated that graphene can be formed on glass substrates, without the need for a | detachment process in certain exemplary modalities. | t 31/51 s | : For soda lime glass, an inner layer comprising 'silicon oxide (eg SiO2 or other suitable stoichiometry) can be deposited on the glass by a technique such as, for example, MSVD. Deposition was also possible on Si tablets, after cleaning, a sub-layer of silicon oxide with a thickness of about 50 nm was thermally cultured in them. In both cases, a PAH monolayer was created by photochemical bonding of the PAH to a self-assembled immobilized monolayer (SAM) of a silane-benzophenone derivative. The substrate was then heated to 750ºC. The final product included a graphene film 10 comprising mainly a bilayer showing the expected Raman fingerprint (described in more detail below), as well as a sheet resistance in the range of 10-200 ohms / square, depending, for example, example, on the substrate, the type of PAH used, as well as the type of inert gas and temperature profiles. Optical Tvis transmission of the film on the glass ranged from 82-87.1%. The sheet resistance of the formed films ranged from 50 ohms / square. at 120 ohms / square. It will be appreciated that the different oxidized sublayers can | be used in connection with exemplary modalities other than the present invention. For example, silicon oxide sublayers or comprising silicon oxide, zinc oxide, and / or transition metal oxides, can be used in connection with certain exemplary embodiments.
The techniques of certain example modalities are advantageous in that no catalyst, no rapid heating and seasoning and / or no acetylene gas may be required. Supramolecules can instead advantageously self-organize into a structure that, when heated to about 750ºC, forms graphene. It will be appreciated that the temperature at which the appearance of graphene growth takes place is not necessarily 750ºC. In effect, the simulations show that, if monolayers supplied with PAH are present, the formation of graphene can start at temperatures as low as about 450ºC under an inert gas atmosphere. Subtle knowledge of how to prepare the surface with a SAM model in order to anchor the PAH molecules to the glass surface so
* 32/51 that the c axis is perpendicular or substantially perpendicular (i.e., they are flat or substantially flat) to the glass is advantageous when trying to achieve this result.
A detailed description is provided below.
In summary, it will be appreciated that the equipment to dispense so much — SAM model and PAH molecules already exists.
In certain example embodiments, the heating can be carried out under vacuum or under an inert atmosphere, and such techniques are advantageously suitable for existing production lines, since the precursor can be made with sufficiently high purity.
The conditions of the sample equipment, the sample process and the sample process that can be used in connection with certain sample modalities are provided below. 'In certain exemplary embodiments, silane-benzophenone can be used as the anchor model for PAH.
This broad class of PAH molecules was first synthesized by S.
Chandrasekhar at the Raman Institute in 1977 (see S.
Chandrasekhar, Liquid Crystals, Cambridge University Press (1992), the entire contents of which are hereby incorporated by reference) and has been studied by researchers at the College de France (see, for example, F.
Rondelez, D.
Koppel, B.K.
Sadashiva, Journale de Physique 43, 9 (1982) and F.
Rondelez et al., Joumal de Physique 48, 1225-1234 (1987), each of which is incorporated herein by reference). Figure 17 shows the example of PAH molecules with variable numbers, N, of hexagonal carbons or sextets.
Represented in figure 17 are N = 10, 17 and 18. It will be appreciated from figure 17 that R alkyl groups are present at the edges of these molecules.
The R groups act as anchors for the substrate, thus orienting the PAH molecules in a perpendicular or substantially perpendicular to the c axis. | The aromatic perylene molecule (CxoH12) is planar in shape, with a very large intrinsic carrier charge mobility at low temperatures.
It has been determined that perylene can be grown both in '30 in monolayer, as well as in a multilayer regime in a var | metal materials, semiconductor, and insulating substrates.
The substrates were cleaned with an ion beam and in most cases were
B DEMO ca VOU 33/51 | coated with highly textured thin films of various metals, Ú semiconductors, as well as insulators.
For example, the material was grown in both (100) and Si (111), as well as highly textured Cu (111). A surprising and unexpected result of these studies was that organic perylene planar molecules were found to grow with the Tr plane oriented almost or completely parallel to the substrate, not only in the monolayer, but also in the multilayer regime.
This situation is also surprising and unexpected, in which the growth was found to be of the epitaxial type and preceded by means of a growth mode layer 10 and layer 10.
For Cu (110) substrates, for example, using HREELS, LEED, and STM, a highly ordered monolayer was observed, with a subsequent transition in a still highly ordered structure to the multilayer.
This initial work helped propel research on the possibility of graphene growth using HBC and HBC derivatives through a chemical route. | For example, when considering the growth of polyacenes such as pentacene and perylene on solid substrates, it would be desirable to look for the largest molecular segment of a graphite plane that can be deposited plane down using sublimation.
Hexaperien-hexabenzocoronena (Ca2His), or HBC is a candidate.
It is one of the largest molecules to be == o and suitable for the organic growth of molecular beam epitaxy of aromatic molecules on solid substrates for applications in the field of organic electronics.
In previous work, it was demonstrated that deposition on recently cleaved pyrolytic graphite substrates (0001) and on molybdenum disulfide (MoS2) surfaces can be used to | form highly ordered films that grow in a bed-like manner | per layer.
This mode of growth, which has been observed to continue until thicknesses of at least 10 nm, is exceptional since it leads to the formation of highly ordered multilayers with a structure different from that observed in bulk HBC.
For greater thicknesses, an S- transky-Krastanov molecular growth mode has been reported, where a transition to the
CG 34/51 bulk talina is observed.
Interestingly, deposition on polycrystalline Au-substrates or surfaces of oxidized Si (100) does not lead to the formation of highly oriented layers of HBC; instead, the results indicated a highly disordered arrangement of HBC.
This apparent difference in the —growth mode over graphite and MoS, on the one hand and on metal surfaces, on the other hand is removed when deposition is carried out on! clean, well-defined substrates prepared under UHV conditions.
Generally, in clean metals the formation of highly ordered monolayers with the molecular CD planes oriented parallel to the substrate is seen e 10 [Au (100) Au (111). In addition, deposition has been shown to result in the growth of highly oriented layers of HBc to a thickness of 2. nm on Au (Ill) and Cu (Il) substrates, with the ring planes aligned parallel to the substrate.
For layers greater than a- 'thickness of approximately 2 nm, a loss of orientation has been reported.
However, recognizing that HBC can be chemically modified so that it becomes soluble, it was possible to deposit thin films through centrifugal coating or a Langmuir-Blodgett technique (described in more detail below). If alkyl chains are linked to HBC, in several cases liquid-crystalline behavior has been observed leading to the formation of columnar structures in the so-called discotic phase.
An alignment of these or columns can be achieved by varying the particular preparation conditions, including, for example, the pH value of the water subphase.
Reaching liquid materials based on crystalline hexabenzocorones may in certain exemplary modalities allow for improvements in synthesis leading to hexabenzocoronene derivatives with six times substitution by alkyl, design and development of molecular materials with improved properties, such as solubility and "processability" "and incorporation of the molecules obtained in optoelectronic devices, such as organic solar cells.
By a new synthetic protocol, it was possible to perform aryl-aryl and aryl-alkyl couplings very late in the reaction sequence that leads to a wide variety of substituted HBC derivatives.
The introduction
'35/51 tion of a phenyl spacer between the HBC core and the alkyl pendant chains when on HBC-PhC12 it had a number of beneficial effects, such as, for example, increased solubility and liquid crystallinity at temperature environment, which helps to ensure the formation of highly ordered films on a variety of substrates necessary for implementation in molecular organic devices. According to E. CLAR (see Aromatic Sextet, 1972), the more sixths present in PAH, the greater the thermal stability of the material. According to Clar, they are "super-benzenoid". Derivatives of triphenylene o and 10 of coal tar are extremely stable. A possible route for HBC is shown, for example, in figures 20 (a) and 20 (b), and an HBC- molecule. PhC12 is shown in figure 21.
A brief description of certain example techniques for creating an example monolayer on a substrate will now be provided. A C96 monolayer (and / or HBC or hexabenzocoronene) was created by | covalent bonding of a chlorosilane benzophenone derivative to a semiconductor substrate such as the anchor model. The benzophenone functional photochemically reactive group was used to covalently attach the desired PAH molecule to the surface. The presence of an alkyl chain HAP molecule helps to become covalently linked with benzophenone after irradiation. As such, certain example modalities may include materials that contain alkyl chains as the source for covalent bonding with benzophenone. A benzophenone derivative was chosen | as the binder between the glass surface and C96, due to chemical stability, the ease of activation with light at 340-360 nm, and its preferential reactivity, sometimes with high specificity, with other forms CH bonds not reactive. Even in the presence of solvent (eg, water) and nucleophiles, reactivity towards non-reactive CH bonds was sustained. A technique that involves photochemical bonding to the surface has also allowed any unbound C96 or HBC molecules to be washed very easily. After irradiation at about 350 nm, benzophenone undergoes a transition where an electron from an n-orbital like sp of not connected
À OO ô) - 'º C 36/51 tion in oxygen moves to an antiligant of Tr * orbital in the carbon of Ú carbonyl.
Naturally, the radiated UV energy can be of any suitable wavelength, although when the materials described above are used, a wavelength of between about 320-380 nm is generally sufficient to make the desired photochemical bond.
A more detailed description of the example techniques for anchoring the model to a substrate will now be provided.
In particular, a description of the example techniques for anchoring benzophenone chlorosilane (CSBP) to a surface of SiO, will now be provided.
CSBP oe 10 can be readily attached to the SiO7 surface or any surfaces'. glass, using the following and / or similar example techniques.
In one example, CSBP was diluted with toluene, and a few drops of tri-ethyl amine added.
The latter helps to bind the resulting HCL and can also catalyze the reaction.
This process can be carried out simply by immersing the glass substrates in this mixture, by immersion coating, etc.
The substrates can then be washed in chloroform and dried in a medium including N2. Surface energy measurements were used to quantify the surface coverage with CSBP.
The surface is then ready to bind PAH molecules.
A more detailed description of the example techniques for the photochemical linkage of PAH to the model will now be provided.
As mentioned above, the PAH photochemical bond to the model involves the preparation of PAH itself.
In certain example embodiments, this may involve a Diels-Alder cycle addition, for example, to synthesize PAH molecules. The finished PAH C96 was purified by column chromatography.
Solutions of various concentrations of C96 were prepared in chloroform or dodecane.
Of course, it will be appreciated that the pre-mixed or pre-formed PAH included solutions can be provided in connection with certain example modalities.
Example details regarding the synthesis of hexabenzochlorene (HBC) will be provided.
As mentioned above, PAH can be manufactured using a variety of techniques namely by a cyclic reaction.
37/51 Diels-Alder clo-addition as the initial step, followed by cyclic-PAH precursor dehydrogenation formed. In the case of example, a lipophilic cyclopentadienone was coupled with a hydrophilic diphenylacetelin by the Diels-Alder reaction, and the final product of that reaction was subjected to oxidative cyclization to give HBC.
Sample details in terms of preparation C96-C12 will now be provided. As an example, 1,3,5 triethylbenzene and 3,4-bis (4-dodecylphenyl) -2-5-diphenylcyclopentadienone were dissolved in xylene and heated for 15-20 hours at 170ºC under an inert atmosphere. The solvent was removed in vacuo, and the residue was purified by chromatography on silica gel (ether / dichloromethane) to obtain C96-C12. The precursor C96 was then dissolved in dichloromethane, and FeCl; 3 was added dropwise. Argon was bubbled through the solution to remove any formed HCI. The final product was about 60% pure C96 which, as noted above, was purified by column chromatography.
Once prepared, the PAH is ready for deposition and photo-attached to the substrate. In this regard, a thin layer of C96 was created by spin casting and centrifuging the modified CSBP surface of the substrate. Various spin rates or immersion coating rates have been used (and the optimal rates can be derived experimentally in certain example modalities depending, for example, on the PAH precursor, the model, the substrate, the deposition medium, etc.), and the solvent was then allowed to evaporate. The samples were then placed on a hot plate for 1 minute to remove any additional or foreign solvent. The surface was irradiated with UV at 365 nm. The UV promotes a n to 1r * transition in benzophenone, which allows a reaction in the C96 alkyl chain. After irradiation, the excess molecules were washed. C96 solutions in dodecane (or chloroform) with a concentration of 10-2 to 10-6 were prepared. Films prepared from dedecan resulted in very flat PAH, which was positionally flat on the substrate. It is assumed that this result refers to the interaction between solvents and molecules, since the alkyl chains
CJ 38/51 la of the solvent disturbs the initial Tr-mr interaction of the PAH molecules and forces to remain flat to the surface. Another possibility is that dodecane moistens better than chloroform.
It will be appreciated that molecules with different numbers of carbon atoms and / or aromatic sextets can be used in connection with different exemplary embodiments of the present invention. In such cases, the details of the photochemical bond may vary, for example, in terms of wavelength and / or energy required. Figure 18, for example, illustrates the variation in LUMO-HOMO energy difference for the and 10 carbon molecules and PAH molecules with variable numbers, N, of hexagonal or sextet carbons. As is known, HOMO and LUMO are si-. glas of highly occupied molecular orbital and less disrupted molecular orbital, respectively. The difference in the energies of HOMO and LUMO is called band space, which can sometimes serve as a measure of the molecule's excitability.
A description of how heat can be used to create graffiti in certain example modalities will now be provided. An example heat source that can be used is a molybdenum-silicide heater plate (for example, 9 centimeters (4 inches) in diameter) placed inside a controlled vacuum chamber using a LABVIEW DAC mxi. oe The maximum achievable temperature is 1250ºC, and the rate of temperature increase can be controlled from 5º C / min to 50º C / min. In some cases, the onset of pyrolysis was observed to occur at around 550ºC, and the formation of graphene was achieved only above 700ºC. In three sets of experiments, graphene films were grown under Ar, He, and CaH> gas at 0.5 Torr. In a set of experiments, the films were heated in an atmosphere of inert gas from room temperature at a rate of 50º C / min. to reach a temperature as high as 600ºC. Graphene films readily form, and Raman results (for example, shown in figure 19 below) suggest that the start for graphene formation starts at about 450ºC or 475ºC in an Air atmosphere. | |
| : 39/51 In the latter case, the CxH7 gas appears to be beneficial in "repairing" the graphene layer (or at least improving the quality of the graphene layer) and providing a lower strength of the sheet.
For example, it has been found that if heating is carried out under an atmosphere that comprises both Ar and C2xH7, then the electrocal characteristics and the quality of the films surprisingly and unexpectedly improve.
No catalyst was used during this example growth process. 'In terms of pyrolysis, in an example using argon-assisted o and 10 thermal reduction, the substrate was first heated to 100 ° C for two hours.
It was then heated to or at a selected high temperature (which can vary from about 600-1000ºC) for 30 min, with a temperature increase rate of 2ºC min-1 under an atmosphere of Air with a rate of flow of 100 scem.
In an example using acetylene-assisted thermal reduction which, as noted above, can assist with repair, the substrate was first heated to 100 ° C for two hours and then to or at the selected temperature (which can vary from around 600-1000 ° C) ) for 30 min with a temperature increase rate of 2 to 30ºC min-1 under an air atmosphere with a flow rate of 100 scem.
During the heating process, the CxH7 and Ar gases flowed for 10 min with a flow rate of 30 sccm and 100 scem, respectively.
In any case, figure 19 shows the Raman and peak G 'spectrum of graphene films grown according to certain example modalities.
However, it will be appreciated that certain exemplary modalities can use catalysts and / or dopants to further alter properties of the film.
As is known, peaks G and D 'can be used to show whether formed films are, in fact, graphene.
G and D 'refer to the alveolar structure ordered in a hybridized sp2 C-C form.
The sharpness of the peaks (with an FWHM of about 25 cm-1 centered at 2685 cm-1) is also related to greatness in quality.
The reduced D peak (1350 cm-1), on the other hand, provides evidence that sp2-related carbon defects are well below the detection limit of the Jobin-Yvon spectrometer
40/51 Raman. The D band map (integrated over 1300-1400 cm-1), which is very sensitive to defects and wrinkles, shows a very clear region, free from defects or folds. Peak G 'can be used as a marker for the number of graphene layers and find films, where n can be as large as 4, although some shift in the G' line from one area to the other is observable. Although certain exemplary embodiments have been described as involving a liquid based precursor, different 'exemplary embodiments may include for example different gaseous precursors. For example, in certain example embodiments, a gaseous stream containing a carrier gas and a precursor molecule (which may be a PAH and / or a discotic molecule such as one of the molecules identified above) may be provided next to a substrate. to be coated, for example, with the monolayer model having already been laid out therein. The precursor molecule can be linked to the mold, for example, through UV irradiation. | It will be appreciated that it may be relatively easy to vaporize the molecules from a low pressure gas stream. Indeed, the inventor of the present patent application has found that HBC can be deposited using sublimation. The molecule is large enough to add molecular side functional groups, making these classes of molecules very interesting for applications. The self-organization of HBC-1-hexa-alkyl-substituted derivatives in a columnar mesophase in organic solvents has been demonstrated, leading to conductors of one dimension with a very high mobility of carrier load (for example, molecular nanowires).
In one example case, HBC molecules were evaporated in vacuo using a Knudsen cell at a temperature of about 620 K. The molecules then coated the substrate and were further pyrolyzed at a temperature of around 600ºC. This device allows the effusion of HBC molecules in a controlled manner leading to the formation of a n-layer of graphene that can be adsorbed onto a substrate that is coated with, for example, a thin film of MoS. The preferred substrate
41/51 will be very clean before the deposition of the HBC molecule.
It will be appreciated that the evaporation beam can also be used in certain sample modes.
Perhaps more generally, however, at the sublimation temperature of 620 (K, the waste increases by about an order of magnitude with a temperature increase of 10 K.
The size of molecules that can be evaporated by molecular beam deposition from a hot crucible is typically limited.
In general, the temperature of sublimation of molecules, which are only weakly linked by Van der Waals forces, o and 10 increases with molecular weight.
The HBC molecule is apparently an exception to this general rule, as HBC molecules grow in layers - like graphite.
The pi-pi interaction is incremental to the Van der Waals dispersive pattern, thus increasing the sublimation temperature between the molecular planes.
If the temperature required for the sublimation of the molecule is higher than the temperature at which the internal molecular bonds dissociate, the molecules are evaporated into fragments.
However, as mentioned above, this apparently does not happen with HBC and its ampiiphylic derivatives.
It will be appreciated that certain exemplary embodiments use an anchoring agent that is bonded to the glass, and that the PAH bonded to it on UV irradiation.
For example, benzophenone dichlorosilane (CSBP) can be used as such an anchoring agent in certain exemplary modalities.
In general, the anchoring agent can be bonded to glass, silica, metal, plastic, or another substrate, which can be cleaned and / or coated, for example, with a suitable inner layer to accommodate the anchoring agent.
PAH can be mixed with a solvent.
For example, in certain example implementations, HBC-C12 or C96-C12 can be dissolved in dodecane at a concentration of 1.5-3 mg ml-1. When dodecane is used as a solvent, it can be supplied at a molar concentration of, for example, 10-6, 10-5, 10-3, or even. | In any case, when wet techniques are to be used, the solution can be coated by rotation, immersion coated,
42/51 roll, curtain coated, sprayed, or supplied to a borosilicate glass, silicon wafer, quartz, or other substrate.
Of course, a PAH precursor can be introduced through a gas stream and then it can be evaporated, sublimated, or otherwise, supplied.
donates the substrate surface.
Photolink, for example, by radiating | UV can be used to attach the PAH to the anchoring agent in | selected areas and / or according to a standard.
PAH can be pyrolyzed, for example, to provide graphene growth, one layer at a time, which can occur in an inert environment (for example, Ar, Ne, or another suitable gas) , with or without acetylene or other | hydrocarbon gas.
In any case, this technique uses the inventor's recognition of those models that have an appropriate natural alignment (for example, by virtue of their thermodynamic properties) | to accommodate the growth of graphene, as well as the inventor's recognition that certain PAH molecules already include the graphene model.
The techniques described in this document are provided so that PAH molecules can be placed in a "flap" in certain example modalities, allowing graphene to be grown across large areas, for example, in areas larger than the individual PAH molecules. o Of course, if these and / or similar techniques are performed in a vacuum, for example, the need for a CSBP model or other anchoring model can be reduced.
Thus, it will be appreciated that not all embodiments of the present invention require an anchor model, such as CSBP.
It will be appreciated that the example techniques described herein can be used to provide layer by layer of graphene growth, directly or indirectly, on substrates (for example, glass substrates, silicon wafers, and / or the like). In other words, the example techniques described here can be used to provide N controlled growth of layers based on graphene, for example, through repeated process steps.
43/51 The example techniques described herein can be used to produce graphene-based stamped layers. For example, the SAM model can be supplied for the glass substrate according to a desired pattern. This can be facilitated, for example, through the use of masks, the selective removal of the SAM model, etc. In addition, or in | Alternatively, photochemical activation (for example, UV light irradiation) can be controlled so as to only cause PAH molecules to adhere to the SAM model is a pre-defined pattern, for example, limiting the areas where UV light is shone by controlling the UV light source, using 10 suitable masks (for example, using a suitable photosensitive material), and / or the like. Pickling can also be used to help standard graphene-based layers, for example, by re- | moving portions of the SAM model, removing portions of the layer | based on resulting graphene, etc. It will be appreciated that such techniques can allow electronic devices, such as, for example, transistors, to be built.
As mentioned above, the search for new electrode materials with good stability, high transparency, and excellent conductivity is underway, with a crucial goal to seek alternatives to TCOs. Indium and tin oxide (ITO) and fluorine and tin oxide (FTO) coatings are widely used as window electrodes in devices; opto-electronics. Despite being extremely successful, these TCOs seem to be increasingly problematic, due to the limited availability of the Indian element on the land, the instability in the presence of acid or base, its susceptibility to the diffusion of ions from bedding. ion conductors, their limited transparency in the region close to the infrared (for example, the power rich spectrum), the high current leakage from FTO devices caused by defects in the FTO structure, etc. Thus, the following section identifies several examples of applications of included graphene where, for example, TCOs, such as ITO, FTO, and / or the like, can be replaced by or supplemented with graphene-based layers.
| . '| '44/51 Example of Graphene Applications Included As mentioned above, graphene-based layers can be used in a wide variety of applications and / or electronic devices.
In such sample applications and / or electronic devices, ITO and / or other conductive layers can simply be replaced with graphene-based layers.
Making devices with graphene will typically involve making contacts with metals, degenerating semiconductors such as ITO, solar cell semiconductors such as a-Si and CdTe among others, and / or the like. o 10 Despite having a zero band space and a state-density density (DOS) with the K points in the Brillouin zone, free graphene in 'foot' exhibits metallic behavior.
However, adsorption on metallic, semiconductor or insulating substrates can alter their electronic properties.
To compensate for this, additionally, or alternatively, in sample applications and / or electronic devices, the graphite-based layer can be doped according to any semiconductor layers adjacent to it.
That is, in certain example modalities, if a graphene-based layer is adjacent to a n-type semiconductor layer, the graphene-based layer can be doped with a tipon dopant.
Likewise, in certain example embodiments, if a graphene-based layer is adjacent to the p-type semiconductor layer, the graphene-based layer can be doped with a p-type dopant.
Of course, the displacement at the Fermi level in graphene with respect to the conic points can be modeled, for example, using the functional density theory (DFT). Bandwidth calculations show that metal / graphene interfaces can be classified into two broad classes, namely, chemisorption and physisorption.
In the latter case, an upward (downward) shift means that electrons (holes) are donated by the metal to graphene.
Thus, it is possible to predict which metal or TCO to use as paraografene contacts, depending on the application.
BR A first example electronic device that can make use of one or more graphene-based layers is a photo-
'45/51 solar voltaic. Such sample devices may include front electrodes] or lap electrodes. In such devices, graphite-based layers can simply replace the ITO typically used in it. Photovoltaic devices are disclosed in, for example, US Patent No. *
6,784,361, 6,288,325, 6,613,603 and 6,123,824; US publications No. 2008 / 0.169.021; 2009 / 0.032.098; 2008 / 0.308.147; and 2009 / 0.020,157; and serial number orders 12/285, 374, 12/285, 890, and 12/457, 006, the descriptions of which are incorporated herein by reference.
Alternatively, or in addition, doped layers based on the graphene can be included in it, so as to correspond with the adjacent semiconductor layers. For example, figure 12 is a schematic cross-sectional view 7 of a solar photovoltaic device incorporating graphene-based layers according to certain exemplary embodiments. In the example embodiment of figure 12, a glass substrate 1202 is provided. For example and without limitation, the glass substrate 1202 can be of any of the glasses described in any of the patent applications Serial No. 11/049, 292 and / or 11/122, 218, the descriptions of which are incorporated herein by reference. The glass substrate can optionally be nano-textured, for example, to increase the efficiency of the solar cell. An anti-reflective (AR) coating 1204 can be provided on an outer surface and surface of the glass substrate 1202, for example, to increase transmission. The anti-reflective coating 1204 can be a layer of a single anti-reflective coating (SLAR) (e.g., a silicon oxide anti-reflective coating) or a multilayer anti-reflective coating (MLAR). Such AR coatings can be provided using any suitable technique.
One or more absorbent layers 1206 can be provided on the glass substrate 1202 opposite the AR coating 1204, for example, in the case of a back electrode device as shown - in the example embodiment of figure 12. The layers 1206 absorbents can be sandwiched between the first and second semiconductors. In the example embodiment of figure 12, absorption layers 1206 are sandwiched between the type n semiconductor layer 1208 (more: near the glass substrate 1202) and type p semiconductor 1210 (further away from the substrate glass 1202). A 1212 turn 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 1210 and back contact 1212, first and second layers based on graphene 1214 and 1216 can be provided. The graphite-based layers 1214 and 1216 can be doped to match the adjacent semiconductor layers 1208 and 1210, respectively. Thus, as an 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 flexible, it will generally conform with the surface on which it is placed. In this way, it is possible to texture the optional layer 1218 so that the texture of that layer can be "transferred" or otherwise reflected in the generally graphene-based layer conformed to 1214. In this regard, the optional textured layer 1218 can comprise der tin oxide and doped zinc (ZTO). It is noted that one or both semiconductors 1208 and 1210 can be replaced with conductive polymer materials in certain exemplary embodiments.
| Because graphene is essentially transparent in the near and medium ranges of IR implies that the wavelength of the longest penetrating radiation can penetrate and generate deep carriers in layer I of both simple and tandem junction solar cells. This implies that the need for texture back contacts may not be necessary with graphene-based layers, when efficiency will be increased by as much as several percentage points.
Screen printing, evaporation, and sintering and CDCI2 technologies
: 47/51 high temperature treatments are currently used in heterojunctions: CdS / CdTe solar cell.
These cells have high filling factors (FF> 0.8). However, resistance in series Rs is an artifact that limits efficiency.
In RS, there is a part distributed from the resistance of the CdS layer and a discrete component associated with the CdTe and contact based on graphite on top of it.
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 contact arrangements and 10 forwards and backwards, a substantial increase in efficiency can be achieved. 'It will be appreciated that certain exemplary modalities may involve single junction of solar cells, while certain exemplary modalities may involve tandem solar cells.
Certain example modalities 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 is a touch panel display.
For example, the touch panel display may be a capacitive touch panel display - our resistive, 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 patent application No. Series 12/292, 406, the descriptions of which are incorporated herein by reference.
ITO and / or other conductive layers can be replaced on such touch panels that can be replaced with graphene based layers.
For example, figure 13 is a schematic cross-sectional view of a touch screen incorporating layers based on graphene according to certain examples.
Figure 13 includes an underlying display 1302, which may, in certain exemplary embodiments, be an LCD, plasma, or other flat panel display; no An optically transparent adhesive 1304 couples the viewfinder 1302 to a thin sheet of glass 1306. Deformable PET sheet 1308 is supplied as the topmost top layer in the example embodiment in the figure
: 48/51
13. PET sheet 1308 is spaced from the top surface of thin glass substrate 1306 by virtual from a plurality of pillar spacers 1310 and edge seals 1312. First and second layers based on graphene 1314 and 1316 can be provided on the surface of PET sheet 1308 closer to the display 1302 and to the thin glass substrate 1306 on the surface facing PET sheet 1308, respectively. One or both layers based on graphene 1314 and 1316 can be modeled, for example, by ion beam and / or laser engraving. It is noted that the graphene-based layer on the PET sheet can be transferred from its growth site to the intermediate product using the PET sheet itself. In other words, the PET sheet can “be used instead of a photo-resistant material or another when lifting graphene and / or moving 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 graphene-based layers. It will be appreciated that the ITO typically found in display 1302 can be replaced with one or more graphene based layers. For example, when display 1302 is an LCD display, graphene based layers can be provided as a common electrode on the color filter substrate and / or electrodes stamped on the substrate so called TFT. Of course, graphene-based layers, doped or undoped, can also be used in connection with the design and manufacture of individual TFTs. Similar arrangements can also be provided in connection with the flat panel and / or plasma displays. Graphene-based layers can also be used to create conductive data / bus lines, bus bars, antennas and / or the like. Such structures can be formed in / applied to glass substrates, silicon wafers, etc. Figure 14 is a flowchart illustrating an example technique for forming a data / bus line according to certain example modalities.
In: step S1401, a layer based on graphene is formed on a suitable 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 standardized.
This removal or standardization can be performed by laser engraving.
In such cases, the need for a protective layer can be reduced, as long as the laser resolution is sufficiently fine.
Alternatively or in addition, pickling can be carried out through exposure and 10 tion to an ion / plasma beam treatment.
In addition, as explained above, H * can be used, for example, in connection with a hot filament.
When an ion / plasma beam treatment is used for recording, a protective layer may be desirable.
For example, a material was | torresistente can be used to protect graphene areas of interest.
Such a photoresist material can be applied, for example, by centrifugation coating 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 suitable photoresists, for example.
In one or more steps not shown, the graphene-based conductive pattern can be transferred to an intermediate and final or intermediate product, if it has not already been formed in it, for example, using any suitable technique (such as, for example, described above). Although certain example modalities have been described as etching or removing layers based on graphene, for example, certain embodiments can simply alter 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.
Figure 15 is a schematic view of a technique for forming a data / bus line according to certain example modalities.
As shown in figure 15, the conductivity of the
: 50/51 graphene is selectively altered due to exposure to a beam of U ions.
A photoresist material is applied in a suitable pattern, for example, in order to protect desired portions of the graphene-based layer, while the other portions of the graphene-based layer remain exposed to the ion / plasma beam.
Data mobility is shown in the table below, after several samples have been deposited and saved. cpm in and recorded Á) Qcm 1 / Qcm cm 2 / Vs: and the 8 10364 [now ——l120000 | and 2% 6 —— js24603 [1010000 - [143000 - | “Le jo 6 —— lsem = or f1600000 - J150000 - | by ls le —— lr14es02 j1500000 - [160000 - | | It will be appreciated that the standardization of graphene in this and / or other | ways can be advantageous for a number of reasons.
For example, the ca- | layer will be practically transparent.
Thus, 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 incorporated in vehicle windows (for example, for defrosting, antenna use, power components, etc.), flat panel o 15 ( for example, LCD, plasma and / or other) display devices, skylights, fridge / freezer / window doors, etc.
This can also advantageously reduce the need for black chips frequently found in these products.
In addition, graphene-based layers can be used in place of ITO in electrochromic devices.
Although certain example 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, oxide of zinc, etc.
As used here, the terms "about", "supported by" and the like should not be interpreted in the sense that two elements are direct | adjacent to each other, unless explicitly stated. |
- =; 51/51 In other words, a first layer can be said to be "over" or "supported by" a second layer, even if there is one or more | 'between them. | Although the invention has been described in connection with what is presently considered to be the most practical and preferred | it is to be understood that the invention is not to be limited to the | disclosed, but on the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the claims. attached instructions. and | | | | and ! | 3 | | | | O " :

权利要求:
Claims (25)
[1]
; 115
CLAIMS i 1. Method of making a coated article, the method comprising: providing a substrate that has a surface to be coated; arrange a self-assembled monolayer (SAM) model on the surface to be coated; providing a precursor comprising a precursor molecule, the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) and the discotic molecule; and 10 dissolving the precursor to form a solution; apply the solution to the substrate having the SAM model arranged on it; photochemically attach the precursor molecule to the 'SAM model, and heat the substrate to at least 450ºC to form an included graphene film.
[2]
A method according to claim 1, wherein the substrate is a glass substrate.
[3]
Method according to claim 1, wherein the substrate is a silicon wafer. oe
[4]
A method according to claim 1, further comprising providing a layer comprising silicon oxide on the surface to be coated, prior to the layout of the SAM model.
[5]
A method according to claim 1, wherein the SAM model is a derivative of silane-benzophenone.
[6]
A method according to claim 5, wherein the SAM model is benzophenone chlorosilane (CSBP).
[7]
A method according to claim 1, wherein the SAM model and / or the precursor molecule comprises (m) one or more alkyl groups.
[8]
A method according to claim 1, wherein the precursor molecule is C96 and / or HBC.
mm o "PNM: 2/5
[9]
A method according to claim 1, further comprising purifying the solution by column chromatography. |
[10]
A method according to claim 9, further comprising preparing the solution in chloroform and / or dodecane.
[11]
A method according to claim 1, wherein the c-axis of the precursor molecule is substantially perpendicular to the substrate before and / or after photochemical attachment.
[12]
12. Method according to claim 1, wherein the photochemical attachment includes irradiation of UV energy to the substrate. oe 10
[13]
13. The method of claim 12, wherein the wavelength of the UV energy is between 320-380 nm. '
[14]
14. The method of claim 1, wherein said heating is carried out in a vacuum. i
[15]
A method according to claim 1, wherein said heating is carried out in an environment comprising inert gas.
[16]
16. The method of claim 15, wherein said heating is carried out in an environment comprising gases of Ar and C2H>.
[17]
17. Method of making a coated article, the method comprising: providing a substrate that has a surface to be coated; o have a self-assembled monolayer (SAM) model on the surface to be coated; applying a solution to the substrate having the SAM model arranged therein, the solution comprising a precursor including a - precursor molecule, the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) molecule; attach the precursor molecule to the SAM model by irradiating UV energy in it; and heat the substrate to at least 450ºC to form an included graphene skin, in which the SAM model and / or the precursor molecule comprises (m) one or more alkyl groups to help ensure that the c axis of the
| EN à is' 3/5 precursor molecule is substantially perpendicular to the substrate before | and / or after photochemical annexation.
[18]
Method according to claim 17, further comprising providing a layer comprising silicon oxide on the surface to be coated, prior to the layout of the SAM model.
[19]
19. The method of claim 17, wherein the SAM model is a derivative of silane-benzophenone.
[20]
20. The method of claim 17, wherein the precursor molecule is C96 and / or HBC. the 10
[21]
21. The method of claim 17, wherein said heating is carried out in a vacuum. '
[22]
22. The method of claim 17, wherein said heating is carried out in an environment comprising inert gas.
[23]
23. Method of making an electronic device, the method comprising: providing a substrate that has a surface to be coated; arrange a self-assembled monolayer (SAM) model on the surface to be coated; providing a precursor comprising a precursor molecule, the precursor molecule being a polycyclic aromatic hydrocarbon oe (PAH) and the discotic molecule; dissolving the precursor to form a solution; apply the solution to the substrate having the SAM model arranged on it; photochemically attach the precursor molecule to the SAM model; heat the substrate to at least 450ºC to form a graphene film included on the substrate, and build the substrate with the graphene film included on the electronic device.
[24]
24. Method of making an electronic device, the method comprising:
providing a substrate that has a surface to be coated; arrange a self-assembled monolayer (SAM) model on the surface to be coated; apply a solution to the substrate having the SAM model available, the solution comprising a precursor including a precursor molecule, the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) molecule; attach the precursor molecule to the SAM model by irradiating UV energy in it; o 10 heat the substrate to at least 450ºC to form an included graphene film, and Na construct the substrate with the included graphene film on the electronic device, in which the SAM model and / or the precursor molecule comprises (m) one or more alkyl groups to help ensure that the c-axis of | precursor molecule is substantially perpendicular to the substrate before | and / or after photochemical annexation. |
[25]
25. Method of making a coated article, the method comprising: providing a substrate that has a surface to be coated; and having a monolayer model on the surface to be coated; providing a gaseous flow comprising a carrier gas and a precursor molecule close to the substrate having the monolayer model arranged therein, the precursor molecule being a polycyclic aromatic hydrocarbon (PAH) molecule; | attach the precursor molecule to the monolayer model by irradiating UV energy therein; and heat the substrate with the monolayer model and the | 30 laprecursor to form an enclosed graphene film, in which the monolayer model and / or the precursor molecule comprises (m) one or more alkyl groups to help ensure that the NS axis c of the precursor molecule is substantially perpendicular to the substrate. | before and / or after photochemical annexation.
o | | | |

类似技术:

---

公开号 | 公开日 | 专利标题

---

BR112012015878A2|2020-09-08|deposition of graphene in a large area on substrate, and products including the same.

---

US9418770B2|2016-08-16|Large area deposition and doping of graphene, and products including the same

---

US8591680B2|2013-11-26|Debonding and transfer techniques for hetero-epitaxially grown graphene, and products including the same

---

US10164135B2|2018-12-25|Electronic device including graphene-based layer|, and/or method or making the same

---

US10167572B2|2019-01-01|Large area deposition of graphene via hetero-epitaxial growth, and products including the same

同族专利:

---

公开号 | 公开日

---

CN102741164B|2016-08-31|

---

US20110143045A1|2011-06-16|

---

WO2011075158A1|2011-06-23|

---

JP5748766B2|2015-07-15|

---

RU2012129980A|2014-01-27|

---

RU2564346C2|2015-09-27|

---

EP2512985A1|2012-10-24|

---

TWI608060B|2017-12-11|

---

TW201129656A|2011-09-01|

---

IN2012DN05093A|2015-10-09|

---

CN102741164A|2012-10-17|

---

EP2512985B1|2016-09-07|

---

US8808810B2|2014-08-19|

---

MX2012006850A|2012-07-23|

---

JP2013513544A|2013-04-22|

引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US4929205A|1988-10-07|1990-05-29|Jones Elene K|Leg immobilizer-drag for training swimmers|

---

US5227038A|1991-10-04|1993-07-13|William Marsh Rice University|Electric arc process for making fullerenes|

---

US5300203A|1991-11-27|1994-04-05|William Marsh Rice University|Process for making fullerenes by the laser evaporation of carbon|

---

US5591312A|1992-10-09|1997-01-07|William Marsh Rice University|Process for making fullerene fibers|

---

DE4313481A1|1993-04-24|1994-10-27|Hoechst Ag|Fullerene derivatives, process for their preparation and their use|

---

WO1995000440A1|1993-06-28|1995-01-05|William Marsh Rice University|Solar process for making fullerenes|

---

US5650597A|1995-01-20|1997-07-22|Dynapro Systems, Inc.|Capacitive touch sensor|

---

US6162926A|1995-07-31|2000-12-19|Sphere Biosystems, Inc.|Multi-substituted fullerenes and methods for their preparation and characterization|

---

US7338915B1|1995-09-08|2008-03-04|Rice University|Ropes of single-wall carbon nanotubes and compositions thereof|

---

US6183714B1|1995-09-08|2001-02-06|Rice University|Method of making ropes of single-wall carbon nanotubes|

---

JP2000516708A|1996-08-08|2000-12-12|ウィリアム・マーシュ・ライス・ユニバーシティ|Macroscopically operable nanoscale devices fabricated from nanotube assemblies|

---

US6123824A|1996-12-13|2000-09-26|Canon Kabushiki Kaisha|Process for producing photo-electricity generating device|

---

US6683783B1|1997-03-07|2004-01-27|William Marsh Rice University|Carbon fibers formed from single-wall carbon nanotubes|

---

EP1015384B1|1997-03-07|2005-07-13|William Marsh Rice University|Carbon fibers formed from single-wall carbon nanotubes|

---

JPH1146006A|1997-07-25|1999-02-16|Canon Inc|Photovoltaic element and manufacture thereof|

---

US6129901A|1997-11-18|2000-10-10|Martin Moskovits|Controlled synthesis and metal-filling of aligned carbon nanotubes|

---

US6863942B2|1998-06-19|2005-03-08|The Research Foundation Of State University Of New York|Free-standing and aligned carbon nanotubes and synthesis thereof|

---

US6077722A|1998-07-14|2000-06-20|Bp Solarex|Producing thin film photovoltaic modules with high integrity interconnects and dual layer contacts|

---

US6057903A|1998-08-18|2000-05-02|International Business Machines Corporation|Liquid crystal display device employing a guard plane between a layer for measuring touch position and common electrode layer|

---

US6204897B1|1998-08-18|2001-03-20|International Business Machines Corporation|Integrated resistor for measuring touch position in a liquid crystal display device|

---

US6692717B1|1999-09-17|2004-02-17|William Marsh Rice University|Catalytic growth of single-wall carbon nanotubes from metal particles|

---

CN1334781A|1998-09-18|2002-02-06|威廉马歇莱思大学|Catalytic growth of single-wall carbon nanotubes from metal particles|

---

AU6044599A|1998-09-18|2000-04-10|William Marsh Rice University|Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof; and use of derivatized nanotubes|

---

US7150864B1|1998-09-18|2006-12-19|William Marsh Rice University|Ropes comprised of single-walled and double-walled carbon nanotubes|

---

US6835366B1|1998-09-18|2004-12-28|William Marsh Rice University|Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof, and use of derivatized nanotubes|

---

EP1137593B1|1998-11-03|2008-08-13|William Marsh Rice University|Gas-phase nucleation and growth of single-wall carbon nanotubes from high pressure carbon monoxide|

---

US6808606B2|1999-05-03|2004-10-26|Guardian Industries Corp.|Method of manufacturing window using ion beam milling of glass substrate|

---

US6790425B1|1999-10-27|2004-09-14|Wiliam Marsh Rice University|Macroscopic ordered assembly of carbon nanotubes|

---

US7008563B2|2000-08-24|2006-03-07|William Marsh Rice University|Polymer-wrapped single wall carbon nanotubes|

---

US6359388B1|2000-08-28|2002-03-19|Guardian Industries Corp.|Cold cathode ion beam deposition apparatus with segregated gas flow|

---

US6784361B2|2000-09-20|2004-08-31|Bp Corporation North America Inc.|Amorphous silicon photovoltaic devices|

---

US6913789B2|2001-01-31|2005-07-05|William Marsh Rice University|Process utilizing pre-formed cluster catalysts for making single-wall carbon nanotubes|

---

US7052668B2|2001-01-31|2006-05-30|William Marsh Rice University|Process utilizing seeds for making single-wall carbon nanotubes|

---

US7090819B2|2001-02-12|2006-08-15|William Marsh Rice University|Gas-phase process for purifying single-wall carbon nanotubes and compositions thereof|

---

US6752977B2|2001-02-12|2004-06-22|William Marsh Rice University|Process for purifying single-wall carbon nanotubes and compositions thereof|

---

US6602371B2|2001-02-27|2003-08-05|Guardian Industries Corp.|Method of making a curved vehicle windshield|

---

US7265174B2|2001-03-22|2007-09-04|Clemson University|Halogen containing-polymer nanocomposite compositions, methods, and products employing such compositions|

---

US6890506B1|2001-04-12|2005-05-10|Penn State Research Foundation|Method of forming carbon fibers|

---

AU2002363352A1|2001-06-15|2003-05-19|The Pennsylvania State Research Foundation|Method of purifying nanotubes and nanofibers using electromagnetic radiation|

---

US7125502B2|2001-07-06|2006-10-24|William Marsh Rice University|Fibers of aligned single-wall carbon nanotubes and process for making the same|

---

WO2003020638A1|2001-08-29|2003-03-13|Georgia Tech Research Corporation|Compositions comprising rigid-rod polymers and carbon nanotubes and process for making the same|

---

US6538153B1|2001-09-25|2003-03-25|C Sixty Inc.|Method of synthesis of water soluble fullerene polyacids using a macrocyclic malonate reactant|

---

DE10228523B4|2001-11-14|2017-09-21|Lg Display Co., Ltd.|touch tablet|

---

US7138100B2|2001-11-21|2006-11-21|William Marsh Rice Univesity|Process for making single-wall carbon nanotubes utilizing refractory particles|

---

US7338648B2|2001-12-28|2008-03-04|The Penn State Research Foundation|Method for low temperature synthesis of single wall carbon nanotubes|

---

TW200307563A|2002-02-14|2003-12-16|Sixty Inc C|Use of BUCKYSOME or carbon nanotube for drug delivery|

---

US7372510B2|2002-03-01|2008-05-13|Planar Systems, Inc.|Reflection resistant touch screens|

---

EP1483202B1|2002-03-04|2012-12-12|William Marsh Rice University|Method for separating single-wall carbon nanotubes and compositions thereof|

---

WO2003078317A1|2002-03-14|2003-09-25|Carbon Nanotechnologies, Inc.|Composite materials comprising polar polyers and single-wall carbon naotubes|

---

US6899945B2|2002-03-19|2005-05-31|William Marsh Rice University|Entangled single-wall carbon nanotube solid material and methods for making same|

---

US7192642B2|2002-03-22|2007-03-20|Georgia Tech Research Corporation|Single-wall carbon nanotube film having high modulus and conductivity and process for making the same|

---

US7135160B2|2002-04-02|2006-11-14|Carbon Nanotechnologies, Inc.|Spheroidal aggregates comprising single-wall carbon nanotubes and method for making the same|

---

AU2003231996A1|2002-04-08|2003-10-27|William Marsh Rice University|Method for cutting single-wall carbon nanotubes through fluorination|

---

US6852410B2|2002-07-01|2005-02-08|Georgia Tech Research Corporation|Macroscopic fiber comprising single-wall carbon nanotubes and acrylonitrile-based polymer and process for making the same|

---

US7061749B2|2002-07-01|2006-06-13|Georgia Tech Research Corporation|Supercapacitor having electrode material comprising single-wall carbon nanotubes and process for making the same|

---

US7250148B2|2002-07-31|2007-07-31|Carbon Nanotechnologies, Inc.|Method for making single-wall carbon nanotubes using supported catalysts|

---

US7195780B2|2002-10-21|2007-03-27|University Of Florida|Nanoparticle delivery system|

---

KR100480823B1|2002-11-14|2005-04-07|엘지.필립스 엘시디 주식회사|touch panel for display device|

---

US7273095B2|2003-03-11|2007-09-25|United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration|Nanoengineered thermal materials based on carbon nanotube array composites|

---

WO2004097853A1|2003-04-24|2004-11-11|Carbon Nanotechnologies, Inc.|Conductive carbon nanotube-polymer composite|

---

US7220818B2|2003-08-20|2007-05-22|The Regents Of The University Of California|Noncovalent functionalization of nanotubes|

---

US7109581B2|2003-08-25|2006-09-19|Nanoconduction, Inc.|System and method using self-assembled nano structures in the design and fabrication of an integrated circuit micro-cooler|

---

US7163956B2|2003-10-10|2007-01-16|C Sixty Inc.|Substituted fullerene compositions and their use as antioxidants|

---

US7211795B2|2004-02-06|2007-05-01|California Institute Of Technology|Method for manufacturing single wall carbon nanotube tips|

---

US7279916B2|2004-10-05|2007-10-09|Nanoconduction, Inc.|Apparatus and test device for the application and measurement of prescribed, predicted and controlled contact pressure on wires|

---

JP2006294933A|2005-04-12|2006-10-26|Sharp Corp|Organic solar cell and manufacturing method thereof|

---

GB0622150D0|2006-11-06|2006-12-20|Kontrakt Technology Ltd|Anisotropic semiconductor film and method of production thereof|

---

US20080169021A1|2007-01-16|2008-07-17|Guardian Industries Corp.|Method of making TCO front electrode for use in photovoltaic device or the like|

---

US7964238B2|2007-01-29|2011-06-21|Guardian Industries Corp.|Method of making coated article including ion beam treatment of metal oxide protective film|

---

WO2008128554A1|2007-04-20|2008-10-30|MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V.|Highly conductive, transparent carbon films as electrode materials|

---

US20080308147A1|2007-06-12|2008-12-18|Yiwei Lu|Rear electrode structure for use in photovoltaic device such as CIGS/CIS photovoltaic device and method of making same|

---

US7875945B2|2007-06-12|2011-01-25|Guardian Industries Corp.|Rear electrode structure for use in photovoltaic device such as CIGS/CIS photovoltaic device and method of making same|

---

US20090032098A1|2007-08-03|2009-02-05|Guardian Industries Corp.|Photovoltaic device having multilayer antireflective layer supported by front substrate|

---

KR101443222B1|2007-09-18|2014-09-19|삼성전자주식회사|Graphene pattern and process for preparing the same|

---

KR100923304B1|2007-10-29|2009-10-23|삼성전자주식회사|Graphene sheet and process for preparing the same|

---

RU2367595C2|2007-11-28|2009-09-20|Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук |Porous carbon nanomaterial and method thereof|

---

KR101344493B1|2007-12-17|2013-12-24|삼성전자주식회사|Single crystalline graphene sheet and process for preparing the same|GB201004554D0|2010-03-18|2010-05-05|Isis Innovation|Superconducting materials|

---

JP5571502B2|2010-08-17|2014-08-13|日本電信電話株式会社|Method for producing graphene film and method for uniformizing the number of layers of graphene film|

---

US9475709B2|2010-08-25|2016-10-25|Lockheed Martin Corporation|Perforated graphene deionization or desalination|

---

US8739728B2|2011-04-07|2014-06-03|Dynamic Micro Systems, Semiconductor Equipment Gmbh|Methods and apparatuses for roll-on coating|

---

IL220677A|2011-06-30|2017-02-28|Rohm & Haas Elect Mat|Transparent conductive articles|

---

WO2013010060A1|2011-07-14|2013-01-17|University Of North Texas|Direct growth of graphene by molecular beam epitaxy for the formation of graphene heterostructures|

---

DE112011100116T5|2011-09-16|2013-12-24|Empire Technology Development Llc|Graphs defect alteration|

---

WO2013039507A1|2011-09-16|2013-03-21|Empire Technology Development Llc|Graphene defect detection|

---

KR101629869B1|2011-09-16|2016-06-13|엠파이어 테크놀로지 디벨롭먼트 엘엘씨|Alteration of graphene defects|

---

US8884310B2|2011-10-19|2014-11-11|Sunedison Semiconductor Limited |Direct formation of graphene on semiconductor substrates|

---

US9040397B2|2011-10-21|2015-05-26|LGS Innovations LLC|Method of making graphene layers, and articles made thereby|

---

US9460827B2|2011-11-07|2016-10-04|Dhkgraphenologies Llc|Physically functionalized graphene hybrid compositeand its applications|

---

TWI562960B|2011-11-14|2016-12-21|Basf Se|Segmented graphene nanoribbons|

---

US8772910B2|2011-11-29|2014-07-08|International Business Machines Corporation|Doping carbon nanotubes and graphene for improving electronic mobility|

---

US8895417B2|2011-11-29|2014-11-25|International Business Machines Corporation|Reducing contact resistance for field-effect transistor devices|

---

US10023468B2|2012-01-06|2018-07-17|Ut-Battelle, Llc|High quality large scale single and multilayer graphene production by chemical vapor deposition|

---

JP5407008B1|2012-02-14|2014-02-05|積水化学工業株式会社|Method for producing exfoliated graphite and exfoliated graphite|

---

KR101461978B1|2012-02-23|2014-11-14|엘지전자 주식회사|Method for manufacturing patterned graphene|

---

KR101348925B1|2012-03-15|2014-01-10|한국수력원자력 주식회사|Fabrication method of organic material-derived graphene using radiation technique and the fabrication of the graphene using the same|

---

IN2014DN07732A|2012-03-21|2015-05-15|Lockheed Corp|

---

US10653824B2|2012-05-25|2020-05-19|Lockheed Martin Corporation|Two-dimensional materials and uses thereof|

---

GB2502560A|2012-05-30|2013-12-04|Univ Exeter|Electrochromic device with graphene electrode|

---

US8608525B1|2012-06-05|2013-12-17|Guardian Industries Corp.|Coated articles and/or devices with optical out-coupling layer stacks , and/or methods of making the same|

---

CN103487143B|2012-06-12|2015-07-29|清华大学|The detection system of light distribution|

---

US9595436B2|2012-10-25|2017-03-14|Applied Materials, Inc.|Growing graphene on substrates|

---

US10315275B2|2013-01-24|2019-06-11|Wisconsin Alumni Research Foundation|Reducing surface asperities|

---

KR20140107968A|2013-02-28|2014-09-05|한국전자통신연구원|Method for transferring graphene|

---

TW201504140A|2013-03-12|2015-02-01|Lockheed Corp|Method for forming perforated graphene with uniform aperture size|

---

JP5583237B1|2013-03-19|2014-09-03|株式会社東芝|Graphene wiring and manufacturing method thereof|

---

CN104134870B|2013-05-08|2017-06-16|中国空空导弹研究院|A kind of Graphene microstrip antenna and preparation method thereof|

---

US9572918B2|2013-06-21|2017-02-21|Lockheed Martin Corporation|Graphene-based filter for isolating a substance from blood|

---

CN104253015B|2013-06-25|2017-12-22|中国科学院微电子研究所|The method for reducing two dimensional crystal material resistance|

---

US20150064451A1|2013-08-29|2015-03-05|General Electric Company|Coating, coating method, and coated article|

---

EP2862839B1|2013-10-17|2016-06-08|University-Industry Foundation, Yonsei University|Hydrogen surface-treated graphene, formation method thereof and electronic device comprising the same|

---

US10815584B2|2013-11-15|2020-10-27|National University Of Singapore|Ordered growth of large crystal graphene by laser-based localized heating for high throughput production|

---

JP2015138901A|2014-01-23|2015-07-30|株式会社東芝|Semiconductor device and manufacturing method of the same|

---

US9744617B2|2014-01-31|2017-08-29|Lockheed Martin Corporation|Methods for perforating multi-layer graphene through ion bombardment|

---

CN105940479A|2014-01-31|2016-09-14|洛克希德马丁公司|Methods for perforating two-dimensional materials using a broad ion field|

---

EP3099645A4|2014-01-31|2017-09-27|Lockheed Martin Corporation|Processes for forming composite structures with a two-dimensional material using a porous, non-sacrificial supporting layer|

---

US10683586B2|2014-02-04|2020-06-16|National University Of Singapore|Method of pulsed laser-based large area graphene synthesis on metallic and crystalline substrates|

---

US10059591B2|2014-02-07|2018-08-28|Empire Technology Development Llc|Method of producing graphene from a hydrocarbon gas and liquid metal catalysts|

---

CN103811862B|2014-02-17|2016-03-09|东莞劲胜精密组件股份有限公司|A kind of manufacture method of transparent antenna|

---

US9834809B2|2014-02-28|2017-12-05|Lockheed Martin Corporation|Syringe for obtaining nano-sized materials for selective assays and related methods of use|

---

CN103903970A|2014-03-10|2014-07-02|中国科学院物理研究所|Method for preparing heterogeneous electrode pair with nanometer gap|

---

EP3116625A4|2014-03-12|2017-12-20|Lockheed Martin Corporation|Separation membranes formed from perforated graphene|

---

JP6308507B2|2014-08-04|2018-04-11|国立研究開発法人物質・材料研究機構|Method for producing positive electrode material for lithium ion battery and method for producing photocatalyst using substrate powder having carbon nano-coating layer|

---

CN104332523B|2014-08-15|2017-01-18|中国空空导弹研究院|Tri-mode composite detector based on graphene|

---

SG11201701654UA|2014-09-02|2017-04-27|Lockheed Corp|Hemodialysis and hemofiltration membranes based upon a two-dimensional membrane material and methods employing same|

---

CN105807450A|2014-12-30|2016-07-27|北京生美鸿业科技有限公司|Novel transparent conducting electrode and intelligent light dimming film comprising same|

---

US9777547B1|2015-06-29|2017-10-03|Milanovich Investments, L.L.C.|Blowout preventers made from plastic enhanced with graphene, phosphorescent or other material, with sleeves that fit inside well pipes, and making use of well pressure|

---

CA2994549A1|2015-08-05|2017-02-09|Lockheed Martin Corporation|Perforatable sheets of graphene-based material|

---

JP2018530499A|2015-08-06|2018-10-18|ロッキード・マーチン・コーポレーション|Nanoparticle modification and perforation of graphene|

---

CN105110324B|2015-08-18|2017-07-21|中国科学院上海微系统与信息技术研究所|A kind of method for the graphene for preparing corrugationless|

---

US10145005B2|2015-08-19|2018-12-04|Guardian Glass, LLC|Techniques for low temperature direct graphene growth on glass|

---

JP6440850B2|2015-09-02|2018-12-19|東京エレクトロン株式会社|Graphene manufacturing method, graphene manufacturing apparatus, and electronic device manufacturing method|

---

EP3356582B1|2015-10-01|2020-12-16|GlobalWafers Co., Ltd.|Epitaxial growth of defect-free, wafer-scale single-layer graphene on thin films of cobalt|

---

WO2017105470A1|2015-12-17|2017-06-22|Intel Corporation|Low-defect graphene-based devices & interconnects|

---

CA3020686A1|2016-04-14|2017-10-19|Lockheed Martin Corporation|Method for treating graphene sheets for large-scale transfer using free-float method|

---

JP2019519756A|2016-04-14|2019-07-11|ロッキード・マーチン・コーポレーション|In-situ monitoring and control of defect formation or defect repair|

---

WO2017180135A1|2016-04-14|2017-10-19|Lockheed Martin Corporation|Membranes with tunable selectivity|

---

US10980919B2|2016-04-14|2021-04-20|Lockheed Martin Corporation|Methods for in vivo and in vitro use of graphene and other two-dimensional materials|

---

JP2019517909A|2016-04-14|2019-06-27|ロッキード・マーチン・コーポレーション|Two-dimensional membrane structure having a flow path|

---

WO2017180141A1|2016-04-14|2017-10-19|Lockheed Martin Corporation|Selective interfacial mitigation of graphene defects|

---

EP3455874A1|2016-05-12|2019-03-20|Globalwafers Co., Ltd.|Direct formation of hexagonal boron nitride on silicon based dielectrics|

---

CN106179918B|2016-07-19|2021-04-09|广州市博欣环境科技有限公司|Graphene reinforced energy-saving composite membrane and preparation method thereof|

---

US10236347B2|2016-08-08|2019-03-19|King Abdullah University Of Science And Technology|Method of producing an electronic device with a graphene device and semiconductor device formed on a common semiconductor substrate|

---

WO2018057744A1|2016-09-23|2018-03-29|3M Innovative Properties Company|Articles with resistance gradients for uniform switching|

---

US10233566B2|2016-12-29|2019-03-19|Ut-Battelle, Llc|Continuous single crystal growth of graphene|

---

CN106816409A|2017-03-09|2017-06-09|武汉华星光电技术有限公司|The preparation method of the preparation method of electrode layer and flexible TFT substrate in TFT substrate|

---

CN107393979B|2017-06-09|2019-07-16|中国科学院宁波材料技术与工程研究所|A kind of transparent electrode and its preparation method and application based on ultrathin metallic film|

---

US11180373B2|2017-11-29|2021-11-23|Samsung Electronics Co., Ltd.|Nanocrystalline graphene and method of forming nanocrystalline graphene|

---

US10756419B2|2018-01-11|2020-08-25|Savannah River Nuclear Solutions, Llc|Laser induced graphene/graphite antenna|

---

US11217531B2|2018-07-24|2022-01-04|Samsung Electronics Co., Ltd.|Interconnect structure having nanocrystalline graphene cap layer and electronic device including the interconnect structure|

---

KR20200011821A|2018-07-25|2020-02-04|삼성전자주식회사|Method of directly growing carbon material on substrate|

---

KR20200037638A|2018-10-01|2020-04-09|삼성전자주식회사|Method of forming graphene|

---

KR20200124556A|2019-04-24|2020-11-03|삼성전자주식회사|Methods of manufacturing pellicle assembly and photomask assembly|

---

TWI708857B|2019-07-29|2020-11-01|國立中央大學|Ion generation composite target and laser-driven ion acceleration apparatus using the same|

---

CN111682089A|2020-04-01|2020-09-18|湘潭大学|Low-angle-dependent thermal radiation self-temperature-control composite material film, preparation method thereof and optical detector|

---

CN112553515A|2020-11-12|2021-03-26|广西友合金属材料科技有限公司|Preparation method of graphene-doped aluminum alloy wire|

法律状态:
2020-09-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

---

2020-10-06| B25A| Requested transfer of rights approved|Owner name: GUARDIAN GLASS, LLC (US) |

---

2020-10-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

---

2021-01-12| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

---

2021-11-23| 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

---

US12/654,269|US8808810B2|2009-12-15|2009-12-15|Large area deposition of graphene on substrates, and products including the same|

---

US12/654,269|2009-12-15|

---

PCT/US2010/003044|WO2011075158A1|2009-12-15|2010-11-24|Large area deposition of graphene on substrates, and products including the same|

---