large grapheme deposition and doping area, and products including the same

专利摘要:
LARGE AREA OF DEPOSITION AND DOPING OF GRAPHENE, AND PRODUCTS INCLUDING THEM.The present invention relates to certain exemplary embodiments of this invention which relate to the use of graphene as a transparent conductive coating (TCC). In certain exemplary embodiments, thin films of graphene grow in large areas hetero-epitaxially, for example, in a thin film of catalyst, of a hydrocarbon gas (such as, for example, C2H2, or the like). Thin graphene films of certain example embodiments can be doped or non-doped. In certain example embodiments, thin films of graphene, once formed, can be taken from their vehicle substrates and transferred to the receiving substrates, for example, for inclusion in an intermediate or final product. Graphene grown, raised and transferred in this way can exhibit low blade resistances (for example, less than 150 ohm / square and lower when doped) and high transmission values (for example, at least in the visible and infrared spectra) .
公开号:BR112012002814A2
申请号:R112012002814-6
申请日:2010-07-22
公开日:2020-08-11
发明作者:Vijayen S. Veerasamy
申请人:Guardian Industries Corp.；
IPC主号:

专利说明:

Descriptive Report of the Patent of Invention for "LARGE AREA OF DEPOSITION AND Doping of GRAPHENE, AND PRODUCTS IN-" CLOSING THE SAME ".
. FIELD OF THE INVENTION Certain exemplary embodiments of this invention pertain to fine particles comprising graphene. More particularly, certain exemplary fashions of this invention relate to the use of graphene as a transparent conductive coating (TCC). In certain exemplary embodiments, thin films of graphene grow in large heterogeneous areas. epitaxially, for example, in a thin film of catalyst, a hydrocarbon gas (such as, for example, C2H2, CH4, or the like). Thin films of graphene of certain exemplary modalities can be doped or non-doped. In certain exemplary embodiments, thin, thick films ..
V k-
H hay, once formed, can be taken from their vehicle substrates and transferred to receive substrates, for example, for inclusion in an intermediate or final product. BACKGROUND AND SUMMARY OF EXEMPLARY MODALITIES OF THE INVENTION Indium tin oxide (ITO) and doped fluorine oxide (FTO or SnO: F) coatings are widely used with window electrodes in opto-devices. electronics. These transparent conductive oxides (TCOS) have been immensely successful in a variety of applications. Unfortunately, however, the use of ITO and FTO is becoming increasingly problematic for several reasons. Such problems 25 include, for example, the fact that there is a limited amount of the Indian element available on Earth, the instability of TCOs in the presence of an acid or base, their susceptibility to diffusion of Ion from the conducting layers of Ion, their limited transparency near the infrared region (for example, energy rich spectrum), high current leakage from 30 FTO devices caused by FTO structure defects, etc. The fragile nature of ITO and its high deposition temperature can also limit its applications. In addition, surface roughness in Sn02: F can cause problematic spark formation. In this way, it will be evident that there is a need in the technique for soft and standardizable electrode materials with good stability. high transparency and excellent conductivity. 5 Research on new electrode materials with good stability, high transparency and excellent conductivity is underway. One aspect of this research involves identifying viable alternatives to such conventional 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 - "atomic graphite, for example, with a single layer of graphene or SGL being able to extend up to n-layers of
W "· graphite (for example, where n cannot have a height of 10). The recent discovery and isolation of graphene (by crystalline cleavage graphite) at the University of Manchester comes at a time when the trend in electronics it is to reduce the dimensions of the circuit elements to the scale of the naometer. In this respect, graphene has unexpectedly led to a new world of unique opto-electronic properties, not found in standard electronic materials. emerges from the linear dispersion relation (E vs. k), which gives rise to graphene charge vehicles having a zero-mass and behaving like relativistic particles. The displaced electrons, with relativistic behavior, that are move around the carbon atoms result from their interaction with the periodic potential of graphene's honeycomb lattice to give rise to new quasi-particles which, at low energies (E "1.2 eV) are described accurately by the equation (2 + l) -dimensi Dirac onal with an effective light speed vf - c / 300 = 106 ms "i. In this way, well-established techniques of quantum electrodynamics (QED) (which deal with photons) can be placed to produce in the study of graphene - with the additional advantageous aspect being that these effects are amplified in graphene by a factor of 300 For example, the a-
universal coupling a is almost 2 in graphene compared to 1/137 in vacuo. See K.S. Novoselov, "Electrical Field Effect in Atomically Thin Carbon
F Films, "Science, vol. 306, pp. 666-69 (2004), whose contents are hereby incorporated into the present. 5 Despite being only the thickness of an atom (at least), graphene is chemically and thermally stable (although graphene may have an oxidized surface at 300 degrees C), thereby allowing graphene-based devices to be successfully manufactured to withstand environmental conditions. High-quality graphene sheets were made first by cleavage micro-mechanics of bulk graphite. The same technique is being fine-tuned to currently provide high quality graphene crystallites - ", up to 100 um2 in size. This size is sufficient for most micro-electronics research purposes. Consequently, most of the techniques developed so far, mainly at 15 universities, have focused more on the microscopic sample, and device preparation and characterization rather than scaling up. Unlike most current research trends, for understanding the full potential of graphene as a possible CBT, depositing large areas of high-quality material on substrates (eg 20 glass or plastic substrates) is essential. So far, most graphene production processes in Large scale features mass graphite exfoliation using moisture-based chemicals and begins with highly ordered pyrolytic graphite (HOPG) and chemical exfoliation. As it is known, HOPG is a highly ordered form of pyrolytic graphite with a spread. angular axis of less than 1 degree, and is usually produced by stress annealing at 3300 K. HOPG behaves very much like a pure metal in which it 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 drawbacks in relation to the exfoliation process. For example, exfoliated graphene tends to bend and become wrinkled, exists as small strips and relies on a bonding / suturing process for deposition, lack of inherent control in the number of graphene layers, etc. The material thus produced is often contaminated by interleaving and, as such, has a low degree of electronic properties. An in-depth analysis of the carbon phase diagram ^ 5 shows appropriate process window conditions to produce not only graphite and diamond, but also other allotropic forms, such as carbon nanotubes (CNT) .The catalytic deposition of nanotubes is made up of a gas phase at temperatures as high as 1000 degrees C by a variety of groups. In contrast to these areas of conventional research and conventional techniques, certain exemplary embodiments of this invention refer to
K ^ a technique that can be scaled to hetero-epitaxially growing mono-crystalline graphite (not as large as about 15) and converts it to -. for high electronic grade (HEG) graphene (n "about 3). Certain exemplary moi also refer to the use of HEG graphene in transparent graphene films (in terms of both visible and infrared spectra) ), ultra-thin conductors, for example, as an alternative to metal oxide window electrodes ubiquitously used for a variety of applications (including, for example, solid state solar cells 20). The growth, technique of certain exemplary modalities is based on a catalytically driven heteroepitaxial CVD process that takes place at a temperature that is low enough to be favorable to the glass. For example, thermodynamic and also kinetic principles allow HEG graphene films to be crystallized from the gas phase in a layer of seed catalyst at a temperature of less than about 700 degrees C. Certain exemplary modalities also use atomic hydrogen, which has proven o being a powerful radical to purify the contamination of amorphous carbonaceous in substrates and being able to do this 30 at low process temperatures. It is also extremely good at removing oxides and other overlays typically left by corrosion procedures.
Certain exemplary embodiments of this invention relate to a method of making a thin film of doped graphene. A thin film of
The intermediate graphene is created hetero-epitaxially on a thin film of catalyst, with the thin catalyst film having a substantially single-orientation ^ 5 crystal granule structure. The intermediate graphene thin film is doped with n- or p-type dopants in the preparation of doped graphene thin film. The doped graphene thin film has a sheet resistance of less than 150 ohms / square. In certain exemplary embodiments, the doping of the intermediate graphene thin film 10 comprises exposing the intermediate graphene thin film to a doping gas comprising a material to be used, such as the dopant; excite a plasma inside a chamber containing the thin film of intermediate graphene and doping gas; and Ion ray of bai - -4 x the energy by implanting the dopant in the thin film of intermediate graphene 15 using the material in the doping gas. In certain exemplary modalities, thin film doping of intermediate graphene comprises providing a target receiving substrate including dopants in that solid state there, as a target receiving substrate including dopants in that place by virtue of a fusion process used to manufacture the target receiving substrate ; and allowing dopants in solid state, in the target receiving substrate, to migrate into the thin film of intermediate graphene through thermal diffusion. In certain exemplary embodiments, doping the thin film of intermediate graphene comprises providing a target receiving substrate 25 including dopants in a solid state at that location, with the target receiving substrate including doping at that location by virtue of the implantation of an ion beam; and allowing dopants in solid state on the target receiving substrate to migrate in the thin film of intermediate graphene by thermal diffusion. In certain exemplary embodiments, doping the thin film of intermediate graphene comprises providing a target receiving substrate having at least one thin film coating disposed therein, with the thin film coating including solid state dopants there; and allowing solid-state dopants in at least one "thin film formed on the target receiving substrate to migrate to the fine grain film
Intermediate hay by thermal diffusion. 5 In certain exemplary embodiments, the doping of the thin film of intermediate graphene comprises pre-implanted solid state dopants in the thin film of the catalyst; and allowing solid state dopants in the thin film of the catalyst to migrate into the thin film of intermediate graphene through thermal diffusion. Thermal diffusion 10 can occur, for example, during the deposition of the thin film of intermediate graphene. Certain exemplary embodiments of this invention relate to a thin film of doped graphene created hetero-epitaxially, directly or indirectly, in a thin film of metal catalyst having a substantially orientation wide grain crystal structure. only. The thin film of graphene is 1-10 thick atomic layers. The doped graphene thin film has a sheet resistance of less than 150 ohms / square. The doped graphene thin film (n "= 2) can, in certain exemplary modalities, be doped with any one or more of. Nitrogen, boron, phosphorus, fluorine, lithium and potassium. The doped graphene thin film can , in certain exemplary modalities, have a plate resistance of 10-20 ohms / squares .. Thin graphene films doped with certain exemplary modalities include n- or p-type dopants. 25 Features, aspects, advantages, and exemplary modalities described here in the present can be combined to further implement additional modalities.
BRIEF DESCRIPTION OF THE DRAWINGS These and other features and advantages can be better and more fully understood by reference to the detailed description to follow of the exemplary illustrative modalities together with the drawings, of which:
Figure 1 is a high-level flow chart illustrating the total techniques of certain modalities in the example;
Figure 2 is a schematic view of the example of catalytic growth techniques for certain embodiments of the example, illustrating the introduction of hydrocarbon gas, dissolving carbon and possible extinction results, according to certain modalities in the example. ; Figure 3 is a flowchart illustrating a first example technique for doping graphene according to certain modalities of the example; Figure 4 is a flowchart illustrating a second technique of the example for doping graphene according to certain modalities of the e-, - example; Figure 5 is a schematic view of the example illustrating a * r -, third technique of the example for doping graphene according to certain embodiments of the example; Figure 6 is a graph plotting temperature versus time involved in doping graphene according to certain examples of the example; Figure 7 is a layer stack of the example useful in releasing graphene or turning off techniques of certain modalities of the example; Figure 8 is a schematic view of the example of a laminating apparatus that can be used to arrange graphene on a glass substrate and according to certain embodiments of the example; Figure 9 is a schematic cross-sectional view of a reactor suitable for depositing high-grade electronic graphene (HEG) according to an example embodiment; Figure 10 is a process flow of the example that illustrates some catalytic CVD growth of the example, Lifting, and Transfer techniques of certain modalities of the example; Figure 11 is an image of a sample of graphene produced in accordance with certain embodiments of the example; Figure 12 is a schematic cross-sectional view of a photographic device.
tovoltaic incorporating layers based on graphene according to certain modalities of the example; . Figure 13 is a schematic cross-sectional view of a to- screen. that incorporating layers based on graphene according to certain modalities of the example; and Figure 14 is a flow chart illustrating an example technique for forming conductive bus data / line according to certain example modalities; and Figure 15 is a schematic view of a technique for forming 10 data on the conductive bus line according to certain embodiments of the example.
, - DETAILED DESCRIPTION OF THE MODALITIES OF THE EXAMPLE OF THE IN- "VENTION" Certain modalities of this invention refer to the scaling technique. W 15 Can be used for monocrystalline graphite with heteroepitaxial growth (n as large as about 15) and convert to high-grade electronic graphene (HEG) (n "about 3). Certain modalities in the example also refer to the use of graphene conductive and ultrafine HEG in graphene films that are transparent (in terms of visible and infrared spectra), for example, 20 as an alternative to the metal oxide window electrodes most ubiquitously employed for a variety of applications (including, for example, solar cells in the solid state.) The growth technique of certain modalities in the example is based on a catalytically driven heteroepithelial CVD process that occurs at a temperature that is low enough to be glass friendly. For example, thermodynamics, as well as kinetic principles, allow HEG graphene films to be crystallized from the gas phase in a layer of seed catalyst (eg au less than about 600 degrees C). 30 Figure 1 is a high-level flow chart illustrating the total techniques of certain modalities in the example. As shown in figure 1, the total techniques of certain modalities in the example can be classified as belonging to one of the four basic steps: crystallization of graphene in a suitable posterior support (step S1O1), release of graphene or shutdown. from the back support (step S103), Graphene transfer
. for the target substrate or surface (step S105), and incorporation of the target substrate or surface in 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.
Example of Graphene Crystallization Techniques Graphene crystallization techniques of certain modalities 10 in the example can be considered to involve "cracking" a hydrocarbon gas and reassembling the carbon atoms in a structure
.- Familiar alveolar structure over a wide area (for example, an area of about 1 meter, or wider), for example, leveraging the catalytic path. - typical of the surface.
Graphene crystallization techniques for certain modalities in the example occur at high temperatures and moderate pressures.
Details illustrating this example process will be described in detail below.
The catalytic growth techniques of certain modalities in the example are, in some way, related to the techniques that were used to cultivate graphite in a heteroepitaxial area.
A catalyst for 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, temperatures up to about 1000 degrees C) such as, for example, certain ceramic or glass, materials including zirconium, aluminum nitride materials, silicon wafers, etc.
A thin film is placed, directly or indirectly, on a posterior support, thus ensuring that its surface is substantially de-contaminated before the crystallization process.
The inventor of the present invention has found that crystallization of graphene is facilitated when the catalyst layer has a substantially uniquely oriented crystal structure.
In this case, small grains were determined to be less advantageous, since their mosaic structure will finally be transferred.
for the graphene layer. In any case, it was found that the particular orientation of the crystal structure was largely insignificant for the .. crystallization of graphene, as long as the catalyst layer, at least
B in the substantial part, have a unique orientation crystal structure. In fact, it was found that the comparative absence of (or low) grain boundaries in the catalyst results in the same or similar orientation for growing graphene, and provides for high-grade graphene in electronics (HEG). The catalyst layer itself can be arranged on the back support by any suitable technique such as, for example, sputtering 10, combustion vapor deposition (CVD), flame pyrolysis, etc. The catalyst layer itself can comprise any suitable a-, - metal or material including metal. For example, the catalyst layer may comprise, for example, metals such as nickel, cobalt, iron, * - permalloy (for example, nickel iron alloys, generally comprising about 2 ° / o iron and 80% iron). nickel), nickel and chromium alloys, copper and combinations thereof. Of course, other metals can be used in connection with certain embodiments of the example. The inventor found that catalyst layers of or including nickel are of particular advantage for graphene crystallization, whereas nickel and chromium alloys are even more advantageous. In addition, the inventor found that the amount of chromium in layers of nickel and chromium (sometimes also called layers of nichrome or NiCr) can be optimized to promote the formation of large crystals. In particular, 3 to 15% Cr in the NiCr layer is preferable, 5 to 12% Cr in the NiCré layer most preferable, and 7 to 10 ° / o Cr in the NiCr layer is even more preferable. It was found that the presence of vanadium in the thin metal film was advantageous to promote the wide growth of the crystal. The catalyst layer can be relatively thin or thick. For example, the thin film can be 50 to 1000 nm thick, more preferably 75 to 750 nm thick, and is most preferably 30 to 100 nm to 500 nm thick. "Wide crystal growth" may, in certain instances, include crystals having a length next to the major axis of the order of 10 microns, and sometimes even wider.
As soon as the catalyst thin film is disposed on the rear support, a hydrocarbon gas (for example, C2H2 gas, CH4 gas, etc.) is introduced into a chamber in which the back support with the vane thin film The lyser disposed therein is located, the hydrocarbon gas can be introduced at a pressure ranging from about 5 to 150 m1 "orr, more preferably 10 to 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 then heated to dissolve or "crack" the hydrocarbon gas. For example, the back support can be raised to a temperature in the range of 10 600 to 1200 degrees C, more preferably 700 to 1000 degrees C, and even more preferably 800 to 900 degrees C. Heating can be carried out by, - any suitable technique such as, for example, through a short wave infrared (lV) heater. Heating can occur in a
R · - environment comprising a gas such as argon, nitrogen, a mixture of nitrogen and hydrogen, or other suitable environment. In other words, the heating of the hydrocarbon gas can occur in an environment comprising other gases in certain embodiments of the example. In certain embodiments of the example, 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 and other inert gas or another gas (for example, CH4 mixed with Air). Graphene will grow in this or another suitable environment. To stop growth and help ensure that graphene is produced on the surface of the catalyst (for example, as opposed to being incorporated into the catalyst), certain embodiments of the example employ an extinguishing process. Extinction can be carried out using an inert gas such as, for example, argon, nitrogen, combinations thereof, etc. To promote the growth of graphene on the surface of the catalyst layer, the extinction must be carried out quickly. More particularly, it has been found that very rapid or very slow extinction results in poor or no growth of graphene on the surface of the catalyst layer. Generally, it has been found that extinction in order to reduce the temperature of the back support and / or substrate from about 900 degrees C to 700 degrees (or less) over the course of several minutes promotes good growth of grain, for example, through chemisorption.
In this regard, figure 2 is
A schematic view of the example of catalytic growth techniques 5 of certain embodiments of the example, illustrating the introduction of hydrocarbon gas, dissolving carbon, and the possible extinction results, according to certain embodiments of the example.
The graphene growth process imposes a strict film thickness ratio t = n x SLG, where n involves some discrete numbers of steps.
Identifying very quickly if graphene was produced and determining the value of n on the film area is roughly equivalent
, - how to measure the quality and uniformity of the film in a single measurement.
Although graphene sheets can be seen through atomic force and
".. reduction of electron microscopy, these techniques are time consuming and also - 15 can hide the contamination of graphene.
Therefore, certain embodiments of the example employ a phase contrast technique that increases the visibility of graphene on the intended catalyst surfaces. This can be done with a view to map any variation in value of n on the deposition surface on the metal catalyst film.
The technique is based on the fact that the contrast of graphene can be substantially increased by centrifuging a material onto it.
For example, a widely used curable UV resistance (for example, PMMA) can be coated by centrifugation, printed on canvas, coated by rotogravure, or otherwise arranged on graphene / metal / back support, for example, in 25 enough thickness to make the film visible and continuous (for example, about 1 micron thick). As explained in more detail below, the inclusion of a polymer resistance can also facilitate the process of lifting graphene before transferring it to the final surface. This is, in addition to providing an indication as to when the formation of graphene has been completed, the strength of the polymer can also provide a support for highly elastic graphene when the metal layer is released or otherwise detached from the back support as ex-
detailed below. In case a layer grows thicker (intentionally or not), the layer can be etched, for example, using hydrogen atoms (H *). This technique can be advantageous in several situations of the example. For example, where growth occurs very quickly, unexpectedly, unevenly, etc., H * can be used to correct such problems. Another example, to ensure that enough graphene is produced, garfite can be created, graphene can be deosite and graphene can be selectively cauterized for HEG graphene at the desired level, for example, using H *. Yet another example, H * can be used to selectively cauterize in addition to graphene, for example example, to create conductive and non-conductive areas, this can be accomplished by applying an appropriate mask, performing cauterization, and then removing the
AP:. mask, for example. 15 Theoretical studies of graphene showed that the mobility of the chargers can be higher than 200,000 cm2 / N · s). Experimental measurements of gas-treated heteroepitaxial growth graphene showed resistivity as low as 3 x 10'6 Q-cm, which is better than that of thin silver films. The sheet strength of such 20 layers of graphene has been found to be about 150 ohms / square. One factor that may vary is the number of layers of graphene that are needed to give the lowest strength and strength of the sheet, and it will be appreciated that the desired thickness of the graphene may vary depending on the target application. In general, suitable fork for most applications can be n = 1 to 25 15 graphenes, more preferably n = 1 to 10 graphenes, even more preferably n = 1 to 5 graphenes, and sometimes n = 2 to 3 graphenes. It was found that a layer of n = 1 graphene resulted in a drop of transmission of about 2.3 to 2.6 ° 6. It was found that this reduction in transmission is generally linear across substantially all spectra, for example, ranging from ultraviolet (UV) to visible, and through lV. In addition, it was found that the transmission loss is substantially linear with each successive increment of n.
Example of Dopaqem Techniques Although a sheet resistance of 150 ohms / square may be suitable for certain applications in the example, it will be necessary that a
. another reduction in sheet strength may be desirable for different uses of the example.
For example, it will be appreciated that a sheet resistance of 10-20 ohms / square is desirable for certain applications of the example.
The inventor of the present invention has determined that the strength of the sheet can be decreased by doping graphene.
In this regard, being just a thick atomic layer, 10 graphene exhibits ballistic transport on a sub-micron scale and can be doped easily - either by gate voltages or molecular adsorbates or
, - interspersed in the case where n> 2 - without significant loss of mobility.
It was determined by the inventor of the present invention that in graphene, in addition to the - "- donor / recipient distinction, there are, in general, two different classes of dopants, namely, paramagnetic and non-magnetic.
In contrast to common semiconductors, this last type of impurities generally acts as weak dopants, while paramagnetic impurities cause strong doping: because of the linear leakage, density of symmetrical states of complete electron (DOS) nearby from the Dirac graphene point, impurity states located without turning gyrus are attached to the center of the pseudolacine.
Thus, graphene impurity states are strongly distinguished from their usual semiconductor counterparts, where DOS in the valence and conduction bands is very different and impurity levels generally exist far from the middle of the gap.
Although one may not expect a strong doping effect that requires the existence of tenths of several levels of well-defined donor (or receiver) electron voltage away from the Fermi level, if the impurity has an Iocal magnetic moment, its levels of energy part more or less symmetrically by the Hund exchange, of the order of 1 eV, which provides a favorable situation for strong doping impurity effects in 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 were both unique paramagnetic molecules and diamagnetic dimer systems for doping graphene and increasing its conductivity from 103 S / cm to "105 S / cm, and at times even 106 S / cm.
W Examples of dopants suitable for use in connection with 5 certain embodiments of the example include nitrogen, boron, phosphorus, fluorides, lithium, potassium, ammonium, etc. Sulfur-based dopants (eg, sulfur dioxide) can also be used in connection with certain modalities in the example. For example, sulfides present on glass substrates can cause infiltration outside the glass and thus dope the layer with graphene base. Several examples of graphene doping techniques are set out in more detail below. Figure 3 is a flowchart illustrating a first example of a technique for doping graphene according to certain modalities of the example. "Figure 3 of the technique example essentially involves an Ion beam 15 implanting the doping material into graphene. In this example of graphene is developed on a metal catalyst (step S301), for example, as described above The catalyst with the graphene formed thereafter is exposed to a gas comprising a material to be used as the dopan (also sometimes referred to as a doping gas) (step S303). A plasma is then excited in a chamber containing the catalyst with the graphene formed thereafter and the doping gas (S305). used to implant the dopant into the graphene (S307). Examples of suitable ion beam techniques for this type of doping are described in, for example, US Patent No. 6,602,371; 6,808,606; and Re. 3,358, and Publication US N "2008/0199702, each of which is dest the form incorporated here by reference. The power of the Ion beam can be about 10 to 200 ev, more preferably 20 to 50 ev, even more preferably 20 to 40 ev. Figure 4 is a flowchart illustrating a second example of a technique for doping graphene according to certain embodiments of the example. Figure 4 of the technique example essentially involves pre-implanting solid-state dopants into the substrate receiving the target, and then causing those solid-state dopants to migrate into the grain.
hay when graphene is applied to the receiving substrate.
In this example of the technique, graphene is developed on a metal catalyst (step "S401), for example, as described above.
The reception substrate is pre-
. manufactured to include dopants in solid state there (step S403). 5 For example, solid-state dopants can be included by melting the formulation into the glass.
Cefca of 1 to 10% atomic, more preferably 1 to 5 ° / 0 atomic, and even more preferably 2 to 3% atomic, dopant can be included in the glass melt.
Graphene is applied to the receiving substrate, for example, using one of the examples of the technique described in detail below (step S405). Then, solid-state dopants in the receiving substrate cause migration into the graphene.
The heat
- used in the deposition of graphene will cause the doping to migrate through. - through the graphene layer being formed.
Similarly, films »·. additionally doped can be included in the glass and the dopants from there 15 can cause migration through these layers through thermal diffusion, for example, creating a layer of doped graphene (n "= 2). An ion beam can also be used to implant the dopants directly in the glass in certain modalities of the example.
The power of the Ion beam can be about 10 to 1000 ev, more preferably 20 to 20 500 ev, even more preferably 20 to 100 ev.
When the intermediate layer is doped and used to provide impurities for graphene, the Ion beam can operate at about 10 to 200 ev, more preferably 20 to 50 ev, even more preferably 20 to 40 ev.
Figure 5 is a schematic view of the example illustrating a third example of the technique for doping graphene according to certain embodiments of the example.
Figure 5 of the examples of the technique essentially involves pre-implantation of solid state dopants 507 in the metal catalyst layer 503, and then causing the migration of these dopants in solid state 507 through the catalyst layer 503 as graphene 30 is. being formed, thereby creating a doped graphene 509 on the surface of the catalyst layer 503. More particularly, in this example of the technique, the catalyst layer 503 is arranged on the back support 505.
The catalyst layer 503 includes solid state dopants 507 therein.
In other words, the catalyst has solid-state doping atoms within its mass (for example, about 1 to 10 ° / 0, more preferably about 1 to 5 ° / 0, and even more preferably about 1 to 3%) * 501 hydrocarbon gas 501 is introduced next to the formed catalyst layer 503 at a high temperature.
Solid state dopants 507 in the layer of catalyst 503 cause migration through the outer surface of the same, for example, through this high temperature, as the crystallization of graphene occurs.
It was found that the rate at which dopants 10 reach the surface has a function of the thickness and temperature of the catalyst.
Crystallization is stopped by extinction and, finally, a graphene
Doped 509 is formed on the surface of the catalyst layer 503 '. Following the formation of doped graphene 509, the catalyst layer 503 'now - ". it has few (if any) 507 solid-state dopants located there. 15 An advantage of this example of technique refers to the potential to control the growth of ultrafine film by judiciously varying the temperature of the metal surface, partial pressure, and residence time of the deposition gas species, as well as the radicals Reactives used in the extinction rate process. 20 It will be appreciated that these examples of doping techniques can be used alone and / or in various combinations and subcombination with each other and / or other techniques.
It will also be appreciated that certain embodiments of the example may include a single doping material or multiple doping materials, for example, using an example of a particular technique once, a particular technique repeatedly, or through a combination of multiple techniques one or more times each.
For example, type p and type n dopants are possible in certain embodiments of the example.
Figure 6 is a graph of plotting temperature versus time involved in doping graphene according to certain modalities in the example.
As indicated above, cooling can be established using, for example, an inert gas.
In general, and also as indicated above, the high temperature can be about 900 degrees C in certain embodiments of the example, and the low temperature can be about 700 degrees C, and the cooling can occur for several minutes. The same heating / cooling profile as shown in figure 6 can be used, regardless
It is possible to determine if the graphene has been doped. 5 Example of Graphene Release and Transfer Techniques Once graphene has been heteroepitaxially developed, it can be released or detached from the metal catalyst and / or the back support, for example, before being placed on the substrate to be incorporated into the intermediate or final product. Several procedures can be implemented to suspend epitaxial films from their growth substrates according to certain modalities of the example. Figure 7 is an example of a stack of layers useful in release or shutdown techniques. graphene of certain modalities of the example. With reference to figure 7, in 6 -, embodiments of the example, an optional release layer 701 can be provided between the back support 505 and the catalyst layer 503. This release layer 701 can be or include, for example, oxide zinc (for example, ZnO or other suitable stoichiometry). Post-graphene deposition, graphene 509 / layer of metal catalyst 503 / stack of release layer 701 / coated substrate 505 can receive a layer of polymer 703 with mostly thick (for example, several microns thick) , for example, applied through a spin coating, dispensed by a meniscus flow, etc., which can be cured. As mentioned above, this polymer layer 703 can act as a structure or support for graphene 509 during elevation and / or shutdown, keeping the continuous graphene film extremely flexible, while also reducing the likelihood of graphene film from curl, bend or deform. Also as mentioned above, PMMA can be used as the polymer that allows graphene to be made visible by phase contrast and for support before and / or during elevation. However, a wide range of 30 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 embodiments of the example.
The lifting work can be carried out in parallel with the main branch of epitaxial growth, for example, experimenting with graphene films that can be chemically exfoliated from garfite.
The release layer can be chemically induced to slip. 5 secure the graphene / metal of the mother substrate once the polymer layer is placed on it.
For example, in the case of a zinc oxide release layer, washing in vinegar can trigger the release of graphene.
The use of a zinc oxide release layer is also advantageous, as the inventor of the present invention has discovered that the metal catalyst layer is also removed from the graphene with the release layer.
This is believed to be a result of the texturing caused
- by the zinc oxide release layer together with its interconnections formed with the grains in the catalyst layer.
It will be appreciated that this and
-, reduce (and sometimes even eliminate) the need to remove the catalyst layer later.
Certain lift-off or transfer techniques essentially refer to the original substrate as a reusable epitaxial growth substrate.
In such a way, a selective recording to undermine and dissolve the thin film of metallic catalyst away from the epitaxy-grown graphene (with polymer on top) may be desirable in such modalities of the example.
Thus, the catalyst layer can be engraved, regardless of whether the release layer is used in certain embodiments of the example.
Suitable corrosives include, for example, acids such as hydrochloric acid, phosphoric acid, etc. The surface of the glass substrate of the final container can be prepared to receive the graphene layer.
For example, a Langmuir Blodgett film (for example, a Langmuir-Blodgett acid) can be applied to the glass substrate.
The substrate of the final container may alternatively or additionally be coated with a soft forksophilic layer such as, for example, a silicone-based polymer, etc., making the latter receptive to graphene. This can help ensure electrostatic bonding, thus preferably permitting Graphene Transfer during transference.
The target substrate can 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 graffiti. 5 Graphene can be applied to the substrate using common stamping and / or lamination in certain embodiments of the example.
Such processes allow the graphene previously grown and qujmioabsoNido in the metal carrier to be transferred to a glass container by contact pressure.
As an example, graphene can be applied to the substrate through one or more laminating rolls, for example, as shown in figure 8. In this regard, figure 8 shows upper and lower rolls 803a and 803b, which will apply pressure and cause graphene 509 and polymer layer 703 to laminate to target substrate 801. As mentioned a-. - above, the target substrate 801 has a silicon layer, inclusive, or another phenophilic grain arranged there to facilitate lamination.
It will be appreciated that the polymer layer 703 will be applied as the outermost layer and that the graphite 509 will be closer (or even directly) to the target substrate 801. In certain embodiments of the example, one or more layers may be provided on the substrate before graphene is applied. 20 As soon as the graphene is disposed on the target substrate, the polymer layer can be removed.
In certain embodiments of the example, the polymer can be dissolved using an appropriate solvent.
When photosensitive material such as PMMA is used, it can be removed through exposure to UV light.
Of course, other removal techniques are also possible.
It will be appreciated that the catalyst thin film can be etched after graphene has been applied to the target substrate in certain embodiments of the example, for example, using one of the corrosive examples described above.
The choice of corrosive can also be based on the presence or absence of any underlying layers of graphene.
Certain embodiments of the example more directly electrochemically anodize the thin merl catalyst film below graphene.
In such embodiments of the example, graphene itself can act as the cathode, as the metal below is anodized in a transparent oxide when it is still "bonded to the original substrate.
Such modalities in the example can be used to ignore the use of the polymer overcoat by essentially performing the one-step transfer and elevation processes.
However, anodizing by electrochemical means can affect the electronic properties of graphene and thus may need to be compensated.
In certain embodiments of the example, the catalyst layer below graphene can be oxidized in other ways to make it transparent.
For example, a con- ductive oxide can be used to "bond" the graphene-based layer to a substrate, semiconductor, or other layer.
In that regard, cobalt, chromium
.. cobalt, nickel, cobalt chromium and / or the like can be ozidated.
In certain embodiments of the example, this can also reduce the need for it. - graphene, making transfer, manipulation and other handling of graphene easier.
Graphene can also be captured using an adhesive or tape-like material in certain embodiments of the example.
The adhesive can be placed on the target substrate.
Graphene can be transferred to the target substrate, for example, following the application of pressure, adhering more strongly to the substrate than the tape, etc.
Example of Reactor Design Shower reactors typically employ a porous or perforated flat surface to distribute reactant gases more or less evenly over a second heated parallel surface.
Such a configuration can be used to grow graphene using the example of heteroepitaxial techniques described here.
Shower reactors are also advantageous for processing square and wide ultra-soft glass or ceramic substrate.
A basic schematic of a shower reactor is figure 9, with the pelno design being increased.
In other words, figure 9 is a schematic cross-sectional view of a reactor suitable for depositing high-grade graphene electronics (HEG) according to an example embodiment.
The reactor includes a portion of body 901 with several inlets and outlets. More particularly, a gas inlet 903 is provided at the top and close to the horizontal center of the reactor body portion 901. The +3903 gas inlet can receive gas from one or more sources and thus can supply gas. various gases including, for example, hydrocarbon gas, O (S) gas (s) used to form the environment during heteroepitaxial growth, O (S) extinguishing gas (s), etc. The flow and flow of the gas will be described in greater detail below, for example, with reference to the plenum shower design
907. A plurality of exhaust ports 905 can be provided at the bottom of the body portion 901 of the reactor. In the example example of figure 9, 10 two exhaust ports 905 are provided close to the ends of the body portion 901 of the reactor, for example, in order to extract the gas provided by the. gas inlet 903 which will generally flow through the substantially total gas. "quality of the body portion 901. It will be appreciated that more or less doors -". exhaust fans 905 can be provided in certain embodiments of example 15 (for example, other exhaust ports 905 can be provided in the horizontal center near the reactor body port 901, at the top or sides of the reactor body portion 901, etc. ). The substrate of the back support 909 can be cleaned and have the thin film of the catalyst disposed in it (for example, by deposition of physical vapor 20 or PVD, crepitation, CVD, flame pyrolysis or the like) before entering the reactor by a load blocking in certain embodiments of the example. In terms of susceptor design, the substrate surface of the back support 909 can be quickly heated (for example, using an RTA heater, a short wave LV heater, or another suitable heater that is capable of heating by induction of the substrate and / or layers degrade without necessarily also heating the entire chamber) to a uniformly controllable temperature level that allows (i) the metal film to crystallize and activate, and (ii) the preferred deposition of substantially thick graphene uniform and controllable from a gas phase precursor 30 on its surface. The heater can be controllable in order to consider the deposition rate of parameter / (temperature * thickness) of the catalyst ratio. The substrate of the rear support 909 can
see through the reactor in the R direction or you can sit stationary under shower 907. Shower 907 can be cooled, for example, using a "cooling fluid or gas introduced through one or more inlets and outlets
0 of refrigerant 913. Soon, and as shown in the enlargement of figure 9, the plenum 5 design can include a plurality of openings in the bottom of shower 907, with each opening only a few millimeters wide.
Changing the gap in the ceiling Hc, or the height between the bottom surface of shower 907 and the top surface on which the substrate of the back support 909 moves, can have several effects.
For example, the chamber volume 10 and thus the surface-volume ratio can be modified, thus affecting the residence time of the gas, consumption time and speed.
. radial cities.
It was found that changes in residence time were for-. influence the extent of gas phase reactions.
A configuration. -. The shower function operated as shown in figure 9 (with a hot surface below the cooled surface) has the potential for natural transmission of the Benard variety if operated at high pressures (for example, in hundreds of Torr), and this tendency is strongly influenced by height through the Rayleigh number (a dimensionless number associated with the triggered buoyancy flow, also known as free transfer 20 or natural transfer; when it exceeds a critical value for the fluid, heat transfer is primarily on form of transmission). Therefore, the gap in the Hc ceiling can be varied through simple changes in the equipment, providing adjustable mounting of the substrate electrode, etc., in order to affect the heteroepitaxial growth of graphene. 25 The modality of the example in figure 9 is not necessarily intended to operate a plasma inside the reactor. This is because the mechanism of growth of the crystalline film is through heteroepitaxy through surface sorption (usually occurring only in the catalyst). The growth of the plasma phase has been found to give rise to most amorphous films and also allows the formation of macroparticles or dust formation which can greatly reduce the quality of the film and result in holes that would be harmful to a film. atomic layer one to ten.
Instead, certain modalities of the example may involve making graphite (for example, monocrystalline garfite), engraving it on graphane (for example, from a
P a certain value n) and transform the graphane into graphene (for example, graphene from HEG). Of course, an endpoint technique in situ can be implemented 5 as a regeneration parameter. In certain embodiments of the example, an Ion beam source can be located in line but on the outside of the reactor of figure 9, for example, to perform the doping according to the examples of the techniques described above. However, in certain embodiments of the example, an Ion beam source can be located within the body portion of a reactor.
H - . Process Flow Example Figure 10 and a process flow example that illustrates certain - "- examples of catalytic CVD growth, elevation of transfer techniques for certain example modalities. The example process shown in the figure 10 begins as the back support glass is inspected, for example, using a conventional glass inspection method (step S1002) and washed (step S1004) .The back support glass can then be cleaned using Ion beam cleaning , piasma calcination, or 20 similar (step S 1006) - The catalyst (for example, a metal catalyst) is arranged on the back support, for example, using PVD (step S1008). cleaning of step S1006 can be established inside the graphene coating coater in certain embodiments of the example of this invention, in other words, the glass of the back support 25 with or without the thin film of the metal catalyst formed therein can be loaded inside the re recreational graphene dressing prior to step S1006 in certain embodiments of the example, for example, depending on whether the metal catalyst layer is deposited within or before the recreational coating. Catalytic deposition of n-layer graphene can then occur (step 30 S1O1O). Graphene can be engraved by introducing hydrogen atoms (H *) in certain embodiments of the example, and graphene can optionally be doped, for example, depending on the target application (step
S1012). The end of graphene formation is detected, for example, by determining whether enough fork has been deposited and / or whether the H * recording has been
Enough W (step S1014). To stop the formation of graphene, a quick one. extinguishing process is used, and the glass of the back support with the graphene 5 formed there removes the reactor / coater (step S 1016). Visual inspection can optionally be performed at this point. Following the formation of graphene, a polymer useful in transferring graphene can be disposed in graphene, for example, by rotation, foil, or another coating technique (step S1018). This product can optionally be inspected, for example, to determine whether the required color change occurs. If it does, the polymer can be cured (for example, using heat, UV radiation, etc.) (step S 1020), and then inspected again. The metal catalyst can be sub-etched or in another form - ", released (step S 1022), for example, to prepare the graphene for elevation 15 (step S1024). As soon as the elevation is reached, the polymer and the graphene optionally they can finally be inspected and then washed, for example, to remove any remaining sub-corrosives and / or uncured polymer (step S1026). Another optional inspection process can be performed at this point. A surfactant can be applied (step S1028), pins are placed at least inside the polymer (step S1030), and the membrane is shaken (step S 1032), for example, with the help of these pins, the lifting process is now complete, and the graphene is now ready to be transferred to the container substrate 25 The container substrate is prepared (step S1034), for example, in a bright room The surface of the container substrate can be made functional, for example, by exposing it UV light to increase your energy in surface, to apply graphenophilic coatings to it, etc. (cover S 1036). The graphene / polymer membrane can then be transferred to the host substrate (step S 1038). As soon as 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 S 1040). This can be done by exposing the polymer to UV light, heat, chemicals, etc.
The substrate with o - graphene and at least the partially dissolved polymer can then be
. washed (step S 1042), with any excess water or other materials evaporated and dried (step S 1044). This process of removing the polymer can be repeated as needed.
Following the removal of the polymer, the resistance of the graphene sheet to the substrate can be measured (step S 1046), for example, using a standard four-point probe.
Optical transmission (eg, Tvis, 10 etc.) can also be measured (step S 1048). In the event that the intermediary or final products receive quality standards, they can be packaged k · P. (step S 1050). Using these techniques, sample films were prepared.
The film samples exhibited high conductivity of 15500 S / cm and transparency of more than 80% over the wavelength from 500 to 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 embodiments of the example.
The image in figure 11 highlights the elevation of the heteroepitaxially grown graph from a thin permalloy film. 20 Example of Inclusive Graphene Applications 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.
Graphene manufacturing devices will typically involve making contacts with metals, degenerated semiconductors such as ITO, solar cell semiconductors such as a-Si and CdT among others, and / or the like.
Despite having a zero band gap and a density of disappearance states (DOS) at K points in the Brillouin zone, free-standing graphene exhibits metallic behavior.
However, absorption in a metallic substrate, semiconductor or insulation can change its properties.
electronic activities. To compensate for this, additionally, or alternatively, in sample applications and / or electronic devices, the graphene-based layer can be doped according to any se- layers. miconductors adjacent to it. This is, in certain embodiments of the example, if a graphene-based layer is adjacent to a n-type semiconductor layer, the graphene-based layer can be doped with a n-type dopant. Also, in certain embodiments of the example, if a graphene-based layer is adjacent to a p-type semiconductor layer, the graphene-based layer can be doped with a p-type dopant. Of course, 10 the change in the Fermi level in graphene with respect to the conical points can be modeled, for example, using functional density theory (DFT).
· Slit band calculations show that metal- / graphene interfaces can be used. "can be classified into two broad classes, namely, che - absorption and d, 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 contacts to graphene depending on the application. A first electronic device in the example that can make use of one or more layers based on graphene is a solar photovoltaic device. Such devices in the example may include electrodes of front or rear electrodes. In such devices, graphene-based layers can simply replace the ITO typically used here. Photovoltaic devices are described in, for example, US Patent Nos. 6,784,361,
6,288,325, 6,613,603 and 6,123,824; U.S. Publication No. 2008/0169021; 2009/0032098; 2008/0308147; and 2009/0020157: and Pedidod and Patent No. Seriaos 12 / 285,374, 12 / 285,890, and 12 / 457,006, the descriptions of which are hereby incorporated by reference. Alternatively, or in addition, doped graphene-based layers can be included here in order to match the adjacent micro-conductive layers. For example, figure 12 is a schematic cross-sectional view of a solar photovoltaic device incorporating layers based on graphene according to certain embodiments of the example. 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 glass described in any of the US Patent Applications Serial No. - 11 / 049.292 and / or 11 / 122.218, the descriptions of which are incorporated herein by reference 5. The glass substrate can optionally be nanotextured, for example, to increase the efficiency of the solar cell. (AR) 1204 can be provided on an outer surface of the glass substrate 1202, for example, to increase transmission The anti-reflective coating 1204 can be a single-layer anti-reflective coating (SLAR) (for example, an anti-reflective coating silicon oxide) or a multi-layered anti-reflective coating (MLAR).
· Such AR coatings can be provided using any suitable technique. The quada.
W One or more absorption layers 1206 can be provided on the glass substrate 1202 opposite the AR coating 1204, for example, in the case of a rear electrode device such as that shown in the example example of figure 12. The absorption layers 1206 can be sandwiched between the first and second semiconductors. In the embodiment of the example in Figure 12, absorption layers 1206 are sandwiched 20 between the semiconductor layer type 1208 (near the glass substrate 1202) and the semiconductor type p 1210 (furthest from the glass substrate 1202). A back contact 1212 (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 25 and / or between semiconductor 1210 and back contact 1212, first and second layers based on graphene 1214 and 1216 can be provided. The graphene-based layers 1214 and 1216 can be doped in order to combine the adjacent semiconductor layers 1208 and 1210, respectively. Thus, in the embodiment of the example in figure 12, a graph-based layer No. 1214 can be doped with type n dopants and a graphene-based layer 1216 can be doped with type p 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 to the surface on which it is placed.
. Consequently, it is possible to texture the optional layer 1218 so that the texture of that layer can be "transferred" or otherwise reflected in the graphene-based layer generally conforming to 1214. In this regard, the optional textured layer 1218 can understand zinc doped oxide (ZTO). Note that one or both semiconductors 1208 and 1210 can be replaced with conductive polymeric materials 10 in certain embodiments of the example. Because graphene is essentially transparent in the vicinity or middle of the IR bands, it implies that the greater penetration of radiation of the long wavelength can penetrate and generate deep carriers in the * -. layer i of both single and tandem junction solar cells. This implies that the need to texturize subsequent contacts may not be necessary with graphene-based layers, since efficiency will already be increased by so many percentage points. Screen printing, evaporation and technologies and CdC12 sintering and treatment at high temperatures are currently used in CdS / CdTe solar cell hetro-functions. These cells have high filling factors (FF> 0.8). However, Rs series resistance is an artifact of limiting efficiency. In Rs, there is a distributed part of the sheet resistance of the CdS layer and a discrete component associated with CdTe and graphite based on the contact on top of it. The use of one or more layers based on graphene can help to reduce both contributions to Rs, while preserving good heterojunction properties. Including graphene in such a solar structure for both front and rear contact arrangements, a substantial increase in efficiency can be achieved. It will be appreciated that certain embodiments of the example may involve single-junction solar cells, while certain embodiments of the example may involve tandem solar cells. Certain modalities of the example can be CdS, CdTe, ClSl CIGS, a-Si, and / or other types of soluble cells
res. Another example model that can incorporate one or more
Graphene-based layers are a touch panel display. For example -. For example, the touch panel dispolay can be a capcitive or resistive touch panel display including ITO or other conductive layers. See, for example, U.S. Patent Nos. 7,436,393; 7,372,510; 7,215,331; 6,204,897; 6,177,918; w 5,650,597, and Patent Application Serial No. 12 / 292,406, the descriptions of which are hereby incorporated by reference. ITO and / or other conductive layers can be replaced so that the 10 touch panels 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 modes. dalities of the example. Figure 13 includes an underlying display 1302, which
K -. it may, in certain embodiments of the example, be an LCD, plasma, or other 15 flat panel display. An optically clean adhesive 1304 joins the display 1302 to a thin sheet of glass 1306. A deformable PET sheet 1308 is provided as the topmost layer in the form of the example in the figure
13. The PET sheet 1308 is placed on the upper surface part of the thin glass substrate 1306 by virtual of a plurality of spacers of 20 pillar 1310 and edge seals 1312. First and second layers based on graphene 1314 and 1316 can be provided on the surface of the PET sheet 1308 near the display 1302 of the thin glass substrate 1306 on the surface facing the PET sheet 1308, respectively. One or both of the layers based on graphene 1314 and 1316 can be modeled, for example, using the ion beam and / or laser engraving. Note that the graphene-based layer on the PET sheet can be transferred from its intermediate product growth location using the PET sheet itself. In other words, the PET sheet can be used instead of a photoresistor or other material when lifting graphene and / or moving it. 30 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, a sheet resistance of less than about 300 ohms / square is advantageous for graphene-based layers.
N It will be appreciated that the ITO is typically found on the display m. 1302 can be replaced with one or more graphene-based layers. 5 For example, when display 1302 is an LCD display, graphene-based layers can be provided as a common electrode in the colored filter substrate and / or as standardized electrodes in the so-called TFT substrate. Of course, graphene-based layers, doped or non-doped, can also be used in design with the design and manufacture of the 10 individual TFTS. Similar arrangements can also be provided in connection with plasma and / or other flat panel displays.
1 Graphene-based layers can also be used for. create data, conductive bus lines, data bus, antennas
R -. and / or the like. Such structures can be formed in / applied to the substrate of glass, silicon wafers, etc. Figure 14 is a flowchart illustrating an example technique for forming data on the conductive bus line according to certain embodiments of the example. In step S 1401, a graphene-based layer is formed on an appropriate substrate. In an optional step, step S1403, a protective layer can be provided on the graphene-based layer. In step S 1405, the graphene-based layer is selectively removed or patterned. This removal or standardization can be established by laser engraving, in such cases, the need for a protective layer can be reduced, as long as the laser resolution is fine enough. Alternatively or in addition, recording can be performed by exposing to an Ion beam / plasma treatment. Also, as explained above, H * can be used, for example, in connection with a hot filament. When a plasma treatment ion beam is used for recording, the protective layer may be desirable. For example, a photoresist material can be used to protect the areas of interest in graphene. Such photoresist can be applied, for example, by spin coating or the like in step S 1403. In such cases, in another optional step, S 1407, the optional protective layer is removed. Exposure to UV radiation can be used with appropriate photoresists, for example. In one or more steps not shown, the conductive graphene-based pattern can be transferred to an intermediate or final product, if it has not already been - formed, for example, using any appropriate technique (such as 5 for example , those described above). Although certain modalities in the example have been described as etching or removing layers based on graphene, certain modalities in the example may simply change the conductivity of the graphene-based layer. In such cases, some or all of the graphene may not be moved. However, because the conductivity has been subtly altered, only the appropriately standardized areas can be conductive. g Figure 15 is a schematic view of a forming technique. "tion of conductive bus data in accordance with certain modalities -" M equities of the example. As shown in figure 15, the conductivity of graphene 15 is selectively changed due to exposure to an ion beam. A resistant layer is applied in a suitable pattern, for example, in order to protect the desired portions of the graphene-based layer, while the other portions of the graphene-based layer remain exposed to the ion beam. 20 Mobility data are shown in the table below after several samples have been removed and recordedj Thickness I Samples Steps Conductivity- Mobility µ recorded ra (Qcm) of (1 / Qcm) (cm ^ 2 / Vs) A 25 8 | 1.03E-04i 970000 120,000 B 20 6 5.24E-03 10 10000 143000 Ç
D 10 5 "" ^ ~ 'i 6 | 1,48E-02 | 1600000 1500000 150000 160000 It will be appreciated that standardization of graphene in this and / or other forms can be advantageous for several reasons. For example, the layer will be largely transparent. Thus, it is possible to provide "seamless" antennas 25 where the pattern cannot be seen. A similar result can be provided in connection with the bus bars that can be incorporated into the windows on the vehicle (for example, for defrosting, using the antenna,
Connecting components, etc.), flat panel (eg LCD, plasma, and / or other) display devices, skylights, refrigerator / freezer doors
Windows, etc. This can also advantageously reduce the need for. black firms in such products. In addition, graphene-based layers 5 can be used in place of ITO in electrochromic devices. Although certain applications in the example devices have been described here, as shown above, it is possible to use conductive graphene-based layers in or in addition to other transparent conductive coatings (TCCs), such as ITO, oxide zinc, etc. 10 As used here, the terms "in", "supported by," and the like should not be interpreted to mean that two elements are directly
Adjacent to one another, unless explicitly indicated. In .
in other words, a first layer can be said as "in" or "supported -" by "a second layer, even if there are one or more layers between them. While the invention has been described in connection with the which is presently considered the most practical and preferred modality, it should be understood that the invention should not be limited to the modality of the description, but on the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the attached claims.

权利要求:
Claims (20)
[1]
1. Method of making a thin film of doping graphene, the method. all comprising: y hetero-epitaxially grow a thin film of graphene in-. 5 intermediate in a thin film of catalyst, the thin film of catalyst having a substantially single-oriented wide-grain crystal structure; doping of intermediate graphene thin film doping type n- or type p- in the preparation of thin film doping graphene, 10 in which the thin film of doping graphene has a foil resistance of less than 150 ohms / square.
[2]
P: f 2. The method of claim 1, wherein the doping of the intermediate graphene thin film comprises:
[3]
THE - . exposing the thin film of intermediate graphene to a doping gas comprising a material to be used as a dopant; exciting a plasma inside a chamber containing the thin film of intermediate graphene and the doping gas; and Ion rays implanting the dopant into the thin film of intermediate graphene using the material in the doping gas. A method according to claim 2, wherein the energy of the radio wave is 10-200eV.
[4]
A method according to claim 2, wherein the energy of the ion beam is 20-40 eV.
[5]
5. Method according to claim 1, wherein the doping 25 of the intermediate graphene thin film comprises: providing a target receiving substrate including dopants in that solid state, the target receiving substrate including dopants in that place because of a fusion process used to manufacture the target receiving substrate; and 30 allowing solid state dopants on the target to receive substrate to migrate into the thin film of intermediate graphene by thermal diffusion.
[6]
A method according to claim 5, wherein the target receiving substrate includes 1-10 percent atomic weight of doping material. "7. Method according to claim 1, wherein the doping
[7]
R. The thin film of intermediate graphene comprises: 5 providing a target receiving substrate including dopants in that solid state, the target receiving substrate including dopants in that place due to the implantation of the ion beam; and allowing solid-state dopants in the target receiving substrate to migrate to the thin film of intermediate graphene by thermal diffusion.
[8]
8. The method of claim 7, wherein the implantation of the ion beam is carried out at a force level of 10-1000 eV. q
[9]
A method according to claim 1, wherein the doping - "of the intermediate graphene thin film comprises: providing a target receiving substrate having at least one thin coated film arranged thereon, the thin coated film including dopants in a solid state in that place, and allowing solid state dopants in at least one thin film formed on the target receiving substrate to migrate to the thin film 20 of intermediate graphene by thermal diffusion.
[10]
A method according to claim 1, wherein the doping of the intermediate graphene thin film comprises: pre-implanting solid state dopants into the thin film of the catalyst; and 25 allowing dopants in the solid state thin film of the catalyst to migrate to the thin film of intermediate graphene by thermal diffusion.
[11]
A method according to claim 10, wherein the thermal diffusion occurs during the deposition of the thin film of intermediate graphene. 30
[12]
A method according to claim 10, wherein the thin film of the catalyst includes 1-5% solid dopant atoms in its mass.
[13]
A method according to claim 12, wherein the thin film of catalyst comprises nickel. THE
V
[14]
A method according to claim 1, wherein the film. fine doped graphene is doped with any one or more of: nitrogen, 5 boron, phosphorus, fluorine, lithium, potassium and sulfur.
[15]
A method according to claim 1, wherein the doping graphene thin film has a blade resistance of 10-20 ohms / squares.
[16]
16. Thin film of doped graphene grown heterologously epitaxially, directly or indirectly, in a thin film of metal catalyst having a broad grain crystal structure substantially in g a single orientation,. in which the thin film of graphene is 1-10 atomic layers
J - - thick, in which the thin film of doping graphene has a blade resistance of less than 150 ohms / squares.
[17]
17. Graphene A doping graphene thin film according to claim 16, wherein a doping graphene thin film includes n- type dopants.
[18]
18. Graphene Doping graphene thin film according to claim 16, wherein the doping graphene thin film includes p-type dopants.
[19]
19. GrapheneDoping graphene thin film according to claim 16, wherein the doping graphene thin film is doped with any one or more of: nitrogen, boron, phosphorus, fluorine, lithium, potassium and 25 sulfur.
[20]
20. GrapheneDoping graphene thin film according to claim 16, wherein the doping graphene thin film has a blade resistance of 10-20 ohms / squares.

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法律状态:
2020-08-25| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-10| B25A| Requested transfer of rights approved|Owner name: GUARDIAN GLASS, LLC (US) |

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2020-12-08| B11B| Dismissal acc. art. 36, par 1 of ipl - no reply within 90 days to fullfil the necessary requirements|

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2021-11-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

优先权:

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申请号 | 申请日 | 专利标题

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US12/461,343|US8507797B2|2009-08-07|2009-08-07|Large area deposition and doping of graphene, and products including the same|

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US12/461,343|2009-08-07|

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PCT/US2010/002058|WO2011016837A1|2009-08-07|2010-07-22|Large area deposition and doping of graphene, and products including the same|

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