CN103682152A - Transparent conductive electrode and forming method therefor, organic light emitting diode (OLED) device and forming method therefor - Google Patents

Abstract

The invention relates to a transparent conductive electrode and a forming method thereof, an organic light emitting diode (OLED) device and a forming method thereof. Using graphene instead of indium tin oxide as a transparent conductive electrode that can be used in organic light-emitting diode (OLED) devices. Using graphene reduces the cost of making OLED devices and also makes OLED devices extremely flexible. The graphene is chemically doped such that the work function of the graphene is shifted to higher values for better hole injection into OLED devices compared to OLED devices comprising undoped graphene layers . Interfacial layers comprising conductive polymers and/or metal oxides can also be used to further reduce the remaining injection barrier.

Description

Transparent conductive electrode and method for forming same, organic light emitting diode (OLED) device and method for forming same

technical field

The present disclosure relates to transparent conductive electrodes and methods of forming the same. More specifically, the present disclosure relates to a doped graphene transparent conductive electrode, an organic light emitting diode (OLED) device comprising the doped graphene transparent conductive electrode, and forming the doped graphene transparent conductive electrode and the comprising The doped graphene transparent conductive electrode method for OLED devices.

Background technique

Organic light emitting diode device technology is emerging as a leading technology for displays and lighting. Key advantages possessed by OLED displays include vivid colors, high contrast, wide viewing angles, and OLED displays are more flexible than conventional liquid crystal displays (LCDs). Additionally, OLED lighting is more efficient than incandescent bulbs and has similar efficiency to nitride-based light-emitting diodes (LEDs).

A typical OLED includes a substrate, usually made of glass or similar transparent material. An anode layer is on the substrate. The anode layer can be made of a material with a relatively high work function and is substantially transparent to visible light. A typical material for the anode layer is indium tin oxide (ITO). A layer of electroluminescent material is located on the anode layer and serves as the emissive layer of the organic OLED. Common materials used to form the emissive layer are molecules such as eg poly-p-phenylene vinylene (PPV) and like tris(8-quinolinolato)aluminum (Alq3). In the case of molecules, the emissive layer typically comprises several layers of molecules. A cathode layer of a material with a lower work function, such as aluminum (Al), calcium (Ca) or magnesium (Mg), is located on the emissive layer. During operation of the OLED, the cathode and anode layers are connected to a power source.

The basic principle of electroluminescence and thus of OLEDs is as follows: an anode layer and a cathode layer inject charge carriers, ie electrons and holes, into the emissive layer. In the emission layer, the charge carriers are transported and the oppositely charged charge carriers form so-called excitons, ie excited states. Excitons decay radiatively to the ground state by generating light. The generated light is then emitted by the OLED through an anode layer made of a transparent material such as ITO. The color of the light produced depends on the material used for the organic emissive layer.

Contents of the invention

In this disclosure, graphene is used instead of indium tin oxide as a transparent conductive electrode that can be used in OLED devices. Using graphene reduces the cost of making OLED devices and also makes OLED devices extremely flexible. The graphene used in this disclosure is chemically doped such that the work function of the graphene is shifted to higher values and holes are better injected into the In OLED devices. Interfacial layers comprising conductive polymers and/or metal oxides can also be used to further reduce the remaining injection barrier.

In one aspect of the present disclosure, a transparent conductive electrode capable of being used as an electrode of an OLED is provided. The transparent conductive electrode of the present disclosure includes a graphene layer doped with a one-electron oxidant.

In another aspect of the present disclosure, there is provided an OLED device comprising: a substrate; a doped graphene layer on an exposed surface of the substrate; an optional interfacial layer on the exposed surface of the doped graphene layer; a layer of electroluminescent material on the exposed surface of the layer of electroluminescent material; and a layer of cathode material on the exposed surface of the layer of electroluminescent material.

In yet another aspect of the present disclosure, a method of forming a transparent conductive electrode is provided. The method of forming a transparent conductive electrode includes: providing a blanket graphene layer; and doping the blanket graphene layer with a one-electron oxidant.

In yet another aspect of the present disclosure, a method of forming an OLED device comprising a doped graphene transparent conductive electrode is provided. The method includes: providing a substrate; forming a doped graphene layer on an exposed surface of the substrate; forming an optional interfacial layer on the exposed surface of the doped graphene layer; forming a layer of electroluminescent material over the graphene layer; and forming a layer of cathode material on an exposed surface of the layer of electroluminescent material.

Description of drawings

FIG. 1 is a diagram illustrating (through a cross-sectional view) a substrate that can be used in one embodiment according to the present disclosure.

FIG. 2 is a diagram illustrating (through a cross-sectional view) the structure of FIG. 1 after forming a doped graphene layer on an exposed surface of a substrate.

3 is a diagram illustrating (through a cross-sectional view) the structure of FIG. 2 after forming an interfacial material layer on the exposed surface of the doped graphene layer.

4A is a diagram illustrating (by cross-sectional view) the structure of FIG. 2 after forming a layer of electroluminescent material on the exposed surface of the doped graphene layer.

4B is a diagram illustrating (through a cross-sectional view) the structure of FIG. 3 after forming a layer of electroluminescent material on an exposed surface of the interface material layer.

5A is a diagram illustrating (through a cross-sectional view) the structure of FIG. 4A after forming a layer of cathode material on an exposed surface of the layer of electroluminescent material.

5B is a diagram illustrating (through a cross-sectional view) the structure of FIG. 4B after forming a layer of cathode material on an exposed surface of the layer of electroluminescent material.

Detailed ways

The present disclosure will now be described in more detail with reference to the following discussion and the accompanying drawings of the present application. The present disclosure provides doped graphene transparent conductive electrodes and OLED devices comprising the doped graphene transparent conductive electrodes, as well as methods for forming The method of the doped graphene transparent conductive electrode and the OLED device comprising the doped graphene transparent conductive electrode.

Note that the drawings of the present application are provided for illustration purposes only and therefore they are not drawn to scale. In the drawings and the following description, like materials are referred to with like reference numerals. For the purposes of the following description, the words "upper", "lower", "right", "left", "vertical", "horizontal", "top", "bottom" and their derivatives shall refer to Oriented components, layers and/or materials.

In the following description, numerous specific details are set forth, such as specific structures, components, materials, dimensions, process steps and techniques, in order to provide a thorough understanding of the present disclosure. It will be understood, however, by one of ordinary skill in the art that the present disclosure may be practiced without these specific details with feasible alternative process options. In other instances, well-known structures or process steps have not been described in detail so as not to obscure the various embodiments of the present disclosure.

In current OLED display and lighting technologies, indium tin oxide transparent conducting electrodes are used as anodes. This OLED construction has the following disadvantages. Transparent conductive electrodes comprising indium tin oxide comprise the rare earth metal indium, which is an expensive material, thus increasing the cost of manufacturing OLED devices comprising indium tin oxide. OLED devices comprising indium tin oxide are prone to failure after bending and are therefore not suitable for flexible applications. Furthermore, indium tin oxide is toxic, thus requiring alternative materials for transparent conducting electrodes.

In the present disclosure, the above-mentioned disadvantages associated with conventional indium tin oxide transparent conducting electrodes are avoided by providing a graphene-containing electrode that is chemically doped such that the graphene-containing electrode The work function of the electrodes is shifted to higher values for better injection of holes into the OLED device compared to an equivalent OLED device comprising an undoped graphene layer. Interfacial layers comprising conductive polymers and/or metal oxides can also be used to further reduce the remaining injection barrier.

Although the description below exemplifies the transparent conductive electrode of the present disclosure as a component of an OLED device, the transparent conductive electrode of the present disclosure is not limited to use only in such a device. Alternatively, the transparent conductive electrodes of the present disclosure may be used in other types of devices, such as for example in photovoltaic devices, solar cells, flat panel displays or touch screens.

Furthermore, although the OLED device is described with the transparent conductive electrode of the present disclosure as the bottom electrode of the OLED device, the present disclosure is not limited to only this OLED device. Alternatively, OLED devices can be fabricated in which the transparent conductive electrode of the present disclosure is the top electrode of the OLED device. In this case, the bottom electrode will comprise one of the cathode materials mentioned herein below.

In addition, OLED devices of the present disclosure may include p-doped carbon nanotubes instead of doped graphene layers as transparent conductive electrodes. In such an embodiment, p-doped carbon nanotubes are produced by first growing the carbon nanotubes using any conventional technique known to those skilled in the art; The carbon nanotubes were doped using a solution deposition process also described herein below. In such an embodiment, the work function of the p-doped carbon nanotubes is improved compared to the undoped carbon nanotubes, and the work function of the p-doped carbon nanotubes is in the same range as the Fermi energy of the electroluminescent material. levels are basically in the same range.

Referring to FIG. 1 , there is illustrated a substrate 10 that can be used in one embodiment of the present disclosure. A substrate 10 capable of use in the present disclosure may be rigid or flexible, and may comprise, for example, semiconductor material, glass, ceramic, tape, or plastic. Typically, the substrate 10 employed in the present disclosure is a transparent substrate. In one embodiment of the present disclosure, substrate 10 is transparent and composed of glass. In another embodiment of the present disclosure, the substrate 10 is transparent and composed of plastic. The substrate 10 employed in the present disclosure may have a thickness ranging from hundreds of micrometers to several millimeters. In another embodiment, the substrate 10 used may have a thickness ranging from tens of microns to several millimeters. Substrate 10 may have other thicknesses above and/or below the above ranges.

Referring to FIG. 2 , substrate 10 is illustrated after forming doped graphene layer 12 on an exposed surface of substrate 10 . In some embodiments, and as shown in the figures of the present disclosure, the doped graphene layer 12 serves as the bottom transparent conductive electrode of the OLED device. In other embodiments, the doped graphene layer 12 can be used as the top transparent conductive electrode of the OLED device. In yet another embodiment of the present disclosure, the doped graphene layer 12 can be used as a transparent conductive electrode for other types of devices such as, for example, photovoltaic devices, solar cells, flat panel displays, or touch screens device.

The doped graphene layer 12 employed in the present disclosure comprises graphene having an increased work function for better hole injection into OLED devices as compared to OLED devices comprising undoped graphene middle. Specifically, undoped graphene has a work function of about 4.5 eV. Doping of graphene as described herein increases the work function of graphene to a range from greater than 4.5 eV to 5.2 eV. The enhanced work function of the doped graphene layer "substantially" matches the Fermi level of a layer of electroluminescent material that will subsequently be formed on top of the doped graphene layer. By "substantially matching" is meant that the difference between the work function of the doped graphene layer and the Fermi level of the electroluminescent material layer is within a range of less than 0.7 eV. Thus, by using a doped graphene layer a better injection of holes into the electroluminescent material layer is provided compared to an undoped graphene layer.

The doped graphene layer 12 may be provided in the present disclosure by first depositing a blanket undoped graphene layer on a handle substrate. The handle substrate is typically composed of a material capable of catalyzing the formation of graphene on its surface. For example, in some embodiments of the present disclosure, the handle substrate may include copper or copper foil.

The handle substrate can be formed using any deposition process known to those skilled in the art. For example, a handle substrate composed of copper may be formed by chemical vapor deposition, plasma enhanced chemical vapor deposition, physical vapor deposition, sputtering, plating, chemical solution deposition, or electroless plating. Typically, copper foil is formed by sputtering copper foil from copper-containing palladium.

In one embodiment, the handle substrate has a thickness of 7 μm to 25 μm. In another embodiment, the handle substrate has a thickness of 20 μm to 30 μm. Other thicknesses of the handle substrate above and/or below the aforementioned thickness ranges may also be employed in the present disclosure.

After selective processing of the substrate, a blanket undoped graphene layer (not shown) is deposited. The term "graphene" as used throughout this disclosure means a one-atom-thick planar sheet of sp2-bonded carbon atoms densely packed in a honeycomb lattice. The graphene employed in the present disclosure has a two-dimensional (2D) hexagonal crystallographic bonding structure.

Blanket graphene layers that can be used in this disclosure are continuous graphene layers that can be composed of single-layer graphene (nominally 0.34 nm thick); few-layer graphene (2-10 graphene layer); multi-layer (multi-layer) graphene (>10 graphene layers); a mixture of single-layer, few-layer and multi-layer graphene; or by Graphene is formed from any combination of graphene layers mixed with amorphous and/or disordered carbon phases. Typically, single-layer graphene is used in this disclosure.

The blanket graphene layer may be formed using a deposition process such as, for example, chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD), and ultraviolet (UV) assisted CVD. In one embodiment, the blanket graphene layer is formed by CVD. In some embodiments, the deposition process that can be used in the present disclosure to form a blanket graphene layer begins on the exposed surface of the handle substrate.

In one embodiment, for PECVD, the deposition of the blanket graphene layer on the exposed surface of the handle substrate may be performed at a temperature up to but not exceeding 500°C. In another embodiment, the deposition (ie, growth) of graphene occurs at a temperature of 800°C to 1080°C. Deposition processes that can be used in the present disclosure to form blanket graphene layers include utilizing any known carbon source including, for example, benzene, propane, ethane, and other hydrocarbons and other carbon-containing gases .

In one embodiment of the present disclosure, the blanket graphene layer may have a thickness of 0.34nm-0.8nm. In another embodiment of the present disclosure, the blanket graphene layer may have a thickness of 0.7nm-3.4nm. The blanket graphene layer may have other thicknesses above the range mentioned above.

After depositing the blanket graphene layer on the treated substrate, the blanket graphene layer can then be chemically doped with a one-electron oxidant using a solution doping process such that one electron is transferred from the blanket graphene layer to the single-electron every molecule of the oxidant. In one embodiment of the present disclosure, the one-electron oxidizing agent that can be employed is an organic one-electron oxidizing agent such as, for example, an antimony compound, such as trialkyloxonium hexachloroantimonate, antimony pentachloride, Nitrosonium ion salts (such as triethyloxonium tetrafluoroborate), tris(pentafluorophenyl)borane, and nitrosonium cations. In one embodiment, triethyloxonium hexachloroantimonate (C ₂ H ₅ ) ₃ O+SbCl ₆ can be used as a one-electron oxidant for doping blanket graphene layers.

In addition to organic one-electron oxidizing agents, the present disclosure can also utilize other one-electron oxidizing agents including, for example, metal-organic complexes, π-electron acceptors, and silver salts. Examples of organometallic complexes include, but are not limited to, tris(2,2'-bipyridyl)cobalt(III) and tris(2,2'-bipyridyl)ruthenium(II). Examples of π electron acceptors include, but are not limited to, tetracyanoquinodimethane, benzoquinone, tetrachlorobenzoquinone, tetrafluorobenzoquinone, tetracyanoethylene, tetrafluoro-tetracyanoquinodimethane, chloranil, tetrabromoquinone p-benzoquinone (tromanil) and dichlorodicyanoquinone. Examples of silver salts include, but are not limited to, silver fluoride and silver trifluoroacetate.

The solution doping process that can be employed in the present disclosure is performed with the one-electron oxidizing agent dissolved in a solvent. Suitable solvents include, for example, dichloromethane, dichloroethane, acetonitrile, chloroform, and mixtures thereof. For organometallic dopants, common organic solvents such as acetonitrile, tetrahydrofuran and aromatic hydrocarbons, and chlorinated solvents such as dichloromethane and chloroform are suitable. For inorganic salts such as silver fluoride, alcohol or a mixture of alcohol and water can be used.

In one embodiment of the present disclosure, the solution doping process is performed at a temperature of 10° C. to 100° C., and the concentration of the one-electron oxidant in the doping solution may be 1 mM to 20 mM. In other embodiments, the temperature may be from 30°C to 100°C, and in still other embodiments, the temperature may be from 70°C to 100°C.

The doped graphene layer 12 is stable under ambient conditions. Any excess one-electron oxidant on the doped graphene layer 12 can be removed by rinsing the doped graphene layer 12 in the same or a different solvent than that used in the solution doping process. After rinsing, the doped graphene layer 12 may be dried under vacuum.

As mentioned above, the doped graphene layer 12 has an improved work function relative to the same graphene layer before doping. In one embodiment of the present disclosure, the doped graphene layer 12 has a work function greater than 4.5 eV to 5.2 eV. In another embodiment, the doped graphene layer 12 has a work function greater than 4.7 eV to 5.0 eV.

According to the present disclosure, the doped graphene layer 12 is a p-doped graphene layer. In some embodiments of the present disclosure, doped graphene layer 12 has a sheet resistance of less than 250 ohms/square. In other embodiments of the present disclosure, the doped graphene layer 12 has a sheet resistance of 60 ohms/square to 150 ohms/square.

In some embodiments of the present disclosure, doped graphene layer 12 may comprise 1E11 atoms/cm ² to 5E13 atoms/cm ² of one-electron oxidizers. In other embodiments of the present disclosure, the doped graphene layer 12 may comprise 1E11 atoms/cm ² to 5E13 atoms/cm ² of one-electron oxidizers.

After subjecting the blanket graphene layer to the aforementioned solution doping process, the doped graphene layer 12 is transferred to the substrate 10 using a bonding process. Bonding can be achieved at room temperature, up to about 300°C. After bonding, the handle substrate can be removed by etching, planarizing or grinding.

Although the illustrated embodiment discloses that the blanket graphene layer is doped prior to being transferred to the substrate 10, first transferring the undoped blanket graphene layer onto the substrate 10 and then doping the transferred The present disclosure also works when the graphene layer is subjected to the aforementioned solution doping process. In the present disclosure, it is also possible to dope the blanket graphene layer with a one-electron oxidant before and after the transfer process.

Referring now to FIG. 3 , there is illustrated the structure of FIG. 2 after forming interface material layer 14 on the exposed surface of doped graphene layer 12 . In some embodiments of the present disclosure, interface material layer 14 is omitted. When the interface material layer 14 is used, the interface material layer can further reduce the energy barrier between the electroluminescent material to be formed subsequently and the doped graphene layer 12 . The interfacial material layer 14 may be referred to herein as a work function modifying material layer.

In one embodiment of the present disclosure, interface material layer 14 is a conductive polymer. In another embodiment of the present disclosure, the interface material layer 14 is a metal oxide. In yet another embodiment of the present disclosure, a stack of conductive polymers and/or metal oxides may be used to provide a multilayer interface structure.

When a conductive polymer is used as the interface material layer 14, the conductive polymer (which may be referred to as an intrinsically conductive polymer) includes a conductive organic polymer.

Examples of conductive polymers that may be used as interface material layer 14 in the present disclosure include, for example, aromatic compounds that do not contain heterocyclic atoms, aromatic compounds that contain nitrogen heterocyclic atoms, aromatic compounds that contain sulfur heterocyclic atoms, aromatic compounds that contain Polymeric compounds with double bonds and/or aromatic compounds which also contain double bonds. In some embodiments of the present disclosure, conductive polymers that can be used in the present disclosure as interface material layer 14 are selected from polyaniline and poly(3,4-ethylenedioxythiophene) poly(styrenesulfonic acid) Or abbreviated as PEDOT:PSS.

The conductive polymer may be formed on the doped graphene layer 12 using any known deposition process, including, for example, evaporation, chemical solution deposition, spin coating, or dip coating.

When a metal oxide is used as the interface material layer 14, the metal oxide includes elemental metals selected from Group IIIB, IVB, VB, VIB, VIIB, VIII or IIIA of the periodic table of elements. Illustrative examples of metal oxides that can be used as interface material layer 14 in the present disclosure include, but are not limited to, MoO ₃ , WO ₃ , V ₂ O ₅ , and Al ₂ O ₃ .

The metal oxide may be formed on the doped graphene layer 12 using any known deposition process, including, for example, evaporation, chemical solution deposition, chemical vapor deposition, and sputtering.

In one embodiment of the present disclosure, the interface material layer 14 may have a thickness of 1 nm-70 nm. In another embodiment, the interface material layer 14 may have a thickness of 15nm-55nm. The interface material layer 14 may have other thicknesses above and/or below the above ranges.

In some embodiments, interface material layer 14 may comprise a single layer structure. In another embodiment, the interface material layer 14 may include a multi-layer structure. When the interface material layer 14 is a multilayer structure, the multilayer structure may include any combination of conductive polymers and/or metal oxides.

Referring to FIGS. 4A-4B , the structures of FIGS. 2 and 3 are illustrated, respectively, after formation of the electroluminescent material layer 16 . In particular, FIG. 4A illustrates the structure of FIG. 2 after forming a layer 16 of electroluminescent material directly on the exposed surface of the doped graphene layer 12 . FIG. 4B illustrates the structure of FIG. 3 after forming the electroluminescent material layer 16 directly on the exposed surface of the interface material layer 14 .

Electroluminescent material layer 16 employed in the present disclosure includes any organic material or multilayer stack of organic materials that emit light in response to an electrical current, including, for example, organometallic chelates, conductive polymers, fluorescent dyes, Phosphorescent dyes and conjugated dendrimers. Examples of organic materials that can be used as the organic electroluminescent material 16 include, but are not limited to, poly-p-phenylene vinylene (PPV), polynaphthalene acetylene (PNV), tris(2-phenylpyridine) iridium (Ir(ppy) ₃ ), and Tris(8-quinolinolato)aluminum (Alq ₃ ).

Layer 16 of electroluminescent material may be formed by conventional techniques including, for example, spin coating, dip coating, immersion, and chemical vapor deposition. Typically, and in one embodiment, the organic electroluminescent material 16 has a thickness ranging from a few nm to hundreds of nm. Other thicknesses, including thicknesses above and/or below the foregoing ranges, may also be employed.

Referring now to FIGS. 5A-5B , the structures of FIGS. 4A and 4B are illustrated, respectively, after formation of the cathode material layer 18 . Cathode material layer 18 may serve as the top electrode of the OLED of the present disclosure. Specifically, FIGS. 5A and 5B illustrate the structure of FIGS. 4A and 4B , respectively, after forming a cathode material layer 18 on the exposed surface of the electroluminescent layer 16 .

Cathode material layer 18 that can be employed in the present disclosure includes a material or multilayer stack of materials that has a lower work function compared to doped graphene transparent conductive electrode 12 . In one embodiment of the present disclosure, the cathode material layer 18 may be composed of aluminum (Al), calcium (Ca), and/or magnesium (Mg). In some embodiments, the layer of cathode material may include a stack of LiF and Al.

Cathode material layer 18 may be formed using any deposition process including, for example, thermal evaporation and sputtering. In some embodiments, the deposition process is performed through a shadow mask. Typically, the cathode material layer 18 has a thickness ranging from 20 nm to 100 nm in one embodiment. Other thicknesses, including thicknesses above and/or below the foregoing ranges, may also be employed.

The transparent conductive electrodes of the present disclosure including p-doped graphene layers are less toxic than conventional ITO transparent conductive electrodes. Furthermore, transparent conducting electrodes composed of p-doped graphene layers are cheaper to fabricate than their ITO counterparts. Furthermore, transparent conducting electrodes made of p-doped graphene layers are extremely flexible and thus can be used in various display and lighting applications. Furthermore, transparent conductive electrodes composed of p-doped graphene layers have higher mechanical strength compared to their ITO counterparts. Furthermore, the transparent conducting electrodes made of p-doped graphene layers are chemically stable. By "chemically stable" is meant that the chemically doped graphene is able to withstand processing steps involving strong acids, bases and/or solvents and maintain its structural integrity.

When used as a component of an OLED device, a transparent conductive electrode composed of a p-doped graphene layer can provide an OLED device with equal or slightly higher conduction than OLED devices containing conventional ITO electrodes. Voltage. In some cases, transparent conductive electrodes composed of p-doped graphene layers can provide OLED devices with zero increase in turn-on voltage compared to OLED devices comprising conventional ITO electrodes.

Furthermore, transparent conductive electrodes composed of p-doped graphene layers can provide OLED devices with higher quantum efficiencies compared to OLED devices comprising conventional ITO electrodes. In some cases, transparent conductive electrodes composed of p-doped graphene layers can provide OLED devices with a few percent increase in quantum efficiency compared to OLED devices comprising conventional ITO electrodes. The external quantum efficiency is greater than 20% without any out-coupling scheme.

Similar results to those mentioned above for p-doped graphene layers can be obtained using doped carbon nanotube layers as transparent conducting electrodes for OLED devices.

While the present disclosure has been particularly shown and described with respect to preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing and other changes in form and details may be made without departing from the spirit and scope of the present disclosure. . It is therefore intended that the disclosure not be limited to the exact forms and details described and illustrated, but fall within the scope of the appended claims.

Claims (50)

1. a transparency conductive electrode, comprising:

Graphene layer doped with one-electron oxidation agent.

2. transparency conductive electrode according to claim 1, wherein said graphene layer is p doping.

3. transparency conductive electrode according to claim 1, wherein said one-electron oxidation agent is selected from trialkyl oxygen hexa chloro-antimonate, Antimony pentachloride, nitrous ion salt, triethyl group oxygen tetrafluoroborate, three (pentafluorophenyl group) boron and nitrous cation.

4. transparency conductive electrode according to claim 1, wherein said one-electron oxidation agent is trialkyl oxygen hexa chloro-antimonate.

5. transparency conductive electrode according to claim 1, wherein the described graphene layer doped with described one-electron oxidation agent has the sheet resistance that is less than 250 ohm-sq.

6. transparency conductive electrode according to claim 1, wherein has the work function value of the Graphene that is greater than non-doping doped with the described Graphene of described one-electron oxidation agent.

7. transparency conductive electrode according to claim 6, wherein the described work function value doped with the described Graphene of described one-electron oxidation agent is being greater than 4.5eV in the scope of 5.2eV.

8. transparency conductive electrode according to claim 1, wherein said one-electron oxidation agent is with 1E11 atom/cm ²to 5E13 atom/cm ²amount be present in described graphene layer.

9. transparency conductive electrode according to claim 1, wherein the described graphene layer doped with described one-electron oxidation agent is single-layer graphene.

10. Organic Light Emitting Diode (OLED) device, comprising:

Substrate;

Be positioned at the graphene layer of the doping on the exposed surface of described substrate;

Be positioned at the electroluminescent material layer of the graphene layer top of described doping;

Be positioned at the cathode material layer on the exposed surface of described electroluminescent material layer.

11. OLED devices according to claim 10, wherein said substrate is transparent and consists of glass or plastics.

12. OLED devices according to claim 10, wherein carry out p doping with one-electron oxidation agent to the graphene layer of described doping.

13. OLED devices according to claim 12, wherein said one-electron oxidation agent is selected from trialkyl oxygen hexa chloro-antimonate, Antimony pentachloride, nitrous ion salt, triethyl group oxygen tetrafluoroborate, three (pentafluorophenyl group) boron and nitrous cation.

14. OLED devices according to claim 12, wherein said one-electron oxidation agent is trialkyl oxygen hexa chloro-antimonate.

15. OLED devices according to claim 10, the graphene layer of wherein said doping has the sheet resistance that is less than 250 ohm-sq.

16. OLED devices according to claim 10, the graphene layer of wherein said doping has and is greater than 4.5eV to the work function value of 5.2eV.

17. OLED devices according to claim 12, the graphene layer of wherein said doping comprises 1E11 atom/cm ²to 5E13 atom/cm ²described one-electron oxidation agent.

18. OLED devices according to claim 10, also comprise: at the graphene layer of described doping and the boundary layer between described electroluminescent material layer.

19. OLED devices according to claim 18, wherein said boundary layer is conducting polymer.

20. OLED devices according to claim 18, wherein said boundary layer is metal oxide.

21. OLED devices according to claim 10, wherein said electroluminescent material layer is selected from p-phenylene vinylene (PPV), poly-naphthalene acetylene (PNV), three (2-phenylpyridine) iridium (Ir (ppy) 3) and three (oxine) aluminium (Alq3).

22. OLED devices according to claim 10, wherein said cathode material layer comprises aluminium (Al), calcium (Ca), magnesium (Mg) or its combination.

23. OLED devices according to claim 10, wherein said cathode material layer comprises the lamination of LiF and Al.

24. 1 kinds of Organic Light Emitting Diodes (OLED) device, comprising:

Substrate;

Be positioned at the carbon nano-tube of the doping on the exposed surface of described substrate;

Be positioned at the electroluminescent material layer of the carbon nano-tube top of described doping;

Be positioned at the cathode material layer on the exposed surface of described electroluminescent material layer.

25. OLED devices according to claim 24, also comprise: at the carbon nano-tube of described doping and the boundary layer between described electroluminescent material layer.

26. 1 kinds of methods that form transparency conductive electrode, comprising:

Blanket formula graphene layer is provided; And

With the one-electron oxidation agent described blanket formula graphene layer that adulterates.

27. methods according to claim 26, wherein said provide blanket formula graphene layer to be included in to process on substrate deposit Graphene.

28. methods according to claim 27, wherein said deposition Graphene comprises chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD) or the auxiliary CVD of ultraviolet (UV).

29. methods according to claim 27, but wherein said deposition is included in the plasma enhanced chemical vapor deposition (PECVD) being up at the temperature that is no more than 500 ℃.

30. methods according to claim 27 are wherein carried out described deposition at the temperature of 800 ℃ to 1080 ℃.

31. methods according to claim 26, the described one-electron oxidation agent doping of wherein said use blanket formula graphene layer comprises solute doping technique.

32. methods according to claim 31, wherein said one-electron oxidation agent is selected from trialkyl oxygen hexa chloro-antimonate, Antimony pentachloride, nitrous ion salt, triethyl group oxygen tetrafluoroborate, three (pentafluorophenyl group) boron and nitrous cation.

33. methods according to claim 31, wherein said one-electron oxidation agent is trialkyl oxygen hexa chloro-antimonate.

34. methods according to claim 26, wherein said doping provides the graphene layer of the p doping with the sheet resistance that is less than 250 ohm-sq.

35. methods according to claim 34, the graphene layer of wherein said p doping has and is greater than 4.5eV to the work function value of 5.2eV.

36. 1 kinds of methods that are formed with OLED (OLED) device, comprising:

Substrate is provided;

On the exposed surface of described substrate, form the graphene layer of doping;

Above the graphene layer of described doping, form electroluminescent material layer; And

On the exposed surface of described electroluminescent material layer, form cathode material layer.

37. methods according to claim 36, wherein saidly provide described substrate to comprise selection transparent material, and wherein said transparent material is glass or plastics.

38. methods according to claim 36, the graphene layer of wherein said formation doping is included in to process and on substrate, deposits Graphene and use the solution of one-electron oxidation agent to carry out solute doping processing to described Graphene.

39. according to the method described in claim 38, and wherein said deposition Graphene comprises chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD) or the auxiliary CVD of ultraviolet (UV).

40. according to the method described in claim 38, but wherein said deposition is included in the plasma enhanced chemical vapor deposition (PECVD) being up at the temperature that is no more than 500 ℃.

41. according to the method described in claim 38, wherein at the temperature of 800 ℃ to 1080 ℃, carries out described deposition.

42. according to the method described in claim 38, and wherein said one-electron oxidation agent is selected from trialkyl oxygen hexa chloro-antimonate, Antimony pentachloride, nitrous ion salt, triethyl group oxygen tetrafluoroborate, three (pentafluorophenyl group) boron and nitrous cation.

43. according to the method described in claim 38, and wherein said one-electron oxidation agent is trialkyl oxygen hexa chloro-antimonate.

44. methods according to claim 36, also comprise: before forming described electroluminescent material layer, on the exposed surface of the graphene layer of described doping, form boundary layer.

45. according to the method described in claim 44, and wherein said boundary layer is conducting polymer.

46. according to the method described in claim 44, and wherein said boundary layer is metal oxide.

47. methods according to claim 36, wherein form described electroluminescent material layer and comprise deposition p-phenylene vinylene (PPV), poly-naphthalene acetylene (PNV), three (2-phenylpyridine) iridium (Ir (ppy) ₃) and three (oxine) aluminium (Alq ₃) in one.

48. methods according to claim 36, the described cathode material layer of wherein said formation comprises that one in deposition of aluminum (Al), calcium (Ca) and magnesium (Mg) is as electrode material.

49. 1 kinds of methods that are formed with OLED (OLED) device, comprising:

Substrate is provided;

On the exposed surface of described substrate, form the carbon nano-tube of doping;

Above the carbon nano-tube of described doping, form electroluminescent material layer; And

On the exposed surface of described electroluminescent material layer, form cathode material layer.

50. according to the method described in claim 49, also comprises: before forming described electroluminescent material layer, on the exposed surface of the carbon nano-tube of described doping, form boundary layer.

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