CN103682152A - Transparent conductive electrode and forming method therefor, organic light emitting diode (OLED) device and forming method therefor - Google Patents
Transparent conductive electrode and forming method therefor, organic light emitting diode (OLED) device and forming method therefor Download PDFInfo
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- CN103682152A CN103682152A CN201310439839.0A CN201310439839A CN103682152A CN 103682152 A CN103682152 A CN 103682152A CN 201310439839 A CN201310439839 A CN 201310439839A CN 103682152 A CN103682152 A CN 103682152A
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- H10K2102/301—Details of OLEDs
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- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/17—Carrier injection layers
Abstract
The invention relates to a transparent conductive electrode and a forming method therefor, an organic light emitting diode (OLED) device and a forming method therefor. Graphene is used as a replacement for indium tin oxide as a transparent conductive electrode which can be used in an organic light emitting diode (OLED) device. Using graphene reduces the cost of manufacturing OLED devices and also makes the OLED device extremely flexible. The graphene is chemically doped so that the work function of the graphene is shifted to a higher value for better hole injection into the OLED device as compared to an OLED device containing an undoped layer of graphene. An interfacial layer comprising a conductive polymer and/or metal oxide can also be used to further reduce the remaining injection barrier.
Description
Technical field
The disclosure relates to transparency conductive electrode and forming method thereof.More specifically, the disclosure relate to doping Graphene transparency conductive electrode, comprise this doping Graphene transparency conductive electrode Organic Light Emitting Diode (OLED) device and form this doping Graphene transparency conductive electrode and described in comprise this doping the method for OLED device of Graphene transparency conductive electrode.
Background technology
Organic light emitting diode device technology occurs as the leader's technology for display and illumination.The key advantage that OLED display has comprises distinct color, high-contrast, wide visual angle, and OLED display is compared more pliable and tougher (flexible) with conventional liquid crystal (LCD).In addition, OLED light ratio incandescent lamp bulb is more efficient and have and the similar efficiency of light-emitting diode (LED) based on nitride.
Typical OLED comprises the substrate of conventionally being made by glass or similar transparent material.Anode layer is positioned on substrate.Anode layer can be made and is substantially transparent for visible ray by the material with relative high work function.Typical material for anode layer is indium tin oxide (ITO).Electroluminescent material layer is positioned on anode layer, as the emission layer of organic OLED.The common materials that is used to form emission layer is such as for example p-phenylene vinylene (PPV) and the molecule as three (oxine) aluminium (Alq3).The in the situation that of molecule, emission layer typically comprises some layers of molecule.The cathode layer with the material (as aluminium (Al), calcium (Ca) or magnesium (Mg)) compared with low work function is positioned on emission layer.In the operating period of OLED, cathode layer and anode layer are connected to power supply.
The basic principle of electroluminescent basic principle and therefore OLED is as follows: anode layer and cathode layer are to iunjected charge charge carrier, i.e. electronics and hole in emission layer.In emission layer, electric charge carrier is transported and the electric charge carrier of opposite charge forms so-called exciton, i.e. excited state.Exciton by producing light radiative decay to ground state.Then the light that produced is launched by the anode layer of being made by the transparent material of for example ITO by OLED.The color of the light producing depends on the material for organic emission layer.
Summary of the invention
In the disclosure, use Graphene to replace indium tin oxide as the transparency conductive electrode that can use in OLED device.Using Graphene to reduce manufactures the cost of OLED device and also makes OLED device extremely pliable and tough.The Graphene using in the disclosure is chemical doping, makes the work function of Graphene be displaced to higher value, compares with the OLED device that comprises unadulterated graphene layer, and hole is injected in OLED device better.The boundary layer that comprises conducting polymer and/or metal oxide also can be used for further reducing residue injection barrier.
In aspect one of the present disclosure, provide the transparency conductive electrode that can be used as the electrode of OLED.Described transparency conductive electrode of the present disclosure comprises the graphene layer doped with one-electron oxidation agent.
In another aspect of the present disclosure, a kind of OLED device is provided, this OLED device comprises: substrate; Be positioned at the graphene layer of the doping on the exposed surface of described substrate; Be positioned at the optional boundary layer on the exposed surface of graphene layer of described doping; Be positioned at the electroluminescent material layer of the graphene layer top of described doping; And be positioned at the cathode material layer on the exposed surface of described electroluminescent material layer.
Of the present disclosure aspect another in, a kind of method that forms transparency conductive electrode is provided.The method of this formation transparency conductive electrode comprises: blanket formula (blanket) graphene layer is provided; And with the one-electron oxidation agent described blanket formula graphene layer that adulterates.
Of the present disclosure aspect another in, the method for the OLED device of the Graphene transparency conductive electrode that a kind of formation comprises doping is provided.The method comprises: substrate is provided; On the exposed surface of described substrate, form the graphene layer of doping; On the exposed surface of the graphene layer of described doping, form optional boundary layer; Above the graphene layer of described doping, form electroluminescent material layer; And form cathode material layer on the exposed surface of described electroluminescent material layer.
Accompanying drawing explanation
Fig. 1 is that (passing through viewgraph of cross-section) exemplify can be according to the diagram of the substrate using in an embodiment of the present disclosure.
Fig. 2 is the diagram that (passing through viewgraph of cross-section) exemplifies on the exposed surface of substrate the structure of the Fig. 1 after the graphene layer that forms doping.
Fig. 3 is the diagram that (passing through viewgraph of cross-section) exemplifies the structure of the Fig. 2 form boundary material layer on the exposed surface of the graphene layer adulterating after.
Fig. 4 A is the diagram that (passing through viewgraph of cross-section) exemplifies the structure of the Fig. 2 form electroluminescent material layer on the exposed surface of the graphene layer adulterating after.
Fig. 4 B is the diagram that (passing through viewgraph of cross-section) exemplifies the structure of the Fig. 3 form electroluminescent material layer on the exposed surface of boundary material layer after.
Fig. 5 A is the diagram that (passing through viewgraph of cross-section) exemplifies the structure of Fig. 4 A form cathode material layer on the exposed surface of electroluminescent material layer after.
Fig. 5 B is the diagram that (passing through viewgraph of cross-section) exemplifies the structure of Fig. 4 B form cathode material layer on the exposed surface of electroluminescent material layer after.
Embodiment
Accompanying drawing referring now to following discussion and the application is described the disclosure in more detail, the method for the OLED device of the OLED device of the Graphene transparency conductive electrode that the disclosure provides the Graphene transparency conductive electrode of doping and comprised this doping and the Graphene transparency conductive electrode that is used to form the Graphene transparency conductive electrode of described doping and comprises described doping.
Note, the application's accompanying drawing only for the object of example provides, so their not drawn on scale.In accompanying drawing and description below, similar material refers to similar Reference numeral.For following description, word " on ", D score, " right side ", " left side ", " vertically ", " level ", " top ", " bottom " and derivative thereof should relate to parts, layer and/or the material being orientated in the application's accompanying drawing.
In the following description, set forth a large amount of specific detail, for example concrete structure, parts, material, size, treatment step and technology, understand of the present disclosure thoroughly to provide.Yet, it will be appreciated by the skilled addressee that the disclosure can not implement with feasible alternative process option in the situation that there is no these specific detail.In other cases, do not describe known structure or treatment step in detail, in order to avoid make various embodiment of the present disclosure smudgy.
In current OLED display and lighting technology, indium tin oxide transparency conductive electrode is used as to anode.This OLED structure has following shortcoming.The transparency conductive electrode that comprises indium tin oxide comprises rare earth metal indium, and indium is expensive material, has therefore increased the cost of manufacturing the OLED device that comprises indium tin oxide.The OLED device that comprises indium tin oxide is easily out of order and is therefore unsuitable for flexible application after bending.In addition, indium tin oxide is poisonous, therefore need to be for the candidate materials of transparency conductive electrode.
In the disclosure, by the electrode that comprises Graphene is provided, avoided the relevant shortcoming of above mentioned and conventional indium tin oxide transparency conductive electrode, the described electrode that comprises Graphene is by chemical doping, make the workfunction shift of this electrode that comprises Graphene to higher value, to compare with the OLED device that is equal to that comprises unadulterated graphene layer, hole is injected in OLED device better.The boundary layer that comprises conducting polymer and/or metal oxide also can be used for further reducing residue injection barrier.
Although following description example the parts of transparency conductive electrode of the present disclosure as OLED device, transparency conductive electrode of the present disclosure is not limited to only for this device.Alternatively, transparency conductive electrode of the present disclosure can the device for other types in, such as for example for photovoltaic device, solar battery cell (solar cell), flat-panel monitor or touch-screen.
In addition,, although in the situation that transparency conductive electrode of the present disclosure has been described OLED device as the bottom electrode of OLED device, the disclosure is not limited to only this OLED device.Alternatively, can manufacture such OLED device: wherein transparency conductive electrode of the present disclosure is the top electrodes of this OLED device.In this case, bottom electrode will be included in one of cathode material of mentioning herein below.
In addition the graphene layer that, OLED device of the present disclosure can comprise the carbon nano-tube alternative dopings that p adulterates is as transparency conductive electrode.In such an embodiment, manufacture as follows the carbon nano-tube of p doping: first utilize any routine techniques carbon nano-tube well known by persons skilled in the art; Also the liquid deposition technique the following describes in this article with one of one-electron oxidation agent of mentioning below herein, utilization afterwards, the described carbon nano-tube of adulterating.In such an embodiment, compare with doped carbon nanometer pipe not, the work function of the carbon nano-tube of p doping improves, and the work function of the carbon nano-tube of p doping is in the substantially the same scope of the Fermi level with electroluminescent material.
With reference to figure 1, example the substrate 10 that can use in an embodiment of the present disclosure.The substrate 10 that can use in the disclosure can be rigidity or flexible, and can comprise for example semi-conducting material, glass, pottery, band or plastics.Typically, the substrate 10 adopting in the disclosure is transparent substrates.In an embodiment of the present disclosure, substrate 10 is transparent and consists of glass.In another embodiment of the present disclosure, substrate 10 is transparent and consists of plastics.The substrate 10 adopting in the disclosure can have the thickness from hundreds of microns to several millimeters.In another embodiment, the substrate 10 adopting can have the thickness from tens of microns to several millimeters.Substrate 10 can have other above and/or following thickness of above-mentioned scope.
With reference to figure 2, example on the exposed surface of substrate 10, form the substrate 10 after the graphene layer 12 of doping.In certain embodiments, and as shown in figure of the present disclosure, the graphene layer 12 of doping is as the bottom transparency conductive electrode of OLED device.In other embodiments, the graphene layer 12 of doping can be as the top transparent conductive electrode of OLED device.In another embodiment of the present disclosure, the graphene layer 12 of doping can be used as the transparency conductive electrode of the device of other type, and the device of described other type is such as being for example photovoltaic device, solar battery cell, flat-panel monitor or touch panel device.
The graphene layer 12 of the doping adopting in the disclosure comprises such Graphene: the work function of this Graphene improves, and with the OLED device with comprising unadulterated Graphene, compares, and hole is injected in OLED device better.Particularly, unadulterated Graphene has the work function of about 4.5eV.As described herein the doping of Graphene is brought up to the work function of Graphene from being greater than 4.5eV to the scope of 5.2eV.The work function of the raising of the graphene layer of doping is mated with the Fermi level " substantially " that subsequently graphene layer in this doping is pushed up to the electroluminescent material layer forming.The meaning of " substantially coupling " is that the work function of graphene layer of doping and the difference of the Fermi level of electroluminescent material layer are in being less than the scope of 0.7eV.Therefore, compare with unadulterated graphene layer, the graphene layer adulterating by employing, provides the better injection of hole to electroluminescent material layer.
In the disclosure, can process the graphene layer 12 that doping is provided on substrate (handle substrate) by first the graphene layer of the non-doping of blanket formula being deposited on.Described processing substrate is typically by forming by the catalytic graphite alkene material forming in its surface.For example, in embodiment more of the present disclosure, described processing substrate can comprise copper or Copper Foil.
Can utilize and well known to a person skilled in the art that any depositing operation forms described processing substrate.For example, can, by chemical vapour deposition (CVD), plasma enhanced chemical vapor deposition, physical vapour deposition (PVD), sputter, plating (plating), chemical solution deposition or electroless plating, form the processing substrate being formed by copper.Typically, by forming Copper Foil from cupric palladium sputtered copper foil.
In one embodiment, described processing substrate has 7 μ m to the thickness of 25 μ m.In another embodiment, described processing substrate has 20 μ m to the thickness of 30 μ m.In the disclosure, also can adopt more than above-mentioned thickness range and/or below other thickness of processing substrate.
After selecting to process substrate, the graphene layer (not shown) of the non-doping of deposition blanket formula.Run through the plane lamina (sheet) of an atom thick that the word " Graphene " that uses in the disclosure represents the carbon atom of the sp2 bonding of dense packing in honeycomb lattice.The Graphene adopting in the disclosure has two dimension (2D) hex crystal and learns bonding structure.
The blanket formula graphene layer that can use in the disclosure is so continuous graphene layer: it can be by single-layer graphene (nominal 0.34nm be thick); Minority layer (few-layer) Graphene (2-10 graphene layer); Multilayer (multi-layer) Graphene (>10 graphene layer); The mixture of individual layer, minority layer and multi-layer graphene; Or constitute by forming at the lower Graphene of lower temperature (200 ℃ to 900 ℃) any of the graphene layer that is mixed with carbon phase amorphous and/or unordered who obtains.Typically, in the disclosure, use single-layer graphene.
Described blanket formula graphene layer can utilize the depositing operation such as the auxiliary CVD of for example chemical vapor deposition (CVD), plasma enhanced chemical vapor deposition (PECVD) and ultraviolet (UV) to form.In one embodiment, by CVD, form described blanket formula graphene layer.The depositing operation that in certain embodiments, can be used to form blanket formula graphene layer in the disclosure starts on the exposed surface of processing substrate.
In one embodiment, for PECVD, but can be up at the temperature that is no more than 500 ℃, carry out the deposition of the blanket formula graphene layer on the exposed surface of processing substrate.In another embodiment, the deposition of Graphene (that is, growth) occurs at the temperature of 800 ℃ to 1080 ℃.The depositing operation that can be used to form blanket formula graphene layer in the disclosure comprises and utilizes any known carbon source, described known carbon source to comprise for example benzene, propane, ethane and other hydrocarbon and other carbonaceous gas.
In an embodiment of the present disclosure, blanket formula graphene layer can have the thickness of 0.34nm-0.8nm.In another embodiment of the present disclosure, blanket formula graphene layer can have the thickness of 0.7nm-3.4nm.Blanket formula graphene layer can have other more than above-mentioned scope thickness.
Deposit blanket formula graphene layer on processing substrate after, then can utilize solute doping technique, with one-electron oxidation agent, described blanket formula graphene layer is carried out to chemical doping, make an electronics from blanket formula graphene layer, transfer to each molecule of one-electron oxidation agent.In an embodiment of the present disclosure, the one-electron oxidation agent that can adopt is organic one-electron oxidation agent, this organic one-electron oxidation agent is such as being for example, antimonial, for example trialkyl oxygen hexa chloro-antimonate, Antimony pentachloride, nitrous ion salt (for example triethyl group oxygen tetrafluoroborate), three (pentafluorophenyl group) borines and nitrous cation.In one embodiment, triethyl group oxygen hexa chloro-antimonate (C
2h
5)
3o+SbCl
6can be with the one-electron oxidation agent that acts on doping blanket formula graphene layer.
Except organic one-electron oxidation agent, the disclosure can also be utilized other one-electron oxidation agent, and described other one-electron oxidation agent comprises for example metallo-organic complex, pi-electron acceptor and silver salt.The example of metallo-organic complex includes but not limited to three (2,2'-bipyridine) cobalts (III) and three (2,2'-bipyridine) rutheniums (II).The example of pi-electron acceptor includes but not limited to four cyano quinone bismethane, benzoquinones, tetrachloroquinone, tetrafluoro benzoquinones, tetracyanoethylene, tetrafluoro-four cyano quinone bismethane, chloranil, tetrabromoquinone (tromanil) and dichlorodicyanobenzoquinone.The example of silver salt includes but not limited to silver fluoride and trifluoroacetic acid silver.
The solute doping technique that can adopt in the disclosure is carried out in one-electron oxidation agent is dissolved in solvent in the situation that.Suitable solvent comprises for example carrene, dichloroethanes, acetonitrile, chloroform and composition thereof.For organic metal dopant, such as the common organic solvent of acetonitrile, oxolane and aromatic hydrocarbon and be suitable such as the chlorinated solvent of carrene and chloroform.For the inorganic salts such as silver fluoride, can adopt the mixture of alcohol or alcohol and water.
In an embodiment of the present disclosure, at the temperature of 10 ℃ to 100 ℃, carry out solute doping technique, and the concentration of one-electron oxidation agent in doped solution can be for 1mM be to 20mM.In other embodiments, described temperature can be 30 ℃ to 100 ℃, and in other other embodiment, described temperature can be 70 ℃ to 100 ℃.
The graphene layer 12 of doping is stable under environmental condition.Can by with solute doping technique in the graphene layer 12 of rinsing doping in the identical or different solvent that uses, remove any excessive one-electron oxidation agent on the graphene layer 12 of doping.After rinsing, can under vacuum, to the graphene layer 12 of doping, be dried.
As mentioned above, the graphene layer 12 of doping has the work function improving with respect to the identical graphene layer before doping.In an embodiment of the present disclosure, the graphene layer 12 of doping has and is greater than 4.5eV to the work function of 5.2eV.In another embodiment, the graphene layer 12 of doping has and is greater than 4.7eV to the work function of 5.0eV.
According to the disclosure, the graphene layer 12 of doping is the graphene layer of p doping.In embodiment more of the present disclosure, the graphene layer 12 of doping has the sheet resistance that is less than 250 ohm-sq.In other embodiment of the present disclosure, the graphene layer 12 of doping has 60 ohm-sq to the sheet resistance of 150 ohm-sq.
In embodiment more of the present disclosure, the graphene layer 12 of doping can comprise 1E11 atom/cm
2to 5E13 atom/cm
2one-electron oxidation agent.In other embodiment of the present disclosure, the graphene layer 12 of doping can comprise 1E11 atom/cm
2to 5E13 atom/cm
2one-electron oxidation agent.
Make blanket formula graphene layer stand after aforementioned solute doping processes, to utilize joint technology that the graphene layer of doping 12 is transferred to substrate 10.Can be at room temperature, at the highest approximately 300 ℃, realize and engaging.After engaging, can remove processing substrate by etching, complanation or grinding.
Although exemplified embodiment disclosed before transferring to substrate 10 blanket formula graphene layer has been adulterated, but first unadulterated blanket formula graphene layer is being transferred on substrate 10 and while then shifted graphene layer being carried out to aforementioned solute doping technique, the disclosure also works.In the disclosure, can also be before transfer process and afterwards with one-electron oxidation agent doping blanket formula graphene layer.
With reference now to Fig. 3,, example the structure of Fig. 2 form boundary material layer 14 on the exposed surface of graphene layer 12 of doping after.In embodiment more of the present disclosure, omit boundary material layer 14.When adopting boundary material layer 14, boundary material layer can further reduce the electroluminescent material that will form subsequently and the energy barrier between the graphene layer 12 of doping.Boundary material layer 14 can be called as work function modification material layer herein.
In an embodiment of the present disclosure, boundary material layer 14 is conducting polymers.In another embodiment of the present disclosure, boundary material layer 14 is metal oxides.In another embodiment of the present disclosure, the lamination of conducting polymer and/or metal oxide can be for providing multilayer interfacial structure.
When conducting polymer is used as to boundary material layer 14, conducting polymer (it can be called intrinsic conducting polymer) comprises the organic polymer of conduction.
The example that can be used as the conducting polymer of boundary material layer 14 in the disclosure for example comprises: do not comprise the aromatic compounds of heteroatom, the aromatic compounds that comprises azacyclo-atom, the aromatic compounds that comprises thia annular atoms, wrap double bond containing polymerizable compound and/or also wrap double bond containing aromatic compounds.In embodiment more of the present disclosure, the conducting polymer that can be used as boundary material layer 14 in the disclosure is selected from polyaniline and poly-(3,4-ethylidene dioxy base thiophene) poly-(styrene sulfonic acid) or is abbreviated as PEDOT:PSS.
Can utilize any known depositing operation conducting polymer to be formed on the graphene layer 12 of doping, described depositing operation comprises for example evaporation, chemical solution deposition, spin coating or dip coated.
When adopting metal oxide as boundary material layer 14, metal oxide comprises the metal element of IIIB, the IVB, VB, VIB, VIIB, VIII or the IIIA family that are selected from the periodic table of elements.The illustrative example that can be used as the metal oxide of boundary material layer 14 in the disclosure includes but not limited to MoO
3, WO
3, V
2o
5and Al
2o
3.
Can utilize any known depositing operation metal oxide to be formed on the graphene layer 12 of doping, described depositing operation comprises for example evaporation, chemical solution deposition, chemical vapour deposition (CVD) and sputter.
In an embodiment of the present disclosure, boundary material layer 14 can have the thickness of 1nm-70nm.In another embodiment, boundary material layer 14 can have the thickness of 15nm-55nm.Boundary material layer 14 can have other above and/or following thickness of above-mentioned scope.
In certain embodiments, boundary material layer 14 can comprise single layer structure.In another embodiment, boundary material layer 14 can comprise sandwich construction.When boundary material layer 14 is sandwich construction, this sandwich construction can comprise any combination of conducting polymer and/or metal oxide.
With reference to figure 4A-4B, respectively example Fig. 2 after forming electroluminescent material layer 16 and the structure of Fig. 3.Particularly, Fig. 4 A example the structure of Fig. 2 after directly forming electroluminescent material layer 16 on the exposed surface of the graphene layer 12 of doping.Fig. 4 B example directly on the exposed surface of boundary material layer 14, form the structure of the Fig. 3 after electroluminescent material layer 16.
The electroluminescent material layer 16 adopting in the disclosure comprises the multilayer laminated of in response to electric current radiative any organic material or organic material, and described organic material comprises for example large molecule of organic metal chelate complex, conducting polymer, fluorescent dye, phosphorescent coloring and conjugated dendritic (conjugated dendrimer).The example that can be used as the organic material of electroluminescent organic material 16 includes but not limited to p-phenylene vinylene (PPV), poly-naphthalene acetylene (PNV), three (2-phenylpyridine) iridium (Ir (ppy)
3) and three (oxine) aluminium (Alq
3).
With reference now to Fig. 5 A-5B,, respectively example Fig. 4 A after forming cathode material layer 18 and the structure of Fig. 4 B.Cathode material layer 18 can be as the top electrode of OLED of the present disclosure.Particularly, Fig. 5 A and Fig. 5 B respectively example on the exposed surface of electroluminescence layer 16, form Fig. 4 A after cathode material layer 18 and the structure of Fig. 4 B.
The cathode material layer 18 that can adopt in the disclosure comprises having the multilayer laminated of the material of low work function or material of comparing with the Graphene transparency conductive electrode 12 of doping.In an embodiment of the present disclosure, cathode material layer 18 can consist of aluminium (Al), calcium (Ca) and/or magnesium (Mg).In certain embodiments, cathode material layer can comprise the lamination of LiF and Al.
It is lower that transparency conductive electrode of the present disclosure and the conventional ITO transparency conductive electrode that comprises the graphene layer of p doping compared toxicity.In addition the transparency conductive electrode that the graphene layer being adulterated by p, forms manufactures more cheap than their ITO homologue.In addition, the transparency conductive electrode that the graphene layer being adulterated by p forms is extremely pliable and tough, therefore can be used in various displays and illumination application.In addition the transparency conductive electrode that the graphene layer being adulterated by p, forms is compared and is had higher mechanical strength with their ITO counter electrode.In addition the transparency conductive electrode that the graphene layer being adulterated by p, forms is chemically stable.The meaning of " chemically stable " is that the Graphene of chemical doping can tolerate the treatment step that comprises strong acid, alkali and/or solvent, and keeps its structural intergrity.
When being used as the parts of OLED device, the transparency conductive electrode that the graphene layer being adulterated by p forms can provide such OLED device: this OLED device is compared and had identical or slightly high conducting voltage with the OLED device that comprises conventional ITO electrode.In some cases, the transparency conductive electrode that the graphene layer being adulterated by p forms can provide such OLED device: this OLED device is compared conducting voltage zero to be increased with the OLED device that comprises conventional ITO electrode.
In addition the transparency conductive electrode that the graphene layer being adulterated by p, forms can provide such OLED device: this OLED device is compared and had higher quantum efficiency with the OLED device that comprises conventional ITO electrode.In some cases, the transparency conductive electrode that the graphene layer being adulterated by p forms can provide such OLED device: this OLED device is compared the quantum efficiency increase with a few percent with the OLED device that comprises conventional ITO electrode.External quantum efficiency without any de-coupling scheme (out-coupling scheme) in the situation that is greater than 20%.
Use the carbon nanotube layer of doping as the transparency conductive electrode of OLED device, can obtain and the similar result of mentioning for the graphene layer of p doping above.
Although illustrate especially and described the disclosure about preferred embodiment of the present disclosure, it will be understood by those skilled in the art that in the situation that not departing from spirit and scope of the present disclosure, can make the variation in aforementioned and other form and details.Therefore, the disclosure be intended to be not limited to exact form and the details of description and example, but fall in the scope of 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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| US13/626,411 | 2012-09-25 | ||
| US13/626,411 US20140084252A1 (en) | 2012-09-25 | 2012-09-25 | Doped graphene transparent conductive electrode |
| US13/660,612 | 2012-10-25 | ||
| US13/660,612 US20140087501A1 (en) | 2012-09-25 | 2012-10-25 | Doped graphene transparent conductive electrode |
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