CN103824975A - Method for improving ITO layer hole injection efficiency and anode structure of display device - Google Patents
Method for improving ITO layer hole injection efficiency and anode structure of display device Download PDFInfo
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- CN103824975A CN103824975A CN201410070215.0A CN201410070215A CN103824975A CN 103824975 A CN103824975 A CN 103824975A CN 201410070215 A CN201410070215 A CN 201410070215A CN 103824975 A CN103824975 A CN 103824975A
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- 238000002347 injection Methods 0.000 title claims abstract description 42
- 239000007924 injection Substances 0.000 title claims abstract description 42
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/805—Electrodes
- H10K50/81—Anodes
- H10K50/816—Multilayers, e.g. transparent multilayers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/60—Forming conductive regions or layers, e.g. electrodes
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Abstract
The invention provides a method for improving ITO layer hole injection efficiency and an anode structure of a display device. The method is applied to the anode manufacturing technology of the display device, and includes the steps of providing a semi-conductor structure with a preset ITO region, manufacturing an ITO layer on the upper surface of the semi-conductor structure located in the ITO region, and manufacturing a graphene oxide film on the surface of the ITO layer after preheating the ITO layer. The anode structure comprises a substrate structure provided with the ITO layer, and a layer of graphene oxide covers the upper surface of the ITO layer. According to the method, a layer of the graphene oxide is manufactured on a common ITO layer to form a novel anode structure, so that a work function of the ITO layer is increased, hole injection efficiency is improved, drive voltage is reduced, stability of the display device can be improved, and the service life of the display device can be prolonged.
Description
Technical field
The present invention relates to a kind of display device structure and improvement in performance method thereof, relate in particular to a kind of method of the ITO of lifting layer hole injection efficiency and the anode construction of display device.
Background technology
(Indium tin oxide is called for short: ITO) due to its character quite stable, and conduct electricity very well, also have the feature of printing opacity, be therefore suitable for very much, as the anode conducting material in display device, being widely used in OLED tin indium oxide.
Because the work function of tin indium oxide only has 4.5eV～4.8eV left and right, lower than highest occupied molecular orbital (Highest occupied molecule orbital, the abbreviation: HOMO) can rank of most of hole mobile material.In addition, the decline of its work function, if any hydrocarbon pollution, can further be caused in ITO layer surface.
For addressing the above problem, the measure that industry generally adopts is at present by after ITO layer deposition, adopts O2 plasma or UV-ozone to process this ITO layer surface, and the work function on ITO layer surface is increased to only 5eV after treatment.But this numerical value still can the about 0.4eV in rank lower than the HOMO of the electric hole of major part transferring material.
Chinese patent (CN1781342A) discloses a kind of preparation method of the ITO film by nitrogen plasma treatment, comprises the step such as surface that uses nitrogen plasma treatment ITO film.
Although can improve to a certain extent the work function of ITO layer by the method for this patent, the amplitude improving is limited, and the HOMO that can not reach most of hole mobile material can rank.
Chinese patent (CN102167523B) discloses a kind of method of UV-irradiation modification ito glass substrate, comprises the following steps: 1) clean ito glass substrate, and ito glass substrate is faced up and is put in ultraviolet lamp, irradiate 1～30min; 2) according to volume ratio preparation OTS-toluene solution, the ito glass substrate having irradiated is put into configuration solution and soak 1s～40min, take out after acetone cleaning, dry; 3) ito glass substrate faces up to be again placed in ultraviolet light etc. and irradiates 1～50min, obtains the functionalization ito glass substrate of surperficial total hydrophilic.
The method that this patent is irradiated by ultraviolet ray improves the work function of ITO layer, and the degree of its raising is also very limited, and the HOMO that does not reach most of hole mobile material can rank.
Summary of the invention
In view of the above problems, the invention provides a kind of method of the ITO of lifting layer hole injection efficiency and the anode construction of display device.
The technical scheme that technical solution problem of the present invention adopts is:
Promote a method for ITO hole injection efficiency, be applied in the anode manufacture craft of display device, wherein, described method comprises:
One semiconductor structure that is preset with ITO region is provided;
Upper surface at the semiconductor structure that is positioned at described ITO region is prepared an ITO layer;
Described ITO layer is carried out, after preheating, preparing graphene oxide film in the surface of this ITO layer.
The method of described lifting ITO hole injection efficiency, wherein, forms described ITO layer by following steps:
Prepare the upper surface that one deck ito thin film covers described semiconductor structure;
Prepare the upper surface that photoresist covers described ito thin film;
To described photoresist expose, after developing process, ito thin film forms described ITO layer described in etching.
The method of described lifting ITO hole injection efficiency wherein, forms described ITO layer under gold-tinted environment.
The method of described lifting ITO hole injection efficiency, wherein, before the described graphene oxide film of preparation, cleans described ITO layer.
The method of described lifting ITO hole injection efficiency, wherein, adopts oxygen plasma body technology to clean described ITO layer.
The method of described lifting ITO hole injection efficiency, wherein, adopts UV-ozone process to clean described ITO layer.
The method of described lifting ITO hole injection efficiency, wherein, described graphene oxide is the composite construction layer of multiple single thin film compositions;
Wherein, the thickness of each described single thin film is 0.55nm～1.5nm.
The method of described lifting ITO hole injection efficiency, wherein, adopts magnetically controlled DC sputtering technique to prepare described graphene oxide, and its power is 10～40W/cm.
The described method of improving ITO hole injection efficiency wherein, is prepared described graphene oxide in the atmosphere of the mist of inert gas or itself and nitrogen.
The method of described lifting ITO hole injection efficiency, wherein, the air pressure environment of described atmosphere is 1 × 10
-3～1 × 10
-2torr.
The method of described lifting ITO hole injection efficiency, wherein, described inert gas comprises any one or the combination between them in helium, argon gas, neon, Krypton, xenon.
The method of described lifting ITO hole injection efficiency, wherein, the temperature of described ITO layer being carried out to preheating should be controlled at 50～300 ℃.
An anode construction for display device, wherein, described anode construction comprises that one has the substrat structure of ITO layer, and the upper surface of this ITO layer is coated with one deck graphene oxide.
Described ITO layer structure, wherein, described graphene oxide is made up of multiple single thin films, and the thickness of each this single thin film is 0.55～1.5nm.
Technique scheme tool has the following advantages or beneficial effect:
The inventive method is by preparing one deck graphene oxide on the ITO layer common, form new anode construction, the work function of ITO layer is increased, promoted the injection efficiency in hole, reduce driving voltage, and then can increase stability and the useful life of display device.
Accompanying drawing explanation
With reference to appended accompanying drawing, to describe more fully embodiments of the invention.But appended accompanying drawing only, for explanation and elaboration, does not form limitation of the scope of the invention.
Fig. 1 is the structural representation of traditional OLED device;
Fig. 2 is the steps flow chart schematic diagram of the inventive method;
Fig. 3 is the structural representation of the OLED device of application ITO layer structure of the present invention.
Embodiment
The invention provides a kind of method of the ITO of lifting layer hole injection efficiency and the anode construction of display device.This anode construction is applicable to Organic Light Emitting Diode, and (Organic Light-Emitting Diode is called for short: OLED) in the preparation of the anode of display device.
The central idea of the inventive method is prepare and form after needed pattern when ITO layer, evaporation one deck material is graphene oxide (Graphene oxide, be called for short: resilient coating GO) covers its surface, to utilize the architectural characteristic of graphene oxide material, make the injection energy barrier in hole originally itself cause a pressure drop, this pressure drop meeting causes the energy barrier between script ITO layer and hole transmission layer NPB to dwindle, and improves hole injection efficiency with this.
As shown in Figure 1, general OLED device all comprises glass substrate (Glass substrate), anode (Anode), hole injection layer (Hole-injection layer, HIL), hole transmission layer (Hole transport layer be called for short:, HTL), luminescent layer (Emission layer be called for short:, EML), (Electron transport layer is called for short: electron transfer layer ETL) and negative electrode (Cathode) be called for short:.Method provided by the invention is to carry out in the anode manufacture craft of preparing at OLED device.
As shown in Figure 2, first, prepare the surface of one deck ito thin film covering device structure, (Physical Vapor Deposition is called for short: PVD) carry out can preferably to adopt physical vaporous deposition for the preparation of this ito thin film.
Then, on ito thin film, apply photoresist, and expose and developing process, in this process, can preferably under gold-tinted environment, carry out, in the photoresist after overexposure and developing process, form the needed pattern in preparation transparency electrode region.
Take the figuratum photoresist of this formation as mask, the ito thin film of its below is carried out to wet etching, make design transfer in photoresist to ito thin film, to form ITO layer.
Afterwards the surface of ITO layer is further cleared up, to peel off the micro-hydrocarbon of device remained on surface.
Then, the substrate that is coated with ITO layer forming after above-mentioned steps is carried out to preheating, make its temperature be controlled between 50 ℃～300 ℃ (as 50 ℃, 100 ℃, 150 ℃, 300 ℃ etc.), and be placed in the atmosphere that inert gas mixes with nitrogen, wherein, inert gas can be the one in helium, neon, argon gas, Krypton, xenon, can be also the mist of above-mentioned concentrated gas, and the atmosphere pressure of the mist of inert gas and nitrogen is controlled to 1 × 10
-3～1 × 10
-2hold in the palm between (torr) (as 1 × 10
-3torr, 5 × 10
-3torr, 8 × 10
-3torr etc.), adopt the spraying method of magnetically controlled DC sputtering, power is controlled between 10-40w/cm (as 10w/cm, 20w/cm, 30w/cm, 40w/cm etc.), at ITO layer surface spraying one graphene oxide layer, wherein, the sandwich construction that the mono-layer graphite oxide alkene that this graphene oxide layer is is 0.55nm～1.5nm by thickness forms, its thickness can need to be selected according to concrete technology, in the time that the thickness of this graphene oxide layer is approximately thick, the pressure drop that hole injection energy barrier itself causes is larger, the thickness of controlling this graphene oxide layer can obtain minimum injection energy barrier.The density of this graphene oxide layer can be controlled according to the concentration of the dispersion liquid of this layer and spray time.
Above-mentioned graphene oxide layer is the product of a kind of graphite powder through chemical oxidation and after peeling off, and is single atomic layer, and it can expand to tens of microns at lateral dimension, has crossed over the typical size of general chemistry and material science.Be regarded as a kind of flexible material of non-traditional form, can as interfacial agent, exist in interface, and reduce the energy between interface.
So, the present invention, by prepare one deck graphene oxide resilient coating on ITO layer, can make the work function of the ITO layer that is coated with this graphene oxide increase, also corresponding rising of its hole injection efficiency simultaneously, reduce driving voltage, and then increased stability and the useful life of OLED device.
Provide two preferred embodiments to be elaborated to the inventive method below.
Embodiment 1:
When technique proceeds to, the surface of transparency electrode is further cleared up, to peel off after the micro-hydrocarbon of device remained on surface, the substrate that is coated with ITO layer is carried out to preheating, its temperature is remained between 150 ℃, and be placed in the mist atmosphere of argon gas and nitrogen, wherein, the accounting of argon gas and nitrogen is 3:7, and control to make the internal pressure of this mist be 1 × 10
-3torr, adopt the spraying method of magnetically controlled DC sputtering, power is controlled to 15w/cm, at ITO layer surface spraying one graphene oxide layer, wherein, the sandwich construction that the mono-layer graphite oxide alkene that this graphene oxide layer is is 0.55nm～1.5nm by thickness forms, its thickness can need to be selected according to concrete technology, in the time that the thickness of this graphene oxide layer is thicker, it is larger that the pressure drop that energy barrier itself causes is injected in hole, and the thickness of controlling this graphene oxide layer can obtain minimum injection energy barrier.
Embodiment 2:
When technique proceeds to, the surface of transparency electrode is further cleared up, to peel off after the micro-hydrocarbon of device remained on surface, the substrate that is coated with ITO layer is carried out to preheating, its temperature is remained between 150 ℃, and be placed in the mist atmosphere of argon gas and nitrogen, wherein, the accounting of argon gas and nitrogen is 1:4, and control to make the internal pressure of this mist be 1 × 10
-3torr, adopt the spraying method of magnetically controlled DC sputtering, power is controlled to 15w/cm, at ITO layer surface spraying one graphene oxide layer, wherein, the sandwich construction that the mono-layer graphite oxide alkene that this graphene oxide layer is is 0.55nm～1.5nm by thickness forms, its thickness can need to be selected according to concrete technology, in the time that the thickness of this graphene oxide layer is thicker, it is larger that the pressure drop that energy barrier itself causes is injected in hole, and the thickness of controlling this graphene oxide layer can obtain minimum injection energy barrier.
Further, in method of the present invention, also can be before preparing graphene oxide layer, first adopt oxygen plasma or ultraviolet ray to irradiate ITO layer is processed.
The present invention also provides a kind of anode construction being applied in display device, and this structure has higher work function and higher hole injection efficiency with respect to existing anode, and this structure is particularly useful in the anode preparation of OLED device.
Anode construction of the present invention comprises an ITO layer and a resilient coating, and this resilient coating is covered in the upper surface of this ITO layer, and the material of this resilient coating is graphene oxide.
As shown in Figure 3, this ITO layer structure applications, in the anode of OLED device, can be reduced to the driving voltage of anode, and then increase stability and the useful life of OLED device.
For a person skilled in the art, read after above-mentioned explanation, various changes and modifications undoubtedly will be apparent.Therefore, appending claims should be regarded whole variations and the correction of containing true intention of the present invention and scope as.Within the scope of claims, scope and the content of any and all equivalences, all should think and still belong to the intent and scope of the invention.
Claims (14)
1. promote a method for ITO hole injection efficiency, be applied in the anode manufacture craft of display device, described method comprises:
One semiconductor structure that is preset with ITO region is provided;
Upper surface at the semiconductor structure that is positioned at described ITO region is prepared an ITO layer;
Described ITO layer is carried out to preheating;
Graphene oxide film is prepared on surface in this ITO layer.
2. the method for lifting ITO hole injection efficiency as claimed in claim 1, is characterized in that, forms described ITO layer by following steps:
Prepare the upper surface that one deck ito thin film covers described semiconductor structure;
Prepare the upper surface that photoresist covers described ito thin film;
To described photoresist expose, after developing process, ito thin film forms described ITO layer described in etching.
3. the method for lifting ITO hole injection efficiency as claimed in claim 2, is characterized in that, forms described ITO layer under gold-tinted environment.
4. the method for lifting ITO hole injection efficiency as claimed in claim 1, is characterized in that, before the described graphene oxide film of preparation, described ITO layer is cleaned.
5. the method for lifting ITO hole injection efficiency as claimed in claim 4, is characterized in that, adopts oxygen plasma body technology to clean described ITO layer.
6. the method for lifting ITO hole injection efficiency as claimed in claim 4, is characterized in that, adopts UV-ozone process to clean described ITO layer.
7. the method for lifting ITO hole injection efficiency as claimed in claim 1, is characterized in that, described graphene oxide is the composite construction layer of multiple single thin film compositions;
Wherein, the thickness of each described single thin film is 0.55nm～1.5nm.
8. the method for lifting ITO hole injection efficiency as claimed in claim 1, is characterized in that, adopts magnetically controlled DC sputtering technique to prepare described graphene oxide, and its power is 10～40W/cm.
9. the method for lifting as claimed in claim 1 ITO hole injection efficiency, is characterized in that, in the atmosphere of the mist of inert gas or itself and nitrogen, prepares described graphene oxide.
10. the method for lifting ITO hole injection efficiency as claimed in claim 9, is characterized in that, the air pressure environment of described atmosphere is 1 × 10
-3～1 × 10
-2torr.
The methods of 11. lifting as claimed in claim 9 ITO hole injection efficiencies, is characterized in that, described inert gas comprises any one or the combination between them in helium, argon gas, neon, Krypton, xenon.
The method of 12. lifting ITO hole injection efficiencies as claimed in claim 1, is characterized in that, the temperature of described ITO layer being carried out to preheating should be controlled at 50～300 ℃.
The anode construction of 13. 1 kinds of display devices, is characterized in that, described anode construction comprises that one has the substrat structure of ITO layer, and the upper surface of this ITO layer is coated with one deck graphene oxide.
14. ITO layer structure as claimed in claim 13, is characterized in that, described graphene oxide is made up of multiple single thin films, and the thickness of each this single thin film is 0.55～1.5nm.
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| CN111204986A (en) * | 2020-01-17 | 2020-05-29 | 苏州领锐源奕光电科技有限公司 | Preparation method of novel graphene oxide-ITO (indium tin oxide) composite film |
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Cited By (9)
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| US9806260B2 (en) * | 2015-02-25 | 2017-10-31 | Boe Technology Group Co., Ltd. | Organic light-emitting diode display device, manufacturing method thereof, and display apparatus |
| EP3262700A4 (en) * | 2015-02-25 | 2018-10-24 | Boe Technology Group Co. Ltd. | Organic light-emitting diode display device, manufacturing method thereof, and display apparatus |
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