CN102931355B - Oled - Google Patents
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- CN102931355B CN102931355B CN201210447338.2A CN201210447338A CN102931355B CN 102931355 B CN102931355 B CN 102931355B CN 201210447338 A CN201210447338 A CN 201210447338A CN 102931355 B CN102931355 B CN 102931355B
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- hole transmission
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Abstract
The present invention relates to a kind of OLED.OLED of the present invention, comprise substrate, transparent anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described transparent anode is arranged on substrate, hole injection layer is arranged on transparent anode, hole transmission layer is arranged on hole injection layer, luminescent layer is arranged on hole transmission layer, electron transfer layer is arranged on luminescent layer, electron injecting layer is arranged on the electron transport layer, negative electrode is arranged on electron injecting layer, it is characterized in that, described hole transmission layer is the sandwich construction comprising 2 ~ 4 layers of hole transmission layer.Beneficial effect of the present invention is, effectively prevent the accumulation of charge carrier in interface, balances Carrier recombination, luminescent layer is limited to luminescent layer, phosphor material is played best effect, thus meets and adopt the OLED of phosphorescent light-emitting materials to use.The present invention is particularly useful for OLED.
Description
Technical field
The present invention relates to a kind of OLED.
Background technology
Kodak company of the U.S. proposes the organic electroluminescence device structure of " sandwich " formula first in the patent US4769292 of 1987, causes the concern in the whole world; After 2 years, remain Kodak company of the U.S. and introduce hole transmission layer first in patent US4885211, disclose the key point of OLED design, from then on opened the research boom of OLED.Due to OLED, there is the plurality of advantages such as self-luminous, all solid state, wide viewing angle, response be fast and be considered in flat panel display, have huge application prospect, being even considered to the flat panel display product of new generation after liquid crystal (LCD), plasma (PDP) and technology.In order to avoid luminescence center deviating electrode makes the luminous cancellation of device, the basis of simple " sandwich " formula device architecture in turn introduces carrier injection layer and transport layer, and defines multilayer OLED structure comparatively common at present gradually.As shown in Figure 1, substrate 1, the ITO transparent anode 2 be placed on substrate, the hole injection layer (HIL) 3 be placed on ITO transparent anode, the hole transmission layer (HTL) 4 be placed on hole injection layer, the luminescent layer (EML) 5 be placed on hole transmission layer, the electron transfer layer (ETL) 6 be placed on luminescent layer, the negative electrode 8 that is placed in the electron injecting layer (EIL) 7 on electron transfer layer and is placed on electron injecting layer.In order to improve the efficiency of device, luminescent layer adopts master/object doped system usually.
But OLED will take advantage on flat panel display market, the driving voltage, luminous efficiency etc. of OLED still need further improvement.And to improve the most effective method of OLED luminous efficiency be the direct efficient electrophosphorescence device of research and development.
According to spin statistics, it is 1: 3 that hole and electronics combine the probability ratio forming singlet state and triplet exciton, and namely the molecule that excites of 25% will form singlet state, and the molecule that excites of 75% can form triplet.Due to the restriction of selection rule, the triplet state of fluorescence luminescent material is prohibited to the transition of ground state, and can only rely on singlet transition luminescence, thus quantum efficiency is the highest reaches 25% only; And owing to there is stronger Effect of Spin-orbit Coupling in phosphorescent light-emitting materials, selection rule is removed to a certain extent, the light radiation transition probability of triplet excited state T1 to ground state S0 increases, singlet state, triplet radioluminescence can be utilized simultaneously, quantum efficiency can reach 100% in theory, is 4 times of fluorescence luminescent material.It can thus be appreciated that, if introduce efficient phosphorescent light-emitting materials in OLED, and appropriate design is carried out to device architecture, greatly can improve the efficiency of device.
But because the radiation lifetime of triplet state phosphorescence is long, make triplet excitons very easily migrate to carrier blocking layers and cause transport layer material emission; In addition, obtain high efficiency, carrier injection that the phosphorescent OLED of low voltage drive must arrange in pairs or groups function admirable and transport layer, these are all had higher requirement to high efficiency phosphorescent OLED device structural design, and current OLED does not also possess the structure supporting high efficiency phosphorescent light-emitting materials.
Summary of the invention
Problem solved by the invention, proposes a kind of high efficiency OLED can supporting phosphorescent light-emitting materials exactly.
The present invention solves the problems of the technologies described above adopted technical scheme: OLED, comprise substrate, transparent anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described transparent anode is arranged on substrate, hole injection layer is arranged on transparent anode, hole transmission layer is arranged on hole injection layer, luminescent layer is arranged on hole transmission layer, electron transfer layer is arranged on luminescent layer, electron injecting layer is arranged on the electron transport layer, negative electrode is arranged on electron injecting layer, it is characterized in that, described hole transmission layer is the sandwich construction comprising 2 ~ 4 layers of hole transmission layer.
Concrete, described hole transmission layer is 3 layers, comprise the first hole transmission layer, the second hole transmission layer and the 3rd hole transmission layer, described second hole transmission layer is arranged on the first hole transmission layer, and described 3rd hole transmission layer is arranged on the second hole transmission layer.
Concrete, the thickness of described first hole transmission layer is greater than the second hole transmission layer, and the thickness of the second hole transmission layer is greater than the 3rd hole transmission layer.
Concrete, described thickness of hole transport layer is not more than 60nm.
Beneficial effect of the present invention is, effectively prevent the accumulation of charge carrier in interface, balance Carrier recombination, and luminescent layer is limited to luminescent layer, thus the best effect that made phosphor material play, device efficiency obtains and effectively improves, thus meets the OLED use adopting phosphorescent light-emitting materials.
Accompanying drawing explanation
Fig. 1 is the structural representation of existing OLED;
Fig. 2 is the structural representation of OLED of the present invention.
Embodiment
Below in conjunction with drawings and Examples, describe technical scheme of the present invention in detail:
As shown in Figure 1, current OLED, comprise substrate 1, transparent anode 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and negative electrode 8, wherein transparent anode 2 arranges on substrate 1, hole injection layer 3 is arranged on transparent anode 2, hole transmission layer 4 is arranged on hole injection layer 3, luminescent layer 5 to be arranged on hole transmission layer 4, electron transfer layer 6 is arranged on luminescent layer 5, electron injecting layer 7 is arranged on electron transfer layer 6, and negative electrode 8 is arranged on electron injecting layer 7.
The present invention overcomes the main technical schemes that prior art adopts, by improving the structure of hole transmission layer 4, originally the individual layer hole transmission layer adopted is improved to the mode of multilayer hole transmission layer superposition, by experiment, hole transmission layer is improved to 2 ~ 4 layers and can effectively avoids charge carrier in the accumulation of interface, equilibrium carrier compound, thus luminescent layer is limited to luminescent layer, thus phosphorescent light-emitting materials is played best effect.Simultaneously in order to reduce driving voltage, improve OLED efficiency, adopt the hole injection structure of P type doping, need to possess a large amount of " free hole " that carrying P type doping injecting structure formed in the hole transmission layer of multilayer and stop injected holes by one deck of P type doping object cancellation, also need the one deck possessing transmission injected holes charge carrier, and with the level-density parameter of luminescent layer, and exciton is limited to the one deck in luminescent layer.
Luminescent layer of the present invention is phosphorescence luminescent layer, consist predominantly of non-emissive material of main part and phosphorescent light-emitting materials, and adopt phosphorescent light-emitting materials to adulterate the mode of non-emissive material of main part, wherein the electron mobility of phosphorescent light-emitting materials is better than hole mobility, can be but be not limited to red phosphorescent luminescent material, green phosphorescent luminescent material, blue phosphorescent luminescent material, yellow phosphorescence luminescent material.In order to reach more satisfactory illumination effect, the doping content of phosphorescent light-emitting materials is at least 0 ~ 12%.
In order to coordinate the new structure can supporting high efficiency phosphorescent light-emitting materials in actual production process, other parts of oled panel can adopt following method:
Substrate adopts in the good clear glass of visible region light transmission or flexible substrates, as polyesters macromolecular compound, polyalkenes macromolecular compound, and has certain oxygen waterproof ability and good profile pattern.
Anode adopts has the stability of good conductivity, good chemistry and form, higher work function and transparency in visible region wants high, usually adopts transparent conductive oxide (as ITO, ZnO, AZO (Al:ZnO) etc.) and metal (Ni, Au, Pt etc.); Further, anode can arrange in pairs or groups some surface treatments (as O
2plasma or UV-ozone treatment) improve its work function.
The hole injection layer adopted requires with the level-density parameter degree of anode and adjacent hole transmission layer good, can be but be not limited to CuPc, TNATA, PEDOT.A kind of preferred scheme is that hole injection layer adopts P type doped structure, by hole mobile material doped with oxygen agent as SbCl
5, FeCl
3, iodine, F4-TCNQ or TBAHA.Certainly other any structures that can improve hole and inject such as quantum well structure can also be adopted.
Luminescent layer adopts host-guest system structure, doping object is phosphor material, and the material of main part adopted need have electron mobility and hole mobility, and best electron mobility is at least ten times of hole mobility, its objective is the efficiency in order to better improve luminescent layer.
The new hole transmission layer with multilayer hole transmission layer superposition formation requires that hole mobility is at least 10-4cm
2/ (VS) magnitude, and the film with high thermal stability, energy vacuum evaporation formation free of pinholes; Selectable hole mobile material is the diamine compounds of paired coupling, as TPD, TAPC, NPB, β-NPB, α-NPD; Triphenyl amine compound, as TDAB, TDAPB, PTDATA, spiro-mTTB; Or some triaryl amine polymer, one in carbazole compound.
Preferably, the gross thickness of described hole transmission layer is no more than 60nm, and the gross thickness of best hole transmission layer is 35nm.The gross thickness of hole transmission layer be every one deck hole transmission layer thickness and, its different thickness major effect be every one deck hole transmission layer characteristic play, prove through experiment, realize improving luminescent layer efficiency preferably, the gross thickness of best hole transmission layer is no more than 60nm.
The electron transfer layer adopted require there is higher electron mobility, higher glass transformation temperature and thermal stability and can be formed evenly via hot evaporation, the film ， of pore-free is one in oxazole derivative, metallo-chelate quinoline, quinoline derivant, phenazine derivative, ferrosin derivative, siliceous heterocyclic compound.
Electron injecting layer can be lithia, lithia boron, silicon potassium oxide, cesium carbonate or alkali metal fluoride, as the one in lithium fluoride, potassium fluoride, cesium fluoride.
Negative electrode can be the metal or metal alloy of low work function, is the one in lithium, magnesium, aluminium, magnesium silver alloy, lithium-aluminium alloy.
The preparation method of OLED of the present invention is: utilize the method for the vacuum evaporation each layer of evaporation successively, and alternative plan is that the evaporation rate of described each layer should control
between.
Embodiment:
As shown in Figure 2, OLED in the present embodiment, comprise substrate 1, transparent anode 2, hole injection layer 3, first hole transmission layer 41, second hole transmission layer 42, 3rd hole transmission layer 43, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and negative electrode 8, wherein transparent anode 2 arranges on substrate 1, hole injection layer 3 is arranged on transparent anode 2, first hole transmission layer 41 is arranged on hole injection layer 3, second hole transmission layer 42 is arranged on the first hole transmission layer 41, 3rd hole transmission layer 43 is arranged on the second hole transmission layer 42, luminescent layer 5 is arranged on the 3rd hole transmission layer 43, electron transfer layer arranges 6 on luminescent layer 5, electron injecting layer 7 is arranged on electron transfer layer 6, negative electrode 8 is arranged on electron injecting layer 7.Wherein the hole mobility of the first hole transmission layer, the second hole transmission layer, the 3rd hole transmission layer is at least 10
-4cm
2/ (VS) magnitude, and the hole mobility of the second hole transmission layer is better than or equals the hole mobility of the first hole transmission layer; The hole mobility of the 3rd hole transmission layer less than or equal to or higher than the hole mobility of the second hole transmission layer.The highest occupied molecular orbital of the first hole transmission layer, the second hole transmission layer, the 3rd hole transmission layer is distributed between described hole injection layer and the highest occupied molecular orbital of luminescent layer simultaneously.
The concrete principle of employing three layers of hole transmission layer is: the first hole transmission layer carries a large amount of charge carrier, avoids charge carrier to accumulate in interface; Second hole transmission layer transmits charge carrier fast; 3rd hole transmission layer carries out level-density parameter, and the exciton of emission layer is limited in luminous zone, thus realizes the object of the efficiency improving OLED, and the advantage simultaneously also possessed is the life-span that can extend OLED further.Prove through experiment, the thickness relationship between three layers of hole transmission layer is: the thickness of the first hole transmission layer is greater than the second hole transmission layer, when the thickness of the second hole transmission layer is greater than the 3rd hole transmission layer, better can improve the efficiency of OLED.
Claims (4)
1.OLED device, comprise substrate, transparent anode, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode, described transparent anode is arranged on substrate, hole injection layer is arranged on transparent anode, hole transmission layer is arranged on hole injection layer, luminescent layer is arranged on hole transmission layer, electron transfer layer is arranged on luminescent layer, electron injecting layer is arranged on the electron transport layer, negative electrode is arranged on electron injecting layer, it is characterized in that, described hole transmission layer is the sandwich construction comprising 2 ~ 4 layers of hole transmission layer, described luminescent layer is phosphorescence luminescent layer, described substrate adopts polyesters macromolecular compound or polyalkenes macromolecular compound, described anode adopts transparent conductive oxide or metal, described hole injection layer adopts P type doped structure, described luminescent layer employing doping object is the host-guest system structure of phosphor material, described phosphorescence luminescent layer includes non-emissive material of main part and phosphorescent light-emitting materials, and adopt phosphorescent light-emitting materials to adulterate the mode of non-emissive material of main part, wherein the electron mobility of phosphorescent light-emitting materials is better than hole mobility, the doping content of phosphorescent light-emitting materials is greater than 0 and is less than or equal to 12%.
2. OLED according to claim 1, it is characterized in that, described hole transmission layer is 3 layers, comprise the first hole transmission layer, the second hole transmission layer and the 3rd hole transmission layer, described second hole transmission layer is arranged on the first hole transmission layer, and described 3rd hole transmission layer is arranged on the second hole transmission layer.
3. OLED according to claim 2, is characterized in that, the thickness of described first hole transmission layer is greater than the second hole transmission layer, and the thickness of the second hole transmission layer is greater than the 3rd hole transmission layer.
4. OLED according to claim 1, is characterized in that, described thickness of hole transport layer is not more than 60nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210447338.2A CN102931355B (en) | 2012-11-09 | 2012-11-09 | Oled |
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|---|---|---|---|
| CN201210447338.2A CN102931355B (en) | 2012-11-09 | 2012-11-09 | Oled |
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| CN102931355A CN102931355A (en) | 2013-02-13 |
| CN102931355B true CN102931355B (en) | 2015-12-09 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104241540A (en) * | 2014-09-04 | 2014-12-24 | 京东方科技集团股份有限公司 | Organic electroluminescent display device, manufacturing method thereof and display unit |
| CN106206961A (en) * | 2015-05-06 | 2016-12-07 | 上海和辉光电有限公司 | A kind of OLED |
| CN106711049B (en) * | 2016-12-22 | 2020-09-29 | 武汉华星光电技术有限公司 | Porous substrate and manufacturing method thereof, and manufacturing method of thin film transistor |
| CN109509840A (en) * | 2017-09-14 | 2019-03-22 | 上海和辉光电有限公司 | A kind of structure of OLED device |
| CN110400883A (en) * | 2018-04-24 | 2019-11-01 | 上海和辉光电有限公司 | A kind of structure of OLED device |
| CN111200044B (en) * | 2020-01-13 | 2021-10-08 | 华南理工大学 | Thin film type white light LED chip |
| CN112599687B (en) * | 2020-12-10 | 2024-05-07 | 北京维信诺科技有限公司 | Light-emitting device and display device |
| KR20230103320A (en) * | 2021-12-31 | 2023-07-07 | 엘지디스플레이 주식회사 | Electroluminescent Display Device |
| CN114512621A (en) * | 2022-02-18 | 2022-05-17 | 京东方科技集团股份有限公司 | Light-emitting device, display panel and display device |
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| KR100611756B1 (en) * | 2004-06-18 | 2006-08-10 | 삼성에스디아이 주식회사 | Organic electroluminescent display device and method of fabricating the same |
| KR101097339B1 (en) * | 2010-03-08 | 2011-12-23 | 삼성모바일디스플레이주식회사 | Organic light emitting diode and method for preparing the same |
| JP5019644B2 (en) * | 2010-03-24 | 2012-09-05 | 株式会社ジャパンディスプレイセントラル | Organic EL device |
| CN102403462B (en) * | 2010-09-13 | 2014-01-08 | 周卓辉 | Organic light emitting diode and manufacturing method thereof |
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Granted publication date: 20151209 Termination date: 20201109 |