CN101388437B - Electroluminescence element - Google Patents
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- CN101388437B CN101388437B CN2008101495294A CN200810149529A CN101388437B CN 101388437 B CN101388437 B CN 101388437B CN 2008101495294 A CN2008101495294 A CN 2008101495294A CN 200810149529 A CN200810149529 A CN 200810149529A CN 101388437 B CN101388437 B CN 101388437B
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Abstract
An EL element includes, between an anode and a cathode, an emissive element layer including a plurality of emissive layers. The emissive element layer includes two or more organic layers containing a hole transporting compound, and one or more of the plurality of emissive layers contain the hole transporting compound. The concentration of the hole transporting compound in the organic layer which is formed closest to the electron injecting electrode among the organic layers containing the hole transporting compound is lower than the concentration of the hole transporting compound in the organic layer which is formed closest to the hole injecting electrode. When three or more organic layers contain a hole transporting compound, the concentration of the hole transporting compound contained in each organic layer can be set such that, as the organic layer is further away from the hole injecting electrode, the concentration is lower. With this setting, the supply amount and supply timing of holes and electrons can be optimized easily with regard to each of the plurality of emissive layers, so that uniform light emission can be generated in any one of the emissive layers.
Description
The application is that application number is 200510107946.9, and the applying date is on September 30th, 2005, application artificial " Sanyo Electric Co., Ltd ", and denomination of invention is divided an application for the one Chinese patent application of " EL part ".
Technical field
The present invention relates to the formation of electroluminescence (Electroluminescence:EL) element.
Background technology
In recent years; For display elements such as flat display apparatus and light sources; The EL part of emissive type receives greatly attractes attention; Especially can send the illuminant colour of multicolour through the organic compound material that adopts and can reach the luminous organic electroluminescent element of high brightness, this correlative study is carried out just energetically.
Organic electroluminescent element is that the light emitting element layer that contains luminescent layer is set between hole injecting electrode (anode) and electron injection electrode (negative electrode); In light emitting element layer; From anode institute injected holes with combine (Recombination) again from negative electrode institute injected electrons; Can be luminous when returning ground state (ground state) because of the light emitting molecule that energy excited that combines again, therefore can utilize this luminous demonstration.
As stated, in organic electroluminescent element, the luminescent organic molecule that can pass through to be adopted obtains the light of all colors.Yet, the color that also exists at present white for example etc. to realize through single luminous organic material.For the light of said color, be to realize through the light of combination multicolour.About said white, also the someone proposes, and lamination forms Yellow luminous layer and the blue light-emitting layer with complementary colours relation in 1 element, and through realizing white light at the sodium yellow that each layer obtained and the additive color of blue light.Yet it is efficient luminous to be difficult to make each layer of multilayer luminescent layer to carry out, and the gap between illuminant colour and the reference white is also not little.
In addition,, but still there are the problems such as durability of the organic material of light emitting molecule etc., still dislike not enough as the life-span of element though organic electroluminescent element generally can carry out the luminous of high brightness.When lamination multilayer luminescent layer obtains additive light, measurablely worsen sooner than other luminescent layer to the bigger luminescent layer of luminescent layer that for example luminous efficiency is minimum or injection current, and component life depends on the luminescent layer that the life-span is the shortest.Therefore,, not only need various illuminant colours are developed the luminous organic material that can reach long-life more and higher luminous efficiency, and must reach the optimization of component construction etc. for all illuminant colours.
Summary of the invention
The invention relates to,, also can make luminescent layer luminous efficiently and realize the technology of long-life element even possess the EL part of multilayer luminescent layer.
The present invention is a kind of EL part; Between hole injecting electrode and electron injection electrode, possesses the light emitting element layer that contains the multilayer luminescent layer; Wherein, Said light emitting element layer possesses the organic layer that contains cavity conveying property compound more than 2 layers; Constitute the said organic layer contain said cavity conveying property compound more than 1 layer in the said multilayer luminescent layer, in said organic layer, the concentration ratio that contains that is formed near the said cavity conveying property compound of the layer of said electron injection electrode is formed at also little near the layer of said hole injecting electrode.
About alternate manner of the present invention, in said EL part, the organic layer that contains said cavity conveying property compound exists more than 3 layers; The said cavity conveying property compound of said organic layer contain concentration, the said hole injecting electrode of distance is far away, the concentration of this layer is lower.
In addition, said cavity conveying property compound for example is an amine derivatives compounds.
About alternate manner of the present invention, in said EL part, this multilayer luminescent layer possesses: be disposed near the 1st luminescent layer of hole injecting electrode and be disposed at the 1st luminescent layer and said electron injection electrode between the 2nd luminescent layer; Between said the 1st luminescent layer and said hole injecting electrode, possesses hole transporting layer at least; The concentration that contains with the said cavity conveying property compound of said hole transporting layer is made as Chi; The concentration that contains with the said cavity conveying property compound of said the 1st luminescent layer is made as Cem1; During with the containing concentration and be made as Cem2 of the said cavity conveying property compound of said the 2nd luminescent layer, satisfy Cem1-Cem2>relation of Chi-Cem1.
About alternate manner of the present invention; In said EL part; In said multilayer luminescent layer, be disposed near the 1st luminescent layer of hole injecting electrode at least and be formed near the luminescent layer of the 1st luminescent layer, respectively contain identical cavity conveying property compound.
So; When the organic layer of multilayer contains cavity conveying property compound separately; More near the organic layer of the side of hole injecting electrode, this cavity conveying property compound to contain concentration higher, it is lower that the organic layer far away of healing then contains concentration; Thus, the hole that can easily carry necessity respectively and measure fully to the multilayer luminescent layer that is formed between hole injecting electrode and the electron injection electrode.
The organic layer of the side of cave injecting electrode; The concentration that contains of this cavity conveying property compound heals high; It is lower that the organic layer far away of healing then contains concentration, thus, and the hole that can easily carry necessity respectively and measure fully to the multilayer luminescent layer that is formed between hole injecting electrode and the electron injection electrode.
About alternate manner of the present invention, in said EL part, in said multilayer luminescent layer, possessing the 1st luminescent layer near the hole injecting electrode place, between the 1st luminescent layer and said electron injection electrode, possess the 2nd luminescent layer; Between said the 1st luminescent layer and said hole injecting electrode, possesses hole transporting layer at least; Between said the 2nd luminescent layer and said electron injection electrode, possesses electron supplying layer at least; The electron transport property compound of said electron supplying layer, said the 2nd luminescent layer and said the 1st luminescent layer contain concentration, the said electron supplying layer of distance is far away, the concentration of this layer is lower.
Through satisfying described relation, in the element that is provided with the multilayer luminescent layer, be not only the hole, also can easily inject electronics equably to each luminescent layer.
About alternate manner of the present invention, in said EL part, in said multilayer luminescent layer,, possess hole transporting layer and hole injection layer at least being disposed between the 1st luminescent layer and this hole injecting electrode near hole injecting electrode; In said multilayer luminescent layer,, possesses electron supplying layer at least being disposed between the 2nd luminescent layer and this electron injection electrode near electron injection electrode; Said the 1st luminescent layer possesses the cavity conveying function; Said the 2nd luminescent layer possesses the electron transport function; Thickness with said hole injection layer is made as Lhi, hole mobility is made as μ hi; Thickness with said hole transporting layer is made as Lht, hole mobility is made as μ ht; Thickness with said the 1st luminescent layer is made as Lem1, hole mobility is made as μ hem1; Thickness with said the 2nd luminescent layer is made as Lem2, electron mobility is made as μ hem2; Thickness with said electron supplying layer is made as Let, when electron mobility is made as μ et, satisfies the relation of (Lhi/ μ hi)+(Lht/ μ ht)+(Lem1/ μ hem1)=α { (Lem2/ μ hem2)+(Let/ μ et) }, and α satisfies 0.5＜α＜2.5.
Through setting α, can on same opportunity, make electronics arrive the 1st luminescent layer and make the hole arrive the 2nd luminescent layer easily in the scope that satisfies 0.5 to 2.5.Therefore, can prevent that electronics and hole are only compound on luminescent layer centrality ground on one side produces luminous and non-luminous inconsistent phenomenon on the luminescent layer at another side.
According to the present invention; When the organic layer of multilayer contains common charge-transporting compound; Make the amount (concentration) of this charge-transporting compound possess gradient; Near the electrode that is asked to most conveying capacity organic layer improves this amount, and along with far reducing amount apart from electrode.At least be in different 2 layers of organic layer to the distance of electrode, improving concentration near the charge-transporting compound of the layer of electrode.Thus, be formed near the luminescent layer the electrode and be formed at than this situation for luminescent layer at a distance even exist, also can be separately positively with the luminescent layer on electronics and cavity conveying to both sides, and combine again easily.Therefore, can promote the luminous harmony of each luminescent layer, realize the additive light of desired color, also realize the long-life element of high efficiency in addition easily.
About alternate manner of the present invention; Be a kind of EL part, between hole injecting electrode and electron injection electrode, possess the light emitting element layer that contains organic compound, wherein; Said light emitting element layer possesses the multilayer luminescent layer; In this multilayer luminescent layer,, possesses hole transporting layer at least being disposed between the 1st luminescent layer and this hole injecting electrode near hole injecting electrode; In said multilayer luminescent layer,, possesses electron supplying layer at least being disposed between the 2nd luminescent layer and this electron injection electrode near electron injection electrode; Said the 1st luminescent layer possesses the cavity conveying function; Said the 2nd luminescent layer possesses the electron transport function; Required time to arrive this hole till said the 2nd luminescent layer through said hole transporting layer and said the 1st luminescent layer from said hole injecting electrode institute injected holes is Th; And be Te from said electron injection electrode institute injected electrons arrives this electronics till said the 1st luminescent layer through said electron supplying layer and said the 2nd luminescent layer required time, both ratio Th/Te satisfy 0.5＜(Th/Te)＜2.5.
About alternate manner of the present invention, said ratio Th/Te satisfies 1≤(Th/Te)＜2.
So, the ratio that hole or electronics are arrived the required time till each luminescent layer is set at for example 0.5 to 2.5 the scope that satisfies as said, thus, can make electronics arrive the 1st luminescent layer easily and makes the hole arrive the 2nd luminescent layer on same opportunity.Therefore, can prevent electronics and hole only on luminescent layer on one side centrality ground combines again to produce luminous and in the non-luminous inconsistent phenomenon of the luminescent layer of another side, and it is balancedly luminous that the multilayer luminescent layer is distinguished.In addition, be more than 1 and if set the ratio of required time less than 2, then can be really and make any one deck of multilayer luminescent layer of stromatolithic structure luminous efficiently.
Through satisfying the relation as said, can be in the element that is provided with the multilayer luminescent layer easily hole and electronics be flow into each luminescent layer equably and luminous.
The effect of invention
According to the present invention, can promote the luminous harmony of the multilayer luminescent layer of institute's lamination, and can realize the additive light of purpose color also realizing high efficiency and long-life element in addition easily.
Description of drawings
Fig. 1 has shown the summary profile construction of the EL part of form of implementation of the present invention.
Fig. 2 has shown a part of summary profile construction of the colour display device of the EL part that adopts form of implementation of the present invention.
Fig. 3 has shown the luminescent spectrum of the EL part of the 1st embodiment.
Fig. 4 has shown the luminescent spectrum of the EL part of 1-2 comparative example.
Fig. 5 has shown the luminescent spectrum of the EL part of 2-2 comparative example.
The main element symbol description
100 substrates, 160 interlayer insulating films
180 planarization insulating layers, 200 light emitting element layers
220 hole injecting electrodes (anode), 240 electron injection electrodes (negative electrode)
242 electron injecting layers, 244 metal levels
300 light emitting element layers, 310 hole injection layers
320 hole transporting layers 330 the 1st luminescent layer
340 the 2nd luminescent layers, 350 electron supplying layers
360 electron injecting layers, 500 EL parts
The CF colored filter
Embodiment
Followingly form of implementation of the present invention (below be called form of implementation) is described with reference to accompanying drawing.Fig. 1 is presented at the summary profile construction of the EL part 500 of this form of implementation that possesses the multilayer luminescent layer between the 1st electrode and the 2nd electrode.
The the 1st and the 2nd electrode, Yi Bian be hole injecting electrode (anode) 220, another side is an electron injection electrode (negative electrode) 240; In the example of Fig. 1; Form anode 220 in the side of substrate, negative electrode 240 then be formed on anode 220 relatively to, double team has the light emitting element layer 300 of organic compound therebetween.
Light emitting element layer 300 possesses the organic layer of the multilayer that contains cavity conveying property compound.In addition, this light emitting element layer 300 possesses the multilayer luminescent layer, in this multilayer luminescent layer, being disposed between the 1st luminescent layer 330 and this anode 220 near anode 220, possesses hole transporting layer 320 at least.In the multilayer luminescent layer,, possesses electron supplying layer 350 at least being disposed between the 2nd luminescent layer 340 and this negative electrode 240 near negative electrode 240.The formation of light emitting element layer 300 is that all differences are arranged according to the organic material that adopted etc.; In the example of Fig. 1; Be that side from anode 220 begins, lamination hole injection layer 310, hole transporting layer the 320, the 1st luminescent layer the 330, the 2nd luminescent layer 340 and electron supplying layer 350 in regular turn.
In addition, in this form of implementation,, adopt orange luminescent layer and blue light-emitting layer to be used as luminescent layer, and be set at the 1st luminescent layer 330 and the 2nd luminescent layer 340 respectively in order to realize white luminous according to additive color.Though be not limited to that lamination orange luminescent layer and blue light-emitting layer constitute in regular turn from the side of hole transporting layer; But comparatively ideally be; In the multilayer luminescent layer; The side that the luminescent layer that the cavity conveying function is higher is arranged on anode 220 is used as the 1st luminescent layer 330, and the side that the luminescent layer that the electron transport function is higher is arranged on negative electrode 240 is used as the 2nd luminescent layer 340.
Luminescent layer is not limited to 2 layers; Also can be more than 3 layers; In the case; In the multilayer luminescent layer, near the 1st luminescent layer 330 of anode 220 (far away) and between the 2nd luminescent layer 340 near negative electrode 240 (far away) apart from anode 220 apart from negative electrode 240, be provided with the 3rd, the 4th ... .., n luminescent layer.Be arranged on the 1st and the 2nd luminescent layer the centre luminescent layer each other or and the 1st or the 2nd luminescent layer between interlayer, can form other functional layer that has beyond luminous.
About anode 220, for example can adopt the conductive metal oxide material, ITO (Indium Tin Oxide, tin indium oxide) and IZO transparent conductivity materials such as (Indium Zinc Oxide, indium zinc oxides) are particularly arranged.Negative electrode 240 is by the metal level 244 that is the main body with the bigger metal material of work function and be used for reducing the stromatolithic structure that the electron injecting layer 242 of the electron transport resistance barrier of electron supplying layer 350 is formed and constituted.About metal level 244, for example can adopt Al, Ag, MgAl alloy, MgAg alloy, LiAl alloy, LiAg alloy etc.And under the less situation of 350 electron transport resistance barrier, also can omit electron injecting layer 242 from negative electrode 240 toward electron supplying layer, electron injecting layer 242 for example can adopt lithium fluoride (LiF), lithium (Li) etc.
In the example of Fig. 1, in the multilayer luminescent layer, be to form continuously on the hole transporting layer 320 in monolayer constructions will near the 1st luminescent layer 330 of anode, this 1st luminescent layer 330 contains the cavity conveying property compound of relative higher concentration.Particularly; It is main material that the 1st luminescent layer 330 adopts cavity conveying property compound; Adopt the luminescent material of orange to be used as dopant material, and will about 10 quality % or this dopant material of its following concentration is doped in cavity conveying property main material and forms.Just, in the 1st luminescent layer 330, contain the cavity conveying property compound that cavity conveying property compound concentrations is approximately (for example about 90 quality %) more than 100 quality % to the 80 quality %.The aromatic amine derivative compound that cavity conveying property compound can adopt said hole transporting layer 320 to be adopted.Luminescent material (dopant material) for orange does not have special qualification, and (Rubrene (5,6 for example can to adopt lycid alkene; 11; 12-tetraphenylnaphthacene)) and DBzR (5,12-bis (4-(6-methylbenzothiazole-2-y1) phenyl)-6,11-diphenyl naphthacene) (DBzR (5; Two (4-(the 6-methylbenzene azoles-2-yl) phenyl)-6 of 12-, 11-diphenyl naphthonaphthalene)).Possess at dopant material under the situation of lighting function and higher cavity conveying property, the cavity conveying property compound concentrations that can be considered the 1st luminescent layer 330 is almost 100 quality %.
In the example of Fig. 1, in the multilayer luminescent layer, be formed on directly over said the 1st luminescent layer 330 near the 2nd luminescent layer 340 of negative electrode 240, and both contact with the 1st luminescent layer 330 and electron supplying layer 350.The 2nd luminescent layer 340 comprises the electron transport property compound of high concentration at least, in this form of implementation, is to adopt said cavity conveying property compound and electron transport property compound both are used as main material, and adopts blue luminescent material to be used as dopant material.This dopant material can by for example 10% or the concentration below it come main material is mixed.
The main material of the cavity conveying property of the 2nd luminescent layer 340 can be identical with said the 1st luminescent layer 330; Adopt the aromatic amine derivative compound; Main material for electron transport property; Except the metal-organic complex compound that said electron supplying layer 350 is adopted, also can adopt polycyclc aromatic compound.The metal complex compounds for example can adopt aforesaid aluminium oxyquinoline complex compound and this derivative.Polycyclc aromatic compound for example can adopt anthracene (Anthracene) series compound.
About an example of this anthracene series compound, ADN (9,10-di (2-naphthyl) anthracene) (AND (9,10-two (2-naphthyl) anthracene)) etc. is for example arranged.Said polycyclc aromatic compound for example can adopt to be possessed electron transport property and cavity conveying property and helps dopant etc. as the 1st luminescent layer 330.In the case help dopant, for example can adopt DPN (5,12-diphenyl naphthacene) (DPN (5,12-diphenyl naphthonaphthalene)) etc.Luminescent material (dopant material) for blueness does not have special qualification, for example can adopt perylene (Perylene) series compound and pyrene (Pyrene) series compound.
The cavity conveying property compound concentrations of the 2nd luminescent layer 340 can be set in 0 quality % to 50 quality %.In addition, electron transport property compound concentrations can be set in 100 quality % to 50 quality %.In addition, for example adopting like Alq
3As the compound with electron transport function and lighting function when being used as the 2nd luminescent layer 340, can adopt the electron transport property luminophor of 100 quality % separately.
As stated; In this form of implementation; Possessing 2 layers luminescent layer 330,340 and in hole transporting layer 320 and the 1st luminescent layer 330, containing under the situation of cavity conveying property compound at least, the cavity conveying property compound of the 1st luminescent layer 330 contain concentration be set as than the cavity conveying property compound of hole transporting layer 320 to contain concentration lower or equal.Possess simultaneously under lighting function and both situation of cavity conveying function at the luminescent material that the 1st luminescent layer 330 is adopted, the concentration that contains of the cavity conveying property compound of the 1st luminescent layer 330 is almost 100 quality %.And in the 2nd luminescent layer 340, also can adopt the cavity conveying property compound of a part, even but when adopting, this contain concentration also than the 1st luminescent layer 330 to contain concentration lower.Just, comparatively ideally be, in the organic layer of the multilayer that contains cavity conveying property compound, setpoint distance anode 220 layer far away of healing, it is lower that it contains concentration.When possessing the organic layer of the multilayer that contains electron transport property compound, the near organic layer but setpoint distance negative electrode 240 is healed, the concentration that contains of its electron transport property compound heals high.
Organic electroluminescent element 500 constitutes through above stromatolithic structure, and each layer begins lamination in regular turn from anode 220 above transparent insulation substrate such as glass or plastic film 100.Anode 220 for example can be formed by sputtering method, and light emitting element layer 300 and negative electrode 240 for example can come to form continuously through vacuum vapour deposition.Be used as the display element (light-emitting component) of each pixel of display unit and transistor be set in each pixel being applicable to keep and to control the situation of so-called active-matrix type display unit of the displaying contents of each pixel with this organic electroluminescent element 500; At the interlayer of said substrate 100 and anode 220, the layer of each image element circuit of transistor formed etc. is formed.
In so constituting, be injected in hole injection layer 310 from 220 injected holes of anode, the hole transporting layer 320 of high concentration ground through containing cavity conveying property compound, and arrive the 1st luminescent layer 330.In addition, be used as main material owing to contain the cavity conveying property compound of high concentration, therefore the 1st luminescent layer 330 also possesses cavity conveying property, so the hole arrives the 2nd luminescent layer 340 through the 1st luminescent layer 330.
On the other hand, from negative electrode 240 (from metal level 244 process electron injecting layers 360) the institute's electron supplying layer 350 of injected electrons high concentration ground, and arrive the 2nd luminescent layer 340 through containing electron transport property compound.As said, the electron transport property compound that also contains high concentration owing to the 2nd luminescent layer 340 possesses electron transport property, so electronics arrives the 1st luminescent layer 330 through the 2nd luminescent layer 340.
Therefore; In the 1st luminescent layer 330; The hole that comes from anode 220 with from negative electrode 240 through the 2nd luminescent layer 340 and the electronics that arrives combines again, and excite the light emitting molecule of dopant, and when returning ground state, can obtain to send the light of orange through the energy that combines again.In the 2nd luminescent layer 340, combine again with electronics from hole that anode 220 arrives through the 1st luminescent layer 330 from negative electrode 240, excite the light emitting molecule of dopant, and when returning ground state, can obtain to send the light of blueness.In the example of Fig. 1, all penetrate toward outside by the formed substrate 100 of transparent insulation materials such as glass from the side process of transparent anode 220 in the 2nd luminescent layer 340 blue light that is obtained and the orange light that is obtained in the 1st luminescent layer 330.Therefore, externally, because the additive color of blue light and orange light, and can observe out white light.
In this form of implementation, as stated, the organic layer that contains the multilayer of cavity conveying property compound at lamination is used as under the situation of light emitting element layer 300, be set at apart from the anode 220 near organic layer of healing, its cavity conveying property compound to contain concentration higher.Yet; Especially be Chi in the concentration that contains with the cavity conveying property compound of hole transporting layer 320; The concentration that contains with the cavity conveying property compound of the 1st luminescent layer 330 is Cem1; During with the containing concentration and be Cem2 of the cavity conveying property compound of the 2nd luminescent layer 340, comparatively ideal is to satisfy Cem1-Cem2>relation of Chi-Cem1.
Through enlarging the concentration difference between the 1st luminescent layer 330 and the 2nd luminescent layer 340, especially reduce the concentration of Cem2, can the cavity conveying property of the 2nd luminescent layer 340 be set at also lower than the 1st luminescent layer 330.When arriving negative electrode 240 if the 2nd luminescent layer 340 is passed in the hole, then this hole becomes idle current, and is unprofitable to luminous.In addition, even combine again with electronics, also, therefore be unprofitable to luminous owing to outside luminescent layer, there is not light emitting molecule usually at the interlayer of the 2nd luminescent layer 340 and negative electrode 240.When the material that has electron transport property and a lighting function in employing was used as electron supplying layer 350, it was luminous then to cause electron supplying layer 350 in non-purpose to produce, thereby caused the reduction of colorimetric purity.Therefore, comparatively ideal is the concentration gradient that is set in as said.
Under the situation that forms the luminescent layer more than 3 layers, as stated, be between the 1st luminescent layer 330 and the 2nd luminescent layer 340, to form luminescent layer again.In the case, in the 1st luminescent layer 330, be asked to higher cavity conveying ability, and comparatively ideal be to set cavity conveying property compound concentrations for example for up to about 100 quality % to 90 quality %.Relatively, in the 2nd luminescent layer 340, be asked to higher electron transport ability, it for example is the higher concentration of 100 quality % to 50 quality % that electron transport property compound is set for.For between the 1st luminescent layer 330 and the 2nd luminescent layer 340 and be formed at,, therefore contain cavity conveying property compound owing to must the hole be sent to the side of the 2nd luminescent layer 340 near the luminescent layer of the 1st luminescent layer 330.The cavity conveying property compound of the luminescent layer in the middle of this contain concentration can be set at also lower than the 1st luminescent layer 330, and than said the 2nd luminescent layer 340 to contain concentration also high.All can adopt identical cavity conveying property compound near luminescent layer of the 1st luminescent layer 330 (under the situation of the luminescent layer of 2 layers of structure, being the 2nd luminescent layer 340) and the 1st luminescent layer 330.Through adopting identical materials, can when for example waiting each layer of lamination light emitting element layer 300, form luminescent layer efficiently and easily adopt identical vapor deposition to originate with vacuum vapour deposition.
The characteristic of the EL part of formed form of implementation under said concentration relationship below is described.At first, will inject and be expressed as Th from anode 220 through the required time that hole injection layer 310, hole transporting layer 320 and the 1st luminescent layer 330 arrive the per unit distance in the hole till the 2nd luminescent layer 340.In addition; Inject and be expressed as Te from negative electrode 240 through the required time that electron supplying layer 350 and the 2nd luminescent layer 340 arrive the per unit distance of the electronics till the 1st luminescent layer 330; Under so representing; In the EL part 500 of this form of implementation that reaches the optimization concentration as said, ratio (Th/Te) satisfies 0.5 < (Th/>Te) < 2.5 relation.Comparatively ideal is to satisfy 1 ≦ (Th/>Te) < 2, and better is to satisfy 1.3 < (Th/>Te) < 1.7 relations.
The ratio of the arrival the 1st through making hole and electronics and the required time of the 2nd luminescent layer satisfies this relation, can make hole and electronics arrive opportunity and the hole of the 1st luminescent layer 330 and opportunity that electronics arrives the 2nd luminescent layer 340 becomes more approaching.
If the gap of said Th and Te is excessive; For example Th is more than 2.5 times of Te, then in 1st luminescent layer 330 nearest apart from anode, even hole and electronics arrived and produce luminous on opportunity much at one; But when arriving in the hole apart from nearest the 2nd luminescent layer 340 of negative electrode 240; Because electronics has passed through the 2nd luminescent layer 340 of electron transport property, so the probability that combines the again reduction of hole and electronics, and be difficult for producing luminous.Certainly, only luminous if on opposite opportunity in the generation of the 2nd luminescent layer, and can be not luminous in the 1st luminescent layer.Therefore, if the ratio of this required time of optimization not is also only luminous at central a part of luminescent layer even the multilayer luminescent layer then is set, and can't obtain the additive light (being white) of harmonious good purpose at this.Yet, through satisfying the ratio relation of said required time, for example being located at 1.3 to 1.7 scope, arrival reaches consistent opportunity, thereby can make the multilayer luminescent layer luminous harmoniously respectively.At this; The ratio Th/Te that sets required time is that one of more suitable reason more than 1 is; Be not only the control that the hole arrives arrival opportunity of the 2nd luminescent layer 340; And can through in light emitting element layer 300 as far as possible thickening cause the layer of the side of concavo-convex more anode because of the influence that receives lower floor, and prevent the broken string of light emitting element layer 300 and promote the poor covering property of section.
In this form of implementation, can consider the charge mobility (cm of charge transport material
2/ Vs) and the concentration of each layer of light emitting element layer 300 (better is also to consider thickness), adjust said required time Th, Te.At this, the charge transport material that light emitting element layer 300 is adopted (hole transporting material, electron transport materials) generally speaking has 10
-3To 10
-6The charge mobility (hole mobility, electron mobility) of scope, usually, this mobility is the value that when certain high concentration, is obtained.In addition, if the concentration increase then mobility also increase.Therefore, can make the concentration that contains of the charge transport material that each layer adopt reach optimization, and adjust the thickness of each layer, can realize said characteristic thus.
Charge mobility, thickness and the concentration of each layer below are described.
The hole mobility of the aromatic amine derivative compound that at first, in the main material of the material of hole transporting layer 320 and the 1st luminescent layer 330, is adopted is 10
-3Cm
2/ Vs to 10
-4Cm
2/ Vs when concentration (about 100 quality %).
The electron mobility of the metal-organic complex that in the main material of the material of electron supplying layer 350 and the 2nd luminescent layer 340, is adopted is 10
-4Cm
2/ Vs to 10
-6Cm
2/ Vs when concentration (about 100 quality %).Adopting polycyclc aromatic compound to be used as under the situation of main material of electron transport property of this 2nd luminescent layer 340, this compound possesses electronics and both conveying property of hole, and electron mobility is 10
-3Cm
2/ Vs to 10
-5Cm
2/ Vs, hole mobility also is 10
-3Cm
2/ Vs to 10
-5Cm
2/ Vs.
Can record said hole mobility and electron mobility through time-of-flight method (TOF:Time of Flight).Particularly; This TOF method be make mensuration material membrane (in this form of implementation; Organic compound material film for each layer) between the electrode of subtend each other, come lamination and double team with the concentration of about 100 quality %, through optical excitation with the interface of the electrode on one side of material membrane on produce electric charge carrier; And measure time of electrode that this electric charge carrier arrives the another side of institute's subtend, try to achieve mobility thus.
As implied above, when coming film forming with the concentration of about 100 quality %, have cavity conveying property and the hole mobility of known organic compound 10
-3Cm
2/ Vs to 10
-5Cm
2The scope of/Vs, and when coming film forming with the concentration of about 100 quality %, have electron transport property and the electron mobility of known organic compound 10
-3Cm
2/ Vs to 10
-6Cm
2The scope of/Vs.
The thickness of each layer then is described, hole injection layer 310 is 0.5nm to 5.0nm (under the situation of CFx) or 10nm to 20nm (under the situation of CuPc).Hole transporting layer 320 is 30nm to 300nm, and the 1st luminescent layer 330 is 10nm to 150nm, and the 2nd luminescent layer 340 is 20nm to 50nm, and electron supplying layer 350 is the thickness of 10nm to 30nm.
The relation of the charge mobility of light emitting element layer 300 and the thickness of each layer can be represented by following formula (1),
(Lhi/ μ hi)+(Lht/ μ ht)+(Lem1/ μ hem1)=α { (Lem2/ μ hem2)+(Let/ μ et) } ... formula (1)
In addition, α satisfies 0.5 < α < 2.5 relation.In said formula (1); Thickness with hole injection layer 310 is that Lhi, hole mobility are μ hi; Thickness with hole transporting layer 320 is that Lht, hole mobility are μ ht; Thickness with the 1st luminescent layer 330 is that Lem1, hole mobility are μ hem1, is that Lem2, electron mobility are μ hem2 with the thickness of the 2nd luminescent layer 340, is that Let, electron mobility are μ et with the thickness of electron supplying layer 350.In addition; Though α is comparatively ideal is to satisfy 1 ≦ α < relation of 2; Better is to be positioned at 1.3 < α < 1.7 scope; But, can obtain to make the 1st luminescent layer 330 and the 2nd luminescent layer 340 both luminous harmoniously and difficult long-life component constructions that produce broken string easily through making α greater than 0.5 and less than 2.5.
Next explain that the thickness that makes each layer is for fixing and change 6 kinds of organic electroluminescent elements 500 of the concentration of charge-transporting compound.For the EL part 500 of the 1st embodiment (real 1), 1-1 comparative example (than 1-1) and 1-2 comparative example (than 1-2), only the cavity conveying property material concentration of the 1st luminescent layer (EML1) and electron transport property material concentration are different.For the EL part 500 of the 2nd embodiment (=real 1), 2-1 comparative example (than 2-1) and 2-2 comparative example (than 2-2), only the cavity conveying property material concentration of the 2nd luminescent layer (EML2) and electron transport property material concentration are different.
Again, EL part 500 is that employing CuPc is hole injection layer (HIL) 310 (thickness 10nm), and the thickness of hole transporting layer (HTL) 320 forms 100nm, and adopts a kind of NPB of aromatic amines compound.The thickness of the 1st luminescent layer (EML1) 330 forms and adds up to 30.9nm; Main material adopts the NPB of cavity conveying property, and dopant adopts DBzR, helps dopant to adopt DPN (5; 12-diphenyl naphthacene) (DPN (5,12-diphenyl naphthonaphthalene)) (orange luminescent layer).The thickness of the 2nd luminescent layer (EML2) 340 forms 41.0nm; Main material adopts polycyclc aromatic compound; Particularly be the ADN (9,10-di (2-naphthyl) anthracene) (AND (9,10-two (2-naphthyl) anthracene)) of anthracene series compound; Dopant adopts perylene (Perylene) series compound, and interpolation NPB is used as cavity conveying property compound (blue light-emitting layer).In addition, the thickness of electron supplying layer (ETL) 350 forms 10nm, and adopts Alq3 (tris (8-hydroxyquinolinato) aluminum (III): aluminium oxyquinoline complex compound).For the said DPN that helps dopant possesses the bipolarity of cavity conveying property and electron transport property, the concentration of therefore assessing this DPN is used as the electron transport property compound concentration of the 1st luminescent layer.
Table 1
Said table 1 shows, concentration (weight %), thickness scaled value (nm) and the element luminous efficiency (cd/A) of each layer of each EL part of the 1st embodiment (real 1), 1-1 comparative example (than 1-1), 1-2 comparative example (than 1-2), the 2nd embodiment (real 2), 2-1 comparative example (than 2-1), 2-2 comparative example (than 2-2).
The concentration of the cavity conveying property compound (NPB) of the HTL/EML1/EML2/ETL of the EL part 500 of the 1st embodiment is 100%/93.9%/7.3%/0%.
In contrast to this, the HTL of 1-1 comparative example and 1-2 comparative example and the NPB concentration of EML2 are all 100% and 7.3%, and the NPB concentration of EML1 then becomes lower by 87.4% and 77.7%.
In addition, the electron transport property compound concentrations of the EL part 500 of the 1st embodiment is 0%/3.2%/90.2%/100% according to the order of HTL/EML1 (DPN concentration)/EML2 (ADN concentration)/ETL (Alq concentration).Than the element of this 1-1 comparative example and 1-2 comparative example, the electron transport property compound concentrations of EHL and EML2 is identical, but the concentration of the electron transport property compound (DPN) of the EML1 between being arranged at is 9.7% and 19.4% to become higher.The luminous efficiency of the 1st embodiment, 1-1 comparative example, 1-2 comparative example respectively is 14,12,10, and along with the minimizing (along with the increase of electron transport property compound concentration) of the cavity conveying property compound concentration of the 1st luminescent layer, luminous efficiency reduces.
At this; The material that can will demonstrate intrinsic mobility separately with 100% concentration for the 1st luminescent layer that contains multiple material and the 2nd luminescent layer is lamination in addition; And convert and try to achieve the α value of each EL part 500 of said each example with in the case thickness, in the 1st embodiment, α=1; In the 1-2 comparative example, α=2.5.
Numerical value according to the conversion benchmark of thickness merges mark with concentration in said table 1; In the 1st embodiment; Beginning from hole transporting layer, is NPB (100nm)/NPB (2.9nm)+DPN (1.0nm)+DBzR (0.9nm)/AND (37.0nm)+NPB (3.0nm)+BD (1.0nm)/Alq (10nm) in regular turn.
Fig. 3 has shown the luminescent spectrum intensity of the EL part 500 (α=1) of this 1st embodiment; This figure demonstrates the 1st luminescent layer 330 and the 2nd luminescent layer 340, and both are harmonious good luminous; And obtain the white light of purpose; And luminous efficiency is the 14cd/A (electrical efficiency is 6.11m/W) as said, therefore possesses excellent characteristic.
Fig. 4 shows, the NPB concentration in these 3 examples in the 1st luminescent layer is the luminescent spectrum intensity of the EL part 500 (α=2.5) of minimum 1-2 comparative example.Can learn that from Fig. 4 though the 1st luminescent layer 330 is luminous, the luminosity of the 2nd luminescent layer 340 is lower, 2 layers luminous harmonious relatively poor, and become near yellow white light.In addition, luminous efficiency is 10cd/A (electrical efficiency is 4.61m/W), is the value also lower than the 1st embodiment.
From Fig. 4, can learn; In the element of 1-2 comparative example; In the 2nd luminescent layer, can't obtain luminously fully, phenomenon can estimate thus, when the cavity conveying property concentration of material of the 1st luminescent layer is low; Cavity conveying quantity not sufficient from anode toward the 2nd luminescent layer 340, and be difficult for making the multilayer luminescent layer balancedly luminous.
Next; The HTL of the EL part 500 of 2-1 comparative example and 2-2 comparative example and the NPB concentration of EML1 respectively are 100% and 93.9%; Though identical with the 2nd embodiment (the 1st embodiment), the NPB concentration of EML2 is 14.6% and 19.5%, go back high than 7.3% of the 1st embodiment.About luminous efficiency; 14cd/A than the 1st embodiment; In the EL part 500 of 2-1 comparative example and 2-2 comparative example,, and descend along with lower (NPB concentration is higher) of the concentration of the ADN of the electron transport property compound in the 2nd luminescent layer (EML2) respectively for 11cd/A and 7cd/A (electrical efficiency is 3.21m/W).
Fig. 5 has shown the luminescent spectrum of the EL part (α=0.5) of 2-2 comparative example; Opposite with said 1-2 comparative example, though the 2nd luminescent layer 340 is luminous, the luminosity of the 1st luminescent layer 330 is lower; 2 layers luminous harmonious relatively poor, and become near blue white light.From this result, can infer; If possess electron transport property compound concentration lower from the 2nd luminescent layer of the function of electron transport to the 1 luminescent layer of electron supplying layer; Then electronics can't ample supply to the 1 luminescent layer, and can't be luminous fully in the 1st luminescent layer.
At this, be that the thickness of setting hole injection layer 310 is that 10nm, mobility [mu] hi are 10 in 1 the said organic electroluminescent element setting α value
-3Cm
2/ Vs, the thickness of hole transporting layer 320 are that 100nm, mobility [mu] ht are 10
-3Cm
2/ Vs, the thickness of the 1st luminescent layer 330 are that 30.9nm, mobility [mu] hem1 are 10
-3Cm
2/ Vs, the thickness of the 2nd luminescent layer 340 are that 41.0nm, mobility [mu] hem2 are 10
-3Cm
2/ Vs, the thickness of electron supplying layer 350 are that 10nm, mobility [mu] et are 10
-4Cm
2/ Vs.Certainly, thickness and mobility are not limited to these combinations, can be through producing said α value greater than 1 and make multilayer luminescent layer equilibrium and luminous efficiently less than 2.5 element.
In addition, can learn from described comparison that the concentration of hole transporting material that is positioned at 2nd luminescent layer also far away than the 1st luminescent layer (at this for blue light-emitting layer) from anode is higher, then luminous efficiency is lower, and luminous in addition harmony is variation also.Explain that from another viewpoint the concentration of hole transporting material that is arranged in 1st luminescent layer nearer apart from anode is lower,, and cause reduction and luminous balanced deterioration of efficient then toward the cavity conveying ability drop of the 2nd luminescent layer.
In addition, the concentration of electron transport materials that is positioned at 1st luminescent layer also far away than the 2nd luminescent layer (at this for the orange luminescent layer) from negative electrode is higher, and then luminous efficiency is lower, and luminous in addition harmony is variation also.Explain that from another viewpoint the concentration of electron transport materials that is arranged in 2nd luminescent layer nearer apart from negative electrode is lower,, and cause reduction and luminous balanced deterioration of efficient then toward the electron transport ability drop of the 1st luminescent layer.
Under tabulate and 2 show, in said the 1st embodiment, 1-1 comparative example, 1-2 comparative example, the relation between the difference of the concentration of the hole transporting material of the difference of the concentration of the hole transporting material of the 1st and the 2nd luminescent layer and hole transporting layer and the 1st luminescent layer.
Table 2
| ? | Cem1-Cem2 | Chi-Cem1 | (Cem1-Cem2)/(Chi-Cem1) | Luminous efficiency (cd/A) |
| The the 1st (2) embodiment | 86.6 | 6.1 | 14.2 | 14 |
| The 1-1 comparative example | 80.1 | 12.6 | 6.4 | 12 |
| The 1-2 comparative example | 70.4 | 22.3 | 3.2 | 10 |
[0098]As stated, the concentration of hole transporting material is comparatively ideal is to satisfy Cem1-Cem2>Chi-Cem1; From the result of said the 1st embodiment, 1-1 comparative example, 1-2 comparative example, can learn; Comparatively ideal is that (Cem1-Cem2) is also big more than (Chi-Cem1), it is desirable to more than 6 times, and better is (to be 14.2 times in the 1st embodiment) about 14 times.
The organic electroluminescent element 500 of this form of implementation not only can be used in through additive color white light is penetrated to outside white escope and planar light source, the display that also applicable to the additive color that passes through other arbitrary hue is penetrated etc.
In addition; As shown in Figure 2; Between white organic electroluminescent element 500 and substrate 10, for example can be and be used for making element formation face to reach between the smooth planarization insulating layer 180 at the interlayer insulating film that makes transistor insulation 160, form any of colored filter CF of 3 looks of corresponding R, G, B; And from the white light composition that organic electroluminescent element 500 is penetrated, only let desired R, G, B light component penetrate, can realize full-color demonstration thus.In addition, can not form colored filter yet, and carry out the colour demonstration through 4 kinds of colors of R, G, B and W (white) in the pixel of a part.Colored filter is not limited to 3 looks of R, G, B, also can be provided with again Y (yellow) and M (fuchsin, Magenta) etc.
Claims (3)
1. an EL part between hole injecting electrode and electron injection electrode, possesses the light emitting element layer that contains organic compound, wherein,
Said light emitting element layer possesses the multilayer luminescent layer, in this multilayer luminescent layer, being disposed between the 1st luminescent layer and this hole injecting electrode near hole injecting electrode, possesses hole transporting layer at least;
In said multilayer luminescent layer,, possesses electron supplying layer at least being disposed between the 2nd luminescent layer and this electron injection electrode near electron injection electrode;
Said the 1st luminescent layer possesses the cavity conveying function;
Said the 2nd luminescent layer possesses the electron transport function;
If arriving the required time in this hole till said the 2nd luminescent layer through said hole transporting layer and said the 1st luminescent layer from said hole injecting electrode institute injected holes is Th; And the required time of this electronics from said electron injection electrode institute injected electrons arrives said the 1st luminescent layer through said electron supplying layer and said the 2nd luminescent layer till is when being Te, and both ratio Th/Te satisfy the relation of following formula:
0.5＜(Th/Te)＜2.5。
2. an EL part possesses the light emitting element layer that contains organic compound between hole injecting electrode and electron injection electrode, wherein,
Said light emitting element layer possesses the multilayer luminescent layer, in this multilayer luminescent layer, being disposed between the 1st luminescent layer and this hole injecting electrode near hole injecting electrode, possesses hole transporting layer at least;
In said multilayer luminescent layer,, possesses electron supplying layer at least being disposed between the 2nd luminescent layer and this electron injection electrode near electron injection electrode;
Said the 1st luminescent layer possesses the cavity conveying function;
Said the 2nd luminescent layer possesses the electron transport function;
Required time to arrive this hole till said the 2nd luminescent layer through said hole transporting layer and said the 1st luminescent layer from said hole injecting electrode institute injected holes is Th, and
When the required time of this electronics from said electron injection electrode institute injected electrons arrives said the 1st luminescent layer through said electron supplying layer and said the 2nd luminescent layer till was Te, both ratio Th/Te satisfied the relation of following formula:
1≤(Th/Te)＜2。
3. an EL part possesses the light emitting element layer that contains organic compound between hole injecting electrode and electron injection electrode, wherein,
Said light emitting element layer possesses the multilayer luminescent layer; In this multilayer luminescent layer; Being disposed between the 1st luminescent layer and this hole injecting electrode near hole injecting electrode, possess hole injection layer at least and be configured in the hole transporting layer on the said hole injection layer;
In said multilayer luminescent layer,, possesses electron supplying layer at least being disposed between the 2nd luminescent layer and this electron injection electrode near electron injection electrode;
Said the 1st luminescent layer possesses the cavity conveying function;
Said the 2nd luminescent layer possesses the electron transport function;
If the thickness of said hole injection layer is Lhi, hole mobility is μ hi; The thickness of said hole transporting layer is that Lht, hole mobility are μ ht; The thickness of said the 1st luminescent layer is that Lem1, hole mobility are μ hem1; The thickness of said the 2nd luminescent layer is that Lem2, electron mobility are μ hem2, and the thickness of said electron supplying layer is Let, when electron mobility is μ et, satisfies the relation of following formula:
(Lhi/μhi)+(Lht/μht)+(Lem1/μhem1)＝α{(Lem2/μhem2)+(Let/μet)}；
Wherein, α satisfies the relation of 0.5＜α＜2.5.
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| JP2004289364 | 2004-09-30 | ||
| JP2004289358A JP2006107790A (en) | 2004-09-30 | 2004-09-30 | Electroluminescent element |
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