CN102270751A - Organic electrophosphorescent luminescent device and preparation method thereof - Google Patents
Organic electrophosphorescent luminescent device and preparation method thereof Download PDFInfo
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Abstract
The invention provides an organic electrophosphorescent luminescent device. The device comprises an anode, a hole transporting layer, a phosphorescent luminescent layer, an electron transporting layer and a cathode, wherein the anode, the hole transporting layer, the phosphorescent luminescent layer, the electron transporting layer and the cathode are stacked up orderly; besides, the device also comprises: a first exciton barrier layer that is arranged between the hole transporting layer and the phosphorescent luminescent layer; and/or a second exciton barrier layer that is arranged between the electron transporting layer and the phosphorescent luminescent layer. Both the first exciton barrier layer and the second exciton barrier layer not only have an electron transporting property but also have a hole transporting property; moreover, triplet state energy levels of the first exciton barrier layer and the second exciton barrier layer are greater than or equal to a triplet state energy level of a phosphorescent luminescent material in the phosphorescent luminescent layer. Compared with the prior art, the technology employed in the invention enables the efficiency and the service life of the organic electrophosphorescent luminescent device to be substantially improved. In addition, the invention also provides a method for preparing the organic electrophosphorescent luminescent device.
Description
Technical field
The present invention relates to a kind of organic electro-phosphorescent luminescent device, also relate to the method that is used to prepare this organic electro-phosphorescent luminescent device.
Background technology
Organic electro-phosphorescent luminescent device comprises anode, hole transmission layer, phosphorescence luminescent layer, electron transfer layer and the negative electrode that stacks successively usually.If the triplet of electron transfer layer or hole transmission layer is lower than the triplet of phosphorescent light-emitting materials in the phosphorescence luminescent layer, the triplet excitons that produces under the operating state just is diffused in electron transfer layer or the hole transmission layer easily, causes that glow color is impure, luminous efficiency descends.But the electron transport material or the hole mobile material that possess high triplet are more limited, so people expect increasing the barrier layer of exciton, hole or electronics in organic electro-phosphorescent luminescent device, exciton is limited to purpose in the luminescent layer thereby when the triplet of electron transfer layer or hole transmission layer is low, also can reach.Baldo etc. in US6097147 with hole barrier materials for example BCP be inserted between luminescent layer and the negative electrode, limiting the migration in hole, and the resulting exciton of electron-hole recombinations is limited in the luminescent layer.Forrest group (referring to Appl.Phys.Lett., 75,4,1999) once added the BCP hole blocking layer between luminescent layer and electron transfer layer, make the efficient of green glow phosphorescence device reach 9%.But, no matter be BCP, the still TPBI (Appl.Phys.Lett. that found afterwards, 81,162,2002), the heterocyclic compound of Bphen and short of electricity is as triazole (Appl.Phys.Lett., 78,1622,2001), triazine (Chem.Mater., 10,3620,1998) oxadiazole (Jpn.J.Appl.Phys.Part2,39, L828,2000), imidazoles (Macromol.Symp., 125,1,1997), 1,8-naphthalimide (J.Am.Chem.Soc., 124,9945,2002) etc., these materials all can cause the lost of life of organic electroluminescence device as hole blocking layer.
In addition, people such as Thompson join electronic barrier layer in the organic electro-phosphorescent luminescent device in US6951694, by add electronic barrier layer between hole transmission layer and luminescent layer, eliminate electron-osmosis, improve luminous efficiency.
Kodak is in the Chinese patent (application number: 200880021085.4) of application on June 3rd, 2008, such organic electro-phosphorescent luminescent device structure has been described, promptly add two-layer electronic barrier layer between hole transmission layer and luminescent layer, it can improve the efficient of organic electro-phosphorescent luminescent device.
Global OLED Technology LLC is in the Chinese patent (application number: 200980110328.6) of application on January 27th, 2009, such organic electro-phosphorescent luminescent device structure has been described, promptly between luminescent layer and electron transfer layer, add two-layer hole blocking layer, improved luminous efficiency.
Yet the use on the barrier layer of these single character is little to the efficient and the improvement amplitude in life-span of device.The efficient and the improvement in life-span at device still have bigger space.
Summary of the invention
The object of the present invention is to provide a kind of organic electro-phosphorescent luminescent device, this device not only significantly improves on luminous efficiency, and also significant prolongation of life-span.
For this reason, the invention provides such organic electro-phosphorescent luminescent device, it comprises the anode that stacks successively, hole transmission layer, the phosphorescence luminescent layer, electron transfer layer and negative electrode, and, this device also comprises at first exciton barrier-layer between hole transmission layer and the phosphorescence luminescent layer and/or second exciton barrier-layer between electron transfer layer and phosphorescence luminescent layer, described first exciton barrier-layer and second exciton barrier-layer had all both had electric transmission character and had also had hole transport character, and its triplet is all more than or equal to the triplet of phosphorescent light-emitting materials in the phosphorescence luminescent layer.
In addition, the invention provides a kind of method for preparing organic electro-phosphorescent luminescent device, described method comprises: deposit the anode that is laminated to each other on substrate successively, hole transmission layer, the phosphorescence luminescent layer, electron transfer layer and negative electrode, encapsulation then, and described method also is included in step that deposits deposition first exciton barrier-layer between hole transmission layer and the deposition phosphorescence luminescent layer and/or the step that deposits second exciton barrier-layer between deposition electron transfer layer and deposition phosphorescence luminescent layer, described first exciton barrier-layer and second exciton barrier-layer had all both had electric transmission character and had also had hole transport character, and its triplet is all more than or equal to the triplet of phosphorescent light-emitting materials in the phosphorescence luminescent layer.
By using first exciton barrier-layer and/or second exciton barrier-layer, organic electro-phosphorescent luminescent device of the present invention not only increases than prior art on luminous efficiency, and with prior art in use the single electronic barrier layer or the device of hole blocking layer to compare the life-span significant prolongation.In addition, use described first exciton barrier-layer and/or second exciton barrier-layer not to influence the colourity of device substantially.
Description of drawings
Fig. 1 is the structural representation of organic electro-phosphorescent luminescent device in the prior art.
Fig. 2 is the structural representation of the organic electro-phosphorescent luminescent device of one embodiment of the invention.
Fig. 3 is the structural representation of the organic electro-phosphorescent luminescent device of another embodiment of the present invention.
Fig. 4 is the structural representation of the organic electro-phosphorescent luminescent device of another embodiment of the present invention.
Embodiment
In the present invention, as do not have other explanations, then all operations carries out under normal temperature and pressure conditions.
Organic electro-phosphorescent luminescent device of the present invention comprises anode, hole transmission layer, phosphorescence luminescent layer, electron transfer layer and the negative electrode that stacks successively, and, it also comprises at first exciton barrier-layer between hole transmission layer and the phosphorescence luminescent layer and/or second exciton barrier-layer between electron transfer layer and phosphorescence luminescent layer, described first exciton barrier-layer and second exciton barrier-layer had all both had electric transmission character and had also had hole transport character, and its triplet is all more than or equal to the triplet of phosphorescent light-emitting materials in the phosphorescence luminescent layer.
Described first exciton barrier-layer can be formed also and can be made up of two or more materials by homogenous material, and the triplet of these materials is all more than or equal to the triplet of phosphorescent light-emitting materials.Under the situation that first exciton barrier-layer is made up of homogenous material, this material has electric transmission character and hole transport character, i.e. bipolarity simultaneously.And preferably its hole mobility is 10
-6～10
-2Cm
2V
-1s
-1, electron mobility is 10
-6～10
-2Cm
2V
-1s
-1, more preferably its hole mobility is 10
-4～10
-2Cm
2V
-1s
-1, electron mobility is 10
-4～10
-2Cm
2V
-1s
-1
Under the situation that first exciton barrier-layer is made up of two or more materials, one or more materials wherein are the material of electric transmission character, and all the other materials are the material of hole transport character.The electron mobility of the material of this electric transmission character is 10
-6～10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1, the hole mobility of the material of this hole transport character is 10
-6～10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1, and the mass ratio of the material of the material of hole transport character and electric transmission character is 1: 0.01～1: 1, is preferably 1: 0.2～1: 0.6, more preferably 1: 0.4-1: 0.5.
Preferably, the lumo energy of forming the material of described first exciton barrier-layer all is higher than the lumo energy of luminescent layer material of main part, thereby plays the effect of block electrons in addition.More preferably wherein the lumo energy of at least a material is higher than-3.0eV, preferably is higher than-2.5eV.
The thickness of described first exciton barrier-layer is preferably 1～50nm, more preferably 3～20nm.
Described second exciton barrier-layer can be formed also and can be made up of two or more materials by homogenous material, and the triplet of these materials is all more than or equal to the triplet of phosphorescent light-emitting materials.Under the situation that second exciton barrier-layer is made up of homogenous material, this material has electric transmission character and hole transport character simultaneously, and preferably its hole mobility is 10
-6～10
-2Cm
2V
-1s
-1, electron mobility is 10
-6～10
-2Cm
2V
-1s
-1, more preferably its hole mobility is 10
-4～10
-2Cm
2V
-1s
-1, and electron mobility is 10
-4～10
-2Cm
2V
-1s
-1
Under the situation that second exciton barrier-layer is made up of two or more materials, one or more materials wherein are the material of electric transmission character, and all the other materials are the material of hole transport character.The electron mobility of the material of this electric transmission character is 10
-6～10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1, the hole mobility of the material of this hole transport character is 10
-6～10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1, and the mass ratio of the material of the material of electric transmission character and hole transport character is 1: 0.01～1: 1, is preferably 1: 0.2～1: 0.6, more preferably 1: 0.4-1: 0.5.
Preferably, the HOMO energy level of forming the material of described second exciton barrier-layer all is lower than the HOMO energy level of luminescent layer material of main part, thereby plays the effect of blocking hole in addition.More preferably in the material of forming described second exciton barrier-layer, wherein the HOMO energy level of at least a material is lower than-5.0eV, preferably is lower than-5.5eV.
The thickness of described second exciton barrier-layer is preferably 1～50nm, more preferably 3～20nm.
Under the situation that first exciton barrier-layer or second exciton barrier-layer are made up of homogenous material, material therefor can be selected from carbazole derivates, quinoxaline derivant, cyano-containing compound, more preferably is selected from CBP, BNPB, PAP-NPA.Material therefor can also be selected from the compound with following general formula:
In the following formula, Ar be selected from naphthylene, connection naphthylene, anthrylene, benzo anthrylene, Ya perylene base, inferior pyrenyl, phenylene pyridine radicals, diphenylene pyridine radicals,
Dibenzo
N is selected from 1 to 3 integer.
Preferred, material therefor is selected from the compound with following structural formula:
Under the situation that first exciton barrier-layer or second exciton barrier-layer are made up of two or more materials, the material of described hole transport character is selected from aromatic compound and carbazole derivates.The material of hole transport character is preferably selected from TPD, TCTA, TAPC, mCP, 4P-NPD, BPAPF, NPAPF, TTP.The material of described electric transmission character is selected from: metallo-chelate, oxazole derivatives, quinoline, quinoline derivant, thiazole, imdazole derivatives, pyridinyl compounds, fluorene derivative, silicon-containing compound, and boron-containing compound.Wherein metallo-chelate preferably contains Be, contains Ga, contains Al, contains Zn and contains the metallo-chelate of In.The material of electric transmission character is preferably selected from Bepp
2, Bebq
2, Bphen, TPBI, BCP, H1, H2, TAZ, BAlq, PH1, PH2, PH3, TBB, F-TBB, TFB, TFPB, TPhB, TBPhB, TTPhB, TTPhPhB.
The structural formula of each material mentioned above is as follows:
The phosphorescence luminescent layer comprises at least a material of main part of at least a phosphorescent light-emitting materials that mixed usually, described phosphorescent light-emitting materials is to contain atomic number greater than 36 compounds less than 84 at least a atom, and described atom is preferably selected from iridium, platinum, osmium, europium, molybdenum, tungsten, silver and golden.Described material of main part can be the material that this area routine is used for this purpose, for example small molecule material such as metal organic complex, carbazole derivates etc.In the material of main part is benchmark, and the doping content of phosphorescent light-emitting materials is generally 0.5～40%, is preferably 5%～25%.
Hole transmission layer and electron transfer layer all can adopt the material that is usually used in hole transmission layer or electron transfer layer in the prior art.As the material of hole transmission layer, can use for example arylamine class material or the low molecular material of branch polymer class etc.As the material of electron transfer layer, can use for example metal organic complex, aromatic condensed ring class or o-phenanthroline class etc.
Negative electrode can adopt metal or metal mixture to make, the Ca that Mg, the Ag that mixes as Ag mixes etc.Also electron injecting layer can be combined with negative electrode, form electron injecting layer/metal-layer structure, as LiF/Al, Li
2Common structure such as O/Al.
Anode can be in the organic electro-phosphorescent luminescent device conventional anode commonly used, ito anode for example, IZO anode.
In addition, between anode and phosphorescence luminescent layer, also can have hole injection layer, and between negative electrode and phosphorescence luminescent layer, also can have electron injecting layer.Hole injection layer and electron injecting layer all can adopt the material that is usually used in hole injection layer or electron injecting layer in the prior art.The hole injection layer material can be for example m-MTDATA, and the electron injecting layer material can be for example LiF.
No matter the barrier layer of using in the prior art is one deck or two-layer, its character all is single, promptly simple electronic barrier layer or simple hole blocking layer for having electric transmission character for having hole transport character.Therefore, when hole in the luminescent layer during more than electronics, interface at luminescent layer/hole blocking layer forms cation easily, cationic accumulation can cause the exciton quencher, thereby can influence the efficient and the life-span of device,, form anion easily at the interface of electronic barrier layer/luminescent layer when electronics in the luminescent layer during more than the hole, anionic accumulation can cause the exciton quencher equally, also can influence the efficient and the life-span of device.
And the inventor finds, character when the barrier layer shows as bipolarity, when promptly having hole transport character and electric transmission character simultaneously, is difficult at luminescent layer/interface, barrier layer accumulation cation or anion, thereby reduced the exciton quencher, can improve the efficient of device and prolong life-span of device.And, because the process that electronics transmits in organic material is a succession of redox process, the material of single character is through long-time redox meeting deterioration, and bipolar materials is compared with the material of single character and more is difficult for deterioration, thereby improved the life-span of device.
In addition, the present invention also provides a kind of method for preparing organic electro-phosphorescent luminescent device, comprise: on substrate, deposit the anode that is laminated to each other successively, hole transmission layer, the phosphorescence luminescent layer, electron transfer layer and negative electrode, encapsulation then, and described method also is included in step that deposits deposition first exciton barrier-layer between hole transmission layer and the deposition phosphorescence luminescent layer and/or the step that deposits second exciton barrier-layer between deposition electron transfer layer and deposition phosphorescence luminescent layer, described first exciton barrier-layer and second exciton barrier-layer had all both had electric transmission character and had also had hole transport character, and its triplet is all more than or equal to the triplet of phosphorescent light-emitting materials in the phosphorescence luminescent layer.Wherein, described at device of the present invention as mentioned to the qualification of each parts.
Described deposition can realize by the conventional deposition process that is used to form these material layers in the prior art, for example by physical vapor deposition, chemical vapor deposition method etc.
Described encapsulation can be undertaken by the method for packing that is usually used in organic electroluminescence device in the prior art.
Hereinafter further specify the present invention, but the invention is not restricted to these specific embodiments by embodiment.
Concrete Comparative Examples and embodiment are as follows:
Used following material among the embodiment:
As bipolar materials: CBP, compound 1-5, compound 2-27;
As hole transport ability material: TCTA;
As electron-transporting material: Bepp
2, Bphen, Bebq
2
As luminescent layer material of main part: Bepp
2, TCTA, Bebq
2
Shown in the following Table A of the character of above-mentioned material.
Table A
Comparative Examples 1
1. glass substrate is cleaned and oven dry.Then at sputter one deck ITO on glass as anode, thickness is 180nm;
2. the above-mentioned glass substrate that has anode is placed in the vacuum chamber, be evacuated to 1 * 10
-5Pa, the method evaporation one deck hole injection layer that on above-mentioned anode layer, adopts double source to steam altogether, deposition material is HIL (m-MTDATA) doping HD (F4-TCNQ), and doping content is 4%, and evaporation speed is 0.1nm/s, and the evaporation thickness is 150nm;
3. on above-mentioned hole injection layer, continue evaporation one deck hole transmission layer, deposition material is NPB, and evaporation speed is 0.1nm/s, and the evaporation thickness is 20nm;
4. the method that adopts double source to steam altogether again, evaporation green glow phosphorescence luminescent layer, the material of phosphorescence luminescent layer is Bepp
2Doping Ir (ppy)
3, doping content is 12%, and the evaporation speed of this layer is 0.1nm/s, and the evaporation thickness is 30nm;
5. on above-mentioned phosphorescence luminescent layer, continue evaporation one deck electron transfer layer Bepp
2
6. last, evaporation LiF layer and Al layer are as the electron injecting layer and the cathode layer of device successively on above-mentioned layer, and wherein the evaporation speed of LiF layer is 0.01～0.02nm/s, and thickness is 0.7nm, and the evaporation speed of Al layer is 2.0nm/s, and thickness is 150nm.
7. deposit after these layers, this experiment slice is delivered in the glove box, encapsulate.
Comparative Examples 2
Preparation process is identical with Comparative Examples 1, except at hole transmission layer NPB and phosphorescence luminescent layer Bepp
2: Ir (ppy)
3Between add the electronic barrier layer TCTA of the thick hole transport character of one deck 10nm.
Embodiment 1
Preparation process is identical with Comparative Examples 1, except at hole transmission layer NPB and phosphorescence luminescent layer Bepp
2: Ir (ppy)
3Between add the first exciton barrier-layer CBP that one deck 10nm possesses hole transport character and electric transmission character thick the time.
Embodiment 2
Preparation process is identical with embodiment 1, except the first exciton barrier-layer material C BP is replaced by TCTA doping Bepp
2, doping content is 50%.
As can be seen from Table 2, the device efficiency of Comparative Examples 2 and life-span are higher than Comparative Examples 1, and device efficiency in embodiment 1 and 2 and life-span all are higher than Comparative Examples 1 and 2.
The device performance of the Comparative Examples 2 of use TCTA layer is higher than the device performance of Comparative Examples 1.This is because after adding the TCTA layer between luminescent layer and the hole transmission layer NPB, because the triplet of TCTA is higher than green glow phosphorescent coloring Ir (ppy)
3Triplet, so triplet excitons can not pass on the triplet of NPB.And the lumo energy of TCTA is higher than the material of main part Bepp of green glow phosphorescence luminescent layer
2Lumo energy, possess the effect of block electrons.So the device in the Comparative Examples 2 is compared in efficient with on the life-span with Comparative Examples 1 and all had a certain upgrade, but the amplitude that improves is not too high.
Embodiment 1 compares with Comparative Examples 2 with 2, is being further enhanced on the efficient He on the life-span.For embodiment 1, both possessed hole transport character as the CBP of first exciton barrier-layer, possess electric transmission character again, this with Comparative Examples 2 in only to possess the TCTA of very strong hole transport character different.Moreover the triplet of CBP is higher than phosphorescent coloring Ir (ppy) in the green glow phosphorescence luminescent layer
3Triplet, so triplet excitons can not pass on the hole transmission layer NPB.And the lumo energy of the first exciton barrier-layer CBP is higher than luminescent layer material of main part Bepp
2Lumo energy, therefore possess the electronics barrier effect.
For embodiment 2, TCTA and Bepp
2Through overdoping, produced first exciton barrier-layer that not only possesses hole transport character but also possess electric transmission character.And TCTA and Bepp
2Triplet all be higher than phosphorescent coloring Ir (ppy) in the green glow phosphorescence luminescent layer
3Triplet.In addition, the lumo energy of TCTA is higher than luminescent layer material of main part Bepp
2Lumo energy, therefore possess the electronics barrier effect.
In addition, as can be seen from Table 2, no matter be embodiment 1, or embodiment 2, compare with Comparative Examples 1, add first exciton barrier-layer after, all do not change device colourity originally substantially.
The device architecture of table 1 Comparative Examples 1-2 and embodiment 1-2
The device performance of table 2 Comparative Examples 1-2 and embodiment 1-2
Comparative Examples 3
Preparation process is identical with the preparation process of Comparative Examples 1, except the material of main part of luminescent layer is replaced by TCTA.
Comparative Examples 4
Identical with the preparation process of Comparative Examples 3, except at luminescent layer TCTA:Ir (ppy)
3With electron transfer layer Bepp
2Between add the hole blocking layer Bphen of the thick electric transmission character of one deck 10nm.
Embodiment 3
Preparation process is identical with Comparative Examples 3, except at phosphorescence luminescent layer TCTA:Ir (ppy)
3With electron transfer layer Bepp
2Between add the second exciton barrier-layer CBP that one deck 10nm possesses hole transport character and electric transmission character thick the time.
Embodiment 4
Preparation process is identical with embodiment 3, and except the second exciton barrier-layer CBP is replaced by Bphen doping TCTA, doping content is 50%.
Bphen and TCTA obtain to possess ambipolar second exciton barrier-layer through overdoping.
The triplet of Bphen and TCTA is higher than luminescent layer dyestuff Ir (ppy)
3Triplet, so second exciton barrier-layer of its composition also can effectively be limited to triplet excitons in the luminescent layer.In addition, the HOMO energy level of Bphen is-6.0eV, and the HOMO energy level of CBP is-5.9eV, and the HOMO energy level of luminescent layer material of main part TCTA is-5.7eV, so all can play the effect of blocking hole.As can be seen from Table 4, device efficiency among the embodiment 3 and 4 and life-span are higher than Comparative Examples 3 and 4.And increasing by second exciton barrier-layer does not influence the colourity of device substantially.
The device architecture of table 3 Comparative Examples 3-4 and embodiment 3-4
The device performance of table 4 Comparative Examples 3-4 and embodiment 3-4
Comparative Examples 5
Preparation process is identical with the preparation process of Comparative Examples 1, except the material of main part of luminescent layer is replaced by CBP.
Comparative Examples 6
Preparation process is identical with the preparation process of Comparative Examples 5, except respectively at hole transmission layer NPB and phosphorescence luminescent layer CBP:Ir (ppy)
3Between add the electronic barrier layer TCTA of one deck hole transport character, and at electron transfer layer Bepp
2With phosphorescence luminescent layer CBP:Ir (ppy)
3Between add the hole blocking layer Bphen of one deck electric transmission character.
Embodiment 5
Preparation process is identical with Comparative Examples 6, except electronic barrier layer TCTA being replaced by the first exciton barrier-layer TCTA doping CBP, and hole blocking layer Bphen is replaced by the second exciton barrier-layer Bphen doping CBP, the doping ratio of CBP in TCTA is that the doping ratio of CBP in Bphen also is 10% in 10%, the second exciton barrier-layer in first exciton barrier-layer.
Embodiment 6
Preparation process is identical with embodiment 5, except the doping ratio with first exciton barrier-layer and second exciton barrier-layer is adjusted into 30% respectively.
Embodiment 7
Preparation process is identical with embodiment 5, except the doping ratio with first exciton barrier-layer and second exciton barrier-layer is adjusted into 50% respectively.
Embodiment 8
Preparation process is identical with embodiment 5, except the thickness with first exciton barrier-layer and second exciton barrier-layer is adjusted into 2nm respectively.
As can be seen from Table 6, the efficient of embodiment 5-8 and life-span all are better than Comparative Examples 5 and 6.
Adopted the first different exciton barrier-layers and the doping content and the thickness of second exciton barrier-layer among the embodiment 5-8, found that, the efficient of embodiment 6 and life-span optimum.
The device architecture of table 5 Comparative Examples 5-6 and embodiment 5-6
The device performance of table 6 Comparative Examples 5-6 and embodiment 5-6
Comparative Examples 7
Preparation process is identical with the preparation process of Comparative Examples 1, except luminescent layer is replaced by Bebq
2Doping Ir (piq)
3, electron transfer layer is replaced by Bebq
2
Embodiment 9
Preparation process is identical with the preparation process of Comparative Examples 7, except at hole transmission layer NPB and phosphorescence luminescent layer Bebq
2: Ir (piq)
3Between add the first exciton barrier-layer compound 1-5.
Comparative Examples 8
Preparation process is identical with the preparation process of Comparative Examples 7, except luminescent layer being replaced by NPB doping Ir (piq)
3
Embodiment 10
Preparation process is identical with the preparation process of Comparative Examples 8, except at electron transfer layer Bebq
2With phosphorescence luminescent layer Bebq
2: Ir (piq)
3Between add the second exciton barrier-layer compound 2-27.
As can be seen from Table 8, the efficient of embodiment 9 and life-span are better than Comparative Examples 7, and the efficient of embodiment 10 and life-span are better than Comparative Examples 8.And embodiment 9 and 10 colourity do not have to change with respect to each Comparative Examples substantially.
The device architecture of table 7 Comparative Examples 7-8 and embodiment 9-10
The device performance of table 8 Comparative Examples 7-8 and embodiment 9-10
Claims (15)
1. organic electro-phosphorescent luminescent device, comprise the anode, hole transmission layer, phosphorescence luminescent layer, electron transfer layer and the negative electrode that stack successively, it is characterized in that, it also comprises at first exciton barrier-layer between hole transmission layer and the phosphorescence luminescent layer and/or second exciton barrier-layer between electron transfer layer and phosphorescence luminescent layer, described first exciton barrier-layer and second exciton barrier-layer had all both had electric transmission character and had also had hole transport character, and its triplet is all more than or equal to the triplet of phosphorescent light-emitting materials in the phosphorescence luminescent layer.
2. the organic electro-phosphorescent luminescent device of claim 1 is characterized in that, described first exciton barrier-layer is made up of homogenous material, and its hole mobility is 10
-6～10
-2Cm
2V
-1s
-1, electron mobility is 10
-6～10
-2Cm
2V
-1s
-1, preferably its hole mobility is 10
-4～10
-2Cm
2V
-1s
-1, electron mobility is 10
-4～10
-2Cm
2V
-1s
-1
3. the organic electro-phosphorescent luminescent device of claim 1, it is characterized in that, described first exciton barrier-layer is made up of two or more materials, one or more materials wherein are the material of electric transmission character, all the other materials are the material of hole transport character, and the electron mobility of the material of described electric transmission character is 10
-6～10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1, the hole mobility of the material of described hole transport character is 10
-6～10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1
4. the organic electro-phosphorescent luminescent device of claim 3 is characterized in that, the mass ratio of the material of the material of described hole transport character and described electric transmission character is 1: 0.01～1: 1, is preferably 1: 0.2～1: 0.6, more preferably 1: 0.4-1: 0.5.
5. the organic electro-phosphorescent luminescent device of claim 1, it is characterized in that, the lumo energy of forming the material of described first exciton barrier-layer all is higher than the lumo energy of luminescent layer material of main part, and more preferably wherein the lumo energy of at least a material is higher than-3.0eV, preferably is higher than-2.5eV.
6. the organic electro-phosphorescent luminescent device of claim 1 is characterized in that, the thickness of described first exciton barrier-layer is 1～50nm, preferred 3～20nm.
7. the organic electro-phosphorescent luminescent device of claim 1 is characterized in that, described second exciton barrier-layer is made up of homogenous material, and its hole mobility is 10
-6～10
-2Cm
2V
-1s
-1, electron mobility is 10
-6～10
-2Cm
2V
-1s
-1, preferably its hole mobility is 10
-4～10
-2Cm
2V
-1s
-1, and electron mobility is 10
-4～10
-2Cm
2V
-1s
-1
8. the organic electro-phosphorescent luminescent device of claim 1 is characterized in that, second exciton barrier-layer is made up of two or more materials, and one or more materials wherein are the material of electric transmission character, and all the other materials are the material of hole transport character.The electron mobility of the material of this electric transmission character is 10
-6～10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1, the hole mobility of the material of this hole transport character is 10
-6-10
-2Cm
2V
-1s
-1, be preferably 10
-4～10
-2Cm
2V
-1s
-1
9. the organic electro-phosphorescent luminescent device of claim 8 is characterized in that, the mass ratio of the material of the material of described electric transmission character and described hole transport character is 1: 0.01-1: 1, be preferably 1: 0.2～1: 0.6, more preferably 1: 0.4-1: 0.5.
10. the organic electro-phosphorescent luminescent device of claim 1, it is characterized in that, the HOMO energy level of forming the material of described second exciton barrier-layer all is higher than the HOMO energy level of luminescent layer material of main part, and the preferred wherein HOMO energy level of at least a material is lower than-5.0eV, preferably is lower than-5.5eV.
11. the organic electro-phosphorescent luminescent device of claim 1 is characterized in that, the thickness of described second exciton barrier-layer is 1～50nm, preferred 3～20nm.
12. the organic electro-phosphorescent luminescent device of claim 2 or 7, it is characterized in that, the material of the material of described first exciton barrier-layer or second exciton barrier-layer is selected from carbazole derivates, quinoxaline derivant and cyano-containing compound, more preferably is selected from CBP, BNPB and PAP-NPA.
13. the organic electro-phosphorescent luminescent device of claim 12 is characterized in that, the material of the material of described first exciton barrier-layer or second exciton barrier-layer is selected from the compound with following general formula:
In the following formula, Ar be selected from naphthylene, connection naphthylene, anthrylene, benzo anthrylene, Ya perylene base, inferior pyrenyl, phenylene pyridine radicals, diphenylene pyridine radicals,
Dibenzo
N is selected from 1 to 3 integer.
14. the organic electro-phosphorescent luminescent device of claim 3 or 8 is characterized in that, the material of described hole transport character is selected from: aromatic compound and carbazole derivates are preferably selected from TPD, TCTA, TAPC, mCP, 4P-NPD, BPAPF, NPAPF, TTP; The material of described electric transmission character is selected from: metallo-chelate, oxazole derivatives, quinoline, quinoline derivant, thiazole, imdazole derivatives, pyridinyl compounds, fluorene derivative, silicon-containing compound, and the compound of boracic, wherein metallo-chelate preferably contains Be, contain Ga, contain Al, contain Zn and the metallo-chelate that contains In, the material of described electric transmission character is preferably selected from Bepp2, Bebq2, Bphen, TPBI, BCP, H1, H2, BAlq, TAZ, PH1, PH2, PH3, TBB, F-TBB, TFB, TFPB, TPhB, TBPhB, TTPhB and TTPhPhB.
15. method for preparing organic electro-phosphorescent luminescent device, be included in and deposit the anode that is laminated to each other on the substrate successively, hole transmission layer, the phosphorescence luminescent layer, electron transfer layer and negative electrode, encapsulation then, it is characterized in that also being included in step that deposits deposition first exciton barrier-layer between hole transmission layer and the deposition phosphorescence luminescent layer and/or the step that between deposition electron transfer layer and deposition phosphorescence luminescent layer, deposits second exciton barrier-layer, described first exciton barrier-layer and second exciton barrier-layer had all both had electric transmission character and had also had hole transport character, and its triplet is all more than or equal to the triplet of phosphorescent light-emitting materials in the phosphorescence luminescent layer.
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