CN101577314B - Organic electroluminescent element - Google Patents
Organic electroluminescent element Download PDFInfo
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- CN101577314B CN101577314B CN 200910111362 CN200910111362A CN101577314B CN 101577314 B CN101577314 B CN 101577314B CN 200910111362 CN200910111362 CN 200910111362 CN 200910111362 A CN200910111362 A CN 200910111362A CN 101577314 B CN101577314 B CN 101577314B
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Abstract
The invention provides an organic electroluminescent element, comprising an anode layer, a cathode layer, an organic luminescent layer and a hole transport layer. The cathode layer comprises adjacent calcium electrode layer and aluminum electrode layer. The organic luminescent layer is arranged between the anode layer and the calcium electrode layer, wherein the material of the luminescent layer comprises a polymer material, a phosphorescence dopant and an organic electronic transportation material; content ratio of the organic electronic transportation material and the polymer material in theluminescent layer is 0.1-1, and the organic electronic transportation material is 1,3-di(4'-tert-butyl phenyl)-(1,3,4-furodiazole)-benzene. The hole transport layer is arranged between the luminescen t layer and the cathode layer. The invention effectively improves luminescence efficiency and has the advantages of simple production technique, high yield and low cost.
Description
[technical field]
The invention relates to a kind of light-emitting component, and particularly relevant for a kind of organic electroluminescent device.
[background technology]
At present, have in light weight and high efficiency display, LCD is for example developed widely and is widely used.Yet LCD still has many problems, and for example the visual angle is wide inadequately, response time can't be used in animation at a high speed inadequately soon, and needs backlight as auxiliary, causes more power consumption or the like.
And the flat-panel screens technology of New Development exhibition in recent years, promptly display of organic electroluminescence then can solve the above problems.Compared to other plane Display Technique, therefore advantages such as display of organic electroluminescence has that self-luminous, no visual angle are interdependent, power saving, processing procedure is simple and easy, low-cost, operating temperature range is big, high answer speed and full-colorization are expected to become the main flow of flat-panel screens of new generation.
Display of organic electroluminescence is a kind of self luminous characteristic of luminous organic material of utilizing, and to reach the display element of display effect, it is made of a pair of electrodes and an organic luminous layer, and wherein organic luminous layer comprises luminous organic material.Between electric current is by anode and metallic cathode, electronics is combined and when producing exciton, high-octane exciton becomes its power conversion light and produces display effect in luminescent material with electric hole.
And in the organic macromolecular LED element, in order to obtain preferable element luminous efficiency, organic luminous layer uses two kinds to mix more than the material usually, for example macromolecule and micromolecule.When producing the phenomenon that is separated between the multiple material of organic luminescent layer, the luminous efficiency of macromolecule element can significantly reduce.Specifically, when mixed effect is not good between macromolecule and the micromolecule, will causes to form between macromolecule and the micromolecule efficient energy and shift.On the other hand, when being separated between the composition material of organic luminescent layer, can make whole active layers surface inhomogeneous, cause electric leakage, cause the luminous efficiency of element to descend.
On the other hand, in existing cathode layer materials, the laminated electrode that uses cesium fluoride/aluminium (CsF/Al) to be constituted usually is used as cathode layer.Because the luminous efficiency of organic electroluminescent device is quite responsive for the varied in thickness of cesium fluoride layer in the cathode material, for example when the too thin or too thick performance that all can make black box of cesium fluoride variation significantly, make the processing procedure control of organic electroluminescent device be difficult for, the thickness variation of a little on manufacture craft of cesium fluoride layer can make that all the qualification rate decline and the consistency of organic electroluminescent device are not good.
Therefore, for organic electroluminescent device, except the factor of considering brightness and luminous efficiency, also need consider the difficulty or ease of manufacture craft and the height of cost.Therefore how when promoting organic electroluminescent device brightness and luminous efficiency, enhancing productivity and qualification rate, is current important problem.
[summary of the invention]
The technical problem to be solved in the present invention is to provide a kind of organic electroluminescent device, and it effectively promotes luminous efficiency, and manufacture craft is simple, formation efficiency is high, cost is low.
The present invention proposes a kind of organic electroluminescent device, comprise an anode layer, a cathode layer and an organic luminous layer, this organic luminous layer is between anode layer and cathode layer, wherein, this organic electroluminescent device also comprises an electric hole transport layer, and this electricity hole transport layer is between described organic luminous layer and this anode layer; Described cathode layer comprises an adjacent calcium electrode layer and an aluminium electrode layer, and calcium electrode layer is adjacent with described organic luminous layer; Described organic luminous layer is between this anode layer and this calcium electrode layer, the material of this organic luminous layer comprises a macromolecular material, a phosphorescent dopant and an organic electronic transferring material, and this organic electronic transferring material and this macromolecular material weight ratio are between 0.1 and 1, and wherein said organic electronic transferring material is 1,3-two (three grades of butyl phenyls of 4-)-(1,3, the 4-oxadiazoles]-benzene (1, and 3-bis (N, Nt-butyl-phenyl)-1,3,4-oxadiazole).
Wherein, the weight ratio of the organic electronic transferring material in the described organic luminous layer and this macromolecular material is 0.4 or 0.7.
The material of described macromolecular material be Polyvinyl carbazole (polyvinyl carbazole, PVK).
Described phosphorescent dopant be iridium (III) two (4,6-two (fluoro phenyl)-pyridine root-N, C2 '] pyridine carboxylic acid salt (iridium (III) bis[(4,6-difluorophenyl)-pyridinate-N, C2 '] pinacolate).
Described phosphorescent dopant is the object of this organic luminous layer.
The phosphorescent dopant in the described organic luminous layer and the weight ratio of macromolecular material are 0.1.
Described organic electronic transferring material is to be scattered between described macromolecular material and the phosphorescent dopant with physical force.
The material of described anode layer is an indium tin oxide.
The work function of described calcium electrode layer is 3.0eV, and the work function of described aluminium electrode layer is 4.2eV.
In sum, organic electroluminescent device of the present invention has following advantage:
The present invention in organic luminous layer in add the organic electronic transferring material of proper proportion, can improve the luminous efficiency of organic electroluminescent device so that carrying out energy between macromolecular material in the organic luminous layer and the phosphorescent dopant efficiently shifts.
2. the cathode layer that organic luminous layer collocation of the present invention is made of calcium electrode layer and aluminium electrode layer reduces the manufacture craft difficulty, can improve the qualification rate and the consistency of organic electroluminescent device, effectively reduces production costs.
[description of drawings]
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is the generalized section according to organic electroluminescent device one preferred embodiment of the present invention.
Fig. 2 is the luminous efficiency performance figure of organic electroluminescent device of the present invention under different organic electronic transferring material content.
Fig. 3 is the luminous power performance figure of organic electroluminescent device of the present invention under different organic electronic transferring material content.
Fig. 4 A is the atomic force microexamination of organic electroluminescent device of the present invention under the different organic electronic transferring material content performance figure of apparent height pattern really.
Fig. 4 B analyzes performance figure mutually for the surface of the atomic force microexamination of organic electroluminescent device of the present invention under different organic electronic transferring material content.
[embodiment]
See also shown in Figure 1ly, Fig. 1 is the generalized section according to organic electroluminescent device one preferred embodiment of the present invention.Organic electroluminescent device 200 comprises anode layer 210, cathode layer 220, organic luminous layer 230 and electric hole transport layer 240.Anode layer 210 is disposed on the substrate 202, and wherein the material of anode layer 210 can be indium tin oxide.Cathode layer 220 is disposed at anode layer 210 tops, and cathode layer 220 comprises adjacent calcium electrode layer 222 and aluminium electrode layer 224.Organic luminous layer 230 is between anode layer 210 and calcium electrode layer 222, and electric hole transport layer 240 is between organic luminous layer 230 and anode layer 210.The material of described organic luminous layer 230 comprises macromolecular material, phosphorescent dopant and organic electronic transferring material, wherein macromolecular material can be Polyvinyl carbazole (polyvinyl carbazole, PVK), and phosphorescent dopant can be an iridium (III) two (4,6-two (fluoro phenyl)-pyridine root-N, C2 '] pyridine carboxylic acid salt iridium (III) bis[(4,6-difluorophenyl)-and pyridinate-N, C2 '] pinacolate.
Organic electronic transferring material of the present invention and the content ratio of macromolecular material in organic luminous layer 230 are between 0.1 and 1, described organic electronic transferring material and the content ratio of macromolecular material in organic luminous layer 230 can be with percentage by weight, also can be that the present invention does not limit with molar percentage.In other words, add the organic electronic transferring material of proper proportion in the organic luminous layer 230, help the energy delivery between macromolecular material and the phosphorescent dopant, further promote the luminous efficiency of organic electroluminescent device 200.Furtherly, macromolecular material is mainly as the main body in the organic luminous layer 230, and phosphorescent dopant is the object in the organic luminous layer 230, and organic luminous layer 230 mainly shifts (energy transfer) by the macromolecular material produce power as main body (Host) to make luminous as the phosphorescent dopant of object (Guest).
Particularly, the organic electronic transferring material can be [1,3-two (three grades of butyl phenyls of 4-)-(1,3, the 4-oxadiazoles]-benzene, its chemical formula is as follows:
In other words, the organic electronic transferring material also can be to be oxadiazoles derivative [2-(4-Biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole, PBD]:
Because of but the organic electronic transferring material has conductive characteristic, it is made an addition in right amount in organic luminous layer 230, help the transmittability of electronics in organic luminous layer 230, particularly, organic electronic transmission molecule is to be scattered between each macromolecule main body and each the phosphorescence doping molecule with physical force in organic luminous layer 230, and wherein physical force for example is Fan Dewali.On the one hand, organic electronic transmission molecule can be used as the bridge between each macromolecule main body and the corresponding phosphorescence doping molecule, reduce the energy loss when energy shifts between macromolecular material and the phosphorescent dopant, help to promote the luminous efficiency of organic electroluminescent device 200.On the other hand, in organic luminous layer 230, be added with the organic electronic transferring material and can reduce the situation that is separated between macromolecular material and the phosphorescent dopant, so, the energy between macromolecular material and the phosphorescent dopant shifts and more can successfully carry out, and avoids energy loss between two interfaces.
The luminous efficiency and the spectrum performance of some real data aid illustration organic electroluminescent device 200 of the present invention below will be proposed.In the present embodiment, making the macromolecular material in the organic luminous layer and the weight ratio or the molar ratio of phosphorescent dopant content is 0.1, and macromolecular material and the phosphorescent dopant content in organic luminous layer 230 is fixing respectively, only change the content of organic electronic transferring material in organic luminous layer 230, specifically see Table one, table one is enumerated the element efficiency performance of organic electroluminescent device in several present embodiments.
Table one
It is maximum outside that organic electroluminescence is sent out the luminous merit of the maximum luminous maximum of organic electronic transmission material
Optical element material content/macromolecule material efficient (cd/A) rate (lm/W) quantum efficiency
Material content (%)
A 10/100 2.68 0.91 1.04
Please consult table one, Fig. 2 and Fig. 3 simultaneously, Fig. 2 is respectively luminous efficiency performance figure and the luminous power performance figure of organic electroluminescent device of the present invention under different organic electronic transferring material content with Fig. 3.Organic electroluminescent device A, B, C, D are that macromolecular material and phosphorescent dopant content are fixed, and change to add the organic electronic transferring material of different content respectively, wherein organic electroluminescent device A, B, C, D represent the content ratio respectively 10%, 40%, 70% and 100% o'clock situation in organic electronic transmission and the macromolecular material respectively.As shown in Table 1, in the organic luminous layer 230 of organic electroluminescent device C, the content ratio of organic electronic transferring material and macromolecular material is 0.4, and the content ratio of organic electronic transferring material and macromolecular material is 0.7 in the organic luminous layer 230 of organic electroluminescent device D.
Mainly, when organic electronic transferring material content/macromolecular material content is increased to 0.7 by 0.1, help to promote the luminous efficiency of organic electroluminescent device 200 referring to table one and shown in Figure 2.Though the organic electronic transferring material helps to reduce macromolecular material and the energy loss of phosphorescent dopant in the time shifting, to make the phosphorescent dopant in the organic luminous layer 230 excessively assemble and produce the phenomenon of the red displacement of spectrum but add excessive organic electronic transferring material, make that the performance of luminous efficiency of organic electroluminescent device 200 can't optimization.Therefore, in the present embodiment, the ratio of organic electronic transferring material content/macromolecular material content is good with 70/100.
Therefore, organic electroluminescent device of the present invention utilizes the composition of organic electronic transferring material as organic luminous layer 230, provides the another kind of organic luminous layer 230 composition materials to select.And, suitably control organic electronic transmission and the preferable proportion of composing of macromolecular material, effectively suppressed easily to produce the phenomenon that is separated between the macromolecule and micromolecule in the prior art, and then promoted the luminous efficiency of organic electroluminescent device.
Fig. 4 A and Fig. 4 B are respectively height pattern (height mode) the performance figure and the surface of the atomic force microexamination of organic electroluminescent device of the present invention under different organic electronic transferring material content and analyze (phase mode) performance figure mutually, and wherein to represent organic transferring material contained ratio in organic luminous layer respectively be 10%, 40%, 70% and 100% to 10,40,70 and 100 among Fig. 4 A and the 4B.Please refer to Fig. 4 A and Fig. 4 B, the content of organic electronic transferring material in organic luminous layer 230 also can influence topographical surface (topography) kenel of organic luminous layer 230, and the topographical surface of organic luminous layer 230 also is the key factor that influences efficiency of element.In the measurement result of reality, shown in Fig. 4 A and Fig. 4 B, utilize atomic force microscope (Atomic Force Microscope, AFM) surface of observation organic luminous layer 230, in the present embodiment, organic transferring material is to be that example compares with OXD-7, and OXD-7 as described above it [1,3-two (three grades of butyl phenyls of 4-)-(1,3, the 4-oxadiazoles]-benzene.
Ratio rising along with organic electronic transferring material content/macromolecular material content, the surface of organic luminous layer 230 gets over smoothly, in the present embodiment, especially the ratio with organic electronic transferring material content/macromolecular material content is 0.7 o'clock, the surface of organic luminous layer 230 is comparatively level and smooth, therefore the organic electronic transferring material has the phenomenon of phase separation of effectively slowing down between macromolecular material and the phosphorescent dopant, and make phosphorescent dopant to be distributed in uniformly in the macromolecular material, and then allow the energy between macromolecular material and the phosphorescent dopant shift more efficient.On the other hand, add the organic electronic transferring material of proper content in organic luminous layer 230, for example OXD-7 can effectively improve the phenomenon that is separated.
Please assist with reference to table one, Fig. 2 and Fig. 3, in the present embodiment, the ratio of organic electronic transferring material content/macromolecular material content is 0.7 o'clock, and the organic electronic transferring material can effectively slow down the phenomenon of phase separation in the organic luminous layer 230, lift elements brightness and luminous efficiency.
Please continue with reference to Fig. 1, on the material selection of cathode layer 220, the present invention uses the electrode of calcium electrode 222 and aluminium electrode layer 224 laminated as cathode layer 220, wherein calcium electrode 222 is between aluminium electrode layer 224 and organic luminous layer 230, so that work function is complementary between the rete of adjacency, and make carrier between adjacent rete, not transmit with being hindered, reduce the energy loss of carrier, wherein the work function of calcium electrode layer 222 is essentially 3.0eV, and the work function of aluminium electrode layer 224 is essentially 4.2eV.On the other hand, the present invention's aluminium coating electrode layer 224 again on calcium electrode layer 222 avoids oxidation in order to further protection calcium electrode layer 222.Specifically, on organic operating mechanism, electronics can be injected organic luminous layer 230 and be formed negative pole beggar (negative ions) by cathode layer 220, and electric hole then can be injected into organic luminous layer 230 and be formed anodal beggar (positive ions) by anode layer 210.Anodal beggar and negative pole beggar move toward relative direction respectively, and in conjunction with forming singlet exciton (exciton), the singlet exciton of part can discharge excess energy to get back to ground state in the luminescent layer in the mode of electroluminescence in luminescent layer.
What deserves to be mentioned is, different with existing cesium fluoride layer is, the thickness of calcium electrode layer 222 of the present invention has more stable variation tendency for the luminous efficiency of organic electroluminescent device 200, making on the practice, a little varied in thickness on the manufacture craft can't influence the qualification rate and the luminous efficiency of organic electroluminescent device 200, therefore can reach preferable product percent of pass and consistency, and material obtains facility, cost is lower.
In addition, on the making aspect, organic electroluminescent device 200 shown in Figure 1 can be to form anode layer 210 with sputtering method earlier on substrate 202.Then, the mode with rotary coating forms electric hole transport layer 240 and organic luminous layer 230 on anode layer 210.Afterwards, respectively calcium electrode layer 222 and aluminium electrode layer 224 are formed on the organic luminous layer 230 with hot vapour deposition method again.
Certainly, it is as shown in Figure 1 four-layer structures that the present invention does not limit organic electroluminescent device 200, and it can be actual required and be designed to five-layer structure or six layers of structure.For example, in one embodiment, except anode layer 210, electric hole transport layer 240, organic luminous layer 230 and cathode layer 220, also can between anode layer 210 and electric hole transport layer 240, dispose an electric hole implanted layer.In another embodiment, except anode layer 210, electric hole transport layer 240, organic luminous layer 230 and cathode layer 220, also can between cathode layer 220 and organic luminous layer 230, dispose an electron transfer layer.In another embodiment, except anode layer 210, electric hole transport layer 240, organic luminous layer 230 and cathode layer 220, also can between cathode layer 220 and organic luminous layer 230, dispose an electron injecting layer.The material of described electric hole implanted layer, electron transfer layer and electron injecting layer is not limited especially, and can adopt employed material in the prior art.And described electric hole implanted layer, electron transfer layer and electron injecting layer select for use also can according to reality required and select one of them, wherein two or three layers all use.
Though disclosed preferred embodiment of the present invention as mentioned above; but it is not in order to limit the present invention; those skilled in the art change and retouching when doing some, so protection scope of the present invention should be as the criterion with claim without departing from the spirit and scope of the present invention.
Claims (8)
1. an organic electroluminescent device comprises an anode layer, a cathode layer and an organic luminous layer, and this organic luminous layer is characterized in that between anode layer and cathode layer:
This organic electroluminescent device also comprises an electric hole transport layer, and this electricity hole transport layer is between described organic luminous layer and this anode layer;
Described cathode layer comprises an adjacent calcium electrode layer and an aluminium electrode layer, and calcium electrode layer is adjacent with described organic luminous layer;
Described organic luminous layer is between this anode layer and this calcium electrode layer, the material of this organic luminous layer comprises a macromolecular material, a phosphorescent dopant and an organic electronic transferring material, and this organic electronic transferring material and this macromolecular material weight ratio are 0.4 or 0.7, and wherein said organic electronic transferring material is 1,3-two (three grades of butyl phenyls of 4-)-(1,3, the 4-oxadiazoles]-benzene (1, and 3-bis (N, Nt-butyl-phenyl)-1,3,4-oxadiazole).
2. organic electroluminescent device as claimed in claim 1 is characterized in that: the material of described macromolecular material be Polyvinyl carbazole (polyvinyl carbazole, PVK).
3. organic electroluminescent device as claimed in claim 1, it is characterized in that: described phosphorescent dopant is an iridium (III) two (4,6-two (fluoro phenyl)-pyridine root-N, C2 '] pyridine carboxylic acid salt (iridium (III) bis[(4,6-difluorophenyl)-and pyridinate-N, C2 '] pinacolate).
4. organic electroluminescent device as claimed in claim 1 is characterized in that: described phosphorescent dopant is the object of this organic luminous layer.
5. organic electroluminescent device as claimed in claim 1 is characterized in that: the phosphorescent dopant in the described organic luminous layer and the weight ratio of macromolecular material are 0.1.
6. organic electroluminescent device as claimed in claim 1 is characterized in that: described organic electronic transferring material is to be scattered between described macromolecular material and the phosphorescent dopant with physical force.
7. organic electroluminescent device as claimed in claim 1 is characterized in that: the material of described anode layer is an indium tin oxide.
8. organic electroluminescent device as claimed in claim 1 is characterized in that: the work function of described calcium electrode layer is 3.0eV, and the work function of described aluminium electrode layer is 4.2eV.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6452218B1 (en) * | 1997-06-10 | 2002-09-17 | Uniax Corporation | Ultra-thin alkaline earth metals as stable electron-injecting electrodes for polymer light emitting diodes |
| CN1373908A (en) * | 1999-07-19 | 2002-10-09 | 优尼爱克斯公司 | Long-lifetime polymer light-emitting devices with improved luminous efficiency and radiance |
| CN1505450A (en) * | 2002-10-24 | 2004-06-16 | ��ʽ��������Զ�֯�������� | Organic electroluminescent device |
| CN1728903A (en) * | 2004-07-29 | 2006-02-01 | 三星Sdi株式会社 | Organic field illuminator |
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2009
- 2009-03-27 CN CN 200910111362 patent/CN101577314B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6452218B1 (en) * | 1997-06-10 | 2002-09-17 | Uniax Corporation | Ultra-thin alkaline earth metals as stable electron-injecting electrodes for polymer light emitting diodes |
| CN1373908A (en) * | 1999-07-19 | 2002-10-09 | 优尼爱克斯公司 | Long-lifetime polymer light-emitting devices with improved luminous efficiency and radiance |
| CN1505450A (en) * | 2002-10-24 | 2004-06-16 | ��ʽ��������Զ�֯�������� | Organic electroluminescent device |
| CN1728903A (en) * | 2004-07-29 | 2006-02-01 | 三星Sdi株式会社 | Organic field illuminator |
Non-Patent Citations (1)
| Title |
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| 张方辉等.基于MEH-PPV/PVK混合发光层的白光PLED发光机理探讨.《陕西科技大学学报》.2008,第26卷(第4期),45-48. * |
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