CN100570919C - Organic electroluminescence device and manufacture method thereof - Google Patents
Organic electroluminescence device and manufacture method thereof Download PDFInfo
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- CN100570919C CN100570919C CNB2005800272895A CN200580027289A CN100570919C CN 100570919 C CN100570919 C CN 100570919C CN B2005800272895 A CNB2005800272895 A CN B2005800272895A CN 200580027289 A CN200580027289 A CN 200580027289A CN 100570919 C CN100570919 C CN 100570919C
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Abstract
Constitute accurately provide on the anode of organic electroluminescence devices have 0.2 to 30nm thickness, seldom projection the smooth intermediate film layer and have superficial layer to the high-adhesiveness of luminescent layer, wherein said organic electroluminescence device comprises the luminophor layer that is present between anode and the negative electrode.Utilizing dry process method by RF plasma processing or the wet treatment method by spin coating method etc. in the middle of forming on the anode, behind the rete, preferably middle rete to be carried out smoothness, adhesiveness and the thickness of optimal treatment (flushing) with the adjustment film.When using wet treatment method, preferably also before forming film, carry out the surface treatment of antianode, with control smoothness and surface condition.Carry out before forming the intermediate layer and thickness, smoothness and adhesiveness that processing afterwards can controlling diaphragm, and can obtain to have high emission efficiency and the organic electroluminescence device of long device lifetime.
Description
The cross reference of related application
The application is based on the application that 35U.S.C. the 111st (a) joint is submitted to, save according to 35U.S.C. the 119th (e) (1), requirement saves the U.S. Provisional Application sequence No.60/607 that submits on September 7th, 2004 according to 35U.S.C. the 111st (b), the No.60/666 that on March 3rd, 257 and 2005 submitted to, 594 priority.
Technical field
The present invention relates to be used for backlight, outside and the upholstery of display unit, lighting apparatus, display unit and the organic electroluminescence device (OLED) that the plane shows the source.More specifically, the present invention relates to have good characteristic aspect luminous efficiency and the durability and between anode and negative electrode, comprising the organic electroluminescence device of luminophor layer, wherein on anode, provide to have 0.2 level and smooth intermediate layer to 30nm thickness.
Background technology
Organic luminescent device has at first been reported its high radiance (luminance) emission (referring to, Appl.Phys.Lett., Vol.51, page 913 (1987)) by the people such as C.W.Tang of Kodak in 1987.From that time, obtain rapid development aspect the improvement of material development and device architecture, and in recent years, in fact organic luminescent device is being used for the demonstration of automobile-used sound equipment or cellular phone.For further widening the purposes of this organic electroluminescent (EL) device, the developing material of the current device performance that has actively carried out being used to improving emission effciency, glow color or durability aspect or the exploitation of panchromatic demonstration.For further improving the organic light-emitting device performance, be necessary to set up device architecture that is suitable for material behavior and the method for making device with the exploitation luminescent material.The method of improving device property is low molecule or polymer material and difference according to luminescent material.Begin to describe background technology from lower-molecular substance.
The luminescent material that is used for organic electroluminescence device that people such as C.W.Tang propose is a low molecular compound.Less than what change be at that time and now, utilize low molecular compound as luminescent material, vacuum deposition method is widely used in being formed with organic electroluminescence devices.In the organic electroluminescence device that people such as C.W.Tang propose, by vapour deposition two kinds of low molecular compounds of sequential aggradation on anode substrate, and further thereon deposition cathode have the device of double-layer structure with formation.Select an organic layer with injection and transporting holes (hole transport compound), and select another organic layer to inject and transmission electronic (electric transmission compound).Interface between two-layer is provided for the light emission (referring to U.S. Patent No. 4,356,429 and be used for other patent publication No. of instantiation) of the position of electrode and hole-recombination and generation.
The above-mentioned organic electroluminescence device that has a double-layer structure in the exploitation has obtained great development in early days, and has provided a plurality of examples, has the improvement that three layers or more multi-layered sandwich construction obtain device performance by employing in these examples.
Therefore, for converting electrical energy into luminous energy, attempt to have the organic compound of different carrier transmission characteristics also further by improving device performance with best-fit order layer by layer deposition compound by combination with minimal losses.Not only aspect hole transport or the electron transport material but also all carrying out being used to obtain the needed material improvement of high-performance aspect the luminescent material.As a result, by replacing fluorescent material with phosphor material, obtained to surpass 5% external quantum efficiency, this external quantum efficiency of 5% is said to be maximal efficiency (the Proceedings of the 11 that adopts fluorescent material
ThInternational Workshopon Inorganic and Organic Electroluminescence (EL2002), pages 283-286,2002).
The factor that helps improving device performance not only is to constitute the luminescent material of device, and luminescent material is applied the anode of voltage and the formation of negative electrode greatly influences performance too.
Known now, by the negative electrode of use low work function and the anode of high work function, can significantly reduce the operating voltage of organic electroluminescent (EL) device.As described in people's such as people's such as Tang U.S. Patent No. 4,885,211 and Van Slyke the U.S. Patent No. 5,059,062, the negative electrode preferably metal by being lower than 4.0eV in conjunction with its work function and its work function metal of being higher than 4.0eV constitutes.People's such as Hung U.S. Patent No. 5,677,572 has been described and has been utilized the LiF-Al bilayer to inject with the electronics that improves organic electroluminescent (EL) device.
In organic electroluminescence device, because its transparency, high conductivity and high work function, anode is formed by tin indium oxide (ITO) usually.But the organic electroluminescence device of making by the film that directly forms the hole transport compound on naked ITO surface has inadequate I-E characteristic and lower job stability usually.It is mainly owing to the dielectric breakdown of the electric field that causes for the high injection barrier in hole, by the lip-deep projection of ITO.A kind of method of avoiding these problems is to introduce the method in intermediate layer between ITO and hole transport compound.For example, people's examples such as Van Slyke when being attached to copper phthalocyanine (CuPc) on the ITO surface in advance, the organic assembly of Zhi Zaoing has stability (the Organic electroluminescent devices with improvedstability of raising thus, S.A.Van Slyke, C.H.Chen and C.W.Tang, Applied Physics Letters, Vol.69,2160,1996).But when inserting the CuPc layer between ITO and the hole transport compound, the hole injection barrier that exists on the interface between CuPc and the hole transmission layer is still very high, and this causes driving voltage to increase.From CuPc, the exploitation of material has been carried out extensive studies to alleviate the injection barrier for the hole.Under any circumstance, utilize the characteristic of low molecular compound, attempt by utilizing the only compound of vacuum moulding machine layer by layer deposition on anode surface to improve device performance.
As mentioned above, although vacuum moulding machine is the method that is widely used in the film that forms low mulecular luminescence material, shortcoming need to be vacuum plant.And the area of the organic film that will form is big more, and just difficult more formation has the organic film of uniform thickness and forms high-resolution patterning.Therefore, this method is unsuitable for the batch process of large tracts of land panel.And this method has in formation and also has difficulty aspect the sandwich construction of suitable film thickness.
As the method that addresses these problems, spin-coating method, ink-jet method and print process that development is considered to suitable organic light-emitting device enlarged areas and batch process form method as film.In these methods, when coating is dissolved in luminescence polymer material in the organic solvent when forming film on anode, the coating of luminescent layer is finished.Have only and when forming negative electrode, just carry out vapour deposition.Even utilizing under the organic light-emitting device situation of luminescence polymer material, the improvement of material is necessary for obtaining high performance device, as the situation of the device that utilizes low mulecular luminescence material.And improved mode is different from the situation of the device of the sandwich construction with low molecular material.
In organic light-emitting device typical structure of the present invention, on transparent substrates, form anode (transparent), intermediate layer, luminescent layer and negative electrode in regular turn.Here, the intermediate layer can be called anode buffer layer, and in order to insert this intermediate layer by making anode surface smoothly prevent electrical short and alleviating the purpose that stops that the hole from the luminescent layer to the anode is injected.The effect of the desired effect of antianode resilient coating and the CuPc that proposes in making low molecule organic luminescent device much at one.Make the polymer organic luminescent device by the polymer that coating is dissolved in the organic solvent, and by subsequently by dry process will on be deposited to and make low molecule organic luminescent device in the lower floor.Therefore, slightly different under required characteristic in the intermediate layer in the polymer organic luminescent device and the low molecule organic luminescent device situation.Just, below during the step that the upper strata is coated on the intermediate layer 2 very crucial: the composition of intermediate layer material must be not dissolved in the solvent that is used on the intermediate layer coating upper strata, if these compositions can not be dissolved in the solvent, then they should not peeled off by physical impacts or disperse when coating.And when finishing drying steps after coating, the interface between upper strata and the intermediate layer should have sufficient adhesive force.Under this condition, electrical characteristics that require the intermediate layer to have to be presented (can make anode surface level and smooth, alleviate for stopping of injecting of hole etc.) and physics and chemical characteristic as low molecule organic electroluminescent device (should not experience change as be accompanied by energising and place and in the crystallization and the diffusion of multilayer).
The aqueous solution that will gather the mixture of ethylidene dioxy thiophene (PEDOT) and polystyrolsulfon acid ester (PSS) usually is used for the intermediate layer.For this intermediate layer, pointed out such problem, the polystyrolsulfon acid ester that promptly comprises as outside dopant infiltrates to be gone up luminescent layer and makes its deterioration thus.
This problem that causes for the counter ion that comprises in the anode buffer layer by moving, although the Japanese translation of announcing of PCT international publication No.2003-509816 (WO2001/01888) discloses the method for the anode buffer layer that utilizes self-doped polyaniline, it does not successfully present enough characteristics of this layer.
As relating to technology of the present invention, the open No.2000-311869 of Japanese Patent Laid discloses the surface modifying method by the organic electroluminescence device of radio frequency (RF) plasma treatment.But it is different with the application of the present invention that wherein forms new layer on anode surface that this plasma is used.The open No.2000-150171 (EP 1026757A2) of Japanese Patent Laid discloses a kind of organic electroluminescence device, be aggregated on the anode by radio frequency plasma wherein that to form its thickness be 0.2 to 3nm, preferred 0.4 to 1nm thin polymer film, and luminous sandwich construction is provided thereon.But the disclosure is not described and is comprised the single luminescent layer of polymer as luminescent material.
Summary of the invention
An object of the present invention is to provide and a kind ofly have the organic electroluminescence device of long-life and high maximum luminosity to solve the aforementioned problems in the prior.And, another object of the present invention is, problem at the intermediate layer that in organic electroluminescence device, comprises, provide improved organic electroluminescence device to avoid the problem in conventional intermediate layer, particularly, provide a kind of and comprise that comprising thickness is 0.2 organic electroluminescence device to the anode in the level and smooth intermediate layer of 30nm.
As result for the problems referred to above broad research of solving prior art, the inventor finds to comprise that comprising thickness in its surface is that the organic electroluminescence device of the anode in 0.2 to 30nm level and smooth intermediate layer presents the emission effciency and the job stability of raising, and has realized the present invention.
Just, the present invention (I) relates to the organic electroluminescence device that comprises the luminophor layer that is present between anode and the negative electrode, and it is 0.2 to the level and smooth intermediate layer of 30nm that wherein said anode comprises thickness in its surface.
The present invention (II) relates to the organic electroluminescence device of invention (I), and wherein said luminophor is the phosphorescent polymer material.
The present invention (III) relates to the organic electroluminescence device of invention (I), and wherein said luminophor is a fluorescent material.
Particularly, the present invention relates to the manufacture method of organic electroluminescence device as described below, the backlight that is used for display unit and lighting device.
1. the manufacture method of an organic electroluminescence device, described organic electroluminescence device comprises the luminophor layer that is present between anode and the negative electrode, it is 0.2 to the intermediate layer of 30nm that wherein said anode comprises thickness in its surface, and described method is characterised in that by the wet treatment coating process and forms described intermediate layer and with the step on the surface in the described intermediate layer of solvent washing of the composition that can dissolve described luminophor.
2. as the method for describing in top 1, wherein said luminophor is the phosphorescent polymer material.
3. as the method for describing in top 1, wherein said luminophor is a fluorescent material.
4. as the method for describing in top 1, wherein said intermediate layer has the 1nm that is expressed as the Ra value or littler surface roughness.
5. as the method for describing in top 1, the lip-deep projection in wherein said intermediate layer has 10nm or lower height.
6. as the method for describing in top 1, be included in the step that forms the surface of the described anode of RF plasma processing before the described intermediate layer.
7. as the method for describing in top 6, wherein in comprising one or more the gas that is selected from oxygen, argon and fluorocarbon, carry out described RF plasma processing, with the height of the lip-deep projection of the surface roughness of adjusting described anode and described anode.
8. as the method for describing in top 1, wherein said intermediate layer comprises organic material.
9. as the method for describing in top 1, wherein said intermediate layer comprises conducting polymer.
10. as the method for describing in top 1, the solvent that wherein can dissolve described luminophor composition is an isopropyl alcohol.
11. a backlight that is used for display unit, its use by as top 1 to 10 in the organic electroluminescence device that obtains of the manufacture method of any one description as flat luminous light source.
12. a lighting device, its use by as top 1 to 10 in the organic electroluminescence device that obtains of the manufacture method of any one description as flat luminous light source.
Description of drawings
Fig. 1 be the stacked package of anode upper strata contain luminophor the layer organic light-emitting device illustrate.
Fig. 2 is phosphorescence part (moiety) and the carrier transport part in non-conjugated phosphorescent polymer.
Fig. 3 is result's the chart of the serviceability test of example organic luminescent device 1 (comparative example 1), organic luminescent device 4 (example 2), organic luminescent device 6 (example 3) and organic luminescent device 7 (example 4).
Embodiment
Hereinafter more detailed description the present invention.
The present invention (I) is necessary but do not obtain the intermediate layer of enough performances as yet in order to improve in conventional organic electroluminescence device.In other words, the invention provides a kind of organic electroluminescence device that comprises the luminophor layer that is present between anode and the negative electrode, its problem that can avoid conventional intermediate layer (promptly, cause deterioration to penetrate into factor in the luminescent layer) as molecule from the intermediate layer, and can keep being arranged on the effect in the intermediate layer between anode and the luminescent layer, that is, anode surface injection level and smooth and that alleviate the hole is stopped.
To specifically describe embodiments of the invention with reference to the accompanying drawings.
Fig. 1 is the sectional view of example that the structure of organic electroluminescence device of the present invention is shown, and wherein forms intermediate layer (3) and luminescent layer (4) in regular turn being arranged between anode (2) on the transparent substrates (1) and the negative electrode (5).
Anode is formed by the conduction and the optical clear layer of ITO representative.The optical transparence of anode is necessary for observing organic light emission by substrate.Simultaneously, the optical transparence of anode under the situation of promptly observing organic light emission by top-emission by top electrode not necessarily, and suitable materials, as metal or metallic compound with 4.1eV or higher work function all can be used for anode.For example, can be separately or use gold, nickel, manganese, iridium, molybdenum, palladium or platinum in combination.Anode can be selected from oxide, nitride, selenides or the sulfide of metal.The film that can will be formed by above-mentioned metal with form of film with 1 to 3nm thickness does not damage the anode of the optical transparence of ITO as being arranged on the ITO surface.The method that forms film on the anode material surface comprises electron beam deposition method, sputtering method, chemical reaction method, coating method and vacuum deposition method.The thickness of anode is preferably 2 to 300nm.
The structure of organic electroluminescence device of the present invention is not limited to the example of Fig. 1.Other example can comprise such device architecture, wherein between anode and negative electrode, be provided with 1 subsequently) intermediate layer/hole transmission layer/luminescent layer, 2) intermediate layer/luminescent layer/electron transfer layer, 3) intermediate layer/hole transmission layer/luminescent layer/electron transfer layer, 4) intermediate layer/comprise hole mobile material, the layer of luminescent material and electron transport material, 5) intermediate layer/the comprise layer of hole mobile material and luminescent material, 6) intermediate layer/the comprise layer of luminescent material and electron transport material, 7) intermediate layer/the comprise layer of hole-electron transport material and luminescent material, perhaps 8) intermediate layer/luminescent layer/hole blocking layer (blocking layer)/electron transfer layer.Perhaps, although the luminescent layer shown in Fig. 1 is single layer, also two or more luminescent layers can be set.In this manual, unless otherwise mentioned, otherwise will comprise that all of electron transport material, hole mobile material and luminescent material or one or more compound (layer) are called luminophor (layer).
Can improve the performance (alleviating of stopping etc. injected in the tack of antianode substrate, the smoothness of finished surface, hole) in intermediate layer by preliminary treatment anode surface before forming the film in intermediate layer.Preprocess method comprises, from RF plasma processing, sputter process, corona discharge (corona) are handled, UV ozone treatment and oxygen plasma treatment.
The first embodiment of the present invention provides the organic electroluminescence device that comprises such anode, and comprising thickness on the surface of this anode is 0.2 to 30nm, the intermediate layer of preferred 0.2 to 10nm organic compound.
Do not limit the composition or the chemical constitution of the organic substance that forms the intermediate layer especially.But, below characteristic be primary for the organic substance that forms behind the intermediate layer, promptly, its composition will be stacked must not dissolved as the luminophor on the upper strata in intermediate layer by coating again, should during applying step, do not peeled off or spread, and have high tack luminophor by physical impacts.As long as its have satisfy above demand characteristics and film thickness, then without limits to the kind of the compound that is used for the intermediate layer.As the examples for compounds with good adhesion, compound preferably comprises the part-structure that has with the strong interaction of luminophor.Particularly preferably in expecting aromatic rings, alkyl chain, fluorine of hydrophobic interaction etc. as comprising with suitable amount in the compound of this part-structure.Compound needs not to be organic material, also can be inorganic material such as metal fluoride, metal oxide or comprises the compound such as the SiO of silicon
2
The method that is used to form the film in intermediate layer broadly is divided into wet treatment method and dry process method such as RF plasma processing, vacuum moulding machine and the laser induced thermal imaging that wherein composition is dissolved in the coated solvent.In arbitrary type, all can adopt normally used various film formation method.
Forming under the situation in intermediate layer by the wet treatment coating, after forming film, carry out optimal treatment by spin coating method, casting method, nick version printing-type coating method, the brush coating method of intaglio process, bar type coating (bar coating) method, method of roll coating, coiling bar type coating (wire-bar coating) method, dip coating method, spraying method, method for printing screen, flexographic printing (flexo printing) method, offset printing method and ink jet printing method.Just, in order to improve or change film characteristics, can be by obtaining the intermediate layer with solvent washing (cleaning) the film surface that can dissolve the luminophor composition.With in the solvent washing step, can with the applying step in intermediate layer in use method similarly as spin coating method, ink ejecting method and dipping method.In other words, by using the solvent washing surface, can remove in the step of stacked luminophor as the upper strata during the new composition that may disperse or spread that produces.And, after the intermediate layer covers not gentle projection on the substrate surface fully, adjust and not only can remove attached to the lip-deep excessive composition that disengages, and can make intermediate layer maintenance surface smoothing with the quantity of solvent washing interlayer surfaces.And, utilize the surface treatment of solvent can adjust surface energy.Based on the state that is right after after forming film, by washing processing again, the water contact angle degree changes to 140 ° from 5 °, and this can be according to the polar character adjustment surface energy of luminophor that will be stacked.In addition, by radiation treatment such as ion injection, UV irradiation and UV ozone irradiation or the oxygen that appends, nitrogen or hydrogen plasma processing, can obtain same effect.
Be not defined for the film formed compound of above-mentioned wet treatment especially, as long as this compound has the good adhesion of antianode surface and luminophor.But preferred the employing is generally used for a kind of of anode buffer.Examples for compounds comprises the mixture of conducting polymer such as PEDOT (poly-(3,4)-ethylidene dioxy thiophene) and polystyrolsulfon acid) and PANI (mixture of polyaniline and polystyrolsulfon acid).And, can add organic solvent such as toluene and isopropyl alcohol to conducting polymer.This conducting polymer can comprise the 3rd component such as surfactant.The example of above-mentioned surfactant is the surfactant that comprises the group that is selected from alkyl, alkylaryl, fluoroalkyl, alkylsiloxane base, sulfate, sulfonate, carboxylate, amino-compound, betaine structure and quaternary ammonium group.Also can use nonionic to fluoridize the thing surfactant.
Can form the film in intermediate layer by dry process method such as vacuum moulding machine and RF plasma processing.Especially, radio frequency plasma is handled and can be obtained tack and the good film of durability, and glow discharge being applied to organic gas in this radio frequency plasma is handled is solid with gas aggradation on solid layer thus.For example, contact with substrate, can on substrate, form the film that comprises fluorocarbon by make the fluorocarbon of gasification by the glow discharge in the RF plasma.By in the RF device to the plasma treatment of fluorocarbon of gasification, can form thin fluorocarbon film, and the fluorocarbon of gasification can be selected from C
3F
8, C
4F
10, CHF
3, C
2F
4And C
4F
8By in device, apply (output) radio frequency (RF) voltage with suitable power level, produce plasma.Although reaction temperature can change according to parameter such as power output, gas flow rate and processing time period, thermoregulator preferably is set in device to obtain the repeatability of film thickness.
When utilizing the dry process method of passing through RF plasma processing to form the intermediate layer, can come the etching anode surface by the condition of control plasma generation.Just, by RF plasma processing, can make anode surface level and smooth in the film formed anode surface etch effects of utilizing simultaneously.
Can with the intermediate layer film that optimization obtained similarly that obtains by above-mentioned coating method.Just, can improve or change the characteristic of film by further surface treatment.Particularly, by smoothness, suitable thickness and the durability of film can being adjusted in the proper range with solvent washing.Here, it is 10nm or littler state for 1nm or littler and protruding height that the smoothness of film is illustrated on the surface of film roughness (Ra value), and the suitable thickness of film is 0.2 to 30nm.Similarly, also can adjust the surface energy of film.And, by the annealing in process under various atmosphere; Radiation treatment such as ion injection, UV irradiation and UV ozone irradiation; Perhaps the oxygen that appends, nitrogen or the hydrogen plasma of film are handled, can be obtained same effect.
As the compound of the organic light emission compound layer that is used for organic electroluminescence device of the present invention, that is,, not only can adopt low molecular compound but also can adopt polymer for luminescent layer, hole transmission layer and electron transfer layer.
The example that forms the luminescent material of the organic light emission compound layer in the organic electroluminescence device of the present invention is included in Ohyoh Butsuri (Applied Physics), Yutaka Ohmori, Vol.70, low molecular compound and the polymer luminescent material described among the No.12, pages 1419-1425 (2001).In these materials of Z, in view of the manufacturing process of having simplified device and the preferred polymers luminescent material, and because high emission efficiency and more preferably phosphorescent light-emitting materials.Therefore, preferred especially phosphorescence light emitting polymer.
Structure to the phosphorescence light emitting polymer of the luminescent layer that is used for organic electroluminescence device of the present invention does not limit especially.The instantiation of polymer architecture comprise phosphorescence luminous position (site) wherein (representative instance comprise the transition metal complex described after a while or the monovalence or the divalent group of rare earth metal complex) and conjugated polymer as poly-(to phenylene), poly-(to phenylene vinylidene), gather the polymer architecture that the skeleton structure of fluorenes, polythiophene, polyaniline, polypyrrole and polypyridine combines.In this polymer architecture, the phosphorescence luminous position can be attached in main chain or the side chain.
Another example of the polymer architecture of phosphorescence light emitting polymer compound comprises the polymer architecture that the skeleton structure of wherein phosphorescence luminous position and unconjugated polymer such as polyvinylcarbazole, polysilane, poly-triphenylamine combines.In this polymer architecture, the phosphorescence luminous position can be attached in main chain or the side chain.
An example again of the polymer architecture of phosphorescence light emitting polymer compound comprises the tree-shaped polymer (dendrimer) that comprises the phosphorescence luminous position.In this case, the phosphorescence luminous position can be combined in center, component or the end of tree-shaped polymer.
When the phosphorescence luminous position that is attached to conjugation or unconjugated skeleton structure was launched phosphorescence in above-mentioned polymer architecture, skeleton structure self can be launched phosphorescence.
As the phosphorescence light emitting polymer that is used for organic electroluminescence device of the present invention, because it has provided the many flexibilities in the material design, and the polymer (after this being called " unconjugated phosphorescence light emitting polymer ") that preferred wherein phosphorescence luminous position combines with the skeleton structure of unconjugated polymer, it can easily obtain phosphorescent emissions, can easily synthesize, and can easily prepare coating solution owing to the highly dissoluble in solvent.
Unconjugated phosphorescence light emitting polymer is made of phosphorescence luminous position and carrier transport position.According to phosphorescence luminous position and carrier transport position in conjunction with situation, typical polymer architecture can be divided into following several:
(1) phosphorescence luminous position and carrier transport position all are present in the main chain of polymer (Fig. 2 (1)),
(2) the phosphorescence luminous position is present in the side chain, and carrier transport position (Fig. 2 (2)) in the main chain of polymer,
(3) the phosphorescence luminous position is present in the main chain, and carrier transport position (Fig. 2 (3)) in the side chain of polymer,
(4) phosphorescence luminous position and carrier transport position all are present in the side chain of polymer (Fig. 2 (4)).
Above-mentioned unconjugated phosphorescence light emitting polymer can comprise cross-linked structure; Can be for wherein hole mobile material, electron transport material or luminescent material are not coupled to each other separate homopolymers; Perhaps can be polymer by two kinds of material polymerizations.And, in these polymeric materials, be selected from least a polymer that should be in three kinds of materials of hole mobile material, electron transport material and luminescent material, and other two kinds of materials can be low molecular weight compound.
Above-mentioned unconjugated phosphorescence light emitting polymer can comprise two or more phosphorescence luminous positions (in main chain of any one be present in polymer of these positions or any one of side chain), and can comprise two or more carrier transport positions (in main chain of any one be present in polymer of these positions or any one of side chain, perhaps can not being bonded to each other).
The molecular weight of preferred above-mentioned unconjugated phosphorescence light emitting polymer is 1,000 to 100,000 weight average molecular weight, more preferably 5,000 to 50,000.
For above-mentioned phosphorescence luminous position, can use the univalent perssad of the compound of at room temperature launching phosphorescence or multivalence (divalence or more multivalence) group, and the monovalence or the divalent group of preferred transition metal or rare earth metal complex.The example that is used for the transition metal of top transition metal complex be included in first transition elements system from Sc (atomicity 21) to Zn (atomicity 30), second transition elements system from Y (atomicity 39) to Cd (atomicity 48), and in the 3rd transition elements is the metal from Hf (atomicity 72) to Hg (atomicity 80).The example that is used for the rare earth metal of top rare earth metal complex is included in the metal of group of the lanthanides from La (atomicity 57) to Lu (atomicity 71) of the periodic table of elements.
The example that is used for the part (ligand) of transition metal or rare earth metal complex is included in G.Wilkinson (Ed.), Comprehensive Coordination Chemistry (Plenum Press, 1987) with at Akio Yamamoto, " Yuuki Kinzoku Kagaku-Kiso to Ohyoh-" (Metalorganic Chemistry-basic and applied-), Shokabo, those parts of describing in 1982.In these parts, preferred halogen ligands, nitrogen heterocyclic ring part (phenylpyridine part, benzoquinoline part, oxyquinoline part, bipyridine ligand, three pyridine ligands, phenanthroline part etc.), diketonate ligand (acetyl acetone ligands, dipivaloylmethane part etc.), carboxylate part (as the acetic acid esters part), phosphorus part (triphenylphosphine ligand, phosphite ester ligand etc.), carbon monoxide part, isonitrile part and cyano group part.Metal complex can comprise one or more these parts in a complex compound.And,, can use dinuclear complex, polynuclear complex or by two or more synthetics that constitute of these complex compounds as metal complex.
For above-mentioned carrier transport position, can use the group of the monovalence of dipole characteristic or multivalence (divalence or more multivalence) with hole transport or electron transport property or transporting holes and electronics.For the hole transport position, can use carbazole, triphenylamine, N, N '-diphenyl-N, N '-(3-aminomethyl phenyl)-1,1 '-biphenyl-4, the group of the monovalence of 4 ' diamines (TPD) or multivalence (divalence or more multivalence).For the electric transmission position, can use oxyquinoline to derive metal complex as three (oxyquinoline) aluminium (Alq
3); The group of the monovalence of oxadiazole derivative, triazole derivative, imdazole derivatives and pyrrolotriazine derivatives or multivalence (divalence or more multivalence); And boron compound.For the bipolar carrier position, can use 4,4 '-N, the group of the monovalence of N '-two carbazoles-biphenyl (CBP) or multivalence (divalence or more multivalence).
Luminescent layer in the organic electroluminescence device of the present invention can only be formed by above-mentioned phosphorescent polymer compounds or conjugated polymer.And in order to replenish the carrier transmission characteristics of polymer compound or conjugated polymer, luminescent layer also can form the component that wherein is mixed with other carrier transport compound.That is, when phosphorescent polymer compounds was hole mobile material, it can be mixed with the electric transmission compound, and when phosphorescent polymer compounds was electron transport material, it can be mixed with the hole transport compound.Here, the carrier transport compound that is mixed with phosphorescent polymer compounds can be low molecular weight compound or polymer.
The example of the hole transport low molecular weight compound that can mix with above-mentioned phosphorescent polymer comprises known hole mobile material, for example, triphenylamine derivative, as N, N '-diphenyl-N, N '-(3-aminomethyl phenyl)-1,1 '-biphenyl-4, and 4 ' diamines (TPD), 4,4 '-two [N-(1-(naphthyl))-N-phenyl amino] biphenyl (α-NPD) with 4,4 ', 4 " (3-methyl phenyl phenyl amino) triphenylamine (m-MTDATA)-three.The example of the hole transport polymer that can mix with above-mentioned phosphorescent polymer comprises by polymerisable functional group is introduced the triphenylamine low molecular weight compound by the compound of producing high-molecular, for example, disclosed polymer in Japanese Patent Application Publication No.H8-157575 with triphenylamine skeleton structure.
The example of the electric transmission low molecular weight compound that can mix with above-mentioned phosphorescent polymer comprises 8-hydroxyquinoline derivative, as three (hydroxyquinoline aluminum) (Alq
3), oxadiazole derivative, triazole derivative, imdazole derivatives and pyrrolotriazine derivatives.The example of the electric transmission polymer that can mix with above-mentioned phosphorescent polymer comprises by polymerisable functional group being introduced above-mentioned electric transmission low molecular weight compound by the compound of producing high-molecular, for example, disclosed poly-PBD in Japanese Patent Application Publication No.H10-1665.
And, in order to improve the characteristic of the film that forms by above-mentioned phosphorescent polymer, can mix other polymer compound of the characteristics of luminescence of not participating in phosphorescent polymer directly, form synthetic thus as luminescent material.For example, can add polymethyl methacrylate (PMMA) and Merlon, so that the film that obtains has flexible.
The preferred 1nm of the thickness of luminescent layer more preferably 5 arrives 300nm to 1 μ m, further more preferably 10 arrives 100nm.
The example that forms the hole mobile material of the hole transmission layer in organic phosphorescence luminescent device of the present invention comprises known low-molecular-weight hole mobile material, for example, triphenylamine derivative, as N, N '-diphenyl-N, N '-(3-aminomethyl phenyl)-1,1 '-biphenyl-4, and 4 ' diamines (TPD), 4,4 '-two [N-(1-naphthyl)-N-phenyl amino] biphenyl (α-NPD) with 4,4 ', 4 " (3-methyl phenyl phenyl amino) triphenylamine (m-MTDATA)-three.Also can use the polymer hole mobile material, and example comprises by polymerisable functional group is introduced the triphenylamine low molecular weight compound by the compound of producing high-molecular, for example, the disclosed polymeric material that has the polymer of triphenylamine skeleton structure and for example gather (to phenylene vinylidene) and poly-diakyl fluorenes in Japanese Patent Application Publication No.H8-157575.Can use separately these hole mobile materials or in conjunction with or stacked two or more that use in them.The preferred 1nm of the thickness of hole transmission layer is to 5 μ m, and more preferably 5nm further preferred 10 arrives 500nm to 1 μ m.
In organic electroluminescence device of the present invention, the example that is used to form electron transfer layer or is used for being mixed into the electron transport material of luminescent layer comprises low molecular electronic transferring material, and for example the 8-hydroxyquinoline derivative metal complex is as three (oxyquinoline) aluminium (Alq
3), oxadiazole derivative, triazole derivative, imdazole derivatives and pyrrolotriazine derivatives.And electron transport material can be by polymerisable functional group being introduced the polymer that above-mentioned low molecular electronic transport compound produces, for example, and in Japanese Patent Application Publication No.H10-1665 disclosed poly-(PBD).Can be individually or mix with other electron transport material or stacked these electron transport materials that uses.The preferred 1nm of the thickness of electron transfer layer is to 5 μ m, and more preferably 5nm further preferred 10 arrives 500nm to 1 μ m.
The phosphorescence light emitting polymer, being used for the hole mobile material of hole transmission layer and being used for each of electron transport material of electron transfer layer all can be individually or by using the polymeric material as binding agent to form each layer.The example that can be used for the polymeric material of binding agent comprises polymethyl methacrylate, Merlon, polyester, polysulfones and polyphenylene oxide.
The method that is used to form luminescent layer, hole transmission layer and electron transfer layer can be resistance heating deposition process, electron beam deposition method, sputtering method, spin coating method, casting method, nick version coating method, gravure coating method, rod coating (bar coating) method, roller coat coating method, wire bar coating (wire-bar coating) method, dip coating method, spraying method, method for printing screen, flexography printing method, offset printing method and ink jet printing method etc.Utilizing under the situation of low molecular weight compound, what mainly adopt is resistance heating deposition process and electron beam deposition method, and utilizing under the situation of polymeric material, what mainly adopt is spin coating method, casting method, nick version coating method, gravure coating method, excellent coating method, roller coat coating method, wire bar coating method, dip coating method, spraying method, method for printing screen, flexography printing method, offset printing method and ink jet printing method.
For making hole and electronics effectively compound in luminescent layer, hole blocking layer (blocking layer) can be set at the cathode side of luminescent layer pass through luminescent layer so that prevent the hole.Compound with the HOMO (highest occupied molecular orbital) that is lower than luminescent material can be used for hole blocking layer.This examples for compounds comprises triazole derivative, oxadiazole derivative, phenanthroline derivative and aluminium complex.
And, for preventing deexcitation, can provide exciton barrier-layer at cathode side adjacent with luminescent layer at cathodic metal place exciton.For exciton barrier-layer, can use the compound that has greater than triple excitation energy of luminescent material, for example, triazole derivative, phenanthroline derivative and aluminium complex.
For the negative electrode in the organic electroluminescence device of the present invention, can use compound with chemical stability and low work function.Example comprises known cathode material, as Al, MgAg alloy and Al and alkali-metal alloy such as AlLi and AlCa.From the angle of chemical stability, the work function of compound is preferably 2.9eV or bigger.By for example method of resistance heating deposition process, electron beam deposition method, sputtering method and ion plating method, form the film of cathode material.The thickness of negative electrode is preferably 10nm to 1 μ m, more preferably 50 arrives 500nm.
Be to reduce the electronics injection barrier from the negative electrode to the organic layer and improve the efficient of injecting electronics, can between negative electrode and the organic layer adjacent, insert cathode buffer layer (metal level) with the work function that is lower than negative electrode with negative electrode.The low workfunction metal that is used for this purpose comprises alkali metal (Na, K, Rb and Cs), alkaline-earth metal (Sr and Ba) and rare earth metal (Pr, Sm, Eu and Yb).The thickness of cathode buffer layer preferred 0.05 to 50nm more preferably 0.1 arrives 20nm, further more preferably 0.5 arrives 10nm.
Cathode buffer layer also can form as having the above-mentioned substance of low work function and the mixture of electron transport material.For the electron transport material that is used for cathode buffer layer, can use the above-mentioned organic compound that is used for electron transfer layer.Codeposition can be used as the method for the film that is formed for cathode buffer layer.And, under levying, can use the method for the formation film of having described by the situation that applies solution formation film, for example, spin coating method, dip coating method, ink ejecting method, printing process, spraying (spray) method and distributor (dispenser) method.In this case, the thickness of cathode buffer layer is preferably 0.1 to 100nm, more preferably 0.5 arrives 50nm, further more preferably 1 arrives 20nm.
In organic electroluminescence device of the present invention, substrate can be for the transparent dielectric substrate of the emission wavelength of luminescent material.Can for example glass and transparent plastic comprise that PET (PETG) and Merlon are used for substrate with known material.
Example
Be described in more detail the present invention below with reference to example and comparative example, but the invention is not restricted to this.
For simplifying material and as follows by its layer abbreviation that forms.
ITO: tin indium oxide (anode),
PEDOTPSS: poly-(3,4-ethylidene dioxy thiophene) and polystyrolsulfon acid ester (anode buffer layer=conventional intermediate layer)
ELP: (terpolymer comprises aromatic amine (hole mobile material part), boryl molecule (electron transport material part) and iridium complex (phosphorescence pigment part) to phosphorescent polymer: poly-[viTPD-viTMB-viIr (ppy)
2(acac)] molecular structure)).
As plasma generator, use can plasma etching (PE) and the capacitive coupling type device of reactive ion etching (RIE).
Ratio example 1:
Utilize the substrate of ITO (tin indium oxide) coating to make organic luminescent device, this substrate is the square glass substrate of 25mm, and forms the wide ITO electrode of two 4mm as anode with bar shaped on a surface of substrate.At first, clean this anode substrate with liquid.That is, carry out ultrasonic waves for cleaning, then with the ultra-pure water flushing of flowing with the commercial cleaning fluid antianode substrate of making.After this, the antianode substrate carries out ultrasonic waves for cleaning in isopropyl alcohol (IPA) and soaks and make its drying.In addition, 3, under the condition of the coating time of the 500rpm speed of rotation and 40 seconds, will be by spin coating method with IPA with poly-(3 of 1: 1 dilution proportion, 4-ethylidene dioxy thiophene)-solution of polystyrolsulfon acid ester (the BAYTRON P (trade name) that is made by Bayer Co.) is applied on the ITO (anode), and 200 ℃ down dry 30 minutes to form conventional intermediate layer.The intermediate layer that is obtained has the thickness of about 50nm, the Ra value of 1.3nm and the height of projection of 20nm.
Then, preparation is used to form the coating solution of luminophor.That is, the ELP of 60mg is dissolved in 1, in the toluene of 940mg (superfine, by Wako Pure Chemical Industries, Ltd. makes), and the filter of the pore size of the solution that makes acquisition by having 0.2 μ m is to obtain coating solution.Next, 3, under the condition of the coating time of the speed of rotation of 000rpm and 30 seconds, the coating solution that will prepare by spin coating method is applied on the intermediate layer, and 100 ℃ dry 30 minutes down, to form luminescent layer.The luminescent layer that is obtained has the thickness of about 90nm.Then, the substrate that is formed with luminescent layer on it is placed precipitation equipment, with the thick calcium of the vapor deposition rate of 0.01nm/s deposition 10nm and subsequently with the thick aluminium of vapor deposition rate deposition 150nm of 1nm/s, with fabricate devices 1.In addition, with the vertical vertical direction of anode on form the calcium layer and the aluminium lamination of the wide bar shaped of two 3mm, on each glass substrate, to make the organic luminescent device of four 4mm (length) * 3mm (width).Suppose that this device is an organic luminescent device 1.
Reference example
The dry substrate with ITO places plasma generator after will cleaning with the mode liquid identical with ratio example 1, and oxygen is provided in the device.By alternating voltage is applied in the device, start discharge, produce oxygen plasma has ITO with exposure substrate then.During the formation of oxygen plasma, the pressure that gas flow rate in the device is controlled to be 1Pa will be provided to.The electrical power that offers device substrate is that 150W and processing time are 30 seconds.Carry out subsequently operation in the mode identical, have the organic luminescent device 2 in conventional intermediate layer with preparation with comparative example 1.The intermediate layer that obtains by operation has the Ra value of 0.7nm and the height of projection of 9nm.
Example 1:
In the mode identical with reference example, the substrate with ITO to be carried out liquid clean, oxygen plasma treatment subsequently is coated with the substrate in conventional intermediate layer with preparation.Measure the thickness in the conventional intermediate layer that obtains and the surface roughness that is coated with the substrate that obtains in conventional intermediate layer, consequently, thickness is 50nm, and the Ra value is 0.7nm, and height of projection is 9nm.Next, optimization is coated with the substrate in conventional intermediate layer.That is, the substrate that is coated with conventional intermediate layer is fixed on the spinner, and, rotates it to clean substrate with 3000rpm simultaneously with the IPA drippage thereon.Carry out 1 minute cleaning.After drippage, further rotated substrate 1 minute with 4000rpm, following dry 1 minute at 200 ℃ then.The intermediate layer that is obtained after optimization has the thickness of 27nm, the Ra value of 0.5nm and the height of projection of 7nm.Carry out from the operation subsequently of ELP coating beginning in the mode identical, with preparation organic luminescent device 3 with comparative example 1.
Example 2:
The dry substrate with ITO places plasma generator after will cleaning with the mode liquid identical with comparative example 1, and oxygen is provided in the device.By alternating voltage is applied in the device, start discharge, produce oxygen plasma then to expose the substrate of concrete ITO.That is, the pressure that carrier of oxygen flow velocity in the device is controlled to be 1Pa will be provided to.Under the supply electrical power of 150W, carried out plasma treatment 30 seconds.Next, the gas that provides is changed into CHF from oxygen
3Gas, and flow velocity is controlled to be the pressure of 7Pa.Then, under the supply electrical power at 300W under the PE pattern, carry out the plasma treatment of substrate 10 seconds.Result as the x-ray photoelectron power spectrum (XPS) on the surface of the substrate with ITO after handling is analyzed finds to form fluorocarbon film (being described as " CFn intermediate layer " in table 1) on the surface of the substrate with ITO.By the analysis of depth direction being found further the fluorocarbon film has the Ra value of the thickness of about 1nm, 0.7nm and the height of projection of 8nm.As above form after the intermediate layer, carry out from the operation subsequently of ELP coating beginning in the mode identical, with preparation organic luminescent device 4 with comparative example 1 by the present invention.
Comparative example 2:
The dry substrate with ITO places plasma generator after will cleaning with the mode liquid identical with comparative example 1, and oxygen is provided in the device.By alternating voltage is applied in the device, start discharge, produce oxygen plasma then to expose the substrate of concrete ITO.That is, the pressure that carrier of oxygen flow velocity in the device is controlled to be 1Pa will be provided to.Under the supply electrical power of 150W, carried out plasma treatment 30 seconds.Next, the gas that provides is changed into CHF from oxygen
3Gas, and flow velocity is controlled to be the pressure of 7Pa.Then, under the supply electrical power at 300W under the PE pattern, carry out the plasma treatment of substrate 2 minutes.Result as the x-ray photoelectron power spectrum (XPS) on the surface of the substrate with ITO after handling is analyzed finds to form the fluorocarbon film on the surface of the substrate with ITO.Find that further the fluorocarbon film has the thickness of about 27nm, the Ra value of 0.5nm and the height of projection of 4nm.As above form after the intermediate layer that constitutes by the fluorocarbon film, carry out from the operation subsequently of ELP coating beginning in the mode identical, with preparation organic luminescent device 5 with comparative example 1.
Example 3:
The dry substrate with ITO places plasma generator after will cleaning with the mode liquid identical with comparative example 1, and oxygen is provided in the device.By alternating voltage is applied in the device, start discharge, produce oxygen plasma then to expose the substrate of concrete ITO.That is, the pressure that carrier of oxygen flow velocity in the device is controlled to be 1Pa will be provided to.Under the supply electrical power of 150W, carried out plasma treatment 30 seconds.Next, the gas that provides is changed into CHF from oxygen
3Gas, and flow velocity is controlled to be the pressure of 7Pa.Then, under the supply electrical power at 100W under the PE pattern, carry out the plasma treatment of substrate 10 seconds.Result as the x-ray photoelectron power spectrum (XPS) on the surface of the substrate with ITO after handling is analyzed finds to form the fluorocarbon film on the surface of the substrate with ITO.Find that further the fluorocarbon film has the Ra value of thickness and the 0.7nm of about 0.2nm.In the mode identical with reference example, make and experienced the above-mentioned coated conventional intermediate layer of substrate of using the plasma treatment of oxygen and fluorine gas, have the substrate in conventional intermediate layer with preparation.Measure the surface roughness of the substrate that obtains by the conventional intermediate layer of coating, and this substrate has the Ra value of thickness and the 1.0nm of 50nm.Next, optimization is coated with the substrate in conventional intermediate layer.That is, the substrate that is coated with conventional intermediate layer is fixed on the spinner, and drips IPA thereon, rotate it to clean substrate with 3000rpm simultaneously.Cleaned 1 minute.After drippage, further rotated substrate 1 minute with 4000rpm, following dry 1 minute at 200 ℃ then.The intermediate layer that is obtained after optimization has the thickness of 30nm, the Ra value of 0.5nm and the height of projection of 8nm.Carry out from the operation subsequently of ELP coating beginning in the mode identical, with preparation organic luminescent device 6 with comparative example 1.
Example 4:
The dry substrate with ITO places plasma generator after will cleaning with the mode liquid identical with comparative example 1, and with CHF
3Gas is provided in the device.With CHF
3Gas flow rate is controlled to be the pressure of 7Pa.Then, under the supply electrical power at 200W under the PE pattern, carry out the plasma treatment of substrate 60 seconds.The measurement result of the surface roughness of the substrate with ITO after handling as the article on plasma body, the surface has the Ra value of tool 0.8nm.And, as the result that the x-ray photoelectron power spectrum (XPS) on the surface of substrate is analyzed, find on the surface of substrate, to form the fluorocarbon film with ITO.Estimate that the fluorocarbon film has the height of projection of thickness and the 3nm of 0.5nm.For having experienced CHF as above
3Substrate after the plasma treatment of gas carries out from the operation subsequently of ELP coating beginning in the mode identical with comparative example 1, with preparation organic luminescent device 7.
By using the DC voltage/current able to programme source TR6143 that makes by Advantest Corporation, between the negative electrode of above-mentioned device and anode, apply voltage respectively, luminous to cause, and by using the luminosity meter BM-8 that makes by Topcon Corporation to measure luminosity.Also observe low luminosity, to carry out durability test.The assessment result of the EL characteristics of luminescence is shown in Table 1.
According to the initial luminosity of supposition is 100cd/m
2The brightness half-life assess durability referred in this.
Table 1
| Element number | The formation of element | Luminous starting voltage [V] | Maximum luminosity (cd/m 2) | External quantum efficiency (%) | Durability (hour) |
| 1 (comparative example 1) | The conventional intermediate layer of ITO//ELP/C aAl | 2.5 | 66,000 | 6.6 | 900 |
| 2 (reference example) | (O 2) the conventional intermediate layer/ELP/CaAl of ITO/ of plasma treatment | 2.5 | 75000 | 6.1 | 1,000 |
| 3 (examples 1) | (O 2) the conventional intermediate layer+optimization of ITO//ELP/CaAl of plasma treatment | 2.5 | 79,000 | 6.0 | 2,500 |
| 4 (examples 2) | (O 2) the ITO/CFn intermediate layer/ELP/CaAl of plasma treatment | 2.4 | 74,000 | 7.5 | 4,300 |
| 5 (comparative examples 2) | (O 2) the ITO/CFn intermediate layer/ELP/CaAl of plasma treatment | - | Not luminous | - | - |
| 6 (examples 3) | (O 2+CHF 3) the conventional intermediate layer+optimization of ITO//ELP/CaAl of plasma treatment | 2.4 | 78,000 | 5.6 | 4,000 |
| 7 (examples 4) | (CHF 3) ITO/ELP/CaAl of plasma treatment | 2.4 | 82,000 | 7.3 | 7,500 |
In comparative example 2, even also do not observe luminous by electric current and when driving voltage is risen to 20V.Discovery is as dielectric film and have above the CFn intermediate layer of 30nm thickness improving not effect of device property, and this layer thickness in the thinner region is optimal.
As to shown in the assessment result of organic luminescent device 1 to 7, clearly, improved the durability of device significantly by the present invention.And it shows by CHF only
3Plasma treatment improved surperficial smoothness, and also improved Devices Characteristics.
Fig. 2 shows the result to the luminous durability test of organic luminescent device 1 (ratio example 1), organic luminescent device 4 (comparative example 2), organic luminescent device 6 (example 3) and organic luminescent device 7 (example 4).It shows with comparing by the present invention of the organic luminescent device 1 with conventional intermediate layer and has significantly improved the organic light-emitting device durability.
Specifically reference example has been described the present invention.But, can in scope of the present invention and order, revise example.
Industrial usability
The organic electroluminescence device of (I) can obtain high emission efficiency and long device lifetime according to the present invention, described organic electroluminescence device comprises the luminophor layer that is present between anode and the negative electrode, and it is 0.2 to the intermediate layer of 30nm that wherein said anode comprises thickness in its surface.
Claims (12)
1. the manufacture method of an organic electroluminescence device, described organic electroluminescence device comprises the luminophor layer that is present between anode and the negative electrode, it is 0.2 to the intermediate layer of 30nm that wherein said anode comprises thickness in its surface, and described method is characterised in that by the wet treatment coating process and forms described intermediate layer and with the step on the surface in the described intermediate layer of solvent washing of the composition that can dissolve described luminophor.
2. method as claimed in claim 1, wherein said luminophor are the phosphorescent polymer material.
3. method as claimed in claim 1, wherein said luminophor are fluorescent material.
4. method as claimed in claim 1, wherein said intermediate layer have the 1nm that is expressed as the Ra value or littler surface roughness.
5. method as claimed in claim 1, the lip-deep projection in wherein said intermediate layer has 10nm or lower height.
6. method as claimed in claim 1 is included in and forms the described intermediate layer step on the surface of the described anode of RF plasma processing before.
7. method as claimed in claim 6 is wherein carried out described RF plasma processing in comprising one or more the gas that is selected from oxygen, argon and fluorocarbon, with the height of the lip-deep projection of the surface roughness of adjusting described anode and described anode.
8. method as claimed in claim 1, wherein said intermediate layer comprises organic material.
9. method as claimed in claim 1, wherein said intermediate layer comprises conducting polymer.
10. method as claimed in claim 1, the solvent that wherein can dissolve described luminophor composition is an isopropyl alcohol.
11. a backlight that is used for display unit, it uses the organic electroluminescence device that obtains by the manufacture method of any one in the claim 1 to 10 as flat luminous light source.
12. a lighting device, it uses the organic electroluminescence device that obtains by the manufacture method of any one in the claim 1 to 10 as flat luminous light source.
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